An electrochemical treatment method and system based on tungsten smelting wastewater detection

Abstract

This invention relates to the field of wastewater treatment technology in metal smelting, specifically an electrochemical treatment method and system based on the detection of tungsten smelting wastewater. The method includes: acquiring workshop wastewater from a tungsten smelter; using a pre-constructed pretreatment device to perform arsenic and fluorine-based filtration control on the workshop wastewater to obtain pretreated wastewater; using a pre-constructed electrochemical treatment device to perform electrocatalytic oxidation on the pretreated wastewater based on COD and ammonia nitrogen to obtain oxide wastewater; performing oxide separation on the oxide wastewater to obtain wastewater to be discharged, and detecting the content of preset substance types in the wastewater to obtain a wastewater composition table; determining whether the wastewater composition table belongs to a preset target emission standard; and obtaining wastewater to be discharged that meets the target emission standard when the wastewater composition table belongs to the target emission standard. This invention can improve the purification level of tungsten smelting wastewater and reduce wastewater treatment costs.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of microbial fermentation regulation, and particularly relates to an electrochemical treatment method and system based on tungsten smelting wastewater detection. BACKGROUND

[0002] A large amount of wastewater difficult to handle is generated in tungsten smelting production, which affects the ecological environment due to the characteristics of multiple pollutant contents and great hazards. The main pollutants in the wastewater are ammonia nitrogen, COD, arsenic, cadmium, fluorine and the like, and the salt content is as high as about 10 g / L. Most of these pollutants are introduced in the process of treating tungsten concentrate, and their contents fluctuate with the change of raw materials.

[0003] Nowadays, the wastewater of enterprises in the industry needs to be discharged to the industrial park wastewater treatment station according to the requirements, however, the mainstream technology of biological method used by the wastewater treatment station is difficult to handle the high-salt wastewater, so the pharmaceutical method is always used to handle the production wastewater. The pharmaceutical method adds reagents for treatment, which makes it difficult to remove fluorine to reach the standard discharge, has the risk of high treatment cost, non-standard drainage and secondary pollution. SUMMARY

[0004] The present application provides an electrochemical treatment method based on tungsten smelting wastewater detection, which mainly aims to improve the purification level of tungsten smelting wastewater and reduce the wastewater treatment cost.

[0005] To achieve the above purpose, the present application provides an electrochemical treatment method based on tungsten smelting wastewater detection, which comprises:

[0006] Obtaining the workshop wastewater of a tungsten smelting plant;

[0007] Using a pre-constructed pretreatment device, performing arsenic and fluorine-based filtration control operation on the workshop wastewater to obtain pretreated wastewater, and detecting the arsenic and fluorine component value in the pretreated wastewater;

[0008] Judging whether the arsenic and fluorine component value is greater than a preset pretreatment qualified standard;

[0009] When the arsenic and fluorine component value is greater than the pretreatment qualified standard, the pretreated wastewater is introduced into the pretreatment device for re-filtration until the arsenic and fluorine component value is less than or equal to the pretreatment qualified standard;

[0010] When the arsenic and fluorine component value is less than or equal to the pretreatment qualified standard, using a pre-constructed electrochemical treatment device, performing COD and ammonia nitrogen-based electro-catalytic oxidation operation on the pretreated wastewater to obtain oxidized wastewater;

[0011] The oxide wastewater is subjected to an oxide separation operation to obtain to-be-discharged wastewater, and the content of a preset substance type in the to-be-discharged wastewater is detected to obtain a wastewater composition table;

[0012] It is judged whether the wastewater composition table belongs to a preset target level discharge standard;

[0013] When the wastewater composition table does not belong to the target level discharge standard, the to-be-discharged wastewater is introduced into the electrochemical treatment device for re-filtering until the wastewater composition table belongs to the target level discharge standard;

[0014] When the wastewater composition table belongs to the target level discharge standard, to-be-discharged wastewater meeting the target level discharge standard is obtained.

[0015] Optionally, the arsenic and fluorine-based filtering control operation on the workshop wastewater is performed by using a pre-constructed pretreatment device to obtain pretreated wastewater, including:

[0016] The workshop wastewater is subjected to primary sedimentation by using a pre-constructed pretreatment device and a pre-constructed calcium salt to obtain arsenic-removed wastewater;

[0017] The arsenic-removed wastewater is subjected to a sedimentation operation by using a pre-constructed iron salt to obtain deeply arsenic-removed wastewater;

[0018] The deeply arsenic-removed wastewater is subjected to an acid-base metal ion sedimentation operation to obtain primary pretreated wastewater;

[0019] The primary pretreated wastewater is subjected to a fluorine ion complex precipitation operation by using a pre-constructed complex fluorine-removing agent according to a preset pH environment to obtain pretreated wastewater.

