CN214880478U - Solution oxidation treatment device - Google Patents

Solution oxidation treatment device Download PDF

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CN214880478U
CN214880478U CN202021916363.7U CN202021916363U CN214880478U CN 214880478 U CN214880478 U CN 214880478U CN 202021916363 U CN202021916363 U CN 202021916363U CN 214880478 U CN214880478 U CN 214880478U
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electrolytic
reaction
tank
solution
oxidation
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叶旖婷
叶涛
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Abstract

The utility model discloses a solution oxidation treatment device, include: the reaction tank is used for containing reaction solution; the oxidation-reduction potential detection device is used for detecting the oxidation-reduction potential of the solution in the reaction tank; the oxidant storage tank is used for containing an oxidant which is added into the reaction tank and participates in the oxidation reaction; and the automatic detection feeding control device is used for controlling the amount of the oxidant in the oxidant storage tank added into the reaction tank according to the time and/or the result obtained by detecting the liquid in the reaction tank by the oxidation-reduction potential detection device. The device can shorten the oxidation treatment time of organic matters in the solution and/or the reductive waste liquid, ensure that the treatment solution is oxidized in safe production and the treatment effect reaches the standard.

Description

Solution oxidation treatment device
Technical Field
The utility model belongs to the chemical plant field, concretely relates to solution oxidation treatment device.
Background
In industrial production and waste liquid treatment, there is often a need to remove impurities and/or contaminants from solutions. Industrial waste liquids generally contain various pollutants harmful to human bodies or natural environments, and therefore, the waste liquids are discharged after being decomposed and/or separated from water by one or more treatment methods such as physical, chemical, biological and the like. In addition to industrial waste liquid treatment, the chemical industry also has a process for removing impurities from production raw materials, so as to avoid the influence of the impurities on the production quality when the production raw materials are used.
Organic toxic pollutants in industrial waste liquid are generally degraded by oxidation with strong oxidizing agents. In addition, the industrial waste liquid may contain some reducing substances which need to be removed by oxidation before complete treatment, such as compounds containing low-valent phosphorus. Fenton reaction is a method commonly used at present for the oxidative treatment of some reducing waste streams containing hypophosphorous acid and/or hypophosphites and/or phosphorous acid and/or phosphites and the like.
Phosphorus is a common chemical element in industry, and is often used in phosphorus chemical production and metal surface treatment. As excessive phosphorus and compounds thereof can destroy the ecological environment and bring harm to the human health, the current regulations limit the discharge standard of the phosphorus content of industrial waste liquid to be controlled below 0.3 ppm. At present, lime and the like are generally adopted in the industry to react with a Fenton reagent and phosphorus-containing waste liquid to enable phosphorus to become insoluble salt, and the insoluble salt is separated from water by adopting a method such as filtration and the like. If the discharge standard of the phosphorus content is reached, the low-valence phosphorus in the phosphorus-containing waste liquid needs to be oxidized to +5 valence to generate insoluble salt, so that the insoluble salt can be effectively separated and removed. However, taking the chemical nickel plating in the metal surface treatment as an example, the plating solution usually contains nickel sulfate, nickel acetate, etc. as main components, and further contains a reducing agent such as hypophosphite, sodium borohydride, borane, hydrazine, etc. and optionally various auxiliary agents to perform the chemical nickel plating operation. Although fenton reagent has strong oxidizability, when the fenton reagent is used for treating the chemical nickel plating waste liquid, the oxidation reaction time is quite long, and even the consumption is increased because hydrogen peroxide is required to be added continuously in the treatment process, so that the fenton reagent is not ideal as an oxidation treatment method of the reducing solution.
In a common process for removing impurities from production raw materials in the chemical industry, taking a current treatment method for removing organic impurities in industrial sulfuric acid as an example, compressed air is generally injected into an industrial sulfuric acid solution to be treated to stir and oxidize the industrial sulfuric acid solution. However, the method has long reaction time and is not suitable for large-scale production.
SUMMERY OF THE UTILITY MODEL
An object of the utility model is to provide a solution oxidation treatment device, the device can shorten and get rid of the organic matter in the solution and/or have its oxidation treatment time of reductive waste liquid, ensure that the processing solution obtains the safety in production oxidation and the treatment effect is up to standard.
The purpose of the utility model is realized through the following technical scheme:
a solution oxidation treatment apparatus comprising:
the reaction tank is used for containing reaction solution;
the oxidation-reduction potential detection device is used for detecting the oxidation-reduction potential of the solution in the reaction tank;
the oxidant storage tank is used for containing an oxidant which is added into the reaction tank and participates in the oxidation reaction;
and the automatic detection feeding control device is used for controlling the amount of the oxidant in the oxidant storage tank added into the reaction tank according to the time and/or the result obtained by detecting the liquid in the reaction tank by the oxidation-reduction potential detection device.
The reaction solution is a solution to be subjected to oxidation treatment, and comprises a solution to be subjected to organic matter removal/a reducing waste liquid/a solution to be subjected to ammonia nitrogen removal, or a mixed solution of the solution and inorganic acid and/or water.
The oxidant of the present invention can oxidize the solution contained in the reaction tank, preferably chlorine and/or peroxide and/or persulfate and/or hypochlorite and/or chlorate and/or perchlorate and/or permanganate and/or percarbonate and/or perborate, and the ratio of the chemical materials is not limited.
The principle of the utility model is as follows: after the oxidant is put into the solution in the reaction tank, the oxidation-reduction potential of the solution can be increased, even the irritant oxidizing gas can escape, so that the arrangement of the oxidation-reduction potential detection device can monitor in time. On the premise of safety, the oxidation-reduction potential of the solution in the reaction tank is controlled in a higher numerical range, and the solution is safely kept for a period of oxidation reaction time in the range, so that trace substances can be effectively oxidized. Wherein the higher the redox potential, the shorter the time required to achieve the same treatment effect. By maintaining and/or monitoring the oxidation-reduction potential of the solution containing the organic matters and/or ammonia nitrogen and/or having the reducing property in a high numerical range on the premise of safety, the oxidation reaction of the solution in the reaction tank can be accelerated under the safe production condition in the whole oxidation reaction process, so that the reaction time is shortened, and the oxidation treatment effect is ensured.
Particularly, when the solution to be treated contains a low-valence phosphorus compound, the oxidation-reduction potential of the solution needs to be maintained at a high value for a long time to completely oxidize the trace low-valence phosphorus compound, so that the trace low-valence phosphorus compound can be effectively removed by generating insoluble salts in the subsequent treatment. The utility model discloses the oxidation chemical reaction of low valence state phosphorus in the technological process of oxidation treatment phosphorus-containing solution is as follows:
PO2 3-+[O]→PO3 3-
PO3 3-+[O]→PO4 3-
and a feeding pump or a solid feeding device is arranged between the oxidant storage tank and the reaction tank, so that the feeding pump pumps the liquid oxidant in the oxidant storage tank into the reaction tank, or the solid feeding device feeds the solid oxidant in the oxidant storage tank into the reaction tank. Preferably, the feeding pump adopts a metering pump, so that the feeding amount of the liquid oxidant is more accurately controlled under the process control, and the oxidation reaction of the treatment liquid in the reaction tank is controlled and maintained within the safe and efficient process index range.
The utility model discloses optional embodiment includes:
(1) when the oxidant is liquid, the automatic detection feeding control device can be set to control the feeding pump, and automatically adjust the feeding flow of the feeding pump or control the starting or stopping of the feeding pump according to the time and/or the result obtained by detecting the liquid in the reaction tank by the oxidation-reduction potential detection device;
(2) when the oxidant is a solid, the automatic detection and feeding control device may be configured to control the solid feeding device, and automatically adjust the action of the solid feeding device to feed the solid oxidant in the oxidant storage tank into the reaction tank according to a time pattern and/or a result obtained by detecting the solution in the reaction tank by the oxidation-reduction potential detection device.
In order to make each component of the liquid in the reaction tank be uniformly distributed, the utility model discloses can the reaction tank in set up agitating unit. The stirring device can adopt any one of a liquid pipeline backflow stirring device, an impeller stirring device and a pneumatic stirring device or any combination thereof, the liquid pipeline backflow stirring device comprises a liquid outlet pipe, a backflow pipe, a controlled pump and/or a valve, and the pneumatic stirring device is equipment capable of introducing gas into the reaction tank to enable the solution in the reaction tank to flow and/or oxidize.
Preferably, the reaction tank and/or the oxidant storage tank is/are provided with a temperature heat exchanger, and the temperature heat exchanger can adjust the speed of the oxidation reaction in the reaction tank by regulating the temperature of the liquid in the reaction tank, or can conveniently prepare the oxidant in the oxidant storage tank by regulating the temperature of the oxidant storage tank.
Preferably, a tail gas treatment system is provided for treating tail gas generated during the oxidation reaction. The tail gas treatment system can be a combination of a tank cover air exhaust cover and a tail gas absorption treatment tank, and can also be a combination of the tank cover air exhaust cover, a vacuum jet device and/or a spraying device and the tail gas absorption treatment tank; the tank cover air exhaust cover is arranged above the reaction tank, and the tail gas absorption treatment tank is loaded with absorption reaction liquid for absorbing tail gas generated by the reaction tank; when the combination of the tank cover air exhaust cover and the reaction tank tail gas absorption treatment tank is used, the air outlet of the tank cover air exhaust cover is arranged in the absorption reaction liquid; when the combination of the tank cover air exhaust cover, the vacuum jet device and/or the spraying device and the tail gas absorption treatment tank is used, the air outlet of the tank cover air exhaust cover is connected with the air suction port of the vacuum jet device and/or the spraying device, and the liquid inlet of the vacuum jet device and/or the spraying device is connected with the tail gas absorption treatment tank through a pipeline; the absorption reaction liquid in the tail gas absorption treatment tank enters a vacuum jet device and/or a spraying device through a liquid inlet of the vacuum jet device and/or the spraying device, and then returns to the tail gas absorption treatment tank through a liquid outlet of the vacuum jet device and/or the spraying device, so that the tail gas generated by the reaction tank is absorbed into the absorption reaction liquid by the vacuum jet device and/or the spraying device to carry out gas-liquid mixed chemical reaction treatment; the absorption reaction liquid is liquid in the reaction tank and/or liquid to be oxidized, or mixed liquid of liquid in the reaction tank and/or liquid to be oxidized and inorganic acid and/or water, or inorganic acid aqueous solution or inorganic alkaline aqueous solution; the inorganic base contains at least one of hydroxide, carbonate and bicarbonate, and comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and the proportion of the inorganic bases is not limited.
