CN101327448B - Preparation of chelated iron catalyst and use thereof for multiphase photocatalysis of hydrogen peroxide - Google Patents
Preparation of chelated iron catalyst and use thereof for multiphase photocatalysis of hydrogen peroxide Download PDFInfo
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- CN101327448B CN101327448B CN2008101445153A CN200810144515A CN101327448B CN 101327448 B CN101327448 B CN 101327448B CN 2008101445153 A CN2008101445153 A CN 2008101445153A CN 200810144515 A CN200810144515 A CN 200810144515A CN 101327448 B CN101327448 B CN 101327448B
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Abstract
The present invention relates to a preparation of complex iron catalyst and an application in multiphase photocatalysis hydrogen peroxide, which relate to the preparation of a catalyst and the application of the catalyst in catalyzing the hydrogen peroxide and solve the problem in a water treatment method of the low multiphase photocatalysis hydrogen peroxide decomposition speed. The preparation method of the complex iron catalyst comprises the steps as follows: ferric ions are combined with complexing agent to form a ferric complex compound; pretreated positive ions are exchanged with resin granules or are dipped in the ferric complex compound to be oscillated under room temperature; then resin is separated from complex compound solution to be washed until no iron ion is dissolved out; the prepared complex iron catalyst is applied in the multiphase photocatalysis hydrogen peroxide. The complex iron catalyst prepared by the present invention can improve the decomposition speed of hydrogen peroxide, the decomposition speed can be 100 percent; the complex iron catalyst has good absorption and oxidation efficiencies towards organic substances in water; under the irradiation of ultraviolet light or visible light, the complex iron catalyst can increase the mineralized degree of the organic substances, and the mineralized degree can be more than 70 percent. The method of the present invention is simple and is convenient for operating.
Description
Technical field
The present invention relates to the application of a kind of Preparation of catalysts and catalyzing hydrogen peroxide thereof; Be specifically related to a kind of preparation of complexing iron catalyst and the application of multiphase photocatalysis of hydrogen peroxide thereof.
Background technology
Hydrogen peroxide is the green oxidation agent, because product is the oxygen G﹠W, so hydrogen peroxide is widely used in the industry.The method of catalyzing hydrogen peroxide has two kinds, and a kind of is base catalysis, and a kind of is transition metal-catalyzed.The reaction rate of base catalysis hydrogen peroxide is slow, and for regulating the pH value, needs to consume a large amount of alkali; The reaction rate of transition metal-catalyzed hydrogen peroxide is more much bigger than the reaction rate of base catalysis.The ferrous ion catalyzing hydrogen peroxide is that Fenton reagent is exactly transition metal-catalyzed model.Fenton in 1894 proposes under the condition of acid pH=2, ferrous ion can catalyzing hydrogen peroxide oxidation tartaric acid effectively.The Fenton oxidation has lot of advantages, simple as method, oxidation rate is fast, reagent concentration is low, economical and efficient etc., and reagent is environmentally friendly, however optimum pH value 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 that 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.Some amine carboxylic complexing agents such as DTPA, EDTA, EGTA, NTA, be introduced in the Fenton system, greater than 6 o'clock, catalytic activity was higher in the pH value for EDTA, DPTA in the pH value greater than 7 o'clock optimum activities.Though after the iron complexing, the oxidability of system does not become, reaction rate than before the complexing not slowly many.In macromolecule loading multiphase photocatalysis of hydrogen peroxide field, ferric iron directly combines with ion exchange resin, perhaps coordinations such as ferric iron and histidine, bipyridyl, do not see about with the report of inorganic part coordination.The effect of part is to make ferric iron stable, its oxidation-reduction potential is reduced, but organic ligand is easily oxidized, and also unstable with the ionic bond coordination with the compound of covalent bond coordination.
