CN103331181B - Magnetic core-shell Fenton-type catalyst, and preparation method and application of catalyst - Google Patents

Magnetic core-shell Fenton-type catalyst, and preparation method and application of catalyst Download PDF

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CN103331181B
CN103331181B CN201310293883.5A CN201310293883A CN103331181B CN 103331181 B CN103331181 B CN 103331181B CN 201310293883 A CN201310293883 A CN 201310293883A CN 103331181 B CN103331181 B CN 103331181B
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nano
cationic polyelectrolyte
layer
particle
shell
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CN103331181A (en
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张建鹏
杨晓玲
钟丽云
王伟萍
胡敏
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Shanghai Wending Water Treatment Engineering Co Ltd
SHANGHAI WINNER ENVIRONMENTAL TECHNOLOGIES Co Ltd
East China University of Science and Technology
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Shanghai Wending Water Treatment Engineering Co Ltd
SHANGHAI WINNER ENVIRONMENTAL TECHNOLOGIES Co Ltd
East China University of Science and Technology
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Abstract

The invention discloses a magnetic core-shell Fenton-type catalyst, and a preparation method and an application of the catalyst. An inner core of the core-shell Fenton-type catalyst is an Fe3O4 microsphere accumulated by nano Fe3O4 particles; a shell layer is an alternate adsorption sequence layer formed by a cationic polyelectrolyte and nano SiO2 particles; and an outermost layer of the alternate adsorption sequence layer is an SiO2 nano particle layer such as -ABABAB, wherein A is the cationic polyelectrolyte, and B is SiO2. The preparation method of the catalyst comprises the steps of preparing the Fe3O4 microsphere by a hydrothermal method, preparing the nano SiO2 particles by a sol-gel method, and assembling the cationic polyelectrolyte with positive charges and the nano SiO2 particles with negative charges on the Fe3O4 microsphere by a layer-by-layer electrostatic self-assembly method. The core-shell Fenton-type catalyst is high in catalysis efficiency and easy to recover, can be used repeatedly, can be coupled with H2O2 to form an inhomogeneous phase Fenton-type system, and can conduct catalytic oxidation on phenolic wastewater.

Description

Magnetic core-shell type type Fenton catalyst of a kind of tool and its preparation method and application
Technical field
The invention belongs to nanomaterial science and environmental science, particularly, relate to a kind of preparation method and application thereof of core-shell type magnetic type Fenton catalyst, its core is Fe 3o 4microballoon, shell is by SiO 2nano particle forms.
Background technology
Phenol and the similar compound containing phenyl ring common are organic pollutants in industrial wastewater, and toxicity is greatly and not easily by the microbial degradation in environment.Processing method common at present has physisorphtion, chemical oxidization method and biological degradation method.In recent years, the Fenton oxidation technology in chemical oxidization method becomes the focus that people pay close attention to gradually, and it utilizes Fe 2+and H 2o 2the hydroxyl radical free radical (OH) that the two association reaction generation oxidisability is very strong carrys out the organic pollution in oxidation Decomposition water.This method has rapidly and efficiently, operating process is simple, without the need to complex device, to follow-up process nonhazardous effect and the advantage such as environmentally friendly, be applied to gradually in the waste water treatment engineerings such as paper pulp papermaking, dyestuff, agricultural chemicals.
There is a lot of deficiencies in actual applications in traditional Fenton oxidation technology, as: H 2o 2utilization rate is not high, and organic matter degradation is incomplete; Oxidation reaction must control to carry out in the acid medium of pH < 3, and the pH value of actual waste water is generally not less than 3, and extremely low acidity requirements adds cost of water treatment.In order to address this problem, a lot of scholar attempts the ferrous salt replacing homogeneous phase with heterogeneous iron system solid catalyst.The solid catalyst of this iron system can discharge ferrous ion in wastewater treatment process, with H 2o 2react thus excite Fenton to react.
