CN107986383A - A kind of method of porphyrin functional membrane photocatalytically degradating organic dye - Google Patents
A kind of method of porphyrin functional membrane photocatalytically degradating organic dye Download PDFInfo
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- CN107986383A CN107986383A CN201711315789.XA CN201711315789A CN107986383A CN 107986383 A CN107986383 A CN 107986383A CN 201711315789 A CN201711315789 A CN 201711315789A CN 107986383 A CN107986383 A CN 107986383A
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- Prior art keywords
- porphyrin
- membrane
- methyl
- dyestuff
- pyridine radicals
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of method of porphyrin functional membrane photocatalysis degradation organic contaminant.This method comprises the following steps：(1) sulfonated polysulfone/polyethersulfone blended anionic membrane is dipped into meso tetra- (4 pyridine radicals of N methyl) porphyrin, meso tetra- (4 pyridine radicals of N methyl) porphyrin is assembled into by film surface by Electrostatic Absorption, constructs porphyrin functionalization perforated membrane；(2) porphyrin functionalization perforated membrane is fixed in photo catalysis reactor；(3) xenon source is opened, aqueous dye solutions are carried through film by pump under visible light illumination, and find to degrade in film surface.The method of the present invention have easy to operate, the cycle is short, catalyst be recycled recycle, degradation efficiency it is high, and advantages of environment protection.
Description
Technical field
The present invention relates to photochemical catalyst field, specifically a kind of porphyrin functional membrane photocatalytically degradating organic dye
Method.
Background technology
China is weaving big country, and science fabric renewal is rapid, produces substantial amounts of waste water from dyestuff every year.Waste water from dyestuff comes
Source is complicated, as textile industry each branch's industry and textile production during each road manufacturing procedure can produce dye
Expect waste water.When producing the textile of different cultivars, the required raw material used, the dyestuff of addition, medicament are had any different, so as to make
The different content and different types of organic chemicals necessarily contained into textile industry waste water, its species is various, and dosage is non-
Chang great, COD/BOD high, cause chemical oxygen demand of water body high.
Organic dyestuff carries certain chromophore, even if concentration is not high, remains to make waste water have compared with dark colour.Due to dyestuff
Species is various, and possessed chromophore is different, so that the color distortion of waste water from dyestuff is larger.In addition, the molecule knot of dyestuff
Often there is ring-type or heterocycle structure, its physical stability and chemical stability are preferable, these molecular structures are often not easy in structure
It is destroyed, it is difficult to degrade certainly under field conditions (factors), or even also tend to be difficult to thoroughly degraded completely using conventional biodegrading process.And
And waste water from dyestuff includes the heavy metal ion for being difficult to degrade toward contact, the growth to animals and plants has very big damaging effect, even
Threaten to health.Based on above-mentioned harm, waste water from dyestuff is the difficulty there is an urgent need for processing faced on current water technology
Topic.Common processing method has absorption method, membrane separation process, common oxidizing process, bioanalysis etc., but these methods have technique stream
Journey is complicated, equipment requirement is high, it is of high cost, destroy the shortcomings of microenvironment.Photocatalytic degradation method is a kind of advanced oxidation processes, in the sun
Under the irradiation of light can effective degradation of dye, and the recyclable recycling of catalysis material will not remain in waste water and environment is caused
Secondary pollution.But photochemical catalyst at present is mainly TiO2, but TiO2Forbidden band it is wide (3.2eV), only wavelength it is short,
Light induced electron is produced under the high ultraviolet light of frequency, and the light induced electron produced is easily again compound with its hole.Therefore, open
Hair has to visible light-responded, under visible light illumination can the photochemical catalyst of efficient degradation dyestuff have great importance.
The content of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of porphyrin functional membrane photocatalytic degradation engine dyeing
The method of material.
