CN115340207A - Method for treating wastewater discharged by circulating water by using reclaimed water source - Google Patents
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Images
Classifications
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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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/52—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
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
- C02F5/06—Softening water by precipitation of the hardness using calcium compounds
Abstract
The invention relates to a method for treating circulating water discharged wastewater by using a reclaimed water source. And (4) after treatment, sending the wastewater to an LEC electrocatalytic oxidation device, and destroying the functional group structure of organic pollutants in the wastewater in an electrolytic catalytic oxidation mode to degrade the organic pollutants into carbon dioxide and water. Circulating water after LEC electrocatalytic oxidation treatment is sent to a circulating water post-treatment device for treatment, and generated waste gas is sent to a tail gas treatment device for treatment. The invention utilizes the combination of hardness and turbidity removal and electrocatalytic oxidation to degrade macromolecular organic matters in the wastewater, and the effluent of the treated circulating water reaches COD Cr The target of less than or equal to 20mg/L, and simultaneously reduces the chroma of the waste water. The invention does not add any chemical agent, has no sludge generation and secondary pollution, and has safe, simple and flexible operation.
Description
Technical Field
The invention belongs to the technical field of industrial water treatment, and relates to a method for treating circulating water discharged wastewater by using a reclaimed water source.
Background
The water consumption of thermal power generation is large and accounts for 20 percent of the total industrial water consumption. The country encourages the use of reclaimed water or other waste water from municipal sewage treatment plants. The reclaimed water refers to reclaimed water which is obtained by carrying out anaerobic and aerobic secondary biochemical treatment on urban sewage and ensures that the quality of the discharged water reaches the relevant standard, is usually reused for flushing toilets, greening, road flushing and the like, is a main way for protecting the environment and preventing and treating water pollution, and is an important link for social and economic sustainable development.
The recycled water is treated and then supplemented to a circulating water system, cooling water is conveyed to the heat exchanger from the tower tank by the circulating water pump, and the circulating water returns to the tower tank after being sprayed and radiated by the cooling tower after passing through the heat exchanger and is recycled, so that a water circulating system is formed. Circulating water can evaporate after being heated, causes evaporation loss, and circulating water quality salt content can increase, in order to prevent circulating water system corrosion, scale deposit, needs to handle.
After the urban sewage is subjected to secondary biochemical treatment, biochemical organic matters are basically degraded into carbon dioxide and water, and most of the rest is macromolecular organic matters. By gas chromatography and mass spectrometry (GC-MS), the organic matter is mainly CHCl 2 、C 5 H 4 O 2 And C 6 H 6 O 2 And contains C 2 H 4 Cl 2 、C 5 H 8 Cl 2 、C 6 H 6 O、C 6 H 5 NO、C 6 H 10 O 5 And the like. In addition, the circulating water scale and corrosion inhibitor usually adopts acrylic acid and maleic anhydride copolymer, and the relative molecular weight of the copolymer is 2000-4000. The circulating water using reclaimed water source has poor biodegradability, high total nitrogen and salt content, and difficult high molecular organic matterDegradation, COD Cr The standard is not reached and the like.
The method for treating the circulating water discharged sewage of the water source in the prior art comprises' UV/H 2 O 2 Advanced oxidative pretreatment, "UV/H 2 O 2 Ozone and other advanced oxidation pretreatment and Fenton advanced oxidation treatment. The study shows that UV/H is adopted 2 O 2 The advanced oxidation treatment process such as ozone and the like can not realize the aim of refractory organic matters, H 2 O 2 And residual components of oxidants such as ozone affect the subsequent treatment process. The defects of Fenton advanced oxidation treatment are as follows: (1) the treatment process is complex, and the equipment investment, the occupied land and the operation cost are high; (2) a large amount of sludge is generated, and the treatment is difficult or the treatment cost is high.
Disclosure of Invention
The invention aims to provide a method for treating circulating water discharged wastewater by using a reclaimed water source, which utilizes a conventional method combining hardness and turbidity removal and electrocatalytic oxidation to degrade high molecular organic matters in the wastewater and treat COD (chemical oxygen demand) of the circulating water discharged water Cr The method reaches the standard, reduces the equipment investment and the operation cost of a power plant, and improves the economic benefit of enterprises.