Chinese invention patent (publication number CN101549294A) discloses one " magnetic Nano material for organic pollution process ", and " magnetic Nano material can catalysis H in invention proposition 2o 2generate OH ", its magnetic Nano material comprises Fe 2o 3and Fe 3o 4magnetic nanoparticle.By using magnet or centrifugal recovery magnetic material, then by follow-up simple its catalytic activity of process regeneration, reclaim reprocessing number of times and can reach more than 5 times.Master thesis " preparation of nano ferriferrous oxide and the process to phenol wastewater thereof " (2010, HeFei University of Technology, author: Liu Zhonghuang, counselor: Chai Duoli) carry out similar work, the Fe that they adopt hydrothermal co-precipitation method to prepare particle diameter to be about 40nm 3o 4nano particle, with H 2o 2form new modified Fenton reaction, to the corresponding research that process phenols wastewater carries out.Catalyst is not only easily separated, reclaim and recycled, and does not have the secondary pollution of catalyst; Without the need to adjust ph before phenolic wastewater treatment, effectively can remove the volatile phenol content in waste water, the COD in waste water can be reduced crvalue.The application of the method, can reduce the processing cost of phenol wastewater.
For improving the catalytic activity of magnetic material further, it mixes or compound with some materials by researcher, such as, Chinese invention patent (publication number CN102295341A) discloses " a kind of method of heterogeneous Fenton-like reaction process chlorine organic wastewater ", with Fe 0, nanometer Fe 3o 4or nanometer Fe 0/ Fe 3o 4mixture is type Fenton catalyst, and H 2o 2there is the chlorinatedorganic in lower degrading waste water simultaneously.Fe 0and Fe 3o 4be spheric granules, particle diameter is respectively 50 ~ 80nm and 50nm.There is catalyst recoverable, economically feasible equally, be suitable for the feature of pH value wider (pH:2.0 ~ 6.0).Chinese invention patent (publication number: CN102327773A) then discloses one " nanometer Fe 3o 4/ CeO 2the preparation method of composite and application ", with nano Ce O 2for carrier, adopt the Fe of Co deposited synthesis nanometer 3o 4/ CeO 2composite, nano Ce O 2as Fe 3o 4the auxiliary agent of catalyst or the additive of catalyst carrier, by the synergy between transition metal and then the activity improving catalyst.
In sum, with nano level Fe 3o 4magnetic nanoparticle, as main body, is directly applied, or and some Material cladding, then with H 2o 2composition modified Fenton reaction, process waste water can play good effect.But, nano level Fe 3o 4magnetic nanoparticle, although have excellent superparamagnetism, in actual use, due to the surface energy that it is high, very easily reunites, cannot keep its high activity.Further, composition complicated in waste water, is also easily adsorbed on the Fe as catalyst 3o 4the surface of magnetic nanoparticle, reduces catalyst activity, causes " catalyst poisoning ".In addition, the Fe of catalyst nano level how is controllably realized 3o 4magnetic nanoparticle and H 2o 2the coupling of amount, gives full play to the treatment effect of modified Fenton reaction, is also the technological difficulties needing to solve.
Summary of the invention
The object of the invention is to solve the deficiencies in the prior art, high, the easy recovery of a kind of catalytic efficiency, reusable be provided, and can and H 2o 2coupling forms heterogeneous Fenton-like system, the catalyst of catalytic oxidation treatment phenol wastewater.Specific as follows:
The magnetic core-shell type type Fenton catalyst of a kind of tool, the kernel of described core-shell type type Fenton catalyst is nano level Fe 3o 4the Fe of particle packing 3o 4microballoon, shell is cationic polyelectrolyte and SiO 2the alternating sorbent sequence layer that nano particle is formed; The outermost layer of described alternating sorbent sequence layer is described SiO 2nano-particle layer, innermost layer is described cationic polyelectrolyte layer.Such as ,-ABABAB, wherein A is cationic polyelectrolyte, and B is SiO 2, the Fe of kernel 3o 4electronegative.
Described Fe 3o 4the particle diameter of microballoon is 200 ~ 500nm.
Described cationic polyelectrolyte is diallyl dimethyl ammoniumchloride (poly (diallyldimethylammonium chloride), or PAH ((polyallyamine hydrochloride, PAH)) PDDA).
Described Nano-meter SiO_2 2the particle diameter of particle is 10 ~ 40nm, and optimum is 30nm.