More preferably, when the reaction tank is of a closed structure and is provided with an air outlet, the tail gas treatment system is arranged to connect the air outlet of the reaction tank with a vacuum jet device/tail gas absorption treatment tank of the tail gas treatment system through a pipeline.
More preferably, when the tail gas treatment system is a combination of a tank cover air exhaust cover and a tail gas absorption treatment tank, the tank cover air exhaust cover is provided with a centrifugal fan, so that the tail gas obtains kinetic energy and is directly injected into the absorption reaction liquid to carry out air floatation stirring, thereby accelerating the reaction.
Preferably, the tail gas is guided back to the reaction tank through a pipeline, and the tail gas is absorbed by the solution in the reaction tank. The tail gas escaping from the reaction tank usually contains more oxidizing gas, so that the production cost can be fully saved by directly pumping the oxidizing gas back into the reaction tank for recycling, and meanwhile, an air outlet is additionally arranged on the reaction tank and is used as an exhaust outlet of the secondary tail gas. The secondary tail gas contains fewer oxidizing substances and is easier to treat.
As an alternative embodiment, the tail gas treatment system is arranged in a multi-stage series connection mode so as to treat tail gas more thoroughly.
Preferably, a gas transmission device is arranged for introducing oxygen into the reaction tank. The oxygen source of the gas delivery device may be an external oxygen source and/or air. And oxygen is introduced into the reaction tank, so that the effects of oxidation and air-floating stirring of liquid in the reaction tank can be achieved. The more the oxygen is introduced, the faster the oxidation speed of the liquid in the reaction tank is, and the more uniform the stirring of the liquid in the reaction tank is.
The utility model discloses can also:
and a solution storage tank to be treated is arranged and used for storing the reaction solution to be treated.
A transfer tank is provided for storing the reaction solution to be treated or in-process.
And a solid-liquid separation device is arranged for carrying out solid-liquid separation on the reaction solution with solid precipitates or the reaction solution with the separated solids in the treatment process.
And arranging an acidity and/or pH value and/or liquid level detection device, wherein the acidity and/or pH value detection device detects the acidity value and/or the pH value of the reaction solution. In actual use, the materials are fed according to the detected values so as to adjust the acidity value and/or the pH value of the treatment liquid. The liquid level detection device is used for determining the liquid level of the treatment liquid in the equipment. In general, the higher the acidity of the solution, the stronger the oxidizing ability of the oxidizing agent, so that the efficiency of the oxidation treatment can be effectively improved by providing an acidity and/or pH detection device.
And arranging a chemical reaction performance improving device in the reaction tank, wherein the chemical reaction performance improving device comprises but is not limited to an ultrasonic generator and the like which can generate at least one of an acoustic field, an electric field, a magnetic field and a centrifugal force field in the reaction tank. When the chemical reaction performance improving device is an ultrasonic generator, the chemical reaction performance improving device can stir the chemicals in the reaction tank and accelerate the reaction, and at the moment, an additional stirring device is not needed.
The utility model discloses can further do following improvement:
the reaction tank is set as an electrolytic cell: arranging an electrolytic separator, an electrolytic anode, an electrolytic cathode and an electrolytic power supply, wherein the reaction tank is divided into an electrolytic anode area and an electrolytic cathode area, and the electrolytic anode and the electrolytic cathode are respectively arranged in the electrolytic anode area and the electrolytic cathode area;
the oxidation-reduction potential detection device is used for detecting the oxidation-reduction potential of the liquid in the electrolysis anode area and controlling the process;
the electrolytic power supply is provided with a current regulator, or a current regulator is additionally arranged to regulate the current output by the electrolytic power supply or control the on/off of the electrolytic power supply. The electrolytic power supply is connected with the automatic detection feeding control device, and the current output value of the current regulator is automatically adjusted according to time and/or the detection result of the oxidation-reduction potential detection device, or the electrolytic power supply is started or stopped.
Such an installation method enables the reaction tank to be changed into an electrolytic oxidation apparatus for treating the oxidation reaction of the reaction solution by electrochemically generating an oxidizing agent to accelerate and maintain a constant oxidizing agent concentration, and can reduce the amount of the oxidizing agent to be purchased. The electrolytic anode area and the electrolytic cathode area are respectively used for containing anolyte and catholyte; the reaction solution of the utility model is used as the anode electrolyte, and the aqueous solution of inorganic acid and/or inorganic alkali and/or soluble salt is used as the cathode electrolyte.
After the electrolysis power supply is started, the electrolysis anode and the electrolysis cathode are subjected to electrochemical reaction to generate oxygen on the electrolysis anode and hydrogen on the electrolysis cathode, and when the electrolyte contains metal ions, oxidation-reduction reaction of the metal ions can also occur on the electrolysis electrode. The oxygen generated on the electrolysis anode is dissolved in the anolyte and can play the same role as the oxygen is introduced into the reaction tank.
In the electrolytic process, when the anolyte contains sulfate radicals, persulfate with strong oxidizing property can be generated in the anolyte, so that the content of an oxidant in the anolyte is further increased to accelerate the oxidation reaction. The specific electrochemical equation is as follows: 2SO4→S2O8 2-+2e-. The anode electrolysisThe sulphate contained in the liquor may be the sulphate it originally contained, may be from sulphuric acid and/or sulphate otherwise added to the anolyte, may be from sulphate generated by a chemical reaction of persulphuric acid and/or persulphate added to the anolyte, or may be sulphate originally present in the catholyte and passing through the electrolytic separator into the anolyte.
In the electrolysis process, when the anolyte contains chloride ions, chlorine gas can be generated on the electrolysis anode. Chlorine gas itself has strong oxidizing property, and hypochlorite having stronger oxidizing property can be generated after the chlorine gas is dissolved in water. Specifically, the electrochemical equation for the conversion of chloride ions to chlorine gas is: 2Cl-→Cl2+2e-(ii) a The chlorine gas can generate hypochlorous acid and hydrochloric acid when dissolved in water, and the chemical reaction formula is as follows: cl2+H2O → HClO + HCl. Hypochlorous acid possesses a stronger oxidizing property than oxygen, and thus can further accelerate the oxidation reaction of the anolyte. The chloride ions contained in the anolyte may be chloride ions originally contained therein, may be chloride ions derived from hydrochloric acid and/or chloride salts additionally added to the anolyte, may be chloride ions generated by chemical reaction of chlorine gas and/or hypochlorous acid and/or hypochlorite and/or chloric acid and/or chlorate and/or perchloric acid and/or perchlorate added to the anolyte, and may also be chloride ions originally present in the catholyte and entering the anolyte through the electrolytic separator.
Because the electrolytic oxidation device can generate oxidizing gas or oxidize low-valence metal ions at the electrolytic anode in the electrolytic process, the reaction tank can be considered to be combined with the oxidant storage tank, and the input of the oxidant can be reduced or even avoided. When the oxidant is not needed to be added additionally, an oxidant storage tank is not needed to be arranged additionally.
The device of the utility model can also be used for the electrolytic cathode area to set up a hydrogen discharge system for the hydrogen generated by the electrolytic reaction in the suction and discharge electrolytic cathode area is avoided the hydrogen to accumulate and bring the production potential safety hazard. The hydrogen gas discharge system can adopt an explosion-proof air draft system meeting the requirement, and can also adopt a simple directly connected exhaust pipeline for high-altitude direct discharge.
Preferably, the electrolytic anode region and/or the electrolytic cathode region is provided with an electrolyte detection device, and the electrolyte detection device comprises at least one detection device selected from a liquid level meter, a specific gravity meter, an acidimeter, an oxidation-reduction potentiometer, a photoelectric color comparator and a pH meter, so as to detect corresponding parameters in the anolyte and/or the catholyte and perform control management.
More preferably, the automatic detection and feeding control device is configured to automatically feed chemical raw materials and/or water to the anolyte and/or catholyte according to time and/or real-time parameters of the anolyte and catholyte.
Preferably, the electrolysis power supply adopts a pulse electrolysis power supply, when sludge is generated in the reaction solution in the treatment process, the electrolysis operation can be operated intermittently by using pulse output current, and the generated mucosa sludge is dissolved and falls off from the electrolysis separator in the period of short stopping the action of the electric field. When the utility model discloses a device adopts tail gas processing system simultaneous processing during the tail gas in electrolysis anode region and electrolysis cathode region, the exhaust hood selects to correspond the pipeline and separately extracts according to the tail gas of electrolysis anode region or electrolysis cathode region effusion, the gas outlet of exhaust hood all does the processing through spray set and/or vacuum fluidic device, spray set and/or vacuum fluidic device set up tail gas absorption cistern, and pass through tail gas absorption liquid in the tail gas absorption cistern carries out the chemical reaction to gas and absorbs.
When the device of the utility model contains the gas transmission device, the gas transmission device is arranged to transmit oxygen to the anolyte and/or catholyte. Preferably, the gas transmission device comprises at least one tank which is arranged independently and is connected with the electrolysis anode area or the electrolysis cathode area to form a circulation loop, so that the anolyte or the catholyte circularly flow in the electrolysis anode area or the electrolysis cathode area and the tank and are oxidized. The tank is provided with a vacuum jet device and/or a spray pipeline type chemical reaction device and/or a gas booster to introduce oxygen into the anolyte and/or the catholyte in the tank. When the catholyte contains variable valence metal ions and the gas transmission device acts on the electrolysis cathode area, the low valence metal ions in the catholyte can be subjected to oxidation reaction, so that hydrogen gas electrolysis on the electrolysis cathode is effectively reduced or prevented. More preferably, chemical feed materials and/or water are added to the anolyte and/or catholyte in the tank.
In order to avoid the electrolytic separator being an anionic membrane or a bipolar membrane and the anolyte containing copper ions and/or iron ions when the separator is easily clogged by metal mud, the utility model discloses can preferably, will the electrolytic separator adopt two-layer anion exchange membrane or constitute the combined type electrolysis trough that three cell bodies combine by one deck bipolar membrane and one deck anion exchange membrane, including electrolysis anode area, electrolysis cathode area, and be located the electrolysis buffer zone between electrolysis anode area and the electrolysis cathode area. The electrolytic buffer solution contained in the electrolytic buffer zone is an aqueous solution which does not contain copper ions or iron ions and contains inorganic acid.
