CN104353500B - The fixing means of a kind of photocatalyst and the continuous method processing dyeing waste water - Google Patents
The fixing means of a kind of photocatalyst and the continuous method processing dyeing waste water Download PDFInfo
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- CN104353500B CN104353500B CN201410614450.XA CN201410614450A CN104353500B CN 104353500 B CN104353500 B CN 104353500B CN 201410614450 A CN201410614450 A CN 201410614450A CN 104353500 B CN104353500 B CN 104353500B
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- waste water
- dyeing waste
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses the fixing means of a kind of photocatalyst and the method processing dyeing waste water continuously, powder photocatalyst is added in the emulsion formed after base polyurethane prepolymer for use as is dissolved in deionized water, high-speed stirred makes its mix homogeneously form stable suspension, add cross-linking agent and initiator, form hydrogel, this hydrogel is cut into regular granule, namely photocatalysis agent it is fixed, the immobilization photocatalyst obtained is filled in cylindricality inside reactor, reactor is positioned under sunlight or artificial light sources, open dyeing waste water water pump, by the organic pollution in photocatalysis continuous degradation dyeing waste water.The advantage of the method is in that the load capacity of photocatalyst is high, immobilization place is easy and simple to handle, operating cost is low, under sunlight, the CODcr clearance in dyestuff and dyeing waste water can be reached more than 50%～95%, also has good promotional value in the process of other industrial wastewaters.
Description
Technical field
The present invention relates to the photocatalyst in a kind of depollution of environment field and preparation method thereof, specifically a kind of method of immobilization photocatalyst and continuous catalysis oxidation processes dyeing waste water thereof.
Background technology
China is in the stage that dyeing is fast-developing, and along with the continuous expansion of printing and dyeing production capacity, series of environmental problems also produces therewith, and one of them is exactly the generation of a large amount of dyeing waste water.Due to the whole process of dyeing and finishing is required for substantial amounts of water for carrying, washing, dispersed material and cooling device etc., the wastewater flow rate therefore produced is very big, generally up to the 70% ~ 90% of printing and dyeing enterprise water consumption.According to statistics, within 2010, in national each industrial trade, textile printing and dyeing industry wastewater discharge is 12.75 tons, occupies the 5th of whole nation discharged volume of industrial waste water, accounts for the 6% of whole nation discharged volume of industrial waste water.Showing according to relevant information, in Taihu Lake basin industrial wastewater COD (CODcr) discharge capacity, about 30% derives from textile printing and dyeing industry.The pollution problem of dyeing waste water has become the social problem of extensive concern.Dyeing waste water has the features such as the water yield is big, colourity deep, complicated component, biological degradability are poor, desolventing technology difficulty, and in dyeing waste water, the deep treatment method of persistent organic pollutants is current study hotspot.Conventional deep treatment method includes: absorption method, biologic treating technique and advanced chemical oxidation.Wherein the photocatalytic oxidation degradation speed in advanced chemical oxidation is fast, does not produce secondary pollution, and reaction condition is gentle, is the active research direction of environmental area.Titanium dioxide is efficient, stable chemical nature, anti-photooxidation type are strong, is widely used in photochemical catalytic oxidation.The energy gap of titanium dioxide (Detitanium-ore-type) is 3.2eV, and absorbing wavelength is less than 388nm, and absorption bands is ultraviolet region.And with rare earth element, nonmetalloid, precious metal element etc., titanium dioxide is modified improving its photocatalytic activity, improve its visible light-responded scope, reduce the energy expenditure during persistent organic pollutants in waste water process, even realize pollutant under sunlight, directly carry out photocatalytic degradation.Researcher goes out different photocatalytic degradation method according to the characteristics design of photocatalytic degradation, it is broadly divided into floating type and support type two kinds, wherein support type photocatalytic degradation is more conducive to recovery and the recycling of catalyst, but it is low to there is load capacity in present load process, catalytic Contact area is little, reduce the catalysis activity of titanium dioxide optical catalyst, cause the problem that degradation efficiency declines, and mostly support type photocatalytic method is that the mode adopting batch processed processes waste water, it is impossible to realize the continuous process of waste water.
