CN108176402A - Support type high dispersive easily regenerates the preparation method of iron-based Fenton catalysts - Google Patents
Support type high dispersive easily regenerates the preparation method of iron-based Fenton catalysts Download PDFInfo
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- CN108176402A CN108176402A CN201810130915.2A CN201810130915A CN108176402A CN 108176402 A CN108176402 A CN 108176402A CN 201810130915 A CN201810130915 A CN 201810130915A CN 108176402 A CN108176402 A CN 108176402A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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Abstract
The present invention relates to the preparation methods that a kind of support type high dispersive easily regenerates iron-based Fenton catalysts, utilize ferrous sulfate (FeSO4) or ferric trichloride (FeCl3) it is source of iron, with coconut husk base granular activated carbon (GAC) for carrier, absolute ethyl alcohol is dispersant, and being prepared for support type high dispersive with electronation two-step method by absorption easily regenerates nano zero valence iron Fenton catalysts.Superiority：Realize a series of activated carbon supported nano zero valence iron Fenton catalyst of monodisperse for preparing different-grain diameters in a certain range.A kind of catalyst of the Fenton reactions of good dispersion is provided, it is made to be not easy to reunite, catalytic efficiency higher, applicable pH range is wider.The preparation method that a kind of high dispersive easily regenerates Fenton catalyst is provided, the preparation method is simple for process, and raw material is cheap and easy to get.
Description
Technical field
The invention belongs to the preparation methods of Fenton catalysts, are related to a kind of support type high dispersive and easily regenerate iron-based
The preparation method of Fenton catalysts.
Background technology
Fenton reacts (Fe2++H2O2) a kind of high-level oxidation technology is used as, with reaction rate is fast, control is simple, toxicity
The features such as low, is widely used in the field of purification of the environmental contaminants such as water process.
Catalyst plays an important role in Fenton reaction process, and nano zero valence iron (nZVI) is used as because of active height
The catalyst of Fenton reactions.But nZVI sizes are small, and there are bad dispersibilities during practical application, easily reunite, to lead to catalytic efficiency
It reduces, and is lost in serious, the defects of catalyst regeneration is difficult.In order to solve this problem, researchers both domestic and external have been
Many researchs have been carried out, point of nZVI is improved using technologies such as addition dispersant, surfactant and load, cladding etc.
Dissipate property.It is easy there is no nZVI is inherently solved although these methods can improve the dispersibility of energy nZVI to a certain extent
In reunite the problem of, and the regeneration step of catalyst is relatively complicated.
Dispersibility is high in order to obtain, the good Fenton catalyst of reproducibility, and the present invention utilizes ferrous sulfate (FeSO4) it is iron
Source, with coconut husk base granular activated carbon (GAC) for carrier, absolute ethyl alcohol is dispersant, passes through absorption and electronation two-step method system
Standby support type easily regenerates Fenton catalysts, with meet Fenton methods in the depollution of environment to catalyst cyclic regeneration and
The demand efficiently utilized.
Invention content
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes that a kind of support type high dispersive easily regenerates iron-based Fenton
The preparation method of catalysts.
The first purpose is to realize a series of activated carbon supported nanometer zero of the monodisperse for preparing different-grain diameters in a certain range
Valency iron Fenton catalyst.
The second purpose is to provide a kind of catalyst of the Fenton reactions of good dispersion, it is made to be not easy to reunite, catalytic efficiency
Higher, applicable pH range are wider.
The third purpose is to provide the preparation method that a kind of high dispersive easily regenerates Fenton catalyst, preparation method technique letter
Single, raw material is cheap and easy to get.
Technical solution
A kind of support type high dispersive easily regenerates the preparation method of iron-based Fenton catalysts, it is characterised in that step is such as
Under：
Step 1：The sieving of coconut husk base granular activated carbon is grain size<1.0mm, deionized water cleaning, with nitric acid (HNO3) or salt
Sour (HCl) is handled 4 hours or more, then is cleaned with deionized water, until cleaning solution pH stable is in neutrality 7.0；
Step 2：Coconut husk base granular activated carbon after cleaning is placed in 105 DEG C of dryings in vacuum drying oven；
Step 3：By coconut husk base granular activated carbon and ferrous sulfate (FeSO4·7H2O) with after deionized water dissolving, adding
Dispersant absolute ethyl alcohol, coconut palm shell granular active carbon charcoal ︰ FeSO4·7H2The ratio of O ︰ Qu Li Shui ︰ dispersant absolute ethyl alcohols is：1g ︰
0.22g ︰ 40ml ︰ 5ml；The deionized water boils 5 minutes, natural cooling；
Nano zero valence iron (the Fe0, nZVI) and presoma FeSO4·7H2The dosage of O determines the different activated carbon of dispersion degree
Load nano zero valence iron (nZVI@GAC) Fenton catalysts；
Step 4：After above-mentioned solution ultrasound 15 minutes or more, 200rpm on constant temperature oscillator is placed in, constant temperature oscillation 24 is small
When more than (25 DEG C), solution is transferred in the four-hole boiling flask equipped with mechanical agitation, titration outfit and import and export of nitrogen；
Step 5：Under nitrogen protection, stir speed (S.S.) 150rpm adds in the boron hydrogen of a concentration of 320mmol/L after fully dissolving
Change sodium solution (NaBH4) 50ml carries out titration reduction, it is to be restored completely, after being precipitated there is no solid content, discard supernatant liquid, obtain
Black solid content；
Step 6：Black solid content with deionized water is cleaned, is transferred to after being filtered in Vacuum filtration device, is placed in vacuum
