CN114516704A - Treatment method of dye wastewater - Google Patents
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- 238000000265 homogenisation Methods 0.000 claims abstract description 4
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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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- 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
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides a dye wastewater treatment method.A dye wastewater treatment system comprises a pretreatment tank, a photocatalytic oxidation reaction tank, a homogeneous regulation tank, a biological reaction tank and a sedimentation tank which are sequentially arranged along the wastewater flowing direction. The wastewater is pretreated to remove suspended pollution particles, part of macromolecular organic dye and other macromolecular organic pollutants are deeply oxidized into nontoxic and harmless micromolecular substances through photocatalytic oxidation, the pH value of the wastewater is adjusted to be more than or equal to 6 through homogenization treatment, the rest of macromolecular organic pollutants are removed through biological treatment, micromolecular organic matters in the wastewater are further decomposed into inorganic matters, sludge in the wastewater is further precipitated through precipitation treatment, and the wastewater can be discharged after reaching the standard. The photocatalytic oxidation treatment in the invention has low energy consumption and low water treatment cost, is beneficial to environmental protection and is beneficial to the development of dyeing enterprises.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a treatment method of dye wastewater.
Background
The dye wastewater has the characteristics of high chromaticity, high content of organic pollutants, high alkalinity, difficult biochemical degradation of organic matters, large change of water quality and the like, so that the dye wastewater becomes one of the industrial wastewater difficult to treat.
Aiming at the characteristics of stable chemical property and difficult degradation of most dyes, degradation and treatment methods of dyes and dye wastewater are in urgent need of research. With the technological progress and the continuous development of pollution treatment technology, mankind has found many effective methods for treating dye wastewater, which are mainly divided into physical, chemical and biological methods. However, in practical application, the conventional treatment means often cannot make the dye wastewater reach the standard and be discharged. The use of the photocatalyst can effectively degrade dyes, can generate substances with strong oxidizing property (such as hydroxyl free radicals, oxygen and the like) under the irradiation of light, and can be used for decomposing organic compounds, partial inorganic compounds, bacteria, viruses and the like. It is less harmful to environment, has a wide pH range, but also has the disadvantages of light corrosion, insufficient specific surface area and the like which limit the application of the catalyst. Therefore, a method for treating dye wastewater by combining photocatalytic oxidation with conventional biological treatment is needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for treating dye wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme:
a dye wastewater treatment method comprises the steps that a dye wastewater treatment system comprises a pretreatment tank, a photocatalytic oxidation reaction tank, a homogeneous regulation tank, a biological reaction tank and a sedimentation tank which are sequentially arranged along the flowing direction of wastewater; a stirring device is arranged in the photocatalytic oxidation reaction tank; a lifting pump is arranged in the homogenizing adjusting tank; the biological reaction tank consists of an anaerobic biochemical reactor and an aerobic biochemical reactor;
the processing method comprises the following steps:
s1, preprocessing: the wastewater enters a pretreatment tank, a flocculating agent is added into the pretreatment tank, the wastewater is stirred for a period of time to generate flocculation reaction so as to remove suspended pollution particles in the wastewater, and supernatant enters the next step after precipitation;
s2, photocatalytic oxidation: the pretreated wastewater further enters a photocatalytic oxidation reaction tank, and load S-C is added into the tank3N4The stirring device is opened to stir, and part of macromolecular organic dye and other macromolecular organic pollutants are deeply oxidized into nontoxic and harmless micromolecular substances, such as CO2And H2O, etc.;
s3, homogenizing: the wastewater after the photocatalytic oxidation reaction is further introduced into a homogenizing adjusting tank, and an adjusting solution is added into the homogenizing adjusting tank to adjust the pH value of the wastewater to be more than or equal to 6;
s4, biological treatment: the biological treatment comprises anaerobic treatment and aerobic treatment; the wastewater after the homogenization treatment is further sent to an anaerobic biochemical reactor by a lift pump for anaerobic treatment to remove the residual macromolecular organic pollutants, and the method mainly decomposes macromolecular organic matters into micromolecular organic matters and converts part of the organic matters into methane and other available energy sources; the wastewater after the anaerobic treatment further enters an aerobic biochemical reactor for aerobic treatment so as to further decompose micromolecular organic matters in the wastewater into inorganic matters;
s5, precipitation treatment: the wastewater after biological treatment further enters a sedimentation tank for mud-water separation, and the supernatant can be discharged after reaching the standard.