The reason why the electrolytic separator is an anionic membrane or a bipolar membrane, the separator is easily clogged with the metal hydroxide slime when the anolyte contains copper ions and/or iron ions and no electrolytic buffer is provided is that: when the electrolysis separator adopts an anion exchange membrane, if hydrogen is generated on the electrolysis cathode and the catholyte is neutral or alkaline, hydroxide ions generated on the electrolysis cathode and/or original hydroxide ions of the catholyte can enter the electrolysis anode region through the anion exchange membrane; when the electrolytic separator is a bipolar membrane, the hydroxide ions generated on the bipolar membrane are directed into the electrolytic anode zone. Once the hydroxide ions enter the electrolytic anode area, they react with copper ions and/or iron ions and form a sludge deposit of copper hydroxide and/or iron hydroxide on the electrolytic separator, and the accumulation of sludge causes clogging of the separator and affects the progress of the electrolytic reaction. When the electrolytic separator is clogged over a large area with said metal sludge, the electrolytic separator must be cleaned or even replaced. It can be seen that the problem of clogging of the electrolytic separators with metal sludge causes a reduction in the service life of the separators, with an inevitable increase in production costs. An electrolysis buffer zone is arranged between the electrolysis anode zone and the electrolysis cathode zone, so that hydroxyl ions are subjected to neutralization reaction with hydrogen ions of inorganic acid in the buffer electrolyte before entering the electrolysis anode zone, the direct contact of the hydroxyl ions with copper ions and/or iron ions in the electrolysis anode zone can be effectively reduced, and further the blockage of metal mud formed on an electrolysis separator is avoided, so that the electrolysis reaction is stable, and the production cost is saved.
As an alternative embodiment, a replenishment solution storage tank is provided for holding a replenishment solution for the catholyte or anolyte or buffer solution to facilitate replenishment of the catholyte or anolyte or buffer solution.
The utility model discloses can also further make following improvement: add chemical analysis check out test set, it is right that reaction solution/anolyte do chemical analysis and detect, it is right the utility model discloses the device carry out process control.
As an embodiment of the present invention:
(1) the electrolytic anode is insoluble electrode. The insoluble electrode can be conductive graphite, bare metal, metal electrode with electrolytic coating or inert metal plating on the surface, other conductive objects or any combination of the above electrodes which can allow current to pass through.
When the electrolytic anode is a bare metal in an insoluble electrode, the metal may be any one of platinum, gold, an alloy containing platinum and/or gold; when the electrolytic anode is a metal electrode with an insoluble electrode, the surface of which is coated with an electrolytic coating or plated with an inert metal, the metal can be any one of titanium, platinum, gold, silver, copper and iron, or an alloy containing at least one of the metals, and can also be stainless steel; the inert metal includes but is not limited to platinum, gold; when the electrolytic anode is other conductive objects, the electrolytic anode can be a non-metallic object with a conductive coating or an inert metal plated on the surface.
(2) The electrolytic cathode is an insoluble electrode. The insoluble anode can be conductive graphite, bare metal, metal electrode coated with inert metal, other conductive object coated with inert metal and capable of passing current, or any combination of the above electrodes.
When bare metal, the metal can be any one of platinum, gold, copper, stainless steel or an alloy containing at least one of the above metals, the selection range of the metal also includes titanium and an alloy containing titanium when the catholyte does not contain sulfuric acid, and the selection range of the metal also includes an iron alloy when the catholyte is neutral or alkaline; when the metal is a metal electrode plated with inert metal on the surface, the metal can be any one of titanium, platinum, gold, silver, copper, iron and aluminum, or an alloy containing at least one of the metals, and can also be stainless steel; the surface inert metal comprises but is not limited to platinum and gold, and the inert metal which can be adopted when the catholyte does not contain sulfuric acid also comprises titanium; when the electrolytic cathode is other conductive objects, the electrolytic cathode can be a non-metallic object with a conductive coating or a metal plated surface.
The electrolytic separator can adopt filter cloth, ceramic filter plate, PE filter plate, electrolytic diaphragm and other materials which can separate the electrolytic anode area and the electrolytic cathode area of the reaction tank, but can not completely block the charge transfer in the solution under the action of an electric field, and the electrolytic diaphragm includes but is not limited to nonselective electrolytic diaphragm, anion exchange membrane, cation exchange membrane and bipolar membrane.
The bipolar membrane is a special ion exchange membrane and is an anion-cation composite membrane prepared by compounding a cation exchange membrane and an anion exchange membrane. Under the action of DC electric field, water (H) between the anion and cation exchange membranes2O) will dissociate into hydrogen ions (H)+) And hydroxide ion (OH)-) And passing through anion exchange membrane and cation exchange membrane, respectively, as H in electrolyte+And OH-An ion source. Along with the progress of the electrolysis reaction, hydrogen ions generated on the bipolar membrane enter the electrolysis cathode area and are separated out as hydrogen gasThe resulting hydroxide ions then enter the electrolytic anode region and an oxidant is generated in the anolyte.
Compared with the prior art, the utility model discloses following beneficial effect has:
1. the device of the utility model has simple system structure and safe and reliable production process;
2. the process of the utility model can shorten the oxidation treatment time of the treated liquid, and particularly can obviously improve the production efficiency when being applied to oxidizing trace substances;
3. the device of the utility model can combine the electrochemical oxidation and the chemical reaction oxidation, and has low manufacturing cost and low operation cost.
4. The device and the process equipment of the utility model have wide application market.
Drawings
The present invention will be further described with reference to the accompanying drawings.
FIG. 1 is a schematic view of a solution oxidation treatment apparatus according to embodiment 1 and embodiment 14 of the present invention.
FIG. 2 is a schematic view of a solution oxidation treatment apparatus according to embodiment 2 of the present invention.
FIG. 3 is a schematic view of a solution oxidation treatment apparatus according to embodiment 3 of the present invention.
FIG. 4 is a schematic view of a solution oxidation treatment apparatus according to embodiment 4 of the present invention.
FIG. 5 is a schematic view of a solution oxidation treatment apparatus according to embodiment 5 of the present invention.
Fig. 6 is a schematic view of a solution oxidation treatment apparatus according to embodiment 6 of the present invention.
FIG. 7 is a schematic view of a solution oxidation treatment apparatus according to embodiment 7 of the present invention.
FIG. 8 is a schematic view of a solution oxidation treatment apparatus according to embodiment 8 of the present invention.
FIG. 9 is a schematic view of a solution oxidation treatment apparatus according to example 9 of the present invention.
FIG. 10 is a schematic view of a solution oxidation treatment apparatus according to embodiment 10 of the present invention.
FIG. 11 is a schematic view of a solution oxidation treatment apparatus according to example 11 of the present invention.
FIG. 12 is a schematic view of a solution oxidation treatment apparatus according to example 12 of the present invention.
FIG. 13 is a schematic view of a solution oxidation treatment apparatus according to example 13 of the present invention.
Reference numerals: 1-a reaction tank; 2-an oxidant storage tank; 3-a redox detection device; 4-a stirring device; 5-a temperature heat and cold exchanger; 6-a source of oxygen; 7-a tank cover air extraction cover; 8-tail gas absorption treatment tank; 9-centrifugal fan; 10-a liquid storage tank to be treated; 11-automatic detection and feeding control device; 12-a vacuum fluidic device; 13-an electrolytic separator; 14-an electrolytic anode; 15-an electrolytic cathode; 16-an electrolytic power supply; 17-catholyte detection means; 18-a hydrogen gas discharge system; 19-a current regulator; 20-material inlet and outlet; 21-air outlet; 22-a valve; 23-a chemical assay detection device; 24-a make-up fluid reservoir; 25-a transit trough; 26-a solid-liquid separation device; 27-a detection device; 28-an electrolytic buffer zone; 29-water source valve; 30-a chemical reaction performance improving device; 31-a gas transmission device; 32-solid material feeding device; p-pump.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
As shown in fig. 1, in order to implement the liquid oxidation treatment apparatus of the present invention, the liquid oxidation treatment apparatus comprises a reaction tank 1, an oxidant storage tank 2, an oxygen reduction potential detection device 3, and an automatic detection and feeding control device 11, wherein:
the reaction tank 1 is used for containing a reaction solution and carrying out oxidation treatment on the reaction solution, the reaction solution contains organic pollutants in the embodiment, and specifically, the reaction tank is used for cleaning circuit board wastewater in a process of carrying out copper surface treatment on a circuit board by using sulfuric acid hydrogen peroxide type microetching solution in circuit board production.
The oxidant storage tank 2 is used for containing an oxidant, and the oxidant is a sodium hypochlorite solution;
the probe of the oxidation-reduction potential detection device 3 is arranged in the reaction solution in the reaction tank;
the automatic detection and feeding control device 11, based on the result obtained by the detection of the oxidation-reduction potential detection device 3, performs automatic control and feeding pump to feed the oxidant in the first oxidant storage tank into the first reaction tank and the second reaction tank, and performs automatic control and feeding pump to feed the oxidant in the second oxidant storage tank into the third reaction tank according to the time program.
In this example, the COD of the board-washing wastewater produced during the production of the sulfuric acid hydrogen peroxide type microetching solution for treating the copper surface of the circuit board was 2000 ppm. The COD of the reaction solution was maintained at 1100mV or more during the treatment, which was 30 hours in total. The COD of the reaction solution was determined to be 250ppm by sampling after the treatment.
Example 2
As shown in fig. 2, it is the embodiment of the liquid oxidation treatment device of the present invention, which is composed of a reaction tank 1, an oxidant storage tank 2, an oxidation-reduction potential detection device 3, an automatic detection feeding control device 11, a stirring device 4, a temperature heat and cold exchange device 5, an oxygen source 6, a tail gas treatment system, and a solution storage tank 9 to be reacted, wherein:
the reaction tank 1 is used for containing a reaction solution and carrying out oxidation treatment on the reaction solution, and is provided with a stirring device 4 and a temperature heat exchange device 5, wherein the reaction solution is a mixture of organic waste liquid, reductive phosphorus-containing waste liquid, organic acid and water, and the stirring device 4 is a liquid pipeline backflow stirring device;
the oxidant storage tank 2 is used for containing an oxidant and is connected with the reaction tank 1 through a pipeline and a feeding pump, and the oxidant is hydrogen peroxide;
a probe of the oxidation-reduction potential detection device 3 is arranged in the reaction solution in the reaction tank 1;
an automatic detection and feeding control device 11 for automatically controlling feeding according to a time program
Adding the solid oxidant in the oxidant storage tank 2 into the reaction tank 1 by a pump;
the oxygen source is used for introducing oxygen into the reaction tank 1;
the tail gas treatment system is a combination of a tank cover air exhaust cover 7 and a tail gas absorption treatment tank 8, the tank cover air exhaust cover 7 is provided with a centrifugal fan 9 and is arranged above the reaction tank, the tail gas absorption treatment tank 8 is loaded with absorption reaction liquid for absorbing tail gas generated by the reaction tank 1, the absorption reaction liquid is a mixture of organic waste liquid to be treated, reductive phosphorus-containing waste liquid, organic acid and water, and an air outlet of the tank cover air exhaust cover 7 is inserted into the absorption reaction liquid through a pipeline of the tank cover air exhaust cover 7 and the fan;
the to-be-reacted solution storage tank 10 is used for holding a liquid to be subjected to oxidation treatment.