A kind of method of porphyrin functional membrane photocatalytically degradating organic dye of the present invention, this method include following step
Suddenly：(1) sulfonated polysulfone/polyethersulfone blended anionic membrane is dipped into the aqueous solution of meso- tetra- (N- methyl -4- pyridine radicals) porphyrin
In, meso- tetra- (N- methyl -4- pyridine radicals) porphyrin is assembled into by film surface by Electrostatic Absorption, it is porous to construct porphyrin functionalization
Film；(2) porphyrin functionalization perforated membrane is fixed in photo catalysis reactor；(3) xenon source is opened, under visible light illumination
100~1000mL aqueous dye solutions circulate through film by pumping conveying, and degrade in film surface；Under visible light illumination into
Row dyestuff 1~10h of degraded, the degradation rate of dyestuff reach 80%~100%；Wherein, the sulfonated polysulfone/polyethersulfone blended it is cloudy from
Sulfonated polysulfone content is 1%~30% in sub- film；The concentration of aqueous solution of meso- tetra- (N- methyl -4- pyridine radicals) porphyrin is
10 μm of ol/L~1000 μm ol/L, pH scopes are 4~9；The xenon source power is 100W~500W；The dyestuff is Luo Dan
Bright B, methylene blue, methyl orange or the mixture of three, dye strength are initially 1mg/L~100mg/L, and pH scopes are 3~10；
The transmembrane pressure that the pump conveying aqueous dye solutions pass through film is 0.01MPa~0.2MPa.
This method used photocatalysis reactor is the organic glass membrane cisterna of light-permeable, membrane cisterna outside diameter 5cm~25cm, on membrane cisterna
Lower two parts organic glass thickness 1cm~5cm, is fixed, diaphragm is sandwiched among membrane cisterna, passes through silicone rubber gasket by screw and nut
Sealed.
Brief description of the drawings
Photo catalysis reactor schematic diagram used in Fig. 1 embodiment of the present invention 1.
The degradation rate of rhodamine B changes over time curve in Fig. 2 embodiment of the present invention 1.
Embodiment
With reference to embodiment, the present invention is further illustrated, its purpose, which is only that, is best understood from present disclosure
The protection domain being not intended to limit the present invention：
Embodiment 1
(1) sulfonated polysulfone/polyethersulfone blended anionic membrane that a piece of a diameter of 5cm sulfonated polysulfone content is 20% is soaked
It is 200 μm of ol/L to 200mL concentration, pH value is in the aqueous solution of 6.5 meso- tetra- (N- methyl -4- pyridine radicals) porphyrin, is passed through
Meso- tetra- (N- methyl -4- pyridine radicals) porphyrin is assembled into film surface by Electrostatic Absorption, constructs porphyrin functionalization perforated membrane；(2) will
Porphyrin functionalization perforated membrane is fixed in photo catalysis reactor；(3) xenon source that power is 300W is opened, in radiation of visible light
Lower 300mL concentration is that the rhdamine B aqueous solution that 20mg/L pH value is 6.5 circulates through film, transmembrane pressure by pumping conveying
For 0.05MPa, dyestuff is degraded in film surface, carries out dyestuff degraded 6h under visible light illumination, and the degradation rate of rhodamine B reaches
To 93.4%；As shown in Figure 1, rhodamine B degradation rate changes over time curve such as attached drawing 2 to used photocatalysis reactor schematic diagram
It is shown.
Embodiment 2
(1) sulfonated polysulfone/polyethersulfone blended anionic membrane that a piece of a diameter of 5cm sulfonated polysulfone content is 30% is soaked
It is 100 μm of ol/L to 300mL concentration, pH value is in the aqueous solution of 6.5 meso- tetra- (N- methyl -4- pyridine radicals) porphyrin, is passed through
Meso- tetra- (N- methyl -4- pyridine radicals) porphyrin is assembled into film surface by Electrostatic Absorption, constructs porphyrin functionalization perforated membrane；(2) will
Porphyrin functionalization perforated membrane is fixed in photo catalysis reactor；(3) xenon source that power is 400W is opened, in radiation of visible light
Lower 500mL concentration is that the methyl orange dye aqueous solution that 20mg/L pH value is 6.5 circulates through film, transmembrane pressure by pumping conveying
For 0.05MPa, dyestuff is degraded in film surface, carries out dyestuff degraded 6h under visible light illumination, and the degradation rate of methyl orange reaches
To 93.4%；As shown in Figure 1, methyl orange degradation rate changes over time curve such as attached drawing 2 to used photocatalysis reactor schematic diagram
It is shown.