[0020] Optionally, the COD and ammonia nitrogen-based electro-catalytic oxidation operation on the pretreated wastewater is performed by using a pre-constructed electrochemical treatment device to obtain oxide wastewater, including:

[0021] The conductivity of the pretreated wastewater is detected by using a pre-constructed electrochemical treatment device, and the conductivity of the pretreated wastewater is regulated to a preset suitable range according to a pre-constructed electrolyte to obtain conductive standard wastewater;

[0022] The conductive standard wastewater is subjected to an oxidation operation to obtain initial oxide wastewater, a pre-constructed high-molecular polymer is used to add the initial oxide wastewater at a preset adding speed, and the content of the oxide in the initial oxide wastewater is detected during the uniform-speed adding to obtain an oxide content change curve;

[0023] The correlation score between the adding speed and the oxide content change curve is calculated;

[0024] stop the operation of adding the initial oxide wastewater at a uniform speed according to a preset adding speed by using the pre-constructed polymer when the correlation score is less than a preset correlation threshold, and identify a change rate of the oxide content change curve;

[0025] when the change rate of the oxide content change curve is less than a preset stability threshold, the initial oxide wastewater is used as the oxide wastewater.

[0026] Optionally, the operation of oxidizing the conductive standard wastewater to obtain the initial oxide wastewater comprises:

[0027] directly oxidizing the conductive standard wastewater according to a preset first control current by using a pre-constructed anode plate in the electrochemical treatment device to obtain primary oxide wastewater;

[0028] generating a strong oxidant according to a preset second control current by using a pre-constructed electrode plate in the electrochemical treatment device, and oxidizing the primary oxide wastewater by using the strong oxidant to obtain the initial oxide wastewater, wherein the electrode plate comprises the anode plate.

[0029] Optionally, after the wastewater to be discharged that meets the target level emission standard is obtained, the method further comprises:

[0030] performing calcium and magnesium ion precipitation on the oxide wastewater by using a pre-constructed double-alkali method to obtain double-alkali softened wastewater;

[0031] performing salt separation on the double-alkali softened wastewater by using a pre-constructed nanofiltration device to obtain divalent salt water and monovalent salt water;

[0032] performing reverse osmosis on the monovalent salt water by using a pre-constructed reverse osmosis device to obtain fresh water and concentrated salt water of a preset concentration;

[0033] performing dialysis on the concentrated salt water by using a pre-constructed double-membrane electrodialysis device to obtain an acid solution and an alkali solution;

[0034] storing the fresh water, discharging the divalent salt water, and storing the acid solution and the alkali solution, and obtaining a preset proportion of the acid and alkali solutions in the stored acid solution and alkali solution, and delivering the acid and alkali solutions to the pretreatment device and the electrochemical treatment device.

[0035] Optionally, after the pretreated wastewater is introduced into the pretreatment device for re-filtering, the method further comprises:

[0036] The pretreated wastewater returned to the pretreatment device is counted to obtain a wastewater circulation flow value, and the wastewater circulation flow value is monitored to obtain a wastewater circulation flow curve;

[0037] The pretreatment control model is used to predict the control parameters of the pretreatment device according to the wastewater circulation flow curve, and a set of predicted pretreatment control parameters is obtained.

[0038] The control parameters of the pretreatment device are updated according to the set of predicted pretreatment control parameters, and an updated wastewater circulation flow curve is obtained, wherein the updated wastewater circulation flow curve is kept within a preset flow limit interval.

[0039] To achieve the above-mentioned purpose, the application also provides an electrochemical treatment system based on tungsten smelting wastewater detection, comprising:

[0040] The pretreatment module is used to obtain the wastewater from the workshop of the tungsten smelting plant, and the pre-constructed pretreatment device is used to perform the filtration control operation based on arsenic and fluorine on the wastewater from the workshop to obtain pretreated wastewater, and detect the arsenic and fluorine component values in the pretreated wastewater, and determine whether the arsenic and fluorine component values are greater than a preset pretreatment qualified standard, and when the arsenic and fluorine component values are greater than the pretreatment qualified standard, the pretreated wastewater is introduced into the pretreatment device for re-filtration until the arsenic and fluorine component values are less than or equal to the pretreatment qualified standard.

[0041] The electrochemical treatment module is used to perform the electro-catalytic oxidation operation based on COD and ammonia nitrogen on the pretreated wastewater using the pre-constructed electrochemical treatment device when the arsenic and fluorine component values are less than or equal to the pretreatment qualified standard to obtain oxidized wastewater, and perform the oxidized wastewater separation operation on the oxidized wastewater to obtain the wastewater to be discharged, and detect the content of the preset substance type in the wastewater to be discharged to obtain a wastewater component table, and determine whether the wastewater component table belongs to a preset target level discharge standard, and when the wastewater component table does not belong to the target level discharge standard, the wastewater to be discharged is introduced into the electrochemical treatment device for re-filtration until the wastewater component table belongs to the target level discharge standard, and when the wastewater component table belongs to the target level discharge standard, the wastewater to be discharged that meets the target level discharge standard is obtained.