The technical scheme of the invention is as follows: the method adopts a circulating water discharge wastewater treatment method of a reclaimed water source and utilizes a circulating water discharge wastewater treatment system of the reclaimed water source for treatment. And (3) homogenizing and equalizing the circulating water discharged wastewater of the reclaimed water source in a raw water adjusting tank, then conveying the wastewater into a flocculation sedimentation tank through a water pump, and adding a hardness remover, a flocculant and PAM (polyacrylamide) for flocculation sedimentation treatment. And pumping the circulating water discharged wastewater after the flocculation precipitation treatment to an LEC electrocatalytic oxidation device by a water pump, and destroying the functional group structure of organic pollutants in the wastewater in an electrolytic catalytic oxidation mode to degrade the organic matters into carbon dioxide and water. And (3) feeding the circulating water subjected to the LEC electrocatalytic oxidation treatment into a circulating water post-treatment device for post-treatment, and feeding the waste gas generated in the LEC electrochemical catalysis process into a tail gas treatment device for treatment.
The hardness removing agent is lime, sodium hydroxide or sodium carbonate, and the dosage of the hardness removing agent is determined according to the change of inlet water quality. The flocculant is polyaluminium, polyferric or polyaluminium-iron, the coagulant aid is PAM, and the dosing type and the dosing amount of the flocculant are determined by a dynamic coagulation test.
After the hardness and turbidity of the circulating water discharged wastewater of the reclaimed water source are removed by the flocculation sedimentation tank, the total hardness of the discharged water is not higher than 500mg/L, and the content of suspended matters is not higher than 20mg/L. Inlet wastewater of LEC electrocatalytic oxidation device requires COD Cr Less than or equal to 200mg/L, the chloride ion content less than or equal to 1500mg/L and the conductivity more than or equal to 5000 mu S/cm. COD of effluent Cr Less than or equal to 20mg/L, ammonia nitrogen less than or equal to 2.0mg/L and colorless effluent.
The voltage between electrodes of the LEC electrocatalytic oxidation device for electrocatalytic oxidation treatment is 5V-10V, the current is 1000A-3000A, and the electrocatalytic oxidation time is 15-30min. Specific voltage, current, conductivity of treated water and COD Cr And its removal rate factor.
The circulating water discharge wastewater treatment system of the reclaimed water source comprises a raw water adjusting tank, a flocculation sedimentation tank, an LEC electrocatalytic oxidation device, a water post-treatment device and a tail gas treatment device. The raw water adjusting tank is connected with the flocculation sedimentation tank through a water pump, and the flocculation sedimentation tank is connected with the LEC electrocatalytic oxidation device through the water pump. LEC electrocatalytic oxidation device is equipped with delivery port and tail gas outlet, and the delivery port is connected with circulating water aftertreatment device, and the tail gas outlet is connected with tail gas treatment device. The flocculation sedimentation tank is provided with a hardening agent removing inlet, a flocculating agent inlet and a PAM inlet, the hardening agent removing inlet is connected with a hardening agent adding box, the flocculating agent inlet is connected with the flocculating agent adding box, and the PAM inlet is connected with the PAM adding box.
The LEC electrocatalytic oxidation device takes titanium as a cathode electrode substrate and an anode electrode substrate, and the surface of the anode electrode is coated with a baking nano coating. The coating is a high-entropy alloy nanoparticle material which adopts manganese and tin elements and adds ruthenium, iridium, tantalum, rhodium and palladium noble metal salt oxides.
The LEC electrocatalytic oxidation device has the most remarkable characteristic that different catalysts are loaded at different gradient positions, and various catalysts can be excited under the action of current. Organic matters in the wastewater are directly oxidized into carbon dioxide and water under the synergistic effect of the catalyst, ammonia nitrogen is directly oxidized into nitrogen, the degradation of the organic matters and the ammonia nitrogen in the wastewater with lower treatment cost is realized, and meanwhile, the chromaticity of the wastewater can be reduced. LEC electrocatalysisThe oxidation device can carry out different selection combinations according to the types and the concentration of the wastewater, and the continuous synergistic effect of various catalysts can ensure that the equipment can obtain high-efficiency and stable operation, so that the effluent COD (chemical oxygen demand) Cr And the chroma can be greatly removed. The technology for treating the circulating water discharged wastewater of the water source is the first time in China, and the industrial test result shows that the degradation of macromolecular organic matters reaches COD Cr A target of less than or equal to 20mg/L.