Summary of the invention
The objective of the invention is in order to solve the low problem of multiphase photocatalysis of hydrogen peroxide decomposition rate in the method for treating water, and a kind of preparation of complexing iron catalyst and the application of multiphase photocatalysis of hydrogen peroxide thereof are provided.The present invention has reduced the oxidation-reduction potential of iron with inorganic part fluorine and oxalic acid and ferric iron coordination, has increased ion exchange resin to organic absorption property, and has increased the decomposition rate to hydrogen peroxide, and organic clearance is improved greatly.The preparation method of complexing iron catalyst of the present invention is as follows: earlier ferric ion and complexing agent are pressed 1～2: 1 mol ratio complexing formation ferric complex; The proportioning that adds 7～8g cationic ion-exchange resin particle or film by every mole of ferric ion is dipped in pretreated cationic ion-exchange resin particle or film in the ferric complex; 0.5～24h at room temperature vibrates; filter then; after cationic ion-exchange resin after the above-mentioned processing or film clean repeatedly with clear water; up to the stripping that does not have iron ion, promptly make the complexing iron catalyst.The complexing iron catalyst that said method makes is applied to multiphase photocatalysis of hydrogen peroxide, adopts ultraviolet light or visible light radiation in the reaction, and catalyst is the complexing iron catalyst, and oxidant is hydrogen peroxide or ozone; Technical parameter in the course of reaction is as follows: the dosage of complexing iron catalyst is 50～200mg/L, the dosage of hydrogen peroxide or ozone is 10～110mmol/L, the mol ratio of hydrogen peroxide or ozone and organic pollution is 1～100: 1, reaction time 5min～2h.
Described ferric ion can load on earlier in charcoal fiber, zeolite, silica gel, bentonite, kaolin, diatomite or the imvite and carry out complexing with complexing agent again, and the load capacity of trivalent iron salt is 1～10% (weight).Also bivalent cupric ion or divalent manganesetion can in ferric ion, have been added, the weight ratio 40～99: 1 of ferric iron and bivalent cupric ion or divalent manganesetion.Above-mentioned ferric ion is provided by trivalent iron salt; Trivalent iron salt is ferric sulfate, iron chloride, ferric nitrate or ferric perchlorate.
Described complexing agent is pyrimidine, porphyrin, disodium ethylene diamine tetraacetate, natrium citricum, sodium tartrate, sodium fluoride or sodium oxalate.
Described cationic ion-exchange resin particle is 001 * 7 cationic ion-exchange resin or D001 cationic ion-exchange resin.Described cation exchange resin membrane is Nafion 117.
Heterogeneous smooth complexing iron catalyst catalyzing hydrogen peroxide is used for handling the organic matter of feedwater, city secondary effluent or pharmacy waste water.
But the complexing agent among the present invention is not limited to above-mentioned example, the part of strong complexing is arranged all in protection scope of the present invention with iron.
Ferric iron and complexing agent coordination are that the oxidation-reduction potential of iron is reduced, the accelerated decomposition hydrogen peroxide, iron as reducing agent by hydrogen peroxide oxidation, chemical valence raises becomes quadrivalent iron, hydrogen peroxide is reduced the generation hydroxyl radical free radical, and the high price iron of generation has oxidability, also can strengthen the decomposition of hydrogen peroxide simultaneously, so the active specy in the course of reaction is the acting in conjunction of hydroxyl radical free radical and high price iron.
The complexing iron catalyst of the present invention's preparation can improve the decomposition rate of hydrogen peroxide, decomposition rate reaches 100%, the organic matter in the water is had good adsorption and oxidation usefulness, under ultraviolet light or visible light radiation, can increase organic salinity, make its mineralization rate reach 70%.Among the present invention method simple, be convenient to operation.