Summary of the invention
One of the object of the invention is the above-mentioned deficiency for prior art, it is provided that the fixing means of a kind of photocatalyst and the continuous method processing dyeing waste water.
The fixing means of a kind of photocatalyst and the continuous method processing dyeing waste water, it is characterised in that comprise the following steps:
(1) powder photocatalyst is added in the emulsion formed after base polyurethane prepolymer for use as is dissolved in deionized water, high-speed stirred makes its mix homogeneously form stable suspension, add cross-linking agent and initiator, the polyurethane hydrogel of immobilization photocatalyst is formed through emulsion free-radical polymerization, this hydrogel is cut into regular granule, namely photocatalysis agent it is fixed
(2) the immobilization photocatalyst obtained is filled in cylindricality inside reactor, reactor is positioned under sunlight or artificial light sources, open dyeing waste water water pump, by the organic pollution in photocatalysis continuous degradation dyeing waste water.
In described immobilization photocatalyst, the mass percent of powder photocatalyst is 5～30%, the mass percent of base polyurethane prepolymer for use as is 10～40%, the mass percent of cross-linking agent is 5～10%, and the mass percent of initiator is 0.1～1.0%, and the mass percent of deionized water is 19～79.9%.
Described photocatalyst is titanium dioxide or zinc oxide and various modified or doping the powder body material with photocatalysis effect, and powder body mean diameter is less than 100 microns.
Described base polyurethane prepolymer for use as is the macromolecule that two ends are structured with:
Wherein PU represents polyurethane skeleton, and the molecular weight of base polyurethane prepolymer for use as is 2000～20000.
Described cross-linking agent is N, N '-methylene acrylic acid amides, polyethyleneglycol diacrylate, one in polyethylene glycol dimethacrylate or its combination.
Described initiator is N, N, N ', one in N '-tetramethylethylenediamine, sulphite, bisulfites or its combination.
The present invention utilizes the method for immobilization photocatalyst continuous catalysis oxidation processes dyeing waste water, the features such as this photocatalyst has raising photocatalyst amount, photon utilization rate, degradation speed is fast, purification efficiency is high, cost is low, preparation technology is simple, and loose powder shape or granular catalyst are more suitable for the operation of photocatalytic oxidation reactor unit relatively.
Monoblock type photocatalyst for dyeing waste water provided by the invention is filled in the cylindrical quartz glass reactor that diameter is 100mm, dyeing waste water is passed into continuously with the flow velocity of 20 ~ 100mL/min, ensure certain intensity of illumination, keep dyeing waste water hydraulic detention time in a reservoir 30～120 minutes, after stable reaction, measure CODcr, the CODcr clearance importing and exporting dyeing waste water and can reach 50～95%.
Detailed description of the invention
Below embodiments of the invention are elaborated: the present embodiment is carried out under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
The base polyurethane prepolymer for use as that 10g molecular weight is 4000 is dissolved in 74.5g deionized water and forms emulsion, emulsion adds 10g nano titanium oxide P25, high-speed stirred makes its mix homogeneously form stable suspension, add 5g polyethyleneglycol diacrylate and 0.5gN, N, N ', N '-tetramethylethylenediamine, form the polyurethane hydrogel of bulk immobilization photocatalyst through emulsion free-radical polymerization, this hydrogel is cut into the cube that the length of side is 3mm, is namely fixed photocatalysis agent.
The monoblock type photocatalyst for dyeing waste water that the present embodiment prepares is filled in the cylindrical quartz glass reactor that diameter is 100mm, dyeing waste water is passed into continuously with the flow velocity of 20mL/min, keep dyeing waste water hydraulic detention time in a reservoir 60 minutes in the sunlight, after stable reaction, measure CODcr, the CODcr clearance importing and exporting dyeing waste water and can reach 65%.
