CN116239271A - Application of self-purification nano-electrode carbon mesh in deep treatment of tail end of printing and dyeing wastewater - Google Patents
Application of self-purification nano-electrode carbon mesh in deep treatment of tail end of printing and dyeing wastewater Download PDFInfo
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- CN116239271A CN116239271A CN202310424545.4A CN202310424545A CN116239271A CN 116239271 A CN116239271 A CN 116239271A CN 202310424545 A CN202310424545 A CN 202310424545A CN 116239271 A CN116239271 A CN 116239271A
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- 238000004043 dyeing Methods 0.000 title claims abstract description 49
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- 150000002513 isocyanates Chemical class 0.000 claims description 4
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- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
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- 229920001778 nylon Polymers 0.000 description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 241000238557 Decapoda Species 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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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
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
- C02F2001/46157—Perforated or foraminous electrodes
- C02F2001/46161—Porous electrodes
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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
- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides an application of self-purifying nano-electrode carbon mesh cloth in deep treatment of printing and dyeing wastewater tail end, which comprises the following steps: taking biochemical effluent of printing and dyeing wastewater as raw water, and pretreating by adopting self-purifying nano-electrode carbon mesh cloth; sequentially carrying out membrane bioreactor treatment and catalytic oxidation on the pretreated effluent to obtain terminal effluent; the self-purification nano-electrode carbon screen cloth comprises a screen cloth substrate and active components compounded on the screen cloth substrate, wherein the active components are porous nano-electrode carbon and titanium dioxide; the porous nanoelectrode carbon has a plurality of pore-like structures of different nanometer pore diameters. The electrode carbon mesh material is applied to the advanced treatment process of the tail end of the printing and dyeing wastewater, and can be used as pretreatment before the membrane, and the porous nano carbon can be used for cooperatively treating to exert better degradation efficiency, so that a stable treatment effect is achieved. The process is built by one-time investment, does not need to be supplemented with medicaments and cleaned, has low operation and maintenance cost, and is beneficial to large-scale popularization and application.
Description
Technical Field
The invention relates to the technical field of printing and dyeing wastewater treatment, in particular to application of self-purifying nano-electrode carbon mesh cloth in printing and dyeing wastewater end deep treatment, a preparation method of the electrode carbon mesh cloth and the like.
Background
Cotton is used as natural cellulose fiber, and active printing and dyeing is a widely applied process, and chemicals such as alkali agents, salts and the like are usually added into dye liquor in the dyeing process, so that the dye-uptake is improved. In the treatment of printing and dyeing wastewater, the wastewater discharge amount of cotton fabric printing and dyeing is large, wherein the concentration of organic pollutants, the salt content and the chromaticity are high, the water quality is changed frequently, and the wastewater is one of the most difficult industrial wastewater to treat.
The coagulation method for treating the printing and dyeing wastewater has the advantages of good treatment effect, low cost and the like, thereby becoming an important means for treating industrial wastewater. The treatment of the printing and dyeing wastewater also adopts a biochemical sludge treatment combined with a physical and chemical treatment process, so that the quality of the effluent water can reach higher emission standard. By adopting the traditional printing and dyeing wastewater end treatment technology, a large amount of sludge is generated, the cost is high, the resource recycling rate is low, the green high-quality development of the textile printing and dyeing industry is restricted, and the method is a major common problem to be solved in the textile printing and dyeing industry.
With the rapid development of advanced oxidation, electrochemistry, membrane separation and other technologies, the method provides selectivity for advanced treatment of printing and dyeing wastewater and realization of recycling. The technology can further improve the quality of effluent water, but has the problems of complex process flow and unstable treatment effect.
Disclosure of Invention
In view of the above, the invention mainly provides an application of the self-purification nano-electrode carbon screen cloth in the advanced treatment of the tail end of printing and dyeing wastewater, and the advanced treatment method of the tail end of the printing and dyeing wastewater provided by the application utilizes the self-purification nano-electrode carbon screen cloth, has simple process flow, can adapt to the water quality with complex changes, has stable treatment effect, particularly has obvious decolorization effect, and is suitable for being widely popularized and applied in the treatment of the printing and dyeing wastewater.
