CN112526099B - High-chlorine wastewater COD detection device and method - Google Patents
High-chlorine wastewater COD detection device and method Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 101
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- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 86
- 238000001514 detection method Methods 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 126
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 36
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 23
- 238000002485 combustion reaction Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 22
- 239000001569 carbon dioxide Substances 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 12
- 239000000446 fuel Substances 0.000 claims description 9
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- 238000004140 cleaning Methods 0.000 claims description 7
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- 238000007599 discharging Methods 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
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- 229940075397 calomel Drugs 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
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- 238000012937 correction Methods 0.000 description 7
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- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012088 reference solution Substances 0.000 description 3
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- 239000012086 standard solution Substances 0.000 description 3
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1806—Biological oxygen demand [BOD] or chemical oxygen demand [COD]
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Abstract
The invention discloses a high chlorine wastewater COD detection device, which comprises a pretreatment system, a preselection system, a detection system and a control system; the pretreatment system comprises a water collecting tank, a pure water tank, a purifier and a pool to be detected; the clear water outlet at the upper part of the water collecting tank is connected with the water inlet end of the purifier, the clear water end of the purifier is connected with the pool to be detected, and the concentrated water end of the purifier and the water outlet at the bottom of the pool to be detected are respectively connected with the lower part of the water collecting tank; the preselection system comprises a reference pool, a preselection electrode and a positioning cloud platform, wherein the reference pool is connected with the common wall of the pool to be detected, and the preselection electrode moves between the reference pool and the pool to be detected through the positioning cloud platform; the detection system comprises a sample injector, an atomizer, a burner and a detector; one end of the sample injector is positioned in the branch pipe of the pool to be detected, and the other end of the sample injector is connected with the atomizer; the outlet of the atomizer is positioned in the combustor; the outlet of the burner is communicated with the detector; the detection signal of the detector is connected with a control system through a lead. The invention can eliminate the interference of high-concentration chloride ions on COD during detection.
Description
Technical Field
The invention belongs to the technical field of industrial wastewater quality detection, and particularly relates to a high-chlorine wastewater COD automatic detection device and method.
Background
Chloride ion (Cl)-) Are commonly found in various waste waters. High-chlorine wastewater is a special industrial wastewater, is commonly used in industries such as petrochemical industry, mining, food processing, rare earth smelting, tanning (tanning), chemical pharmacy, papermaking, textile, paint, pigment, mechanical manufacturing and the like, is named after high in chloride ion content, and generally has the chloride ion content of 10000-100000 mg/L or even higher. High chlorine means high salinity and strong corrosivity, has special requirements on contacting pipes, has extremely high treatment difficulty, and can cause huge damage to the natural environment when being discharged in large quantities. Chemical Oxygen Demand (COD) isThe COD discharge limit value reaching the standard is continuously reduced along with the continuous strengthening of the environmental protection strength of China by the important wastewater pollutant total amount control index, but the COD determination is obviously interfered by the existence of a large amount of chloride ions in the wastewater, so that the COD is virtual high, theoretically, every 1000mg/L of chloride ions can increase the COD of the wastewater to be measured by about 250mg/L, and the accuracy of the measurement result is seriously influenced. Therefore, aiming at the high-chlorine wastewater, equipment and a method capable of effectively detecting COD are developed, the accuracy and the reliability of detection data are ensured, and the detection method has great significance for environmental protection and environment detection.
At present, the COD detection method of high-chlorine wastewater mainly comprises a chloride ion correction method (GB/T31195-2014), a chlorine gas correction method (HJ/T70-2001), a spectrophotometry method, a total organic carbon method and the like, wherein the chloride ion correction method and the chlorine gas correction method are most commonly applied, but the upper limit of detection of the chloride ion correction method is only 2000mg/L, and the upper limit of detection of the chlorine gas correction method reaches 20000mg/L, but the existing high-chlorine wastewater cannot be completely covered. In addition, the two correction methods have the problems of complicated operation steps and long detection time, and are difficult to perform large-batch and high-efficiency detection. The spectrophotometry firstly adopts the measures of dilution or chlorine reduction to pretreat the high-chlorine wastewater, then utilizes potassium dichromate to oxidize the wastewater to be detected, and finally adopts the photometry to detect the residual potassium dichromate, and the upper limit of the chloride ion detection also reaches 20000mg/L. However, in all of the three methods, potassium dichromate is used as an oxidant, mercury sulfate is used as a masking agent, a large amount of chromium-containing and mercury-containing heavy metal detection waste liquid is generated, and the environmental hazard is great.