The preparation method of the magnetic core-shell type type Fenton catalyst of above-mentioned tool, comprises the steps: first to adopt hydro-thermal method to prepare Fe 3o 4microballoon, then adopt sol-gal process to prepare Nano-meter SiO_2 2particle, then adopts layer upon layer electrostatic self-assembly method by positively charged cationic polyelectrolyte and electronegative described Nano-meter SiO_2 2groups of grains is contained in described Fe 3o 4on microballoon.
Described hydro-thermal method prepares Fe 3o 4microballoon refers to, by FeCl 3: natrium citricum: sodium acetate take mass ratio as 1:(0.1 ~ 0.4, optimum is 0.2): (1 ~ 3, optimum is 2) join successively in ethylene glycol, after stirring, transfer in water heating kettle, at 180 ~ 250 DEG C after hydro-thermal reaction 8 ~ 12h, cool to room temperature, centrifugal, after product absolute ethyl alcohol and ultra-pure water clean 3 times respectively, drying for standby;
Described sol-gal process prepares Nano-meter SiO_2 2particle refers to, ethyl orthosilicate, absolute ethyl alcohol and water are configured to solution in 1:1.5 ~ 2:1.5 ~ 2 by volume, are warming up to 60 ~ 90 DEG C, stir 0.5 ~ 2h, then the ammonia solution of 0.5 ~ 3.0mol/L is added, obtained described Nano-meter SiO_2 after continuing reaction 0.5 ~ 2h 2particle.(description (Guo Yu etc., sol-gal process prepares nano silicon, Tianjin chemical industry, 2005) according in document)
Described layer upon layer electrostatic self-assembly method carries out according to following step:
A: the described Fe obtained by hydro-thermal method 3o 4microballoon joins in the reactor of the aqueous solution that cationic polyelectrolyte and soluble-salt are housed, and described reactor is placed on shaking table after vibration absorption 10min, and described cationic polyelectrolyte is just adsorbed on described Fe 3o 4microsphere surface, after Magneto separate, deionized water washing, the operation in tandem that again disperses 3 times, with deionized water dispersion, forms Fe 3o 4/ cationic polyelectrolyte complex microsphere (Fe 3o 4/ PE) suspension; Wherein, Fe 3o 4microballoon and cationic mass ratio are 0.01 ~ 0.1; The concentration of cationic polyelectrolyte is 0.1g/mL ~ 5g/mL, optimum 3g/mL; Described soluble-salt refers to sodium chloride, and concentration is 0.1 ~ 0.6moL/L, and optimum is 0.5moL/L;
B: will containing Nano-meter SiO_2 2granular mass joins described Fe than the aqueous solution being 0.5 ~ 10% 3o 4in/cationic polyelectrolyte complex microsphere suspension, pH value of water solution is regulated to be 9 ~ 11, Nano-meter SiO_2 2particle and Fe 3o 4the mass ratio of/cationic polyelectrolyte complex microsphere is 0.1 ~ 2(optimum 0.8), on shaking table after vibration absorption 20min, Nano-meter SiO_2 2particle is just adsorbed on Fe 3o 4the surface of/cationic polyelectrolyte complex microsphere, equally after Magneto separate, deionized water washing, the operation in tandem that again disperses 3 times, then with deionized water dispersion, forms Fe 3o 4/ cationic polyelectrolyte/Nano-meter SiO_2 2particles dispersed microballoon (Fe 3o 4/ PE/SiO 2) suspension;
C: repeat above-mentioned steps A and step B, repeatedly, can obtain kernel is Fe to circulation absorption 3o 4microballoon, shell are by multilayer cationic polyelectrolyte/Nano-meter SiO_2 2the described tool magnetic core-shell type Fenton catalyst of particle composition, i.e. Fe 3o 4/ (PE/SiO 2) nmicroballoon, wherein, n represents PE and SiO 2at Fe 3o 4the number of plies of upper alternately adsorbent serial layer, the number of plies is not particularly limited.
The application of the magnetic core-shell type type Fenton catalyst of above-mentioned tool, at the magnetic core-shell type type Fenton catalyst of described tool and H 2o 2existence simultaneously descends and phenol wastewater reacts, the phenolic comp ' ds pollution in degrading waste water;
When the phenolic concentration of phenol wastewater is 10mg/L ~ 120mg/L, the consumption of the magnetic core-shell type type Fenton catalyst of described tool is 20 ~ 100mg/L, described H 2o 2consumption be 10 ~ 50mmoL/L.
