CN100462147C - Method of preparing metalloporphyrin/silicon dioxide degradation agent - Google Patents
Method of preparing metalloporphyrin/silicon dioxide degradation agent Download PDFInfo
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- CN100462147C CN100462147C CNB2007100672403A CN200710067240A CN100462147C CN 100462147 C CN100462147 C CN 100462147C CN B2007100672403 A CNB2007100672403 A CN B2007100672403A CN 200710067240 A CN200710067240 A CN 200710067240A CN 100462147 C CN100462147 C CN 100462147C
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- degradation agent
- organic solvent
- metal porphyrin
- metalloporphyrin
- silicon dioxide
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Abstract
This invention relates to a method for preparing degradation agent of organic infectants, characterizing in dissolving a metal porphyrin derivant in an organic solvent then adding metasilicic acid ethyl and a catalyst[HNR2 (R refers to cymene, ethyl, propyl, butyl, H or phenyl), HCl, H2SO4, MeC6H4SO3H, AcOH, Al2O3, ZnO or M(OH)n (M is a metal, n=1,2)] in the mol ratio: 0.002-0.006 : 1, mixing them fully and heating them for reacting sufficiently then to be cleaned with an organic solvent of 100-400ml/g metal porphyrin derivant to be dried to get the metal porphyrin/SiO2 degradation agent.
Description
Technical field
The present invention relates to field of fine chemical, specifically be a kind of preparation method of degradation agent of degradable organic pollutant, this catalyst is specially adapted to waste water from dyestuff (various reactive dye), paranitrobenzoic acid, p-aminobenzoic acid, aromatic series organic pollution or their mixtures such as trichlorophenol, 2,4,6,-T.
Background technology
Water pollution is one of serious problems of facing of China.The industrial methods such as absorption, flocculation that generally adopt are handled waste water, and these methods have advantages such as equipment is simple, easy and simple to handle, technology is simple.But this class treatment facility is normally transferred to solid phase or gas phase with organic matter from liquid phase, does not eliminate organic pollution fully, has pluses and minuses separately at aspects such as treatment effeciency, removal effect, secondary pollutions.Bioremediation has been widely used in the processing of sanitary wastewater and industrial wastewater, and its treatment facility and operational management are simple, operating cost is low, but long processing period, hold facility area are big, and the organic matter of some difficult degradations is difficult to handle.
Because the organic pollution efficient in traditional treatment process degradation water is lower, so developing low-cost new catalyst and use new processing method to become the emphasis of present research efficiently.In recent years, people have developed the method for organic pollution in some new processing water, and such as irradiation method, supercritical water oxidation method, ultrasonotomography method, impulse electric corona technology, especially relevant with photochemistry new method constantly occurs, and comprises ultraviolet light photodissociation, UV/H
2O
2, UV/O
3, H
2O
2/ O
3/ UV, UV/H
2O
2/ Fe
2+Or Fe
3+And conductor photocatalysis.These processes can produce the very strong hydroxyl free radical of oxidability, thereby organic matter is effectively degraded.In recent years, metalloporphyrin and metal phthalocyanine had been obtained very big progress aspect water treatment.People such as Sorokin have promoted trichlorophenol, 2,4,6,-T by H by iron-phthalocyanine
2O
2Oxidation Decomposition is peroxide or hydroxyl radical free radical [Sorokin A, SerisJ-L, Meunier B., Science, 1995,268:1163-1166] as the organic reactive intermediate of mineral wherein.King's kitchen range is given birth to and is waited the people to adopt the sulfonation iron-phthalocyanine to utilize hydrogen peroxide that the dye wastewater reactive brilliant red x-3b is carried out the photocatalytic degradation test as catalyst; the result reaches reasonable effect, and [king's kitchen range is given birth to, Xu Yiming, Shanghai environmental science; 2001,20 (10): 480-481].People's p-sulfonic acid iron-phthalocyanine/H such as Tao Xia
2O
2Architectural study shows, can quicken the degraded [Tao Xia, Beijing: chemistry institute of the Chinese Academy of Sciences, 2002] of organic pollution under radiation of visible light greatly.