The total organic carbon method is characterized in that combustible organic matters in the wastewater to be detected are oxidized into carbon dioxide by high temperature according to HJ 501-2009 standard, then the COD value of the wastewater is obtained by converting the concentration of the carbon dioxide, the interference of chloride ions can be completely shielded theoretically, and the total organic carbon method is an ideal high-chlorine wastewater COD detection method. And the higher the chloride ion concentration is, the higher the salinity and impurity content in the wastewater are, and the larger the interference generated during detection is.
In summary, the development of a high-chlorine wastewater COD detection device and method which are automatic, intelligent and strong in water quality change adapting capability is urgently needed.
Disclosure of Invention
In order to solve the technical defects of complex operation steps, low detection efficiency, serious secondary pollution, poor stability, low automation degree and the like of the conventional high-chlorine wastewater COD detection method, the invention provides the high-chlorine wastewater COD automatic detection device and method, which can effectively eliminate the interference of high-concentration chloride ions on COD, are convenient to operate, have strong selectivity, are highly automated, have no secondary pollution and have wide application range.
In order to achieve the purpose, the invention provides the following technical scheme:
an automatic COD detection device for high-chlorine wastewater comprises a pretreatment system, a preselection system, a detection system and a control system;
the pretreatment system comprises a water collecting tank, a pure water tank, a purifier and a pool to be detected; a clear water outlet at the upper part of the water collecting tank is connected with a water inlet end of a purifier through a first booster pump, a clear water end of the purifier is connected with a pool to be detected, and a concentrated water end of the purifier and a water outlet at the bottom of the pool to be detected are respectively connected with the lower part of the water collecting tank; the pure water tank is respectively connected with the pool to be detected and the water collecting tank, and the pool to be detected and the water collecting tank are cleaned by the distilled water without carbon dioxide in the pure water tank;
the preselecting system comprises a reference pool, a preselecting electrode and a positioning cloud platform, wherein the reference pool is connected with the common wall of the pool to be detected, at least half of the preselecting electrode is immersed in reference liquid of the reference pool or high-chlorine wastewater to be detected of the pool to be detected, the preselecting electrode is connected with the positioning cloud platform, and the preselecting electrode moves between the reference pool and the pool to be detected through the positioning cloud platform;
the detection system comprises a sample injector, an atomizer, a burner and a detector; one end of the sample injector is positioned in the branch pipe of the pool to be detected, the other end of the sample injector is connected with the sample injection end of the atomizer through a pipeline, and the sample injector absorbs the high-chlorine wastewater in the pool to be detected and injects the high-chlorine wastewater into the atomizer; the inlet end of the atomizer is connected with the gas pump, the combustion improver is pumped into the atomizer by the gas pump, the outlet of the atomizer is positioned in the burner, and the high-chlorine wastewater is atomized into tiny droplets in the atomizer and flows with the combustion improverCompletely combusting in a combustor; the outlet of the burner is communicated with a detector, and the detector detects CO2The content is converted into the COD value of the high chlorine wastewater to be measured according to a standard curve; the gas outlet pipeline of the detector is provided with a gas outlet pipe for discharging gas into air through a draught fan; and the detection signal of the detector is connected with the control system through a lead.
The pretreatment system, the preselection system, the detection system and the control system are arranged in the shell.
Preferably, a water inlet pipeline is arranged at the upper part of the water collecting tank; the lower part of the water collecting tank is narrower than the upper part of the water collecting tank so as to facilitate the rapid sedimentation of large particles; and an outlet pipeline at the bottom of the water collecting tank is provided with a first electromagnetic valve.
The invention has no clear requirements on the high and low order of the water collecting tank, the pool to be detected, the pure water tank and the water purifier; according to the conventional habit, the pure water tank, the to-be-detected pool and the water purifier are all higher than the water collecting pool.
Preferably, wait to examine pond branch pipe lower extreme and wait to examine that the pond communicates with each other and make and wait to examine pond branch pipe and wait to examine the pond and constitute the Y shape. The junction of the sample injector and the branch pipe of the pool to be detected is sealed through a rubber plug.
Preferably, the working pressure of the first booster pump is 0.1MPa to 2.5MPa.