In order to optimize the technical scheme, the specific measures adopted further comprise:
further, the load S-C3N4The active carbon nano-particles are prepared by the following method:
(1) placing the crucible with the cover containing the thiourea powder in a muffle furnace, and calcining for 4 hours at 450-550 ℃;
(2) collecting the calcined product, and grinding into powder to obtain S-C3N4；
(3) Will S-C3N4Adding into activated carbon solution, wherein S-C3N4And the mass ratio of the activated carbon is 1: 2, ultrasonically dipping for 12-15 hours, and centrifugally drying to obtain the load S-C3N4The activated carbon nanoparticles of (1).
Further, the flocculating agent is FeCl3And a mixed solution of PAM, and FeCl3And PAM in a weight ratio of 5: 0.5.
further, in step S1, the stirring time is 5 to 15 minutes.
Further, in step S2, the load S-C3N4The unit adding amount of the active carbon nano-particles is 0.8-1.2 g/L.
Further, in step S3, the adjusting solution is a lime solution.
Further, in step S4, the duration of the anaerobic treatment and the aerobic treatment is 1-2 hours.
Further, in step S5, the sedimentation tank is a radial sedimentation tank.
Further, in step S5, the mud-water separation reaction time is 1 hour.
The invention has the beneficial effects that:
(1) before biological treatment, the photocatalytic oxidation treatment is carried out, so that the organic load of the biological treatment is effectively reduced, and the high-efficiency operation of the biological treatment is ensured; the added photocatalyst active carbon loads S-C3N4The nano particles can further destroy chromophoric groups and molecular structures of dye molecules, so that the aims of deep decolorization and degradation are fulfilled; activated carbon loaded with S-C3N4Nanoparticles compared to pure S-C3N4The nanoparticles have a larger specific surface area and a stronger photocurrent-responsive behavior.
(2) Activated carbon Supported S-C as mentioned in the present invention3N4Nano-particle and common photocatalyst-metal semiconductor TiO2In contrast, it is a green photocatalytic material without secondary pollution caused by metal leaching, and S-C3N4Is at C3N4Further modifying, and increasing C by doping sulfur element3N4The visible light range and the adsorption performance of the material are reduced, the recombination of electrons and holes is reduced, and the photocatalytic performance of the material is further improved; loading S-C with activated carbon3N4Is S-C3N4A large number of adsorption sites are provided, so that the retention property of the dye wastewater is increased, and the internal organic matters of the dye wastewater are adsorbed and decomposed, so that the performance of the photocatalyst is further improved;
(3) the photocatalytic oxidation treatment provided by the invention has the advantages of low energy consumption and low water treatment cost, is beneficial to environmental protection, and is beneficial to the development of dyeing enterprises.
Drawings
FIG. 1 is a process flow chart of the treatment of dye wastewater using the "treatment method of dye wastewater" of the present invention.
FIG. 2 is S-C3N4Nanoparticles and activated carbon loaded S-C3N4A spectrum of the specific surface area of the nanoparticles;
FIG. 3 is S-C3N4Nanoparticles and activated carbon loaded S-C3N4The transient photocurrent of the nano-particles corresponds to the spectrum.
Detailed Description
The invention will now be described in further detail with reference to fig. 1-3.