There are two defectives in metalloporphyrin itself: self is easily oxidized and irreversible aggrengation takes place, and catalytic activity is reduced.The effective ways that address the above problem are carried on metalloporphyrin on the insoluble carrier exactly and form heterogeneous system.People's trial loads to them on carriers such as resin, molecular sieve and all obtains effect preferably.People such as Huang Fei load to four azepine ferriporphyrins on the resin, test its catalytic performance subsequently, and the result shows four azepine ferriporphyrin/H
2O
2With four azepine ferriporphyrin/O
2System has good oxidisability [Huang Fei, Wu Ming, Han Duanzhuan, Lan Weizhen, South-Center University For Nationalities's journal (natural science edition), 2003,22 (3): 6-9] to acid fuchsin, methyl orange etc.People such as Chan can simulate the methane monooxygenase system with manganoporphyrin is immobilized to molecular sieve, oxidizing of methylene obtains methyl alcohol [Chan Y.W., Wilson R.B., ACS Prepr.Div FuelChem, 1988,33:453~461].Silica chemistry is stable, even under violent reaction condition, do not participate in reaction yet, therefore be a kind of attractive carrier, people such as Hidekazu Tanaka adopt sol-gel process will singly replace performance [the Hidekazu Tanaka that porphyrin loads on the silica and tested material, ToshiyukiYamada, Shinichiro Sugiyama, Hideo Shiratori, Ryozi Hino, Journal of Colloidand Interface Science, 2005,286:812-815].
Summary of the invention
The technical issues that need to address of the present invention are, provide a kind of preparation easily, good reproducibility, good stability and segregative degradation agent come degradable organic pollutant, with the degradation agent of tetraethoxysilance (TEOS) with the method preparation of metal porphyrin derivative employing copolycondensation, effectively degradable organic pollutant.
The preparation method of metalloporphyrin-silicon dioxide degradation agent of the present invention, it is characterized in that earlier metal porphyrin derivative being dissolved in the organic solvent, add ethyl orthosilicate and catalyst subsequently, fully stir, fully reaction again heats up, use organic solvent washing at last, oven dry promptly gets metalloporphyrin-silicon dioxide degradation agent; This degradation agent is granular, separates easily.
Described metal porphyrin derivative, its general formula are (1) formula, R in the formula, R ', R ", R " ' be H, OH, OSi R
1R
2R
3[R
1, R
2, R
3Be Me, Et, H, Vi, Ph, Cl, Me
3Si (OSiMe
2)
n, OMe, a kind of among the OEt], NH
2, COOH, a kind of in the alkoxyl; M is Co, Cu, Fe, Mn, a kind of among the Zn;
Described organic solvent is oxolane (THF), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), acetonitrile (CNCH
3), chloroform (CHCl
3), carrene (CHCl
2), methyl alcohol (CH
3OH), ethanol (C
2H
5The mixture of one or more OH);
Described catalyst is HNR
2: R is methyl, ethyl, propyl group, butyl, hydrogen, phenyl, HCl, H
2SO
4, MeC
6H
4SO
3H, AcOH, Al
2O
3, ZnO, M (OH)
n: M is metal, n=1,2, a kind of in ammoniacal liquor and the hydrochloric acid; Be preferably a kind of in ammoniacal liquor and the hydrochloric acid.
The mol ratio of described metal porphyrin derivative and ethyl orthosilicate is that 0.002~0.006:1 (is preferably 0.002~0.004:1); Organic solvent is 100~400 (being preferably 200~300) mL/g metal porphyrin derivative.
Adopt atomic absorption spectrum test load amount, adopt the organic pollution of the different pH values of this catalyst degradation,, analyze catabolite with liquid phase look-matter combined instrument with ultraviolet-visible spectrum or efficient liquid phase chromatographic analysis palliating degradation degree.