Preferably, the purifier is an ultrafiltration membrane component with the pore diameter of 0.05-0.45 micron. The ultrafiltration membrane in the purifier intercepts solid substances in the high-chlorine wastewater, and the chloride ions are in a dissolved ion state in the wastewater, so that the loss of the chloride ions is avoided.
Preferably, a second electromagnetic valve is arranged on a connecting pipeline between the concentrated water end of the purifier and the water collecting tank; and a third electromagnetic valve is arranged on a connecting pipeline of the water outlet at the bottom of the inspection tank and the water collecting tank.
The pure water tank holds distilled water for removing carbon dioxide.
Preferably, a water outlet pipeline of the pure water tank is provided with a second booster pump, and an outlet of the second booster pump is respectively connected with the top of the to-be-detected pool and the upper part of the water collecting tank. Preferably, a fourth electromagnetic valve is arranged on a connecting pipeline between the second booster pump and the pool to be detected; and a fifth electromagnetic valve is arranged on the connecting pipeline of the second booster pump and the water collecting tank.
Preferably, the pre-selection electrode consists of a chloride ion selective electrode and a calomel reference electrode.
Preferably, the positioning holder consists of a transverse holder and a longitudinal holder, the transverse holder enables the preselection electrode to rotate left and right, the longitudinal holder enables the preselection electrode to rotate front and back, and the preselection electrode moves between the reference cell and the cell to be detected through the positioning holder. More specifically, the shaft of the transverse holder is vertically arranged, and the longitudinal holder and the preselected electrode are driven by the transverse holder to swing around in the horizontal plane (overlooking angle); the axis of the longitudinal holder is horizontally arranged, the preselection electrode is fixed by a jacket connected with the axis of the longitudinal holder, and the longitudinal holder drives the preselection electrode to circumferentially swing back and forth in a paper plane (front view angle). The mounting between the longitudinal pan-tilt, the transverse pan-tilt and the preselected electrode can be carried out by a person skilled in the art. The positioning cradle head realizes the movement of the preselected electrode between the reference pool and the pool to be detected by the following modes: the longitudinal holder rotates forwards or backwards for a certain angle to drive the preselection electrode to leave the reference cell; then the transverse holder rotates to the left to drive the longitudinal holder and the pre-selection electrode to come above the pool to be detected; the longitudinal holder rotates backwards or forwards to enable the pre-selection electrode to enter the interior of the pool to be detected; and after the detection is finished, the program is reversely executed to enable the preselected electrode to be reset.
Preferably, the reference solution is a sodium chloride standard solution prepared from distilled water with carbon dioxide removed, and the concentration of the sodium chloride standard solution is 50000mg/L in terms of chloride ion concentration. In actual operation, the concentration of chloride ions in the reference solution can be adjusted by those skilled in the art according to actual needs.
Preferably, the fuel device is a hollow tubular resistance-type heating pipe, grooves or circular protrusions are distributed on the inner surface of the inner wall of the burner, so that atomized liquid drops can be fully contacted with the burner, the combustion is full, gas diffusion is facilitated, and the deposition of combustion solid products is avoided; the material of the burner is ceramic which is resistant to chloride ion corrosion; the operating temperature of the burner was 900 ℃. The main components of the gas generated by the combustion of the high-chlorine wastewater to be measured in the combustor are carbon dioxide and excessive oxygen, and the gas belongs to harmless substances and is very small in amount.
Preferably, the detector is CO2Infrared detector or CO2Sensor, detecting CO by detector2And (4) converting the content into the COD value of the high-chlorine wastewater to be detected according to a standard curve.
Preferably, the air inlet end of the atomizer is connected with an external air source, and the combustion improver in the external air source is pumped into the atomizer by a gas pump.
In view of the fact that detection accuracy of the detector and the life of the detector are affected if the gas is directly detected without cooling after combustion, a cooling chamber is further provided between the burner and the detector for cooling the gas discharged from the burner.
Preferably, the cooler is a hollow cooler, the volume of the cooler is 30-50 times of the volume of the fuel, the high-temperature gas discharged by the combustor enters the cooling chamber, the volume is suddenly enlarged, and the gas temperature is reduced to be lower than 100 ℃ by performing rapid heat exchange with the outer periphery of the cooling chamber. The cooling chamber is made of stainless steel.
Preferably, the control system comprises a controller and a display screen; cl measured by a preselected electrode-Content, CO measured by the detector2The content is fed back to the controller, and the result is stored and displayed on a display screen or output by the controller. The control system controls the sample injector, the positioning cradle head, the pre-selection electrode, the fuel device, the detector, the electromagnetic valve and the like, and the control method is a conventional signal feedback response method.