65 DEG C of vacuum drying, obtain black Fenton catalysts in drying box.
With FeCl in the step 33Replace FeSO4·7H2O participates in reaction, the Fe0Presoma FeCl3Dosage, determine
The different nZVI@GAC Fenton catalysts of dispersion degree.
Activated carbon and ferrous sulfate (FeSO in the step 34·7H2O mass ratio) is 1:0.22.
The nitric acid HNO3A concentration of 1M, hydrochloric acid HCl a concentration of 5%.
The resistance R of the deionized water>18MΩ.
Advantageous effect
A kind of support type high dispersive proposed by the present invention easily regenerates the preparation method of iron-based Fenton catalysts, utilizes
Ferrous sulfate (FeSO4) or ferric trichloride (FeCl3) it is source of iron, with coconut husk base granular activated carbon (GAC) for carrier, absolute ethyl alcohol
For dispersant, it is prepared for support type high dispersive with electronation two-step method and easily regenerates nano zero valence iron Fenton reacting by adsorbing
Catalyst, to meet Fenton methods in the depollution of environment to catalyst cyclic regeneration and the needs of efficiently utilize.
Superiority of the present invention：Realize a series of activated carbon supported nanometer of monodisperse for preparing different-grain diameters in a certain range
Zero-valent Iron Fenton catalyst.A kind of catalyst of the Fenton reactions of good dispersion is provided, it is made to be not easy to reunite, catalytic efficiency
Higher, applicable pH range are wider.The preparation method that a kind of high dispersive easily regenerates Fenton catalyst is provided, the preparation method technique
Simply, raw material is cheap and easy to get.
Description of the drawings
Fig. 1 is the SEM photograph of the Fenton catalyst of embodiment 1.
Fig. 2 is the SEM photograph of the Fenton catalyst of embodiment 2.
Specific embodiment
In conjunction with embodiment, attached drawing, the invention will be further described：
Embodiment 1
Coconut husk base granular activated carbon crosses 30 mesh sieve (grain size<0.6mm), deionized water (resistance R>18M Ω) it cleans 3 times, 1M
Nitric acid (HNO3) handle 5 hours, then cleaned with deionized water, until cleaning solution pH stable；The coconut husk base particle that will be cleaned
Activated carbon, 105 DEG C of dryings 24 hours in vacuum drying oven；Weigh 1.123g FeSO4·7H2O adds in 200mL and boils in beaker
Boil (20mmolL in the deionized water after letting cool-1) dissolving, then weigh 5.0g activated carbons and be included in beaker, and add in 10mL without
Water-ethanol makees dispersant, after ultrasonic 15min, is placed on 200rpm oscillations in constant temperature oscillator and for 24 hours, solution is transferred to four-hole boiling flask
In, under 150rpm stirring conditions, use 80mmolL-1NaBH4In N2It is quickly restored in atmosphere, stands 20min, discard supernatant liquid,
It is cleaned 3 times with deionized water, obtains the solid content of black, after vacuum filtration, be placed in 65 DEG C of vacuum drying 12 in vacuum drying chamber
Hour to get to Fenton catalysts.
Embodiment 2
Coconut husk base granular activated carbon crosses 30 mesh sieve (grain size<0.6mm), deionized water (resistance R>18M Ω) it cleans 3 times, 1M
Nitric acid (HNO3) handle 5 hours, then cleaned with deionized water, until cleaning solution pH stable；The coconut husk base particle that will be cleaned
Activated carbon, 105 DEG C of dryings 24 hours in vacuum drying oven；Weigh 0.65g FeCl3In beaker, addition 200mL, which boils, to be let cool
(20mmolL in deionized water afterwards-1) dissolving, then weigh 5.0g activated carbons and be included in beaker, and add in 10mL absolute ethyl alcohols
Make dispersant, after ultrasonic 15min, be placed on 200rpm oscillations in constant temperature oscillator and for 24 hours, solution is transferred in four-hole boiling flask,
Under 150rpm stirring conditions, 80mmolL is used-1NaBH4In N2It is quickly restored in atmosphere, stands 20min, discard supernatant liquid, used
Deionized water is cleaned 3 times, obtains the solid content of black, and after vacuum filtration, it is small to be placed in 65 DEG C of vacuum drying 12 in vacuum drying chamber
When to get to Fenton catalysts.