Said method can load to silica with metal porphyrin derivative easily and get on, and overcomes the porphyrin monomer and assembles shortcomings such as reaching difficult recovery easily.This degradation agent has good stability, advantages such as easily separated and good reproducibility.
The method of metalloporphyrin of the present invention-silica system degradable organic pollutant has reaction and easily carries out, good reproducibility, good degrading effect, advantage such as practicality is extensive.
The specific embodiment
Below will be by instantiation, the invention will be further described.
The preparation method of metalloporphyrin-silicon dioxide degradation agent of the present invention specifically is, earlier metal porphyrin derivative is dissolved in the organic solvent, add ethyl orthosilicate (TEOS) and catalyst subsequently, at room temperature fully stir, be warmed up to 150~170 ℃ (being preferably 160~165 ℃) reaction, 1~5h subsequently and (be preferably 2~4h), use the organic solvent washing product at last, oven dry promptly gets metalloporphyrin-silicon dioxide degradation agent.
Preparation embodiment 1
1g tetrahydroxy cobalt porphyrin (CoTHPP) is joined in the 2L flask, add 300mL THF, add 380mL TEOS and 130mL4mol.L
-1Ammoniacal liquor at room temperature fully stirs 8h, puts into baking oven subsequently, keeps 2h at 150~170 ℃, takes out reactant, adopts CH
3OH and THF washing, oven dry makes tetrahydroxy cobalt porphyrin/SiO
2Degradation agent (CoTHPP/SiO
2), adopting the atomic absorption spectrum test to calculate its load capacity is 1.21%.
Preparation embodiment 2
1g tetrahydroxy ferriporphyrin (FeTHPP) is joined in the 2L flask, add 300mL THF, add 380mL TEOS and 130mL 4mol.L
-1Ammoniacal liquor at room temperature fully stirs 8h, puts into baking oven subsequently, keeps 2h at 150~170 ℃, takes out reactant, adopts CH
3OH and THF washing, oven dry makes tetrahydroxy ferriporphyrin/SiO
2Degradation agent (FeTHPP/SiO
2), adopting the atomic absorption spectrum test to calculate its load capacity is 1.4%.
Preparation embodiment 3
1g tetrahydroxy copper porphyrin (CuHPP) is joined in the 2L flask, add 300mL THF, add 380mL TEOS and 130mL 4mol.L
-1Ammoniacal liquor at room temperature fully stirs 8h, puts into baking oven subsequently, keeps 2h at 150~170 ℃, takes out reactant, adopts CH
3OH and THF washing, oven dry makes tetrahydroxy copper porphyrin/SiO
2Degradation agent (CuHPP/SiO
2), adopting the atomic absorption spectrum test to calculate its load capacity is 1.32%
Application examples 4
With 1g CoTHPP/SiO
2Degradation agent places the 500mL round-bottomed flask, adds 200mL reactive golden yellow B-4RFN (1.0 * 10
-4Mol.L
-1) aqueous solution (simulated wastewater), add 200mL citric acid solution (pH=3) again, the H of 5mL 30%
2O
2Solution, stir 48h at normal temperatures after, after the separation, adopt ultraviolet-visible spectrum to detect the back and calculate degradation rate (degradation rate=(A
0-A
1)/A
0, A
0Be the absorption intensity of original solution in the maximum absorption wave strong point, A
1Absorption intensity for maximum absorption wave strong point behind the reaction certain hour), the degradation rate that calculates is 54.4%.
Application examples 5
With 1g CoTHPP/SiO
2Degradation agent places the 500mL round-bottomed flask, adds 200mL reactive golden yellow B-4RFN (1.0 * 10
-4Mol.L
-1) aqueous solution, add 200mL Potassium Hydrogen Phthalate cushioning liquid (pH=4) again, the H of 5mL 30%
2O
2Solution, stir 48h at normal temperatures after, after the separation, adopting ultraviolet-visible spectrum to detect the back, to calculate degradation rate be 42.4%.