The invention provides a method for deeply treating the tail end of printing and dyeing wastewater, which comprises the following steps:
taking biochemical effluent of printing and dyeing wastewater as raw water, and pretreating by adopting self-purifying nano-electrode carbon mesh cloth; the self-purification nano-electrode carbon screen cloth comprises a screen cloth substrate and active components compounded on the screen cloth substrate, wherein the active components are porous nano-electrode carbon and titanium dioxide; the porous nano electrode carbon has a porous structure with a plurality of different pore diameters between 5 and 100 nm;
and (3) sequentially carrying out membrane bioreactor treatment and catalytic oxidation on the pretreated effluent to obtain terminal effluent.
Preferably, the porous nano-electrode carbon has a pore-like structure with different pore diameters ranging from 5 to 30nm, from 50 to 80nm, and from 80 to 100nm.
Preferably, the porous nano-electrode carbon comprises a specific surface area of 1500-2000 m 2 First electrode carbon per gram and specific surface area of 2000-3000 m 2 And/g of second electrode carbon.
Preferably, the self-purifying nano-electrode carbon mesh cloth is obtained according to the following operation:
and (3) taking the mesh as a base material, spraying an adhesive on the surface of the mesh, then spraying finishing liquid containing porous nano-electrode carbon and titanium dioxide on the same surface, and drying to obtain the porous nano-electrode carbon-titanium dioxide composite material.
Preferably, the mesh component is selected from one or more of polyethylene, polytetrafluoroethylene and polyamide; the adhesive is selected from one or more of epoxy resin, polyurethane and isocyanate.
Preferably, the porous nano electrode carbon is prepared from resorcinol and formaldehyde as raw materials by gel method treatment, high-temperature carbonization and CO trapped by power plant flue gas 2 And (5) activating to obtain the product.
Preferably, the self-purification nano-electrode carbon mesh cloth pretreatment is arranged at the position of 0.5-1 m under water, and the environmental pH is 6-9.
Preferably, the COD of the biochemical effluent of the printing and dyeing wastewater is 280-2150 mg/L, and the raw water inflow rate is 20-400 m 3 Between/h.
Preferably, the catalytic oxidation further comprises reverse osmosis, advanced treatment and evaporation which are sequentially carried out; and recycling the reverse osmosis, advanced treatment and evaporated effluent.
Preferably, the chromaticity removal rate of the terminal effluent is more than 87%.
Compared with the prior art, the invention uses electrode carbon mesh cloth materials with various apertures between 5 and 100nm to pretreat biochemical effluent of printing and dyeing wastewater, and then adopts advanced oxidation advanced treatment process to obtain terminal effluent. The electrode carbon mesh material is applied to the advanced treatment process of the tail end of the printing and dyeing wastewater, can be used as pretreatment before the membrane, and can play a role in better degradation efficiency through the cooperative treatment of the porous nano carbon, so that a stable treatment effect is achieved, and particularly, the decolorizing effect is obvious. The process is built by one-time investment, does not need to be supplemented with medicaments and cleaned, and has low operation and maintenance cost. By adopting the method, the problems of increased wastewater salt content, increased wastewater running cost, long treatment flow caused by adopting a biological strengthening method, large occupied area and the like caused by adopting a materialization method in the prior conventional process can be solved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic illustration of a treatment process flow according to some embodiments of the invention;
FIG. 2 is a flow chart of the production of nanoelectrode carbon in some embodiments of the present invention;
FIG. 3 is a scanning electron microscope image of the carbon nano-electrode obtained in example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
The invention provides a method for deeply treating the tail end of printing and dyeing wastewater, which comprises the following steps:
taking biochemical effluent of printing and dyeing wastewater as raw water, and pretreating by adopting self-purifying nano-electrode carbon mesh cloth; the self-purification nano-electrode carbon screen cloth comprises a screen cloth substrate and active components compounded on the screen cloth substrate, wherein the active components are porous nano-electrode carbon and titanium dioxide; the porous nano electrode carbon has a porous structure with a plurality of different pore diameters between 5 and 100 nm;
and (3) sequentially carrying out membrane bioreactor treatment and catalytic oxidation on the pretreated effluent to obtain terminal effluent.