The invention adopts a method for treating the circulating water discharge wastewater of a reclaimed water source, and utilizes a method combining conventional hardness and turbidity removal and electrocatalytic oxidation to degrade high molecular organic matters in the wastewater, thereby treating the COD of the circulating water discharge water Cr And (5) reaching the standard. Compared with the prior art, the invention has the beneficial effects that: (1) the electrocatalytic advanced oxidation process only consumes electric energy, does not add any chemical agent, and has no secondary pollution; (2) the reaction is carried out under the conditions of normal temperature and normal pressure, and the operation is safe, simple and flexible; (3) the catalysts are excited by various combined electric energy, can be freely combined according to the requirements of customers, and are efficient and stable; (4) the catalyst carrier is stable alloy without consumption, the chemical properties of the components are stable and nontoxic, the service life is long, the catalyst can be repeatedly used, and the long-lasting and high-efficiency catalytic reaction is ensured; (5) no sludge is produced, and the equipment investment and the operation cost are low.
Drawings
FIG. 1 is a schematic view of a wastewater treatment system using recycled water source circulating water discharge;
FIG. 2 is a schematic diagram of an oxidation catalytic process of an LEC electrocatalytic oxidation device;
wherein: 1-raw water adjusting tank, 2-flocculation sedimentation tank, 3-LEC electrocatalytic oxidation device, 4-water post-treatment device, 5-tail gas treatment device, 6-hardness remover inlet, 7-flocculant inlet and 8-PAM inlet.
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings. The scope of protection of the invention is not limited to the embodiments, and any modification made by those skilled in the art within the scope defined by the claims also falls within the scope of protection of the invention.
A reclaimed water source circulating water discharge wastewater treatment system is adopted, as shown in figure 1, and comprises a raw water adjusting tank 1, a flocculation sedimentation tank 2, an LEC electrocatalytic oxidation device 3, a water post-treatment device 4 and a tail gas treatment device 5, wherein the LEC electrocatalytic oxidation device has the following models: LEC-TAX-900. The raw water equalizing basin passes through the water pump and is connected with the flocculation and precipitation pond, and the flocculation and precipitation pond passes through the water pump and is connected with LEC electricity catalytic oxidation device, and LEC electricity catalytic oxidation device is equipped with delivery port and tail gas outlet, and the delivery port is connected with circulating water aftertreatment device 4, and the tail gas outlet is connected with tail gas treatment device. The flocculation sedimentation tank 2 is provided with a hardening agent inlet 6, a flocculating agent inlet 7 and a PAM inlet 8, the hardening agent inlet is connected with a hardening agent dosing box, the flocculating agent inlet is connected with the flocculating agent dosing box, and the PAM inlet is connected with the PAM dosing box. The LEC electrocatalytic oxidation device takes titanium as a cathode electrode substrate and an anode electrode substrate, and the surface of the anode electrode is coated with a baked nano coating. The coating is a high-entropy alloy nanoparticle material which is prepared by adding noble metal salt oxides such as ruthenium, iridium, tantalum, rhodium and palladium into elements such as manganese and tin.
The method for treating the circulating water discharged wastewater of the reclaimed water source comprises the step of carrying out homogenization and uniform treatment on the circulating water discharged wastewater of the reclaimed water source by using the raw water regulating tank 1, wherein the analysis data of the circulating water discharged from the reclaimed water source is shown in a table 1. The discharged wastewater after homogenization and average treatment is pumped into a flocculation and precipitation tank 2 by a water pump, lime serving as a hardening agent is added through a hardening agent inlet 6, a flocculating agent is added through a flocculating agent inlet 7, and PAM is added through a PAM inlet to perform flocculation and precipitation treatment. The selection of polymeric aluminum, polymeric iron or polymeric aluminum iron and the dosage of the hardness remover are determined by a dynamic coagulation test. And pumping the discharged wastewater after the flocculation precipitation treatment to an LEC electrocatalytic oxidation device 3 by a water pump, and destroying the functional group structure of organic pollutants in the wastewater in an electrolytic catalytic oxidation mode to degrade the organic matters into carbon dioxide and water. Circulating water after LEC electrocatalytic oxidation treatment is sent to a circulating water post-treatment device 4 for post-treatment, and waste gas generated in the LEC electrochemical catalysis process is sent to a tail gas treatment device 5 for treatment. The water quality analysis results of the water outlet of the EC electrocatalytic oxidation device are shown in Table 2.