In this example, the COD of the reaction solution before oxidation treatment was 3700ppm, and the phosphorus content of the solution was 1900ppm because it contained reducing phosphorus. The treatment time was 26 hours in total. And controlling the oxidation-reduction potential of the reaction solution in the reaction tank to be not less than 800mV within a period of time in the reaction process. COD of the reaction solution was measured by sampling after oxidation treatment to be 60ppm, and phosphorus content was measured by sampling after conventional dephosphorization to be 0.3 ppm.
Example 3
As shown in fig. 3, for the embodiment of the liquid oxidation treatment device of the present invention, it is composed of a reaction tank 1, an oxidant storage tank 2, an oxidation-reduction potential detection device 3, a stirring device 4, a temperature heat exchanger 5, an automatic detection feeding control device 11, a tail gas treatment system, a solid-liquid separation device 26, a chemical reaction performance improvement device 30, a valve 22 and a pump, wherein:
the reaction tank 1 is used for containing and treating a reaction solution and is provided with a stirring device 4, a temperature cold and heat exchange device 5, a material inlet and outlet, a gas outlet and a chemical reaction performance improving device 30, wherein the reaction solution is alkaline film removing waste liquid with organic film dry film components dissolved in a circuit board, the stirring device 4 is a pneumatic stirring device and an impeller stirring device, and the chemical reaction performance improving device 30 is an ultrasonic generator;
the oxidant storage tank 2 is used for containing an oxidant, and the oxidant is a mixture of solid sodium percarbonate and sodium perborate;
the probe of the oxidation-reduction potential detection device 3 is arranged in the reaction solution in the reaction tank;
an automatic detection feeding control device 11 for automatically controlling feeding equipment to feed the solid oxidant in the oxidant storage tank 2 into the reaction tank according to the time program and the result obtained by the detection of the oxidation-reduction potential detection device 3;
the tail gas treatment system is a combination of a tank cover air exhaust cover 7, a vacuum jet device 12 and a tail gas absorption treatment tank 8, the first-stage tail gas treatment system in the embodiment directly adopts the reaction tank 1 as the tail gas absorption treatment tank 8 to carry out primary tail gas treatment, and liquid in the reaction tank 1 is used as absorption reaction liquid for absorbing tail gas generated by the reaction tank 1; the tank cover air exhaust cover 7 is arranged above the reaction tank, the air outlet of the tank cover air exhaust cover 7 is connected with the air suction port of the vacuum jet device 12, the liquid inlet of the vacuum jet device 12 is connected with the reaction tank, the liquid in the reaction tank 1 enters the vacuum jet device 12 through the liquid inlet of the vacuum jet device 12, and then the liquid returns to the reaction tank 1 from the liquid outlet after the gas-liquid mixing reaction by the vacuum jet device 12; and the other gas outlet of the reaction tank 1 in the second-stage tail gas treatment system is inserted into a tail gas absorption treatment tank of the second-stage tail gas treatment system through a pipeline to carry out secondary treatment on the tail gas.
In this example, the COD of the reaction solution before the oxidation treatment was 28000ppm, and the treatment was carried out twice in total. The oxidation treatment time for the first addition of the oxidizing agent is 5 hours, the oxidation-reduction potential of the reaction solution in the reaction tank is controlled to not less than 900mV during the reaction, and the chemical reaction performance improving apparatus 30 is started to accelerate the chemical reaction. After the time, use sulphuric acid to adjust the pH value of the reaction solution who has accomplished the first treatment process to pH2 and have solid in this liquid and precipitate out, carry out sample detection to gained clear solution after solid-liquid separation and record its COD and be 8700ppm, resume afterwards to adopt the utility model discloses an equipment carries out the second time to the clear solution that solid-liquid separation gained and throws oxidant oxidation treatment. The duration of the second oxidation treatment was 15 hours, during which the oxidation-reduction potential of the reaction solution was controlled to not less than 1100 mV. And (3) after the second oxidation treatment is finished, adjusting the pH value of the reaction solution after the second treatment to be neutral by using inorganic base, separating out solids in the solution again, carrying out solid-liquid separation, detecting the filtered clear liquid, and measuring the COD of the clear liquid to be 275 ppm.
Example 4
As shown in fig. 4, which is an embodiment of the liquid oxidation treatment apparatus of the present invention, it is composed of a reaction tank 1, two oxidant storage tanks 2, an oxygen reduction potential detection apparatus 3, a detection apparatus 27, an automatic detection feeding control apparatus 11, a tail gas treatment system and two supplementary liquid storage tanks 24, wherein:
the reaction tank 1 is an electrolysis device, and is internally provided with an electrolysis separator 13, an electrolysis anode 14, an electrolysis cathode 15 and an electrolysis power supply 16; the electrolytic partition 13 divides the reaction tank 1 into an electrolytic anode area and an electrolytic cathode area, the electrolytic anode area and the electrolytic cathode area are respectively used for containing an anolyte and a catholyte, the anolyte is a reaction solution, the reaction solution in the embodiment is a chemical nickel deposition waste liquid, and the catholyte is an aqueous solution of hydrochloric acid and soluble chloride; the electrolytic anode 14 and the electrolytic cathode 15 are insoluble electrodes and are respectively connected with the anode and the cathode of an electrolytic power supply 16, and the electrolytic anode 14 and the electrolytic cathode 15 are respectively arranged in an electrolytic anode area and an electrolytic cathode area; the electrolysis power supply 16 is a pulse power supply;
the two oxidant storage tanks 2 are used for containing an oxidant, wherein the oxidant in one oxidant storage tank 2 is a sodium hypochlorite solution and is connected with the reaction tank 1 through a pipeline and a feeding pump, the other oxidant storage tank 2 is internally provided with hydrochloric acid and solid sodium chlorate and controls the reaction to prepare chlorine, the oxidant storage tank 2 is connected with a pipeline with a controlled valve 22, and the pipeline is inserted into the reaction solution in the reaction tank 1;
a probe of the oxidation-reduction potential detection device 3 is arranged in the reaction solution in the reaction tank 1;
the probe groups of the two detection devices 27 are respectively arranged in the solutions in the electrolytic anode region and the electrolytic cathode region;
the replenisher liquid storage tanks 24 are respectively used for containing a replenisher liquid taking an aqueous solution with main components of hydrochloric acid and soluble chloride as a catholyte and a replenisher liquid taking a reaction solution as an anolyte, and the replenisher liquid storage tanks 24 are respectively connected with an electrolysis anode region and an electrolysis cathode region of the reaction tank 1 through pipelines, pumps and valves;
an automatic detection feeding control device 11 for automatically controlling the start or stop of the feeding pump of the liquid oxidant storage tank 2 and the opening or closing or flow of the valve of the gas oxidant storage tank according to the time program and the detection result of the oxidation-reduction potential detection device, automatically controlling the start or stop of the pump of the anolyte make-up liquid storage tank 2 and automatically controlling the current regulator 19 of the electrolysis power supply 16 to regulate the electrolysis current according to the detection result of the detection device of the electrolysis anode region, and automatically controlling the start or stop of the pump of the catholyte make-up liquid storage tank 24 and automatically controlling the current regulator 19 of the electrolysis power supply 16 to regulate the electrolysis current according to the detection result of the detection device of the electrolysis cathode region;
the tail gas treatment system is a combination of a tank cover exhaust hood 7, a vacuum jet device 12 and a tail gas absorption treatment tank 8, the tail gas absorption treatment tank 8 is loaded with absorption reaction liquid for absorbing tail gas generated by the reaction tank 1, and the absorption reaction liquid is inorganic alkaline water solution; the cover air exhaust cover 7 is arranged above the anode area of the electrolysis, the air outlet of the cover air exhaust cover 7 is connected with the air suction port of the vacuum jet device 12, the liquid inlet of the vacuum jet device 12 is connected with the tail gas absorption treatment tank 8, the absorption reaction liquid in the tail gas absorption treatment tank 8 enters the vacuum jet device 12 through the liquid inlet of the vacuum jet device 12, and then returns to the tail gas absorption treatment tank 8 from the liquid outlet of the vacuum jet device 12 after gas-liquid mixing reaction.
In this example, the reaction solution contained reducing phosphorus before the oxidation treatment, and the phosphorus content of the solution was 3000ppm, and the treatment process used both electrochemical oxidation and chemical oxidation, with a total treatment time of 18 hours. And controlling the oxidation-reduction potential of the reaction solution in the reaction tank to be not less than 1300mV within a period of time in the reaction process. After the treatment, the treated solution was subjected to conventional dephosphorization treatment, and then the phosphorus content of the reaction solution was measured by sampling and found to be 0.2 ppm.