The advanced treatment method for the tail end of the printing and dyeing wastewater, which is provided by the application, utilizes the self-purification nano electrode carbon screen cloth, has the characteristics of simple process flow, stable treatment effect and the like, and is suitable for wide popularization and application in the treatment of the printing and dyeing wastewater.
Referring to fig. 1, fig. 1 is a schematic illustration of a treatment process according to some embodiments of the invention. Aiming at the inflow water of the printing and dyeing wastewater to be subjected to the end advanced treatment, the embodiment of the invention applies self-purifying nano-electrode carbon screen cloth to perform pretreatment before membrane treatment; and then MBR technology (membrane biological reaction technology) and catalytic oxidation can be carried out to obtain effluent which meets the standards, and then primary reverse osmosis (primary RO), advanced treatment and four-effect evaporation are carried out to obtain better terminal effluent and a byproduct of crystalline salt with better purity.
The embodiment of the invention takes biochemical effluent of printing and dyeing wastewater as raw water for water inflow, certain chromaticity and organic matters still exist, and the water quality is relatively complex. In the embodiment of the invention, the COD of the biochemical effluent of the printing and dyeing wastewater is generally 280-2150 mg/L; the inflow rate of raw water can be 20-400 m 3 Between/h. In some specific embodiments, the inflow water flow is 375-400 m 3 And/h, COD is 280-320 mg/L, chromaticity is 500-640 times, and ammonia nitrogen is 5-10 mg/L. Or the inflow rate is 75-100 m 3 And/h, COD is 762-1320 mg/L, chromaticity is 1100-1700 times, and ammonia nitrogen is 65-80 mg/L. In other embodiments, the inflow rate is 20-25 m 3 And/h, COD is 1710-2150 mg/L, chromaticity is 1500-2300 times, and ammonia nitrogen is 125-170 mg/L. Chemical oxygen demand COD (Chemical Oxygen Demand) is the amount of reducing substances in a water sample that need to be oxidized measured chemically; the unit is usually mg/L.
In order to meet the continuous and efficient operation of membrane treatment and reduce membrane pollution and the like, the deep water treatment process comprises the steps of pretreating the electrode carbon mesh cloth; and the collocation and synergistic effect of the porous nano carbon with different pore sizes are determined according to the water quality, so that the subsequent degradation efficiency is improved. In the embodiment of the invention, the self-purifying nano-electrode carbon mesh cloth is a flexible two-dimensional porous carbon material and has the functions of self purification and the like; the porous nano-electrode carbon comprises a mesh substrate and active ingredients compounded on the mesh substrate, wherein the active ingredients are porous nano-electrode carbon and titanium dioxide. Wherein the porous nano-electrode carbon has a porous structure with a plurality of different pore diameters between 5 and 100nm.
Preferably, the porous nano-electrode carbon has a pore structure with different pore diameters ranging from 5 to 30nm, from 50 to 80nm and from 80 to 100nm. Further, the porous nano-electrode carbon includes: specific surface area of 1500-2000 m 2 First electrode carbon per gram and specific surface area of 2000-3000 m 2 A second electrode carbon per gram; the carbon particle diameter of the nano electrode is 300-700 nm. According to the embodiment of the invention, the nano electrode carbon with various pore diameters and specific surface area specifications is screened and matched, and the optimal matching proportion is determined, so that the higher requirements of sewage deep treatment are met.
The porous nano electrode carbon material is obtained according to a certain preparation process, and the process flow is preferably shown in figure 2, wherein m-cresol (m-cresol and p-cresol) and formaldehyde (HCHO) are used as raw materials, and are subjected to gel processing such as batching, culturing and the like to obtain a semi-finished product, and then carbonized at high temperature, and CO trapped by power plant flue gas is utilized 2 Activating to obtain the super electrode carbon, namely the porous nano electrode carbon, which comprises a plurality of different nano aperture morphologies and a certain specific surface area specification.