Claims (5)
1. a kind of support type high dispersive easily regenerates the preparation method of iron-based Fenton catalysts, it is characterised in that step is such as
Under：
Step 1：The sieving of coconut husk base granular activated carbon is grain size<1.0mm, deionized water cleaning, with nitric acid (HNO3) or hydrochloric acid
(HCl) it handles 4 hours or more, then is cleaned with deionized water, until cleaning solution pH stable is in neutrality 7.0；
Step 2：Coconut husk base granular activated carbon after cleaning is placed in 105 DEG C of dryings in vacuum drying oven；
Step 3：By coconut husk base granular activated carbon and ferrous sulfate (FeSO4·7H2O) with after deionized water dissolving, adding dispersion
Agent absolute ethyl alcohol, coconut palm shell granular active carbon charcoal ︰ FeSO4·7H2The ratio of O ︰ Qu Li Shui ︰ dispersant absolute ethyl alcohols is：1g ︰
0.22g ︰ 40ml ︰ 5ml；The deionized water boils 5 minutes, natural cooling；
Nano zero valence iron (the Fe0, nZVI) and presoma FeSO4·7H2The dosage of O determines different activated carbon supported of dispersion degree
Nano zero valence iron (nZVI@GAC) Fenton catalysts；
Step 4：After above-mentioned solution ultrasound 15 minutes or more, be placed in 200rpm on constant temperature oscillator, constant temperature oscillation 24 hours with
Upper (25 DEG C), solution is transferred in the four-hole boiling flask equipped with mechanical agitation, titration outfit and import and export of nitrogen；
Step 5：Under nitrogen protection, stir speed (S.S.) 150rpm adds in the sodium borohydride of a concentration of 320mmol/L after fully dissolving
Solution (NaBH4) 50ml carries out titration reduction, it is to be restored completely, after being precipitated there is no solid content, discard supernatant liquid, obtain black
Solid content；
Step 6：Black solid content with deionized water is cleaned, is transferred to after being filtered in Vacuum filtration device, is placed in vacuum drying
65 DEG C of vacuum drying, obtain black Fenton catalysts in case.
2. support type high dispersive easily regenerates the preparation method of iron-based Fenton catalysts according to claim 1, special
Sign is：With FeCl in the step 33Replace FeSO4·7H2O participates in reaction, the Fe0Presoma FeCl3Dosage, determine
The different nZVI@GAC Fenton catalysts of dispersion degree.
3. support type high dispersive easily regenerates the preparation method of iron-based Fenton catalysts according to claim 1, special
Sign is：Activated carbon and ferrous sulfate (FeSO in the step 34·7H2O mass ratio) is 1:0.22.
4. support type high dispersive easily regenerates the preparation method of iron-based Fenton catalysts according to claim 1, special
Sign is：The nitric acid HNO3A concentration of 1M, hydrochloric acid HCl a concentration of 5%.
5. support type high dispersive easily regenerates the preparation method of iron-based Fenton catalysts according to claim 1, special
Sign is：The resistance R of the deionized water>18MΩ.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109453775A (en) * | 2018-10-26 | 2019-03-12 | 东莞理工学院 | A kind of porous carbon load simple substance iron catalyst and its preparation method and application using humin preparation |
| CN110394443A (en) * | 2019-07-03 | 2019-11-01 | 南昌大学 | A kind of zeroth order Nanoscale Iron nickel powder body and preparation method thereof for handling waste water from dyestuff |
| CN112919674A (en) * | 2021-01-26 | 2021-06-08 | 王龙花 | Multi-stage remediation process for groundwater pollution treatment |
| CN114887588A (en) * | 2022-05-11 | 2022-08-12 | 桂林理工大学 | Method for preparing activated carbon loaded nano zero-valent iron material by using solid reducing agent |
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| CN112919674A (en) * | 2021-01-26 | 2021-06-08 | 王龙花 | Multi-stage remediation process for groundwater pollution treatment |
| CN114887588A (en) * | 2022-05-11 | 2022-08-12 | 桂林理工大学 | Method for preparing activated carbon loaded nano zero-valent iron material by using solid reducing agent |
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Application publication date: 20180619 |