CN108043458A - A kind of preparation method and applications of the heterogeneous fenton catalyst of immobilization - Google Patents
A kind of preparation method and applications of the heterogeneous fenton catalyst of immobilization Download PDFInfo
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- CN108043458A CN108043458A CN201810009234.0A CN201810009234A CN108043458A CN 108043458 A CN108043458 A CN 108043458A CN 201810009234 A CN201810009234 A CN 201810009234A CN 108043458 A CN108043458 A CN 108043458A
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- catalyst
- immobilization
- heterogeneous fenton
- molecular sieve
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
Abstract
The invention belongs to environment functional material and technical field of waste water processing, are specially a kind of preparation method and application of the heterogeneous fenton catalyst of immobilization.Catalyst of the present invention is surface modified carrier with organic acid using mesopore molecular sieve as carrier, then is loaded by active component of iron, most forms iron acylate on mesopore molecular sieve surface through high-temperature process afterwards.The catalyst has efficient degradation effect to the phenol organic pollution in industrial wastewater, room temperature and close under neutrallty condition to phenol in wastewater class degradation rate up to more than 90%, and catalyst flowing molten iron vector is few.The heterogeneous Fenton-like system that the present invention is built need not adjust pH value, be generated in system without chemical sludge, and technological process is simple, easily controllable, has preferable actual application prospect.
Description
Technical field
The invention belongs to environment functional material and technical field of waste water processing, are related to a kind of heterogeneous Fenton catalysis of immobilization
The synthetic method of agent and application, and in particular to a kind of surface is through the organic acid modified heterogeneous Fenton of mesoporous molecular sieve carried swage
The preparation of catalyst and its method of catalytic degradation phenol organic pollution.
Background technology
Fenton catalyst system and catalyzing is a kind of high-level oxidation technology, can be with based on the free radical that Strong oxdiative activity is generated in system
The organic pollution that can not be decomposed in the removal of non-selectivity and degradation conventional method, has been widely used for phenols, drug, rubbish
In the processing of the waste water such as rubbish percolate [Pouran S.R.et al., Journal of Cleaner Production.2014,
64,24].Fenton catalyst early stage research is concentrated mainly on homogeneous aspect, custom catalysts are transition metal, as iron, cobalt, copper,
Manganese, nickel etc., the hydroxyl radical free radical catalytic degradation organic pollution generated using decomposing hydrogen dioxide solution are had and are swift in response, without mass transfer
The advantages that resistance, reaction condition is mild, but with research and application go deep into, homogeneous fenton catalyst shows pH value simultaneously
The problems such as narrow range, catalyst be difficult to be recycled, chemical sludge yield is big and difficult, therefore, heterogeneous fenton catalyst
It is increasingly becoming the focal point of Fenton research system.
The key of heterogeneous fenton catalyst is carrier selection and application.Patent CN104383958A utilizes amino functional
SiO2 mesopore film load irons are prepared for a kind of heterogeneous ultraviolet-Fenton oxidation catalyst.Patent CN103496764A utilizes poly-
The modified iron carbon of tetrafluoroethene is heterogeneous catalysis, builds efficiently heterogeneous electric Fenton-like system.Patent CN103041815A
The preparation method that a kind of attapulgite carries the heterogeneous fenton catalyst of iron is invented.Patent CN103111321A discloses a kind of load
The preparation method of iron molecule sieve-type class fenton catalyst and the catalyst made from this method are in nitrobenzene waste water processing system
Application.Patent CN102626627A discloses a kind of system of the heterogeneous Fenton reagent oxidation catalyst of activated carbon supported ferrous iron
Preparation Method.
Molecular sieve is a kind of inorganic silicon-aluminum hydrochlorate polyporous materials, with duct is regular, aperture is adjusted, specific surface area
Greatly, the advantages that acidic site is more, gradually applied in the preparation and application of heterogeneous fenton catalyst.And mesopore molecular sieve have compared with
Big duct can be matched with phenol organic pollution size, be conducive to such degradation target molecule and entered inside molecular sieve
Catalytic activity with catalytic active site close contact, is improved in duct.