TABLE 1 analysis of quality of circulating external drainage water using reclaimed water source
| Item | pH | Electrical conductivity | Hardness of | Ammonia nitrogen | COD Cr | Chloride ion |
| Unit of | μS/cm | mg/L | mg/L | mg/L | mg/L | |
| Quality of water | 7.31 | 7180 | 2050 | 11.2 | 118 | 1489 |
Table 2 analysis of effluent quality of circulating water discharge wastewater treatment of reclaimed water source
The operating parameters of the recycled water source circulating water discharged wastewater treatment are as follows: inlet COD of LEC electrocatalytic oxidation device Cr Less than or equal to 200mg/L, hardness less than or equal to 1500mg/L (the hardness is inversely related to the chemical cleaning period), chloride ion content more than or equal to 500mg/L, and conductivity more than or equal to 5000 mu S/cm. The voltage of electrocatalytic oxidation treatment is 5V-10V, the current is 1000A-3000A, the voltage and the current are as well as the conductivity and COD of the treated water Cr And removal rate thereof. The time of the electrocatalytic oxidation treatment is related to voltage and current, generally 15-30min, and the optimal time needs to be determined by experiments aiming at a specific water sample.
After the wastewater is subjected to hardness removal and turbidity removal by the high-efficiency flocculation sedimentation tank, the total hardness of effluent is not higher than 500mg/L, and the content of suspended matters is not higher than 20mg/L. The results in Table 2 show that the COD of the effluent is 20min after electrocatalytic oxidation treatment Cr 19.65mg/L, COD Cr The removal rate is 83.3%; the ammonia nitrogen is 1.8mg/L, and the removal rate reaches 83.9 percent; the color of the discharged water is colorless. Realizes the degradation of macromolecular organic matter COD Cr Less than or equal to 20mg/L.
The LEC electrocatalytic oxidation technology is based on the advanced oxidation treatment technology principle, and free radicals, strong oxidation particles and oxidative free radicals (OH, O) are generated in the microchannel catalytic oxidation process 2 、SO4· - 、H 2 O 2 、O 3 、OCl - Etc.) to perform oxidation degradation without selection with organic pollutants in wastewater, improve B/C ratio, and completely decompose difficultly biochemically degradable macromolecular organic substances into CO 2 And H 2 O, etc., degrading COD Cr . In the treatment process, electron transfer is only carried out between the electrode and the wastewater components, oxidation reaction is carried out by means of oxidative free radicals generated by the system, no redox agent is added, no sludge is generated, no secondary pollution is caused, and the method is a clean treatment method and an environment-friendly technology. The schematic diagram of the oxidation catalytic process is shown in fig. 2, and the relevant reactions are as follows:
organic waste water: (1) r +. OH → CO 2 +H 2 O
②NH 3 +·OH→H + +NO 3 - +H 2 O
Chlorine-containing wastewater: (3) r + ClO - →H 2 O+CO 2 +Cl -
④NH 3 +ClO - →H + +N 2 +H 2 O
Sulfate-containing wastewater: (5) SO 4 · - +R→CO 2 +H 2 O
The electrode of the electrocatalytic advanced oxidation equipment is a core component. Titanium is used as a base material of the cathode and the anode, 16 layers of nano coatings are coated and roasted on the surface of the anode through a plurality of special precise procedures, and the processing methods of all the layers are different, so that the titanium-titanium composite nano-electrode has better electrocatalytic activity, higher acid-base stability, electrolytic oxidation resistance, stable current efficiency and high current density compared with other electrodes. The distributed electrode group in the microchannel is more reasonable in design, the resistance on the connecting piece is reduced, the electrolysis efficiency is improved, the energy consumption is reduced, and the maintenance is avoided. The composite coating structure combining the surface active layer and the titanium-based layer improves the service life of the anode electrode by more than five times of that of a national standard high-quality product.