The method for detecting the COD of the high-chlorine wastewater based on the detection device comprises the following steps:
step (1), cleaning a pool to be detected and a water collection tank by using distilled water without carbon dioxide;
step (2), allowing the high-chlorine wastewater to be detected to enter a water collecting tank, standing, allowing large particles in the wastewater to sink to the bottom of the water collecting tank under the action of gravity, sequentially starting a first booster pump (with the working pressure of 0.1-2.5 MPa) and a second electromagnetic valve, allowing the wastewater to enter a purifier through the first booster pump for filtering, completely intercepting fine suspended particles in the high-chlorine wastewater, allowing the purified high-chlorine wastewater (namely fresh water) to enter a pond to be detected, returning concentrated water to the water collecting tank through the second electromagnetic valve, and then closing the first booster pump;
step (3), starting the burner and the detector in sequence for preheating, and preheating the burner to 300-500 ℃; air is adopted to clean the combustor, the cooling chamber and the detector; then starting the transverse holder and the longitudinal holder, transferring the preselection electrode from the reference pool to a pool to be detected, carrying out preselection detection on the purified high-chlorine wastewater, and determining the content of chloride ions;
step (4) according to the preselection detection result in the step (3), high-chlorine wastewater is sucked from the pool to be detected by a sample injector and injected into an atomizer, a combustion improver is introduced into the atomizer by a gas pump, the high-chlorine wastewater enters a combustor (the working temperature of the combustor is 900 ℃) along with the combustion improver for internal combustion after being atomized, the generated high-temperature gas is cooled to be lower than 100 ℃ by a cooling chamber and then enters a detector for detection, and CO is obtained2Feeding back the detection data to the controller, and converting the COD value of the high-chlorine wastewater to be detected according to a standard curve; after the detection is finished, discharging gas under the action of a draught fan, and finishing the primary detection; carrying out parallel detection for three times, and taking an average value;
step (5), closing the sample injector and the combustor in sequence, and closing the gas pump, the detector and the induced draft fan in sequence after the combustor is cooled; starting the transverse holder and the longitudinal holder, and transferring the preselected electrode from the pool to be detected to a reference pool for soaking; and then opening the first electromagnetic valve and the third electromagnetic valve in sequence, emptying the high-chlorine wastewater, and finishing the detection of one sample.
In the step (1), the method for cleaning the pool to be detected and the water collection tank comprises the following steps: opening the first electromagnetic valve and the third electromagnetic valve, then opening the fourth electromagnetic valve and the fifth electromagnetic valve in sequence, then opening the second booster pump, under the action of the second booster pump, enabling the distilled water without carbon dioxide in the pure water tank to enter the pool to be detected through the fourth electromagnetic valve, and enter the water collecting tank through the fifth electromagnetic valve, and leaching the pool to be detected and the water collecting tank; and after the leacheate is emptied, the second booster pump, the fourth electromagnetic valve and the fifth electromagnetic valve are closed in sequence, and then the third electromagnetic valve and the first electromagnetic valve are closed in sequence.
In the step (3), the cleaning method of the combustor, the cooling chamber and the detector comprises the following steps: and sequentially starting the gas pump and the induced draft fan, and cleaning the combustor, the cooling chamber and the detector by air.
Specifically, the content of chloride ions in the purified high-chlorine wastewater is detected for three times, and an average value is taken.
In the step (4), the content of chloride ions in the high-chlorine wastewater is 10000-100000 mg/L. According to the different chloride ion content of preselection testing result, the sample injection volume of injector is different, and higher the chloride ion, the sample injection volume is bigger to furthest reduces the error. When the content of the chloride ions is less than or equal to 50000mg/L, the sample amount of the sample injector is less than or equal to 1000 mu L and less than or equal to 50 mu L; when the content of the chloride ions is more than 50000mg/L, the sample amount of the sample injector is more than 1000 mu L and less than or equal to 5000 mu L.
The combustion improver is high-purity oxygen with the purity of 99.9999 percent. The combustion improver is excessive relative to the high-chlorine wastewater, and generally, the flow of the combustion improver is 0.2L/s-2.5L/s.