The present invention passes through chlorosulfonic acid class organic molecule and molecular sieve surface sial hydroxyl using a variety of mesopore molecular sieves as carrier
The graft reaction of base carries out molecular sieve surface sulfonation modification back loading Fe salt, and high-temperature process prepares high stability class Fenton and urges
Agent.The catalyst by sulfonic acid group and very tight close bonding, effectively inhibits iron leakage, and sulfonic acid modified by chemical bond
Molecular sieve surface acidic site is enhanced, microcosmic acidic region is formd in carrier surface, is conducive to phenol organic molecule and is carrying
Body surface surface catalysis is degraded, and reduces the dependence to medium highly acid in homogeneous Fenton catalyst system and catalyzing.The catalyst is in room temperature and approaches
Energy efficient degradation phenols wastewater under neutrallty condition, and can conveniently recycle.
The content of the invention
It is an object of the invention to propose a kind of room temperature with having the high stable of excellent catalytic activity under neutral pH conditions
Property, iron ion number of dropouts be small, renewable heterogeneous fenton catalyst and preparation method thereof and in degradation of phenol class organic wastewater
In application.
The heterogeneous fenton catalyst of immobilization proposed by the present invention, with chlorosulfonic acid class organic molecule and mesopore molecular sieve table
Face sial hydroxyl graft reaction carries out sulfonation modification to mesopore molecular sieve surface, using the mesopore molecular sieve after modification as carrier,
It is prepared by active component of transition-metal Fe.Active component is 5-25wt.% in the load capacity of catalyst.The catalyst exists
Room temperature (<30 DEG C) and (pH=6-8) and H close under neutrallty condition2O2Collective effect shows Strong oxdiative ability, and phenol is in 2h
Degradation rate can be more than 90%, and catalyst stability and reproducibility are good, iron ion number of dropouts is low.
The preparation method of heterogeneous fenton catalyst proposed by the present invention, is as follows：
(1) mesopore molecular sieve is distributed in a certain amount of chloroform, chlorosulfonic acid and ethylenediamine is added in, under nitrogen protection
4h is heated to reflux, is cooled to room temperature, filtering, chloroform and acetone are washed to no chlorion.150 DEG C of vacuum drying 12h, are carried
Body；
(2) presoma of active component Fe is configured to precursor salt solution；
(3) active component precursor salt solution is impregnated on molecular sieve carrier at room temperature using incipient impregnation method,
Impregnate 12 it is small when after at 140 DEG C dry 12h to get to required heterogeneous fenton catalyst.
In the above method, the mesopore molecular sieve is MCM-41 molecular sieves and SBA-15 molecular sieves.
In the above method, source of iron (presoma of metal Fe active components) used for ferric nitrate, ferric sulfate, ferrous sulfate,
Iron chloride etc..
Catalyst prepared by the present invention, available for efficient degradation phenol waste water.
Specifically, a small amount of hydrogen peroxide is added in phenol waste water and the heterogeneous fenton catalyst of above-mentioned immobilization is formed
Class Fenton's reaction system is reacted.The wherein pH=6-8 of reaction system, reaction temperature are 10-30 DEG C.
The design principle and catalyticing mechanism of the present invention is as follows：
In the System Design of catalyst material, mesopore molecular sieve is used as carrier, passes through chlorosulfonic acid class organic molecule
Sulfonation modification is carried out to molecular sieve surface with the graft reaction of molecular sieve surface sial hydroxyl, is formed using sulfonic acid group and Fe
The chemical bond combined closely, dispersiveness of the enhancing active component on carrier and the chemical valence with reference to power, also adjusting active component
State, and then improve the catalytic efficiency of Fenton's reaction.
Hydrogen peroxide and organic molecule are adsorbed onto by diffusion on the activated centre of catalyst surface, hydrogen peroxide molecule
Hydroxyl radical free radical is generated under iron catalytic action, by radical reaction oxidative degradation organic matter, and catalyst surface sulfonic group
Proton in group can form sour environment in film micro area, and catalyst promotes hydrogen peroxide decomposition from this sour environment generated
And from catalyst surface desorption escape occurs for subsequent catalyst reaction, last catabolite.
Description of the drawings
Fig. 1 is the XRD spectrum of the heterogeneous fenton catalyst of Fe/SMCM-41 molecular sieves prepared by embodiment 1.Catalyst has
Apparent MCM-41 diffraction maximums.
Fig. 2 is the transmission electron microscope picture of the heterogeneous fenton catalyst of Fe/SMCM-41 molecular sieves prepared by embodiment 1.Catalysis
The uniform cavernous structure of light and shade is presented in agent, shows its apparent square arrangement meso-hole structure.
Specific embodiment
It is further illustrated the present invention below by embodiment.