[0042] To solve the above-mentioned problems, the application also provides an electronic device, which comprises:

[0043] The memory stores at least one instruction;

[0044] The processor executes the instructions stored in the memory to implement the electrochemical treatment method based on tungsten smelting wastewater detection.

[0045] To solve the above problems, the application further provides a computer readable storage medium, wherein at least one instruction is stored in the computer readable storage medium, and the at least one instruction is executed by a processor in an electronic device to implement the electrochemical treatment method based on tungsten smelting wastewater detection.

[0046] To solve the problems in the background art, the application first removes arsenic and fluorine in the workshop wastewater by the pretreatment device to obtain pretreated wastewater, wherein, in the pretreatment process, some metal ions which are affected by the acidity and alkalinity and precipitate can also be effectively removed by adjusting the pH value; then, by the principle of electro-catalytic oxidation, the COD and ammonia nitrogen are directly electro-catalytic oxidized on the surface of the electrode plate by the electrode plate, and the COD and ammonia nitrogen can also be indirectly oxidized by the strong oxidizing agent generated by electrolysis, so as to reduce the COD and ammonia nitrogen, wherein, the electric treatment process only needs to adjust the current and the residence time, and does not need to add other reagents, so that the secondary pollution is avoided, that is, the wastewater treatment cost is saved, and the environmental protection is improved. Therefore, the application can improve the purification level of tungsten smelting wastewater and reduce the wastewater treatment cost. BRIEF DESCRIPTION OF DRAWINGS

[0047] Figure 1 The flowchart of the electrochemical treatment method based on tungsten smelting wastewater detection provided by an embodiment of the application is shown;

[0048] Figure 2 The device structure schematic diagram of the electrochemical treatment system based on tungsten smelting wastewater detection provided by an embodiment of the application is shown;

[0049] Figure 3 The function module diagram of the electrochemical treatment system based on tungsten smelting wastewater detection provided by an embodiment of the application is shown;

[0050] Figure 4 The structure schematic diagram of the electronic device for implementing the electrochemical treatment method based on tungsten smelting wastewater detection provided by an embodiment of the application is shown.

[0051] REFERENCE SIGNS:

[0052] 1, electronic device; 10, processor; 11, memory; 12, bus.

[0053] The implementation, functional features and advantages of the application will be further described with reference to the embodiments and the accompanying drawings. DETAILED DESCRIPTION

[0054] It should be understood that the specific embodiments described herein are only used to explain the application, and are not used to limit the application.

[0055] The embodiment of the present application provides an electrochemical treatment method based on tungsten smelting wastewater detection. The execution subject of the electrochemical treatment method based on tungsten smelting wastewater detection includes but is not limited to at least one of electronic devices capable of being configured to execute the method provided by the embodiment of the present application, such as a server, a terminal and the like. In other words, the electrochemical treatment method based on tungsten smelting wastewater detection can be executed by software or hardware installed in a terminal device or a server device, and the software can be a blockchain platform. The server includes but is not limited to a single server, a server cluster, a cloud server or a cloud server cluster and the like.

[0056] Referring to Figure 1 Fig. 1 is a flowchart of an electrochemical treatment method based on tungsten smelting wastewater detection provided by an embodiment of the present application. In the embodiment, the electrochemical treatment method based on tungsten smelting wastewater detection includes the following steps.

[0057] S1, obtaining workshop wastewater of a tungsten smelting plant.

[0058] Among them, the main pollutants in the workshop wastewater are ammonia nitrogen, COD, arsenic, fluorine and the like. Among them, the COD refers to the chemical oxygen demand, which is one of the important indicators for measuring the degree of organic pollution in water. The higher the COD, the more pollutants that can be oxidized in the water, and the higher the degree of pollution.

[0059] Specifically, in the embodiment of the present application, the production speed of the workshop wastewater is 100 cubic meters per hour.

[0060] S2, using a pre-constructed pretreatment device to perform arsenic and fluorine-based filtering control operation on the workshop wastewater to obtain pretreated wastewater, and detecting the arsenic and fluorine component value in the pretreated wastewater.

[0061] Among them, referring to Figure 2 Fig. 2, the pretreatment device includes a 2# adjusting pool, a 1# horizontal flow sedimentation tank, a 2# horizontal flow sedimentation tank, a pretreatment system 1 and a pretreatment system 2. Among them, the pretreatment system 1 is used to control calcium salt (such as calcium chloride) and iron salt (such as ferrous sulfate) to remove arsenic. The pretreatment system 2 is used to control the complex fluoride removal agent (such as aluminum sulfate, ferrous sulfate) to remove fluorine. Among them, the pretreatment system 1 and the pretreatment system 2 can also control the amount of alkali solution (such as liquid alkali) and acid solution (such as hydrochloric acid), so as to control the acidity and alkalinity of the workshop wastewater.

[0062] Among them, the arsenic and fluorine component value refers to the content value of arsenic and fluorine in wastewater.