Compared with the prior art, the invention has the beneficial effects that:
the high-chlorine wastewater COD detection device provided by the invention can eliminate the interference of high-concentration chloride ions on wastewater COD during detection by preselecting chloride ions and differentiating the detection dosage of the wastewater, has stronger detection interference resistance, realizes continuous and automatic detection of the high-chlorine wastewater COD, does not use and generate detection waste liquid containing chromium and mercury heavy metals during detection, is green and environment-friendly, is simple and convenient to operate, and has high sensitivity.
Drawings
FIG. 1 is a schematic structural diagram of a COD detection device for high-chlorine wastewater.
FIG. 2 is a schematic diagram of a pretreatment system of the automatic COD detection device for high-chlorine wastewater.
FIG. 3 is a schematic diagram of a preselection system of the automatic COD detection device for high-chlorine wastewater.
FIG. 4 is a schematic diagram of a detection system and a control system of the automatic COD detection device for high chlorine wastewater.
The device comprises a shell, a water collecting tank, a pure water tank, a purifier, a 5-to-be-detected pool, a 6-to-be-detected pool branch pipe, a 7-water inlet pipe, a 8-first electromagnetic valve, a 9-first booster pump, a 10-second electromagnetic valve, a 11-third electromagnetic valve, a 12-second booster pump, a 13-fourth electromagnetic valve, a 14-fifth electromagnetic valve, a 15-reference pool, a 16-preselection electrode, a 17-transverse holder, an 18-longitudinal holder, a 19-sample injector, a 20-atomizer, a 21-combustor, a 22-cooling chamber, a 23-detector, a 24-gas pump, a 25-induced draft fan, a 26-controller and a 27-display screen.
Detailed Description
The technical solution of the invention will be described clearly and completely with reference to the accompanying drawings and examples. It should be apparent that the described embodiments are only a few embodiments of the present invention, and not all embodiments.
Example 1
As shown in fig. 1-4, a high chlorine wastewater COD detection device comprises a pretreatment system, a preselection system, a detection system and a control system; the pretreatment system, the preselection system, the detection system and the control system are arranged in the shell 1.
The pretreatment system comprises a water collecting tank 2, a pure water tank 3, a purifier 4 and a pool 5 to be detected; a water inlet pipe 7 is arranged at the upper part of the water collecting tank 2, and a first electromagnetic valve 8 is arranged at an outlet pipeline at the bottom of the water collecting tank 6; a clear water outlet at the upper part of the water collecting tank 2 is connected with a water inlet end of the purifier 4 through a first booster pump 9, a clear water end of the purifier 4 is connected with the pool 5 to be detected through a pipeline, and a concentrated water end of the purifier 5 is connected with the bottom of the water collecting tank 2 through a second electromagnetic valve 10; the bottom of the pool to be detected 5 is connected with the lower part of the water collecting tank 2 through a third electromagnetic valve 11; a water outlet pipeline of the pure water tank 3 is provided with a second booster pump 12, an outlet of the second booster pump 12 is respectively connected with the top of the pool 5 to be detected and the upper part of the water collecting tank 2, a connecting pipeline of the second booster pump 12 and the pool 5 to be detected is provided with a fourth electromagnetic valve 13, a connecting pipeline of the second booster pump 12 and the water collecting tank 2 is provided with a fifth electromagnetic valve 14, and the pool to be detected and the water collecting tank are cleaned by the distilled water with carbon dioxide removed in the pure water tank;
the preselecting system comprises a reference cell 15, a preselecting electrode 16 and a positioning holder, wherein the reference cell 15 is connected with the common wall of the cell to be detected 5; the preselection electrode 16 consists of a chloride ion selective electrode and a calomel reference electrode, and at least half of the preselection electrode 16 is immersed in the reference liquid of the reference pool or the high-chlorine wastewater to be detected in the pool to be detected; the positioning cloud platform consists of a transverse cloud platform 17 and a longitudinal cloud platform 18, wherein the shaft of the transverse cloud platform 17 is vertically arranged, and the transverse cloud platform 17 drives the longitudinal cloud platform and the preselection electrode to circumferentially swing left and right in a horizontal plane (overlooking angle); the axis of the longitudinal holder 18 is horizontally arranged, the preselection electrode 16 is fixed by a jacket connected with the axis of the longitudinal holder, and the longitudinal holder drives the preselection electrode to circumferentially swing back and forth in a paper plane (front view angle); and the pre-selection electrode is moved between the reference pool and the pool to be detected through the positioning cradle head.