Example 5
As shown in fig. 5, which is an embodiment of the liquid oxidation treatment device of the present invention, the liquid oxidation treatment device comprises a reaction tank 1, an oxidant storage tank 2, an oxygen reduction potential detection device 3, an automatic detection feeding control device 11 and a tail gas treatment system, wherein:
the reaction tank 1 is an electrolysis device, and is internally provided with an electrolysis separator 13, an electrolysis anode 14, an electrolysis cathode 15, an electrolysis power supply 16, a cathode electrolyte detection device 17, a hydrogen gas discharge system 18 and a current regulator 19; the electrolytic partition 13 is a bipolar membrane, which divides the reaction tank 1 into an electrolytic anode area and an electrolytic cathode area, the electrolytic anode area and the electrolytic cathode area are used for respectively holding anolyte and catholyte, the anolyte is a reaction solution, the reaction solution in this embodiment is organic waste liquid, and the catholyte is an aqueous solution of electrolyte; the current regulator 19 is connected with an electrolysis power supply 16, the electrolysis anode 14 and the electrolysis cathode 15 are insoluble electrodes and are respectively connected with the anode and the cathode of the electrolysis power supply, and the electrolysis anode 14 and the electrolysis cathode 15 are respectively arranged in the electrolysis anode area and the electrolysis cathode area; the hydrogen discharge system is an explosion-proof air draft system and is arranged above the electrolytic cathode region;
the oxidant storage tank 2 is used for containing an oxidant and is connected with the reaction tank 1 through a pipeline and a feeding pump, and the oxidant is a mixed solution of potassium permanganate and sodium permanganate;
a probe of the oxidation-reduction potential detection device 3 is arranged in the reaction solution in the reaction tank 1;
the automatic detection feeding control device 11 is used for automatically adjusting the flow of the feeding pump according to the detection result of the oxidation-reduction potential detection device;
the current regulator 19 controls the start or stop of the electrolysis power supply 16 according to time;
the tail gas treatment system is a combination of a tank cover exhaust hood 7, a vacuum jet device 12 and a tail gas absorption treatment tank 8, the tail gas absorption treatment tank 8 is loaded with absorption reaction liquid for absorbing tail gas generated by the reaction tank 1, and the absorption reaction liquid is inorganic acid aqueous solution; the reaction tank 1 top is located to the capping suction hood 7, and the gas outlet of capping suction hood 7 links to each other with the induction port of vacuum fluidic device 12, and the income liquid mouth of vacuum fluidic device 12 links to each other with tail gas absorption treatment tank 8, and absorption reaction liquid in the tail gas absorption treatment tank 8 passes through the income liquid mouth of vacuum fluidic device 12 and gets into vacuum fluidic device 12, then returns in the tail gas absorption treatment tank 8 through the liquid outlet of vacuum fluidic device 12.
In this example, the COD of the reaction solution before the oxidation treatment was 11000 ppm. The electrochemical oxidation reaction and the chemical oxidation reaction are simultaneously adopted in the treatment process, the treatment time is 16 hours in total, and the oxidation-reduction potential of the reaction solution in the anode region of the reaction tank is controlled to be not less than 1100mV within a period of time in the reaction process. After the treatment, a sample was taken to determine the COD of the reaction solution to be 70 ppm. When the reaction solution contains heavy metal ions to be treated, the treatment can be carried out by adopting a conventional method for removing the heavy metal ions before or after the treatment of the equipment.
Example 6
As shown in fig. 6, which is an embodiment of the liquid oxidation treatment apparatus of the present invention, the liquid oxidation treatment apparatus comprises a reaction tank 1, an oxidant storage tank 2, an oxygen reduction potential detection device 3, an automatic detection feeding control device 11, a tail gas treatment system, a transfer tank 25 and a solid-liquid separation device 26, wherein:
the reaction tank 1 is an electrolysis device, and is internally provided with an electrolysis separator 13, an electrolysis anode 14, an electrolysis cathode 15, an electrolysis power supply 16, a cathode electrolyte detection device 17 and a hydrogen discharge system 18; the electrolytic separator 13 divides the reaction tank 1 into an electrolytic anode area and an electrolytic cathode area, the electrolytic anode area and the electrolytic cathode area are respectively used for containing an anolyte and a catholyte, the anolyte is a reaction solution, the reaction solution in the embodiment is a pretreated acidic clear liquid obtained by mixing, reacting and filtering the circuit board organic amine alkaline stripping waste liquid and sulfuric acid, and the catholyte is hydrochloric acid; the electrolytic anode 14 and the electrolytic cathode 15 are insoluble electrodes and are respectively connected with the anode and the cathode of an electrolytic power supply 16, and the electrolytic anode 14 and the electrolytic cathode 15 are respectively arranged in an electrolytic anode area and an electrolytic cathode area; the hydrogen discharge system is a direct exhaust pipeline and is arranged above the electrolytic cathode region;
the oxidant storage tank 2 is used for containing an oxidant, and the oxidant is a mixed solution of magnesium perchlorate, potassium perchlorate and sodium perchlorate;
the probe of the oxidation-reduction potential detection device 3 is arranged in the reaction solution in the electrolysis anode area;
an automatic detection and feeding control device 11 for automatically feeding a mixed liquid of chemical raw materials and water into the catholyte according to the time and the detection result of the catholyte detection device 17, automatically feeding an oxidant into the anolyte according to the detection result of the oxidation-reduction potential device 3, and automatically controlling a current regulator 19 of an electrolysis power supply 16 to adjust the electrolysis current;
the tail gas treatment system is a combination of a tank cover exhaust hood 7, a vacuum jet device 12 and a tail gas absorption treatment tank 8, the tail gas absorption treatment tank 8 is loaded with absorption reaction liquid for absorbing tail gas generated by the reaction tank 1, and the absorption reaction liquid is a mixed liquid of a solution to be reacted and the reaction solution; the tank cover air exhaust cover 7 is arranged above the reaction tank 1, the air outlet of the tank cover air exhaust cover 7 is connected with the air suction port of the vacuum jet device 12, the liquid inlet of the vacuum jet device 12 is connected with the tail gas absorption treatment tank 8, the absorption reaction liquid in the tail gas absorption treatment tank 8 enters the vacuum jet device 12 through the liquid inlet of the vacuum jet device 12, and then returns to the tail gas absorption treatment tank 8 from the liquid outlet thereof through the vacuum jet device 12 by gas-liquid mixing reaction;
the transfer tank 25 is used to temporarily store the reaction solution after the oxidation treatment is completed.
In this example, the COD of the reaction solution before the oxidation treatment was 24000 ppm. The treatment time is 36 hours in total, the whole reaction process is to oxidize the reaction solution by chemical oxidation reaction generated by adding oxidant and electrochemical oxidation reaction generated by electrolysis, and the oxidation-reduction potential of the reaction solution is controlled to be not less than 1200mv in the process. After the oxidation treatment is finished, the treatment solution is pumped out from the anode area of the electrolytic cell to a transfer tank, and then inorganic alkali is added into the transfer tank to adjust the pH value of the solution to be neutral. The solid-liquid separation was carried out again because of the precipitation of the solid. Sampling of the obtained filtrate revealed that the COD of the obtained clear solution was 70 ppm.
Example 7
As shown in fig. 7, in order to implement the embodiment of the liquid oxidation treatment apparatus of the present invention, it is composed of a reaction tank 1, an oxidant storage tank 2, an oxygen reduction potential detection device 3, a stirring device 4 and an automatic detection feeding control device 11, wherein:
the reaction tank 1 is an electrolysis device, and is internally provided with an electrolysis separator 13, an electrolysis anode 14, an electrolysis cathode 15, an electrolysis power supply 16, a cathode electrolyte detection device 17 and a hydrogen discharge system 18; the electrolytic separator 13 is a bipolar membrane, which divides the reaction tank 1 into an electrolytic anode area and an electrolytic cathode area, the electrolytic anode area and the electrolytic cathode area are used for respectively holding anolyte and catholyte, the anolyte is a reaction solution, the reaction solution contains organic impurities and is specifically an aqueous solution of industrial dilute sulfuric acid in the embodiment, and the catholyte is water; the electrolytic anode 14 and the electrolytic cathode 15 are insoluble electrodes and are respectively connected with the anode and the cathode of an electrolytic power supply 16, and the electrolytic anode 14 and the electrolytic cathode 15 are respectively arranged in an electrolytic anode area and an electrolytic cathode area; the hydrogen discharge system is a direct exhaust pipeline and is arranged above the electrolytic cathode region; the electrolysis power supply 16 is a pulse power supply;
the oxidant storage tank 2 is used for containing an oxidant, and the oxidant is a hydrogen peroxide solution;
a probe of the oxidation-reduction potential detection device 3 is arranged in the reaction solution in the reaction tank 1;
the automatic detection feeding control device 11 automatically feeds water into the catholyte according to the detection result of the catholyte detection device 17, automatically feeds an oxidant into the anolyte according to the detection result of the oxidation-reduction potential device 3, and automatically controls a current regulator 19 of the electrolysis power supply 16 to adjust the electrolysis current and stop the electrolysis.
In this example, the COD of the reaction solution before the oxidation treatment was 4600 ppm. The treatment time was 13 hours in total, and the COD of the reaction solution was measured by sampling after the treatment to be 370 ppm. The scheme of the embodiment can rapidly produce and purify industrial sulfuric acid.
Example 8
As shown in fig. 8, which is an embodiment of the liquid oxidation treatment apparatus of the present invention, it is composed of a reaction tank 1, an oxidant storage tank 2, an oxygen reduction potential detection device 3, an automatic detection feeding control device 11 and a chemical analysis detection device 23, wherein:
the reaction tank 1 is an electrolysis device, and is internally provided with an electrolysis separator 13, an electrolysis anode 14, an electrolysis cathode 15, an electrolysis power supply 16, a cathode electrolyte detection device 17 and a hydrogen discharge system 18; the electrolytic partition 13 is an anionic membrane which divides the reaction tank 1 into an electrolytic anode region and an electrolytic cathode region for holding an anolyte and a catholyte, respectively; the anolyte is a reaction solution, the reaction solution in the embodiment is an aqueous solution containing organic impurities obtained after organic waste gas in a silk-screen workshop of a circuit board factory is subjected to gas-liquid mixing through a jet flow absorption tower, and the catholyte is a mixed solution of sulfuric acid and sodium sulfate; the electrolytic anode 14 and the electrolytic cathode 15 are insoluble electrodes and are respectively connected with the anode and the cathode of an electrolytic power supply 16, and the electrolytic anode 14 and the electrolytic cathode 15 are respectively arranged in an electrolytic anode area and an electrolytic cathode area; the hydrogen discharge system is a direct exhaust pipeline and is arranged above the electrolytic cathode region;
the oxidant storage tank 2 is used for containing an oxidant, and the oxidant is a mixed solution of potassium persulfate and sodium persulfate; the replenishment liquid tank 24 contains a sulfuric acid solution.