[0063] In detail, in the embodiment of the present application, the use of a pre-constructed pretreatment device to perform arsenic and fluorine-based filtering control operation on the workshop wastewater to obtain pretreated wastewater includes:

[0064] The workshop wastewater is subjected to primary settling by using a pre-constructed pretreatment device and a pre-constructed calcium salt, to obtain arsenic-removed wastewater;

[0065] The arsenic-removed wastewater is subjected to settling operation by using a pre-constructed iron salt, to obtain deep-arsenic-removed wastewater;

[0066] The deep-arsenic-removed wastewater is subjected to acid-base metal ion settling operation, to obtain primary pretreated wastewater;

[0067] The primary pretreated wastewater is subjected to fluoride ion complexing precipitation operation according to a pre-set pH environment by using a pre-constructed complexing fluoride removal agent, to obtain pretreated wastewater.

[0068] The calcium salt is calcium chloride, the primary settling is settling of most arsenic, and the arsenic-removed wastewater is wastewater with reduced arsenic content.

[0069] The iron salt is ferrous sulfate, the settling operation is operation of maximum settling of residual arsenic, and the deep-arsenic-removed wastewater is wastewater with arsenic ion content less than a set concentration, which is considered as arsenic-free wastewater in the embodiment of the application.

[0070] In the embodiment of the application, the deep means further.

[0071] The complexing fluoride removal agent is a chemical agent for removing fluoride ions (F-) in wastewater, which usually converts fluoride ions into compounds insoluble in water through complexing reaction or precipitation reaction, so as to remove fluoride ions.

[0072] The acid-base metal ion settling operation is operation of removing metal when the acid-base degree (pH value) of wastewater is adjusted, so that the dissolution equilibrium changes, metal ions react with a precipitant to form a hardly soluble compound.

[0073] The pre-set pH environment refers to a pH value meeting the complexing fluoride removal agent, and different complexing fluoride removal agents may be complexed with fluoride ions under different pH value environments and then settled.

[0074] Specifically, in the embodiment of the application, since calcium ions can react with arsenate ions (AsO4 3- ) or hydrogen arsenate ions (HAsO4 2- ) in water to form insoluble precipitates, the calcium salt pretreatment can preliminarily obtain arsenic-removed wastewater. Further, the iron salt (especially Fe 3+ ) can act as an oxidant to promote arsenic to be oxidized from toxic arsenic compounds (such as As 3+ ) to less toxic arsenate (As 5+), thereby enhancing its removal effect. The present application further adds ferric salt for deep treatment, further forms a precipitate, and obtains deep-arsenic-removal wastewater, thereby achieving the effect of arsenic removal. This can reduce the arsenic content of the effluent to below the standard. At the same time, through the change of pH value (here, through the adjustment of lye), other heavy metals contained in the wastewater can also be effectively removed. The arsenic and part of other heavy metals removed in the embodiment of the present application are collected in the 1st horizontal-flow sedimentation tank.

[0075] Specifically, in the embodiment of the present application, after the calcium salt (such as calcium hydroxide, calcium chloride, etc.) is dissolved in water, calcium ions (Ca 2+ ) are released. The principle that the fluoride ions react with the calcium ions to generate an insoluble calcium fluoride (CaF2) precipitate is that, after the calcium salt pretreatment, most of the fluoride ions are generated into calcium fluoride precipitate; then, aluminum sulfate or a complex fluoride removal agent is added for deep treatment, so that the fluoride ions form a complex with the metal ions in the fluoride removal agent, and finally, the precipitate is precipitated at a suitable pH value (here, adjusted by hydrochloric acid), thereby achieving the effect of fluoride removal. Among them, the fluoride ions and other some heavy metals are collected in the 2nd horizontal-flow sedimentation tank.

[0076] S3, judging whether the arsenic-fluorine component value is greater than a preset pretreatment qualified standard.

[0077] The pretreatment qualified standard includes:

[0078] (1) arsenic stable treatment to 0.1 mg / L or less;

[0079] (2) fluoride stable treatment to 10 mg / L or less.

[0080] When the arsenic-fluorine component value is greater than the pretreatment qualified standard, the pretreatment wastewater is introduced into the pretreatment device for re-filtering until the arsenic-fluorine component value is less than or equal to the pretreatment qualified standard.

[0081] In the embodiment of the present application, the more purified pretreatment wastewater will enter the step of electrochemical treatment together with the pretreatment wastewater meeting the pretreatment qualified standard.

[0082] Specifically, in the embodiment of the present application, the effluent of the 2nd horizontal-flow sedimentation tank can be discharged to a pre-constructed intermediate water tank. If the arsenic-fluorine component value is greater than the pretreatment qualified standard, it indicates that the wastewater pollutants may be harmful to the environment, and can be re-introduced into the 2nd adjustment tank for repeated arsenic and fluoride removal.