The detection system comprises an injector 19, an atomizer 20, a burner 21, a cooling chamber 22 and a detector 23; one end of the sample injector 19 is positioned in the branch pipe 6 of the pool to be detected, the other end of the sample injector is connected with the sample injection end of the atomizer 20 through a pipeline, the high-chlorine wastewater in the pool to be detected is absorbed by the sample injector and is injected into the atomizer, and the joint of the sample injector 19 and the branch pipe 6 of the pool to be detected is sealed through a rubber plug; the inlet end of the atomizer 20 is connected with an external air source through a gas pump 24, a combustion improver (99.9999% high-purity oxygen) is pumped into the atomizer through the gas pump, the outlet of the atomizer 20 is positioned in the burner 21, high-chlorine wastewater is atomized into tiny droplets in the atomizer, and enters the burner along with the combustion improver to be completely combusted; the outlet of the burner 21 is communicated with a detector 23 through the cooling chamber 22, the gas discharged by the burner enters the detector after being cooled, and the detector detects CO2The content is converted into the COD value of the high chlorine wastewater to be measured according to a standard curve; the pipeline at the air outlet of the detector 23 is provided with a draught fan 25 for discharging air into the air; the detection signal of the detector 23 is connected with the control system through a lead.
The control system includes a controller 26 and a display screen 27; cl measured by a preselected electrode-Content, CO measured by the detector2The content is fed back to the controller, and the result is stored and displayed on a display screen or output by the controller. The control system controls the sample injector, the positioning cradle head, the pre-selection electrode, the fuel device, the detector, the electromagnetic valve and the like, and the control method is a conventional signal feedback response method.
In particular, the lower portion of the header tank 2 is narrowed compared to the upper portion, so that large particles are rapidly settled.
The pure water in the pure water tank 3 is distilled water from which carbon dioxide is removed.
The purifier 4 is an ultrafiltration membrane component with the aperture of a microfiltration membrane of 0.45 micron.
The reference solution is a sodium chloride standard solution prepared from distilled water with carbon dioxide removed, and the concentration of chloride ions is 50000mg/L.
The fuel device 21 is a hollow tubular resistance heating pipe, and grooves or circular bulges are distributed on the inner surface of the inner wall of the fuel device; the material of the burner is ceramic which is resistant to chloride ion corrosion; the operating temperature of the burner was 900 ℃.
The cooler 22 is a hollow cooler, and the cooling chamber is made of stainless steel. The volume of the cooler is 30-50 times of that of the fuel device, high-temperature gas discharged by the combustor enters the cooling chamber, the volume is suddenly enlarged, and the gas temperature is reduced to be lower than 100 ℃ by performing rapid heat exchange with the outer periphery of the cooling chamber.
The detector 23 is CO2Infrared detector or CO2Sensor, detecting CO by detector2And (4) converting the content into the COD value of the high-chlorine wastewater to be detected according to a standard curve.
The method for detecting the COD of the high-chlorine wastewater based on the high-chlorine wastewater detection device comprises the following steps:
step (1), starting the device, and electrifying the controller 26 and the display screen 27; cleaning a pool to be detected and a water collecting tank: opening the first electromagnetic valve 8 and the third electromagnetic valve 11, then opening the fourth electromagnetic valve 13 and the fifth electromagnetic valve 14 in sequence, then opening the second booster pump 12, under the action of the second booster pump, introducing the distilled water without carbon dioxide in the pure water tank 3 into the pool 4 to be detected through the fourth electromagnetic valve 13, introducing the distilled water into the water collecting tank 2 through the fifth electromagnetic valve 14, and leaching the pool and the water collecting tank to be detected for 3 minutes; after the leacheate is emptied, the second booster pump 12, the fourth electromagnetic valve 13 and the fifth electromagnetic valve 14 are closed in sequence, and then the third electromagnetic valve 11 and the first electromagnetic valve 8 are closed in sequence;
step (2), the high-chlorine wastewater to be detected enters a water collecting tank 2 through a water inlet pipe 7, standing is carried out, large particles in the wastewater sink to the bottom of the water collecting tank under the action of gravity, a first booster pump 9 (with the working pressure of 0.1-2.5 MPa) and a second electromagnetic valve 10 are sequentially started, the wastewater enters a purifier 4 through the first booster pump for filtering, fine suspended particles in the high-chlorine wastewater are completely intercepted, fresh water enters a pool 5 to be detected, concentrated water returns to the water collecting tank 2 through the second electromagnetic valve 10, and the first booster pump 9 is closed;