A probe of the oxidation-reduction potential detection device 3 is arranged in the reaction solution in the reaction tank 1;
the automatic detection feeding control device 11 automatically feeds sulfuric acid solution into the catholyte from the replenishing liquid tank 24 according to the detection result of the catholyte detection device 17, automatically feeds oxidant into the anolyte according to the detection result of the oxidation-reduction potential device 3 and automatically controls the current regulator 19 of the electrolysis power supply 16 to adjust the electrolysis current and start and stop;
the chemical analysis detection device is connected with the electrolytic anode area of the reaction tank 1 and sends a feedback signal according to the analysis result of the anolyte, and the chemical analysis detection device is a COD value on-line detection device in the embodiment.
The reaction solution in this embodiment is derived from a typical process conversion treatment method of converting organic waste water which is difficult to treat into a disposable organic waste water by gas-liquid mixing through a vacuum jet device. In this example, the COD of the reaction solution before the oxidation treatment was 2500 ppm. The treatment time was 18 hours in total, while the oxidation-reduction potential of the reaction solution was controlled to not less than 800mV, and after the treatment, the COD of the reaction solution was 150ppm as measured by sampling.
Example 9
As shown in fig. 9, which is an embodiment of the liquid oxidation treatment apparatus of the present invention, it is composed of a reaction tank 1, an oxidant storage tank 2, an oxygen reduction potential detection device 3, a detection device 27, an automatic detection feeding control device 11 and two supplementary liquid storage tanks 24, wherein:
the reaction tank 1 is an electrolysis device, and is internally provided with an electrolysis separator 13, an electrolysis anode 14, an electrolysis cathode 15 and an electrolysis power supply 16; the electrolytic separator 13 adopts a combined diaphragm with two interlayers as anion exchange membranes to divide the reaction tank 1 into an electrolytic anode region, an electrolytic buffer region 28 and an electrolytic cathode region, wherein the electrolytic anode region, the electrolytic buffer region 28 and the electrolytic cathode region are respectively used for containing anolyte, electrolytic buffer solution and catholyte, the anolyte is reaction solution, the reaction solution in the embodiment is reductive phosphorus-containing waste liquid, the electrolytic buffer solution is hydrochloric acid, and the catholyte is aqueous solution of soluble sodium chloride; the electrolytic anode 14 and the electrolytic cathode 15 are insoluble electrodes and are respectively connected with the anode and the cathode of an electrolytic power supply 16, and the electrolytic anode 14 and the electrolytic cathode 15 are respectively arranged in an electrolytic anode area and an electrolytic cathode area; the electrolysis power supply 16 is a pulse power supply;
the oxidant storage tank 2 is used for containing an oxidant, the oxidant is a sodium hypochlorite solution and is connected with the reaction tank through a pipeline and a feeding pump;
a probe of the oxidation-reduction potential detection device 3 is arranged in the reaction solution in the reaction tank 1;
the probes of the detection device 27 are respectively placed in the solution of the electrolytic buffer zone 28 and the electrolytic catholyte;
one supplementary liquid storage tank 24 is used for containing hydrochloric acid as supplementary liquid of electrolytic buffer solution, the supplementary liquid storage tank 24 is connected with the electrolytic buffer area 28 through a pipeline, a pump and a valve, and the other supplementary liquid storage tank 24 is used for containing sodium chloride aqueous solution as adjustment supplementary liquid of electrolytic cathode liquid;
the automatic detection feeding control device 11 automatically controls the starting or stopping of the feeding pump of the oxidant storage tank 2 according to the detection result of the oxidation-reduction potential detection device 3, automatically controls the current regulator 19 of the electrolysis power supply 16 to adjust the electrolysis current and start or stop, and automatically controls the starting or stopping of the pumping of the supplementary liquid storage tank 24 according to the detection result of the detection device of the electrolysis buffer area 28.
In this example, the phosphorus content of the reaction solution was 3000ppm because the solution contained reducing phosphorus before the oxidation treatment, and the total treatment time of the chemical oxidation reaction and the electrochemical oxidation reaction was 10 hours. And controlling the oxidation-reduction potential of the reaction solution in the reaction tank to be not less than 1400mV in the reaction process, wherein the overflowed catholyte is a mixed aqueous solution of sodium hydroxide and sodium chloride and is used as a neutralization absorption treatment solution of the tail gas discharged out of the anode area of the electrolytic tank and/or a neutralization treatment solution of the acidic waste liquid. And after the oxidation treatment is finished, carrying out conventional dephosphorization process treatment, then sampling to obtain the phosphorus content of the reaction solution of 0.2ppm, and then carrying out conventional heavy metal ion process treatment on the reaction solution.
Example 10
As shown in fig. 10, in order to implement the present invention, the liquid oxidation treatment apparatus comprises two reaction tanks 1, an oxidant storage tank 2, two oxidation-reduction potential detection devices 3, a cold-hot temperature exchange device 5, an oxygen source 6, a solid-liquid separation device 26, a gas transmission device 31, a detection device 27, an automatic detection feeding control device 11, and a supplementary liquid storage tank 24, wherein:
one of the reaction tanks 1 is a common through tank, and the other one is an electrolytic tank device; the common through groove is used for containing reaction solution and/or reaction solution processed by the reaction groove 1 of the electrolysis device, or two reaction grooves 1 are connected with each other through a pipeline and a pump to jointly oxidize the same liquid, and a stirring device 4 is arranged in each reaction groove 1. In this embodiment, the reaction solution is a chemical nickel plating waste solution, and the stirring device 4 is a liquid pipeline reflux stirring device; the electrolytic cell device is internally provided with an electrolytic separator 13, an electrolytic anode 14, an electrolytic cathode 15 and an electrolytic power supply 16; the electrolytic separator 13 is a cation exchange membrane and divides the reaction tank into an electrolytic anode area and an electrolytic cathode area, the electrolytic anode area and the electrolytic cathode area are respectively used for containing an anolyte and a catholyte, the anolyte is a reaction solution, and the catholyte is an aqueous solution of an inorganic acid and/or an inorganic base and/or soluble salt; the electrolytic anode 14 and the electrolytic cathode 15 are insoluble electrodes and are respectively connected with the anode and the cathode of an electrolytic power supply 16, and the electrolytic anode 14 and the electrolytic cathode 15 are respectively arranged in an electrolytic anode area and an electrolytic cathode area;
the oxidant storage tank 2 is used for containing an oxidant, the oxidant is a sodium hypochlorite solution and is connected with a reaction tank of a common tank through a pipeline and a feeding pump;
probes of the two oxidation-reduction potential detection devices 3 are respectively arranged in the reaction tank 1 of the common groove and the electrolytic anode liquid in the reaction tank 1 of the electrolysis device;
the probe of the detection device is placed in the solution of the electrolytic cathode region;
the supplementary liquid storage tank 24 is used for containing supplementary liquid for adjusting the pH value of the catholyte in the reaction tank 1 of the electrolysis device, and the supplementary liquid storage tank 24 is connected with the electrolysis cathode area of the reaction tank 1 of the electrolysis device through a pipeline, a pump and a valve;
the gas transfer means 31 is a device for directly feeding the oxygen-containing gas into the liquid in the reaction tank 1 and stirring the oxygen-containing gas.
The automatic detection feeding control device 11 automatically controls the starting or stopping of the feeding pump of the oxidant storage tank 2 according to the result detected by the oxidation-reduction potential detection device 3 of the reaction tank 1 of the common tank, automatically controls the starting or stopping of the pump of the supplementary liquid storage tank 24 according to the result detected by the detection device of the electrolytic cathode region, and automatically controls the current regulator 19 of the electrolytic power supply 16 to adjust the electrolytic current or stop according to the result detected by the oxidation-reduction potential detection device 3 of the reaction tank 1 of the electrolytic device.
In this example, the phosphorus content of the reaction solution before the oxidation treatment was 7000ppm, the nickel content was 1.3g/L, the reaction tank of the electrolysis apparatus was connected to the reaction tank of the normal tank through a pipe and a pump to co-oxidize the same liquid, and the co-treatment time of the chemical oxidation and the electrochemical oxidation was 15 hours. In the reaction process, the oxidation-reduction potential of the reaction solution is controlled to be not less than 1000 mV. After the oxidation treatment, the reaction solution was treated by a conventional phosphorus removal process, and then a sample was taken to measure that the phosphorus content of the reaction solution was 0.2ppm and the nickel content was 165 ppm.
During the reaction in the reaction cell of the electrolyzer, nickel in the reaction solution enters the electrolytic cathode zone through the electrolytic partition 13, while oxidation of phosphorus in a reduced state takes place in the electrolytic anode zone. When the catholyte is acidic, the catholyte treated by the reaction tank 1 of the electrolysis device contains nickel salt, nickel ions can be changed into nickel hydroxide precipitate for separation by adjusting the pH value of the solution after the catholyte is pumped out of the electrolysis tank, and the nickel hydroxide can be further changed into nickel salt for sale or recycling. When the catholyte is neutral or alkaline, nickel ions transferred from the anolyte to the electrolytic cathode region generate nickel hydroxide precipitate in the catholyte, the nickel hydroxide precipitate can be directly separated from the solution through a solid-liquid separation device, and the nickel hydroxide precipitate is converted into nickel salt for sale or recycling, but the scheme can cause the electrolytic separator 13 to be blocked by the nickel hydroxide precipitate, so that the service life of the electrolytic separator 13 is shortened.
Example 11
As shown in fig. 11, in order to implement the embodiment of the liquid oxidation treatment apparatus of the present invention, it is composed of a reaction tank 1, an oxidant storage tank 2, an oxygen reduction potential detection device 3, a detection device 27, an automatic detection feeding control device 11 and a supplementary liquid storage tank 24, wherein:
the reaction tank 1 is an electrolysis device; the electrolysis device is internally provided with an electrolysis separator 13, an electrolysis anode 14, an electrolysis cathode 15 and an electrolysis power supply 16; the electrolytic separator 13 is a cation exchange membrane and divides the reaction tank 1 into an electrolytic anode area and an electrolytic cathode area, the electrolytic anode area and the electrolytic cathode area are respectively used for containing an anolyte and a catholyte, the anolyte is a reaction solution, the reaction solution in the embodiment is chemical nickel plating waste liquid, and the catholyte is an aqueous solution of inorganic acid and/or inorganic base and/or soluble salt; the electrolytic anode 14 and the electrolytic cathode 15 are insoluble electrodes and are respectively connected with the anode and the cathode of an electrolytic power supply 16, and the electrolytic anode 14 and the electrolytic cathode 15 are respectively arranged in an electrolytic anode area and an electrolytic cathode area;
the oxidant storage tank 2 is used for containing an oxidant, the oxidant is a sodium hypochlorite solution and is connected with the reaction tank through a pipeline and a feeding pump;
the probe of the oxidation-reduction potential detection device 3 is arranged in the reaction solution in the electrolytic anode area of the reaction tank 1;
the probe of the detection device is placed in the solution of the electrolytic cathode region;
the supplementary liquid storage tank 24 is used for containing supplementary liquid for adjusting the pH value of the cathode electrolyte, and the supplementary liquid storage tank 24 is connected with the electrolytic cathode region of the reaction tank 1 of the electrolytic device through a pipeline, a pump and a valve;
the automatic detection feeding control device 11 automatically controls the starting or stopping of the feeding pump of the oxidant storage tank 2 according to the detection result of the oxidation-reduction potential detection device 3, automatically controls the starting or stopping of the pump of the supplementary liquid storage tank 24 according to the detection result of the detection device of the electrolytic cathode region, and automatically controls the current magnitude and/or the starting or stopping of the electrolytic power supply according to the time program and/or the detection result of the oxidation-reduction potential detection device 3.