Wherein, the mol ratio of the m-cresol to the formaldehyde can be 1:1-3. Mixing the raw materials in water, adding an alkali catalyst, transferring the mixture to a constant temperature cabinet for culturing the intermediate, preferably culturing the intermediate at 25-35 ℃ for 1 day, then culturing the intermediate at 45-55 ℃ for 1 day, and finally culturing the intermediate at 85-96 ℃ for 3 days to obtain the wet intermediate. Immersing the wet intermediate into a polyether solution (such as allyl alcohol polyoxyalkyl ether solution), performing water replacement at normal temperature, and drying after 5-10 hours to obtain a dry intermediate. The dry intermediate is carbonized for a certain time at the temperature of 1000-1100 ℃ to obtain carbonized electrode carbon;the activation temperature can be 900-1000 ℃, and the heat preservation temperature is 100-120 ℃. In the production process of the nano electrode carbon, the carbon dioxide trapped by the flue gas of the power plant is preferably used for activation, so that the method is easy to operate and simple in process, and can realize CO 2 And (5) recycling. The trapped CO 2 With pure CO 2 Different sources, and lower cost; CO recovered by power plant for cost reduction 2 The property of the trapped carbon dioxide is that the purity is more than 98%, so that the cost of the material is reduced.
In addition, the nano electrode carbon material in the embodiment of the invention is fixed on the surface of the mesh cloth in a spray finishing liquid mode, so that the self-purifying nano electrode carbon mesh cloth is obtained. The self-purification nano electrode carbon finishing liquid is prepared from porous nano electrode carbon with different particle sizes and nano titanium dioxide. Preferably, the mass ratio of the electrode carbon to the nano titanium dioxide is 10-20: 1, a step of; the particle size range of the nano titanium dioxide can be 20-100 nm.
Specifically, the self-purifying nano-electrode carbon mesh cloth according to the embodiment of the invention is preferably obtained according to the following operation: and (3) taking the mesh as a base material, spraying an adhesive on the surface of the mesh, then spraying finishing liquid containing porous nano-electrode carbon and titanium dioxide on the same surface, and drying to obtain the porous nano-electrode carbon-titanium dioxide composite material.
In an embodiment of the present invention, the mesh material may be one or more of polyethylene, polytetrafluoroethylene, nylon (polyamide) and preferably nylon mesh. Illustratively, the grammage of the web may be 100-400 g/m 2 The thickness is 20-60 mm; the pore range is 50-200 nm. The binder is preferably one or more of epoxy, polyurethane and isocyanate. And (3) drying the mesh cloth sprayed with the finishing liquid at the temperature of 100-120 ℃ for 8-20 min to obtain the finished product. The diameter of the sprayed rope-shaped mesh cloth can be 50-80mm, and electrode carbon and adhesive are sprayed in multiple layers, so that the self-purification of mesh cloth treatment is realized, the durability is obviously improved, and the mesh cloth can be operated in an alkaline environment (pH 6-9) without flushing.
The printing and dyeing wastewater tail end advanced treatment process specifically comprises the following steps: pretreatment (electrode carbon mesh treatment), MBR, catalytic oxidation, primary RO, advanced treatment and four-effect evaporation.
Wherein the self-purification nano-electrode carbon screen cloth pretreatment is arranged at the position of 0.5-1 m under water, and the environmental pH is 6-9. The treatment process comprises the following steps: the flow rate is 200% of the inflow water flow rate, such as 300 square/h of the inflow water flow rate and 600 square/h of the circulation rate. Alkali resistance and impact load resistance are realized after the nano electrode carbon is coated on the mesh cloth; after the electrode carbon mesh cloth is arranged, the electrode carbon mesh cloth is forced to circulate by a circulating pump, the electrode carbon mesh cloth is treated from bottom to top, and effluent overflows to the shrimp and clams unit.