step (3), sequentially starting the burner 21 and the detector 23 for preheating, and preheating the burner to 300-500 ℃; then, a gas pump 24 and an induced draft fan 25 are sequentially started to clean the combustor 21, the cooling chamber 22 and the detector 23; starting a transverse holder 17 and a longitudinal holder 18, transferring a preselection electrode 16 from a reference pool 15 into a pool 5 to be detected, carrying out preselection detection on the purified high-chlorine wastewater, determining the content of chloride ions, carrying out detection three times, and taking an average value, wherein the content of the chloride ions is less than 50000 mg/L;
step (4), starting a sample injector 19, sucking 500 micro-high chlorine wastewater, injecting the high chlorine wastewater into an atomizer 20, atomizing the high chlorine wastewater into micro droplets, feeding the high chlorine wastewater into a preheated combustor 21 (the working temperature of the combustor is 900 ℃) along with a combustion improver, completely combusting, feeding generated high-temperature gas into a cooling chamber 22, cooling to a temperature lower than 100 ℃, feeding the high chlorine wastewater into a detector 23 for detection, feeding detection data back to the controller 26 after the detection is finished, discharging the residual gas into air under the action of an induced draft fan 25, and finishing primary detection;
step (5), repeating the step (4), performing parallel detection for three times, and then taking an average value to obtain the COD value in the high-chlorine wastewater of 150.03 mg/L; close in proper order sample injector 19 and combustor 21 wait to close gas pump 24, detector 23 and draught fan 25 in proper order again after combustor 21 cools off, start horizontal cloud platform 17 and vertical cloud platform 18, transfer to reference pond 15 with preliminary election electrode 16 in waiting to examine pond 5 and soak, open in proper order again first solenoid valve 8 and third solenoid valve 11, the evacuation high chlorine waste water, a sample detects the end.
Example 2
This example differs from example 1 in that: when the high-chlorine wastewater to be detected is different, the pre-selection detection result shows that the content of chloride ions is more than 50000mg/L, the sample injector 19 sucks 1500 micro-high-chlorine wastewater to enter the atomizer 20, and finally, the COD value in the high-chlorine wastewater is 185.9mg/L.
Claims (10)
1. A high chlorine wastewater COD detection device is characterized by comprising a pretreatment system, a preselection system, a detection system and a control system;
the pretreatment system comprises a water collecting tank, a pure water tank, a purifier and a pool to be detected; a clear water outlet at the upper part of the water collecting tank is connected with a water inlet end of a purifier through a first booster pump, a clear water end of the purifier is connected with a pool to be detected, and a concentrated water end of the purifier and a water outlet at the bottom of the pool to be detected are respectively connected with the lower part of the water collecting tank; the pure water tank is respectively connected with the pool to be detected and the water collecting tank, and the pool to be detected and the water collecting tank are cleaned by the distilled water without carbon dioxide in the pure water tank;
the preselection system comprises a reference pool, a preselection electrode and a positioning cloud platform, wherein the reference pool is connected with the common wall of the pool to be detected, at least half of the preselection electrode is immersed in reference liquid of the reference pool or high-chlorine wastewater to be detected of the pool to be detected, the preselection electrode is connected with the positioning cloud platform, and the preselection electrode is moved between the reference pool and the pool to be detected through the positioning cloud platform;
the detection system comprises a sample injector, an atomizer, a burner and a detector; one end of the sample injector is positioned in the branch pipe of the pool to be detected, the other end of the sample injector is connected with the sample injection end of the atomizer through a pipeline, and the sample injector absorbs the high-chlorine wastewater in the pool to be detected and injects the high-chlorine wastewater into the atomizer; the gas inlet end of the atomizer is connected with a gas pump, the combustion improver is pumped into the atomizer by the gas pump, the outlet of the atomizer is positioned in the burner, and the high-chlorine wastewater is atomized in the atomizer and enters the burner along with the combustion improver for combustion; the outlet of the burner is communicated with a detector, and the detector detects CO2The content is calculated out according to the standard curve, and the COD value of the high chlorine wastewater to be measured is calculated out; the gas outlet pipeline of the detector is provided with a gas outlet pipe for discharging gas into air through a draught fan; and the detection signal of the detector is connected with the control system through a lead.
2. The COD detector for high chlorine waste water according to claim 1, wherein the lower part of the water collecting tank is narrower than the upper part; a water inlet pipeline is arranged at the upper part of the water collecting tank; and an outlet pipeline at the bottom of the water collecting tank is provided with a first electromagnetic valve.