The specific embodiment
The specific embodiment one: the preparation method of the complexing iron catalyst of present embodiment is as follows: earlier ferric ion and complexing agent are pressed 1～2: 1 mol ratio complexing formation ferric complex; The proportioning that adds 7～8g cationic ion-exchange resin particle or film by every mole of ferric ion is dipped in pretreated cationic ion-exchange resin particle or film in the ferric complex; 0.5～24h at room temperature vibrates; filter then; after cationic ion-exchange resin after the above-mentioned processing or film clean repeatedly with clear water; up to the stripping that does not have iron ion, promptly make the complexing iron catalyst.
Described cationic ion-exchange resin particle grain size is 0.05～1.2mm.
The specific embodiment two: present embodiment and the specific embodiment one are different is that the mol ratio of ferric ion and complexing agent is 1.2～1.8: 1.Other is identical with the specific embodiment one.
The specific embodiment three: present embodiment and the specific embodiment one are different is that the mol ratio of ferric ion and complexing agent is 1.5: 1.Other is identical with the specific embodiment one.
The specific embodiment four: what present embodiment and the specific embodiment one were different is that every mole of ferric ion adds 7.5g cationic ion-exchange resin particle or film.Other is identical with the specific embodiment one.
The specific embodiment five: the present embodiment and the specific embodiment one are not both cationic ion-exchange resin pretreatment of particles method: till at first with clear water resin being washed, free from admixture muddy to the limpid nothing of water outlet; Then in exchange column, alternately soaked successively 2～4 hours with 3～5% HCl and NaOH, between soda acid with the drip washing of mixed bed high-purity deionized water to water outlet near neutral, so repeat 2～3 times, each soda acid consumption is 2 times of resin volume; The last HCl solution of handling application 4～5% carries out; Drain acid solution, promptly finish the cationic ion-exchange resin pretreatment of particles with clear water drip washing to neutrality.Other is identical with the concrete specific embodiment one.
The specific embodiment six: what present embodiment and the specific embodiment one were different is the cation exchange resin membrane preprocess method: under 75 ℃ of conditions, cation exchange resin membrane is incubated 1 hour in 5% (weight) hydrogen peroxide and 10% (weight) sulfuric acid solution, cleans with distilled water then and promptly finish the cation exchange resin membrane preliminary treatment three times.Other it identical with the specific embodiment one.
The specific embodiment seven: what present embodiment and the specific embodiment one were different is ferric ion to be loaded in charcoal fiber, zeolite, silica gel, bentonite, kaolin, diatomite or the imvite to carry out complexing with complexing agent more earlier, and the load capacity of trivalent iron salt is 1～10% (weight).Other is identical with the specific embodiment one.
The specific embodiment eight: what present embodiment was different with the specific embodiment one or eight is to have added bivalent cupric ion or divalent manganesetion in ferric ion, the weight ratio 40～99: 1 of ferric iron and bivalent cupric ion or divalent manganesetion.Other is identical with the specific embodiment one or eight.
The specific embodiment nine: what present embodiment was different with the specific embodiment one or eight is that ferric ion is provided by trivalent iron salt; Trivalent iron salt is ferric sulfate, iron chloride, ferric nitrate or ferric perchlorate.Other is identical with the specific embodiment one or eight.
The specific embodiment ten: what present embodiment and the specific embodiment one were different is that complexing agent is pyrimidine, porphyrin, disodium ethylene diamine tetraacetate, natrium citricum, sodium tartrate, sodium fluoride or sodium oxalate.Other is identical with the specific embodiment one.
The specific embodiment 11: what present embodiment and the specific embodiment one were different is that the cationic ion-exchange resin particle is 001 * 7 cationic ion-exchange resin or D001 cationic ion-exchange resin.Other is identical with the specific embodiment one.
Cationic ion-exchange resin particle in the present embodiment is the commercial goods.
The specific embodiment 12: what present embodiment and the specific embodiment one were different is that cation exchange resin membrane is Nafion 117.Other is identical with the specific embodiment one.
Cationic ion-exchange resin particle in the present embodiment is the commercial goods.