Embodiment 1：A kind of preparation method of the heterogeneous fenton catalyst of Fe/SMCM-41 molecular sieves, this method include following
Step：
2g MCM-41 mesopore molecular sieves are distributed in 30ml chloroforms by the first step, add 1.5g chlorosulfonic acids and
0.6g ethylenediamines are heated to reflux 4h under nitrogen protection, are cooled to room temperature, filtering, chloroform and acetone are washed to no chlorion.
150 DEG C of vacuum drying 12h, obtain the SMCM-41 molecular sieves of sulfonic acid surface modification.
0.5g ferrous sulfate is dissolved in 2ml water by second step.
Ferrous sulfate solution is impregnated into using isometric method on SMCM-41 molecular sieves by the 3rd step at room temperature, dipping 12
After hour again at 140 DEG C dry 12h to get to required heterogeneous fenton catalyst.
Embodiment 2：A kind of preparation method of the heterogeneous fenton catalyst of Fe/SSBA-15 molecular sieves, this method include following
Step：
1.5g SBA-15 mesopore molecular sieves are distributed in 30ml chloroforms by the first step, add 1.0g chlorosulfonic acids and
0.5g ethylenediamines are heated to reflux 4h under nitrogen protection, are cooled to room temperature, filtering, chloroform and acetone are washed to no chlorion.
150 DEG C of vacuum drying 12h, obtain the SSBA-15 molecular sieves of sulfonic acid surface modification.
0.75g ferric nitrates are dissolved in 2ml water by second step.
Iron nitrate solution is impregnated into using isometric method on SSBA-15 molecular sieves by the 3rd step at room temperature, and dipping 12 is small
Dry 12h is to get to required heterogeneous fenton catalyst at 140 DEG C of Shi Houzai.
Embodiment 3：The heterogeneous fenton catalysts of Fe/SMCM-41 remove removal organic polluter
Using the phenol solution of 1g/L as experiment water sample, 10ml is taken to test water sample in beaker, catalyst usage amount is 0.5g,
The hydrogen peroxide 0.2ml of 30% concentration is added in beaker, reacts and is carried out at 30 DEG C, reaction time 2h.
Embodiment 4：The heterogeneous fenton catalysts of Fe/SSBA-15 remove removal organic polluter
Using the phenol solution of 1g/L as experiment water sample, 10ml is taken to test water sample in beaker, catalyst usage amount is 0.5g,
The hydrogen peroxide 0.2ml of 30% concentration is added in beaker, reacts and is carried out at 30 DEG C, reaction time 2h.
Embodiment 5：The heterogeneous fenton catalysts of Fe/SMCM-41 remove removal organic polluter
Using the phenol solution of 1g/L as experiment water sample, 10ml is taken to test water sample in beaker, catalyst usage amount is 0.3g,
The hydrogen peroxide 0.2ml of 30% concentration is added in beaker, reacts and is carried out at 30 DEG C, the reaction time is for 24 hours.
Embodiment 6：The heterogeneous fenton catalysts of Fe/SSBA-15 remove removal organic polluter
Using the phenol solution of 1g/L as experiment water sample, 10ml is taken to test water sample in beaker, catalyst usage amount is 0.3g,
The hydrogen peroxide 0.2ml of 30% concentration is added in beaker, reacts and is carried out at 30 DEG C, the reaction time is for 24 hours.
Comparative example 1：Traditional Fenton reagent is by being Fe and be that 150-400mg/L is added in waste water by concentration by concentration
3.5-15ml/L adds in the hydrogen peroxide composition in processed sewage, and the optimum pH value reacted is 3 or so.Specific reaction item
Part is：Using the phenol solution of 1g/L as experiment water sample, 10ml is taken to test water sample in beaker, Fe is added in by 400mg/L, in beaker
The middle hydrogen peroxide 0.2ml for adding in 30% concentration, reaction carry out at room temperature, and reaction time 2h, pH value is 3 or so.
It is measured respectively through in the heterogeneous fenton catalyst of immobilization in embodiment 3-6 and comparative example 1 at traditional Fenton reagent
Waste water phenol degrading rate after reason, while the concentration of total Fe in solution after reaction is measured, the results are shown in Table 1.