3. The COD detection device for high chlorine wastewater according to claim 1 or 2, characterized in that the connecting pipeline between the concentrated water end of the purifier and the water collection tank is provided with a second electromagnetic valve; a third electromagnetic valve is arranged on a connecting pipeline between the water outlet at the bottom of the pool to be detected and the water collecting tank; a water outlet pipeline of the pure water tank is provided with a second booster pump, and an outlet of the second booster pump is respectively connected with the top of the pool to be detected and the upper part of the water collecting tank; a fourth electromagnetic valve is arranged on a connecting pipeline of the second booster pump and the pool to be detected; and a fifth electromagnetic valve is arranged on a connecting pipeline of the second booster pump and the water collecting tank.
4. The COD detector for high chlorine waste water according to claim 1, wherein the purifier is an ultrafiltration membrane module with an ultrafiltration membrane pore size of 0.05-0.45 microns.
5. The high chlorine wastewater COD detection device of claim 1, characterized in that the lower end of the branch pipe of the tank to be detected is communicated with the tank to be detected, so that the branch pipe of the tank to be detected and the tank to be detected form a Y shape; the junction of the sample injector and the branch pipe of the pool to be detected is sealed through a rubber plug.
6. The high chlorine wastewater COD detection device of claim 3, characterized in that said pre-selection electrode consists of a chloride ion selective electrode and a calomel reference electrode; the positioning holder is composed of a transverse holder and a longitudinal holder, the transverse holder enables the pre-selection electrode to rotate left and right, and the longitudinal holder enables the pre-selection electrode to rotate back and forth.
7. The COD detector for high chlorine wastewater according to claim 1, wherein the fuel device is a hollow tubular resistive heating tube, and grooves or circular protrusions are distributed on the inner surface of the inner wall of the burner; the detector is CO2Infrared detector or CO2A sensor.
8. The COD detector for high chlorine waste water according to claim 6, characterized in that a cooling chamber is further provided between the burner and the detector; the volume of the cooler is 30-50 times of the volume of the fuel device.
9. The COD detector for high chlorine waste water of claim 8, wherein said control system comprises a controller and a display screen.
10. The method for detecting COD in high-chlorine wastewater based on the COD detection device of claim 9, comprising the following steps:
step (1), cleaning a pool to be detected and a water collection tank by using distilled water without carbon dioxide;
step (2), allowing the high-chlorine wastewater to be detected to enter a water collecting tank, standing, allowing large particles in the wastewater to sink to the bottom of the water collecting tank under the action of gravity, sequentially starting a first booster pump and a second electromagnetic valve, allowing the wastewater to enter a purifier through the first booster pump for filtering, completely intercepting fine suspended particles in the high-chlorine wastewater, allowing the purified high-chlorine wastewater to enter a pond to be detected, returning concentrated water into the water collecting tank through the second electromagnetic valve, and then closing the first booster pump; wherein the working pressure of the first booster pump is 0.1 MPa-2.5 MPa;
step (3), starting the burner and the detector in sequence for preheating, and preheating the burner to 300-500 ℃; cleaning the combustor, the cooling chamber and the detector by using air; then starting the transverse holder and the longitudinal holder, transferring the pre-selection electrode from the reference pool to the pool to be detected, performing pre-selection detection on the purified high-chlorine wastewater, and determining the content of chloride ions;
step (4) according to the pre-selection detection result in the step (3), high-chlorine wastewater is sucked from the pool to be detected by a sample injector and is injected into an atomizer, a combustion improver is introduced into the atomizer by a gas pump, the high-chlorine wastewater enters a combustor for combustion along with the combustion improver after being atomized, the generated high-temperature gas is cooled to be lower than 100 ℃ by a cooling chamber and then enters a detector for detection, and CO is obtained2Feeding back the detection data to the controller, and converting the COD value of the high-chlorine wastewater to be detected according to a standard curve; after the detection is finished, the induced draft fan exhausts gas, and the primary detection is finished; three parallel assaysTaking an average value;
step (5), closing the sample injector and the combustor in sequence, and closing the gas pump, the detector and the induced draft fan in sequence after the combustor is cooled; starting the transverse holder and the longitudinal holder, and transferring the preselected electrode from the pool to be detected to a reference pool for soaking; and then opening the first electromagnetic valve and the third electromagnetic valve in sequence, emptying the high-chlorine wastewater, and finishing the sample detection.
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