Claims (8)
1. A method for treating circulating water discharged wastewater by using a reclaimed water source utilizes a circulating water discharged wastewater treatment system of the reclaimed water source to carry out treatment, and is characterized in that: after being homogenized and equalized by a raw water adjusting tank (1), the circulating water discharged wastewater of the reclaimed water source is sent into a flocculation sedimentation tank (2) by a water pump, and a hardness remover, a flocculating agent and PAM are added for flocculation sedimentation treatment; pumping the discharged wastewater after the flocculation precipitation treatment to an LEC electrocatalytic oxidation device (3) by a water pump, and destroying the functional group structure of organic pollutants in the wastewater in an electrolytic catalytic oxidation mode to degrade the organic pollutants into carbon dioxide and water; circulating water after LEC electrocatalytic oxidation treatment is sent to a circulating water post-treatment device (4) for post-treatment, and waste gas generated in the LEC electrochemical catalysis process is sent to a tail gas treatment device (5) for treatment.
2. The method for treating the circulating water discharge wastewater by using the reclaimed water source as claimed in claim 1, which is characterized in that: the hardness removing agent is lime, sodium hydroxide or sodium carbonate; the flocculant is polymeric aluminum, polymeric iron or polymeric aluminum iron, and the coagulant aid is PAM.
3. The method for treating the circulating water discharge wastewater by using the reclaimed water source as claimed in claim 1, which is characterized in that: the total hardness of the discharged water after the circulating water discharged from the reclaimed water source is subjected to hardness removal and turbidity removal by the flocculation sedimentation tank (2) is not higher than 500mg/L, and the content of suspended matters is not higher than 20mg/L.
4. The method for treating circulating water efflux wastewater from a reclaimed water source as claimed in claim 1, wherein the method comprises the following steps: inlet wastewater of LEC electrocatalytic oxidation device (3) requires COD Cr Less than or equal to 200mg/L, the hardness is less than or equal to 1500mg/L, the content of chloride ions is more than or equal to 500mg/L, and the conductivity is more than or equal to 5000 mu S/cm; COD of effluent Cr Less than or equal to 20mg/L, ammonia nitrogen less than or equal to 2.0mg/L and colorless effluent.
5. The method for treating circulating water efflux wastewater from a reclaimed water source as claimed in claim 1, wherein the method comprises the following steps: the voltage between electrodes of the LEC electrocatalytic oxidation device (3) for electrocatalytic oxidation treatment is 5V-10V, the current is 1000A-3000A, and the electrocatalytic oxidation time is 10-30min.
6. The method for treating circulating water efflux wastewater from a reclaimed water source as claimed in claim 1, wherein the method comprises the following steps: the circulating water external discharge wastewater treatment system at the reclaimed water source comprises a raw water adjusting tank (1), a flocculation sedimentation tank (2), an LEC (electrolytic oxidation) device (3), a water post-treatment device (4) and a tail gas treatment device (5), wherein the raw water adjusting tank is connected with the flocculation sedimentation tank through a water pump, the flocculation sedimentation tank is connected with the LEC through the water pump, the LEC is provided with a water outlet and a tail gas outlet, the water outlet is connected with the circulating water post-treatment device, and the tail gas outlet is connected with the tail gas treatment device.
7. The method for treating circulating water efflux wastewater from a reclaimed water source as claimed in claim 6, wherein the method comprises the following steps: the flocculation sedimentation tank (2) is provided with a hardening agent inlet (6), a flocculating agent inlet (7) and a PAM inlet (8), the hardening agent inlet is connected with a hardening agent dosing box, the flocculating agent inlet is connected with the flocculating agent dosing box, and the PAM inlet is connected with the PAM dosing box.
8. The method for treating wastewater discharged by circulating water and provided with reclaimed water source as claimed in claim 6, wherein the method comprises the following steps: the LEC electrocatalytic oxidation device takes titanium as a cathode electrode substrate and an anode electrode substrate, and the surface of the anode electrode is coated with a roasting nano coating; the coating is a high-entropy alloy nanoparticle material which adopts manganese and tin elements and adds ruthenium, iridium, tantalum, rhodium and palladium noble metal salt oxides.
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