Embodiment 2:
The base polyurethane prepolymer for use as that 20g molecular weight is 3000 is dissolved in 52g deionized water and forms emulsion, emulsion adds 20g nano titanium oxide P25, high-speed stirred makes its mix homogeneously form stable suspension, add 7.5g polyethyleneglycol diacrylate and 0.5gN, N, N ', N '-tetramethylethylenediamine, form the polyurethane hydrogel of bulk immobilization photocatalyst through emulsion free-radical polymerization, this hydrogel is cut into the cube that the length of side is 5mm, is namely fixed photocatalysis agent.
The monoblock type photocatalyst for dyeing waste water that the present embodiment prepares is filled in the cylindrical quartz glass reactor that diameter is 100mm, dyeing waste water is passed into continuously with the flow velocity of 20mL/min, keep dyeing waste water hydraulic detention time in a reservoir 60 minutes in the sunlight, after stable reaction, measure CODcr, the CODcr clearance importing and exporting dyeing waste water and can reach 72.5%.
Embodiment 3:
The base polyurethane prepolymer for use as that 15g molecular weight is 5000 is dissolved in 52g deionized water and forms emulsion, emulsion adds 25g nano titanium oxide P25, high-speed stirred makes its mix homogeneously form stable suspension, add 7.5gN, N '-methylene acrylic acid amides and 0.5g sodium sulfite, form the polyurethane hydrogel of bulk immobilization photocatalyst through emulsion free-radical polymerization, this hydrogel is cut into the cube that the length of side is 4mm, is namely fixed photocatalysis agent.
The monoblock type photocatalyst for dyeing waste water that the present embodiment prepares is filled in the cylindrical quartz glass reactor that diameter is 100mm, dyeing waste water is passed into continuously with the flow velocity of 40mL/min, keep dyeing waste water hydraulic detention time in a reservoir 30 minutes in the sunlight, after stable reaction, measure CODcr, the CODcr clearance importing and exporting dyeing waste water and can reach 66.5%.
Embodiment 4:
The base polyurethane prepolymer for use as that 10g molecular weight is 10000 is dissolved in 69.5g deionized water and forms emulsion, emulsion adds 15g nano titanium oxide P25, high-speed stirred makes its mix homogeneously form stable suspension, add 5g polyethylene glycol dimethacrylate and 0.5g sodium sulfite, the polyurethane hydrogel of bulk immobilization photocatalyst is formed through emulsion free-radical polymerization, this hydrogel is cut into the cube that the length of side is 4mm, is namely fixed photocatalysis agent.
The monoblock type photocatalyst for dyeing waste water that the present embodiment prepares is filled in the cylindrical quartz glass reactor that diameter is 100mm, dyeing waste water is passed into continuously with the flow velocity of 10mL/min, keep dyeing waste water hydraulic detention time in a reservoir 120 minutes in the sunlight, after stable reaction, measure CODcr, the CODcr clearance importing and exporting dyeing waste water and can reach 83.6%.
Embodiment 5:
The base polyurethane prepolymer for use as that 20g molecular weight is 10000 is dissolved in 46.5g deionized water and forms emulsion, emulsion adds 25g nano titanium oxide P25, high-speed stirred makes its mix homogeneously form stable suspension, add 7.5g polyethylene glycol dimethacrylate and 1g sodium sulfite, the polyurethane hydrogel of bulk immobilization photocatalyst is formed through emulsion free-radical polymerization, this hydrogel is cut into the cube that the length of side is 2mm, is namely fixed photocatalysis agent.
The monoblock type photocatalyst for dyeing waste water that the present embodiment prepares is filled in the cylindrical quartz glass reactor that diameter is 100mm, dyeing waste water is passed into continuously with the flow velocity of 10mL/min, keep dyeing waste water hydraulic detention time in a reservoir 120 minutes in the sunlight, after stable reaction, measure CODcr, the CODcr clearance importing and exporting dyeing waste water and can reach 92.6%.