Application examples 6
With 1g CoTHPP/SiO
2Degradation agent places the 500mL round-bottomed flask, adds 200mL reactive golden yellow B-4RFN (1.0 * 10
-4Mol.L
-1) aqueous solution, add 200mL PBS (pH=6.86) again, the H of 5mL 30%
2O
2Solution, stir 48h at normal temperatures after, after the separation, adopt ultraviolet-visible spectrum to detect the back and calculate degradation rate 30%.
Application examples 7
With 1g CoTHPP/SiO
2Degradation agent places the 500mL round-bottomed flask, adds 200mL reactive golden yellow B-4RFN (1.0 * 10
-4Mol.L
-1) aqueous solution, add 200mL borax buffer solution (pH=9.18) again, the H of 5mL 30%
2O
2Solution, stir 48h at normal temperatures after, after the separation, adopt ultraviolet-visible spectrum to detect the back and calculate degradation rate 45.7%.
Application examples 8
With 1g FeTHPP/SiO
2Degradation agent places the 500mL round-bottomed flask, adds 200mL reactive golden yellow B-4RFN (1.0 * 10
-4Mol.L
-1) aqueous solution, add 200mL citric acid solution (pH=3) again, the H of 5mL 30%
2O
2Solution, stir 48h at normal temperatures after, after the separation, adopting ultraviolet-visible spectrum to detect the back, to calculate degradation rate be 49%.
Application examples 9
With 1g CoTHPP/SiO
2Degradation agent places the 500mL round-bottomed flask, adds 200mL hair active scarlet dye (1.0 * 10
-4Mol.L
-1) aqueous solution, add 200mL borax buffer solution (pH=9.18) again, the H of 5mL 30%
2O
2Solution, stir 48h at normal temperatures after, after the separation, adopt ultraviolet-visible spectrum to detect the back and calculate degradation rate, the degradation rate that calculates is 51%.
Application examples 10
With 1g CuHPP/SiO
2Degradation agent places the 500mL round-bottomed flask, adds 200mL hair active scarlet dye (1.0 * 10
-4Mol.L
-1) aqueous solution, add 200mL borax buffer solution (pH=9.18) again, the H of 5mL 30%
2O
2Solution, stir 48h at normal temperatures after, after the separation, adopt ultraviolet-visible spectrum to detect the back and calculate degradation rate, the degradation rate that calculates is 71%.
Application examples 11
With 1g CuHPP/SiO
2Degradation agent places the 500mL round-bottomed flask, adds 200mL B-4RFN (1.0 * 10
-4Mol.L
-1) aqueous solution, add 200mL borax buffer solution (pH=9.18) again, the H of 5mL 30%
2O
2Solution, stir 48h at normal temperatures after, after the separation, adopt ultraviolet-visible spectrum to detect the back and calculate degradation rate, the degradation rate that calculates is 68%.
Application examples 12
With 1g CuHPP/SiO
2Degradation agent places the 500mL round-bottomed flask, adds 200mL B-4RFN (1.0 * 10
-4Mol.L
-1) aqueous solution, add 200mL borax buffer solution (pH=3) again, the H of 5mL 30%
2O
2Solution, stir 48h at normal temperatures after, after the separation, adopt ultraviolet-visible spectrum to detect the back and calculate degradation rate, the degradation rate that calculates is 57%.
Application examples 13
With 1g FeTHPP/SiO
2Degradation agent places the 500mL round-bottomed flask, adds 200mL paranitrobenzoic acid (1.0 * 10
-4Mol.L
-1) aqueous solution, add 200mL citric acid solution (pH=3) again, stir 48h at normal temperatures after, after the separation, adopt the high-performance liquid chromatogram determination extent of reaction, the degradation rate that calculates is 55%.