After wastewater treatment completes, utilize Fe 3o 4/ (PE/SiO 2) nthe magnetic of microballoon by mixture sedimentation, the Fe of bottom precipitation 3o 4/ (PE/SiO 2) nmicroballoon is reusable after reclaiming.
Beneficial effect of the present invention is embodied in: (1) catalyst has magnetic, easily reclaims, and can reuse; (2) as the Fe of core 3o 4microballoon is by nanoscale Fe 3o 4particle formed, and has good superparamagnetism; (3) (the PE/SiO that electrostatic self-assembled is coated 2) nshell, both reduced Fe 3o 4the surface energy of microballoon, prevents it from reuniting, and can play protection Fe in the treatment of waste water 3o 4the effect of microballoon, reduces the pollution of catalyst and poisoning possibility; (4) (the PE/SiO that electrostatic self-assembled is coated 2) nshell, i.e. polyelectrolyte and Nano-meter SiO_2 2the absorption of particle is all loose structure, for Fenton reaction carry out smoothly provide passage; (5) (PE/SiO 2) nthe thickness of shell is controlled, by the selection of technique, as coated different cycle-index, or can select the SiO of different-grain diameter 2particle.The change of shell thickness, can control the degradation rate of phenol wastewater.To the phenolic waste water of high concentration, H 2o 2use amount is large, at this moment selects the Fe that shell thickness is little 3o 4/ (PE/SiO 2) nmicroballoon, catalytic activity is high, and degradation speed is fast, successful.To the phenolic waste water of low concentration, H 2o 2use amount is relatively little, at this moment selects the Fe that shell is thicker 3o 4/ (PE/SiO 2) nmicroballoon, reduces the use amount of real time catalyst, in the service life of extending catalyst, reduces costs.
Accompanying drawing explanation
Fig. 1 is the Fe that embodiment 1 obtains 3o 4the SEM photo of microballoon;
Fig. 2 is the Fe that embodiment 1 obtains 3o 4the high-resolution TEM photo of microballoon;
Fig. 3 is the Fe that embodiment 1 obtains 3o 4/ (PDDA/30nm-SiO 2) 3complex microsphere TEM photo.
Detailed description of the invention
By the following examples the preparation method of a kind of core-shell type magnetic type Fenton catalyst of the present invention and application thereof are specifically described, but embodiment is only for the present invention is further described, does not limit the scope of the invention.
Embodiment 1
(1) Fe 3o 4the preparation of microballoon: by the FeCl of 1.3g 3, the natrium citricum of 0.5g, the sodium acetate of 2.0g joins in the ethylene glycol of 40mL, after stirring successively, transfer in the water heating kettle of 100mL, at 200 DEG C after hydro-thermal reaction 10h, cool to room temperature, centrifugal, after product absolute ethyl alcohol and ultra-pure water clean 3 times respectively, drying for standby; Product Fe 3o 4as shown in Figure 1, high-resolution TEM photo as shown in Figure 2 for the SEM photo of microballoon;
(2) Nano-meter SiO_2 2the preparation of particle: by ethyl orthosilicate, absolute ethyl alcohol and water by volume 1:2:2 be configured to solution, be warming up to 70 DEG C, stir 1.5h, then add 2.0mol/L ammonia solution, continue the Nano-meter SiO_2 of obtained 30nm after reaction 1h 2particle;
(3) Fe 3o 4/ (PE/SiO 2) nthe preparation of microballoon:
I. cationic polyelectrolyte (PDDA) and soluble-salt (sodium chloride) are mixed with water solution A; The concentration of PDDA is the concentration of 3g/mL, NaCl is 0.5moL/mL.
II. by the Fe of preparation in abovementioned steps (1) 3o 4microballoon joins in above-mentioned water solution A, Fe 3o 4microballoon and cationic mass ratio are 0.05:1.Vibration absorption 10min on shaking table, then after carrying out repeating 3 times according to Magneto separate, deionized water washing, the order of again disperseing successively, deposit deionized water is disperseed, and forms aqueous solution B.