Example 1
Dye wastewater treatment of certain dye chemical industry Co., Ltd, daily treatment capacity of 50m3And d, the pH value of the inlet water is 5.05, the COD is 7500mg/L, and the chroma is 3000 times. The invention is used for treating enterprise wastewater, and the treatment process comprises the following steps:
the dye wastewater treatment system comprises a pretreatment tank, a photocatalytic oxidation reaction tank, a homogeneous regulation tank, a biological reaction tank and a sedimentation tank which are sequentially arranged along the wastewater flowing direction; a stirring device is arranged in the photocatalytic oxidation reaction tank; a lifting pump is arranged in the homogenizing adjusting tank; the biological reaction tank consists of an anaerobic biochemical reactor and an aerobic biochemical reactor; the sedimentation tank is a radial flow sedimentation tank, a rotary mud scraper is arranged in the sedimentation tank, a sludge hopper and a sludge pump are arranged at the bottom of the sedimentation tank, and the sludge hopper is connected with the sludge pump;
the processing method comprises the following steps:
s1, preprocessing: the wastewater enters a pretreatment tank, and 2.5 tons of FeCl are added into the pretreatment tank3And 0.5 ton PAM, stirring for 10 minutes to generate flocculation reaction so as to remove suspended pollution particles in the wastewater, and allowing supernatant after precipitation to enter the next step;
s2, photocatalytic oxidation: the pretreated wastewater further enters a photocatalytic oxidation reaction tank, and 50kg of loaded S-C is added into the tank3N4The stirring device is opened to stir, and part of macromolecular organic dye and other macromolecular organic pollutants are deeply oxidized into nontoxic and harmless micromolecular substances, such as CO2And H2O, etc.;
s3, homogenizing: the wastewater after the photocatalytic oxidation reaction is further introduced into a homogenizing adjusting tank, and a lime solution is added into the homogenizing adjusting tank to adjust the pH value of the wastewater to be more than or equal to 6;
s4, biological treatment: the biological treatment comprises anaerobic treatment and aerobic treatment; the wastewater after the homogenization treatment is further sent to an anaerobic biochemical reactor by a lift pump for anaerobic treatment for 1.5 hours to remove the residual macromolecular organic pollutants, and the method mainly decomposes the macromolecular organic matters into micromolecular organic matters and converts a part of the organic matters into methane and other available energy sources; the wastewater after the anaerobic treatment further enters an aerobic biochemical reactor for aerobic treatment for 1.5 hours so as to further decompose micromolecular organic matters in the wastewater into inorganic matters;
s5, precipitation treatment: the wastewater after biological treatment further enters a radial flow sedimentation tank for sludge-water separation for 1 hour, sludge deposited at the bottom of the tank is scraped to a sludge hopper at the center of the tank by a scraper on a rotary sludge scraper, then the sludge in the sludge hopper is discharged by a sludge pump, and the supernatant can be discharged after reaching the standard.
Wherein S-C in step S23N4The preparation method comprises the following steps:
(1) placing a 100kg crucible with a cover of thiourea powder in a muffle furnace, and calcining for 4 hours at 500 ℃;
(2) collecting the calcined product, and grinding into powder to obtain S-C3N4；
(3) 25kg of S-C3N4Adding into 50kg of active carbon-containing aqueous solution, ultrasonically dipping for 13 hours, and centrifugally drying to obtain the loaded S-C3N4The activated carbon nanoparticles of (1).
As can be seen from FIG. 2, S-C is supported on activated carbon3N4The specific surface area of the nano-particles is higher than that of S-C3N4The nano particles have larger specific surface area, so that a stronger photocatalytic effect can be brought; as can be seen from FIG. 3, S-C is supported on activated carbon3N4The nano-particle has higher photocurrent response, which shows that the separation efficiency of electron-hole pairs can be obviously improved and the charge transfer is accelerated after the active carbon is loaded, so that the active carbon is loaded with S-C3N4Has remarkable photocatalytic performance.