MBR is also called Membrane bioreactor (Membrane Bio-Reactor), and is a novel water treatment technology combining an activated sludge process and a Membrane separation technology. Sorting according to separation mechanism, including reaction membrane, ion exchange membrane, osmosis membrane, etc.; there are natural films (biological films) and synthetic films (organic films and inorganic films) classified by the properties of the films; the membrane is classified into a flat type, a tubular type, a spiral type, a hollow fiber type, and the like. The membrane modules commonly used in MBR technology are: plate frame, circular tube, hollow fiber.
The catalytic oxidation further comprises reverse osmosis, advanced treatment and evaporation which are sequentially carried out, and the reverse osmosis, the advanced treatment and the evaporation are respectively preferably primary RO and four-effect evaporation; and recycling the reverse osmosis, advanced treatment and evaporated effluent.
The self-purification nano-electrode carbon mesh cloth prepared by the embodiment of the invention is applied to the advanced treatment of the tail end of printing and dyeing wastewater as a pretreatment process, the chromaticity removal rate of the terminal effluent is more than 87%, and the decoloring rate is as high as 98.5%; the removal rates of pollutants (COD and ammonia nitrogen) are up to 85.7.4 percent, 94.1 percent and the removal rate of heavy metal ions is 97.9 percent respectively. And the self-purification, maintenance-free and low-treatment cost, the water cost per ton is 0.15-0.20 yuan, the treatment effect is stable, and the method is suitable for being widely popularized and applied in printing and dyeing wastewater.
In order to better understand the technical content of the present invention, the following provides specific examples to further illustrate the present invention. The reagents and materials described in the examples below, unless otherwise indicated, are all commercially available.
Example 1
The advanced treatment experiment is carried out by selecting biochemical effluent from a cotton printing and dyeing mill in coast state, and biochemical water inflow is carried outFlow rate is 375-400 m 3 And/h, COD is 280-320 mg/L, chromaticity is 500-640 times, and ammonia nitrogen is 5-10 mg/L. The treatment effect is shown in Table 1.
A self-purification nano-electrode carbon mesh cloth for advanced treatment of printing and dyeing wastewater tail ends and a preparation method thereof comprise the following steps:
(1) Production of nano-electrode carbon and preparation of self-purification nano-electrode carbon finishing liquid; (2) Uniformly spraying an adhesive on the surface of nylon mesh cloth by using the nylon mesh cloth as a base material through a glue spraying machine, and then spraying the self-purifying nano electrode carbon finishing liquid obtained in the step (1) on the surface of the base material; (3) And (3) drying the self-purifying nano-electrode carbon screen cloth obtained in the step (2) to obtain the self-purifying nano-electrode carbon screen cloth.
Adding m-cresol and p-cresol into deionized water at normal temperature, adding formaldehyde solution according to a molar ratio of 1:2, and finally adding sodium hydroxide powder, and continuously stirring for 1h; after the ingredients are mixed, the mixture is transferred to a constant temperature cabinet to culture the intermediate, firstly, the mixture is cultured for 1 day at 25-35 ℃, then is cultured for 1 day at 45-55 ℃, and finally is cultured for 3 days at 85-96 ℃, thus obtaining the wet intermediate (wet gel block). The wet intermediate was immersed in a 1wt% strength allyl alcohol polyoxyalkylene ether solution, water substitution was performed at normal temperature, and after 8 hours, it was dried at 50℃to obtain a dry intermediate (xerogel). The dry intermediate is carbonized for a certain time at 1050 ℃ under nitrogen division to obtain carbonized electrode carbon, and then transferred into an activation furnace, and CO trapped by power plant flue gas is utilized 2 Activated at 950 ℃ to obtain porous nano-electrode carbon, and crushing and sieving to obtain carbon activated materials with different particle sizes.