In this example, the phosphorus content of the reaction solution before the oxidation treatment was 6500ppm, the nickel content was 1.37g/L, the treatment time of the reaction tank was 40 hours, and the oxidation-reduction potential of the reaction solution in the electrolytic anode region of the reaction tank 1 was controlled to not less than 1000mV during the reaction. After the oxidation treatment, the reaction solution was treated by a conventional phosphorus removal process and a heavy metal ion removal process, and then a sample was taken to measure that the phosphorus content of the reaction solution was 0.2ppm and the nickel content was 58 ppm. During the reaction in the reaction tank 1, nickel in the reaction solution enters the electrolytic cathode region through the electrolytic partition 13, while oxidation of low-valence phosphorus occurs in the electrolytic anode region. When the catholyte is acidic, the catholyte treated in the reaction tank 1 contains nickel salt, and after the catholyte is taken out of the electrolytic tank, nickel ions can be changed into nickel hydroxide precipitate for separation by adjusting the pH value of the solution, and the nickel hydroxide precipitate can be further changed into nickel salt for sale or recycling. When the catholyte is neutral or alkaline, nickel ions transferred from the anolyte to the electrolytic cathode region generate nickel hydroxide precipitate in the catholyte, the nickel hydroxide precipitate can be directly separated from the solution through a solid-liquid separation device, and the nickel hydroxide precipitate is converted into nickel salt for sale or recycling, but the scheme can cause the electrolytic separator 13 to be blocked by the nickel hydroxide precipitate, so that the service life of the electrolytic separator 13 is shortened.
Example 12
As shown in fig. 12, in order to implement the embodiment of the liquid oxidation treatment apparatus of the present invention, it is composed of a reaction tank 1, an oxidant storage tank 2, an oxidation-reduction potential detection device 3, a stirring device 4, a temperature heat exchanger 5, a tail gas treatment system, an automatic detection feeding control device 11, a detection device 27, and a gas transmission device 31, wherein:
the reaction tank 1 is an electrolysis device; the electrolysis device is internally provided with an electrolysis separator 13, an electrolysis anode 14, an electrolysis cathode 15 and an electrolysis power supply 16; the electrolytic separator 13 is filter cloth and divides the reaction tank 1 into an electrolytic anode area and an electrolytic cathode area, the electrolytic anode area and the electrolytic cathode area are respectively used for containing an anolyte and a catholyte, the anolyte is a reaction solution, and the catholyte is an aqueous solution of acidic ferric chloride or aqueous solutions of ferric chloride, ferric dichloride and hydrochloric acid; in the embodiment, the reaction solution is a phosphorus-containing chemical nickel plating waste liquid or a phosphorus-containing chemical nickel plating waste liquid subjected to heavy metal ion removal pretreatment, the pretreatment method is to mix the chemical nickel plating waste liquid with oxalic acid or sodium hydroxide and/or potassium hydroxide and/or sodium carbonate and/or potassium carbonate for chemical reaction, after the reaction, a solid is separated out and subjected to solid-liquid separation to obtain a filtrate and a filter residue of which the main component is nickel salt and/or nickel hydroxide, wherein the obtained filtrate is the reaction solution; in order to obtain better oxidation effect, the pH value of the reaction solution can be adjusted to be acidic, and/or an oxidant and/or soluble chloride salt are added and then electrolysis is carried out; the electrolytic anode 14 and the electrolytic cathode 15 are insoluble electrodes and are respectively connected with the anode and the cathode of an electrolytic power supply 16, and the electrolytic anode 14 and the electrolytic cathode 15 are respectively arranged in an electrolytic anode area and an electrolytic cathode area;
the probe of the oxidation-reduction potential detection device 3 is respectively arranged in the reaction solution in the electrolytic anode area of the reaction tank and the catholyte in the electrolytic cathode area;
the tail gas treatment system is a combination of a tank cover air exhaust cover 7, a vacuum jet device 12 and a tail gas absorption treatment tank 8, the tank cover air exhaust cover 7 is arranged above the reaction tank 1, an air outlet of the tank cover air exhaust cover 7 is connected with an air suction port of the vacuum jet device 12, a liquid inlet of the vacuum jet device 12 is connected with the tail gas absorption treatment tank 8, liquid in the tail gas absorption treatment tank 8 enters the vacuum jet device 12 through a liquid inlet of the vacuum jet device 12, and then the vacuum jet device 12 is used for gas-liquid mixing reaction and then returns to the tail gas absorption treatment tank 8 from a liquid outlet of the vacuum jet device 12;
the probe of the detection device is placed in the solution of the electrolytic cathode area, and the detection device preferably comprises an acidimeter;
the gas transmission device 31 is used for inflating and oxidizing the catholyte, and oxygen can be blown into the electrolytic catholyte by adopting a jet flow, an air compressor and a centrifugal fan;
the automatic detection feeding control device 11 automatically controls the operation of the working capacity of the gas transmission device and/or the starting or stopping of the feeding pump of the replenishing liquid storage tank 24 according to the detection result of the detection device of the electrolytic cathode region, automatically controls the starting or stopping of the electrolytic power supply 16 according to the time program and/or the detection result of the oxidation-reduction potential detection device 3, adjusts the electrolytic current according to the oxidation-reduction potential detection device 3 and is safely interlocked with the temperature cold-heat exchanger 5.
In the embodiment, the phosphorus-containing chemical nickel plating waste liquid originally contains 1.1g/L of nickel ions, heavy metal ion removal pretreatment is carried out before oxidation treatment, the phosphorus content is 6500ppm, the nickel content is 0.08ppm, the chemical oxidation and electrochemical oxidation treatment time of the reaction tank 1 is 32 hours, and the oxidation-reduction potential of the reaction solution in the electrolytic anode area of the reaction tank 1 is controlled to be not less than 1000mV in the reaction process. After the oxidation treatment is finished, the reaction solution is treated by a conventional phosphorus removal process, and the phosphorus content of the reaction solution after the oxidation and phosphorus removal is measured to be 0.3ppm by sampling. In the reaction process in the reaction tank 1, chlorine gas generated on the electrolysis anode 13 and low-valence phosphorus in the electrolysis anode region are subjected to oxidation reaction, ferric ions are mainly reduced to ferrous ions on the electrolysis cathode 14, and little or no hydrogen is separated out from the electrolysis cathode 14 in the reaction process. The replenishing solution of the catholyte contains hydrochloric acid, and the hydrochloric acid is automatically added according to the result measured by the detection device so as to maintain the oxidation reaction of ferrous ions in the catholyte under the acidic condition.
The gas transmission device 31 may be any device capable of introducing oxygen into the catholyte so that the ferrous ions in the catholyte are continuously oxidized into ferric ionsHydrogen is prevented from being generated during the electrochemical reaction, and the oxygen can be oxygen from an oxygen product and/or oxygen from air. In a preferred embodiment, the gas transmission device 31 comprises at least one additional tank which is arranged independently and is connected with the electrolytic cathode area through a pump and a pipeline to form a circulation loop, so that the catholyte circularly flows in the electrolytic cathode area and the tank of the gas transmission device 31 and is oxidized. The tank of the gas transmission device 31 is provided with a vacuum jet device 12 and/or a spray pipeline type chemical reaction device and/or a gas booster to introduce oxygen into the catholyte in the tank, so that the low-valence iron ions in the catholyte undergo oxidation reaction: 4FeCl2+4HCl+O2→4FeCl3+2H2And O. The automatic detection feeding control device also adjusts the power of the gas transmission device according to the technological parameter requirement of the oxidation-reduction potential of the catholyte, so as to meet the oxygen transmission amount of the low-valence iron ion oxidation process reaction.
After the reaction is finished, the pH value of the anolyte is adjusted to 4-8, the anolyte is treated by a phosphorus removal agent and is subjected to solid-liquid separation to remove phosphorus-removed compound solids, and the obtained filtrate is subjected to sampling detection to obtain the anolyte with the phosphorus content of 0.28ppm and the nickel content of 0.05 ppm. The chlorine tail gas generated in the treatment process of the equipment can be absorbed by sodium hydroxide solution to prepare sodium hypochlorite solution. The obtained sodium hypochlorite solution can be used as an oxidant in the oxidation treatment process, namely, the sodium hypochlorite solution is added into the anolyte to accelerate the oxidation of the reaction solution and shorten the electrolysis time, and can also be used as the oxidant in the oxidation treatment process of other waste liquid.