Claims (3)
- A kind of 1. method of porphyrin functional membrane photocatalytically degradating organic dye, it is characterised in that this method comprises the following steps： (1) sulfonated polysulfone/polyethersulfone blended anionic membrane is dipped into the aqueous solution of meso- tetra- (N- methyl -4- pyridine radicals) porphyrin, Meso- tetra- (N- methyl -4- pyridine radicals) porphyrin is assembled into by film surface by Electrostatic Absorption, constructs porphyrin functionalization perforated membrane； (2) porphyrin functionalization perforated membrane is fixed in photo catalysis reactor；(3) xenon source is opened, under visible light illumination 100~ 1000mL aqueous dye solutions circulate through film by pumping conveying, and degrade in film surface；Sulfonated polysulfone content is 1%~30% in the sulfonated polysulfone/polyethersulfone blended anionic membrane；The concentration of aqueous solution of meso- tetra- (N- methyl -4- pyridine radicals) porphyrin is 10 μm of ol/L~1000 μm ol/L, pH scopes For 4~9；The xenon source power is 100W~500W；The dyestuff is rhodamine B, methylene blue, the mixture of methyl orange or three, dye strength be initially 1mg/L~ 100mg/L, pH scope are 3~10；The transmembrane pressure that the pump conveying aqueous dye solutions pass through film is 0.01MPa~0.2MPa.
- A kind of 2. method of porphyrin functional membrane photocatalytically degradating organic dye according to claim 1, it is characterised in that The photo catalysis reactor is the organic glass membrane cisterna of light-permeable, membrane cisterna outside diameter 5cm~25cm, membrane cisterna two parts organic glass up and down Thickness 1cm~5cm, is fixed by screw and nut, and diaphragm is sandwiched among membrane cisterna, is sealed by silicone rubber gasket.
- A kind of 3. method of porphyrin functional membrane photocatalytically degradating organic dye according to claim 1, it is characterised in that Dyestuff 1~10h of degraded is carried out under visible light illumination, and the degradation rate of dyestuff reaches 80%~100%；The dyestuff is rhodamine B, methylene blue, the mixture of methyl orange or three, dye strength be initially 1mg/L~ 100mg/L, pH scope are 3~10.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467710A (en) * | 2018-10-31 | 2019-03-15 | 河南科技学院 | Two-dimensional metallic porphyryl COF material and method for manufacturing thin film and application |
| CN111204838A (en) * | 2020-03-09 | 2020-05-29 | 泰州九润环保科技有限公司 | Application of metalloporphyrin covalent grafting photocatalytic membrane in organic wastewater treatment |
| CN111249931A (en) * | 2020-03-09 | 2020-06-09 | 泰州九润环保科技有限公司 | Preparation method of metalloporphyrin covalent grafting photocatalytic membrane |
| CN115672396A (en) * | 2022-10-26 | 2023-02-03 | 西安工程大学 | Preparation method of glass-based porphyrin film photocatalyst |
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| WO2008137082A1 (en) * | 2007-05-02 | 2008-11-13 | Yale University | Method for designing membranes for osmotically driven membrane processes |
| CN104524993A (en) * | 2014-12-30 | 2015-04-22 | 张一琛 | Cross-linked sulfonated polysulfone/polyether sulfone-sulfonated polysulfone composite membrane and manufacturing method thereof |
| CN105289734A (en) * | 2015-10-28 | 2016-02-03 | 湖南大学 | Method for degrading organic dye through metal organic framework film based on metalloporphyrin |
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2017
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| WO2008137082A1 (en) * | 2007-05-02 | 2008-11-13 | Yale University | Method for designing membranes for osmotically driven membrane processes |
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| CN105289734A (en) * | 2015-10-28 | 2016-02-03 | 湖南大学 | Method for degrading organic dye through metal organic framework film based on metalloporphyrin |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467710A (en) * | 2018-10-31 | 2019-03-15 | 河南科技学院 | Two-dimensional metallic porphyryl COF material and method for manufacturing thin film and application |
| CN111204838A (en) * | 2020-03-09 | 2020-05-29 | 泰州九润环保科技有限公司 | Application of metalloporphyrin covalent grafting photocatalytic membrane in organic wastewater treatment |
| CN111249931A (en) * | 2020-03-09 | 2020-06-09 | 泰州九润环保科技有限公司 | Preparation method of metalloporphyrin covalent grafting photocatalytic membrane |
| CN111204838B (en) * | 2020-03-09 | 2022-01-04 | 泰州九润环保科技有限公司 | Application of metalloporphyrin covalent grafting photocatalytic membrane in organic wastewater treatment |
| CN115672396A (en) * | 2022-10-26 | 2023-02-03 | 西安工程大学 | Preparation method of glass-based porphyrin film photocatalyst |
| CN115672396B (en) * | 2022-10-26 | 2024-03-08 | 西安工程大学 | Preparation method of glass-based porphyrin film photocatalyst |
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