[0083] In detail, in the embodiment of the present application, after the pretreatment wastewater is introduced into the pretreatment device for re-filtering, the method further includes:

[0084] The pretreated wastewater returned to the pretreatment device is statistically quantified to obtain a wastewater circulation flow value, and the wastewater circulation flow value is monitored to obtain a wastewater circulation flow curve;

[0085] A pretreatment feeding control model is pre-trained, and the pretreatment device is controlled according to the wastewater circulation flow curve to obtain a predicted pretreatment control parameter set.

[0086] The pretreatment device is parameter updated according to the predicted pretreatment control parameter set to obtain an updated wastewater circulation flow curve, wherein the updated wastewater circulation flow curve is kept within a preset flow limit interval.

[0087] The speed of the pretreated wastewater introduced into the pretreatment device is recorded.

[0088] The wastewater circulation flow value refers to the amount of pretreated wastewater returned to the pretreatment device per unit time, and the unit is liter / hour.

[0089] The monitoring refers to the operation of recording the wastewater circulation flow value according to the change of the time stamp.

[0090] The wastewater circulation flow curve refers to the record of the wastewater circulation flow value in a period, such as a day or a week.

[0091] The pretreatment feeding control model refers to a neural network model that can adjust some parameters in the pretreatment device according to the wastewater circulation flow curve, so that the wastewater circulation flow curve changes relatively smoothly, for example, the change rate of the wastewater circulation flow curve is less than a certain value.

[0092] The control parameter prediction refers to the process of predicting the mapping relationship between the change of the wastewater circulation flow curve and the change of the feeding amount of the pretreatment device obtained in the pre-training process, which is not described here.

[0093] The predicted pretreatment control parameter set at least includes the feeding speed or feeding amount of substances such as liquid alkali, hydrochloric acid, and calcium chloride. The pretreatment device will perform filtration control operation based on arsenic and fluorine according to the predicted pretreatment control parameter set.

[0094] The flow limit interval is related to the actual specifications of the wastewater treatment plant and can be modified according to specific circumstances.

[0095] Specifically, the present application can automatically control the pretreatment parameters through the pre-trained pretreatment feed control model, so that the pretreatment wastewater can be filtered again, and the stability can be improved. In addition, by training, the input amount of iron salt, calcium salt, acid and alkali and the like in the pretreatment equipment can be determined according to the feed record of the tungsten smelting plant and the production speed of the wastewater in the workshop, so that the number of times of filtering the pretreatment wastewater again can be reduced, and even the filtering process of the pretreatment wastewater again can be cancelled.

[0096] When the arsenic fluoride component value is less than or equal to the pretreatment qualified standard, S4, using a pre-constructed electrochemical treatment device, performing an electro-catalytic oxidation operation on the pretreatment wastewater based on COD and ammonia nitrogen to obtain oxidized wastewater.

[0097] In the embodiment of the present application, when the arsenic fluoride component value is less than or equal to the pretreatment qualified standard, it indicates that the pretreatment wastewater meets the specification.

[0098] As shown in the reference Figure 2 The electrochemical treatment device includes an electro-catalytic device and a nanocrystalline magnetic separation device.

[0099] The electro-catalytic device can directly oxidize the easily oxidizable substances in the wastewater, or indirectly oxidize some easily oxidizable substances in the wastewater by generating a strong oxidizing agent.

[0100] The nanocrystalline magnetic separation is a method of realizing efficient separation and enrichment of target substances by using the special properties of magnetic nanoparticles (such as polyacrylamide and other high molecular polymers) and the action of an external magnetic field. Some ions in the wastewater are combined with the magnetic nanoparticles through physical adsorption, chemical bonding or biological recognition.

[0101] The electro-catalytic oxidation operation refers to an operation of oxidizing some substances in the wastewater by electric current.

[0102] In detail, in the embodiment of the present application, the electro-catalytic oxidation operation on the pretreatment wastewater based on COD and ammonia nitrogen using the pre-constructed electrochemical treatment device to obtain oxidized wastewater includes:

[0103] Using the pre-constructed electrochemical treatment device, the conductivity of the pretreatment wastewater is detected, and the conductivity of the pretreatment wastewater is regulated to a pre-set suitable range according to the pre-constructed electrolyte to obtain conductive standard wastewater.

[0104] The conductive standard wastewater is subjected to an oxidation operation to obtain initial oxidized wastewater, a pre-constructed high molecular polymer is used to uniformly add the initial oxidized wastewater according to a pre-set addition speed, and the initial oxidized wastewater is subjected to an oxidized content detection during the uniform addition to obtain an oxidized content change curve.

[0105] calculating a correlation score between the addition speed and the oxide content change curve;

[0106] stopping the operation of adding the initial oxide wastewater at the preset addition speed using the pre-constructed polymer, and identifying a change rate of the oxide content change curve when the correlation score is less than a preset correlation threshold;

[0107] treating the initial oxide wastewater as oxide wastewater when the change rate of the oxide content change curve is less than a preset stability threshold.

[0108] The electrolyte is sodium chloride.

[0109] The suitable range is 1 mS / cm-5 mS / cm.