The specific embodiment 13: present embodiment complexing iron catalyst is applied to multiphase photocatalysis of hydrogen peroxide, adopts ultraviolet light or visible light radiation in the reaction, and catalyst is the complexing iron catalyst, and oxidant is hydrogen peroxide or ozone; Technical parameter in the course of reaction is as follows: the dosage of complexing iron catalyst is 50～200mg/L, the dosage of hydrogen peroxide or ozone is 10～110mmol/L, the mol ratio of hydrogen peroxide or ozone and organic pollution is 1～100: 1, reaction time 5min～2h.
The organic resolution ratio of present embodiment reaches 100%, and organic mineralization rate reaches more than 70%.Organic percent of decolourization is 100%, and the COD clearance reaches more than 90%.
The specific embodiment 14: present embodiment and the specific embodiment 13 are different is that to be added into dosage in reaction be the oxygen of 10～1000mmol/L.Other is identical with the specific embodiment 13.
The specific embodiment 15: what present embodiment and the specific embodiment 13 were different is the organic matter that heterogeneous smooth complexing iron catalyst catalyzing hydrogen peroxide is used for handling feedwater, city secondary effluent or pharmacy waste water.Other is identical with the specific embodiment 13.
The specific embodiment 16: in the present embodiment with the NaF of 0.1mmol/L and the Fe (NO of 0.1mmol/L
3)
3Each 10mL equal-volume mixes, and adds the 50mgD001 cationic ion-exchange resin, and room temperature is put into constant temperature oscillator, shakes 12 hours, filters then, and is clean with distilled water flushing ion exchange resin, obtains the complexing iron catalyst; To be applied to multiphase photocatalysis of hydrogen peroxide through the complexing iron catalyst that above-mentioned reaction makes, technical parameter in the course of reaction is as follows: 0.5mmol/L dye of positive ion malachite green (MG) 100mL, add the 10mmol/L hydrogen peroxide, and pH is 6, under sunshine, reacted 1 hour.
The percent of decolourization of MG reaches 100% in the present embodiment, and the COD clearance is 90%.
The specific embodiment 17: present embodiment is to adopt sodium oxalate to make complexing agent with the different of the specific embodiment 16, and sodium oxalate and ferric mol ratio are 1: 2, and complexing iron catalyst multiphase photocatalysis of hydrogen peroxide is reflected under the sunshine and reacted 5 minutes.Other is identical with the specific embodiment 16.
The percent of decolourization of MG reaches 100% in the present embodiment, and the clearance of COD is 97%.
The specific embodiment 18: present embodiment and the specific embodiment 16 different are to adopt 001 * 7 cationic ion-exchange resin, complexing iron catalyst multiphase photocatalysis of hydrogen peroxide to be reflected under the sunshine reaction 10 minutes.Other is identical with the specific embodiment 16.
The percent of decolourization of MG is 100% in the present embodiment, and the clearance of COD is 97%.