Application examples 14
(repeated experiments of degraded is CoTHPP/SiO with repeated use after the degradation agent filtration of application examples 7
2/ H
2O
2System is degraded in borax buffer solution behind the B-4RFN 48h, test, with the catalyst centrifugation, fully wash drying subsequently, and then with last time experiment the same terms under be used for degradation of contaminant again), after reusing three times, calculate degradation rate and be respectively 43%, 44%, 42.6%, show better repeatability.
Application examples 15
The real application tested its load capacity after 7 degradation agent filters once more, and adopting atomic absorption spectrum to test its load capacity is 1.20% (load capacity is 1.21% before the reaction), illustrate before and after the reaction that load capacity does not have that great changes will take place, good stability.
Claims (3)
1. the preparation method of a metalloporphyrin-silicon dioxide degradation agent, it is characterized in that earlier metal porphyrin derivative being dissolved in the organic solvent, add ethyl orthosilicate and catalyst subsequently, fully stir, fully reaction again heats up, use organic solvent washing at last, oven dry promptly gets metalloporphyrin-silicon dioxide degradation agent;
Described metal porphyrin derivative general formula is (1) formula, R in the formula, R ', R ", R, and " ' is H, OH, OSi R
1R
2R
3: R
1, R
2, R
3Be Me, Et, H, Vi, Ph, Cl, Me
3Si (OSiMe
2)
n, OMe, a kind of among the OEt, NH
2, COOH, a kind of in the alkoxyl; M is Co, Cu, Fe, Mn, a kind of among the Zn;
Described organic solvent is an oxolane, dimethyl formamide, dimethyl sulfoxide (DMSO), acetonitrile, chloroform, carrene, methyl alcohol, the mixture of one or more in the ethanol;
Described catalyst is HNR
2: R is methyl, ethyl, propyl group, butyl, hydrogen or phenyl, HCl, H
2SO
4, MeC
6H
4SO
3H, AcOH, Al
2O
3, ZnO, M (OH)
n: M is metal, n=1,2, a kind of in ammoniacal liquor and the hydrochloric acid;
The mol ratio of described metal porphyrin derivative and ethyl orthosilicate is 0.002~0.006:1; Organic solvent is 100~400ml/g metal porphyrin derivative;
Described temperature reaction is warmed up to 150~170 ℃, reaction 1~5h.
2. the preparation method of metalloporphyrin-silicon dioxide degradation agent according to claim 1, the mol ratio that it is characterized in that described metal porphyrin derivative and ethyl orthosilicate is 0.002~0.004:1; Organic solvent is 200~300mL/g metal porphyrin derivative; Described catalyst is a kind of in ammoniacal liquor and the hydrochloric acid.
3. the preparation method of metalloporphyrin-silicon dioxide degradation agent according to claim 1 and 2 is characterized in that described temperature reaction, is warmed up to 160~165 ℃, reaction 2~4h.
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CN101898156B (en) * | 2010-07-27 | 2012-11-07 | 湖南大学 | Preparation method for CeO2 doped organosilicon nanometer microsphere metal cobalt loaded (ii) porphyrin catalyst |
CN102070237B (en) * | 2010-11-26 | 2012-11-28 | 常州大学 | COD degradation agent for removing sulfamide from industrial wastewater |
CN104475159B (en) * | 2014-12-21 | 2017-05-03 | 福建师范大学 | Preparation method and application of 1-3-generation poly (aryl ether) dendritic phthalocyanine complex loaded SiO2 visible light photocatalyst |
CN105289734B (en) * | 2015-10-28 | 2018-01-19 | 湖南大学 | A kind of method of the metallic organic frame films degradating organic dye based on metalloporphyrin |
CN108187076B (en) * | 2018-04-02 | 2020-10-23 | 上海市第十人民医院 | Cobalt porphyrin/porous silicon oxide composite particle with photoacoustic imaging performance and cell protection function and preparation method and application thereof |
CN111841637B (en) * | 2020-06-23 | 2021-04-16 | 泰州九润环保科技有限公司 | Metalloporphyrin-mesoporous organic silicon oxide photocatalytic material and preparation method thereof |
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