[0110] The oxidation operation includes electrocatalytic oxidation of COD and ammonia nitrogen. The COD degradation mechanism is that the anode generates hydroxyl radicals (·OH) or other strong oxidizing substances (such as Q2, Cl2, hypochlorite ClO - , which directly oxidize organic matter in wastewater to reduce COD. The active chlorine (Cl2, ClO - ) produced by anodic oxidation reacts with ammonia nitrogen to generate nitrogen (N2) or other intermediate products.

[0111] The uniform addition refers to uniformly introducing the polymer into the initial oxide wastewater.

[0112] The addition speed is related to the type and concentration of the polymer and the concentration of pollutants in the wastewater, and can be configured according to actual conditions.

[0113] The change rate refers to the slope of the curve on the oxide content change curve.

[0114] The correlation score refers to the degree of influence of the change in the content of the polymer on the change in the content of the oxide.

[0115] The correlation threshold can be adaptively configured according to the specific conditions of the polymer and the oxide content change, to ensure that the actual polymer is just right for the oxide content to be completely measured through the correlation threshold.

[0116] The oxide wastewater refers to wastewater after all oxidizable substances in the wastewater are oxidized.

[0117] The initial oxide wastewater refers to oxide wastewater when some substances have not been completely oxidized.

[0118] The stable threshold is configured according to the experimental test result of the oxide content stopping growth in a specific scene.

[0119] Specifically, in the embodiment of the present application, the conductivity of the pretreated wastewater is first measured, and then sodium chloride is poured to make the conductivity between 1 mS / cm and 5 mS / cm. Then, electrocatalytic oxidation operation is performed to obtain initial oxide wastewater. However, in order to measure the oxidation degree in the initial oxide wastewater, nanocrystalline magnetic separation is needed for measurement, and high molecular polymers are also needed as carriers for various ions. Excessive high molecular polymers increase the volume of wastewater, affecting the accuracy of oxide measurement, and too little high molecular polymer causes the oxide to be unable to be extracted completely, affecting the accuracy of oxide measurement. Therefore, controlling the amount of high molecular polymer is of great significance to measuring the oxide content.

[0120] Specifically, in the embodiment of the present application, when the high molecular polymer is added at a uniform speed, the oxide measurement value should also gradually increase. When the high molecular polymer is added at a uniform speed and the oxide measurement value increases slowly, it indicates that the carrier capacity of the high molecular polymer is redundant, and the input can be reduced. Therefore, by calculating the correlation score between the addition speed and the oxide content change curve, the relationship between the high molecular polymer and the oxide can be roughly known. A smaller correlation score indicates that the high molecular polymer has little effect on the measurement of the oxide content, indicating that the COD and ammonia nitrogen in the initial oxide wastewater are basically completely oxidized, and the addition of the high molecular polymer can be stopped, so that the remaining high molecular polymer in the initial oxide wastewater can slowly extract the remaining oxide. When the change rate of the oxide content change curve is less than the preset stable threshold, it indicates that no oxide is generated in the initial oxide wastewater, and the initial oxide wastewater can be output as oxide wastewater.

[0121] In detail, in the embodiment of the present application, the oxidation operation on the conductive standard wastewater to obtain initial oxide wastewater comprises:

[0122] The conductive standard wastewater is directly oxidized according to a preset first control current by using the anode plate pre-constructed in the electrochemical treatment equipment to obtain first-stage oxide wastewater.

[0123] The strong oxidant is generated according to a preset second control current by using the electrode plate pre-constructed in the electrochemical treatment equipment, and the first-stage oxide wastewater is oxidized by using the strong oxidant to obtain initial oxide wastewater, wherein the electrode plate comprises the anode plate.

[0124] The first-stage oxide wastewater and the initial oxide wastewater are contained in the oxide wastewater.

[0125] Specifically, in the embodiment of the present application, the process of electrochemical treatment of wastewater mainly relies on the redox reaction of the electrode, which can be divided into direct oxidation and indirect oxidation mechanisms.

[0126] Among them, the pollutants such as ammonia nitrogen directly oxidize on the surface of the anode and are decomposed into harmless substances. This reaction depends on the catalytic performance of the anode material, and in the embodiment of the present application, the anode plate can be made of lead dioxide (PbO2), titanium-based coating (such as RuO2, IrO2) and other materials. Indirect oxidation is through the electrode to produce strong oxidizing substances (such as Cl2, ClO - , O3, H2O2, etc.) in wastewater, which further reacts with pollutants to degrade COD and ammonia nitrogen.

[0127] Specifically, in the electrochemical treatment process of the present application, the total current is distributed to direct electrocatalytic reaction and indirect electrocatalytic reaction to obtain first control current and second control current. Among them, the first control current is determined by the rate of oxidation or reduction of pollutants directly on the electrode surface, and if the catalytic activity of the electrode surface is strong and the concentration of pollutants is high, the current contribution of direct electrocatalysis will be larger. The second control current is determined by the rate of electrochemical generation of intermediate active substances (such as hydroxyl radicals, hypochlorous acid, etc.), and if the generation and consumption rate of intermediate active substances in the system is high, the current contribution of indirect electrocatalysis will be larger.