Claims (1)
1. the application of complexing iron catalyst in multiphase photocatalysis of hydrogen peroxide is characterized in that adopting ultraviolet light or visible light radiation in the reaction, and catalyst is the complexing iron catalyst, and oxidant is a hydrogen peroxide; Technical parameter in the course of reaction is as follows: the dosage of complexing iron catalyst is 50～200mg/L, and the dosage of hydrogen peroxide is 10～110mmol/L, and the mol ratio of hydrogen peroxide and organic pollution is 1～100: 1, reaction time 5min～2h; The preparation method of described complexing iron catalyst is as follows: earlier ferric ion and complexing agent are pressed 1～2: 1 mol ratio complexing formation ferric complex; The proportioning that adds 7～8g cationic ion-exchange resin particle or film by every mole of ferric ion is dipped in pretreated cationic ion-exchange resin particle or film in the ferric complex, 0.5～24h at room temperature vibrates, filter then, after cationic ion-exchange resin after the above-mentioned processing or film clean repeatedly with clear water, up to the stripping that does not have iron ion, promptly make the complexing iron catalyst; Described ferric ion is provided by trivalent iron salt; Trivalent iron salt is ferric sulfate, iron chloride, ferric nitrate or ferric perchlorate; Described complexing agent is pyrimidine, porphyrin, disodium ethylene diamine tetraacetate, natrium citricum, sodium tartrate, sodium fluoride or sodium oxalate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101445153A CN101327448B (en) | 2007-09-05 | 2008-07-24 | Preparation of chelated iron catalyst and use thereof for multiphase photocatalysis of hydrogen peroxide |
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| CNA2007100727514A CN101130169A (en) | 2007-09-05 | 2007-09-05 | Production of complexing iron catalyzer and application of polyphase photocatalysis hydrogen phosphide |
| CN200710072751.4 | 2007-09-05 | ||
| CN2008101445153A CN101327448B (en) | 2007-09-05 | 2008-07-24 | Preparation of chelated iron catalyst and use thereof for multiphase photocatalysis of hydrogen peroxide |
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| CN101327448B true CN101327448B (en) | 2010-07-14 |
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| CN2008101445153A Expired - Fee Related CN101327448B (en) | 2007-09-05 | 2008-07-24 | Preparation of chelated iron catalyst and use thereof for multiphase photocatalysis of hydrogen peroxide |
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| FR2951096B1 (en) * | 2009-10-09 | 2013-03-15 | Total Sa | PROCESS FOR OXIDATION OF ORGANIC COMPOUNDS |
| IT1396226B1 (en) * | 2009-11-11 | 2012-11-16 | Ct Di Ricerca Interd Sulla Risonanza Magn Nucl Per L Ambiente L Agro Alimentare Ed I Nuovi Mat Dell | METODOPER SEQUESTING THE ORGANIC CARBON IN A SOIL |
| EP2687489A1 (en) * | 2012-07-17 | 2014-01-22 | Solvay Sa | A process for removal of hydrogen peroxide from an aqueous solution |
| CN104229974B (en) * | 2014-09-18 | 2016-09-07 | 浙江理工大学 | A kind of method of quick process organic wastewater |
| CN104646021B (en) * | 2015-01-20 | 2015-12-02 | 郑州轻工业学院 | Tri-iron tetroxide/silica/manganese dioxide-catalyst and preparation method thereof |
| CN106946314B (en) * | 2017-04-01 | 2020-06-30 | 东南大学 | Method for efficiently degrading organic wastewater |
| CN108786933A (en) * | 2018-06-19 | 2018-11-13 | 中盐金坛盐化有限责任公司 | A kind of low sodium type cation resin regeneration agent and its preparation method and application |
| CN109569721B (en) * | 2018-12-27 | 2020-07-10 | 南京医科大学 | Preparation method and application of porphyrin iron modified mesoporous silica composite material |
| CN110038573A (en) * | 2019-05-15 | 2019-07-23 | 沈阳工大蓝金环保产业技术研究院有限公司 | Heterogeneous fenton catalyst Nafion/Fe3+Composite membrane and preparation method thereof |
| CN110255812B (en) * | 2019-06-05 | 2021-12-21 | 华东理工大学 | Biochemical and advanced oxidation combined method for retaining ammonia nitrogen and removing antibiotics in livestock and poultry breeding sewage treatment process |
| CN110240250A (en) * | 2019-06-06 | 2019-09-17 | 南京融众环境工程研究院有限公司 | A kind of method of degrading decabromodiphenyl ether |
| CN111607100A (en) * | 2020-06-10 | 2020-09-01 | 苏州大学 | Crystalline material based on iron-based porphyrin ligand, preparation and application thereof |
| CN112517084A (en) * | 2020-12-09 | 2021-03-19 | 北京理工大学 | Nano-channel slow-release photodegradation catalyst, preparation method and application thereof |
| CN115520952B (en) * | 2021-06-24 | 2024-06-28 | 中国石油化工股份有限公司 | Fenton oxidation treatment method for organic wastewater |
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