Embodiment 6:
The base polyurethane prepolymer for use as that 25g molecular weight is 5000 is dissolved in 36.5g deionized water and forms emulsion, emulsion adds 30g nano titanium oxide P25, high-speed stirred makes its mix homogeneously form stable suspension, add 7.5g polyethylene glycol dimethacrylate and 1g sodium sulfite, the polyurethane hydrogel of bulk immobilization photocatalyst is formed through emulsion free-radical polymerization, this hydrogel is cut into the cube that the length of side is 2mm, is namely fixed photocatalysis agent.
The monoblock type photocatalyst for dyeing waste water that the present embodiment prepares is filled in the cylindrical quartz glass reactor that diameter is 100mm, dyeing waste water is passed into continuously with the flow velocity of 10mL/min, keep dyeing waste water hydraulic detention time in a reservoir 120 minutes in the sunlight, after stable reaction, measure CODcr, the CODcr clearance importing and exporting dyeing waste water and can reach 92.4%.
Claims (6)
1. the method that an immobilization photocatalysis processes dyeing waste water continuously, it is characterised in that comprise the following steps:
(1) powder photocatalyst is added in the emulsion formed after base polyurethane prepolymer for use as is dissolved in deionized water, high-speed stirred makes its mix homogeneously form stable suspension, add cross-linking agent and initiator, the polyurethane hydrogel of immobilization photocatalyst is formed through emulsion free-radical polymerization, this hydrogel is cut into regular granule, namely photocatalysis agent it is fixed
(2) the immobilization photocatalyst obtained is filled in cylindricality inside reactor, reactor is positioned under sunlight or artificial light sources, open dyeing waste water water pump, by the organic pollution in photocatalysis continuous degradation dyeing waste water.
2. the method that a kind of immobilization photocatalysis according to claim 1 processes dyeing waste water continuously, it is characterized in that, in described immobilization photocatalyst, the mass percent of powder photocatalyst is 5～30%, the mass percent of base polyurethane prepolymer for use as is 10～40%, the mass percent of cross-linking agent is 5～10%, the mass percent of initiator is 0.1～1.0%, and the mass percent of deionized water is 19～79.9%.
3. the method that a kind of immobilization photocatalysis according to claim 1 processes dyeing waste water continuously, it is characterized in that, described photocatalyst is titanium dioxide or zinc oxide and various modified or doping the powder body material with photocatalysis effect, and powder body mean diameter is less than 100 microns.
4. the method that a kind of immobilization photocatalysis according to claim 1 processes dyeing waste water continuously, it is characterised in that described base polyurethane prepolymer for use as is the macromolecule that two ends are structured with:
Wherein PU represents polyurethane skeleton, and the molecular weight of base polyurethane prepolymer for use as is 2000～20000.
5. the method that a kind of immobilization photocatalysis according to claim 1 processes dyeing waste water continuously, it is characterized in that, described cross-linking agent is N, N '-methylene acrylic acid amides, polyethyleneglycol diacrylate, one in polyethylene glycol dimethacrylate or its combination.
6. the method that a kind of immobilization photocatalysis according to claim 1 processes dyeing waste water continuously, it is characterised in that described initiator is N, N, N ', one in N '-tetramethylethylenediamine, sulphite, bisulfites or its combination.
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| CN106492882B (en) * | 2016-10-20 | 2019-04-05 | 南京大学 | Have amide groups and loads the preparation method and application of photocatalyst of Nano cadmium sulphide composite hydrogel |
| CN109293093A (en) * | 2018-10-17 | 2019-02-01 | 东莞绿邦智能科技有限公司 | A kind of processing unit containing organic pollutant wastewater |
| CN115108861B (en) * | 2022-05-06 | 2023-04-07 | 广州大丘有机农产有限公司 | Fermentation treatment process of traditional Chinese medicine residues |
| CN115069301B (en) * | 2022-05-27 | 2023-04-21 | 恒天嘉华非织造有限公司 | Composite material for treating printing and dyeing textile wastewater and preparation method thereof |
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| CN103937022B (en) * | 2014-05-06 | 2016-08-17 | 盛宇星 | A kind of immobilized photocatalyst of nanometer, preparation method and its usage |
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