III. by the Nano-meter SiO_2 of preparation in abovementioned steps (2) 2particle joins in above-mentioned aqueous solution B, Nano-meter SiO_2 2particle and Fe 3o 4the mass ratio of/cationic polyelectrolyte complex microsphere is 0.8:1, by the NaOH aqueous solution adjust ph to 10 of 0.1moL/L, vibration absorption 20min on shaking table, after the step of wash according to Magneto separate, deionized water, again disperseing repeats 3 times, deposit deionized water is disperseed.
IV. repeat above-mentioned steps II and Step II I more each 2 times, obtain Fe 3o 4/ (PDDA/30-SiO 2) 3complex microsphere.Shell thickness is about 150nm.Fe 3o 4/ (PDDA/30nm-SiO 2) 3the TEM photo of complex microsphere as shown in Figure 3.
Embodiment 2
Adopt heterogeneous Fenton-like method Phenol-Containing Wastewater Treatment, take conical flask as reactor, waste water initial concentration is 15mg/L, adds Fe prepared by 100mg/L embodiment 1 simultaneously 3o 4/ (PDDA/30-SiO 2) 3the H of complex microsphere and 10mmoL/L 2o 2, reactor is placed in water bath chader, and rotating speed is 150rpm, and temperature is 30 DEG C.
Measure according to the direct method Pyrogentisinic Acid concentration in GB (GB7491.87).Result shows, with Fe 3o 4/ (PDDA/30-SiO 2) 3complex microsphere is fine as the effect of the heterogeneous Fenton method process phenolic waste water of catalyst, and after reaction 1h, the clearance of phenol reaches more than 90%.
Embodiment 3
Save the IV step of step (3) in embodiment 1, other steps are all identical with embodiment 1, obtain Fe 3o 4/ (PDDA/30-SiO 2) 1complex microsphere, shell thickness is about 60nm, and shell thickness compares Fe 3o 4/ (PDDA/30-SiO 2) 3the shell thickness of complex microsphere is little.
" waste water initial concentration is 15mg/L " in embodiment 2 is adjusted to " waste water initial concentration is 100mg/L ", " Fe of 100mg/L will be added simultaneously 3o 4/ (PDDA/30-SiO 2) 3the H of complex microsphere and 10mmoL/L 2o 2" be adjusted to and " add the Fe of 200mg/L simultaneously 3o 4/ (PDDA/30nm-SiO 2) H of complex microsphere and 50mmoL/L 2o 2", other are identical with the step in embodiment 2.
After reaction 1h, phenol clearance reaches more than 96%.
Embodiment 4
The preparation process of material is with embodiment 3.
Adopt heterogeneous Fenton method process phenolic waste water, take conical flask as reactor, waste water initial concentration is 10mg/L, adds the Fe of 20mg/L simultaneously 3o 4/ (PDDA/30-SiO 2) 3the H of complex microsphere and 10mmoL/L 2o 2, reactor is placed in water bath chader, and rotating speed is 150rpm, and temperature is 30 DEG C, by Fe 3o 4/ (PDDA/30-SiO 2) 3complex microsphere reuses 12 times after reclaiming, and still have good catalytic performance, phenol clearance reaches 93.2%.
Comparative example
By the Fe in embodiment 1 3o 4/ (PDDA/30-SiO 2) 3complex microsphere is adjusted to Fe 3o 4microballoon, other conditions are all identical.
After reaction 1h, the clearance of phenol only has 24%; After reaction 4h, the clearance of phenol only 27%.

Claims (6)

1. the magnetic core-shell type type Fenton catalyst of tool, is characterized in that, the kernel of described core-shell type type Fenton catalyst is nano level Fe 3o 4the Fe of particle packing 3o 4microballoon, shell is cationic polyelectrolyte and SiO 2the alternating sorbent sequence layer that nano particle is formed; The outermost layer of described alternating sorbent sequence layer is SiO 2nano-particle layer, innermost layer is cationic polyelectrolyte layer;
Described Fe 3o 4the particle diameter of microballoon is 200 ~ 500nm;
Described Nano-meter SiO_2 2the particle diameter of particle is 10 ~ 40nm.
2. the magnetic core-shell type type Fenton catalyst of tool according to claim 1, is characterized in that, described cationic polyelectrolyte is diallyl dimethyl ammoniumchloride or PAH.