The morphology of the obtained nanoelectrode carbon is seen in fig. 3 (scale 1:5 micron, 20K), and it can be seen that the obtained sample is a typical nanoporous structure, and has a large specific surface area and a large number of pores, mainly due to the CO trapped by the flue gas 2 Activation; and the production flow of the nano electrode carbon is simple and easy to operate. The porous nano electrode carbon has a porous structure with different pore diameters ranging from 5 nm to 30nm, from 50 nm to 80nm and from 80nm to 100nm. Further, the porous nano-electrode carbon includes: specific surface area of 1500-2000 m 2 First electrode carbon per gram and specific surface area of 2000-3000 m 2 And/g of second electrode carbon.
Fully stirring nano electrode carbon with the particle size of 300-500 nm and nano titanium dioxide (the mass ratio is 10:1), and preparing to obtain the self-purifying nano electrode carbon finishing liquid.
The self-purification nano electrode carbon finishing liquid is coated in a double-layer mode, a polyurethane adhesive is sprayed on the mesh cloth of the nylon material, and then the nano electrode carbon finishing liquid is sprayed; the drying temperature is 105 ℃ and the drying time is 20min, and the self-purifying nano-electrode carbon mesh cloth is obtained. The gram weight of the mesh cloth is 100g/m 2 A thickness of 20mm; the pore range is 50-200 nm. Alkali resistance and impact load resistance are realized after the nano electrode carbon is coated on the mesh cloth; after the electrode carbon mesh cloth is arranged, the electrode carbon mesh cloth is forced to circulate by a circulating pump, the electrode carbon mesh cloth is treated from bottom to top, and effluent overflows to the shrimp and clams unit.
The printing and dyeing wastewater end advanced treatment process comprises the following steps: electrode carbon mesh cloth treatment process, MBR, catalytic oxidation, primary RO, advanced treatment and four-effect evaporation. The obtained self-purification nano-electrode carbon screen cloth is applied to the advanced treatment process of the tail end of the printing and dyeing wastewater, is arranged at the position of 0.5-1 m under water, and cannot fall off in the environment with pH=6-9. The treatment results are shown in Table 1, and Table 1 shows the actual effects of examples 1 to 3 applied to the advanced treatment of the printing and dyeing wastewater terminals.
Table 1 examples 1 to 3 self-cleaning nanoelectrode carbon net cloth treatment effect
Example 2
The NF treatment concentrated water of a cotton printing and dyeing factory in the coastal state is selected for advanced treatment experiments, and the inflow rate of the NF water is 75-100 m 3 And/h, COD is 762-1320 mg/L, chromaticity is 1100-1700 times, and ammonia nitrogen is 65-80 mg/L. The treatment effect is shown in Table 1.
Wherein porous nanoelectrode carbons were obtained in the same manner as in example 1, and the sieving particle diameters were different. The nano electrode carbon with the particle size of 500-700 nm and nano titanium dioxide are fully stirred to prepare the self-purifying nano electrode carbon finishing liquid.
The self-purification nano electrode carbon finishing liquid is coated in a double-layer mode, isocyanate adhesives are sprayed on the mesh cloth of the nylon material, and then the nano electrode carbon finishing liquid is sprayed; the drying temperature is 120 ℃, the drying time is 15min, and the self-purifying nano-electrode carbon mesh cloth is obtained.
According to the treatment process in example 1, the obtained self-purification nano-electrode carbon mesh cloth is applied to the advanced treatment process of the tail end of the printing and dyeing wastewater, is arranged at the position of 0.5-1 m under water, and cannot fall off under the environment of pH=6-9.
Example 3
The DTRO concentrated water of a cotton printing and dyeing factory in coast state is selected for advanced treatment experiments, and the water quantity is 20-25 m 3 And/h, COD is 1710-2150 mg/L, chromaticity is 1500-2300 times, and ammonia nitrogen is 125-170 mg/L. The treatment effect is shown in Table 1.
Wherein porous nanoelectrode carbons were obtained in the same manner as in example 1, and the sieving particle diameters were different. The nano electrode carbon with the particle size of 500-700 nm and nano titanium dioxide are fully stirred to prepare the self-purifying nano electrode carbon finishing liquid.