[0128] S5, performing an oxide separation operation on the oxide wastewater to obtain a to-be-discharged wastewater, and detecting the content of a preset substance type of the to-be-discharged wastewater to obtain a wastewater composition table.

[0129] Among them, the oxide separation operation is completed by the above-mentioned nanocrystalline magnetic separation device, which refers to the separation operation of various oxides in the oxide wastewater.

[0130] Among them, the preset substance type includes ammonia nitrogen, COD, arsenic and fluorine.

[0131] Among them, the to-be-discharged wastewater is wastewater that can be directly discharged or used for other purposes.

[0132] Among them, the wastewater composition table refers to a table recording the concentration of each substance in the wastewater.

[0133] Specifically, in the embodiment of the present application, the to-be-discharged wastewater is obtained by the nanocrystalline magnetic separation device, and then the content of ammonia nitrogen, COD, arsenic and fluorine is obtained according to the titration method and colorimetric method, and a wastewater composition table is obtained. Among them, the titration method and colorimetric method are some easy-to-operate detection methods, which are not described here.

[0134] S6, judging whether the wastewater composition table belongs to a preset target level discharge standard.

[0135] The target level discharge standard is at least higher than the first level A discharge standard in the pre-constructed urban sewage treatment plant pollutant discharge standard.

[0136] In the wastewater composition table, the COD stable treatment is below 50 mg / L; the ammonia nitrogen stable treatment is below 5 mg / L; the arsenic stable treatment is below 0.1 mg / L in the pretreatment process; the fluorine stable treatment is below 10 mg / L, which meets the first level A discharge standard in the Urban Sewage Treatment Plant Pollutant Discharge Standard.

[0137] When the wastewater composition table does not belong to the target level discharge standard, the to-be-discharged wastewater is introduced into the electrochemical treatment equipment for re-filtering until the wastewater composition table belongs to the target level discharge standard.

[0138] The more purified to-be-discharged wastewater and the to-be-discharged wastewater meeting the target level discharge standard can be discharged together or stored together in a pre-constructed recovery pool for making fresh water, acid and alkali solution.

[0139] In the embodiment of the application, when the tungsten ore raw material of the tungsten smelting plant changes, the wastewater content changes dramatically, which can be realized by re-filtering, and the wastewater treatment meets the standard.

[0140] When the wastewater composition table belongs to the target level discharge standard, S7, the to-be-discharged wastewater meeting the target level discharge standard is obtained.

Claims

1. An electrochemical treatment method based on the detection of tungsten smelting wastewater, characterized in that, The method includes: Obtain wastewater from a tungsten smelter's workshop; Using a pre-constructed pretreatment device, the workshop wastewater is subjected to arsenic and fluorine-based filtration control operations to obtain pretreated wastewater, and the arsenic and fluorine content in the pretreated wastewater is detected. Determine whether the arsenic and fluorine content value is greater than the preset pretreatment qualification standard; When the arsenic and fluorine content value is greater than the pretreatment qualification standard, the pretreated wastewater is introduced into the pretreatment equipment for further filtration until the arsenic and fluorine content value is less than or equal to the pretreatment qualification standard. When the arsenic and fluorine content is less than or equal to the pretreatment qualification standard, the pretreated wastewater is subjected to electrocatalytic oxidation based on COD and ammonia nitrogen using a pre-constructed electrochemical treatment device to obtain oxide wastewater. The oxide wastewater is subjected to oxide separation to obtain wastewater to be discharged, and the content of preset substance types in the wastewater to be discharged is detected to obtain a wastewater composition table. Determine whether the wastewater composition table meets the preset target level emission standard; When the wastewater composition table does not meet the target emission standard, the wastewater to be discharged is introduced into the electrochemical treatment equipment for further filtration until the wastewater composition table meets the target emission standard. When the wastewater composition table falls within the target level emission standard, wastewater that meets the target level emission standard is obtained; The process of using pre-constructed pretreatment equipment to perform arsenic and fluorine-based filtration control on the workshop wastewater to obtain pretreated wastewater includes: The workshop wastewater was subjected to primary sedimentation using pre-constructed pretreatment equipment and pre-constructed calcium salts to obtain arsenic-removed wastewater. The arsenic-removed wastewater was subjected to sedimentation using a pre-constructed iron salt to obtain deeply arsenic-removed wastewater. The deep arsenic removal wastewater is subjected to acid-base metal ion precipitation to obtain primary pretreated wastewater; Using a pre-constructed complexing defluoridating agent, and according to a preset pH environment, the primary pre-treated wastewater is subjected to a fluoride ion complexation precipitation operation to obtain pre-treated wastewater. The pre-constructed electrochemical treatment equipment is used to perform electrocatalytic oxidation of the pretreated wastewater based on COD and ammonia nitrogen to obtain oxide wastewater, including: Using a pre-constructed electrochemical treatment device, the conductivity of the pretreated wastewater is detected, and the conductivity of the pretreated wastewater is adjusted to a preset suitable range according to the pre-constructed electrolyte to obtain conductive standard wastewater. The conductive standard wastewater is oxidized to obtain initial oxide wastewater. A pre-constructed polymer is then added to the initial oxide wastewater at a predetermined rate. During the uniform addition process, the oxide content of the initial oxide wastewater is detected to obtain an oxide content change curve. Calculate the correlation score between the addition rate and the oxide content change curve; When the correlation score is less than a preset correlation threshold, the operation of using the pre-constructed polymer is stopped, and the initial oxide wastewater is added at a uniform rate according to a preset addition rate, and the rate of change of the oxide content change curve is identified. When the rate of change of the oxide content change curve is less than the preset stability threshold, the initial oxide wastewater is regarded as oxide wastewater.