The COD and the chroma of the wastewater treated by the method are shown in the following table 1:
TABLE 1 quality of influent water and effluent water quality of each treatment unit
| Unit cell | COD(mg/L) | Chroma (double) |
| Inflow water | 7500 | 3000 |
| Pretreated effluent | 5240 | 2000 |
| Photocatalytic oxidation effluent | 1020 | 800 |
| Biological treatment of effluent | 236 | 50 |
| Final sinking of the |
30 | 50 |
As can be seen from Table 1, the COD of the dye wastewater is reduced to 300mg/L from 7500mg/L during water inlet, the chroma is reduced to 50 times from 30000 times, and especially the COD and chroma of the wastewater are greatly reduced after photocatalytic oxidation treatment. The invention has good treatment effect on dye wastewater, especially on high COD and high chroma dye wastewater.
It should be noted that the terms "upper", "lower", "left", "right", "front", "back", etc. used in the present invention are for clarity of description only, and are not intended to limit the scope of the present invention, and the relative relationship between the terms and the terms is not limited by the technical contents of the essential changes.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention.
Claims (9)
1. A method for treating dye wastewater is characterized in that,
the dye wastewater treatment system comprises a pretreatment tank, a photocatalytic oxidation reaction tank, a homogeneous regulation tank, a biological reaction tank and a sedimentation tank which are sequentially arranged along the wastewater flowing direction; a stirring device is arranged in the photocatalytic oxidation reaction tank; the biological reaction tank consists of an anaerobic biochemical reactor and an aerobic biochemical reactor;
the processing method comprises the following steps:
s1, pretreatment: the wastewater enters a pretreatment tank, a flocculating agent is added into the pretreatment tank, the mixture is stirred to generate flocculation reaction, and supernatant enters the next step after precipitation;
s2, photocatalytic oxidation: the pretreated wastewater further enters a photocatalytic oxidation reaction tank, and load S-C is added into the tank3N4The stirring device is opened to stir the activated carbon nano-particles;
s3, homogenizing: the wastewater after the photocatalytic oxidation reaction is further introduced into a homogenizing adjusting tank, and an adjusting solution is added into the homogenizing adjusting tank to adjust the pH value of the wastewater to be more than or equal to 6;
s4, biological treatment: the biological treatment comprises anaerobic treatment and aerobic treatment; the wastewater after the homogenization treatment is further sent to an anaerobic biochemical reactor for anaerobic treatment; the wastewater after the anaerobic treatment further enters an aerobic biochemical reactor for aerobic treatment;
s5, precipitation treatment: the wastewater after biological treatment further enters a sedimentation tank for mud-water separation, and the supernatant can be discharged after reaching the standard.
2. The method for treating dye-loaded wastewater according to claim 1, wherein the load of S-C is3N4The active carbon nano-particles are prepared by the following method:
(1) placing the crucible with the cover containing the thiourea powder in a muffle furnace, and calcining for 4 hours at 450-550 ℃;
(2) collecting the calcined product, and grinding into powder to obtain S-C3N4；
(3) Will S-C3N4Adding into activated carbon solution, wherein S-C3N4And the mass ratio of the activated carbon is 1: 2, ultrasonically dipping for 12-15 hours, and centrifugally drying to obtain the load S-C3N4The activated carbon nanoparticles of (1).
3. The method for treating dye wastewater according to claim 1, wherein the flocculant is FeCl3And a mixed solution of PAM, and FeCl3And PAM in a weight ratio of 5: 0.5.
4. the method for treating dye wastewater according to claim 1, wherein in step S1, the stirring time is 5-15 minutes.
5. The method for treating seed dye wastewater according to claim 1, wherein in step S2, the load is S-C3N4The unit adding amount of the active carbon nano-particles is 0.8-1.2 g/L.
6. The method for treating dye wastewater according to claim 1, wherein in step S3, the conditioning solution is lime solution.
7. The method for treating dye wastewater according to claim 1, wherein the anaerobic treatment and the aerobic treatment are carried out for 1 to 2 hours in step S4.
8. The method for treating seed dye wastewater according to claim 1, wherein in step S5, the sedimentation tank is a radial sedimentation tank.
9. The method for treating dye wastewater according to claim 1, wherein the slurry-water separation reaction is carried out for 1 hour in step S5.
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