The self-purification nano electrode carbon finishing liquid is coated in a double-layer mode, a polyurethane adhesive is sprayed on the mesh cloth of the nylon material, and then the nano electrode carbon finishing liquid is sprayed; the drying temperature is 105 ℃ and the drying time is 20min, and the self-purifying nano-electrode carbon mesh cloth is obtained.
According to the treatment process in example 1, the obtained self-purification nano-electrode carbon mesh cloth is applied to the advanced treatment process of the tail end of the printing and dyeing wastewater, is arranged at the position of 0.5-1 m under water, and cannot fall off under the environment of pH=6-9.
From the above embodiments, it can be seen that the self-cleaning nano-electrode carbon mesh cloth is applied to the advanced treatment of the tail end of the printing and dyeing wastewater, so that the treatment effect is obvious, and particularly the decoloring effect is obvious. In conclusion, the method has the advantages of simple production flow, easy operation, high and stable treatment effect, no maintenance and low operation and maintenance cost, and is suitable for wide popularization and application in printing and dyeing wastewater treatment.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the method of the present invention and its core ideas. The foregoing is merely illustrative of the preferred embodiments of this invention, and it is noted that there is objectively no limit to the specific structure disclosed herein, since numerous modifications, adaptations and variations can be made by those skilled in the art without departing from the principles of the invention, and the above-described features can be combined in any suitable manner; such modifications, variations and combinations, or the direct application of the inventive concepts and aspects to other applications without modification, are contemplated as falling within the scope of the present invention.
Claims (10)
1. The method for deeply treating the tail end of the printing and dyeing wastewater is characterized by comprising the following steps of:
taking biochemical effluent of printing and dyeing wastewater as raw water, and pretreating by adopting self-purifying nano-electrode carbon mesh cloth; the self-purification nano-electrode carbon screen cloth comprises a screen cloth substrate and active components compounded on the screen cloth substrate, wherein the active components are porous nano-electrode carbon and titanium dioxide; the porous nano electrode carbon has a porous structure with a plurality of different pore diameters between 5 and 100 nm;
and (3) sequentially carrying out membrane bioreactor treatment and catalytic oxidation on the pretreated effluent to obtain terminal effluent.
2. The method of claim 1, wherein the porous nanoelectrode carbon has a pore structure with different pore size ranges of 5 to 30nm, 50 to 80nm and 80 to 100nm.
3. The method of claim 2, wherein the porous nanoelectrode carbon comprises a specific surface area of 1500 to 2000m 2 First electrode carbon per gram and specific surface area of 2000-3000 m 2 And/g of second electrode carbon.
4. A method according to any one of claims 1-3, wherein the self-cleaning nanoelectrode carbon mesh is obtained by:
and (3) taking the mesh as a base material, spraying an adhesive on the surface of the mesh, then spraying finishing liquid containing porous nano-electrode carbon and titanium dioxide on the same surface, and drying to obtain the porous nano-electrode carbon-titanium dioxide composite material.
5. A method according to claim 4, wherein the mesh component is selected from one or more of polyethylene, polytetrafluoroethylene, and polyamide; the adhesive is selected from one or more of epoxy resin, polyurethane and isocyanate.
6. The method according to claim 4, wherein the porous nano-electrode carbon is prepared from m-cresol, p-cresol and formaldehyde by gel method treatment, high-temperature carbonization, and CO trapped by power plant flue gas 2 And (5) activating to obtain the product.
7. A method according to any one of claims 1-3, wherein the self-cleaning nanoelectrode carbon mesh pretreatment is arranged at 0.5-1 m under water and the environmental pH is 6-9.
8. A method according to any one of claims 1 to 3, wherein the biochemical effluent of the printing and dyeing wastewater has a COD of 280 to 2150mg/L and a raw water inflow of 20 to 400m 3 Between/h.
9. A method according to any one of claims 1-3, wherein the catalytic oxidation is followed by reverse osmosis, further treatment and evaporation, which are carried out sequentially; and recycling the reverse osmosis, advanced treatment and evaporated effluent.
10. A method according to any one of claims 1 to 3, wherein the chromaticity removal rate of the terminal effluent is above 87%.
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