2. The electrochemical treatment method based on the detection of tungsten smelting wastewater as described in claim 1, characterized in that, The oxidation process of the conductive standard wastewater to obtain initial oxide wastewater includes: Using the pre-constructed anode plate in the electrochemical treatment equipment, the conductive standard wastewater is directly oxidized according to the preset first control current to obtain primary oxide wastewater; Using the pre-constructed electrode plate in the electrochemical treatment device, a strong oxidant is generated according to a preset second control current. The strong oxidant is used to oxidize the primary oxide wastewater to obtain initial oxide wastewater. The electrode plate includes the anode plate.

3. The electrochemical treatment method based on the detection of tungsten smelting wastewater as described in claim 2, characterized in that, After obtaining the wastewater to be discharged that meets the target emission standard, the method further includes: The oxide wastewater was subjected to calcium and magnesium ion precipitation using a pre-constructed dual-alkali method to obtain dual-alkali softened wastewater. Using a pre-constructed nanofiltration device, the dual-alkali softening wastewater is subjected to salt separation to obtain divalent brine and monovalent brine. The monovalent brine is subjected to reverse osmosis using a pre-constructed reverse osmosis device to obtain fresh water and concentrated brine of a preset concentration. The concentrated brine was dialysisd using a pre-constructed dual-membrane electrodialysis device to obtain an acid solution and an alkaline solution. The fresh water is stored, the divalent salt water is discharged, and the acid and alkali solutions are stored. A predetermined ratio of acid and alkali solutions is obtained from the stored acid and alkali solutions, and the acid and alkali solutions are transported to the pretreatment equipment and electrochemical treatment equipment.

4. The electrochemical treatment method based on the detection of tungsten smelting wastewater as described in claim 3, characterized in that, After introducing the pretreated wastewater into the pretreatment equipment for further filtration, the method further includes: The volumetric parameters of the pretreated wastewater returned to the pretreatment equipment are statistically analyzed to obtain the wastewater circulation flow rate value, and the wastewater circulation flow rate value is monitored to obtain the wastewater circulation flow rate curve. Using a pre-trained pretreatment feeding control model, the control parameters of the pretreatment equipment are predicted based on the wastewater circulation flow curve, resulting in a set of predicted pretreatment control parameters. Based on the predicted pretreatment control parameter set, the parameters of the pretreatment equipment are updated to obtain an updated wastewater circulation flow curve, wherein the updated wastewater circulation flow curve is maintained within a preset flow limit range.

5. An electrochemical treatment system based on the detection of tungsten smelting wastewater, used to execute the electrochemical treatment method based on the detection of tungsten smelting wastewater as described in claim 1, characterized in that, The system includes: The pretreatment module is used to acquire workshop wastewater from a tungsten smelter and to perform arsenic and fluorine-based filtration control operations on the workshop wastewater using pre-constructed pretreatment equipment to obtain pretreated wastewater. The module also detects the arsenic and fluorine content values ​​in the pretreated wastewater and determines whether the arsenic and fluorine content values ​​are greater than a preset pretreatment qualification standard. When the arsenic and fluorine content values ​​are greater than the pretreatment qualification standard, the pretreated wastewater is introduced into the pretreatment equipment for further filtration until the arsenic and fluorine content values ​​are less than or equal to the pretreatment qualification standard. An electrochemical treatment module is used to perform electrocatalytic oxidation of the pretreated wastewater based on COD and ammonia nitrogen using a pre-constructed electrochemical treatment device when the arsenic and fluorine content is less than or equal to the pretreatment qualification standard, to obtain oxide wastewater, and to perform oxide separation operation on the oxide wastewater to obtain wastewater to be discharged, and to detect the content of preset substance types in the wastewater to be discharged to obtain a wastewater composition table, and to determine whether the wastewater composition table belongs to the preset target level emission standard, and when the wastewater composition table does not belong to the target level emission standard, to introduce the wastewater to be discharged into the electrochemical treatment device for further filtration until the wastewater composition table belongs to the target level emission standard, and when the wastewater composition table belongs to the target level emission standard, to obtain wastewater to be discharged that meets the target level emission standard.

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