3. the preparation method of the magnetic core-shell type type Fenton catalyst of tool described in claim 1 or 2, is characterized in that, comprises the steps: first to adopt hydro-thermal method to prepare Fe 3o 4microballoon, then adopt sol-gal process to prepare Nano-meter SiO_2 2particle, then adopts layer upon layer electrostatic self-assembly method by positively charged cationic polyelectrolyte and electronegative described Nano-meter SiO_2 2groups of grains is contained in described Fe 3o 4on microballoon.
4. preparation method according to claim 3, is characterized in that, described hydro-thermal method prepares Fe 3o 4microballoon refers to, by FeCl 3: natrium citricum: sodium acetate is that 1:0.1 ~ 0.4:1 ~ 3 join in ethylene glycol successively with mass ratio, after stirring, transfer in water heating kettle, at 180 ~ 250 DEG C after hydro-thermal reaction 8 ~ 12h, cool to room temperature, centrifugal, after product absolute ethyl alcohol and ultra-pure water clean 3 times respectively, drying for standby;
Described sol-gal process prepares Nano-meter SiO_2 2particle refers to, ethyl orthosilicate, absolute ethyl alcohol and water are configured to solution in 1:1.5 ~ 2:1.5 ~ 2 by volume, are warming up to 60 ~ 90 DEG C, stir 0.5 ~ 2h, then the ammonia solution of 0.5 ~ 3.0mol/L is added, obtained described Nano-meter SiO_2 after continuing reaction 0.5 ~ 2h 2particle.
5. preparation method according to claim 3, is characterized in that, described layer upon layer electrostatic self-assembly method carries out according to following step:
A: the described Fe obtained by hydro-thermal method 3o 4microballoon joins in the reactor of the aqueous solution that cationic polyelectrolyte and soluble-salt are housed, and described reactor is placed on shaking table after vibration absorption 10min, and described cationic polyelectrolyte is just adsorbed on described Fe 3o 4microsphere surface, after Magneto separate, deionized water washing, the operation in tandem that again disperses 3 times, with deionized water dispersion, forms Fe 3o 4/ cationic polyelectrolyte complex microsphere suspension; Wherein, Fe 3o 4microballoon and cationic mass ratio are 0.01 ~ 0.1; The concentration of cationic polyelectrolyte is 0.1g/mL ~ 5g/mL; Described soluble-salt refers to sodium chloride, and concentration is 0.1 ~ 0.6moL/L;
B: will containing Nano-meter SiO_2 2granular mass joins described Fe than the aqueous solution being 0.5 ~ 10% 3o 4in/cationic polyelectrolyte complex microsphere suspension, pH value of water solution is regulated to be 9 ~ 11, Nano-meter SiO_2 2particle and Fe 3o 4the mass ratio of/cationic polyelectrolyte complex microsphere is 0.1 ~ 2, on shaking table after vibration absorption 20min, and Nano-meter SiO_2 2particle is just adsorbed on Fe 3o 4the surface of/cationic polyelectrolyte complex microsphere, equally after Magneto separate, deionized water washing, the operation in tandem that again disperses 3 times, then with deionized water dispersion, forms Fe 3o 4/ cationic polyelectrolyte/Nano-meter SiO_2 2particles dispersed microsphere suspension liquid;
C: repeat above-mentioned steps A and step B, repeatedly, can obtain kernel is Fe to circulation absorption 3o 4microballoon, shell are by multilayer cationic polyelectrolyte/Nano-meter SiO_2 2the magnetic core-shell type type Fenton catalyst of described tool of particle composition.
6. the application of the magnetic core-shell type type Fenton catalyst of tool described in claim 1 or 2, is characterized in that, at the magnetic core-shell type type Fenton catalyst of described tool and H 2o 2existence simultaneously descends and phenol wastewater reacts, the phenolic comp ' ds pollution in degrading waste water;
When the phenolic concentration of phenol wastewater is 10mg/L ~ 120mg/L, the consumption of the magnetic core-shell type type Fenton catalyst of described tool is 20 ~ 100mg/L, described H 2o 2consumption be 10 ~ 50mmoL/L.
CN201310293883.5A 2013-07-12 2013-07-12 Magnetic core-shell Fenton-type catalyst, and preparation method and application of catalyst Expired - Fee Related CN103331181B (en)

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