Table 1 is that the heterogeneous fenton catalyst of immobilization is directed to phenol with fenton catalyst in comparative example in embodiment 3-6
Degradation rate
| Phenol degrading rate (%) | Total concentration of iron (mg/L) after reaction | |
| Embodiment 3 | 91.02 | 11.26 |
| Embodiment 4 | 93.24 | 9.52 |
| Embodiment 5 | 96.77 | 12.45 |
| Embodiment 6 | 98.12 | 13.22 |
| Comparative example 1 | 41.32 | 39.80 |
By upper table as can be seen that embodiment 3-6 prepare the heterogeneous fenton catalyst of immobilization during the reaction, it is molten
Go out iron ion and be far below traditional Fenton reagent, in the case of than traditional Fenton reagent excellent effect, solve comparative catalyst
It is difficult to recycle and generate the problem of a large amount of chemical sludges.
Claims (8)
1. a kind of heterogeneous fenton catalyst of immobilization, which is characterized in that this method comprises the following steps：
(1) mesopore molecular sieve is distributed in a certain amount of chloroform, adds in chlorosulfonic acid and ethylenediamine, the lower heating of nitrogen protection
Flow back 4h, is cooled to room temperature, filtering, and chloroform and acetone are washed to no chlorion, and 150 DEG C of vacuum drying 12h obtain carrier；
(2) presoma of active component Fe is configured to precursor salt solution；
(3) active component precursor salt solution is impregnated on molecular sieve carrier at room temperature using dipping method, impregnate 12h after
Dry 12h is to get to required heterogeneous fenton catalyst at 140 DEG C.
2. method for preparing catalyst according to claim 1, which is characterized in that step (1) intermediary porous molecular sieve is MCM-
41st, the mesopore molecular sieves such as SBA-15.
3. method for preparing catalyst according to claim 1, which is characterized in that the forerunner of active component Fe in step (2)
Body is ferric nitrate, ferric sulfate, ferrous sulfate, iron chloride etc..
4. method for preparing catalyst according to claim 1, which is characterized in that dipping method is isometric in step (3)
Infusion process.
5. catalyst according to claim 1, which is characterized in that the Fe members containing 5-25% (weight) in the catalyst
Element.
6. the heterogeneous fenton catalyst of immobilization according to claim 1 answering in phenolic waste water system for handling is handled
With.
7. application according to claim 6, which is characterized in that put into the heterogeneous fenton catalyst of immobilization and hydrogen peroxide
Class Fenton catalysis oxidation wastewater treatment system is built into phenolic waste water.
8. application according to claim 7, which is characterized in that when degradation 10ml concentration is 1g/L phenol, immobilization is non-
Phase fenton catalyst addition is 0.3-0.5g, and hydrogen peroxide addition is 0.2ml, reaction time 2-24h, the pH of reaction system
It is worth for 6-8, reaction temperature is 10-30 DEG C.
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Cited By (7)
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| CN109772370A (en) * | 2019-03-01 | 2019-05-21 | 华东理工大学 | A kind of water purification beaded catalyst and its preparation method and application |
| CN111420662A (en) * | 2020-05-14 | 2020-07-17 | 宜兴国际环保城科技发展有限公司 | Neutral Fenton catalyst, preparation and application |
| CN113060819A (en) * | 2021-03-31 | 2021-07-02 | 南京理工大学 | Device and method for realizing free radical targeted oxidation in heterogeneous Fenton oxidation process |
| CN113231082A (en) * | 2021-06-02 | 2021-08-10 | 南京泽佑环保科技有限公司 | High-activity iron-based-sulfide heterogeneous Fenton composite material and method for removing organic pollutants by using same |
| CN113842924A (en) * | 2021-09-24 | 2021-12-28 | 铜仁学院 | Heterogeneous Fenton catalyst, preparation method thereof and wastewater treatment method |
| CN114249502A (en) * | 2021-12-27 | 2022-03-29 | 华夏碧水环保科技有限公司 | Cephalosporin antibiotic production wastewater treatment system and process |
| CN114797945A (en) * | 2022-04-11 | 2022-07-29 | 中国石油大学胜利学院 | Bonded phase Fenton-like catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113231082A (en) * | 2021-06-02 | 2021-08-10 | 南京泽佑环保科技有限公司 | High-activity iron-based-sulfide heterogeneous Fenton composite material and method for removing organic pollutants by using same |
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| CN114249502A (en) * | 2021-12-27 | 2022-03-29 | 华夏碧水环保科技有限公司 | Cephalosporin antibiotic production wastewater treatment system and process |
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| CN114797945A (en) * | 2022-04-11 | 2022-07-29 | 中国石油大学胜利学院 | Bonded phase Fenton-like catalyst and preparation method thereof |
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Application publication date: 20180518 |