Example 13
As shown in fig. 13, it is the embodiment of the liquid oxidation treatment device of the present invention, which is composed of two reaction tanks 1, an oxidant storage tank 2, an oxidation-reduction potential detection device 3, a stirring device 4, a cold-hot temperature exchange device 5, an oxygen source 6, two sets of tail gas treatment systems, a vacuum jet device 12, a chemical analysis detection device 23, a detection device 27, an automatic detection feeding control device 11, a make-up liquid storage tank 24 and a gas transmission device 31, wherein:
one of the reaction tanks 1 is a common tank, and the other one is an electrolytic tank device; an electrolytic separator 13 anion exchange membrane, an electrolytic anode 14, an electrolytic cathode 15 and an electrolytic power supply 16 are arranged in the electrolytic cell device; the electrolytic partition 13 divides the reaction tank into an electrolytic anode area and an electrolytic cathode area, the electrolytic anode area and the electrolytic cathode area are respectively used for containing anolyte and catholyte, the anolyte is a reaction solution, and the catholyte is an acidic aqueous solution of iron dichloride and/or iron trichloride; in the embodiment, the reaction solution in the electrolytic cell device is phosphorus-containing chemical nickel plating waste liquid or phosphorus-containing chemical nickel plating waste liquid after pretreatment, the pretreatment method is to mix the chemical nickel plating waste liquid with oxalic acid or sodium hydroxide and/or potassium hydroxide and/or sodium carbonate and/or potassium carbonate for chemical reaction, and after the reaction, solid-liquid separation is carried out to obtain filtrate and filter residue of which the main component is nickel salt and/or nickel hydroxide, wherein the obtained filtrate is the reaction solution; in order to obtain better oxidation effect, the reaction solution can also adjust the pH value to be acidic and/or carry out electrolysis or oxidation after adding an oxidant and/or soluble chloride; the electrolytic anode 14 and the electrolytic cathode 15 are insoluble electrodes and are respectively connected with the anode and the cathode of an electrolytic power supply 16, and the electrolytic anode 14 and the electrolytic cathode 15 are respectively arranged in an electrolytic anode area and an electrolytic cathode area; the common tank in the reaction tank is filled with organic waste liquid discharged by a circuit board production plant or organic waste liquid which is subjected to heavy metal ion removal, glue residue removal or acidification pretreatment;
the tail gas treatment system is divided into two sets, the first set is a combination of a tank cover air exhaust cover 7, a vacuum jet device 12 and a tail gas absorption treatment tank 8, the other set of corresponding tail gas absorption treatment tank 8 is a common tank in the reaction tank 1, the air outlet of the tank cover air exhaust cover 7 is connected with the air suction port of the vacuum jet device 12 through a pipeline of the tank cover air exhaust cover 7, and the gas escaping from the anode area of electrolysis is introduced into the liquid in the reaction tank 1 of the common tank through the vacuum jet device 12; the first set of tail gas treatment system is a combination of a tank cover air exhaust cover 7 and a tail gas absorption treatment tank 8, the tank cover air exhaust cover 7 is provided with a centrifugal fan 9, the tank cover air exhaust cover 7 is respectively arranged above an electrolysis cathode area of an electrolysis device of the reaction tank 1 and above a common tank in the reaction tank, an air outlet of the tank cover air exhaust cover 7 is inserted into absorption reaction liquid in the tail gas absorption treatment tank 8 through a pipeline and the fan of the tank cover air exhaust cover 7, and the corresponding tail gas absorption treatment tank 8 is loaded with aqueous solution of sodium hydroxide and/or sodium carbonate as absorption reaction liquid for absorbing tail gas generated in the electrolysis cathode area of the electrolysis device and the common tank in the reaction tank;
the oxidant tank 2 is respectively communicated with an electrolysis anode area of an electrolysis device of the reaction tank 1, a common through tank in the reaction tank and a tank of the oxygenation oxidation device through pipelines provided with controllable pumps;
the probes of the oxidation-reduction potential detection device 3 are respectively placed in a reaction solution in an electrolysis anode area of an electrolysis device in a reaction tank, a catholyte in an electrolysis cathode area of the electrolysis device and a reaction solution in a common tank in the reaction tank;
the detector 27 has probes respectively arranged in the solution in the electrolyzer in the reaction tank and the solution in the ordinary tank in the reaction tank, and the solution in the aeration oxidation device 31 is respectively provided with the oxidation-reduction potential detector 3 and the detector 27.
The supplementary liquid storage tank 24 is used for containing hydrochloric acid supplementary liquid for supplementing and adjusting the catholyte, and the supplementary liquid storage tank 24 is connected with the electrolytic cathode region of the reaction tank 1 of the electrolytic device through a pipeline, a pump and a valve;
the gas transmission device 31 is used for inflating and oxidizing the catholyte, and oxygen can be blown into the electrolytic catholyte by adopting a jet flow, an air compressor and a centrifugal fan;
the automatic detection feeding control device 11 is used for automatically controlling the starting or stopping of the hydrochloric acid pump of the replenishing liquid storage tank 24 and the starting or stopping of the pump for feeding the oxidant to the inflating oxidation device by the oxidant tank 2 according to the detection result of the detection device of the electrolytic cathode region of the electrolysis device; automatically controlling the size of the electrolytic current of the electrolytic power supply and/or the starting and stopping of the electrolytic power supply according to the detection result of the detection device of the electrolytic anode area of the electrolytic device; automatically controlling the start or stop of a feeding pump between the oxidant storage tank 2 and the electrolytic anode area of the electrolytic device according to the detection result of the oxidation-reduction potential detection device 3 of the electrolytic anode area of the electrolytic device; and automatically controlling the starting or stopping of a feeding pump between the oxidant storage tank 2 and the common tank according to the detection result of the oxidation-reduction potential detection device 3 of the common tank.
In this example, the reaction solution in the anode reaction tank of the electrolytic tank apparatus was a phosphorus-containing chemical nickel plating waste solution which had been subjected to a preliminary treatment for removing metals in advance, the phosphorus content of the reaction solution after the preliminary treatment was 6500ppm, and the COD of the reaction solution in the reaction tank of the ordinary tank was 21000ppm or more. The treatment time of the oxidation reaction is 34 hours, in the reaction process, the reaction solution in the electrolysis anode area of the electrolysis bath device 1 in the reaction bath is subjected to chemical oxidation and electrochemical oxidation, the oxidation-reduction potential is controlled to be not less than 1000mV, and the oxidation-reduction potential of the reaction solution in the common bath in the reaction bath is controlled to be not less than 1100 mV. After the oxidation treatment, the reaction solution in the electrolytic anode area of the electrolytic cell device in the reaction tank is subjected to the conventional dephosphorization process treatment, and then the phosphorus content of the reacted solution is measured by sampling, and the COD of the reacted solution in the common cell in the reaction tank is measured by sampling, wherein the phosphorus content of the reacted solution is 0.2 ppm.
Chlorine tail gas generated in the oxidation process in the reaction tank 1 of the electrolytic tank device is used as an oxidant for oxidation treatment of reaction solution in the reaction tank 1 of a common tank, is supplemented as an external oxidant of the oxidant tank, and is used for assisting the reaction solution in the common reaction tank to accelerate oxidation in addition to the oxidant mainly added into the oxidant tank 2. In the reaction process in the electrolyzer in the reaction tank, chlorine gas generated on the electrolysis anode and low-valence phosphorus are subjected to oxidation reaction. After the oxidation reaction is finished, the pH value of the anolyte is adjusted to 4-8, a phosphorus removing agent is added for treatment, then solid is separated out, and then solid-liquid separation is carried out to remove phosphorus compounds. If the reaction solution is not subjected to the process pretreatment for removing the heavy metal ions, the pH value of the filtrate obtained after the dephosphorization process can be adjusted to a proper range again, the conventional method for removing the metal ions is adopted, the sediment is separated again through filtration to remove the heavy metal ions, and then the pH value of the filtrate obtained at this time is adjusted to be neutral, so that the filtrate can reach the standard and be discharged.
Example 14
As shown in fig. 1, in order to implement the liquid oxidation treatment apparatus of the present invention, the apparatus comprises a reaction tank 1, an oxidant storage tank 2, an oxygen reduction potential detection device 3, and an automatic detection and feeding control device 11, wherein:
the reaction tank 1 is used for containing a reaction solution and carrying out oxidation treatment on the reaction solution, and the reaction solution contains ammonia nitrogen pollutants in the embodiment.
The oxidant storage tanks 2 are used for containing an oxidant, the oxidant contained in one of the oxidant storage tanks is hydrogen peroxide solution, and the oxidant contained in the other oxidant storage tank is sodium hypochlorite solution;
the probe of the oxidation-reduction potential detection device 3 is arranged in the reaction solution in the reaction tank;
an automatic detection and feeding control device 11 for automatically controlling the feeding pump to feed the oxidant in the first oxidant storage tank to the first reaction tank and the second reaction tank according to the result of the detection 3 by the oxidation-reduction potential detection device, and for automatically controlling the feeding pump to feed the oxidant in the second oxidant storage tank to the third reaction tank according to the time program.
In this example, an oxidizing agent was added during the treatment according to the result measured by the oxidation-reduction potential measuring device, during which the COD of the reaction solution was maintained at 600mV or more, and the treatment time was 48 hours in total. And after treatment, the ammonia nitrogen content of the reaction solution is measured by sampling and reaches the discharge standard.
It should be noted that the above-mentioned embodiments are only illustrative and not restrictive, and any modifications or changes within the meaning and range of equivalents of the technical solution of the present invention by those skilled in the art should be considered as included in the protection scope of the present invention.

Claims (10)

1. A solution oxidation treatment apparatus, comprising:
the reaction tank is used for containing reaction solution;
the oxidation-reduction potential detection device is used for detecting the oxidation-reduction potential of the solution in the reaction tank;
the oxidant storage tank is used for containing an oxidant which is added into the reaction tank and participates in the oxidation reaction;
and the automatic detection feeding control device is used for controlling the amount of the oxidant in the oxidant storage tank added into the reaction tank according to the time and/or the result obtained by detecting the liquid in the reaction tank by the oxidation-reduction potential detection device.
2. The solution oxidation treatment apparatus according to claim 1, wherein a feed pump or a solid feed device is provided between the oxidizing agent storage tank and the reaction tank, so that the feed pump pumps the oxidizing agent in a liquid state in the oxidizing agent storage tank into the reaction tank, or the solid feed device feeds the oxidizing agent in a solid state in the oxidizing agent storage tank into the reaction tank.
3. The solution oxidizing treatment apparatus according to claim 1, wherein said reaction tank and/or said oxidizing agent storage tank is provided with a temperature heat exchanger.
4. The solution oxidation treatment apparatus according to claim 1, wherein a tail gas treatment system is provided for treating tail gas generated during the oxidation reaction.
5. The solution oxidizing treatment apparatus according to claim 1, wherein a gas supply means is provided for supplying oxygen into said reaction tank.
6. The solution oxidation treatment apparatus according to claim 1, wherein a chemical reaction performance improving means is provided in the reaction tank.
7. The solution oxidizing treatment apparatus according to claim 1, wherein said reaction tank is provided as an electrolytic cell: arranging an electrolytic separator, an electrolytic anode, an electrolytic cathode and an electrolytic power supply, dividing the reaction tank into an electrolytic anode area and an electrolytic cathode area, and respectively placing the electrolytic anode and the electrolytic cathode in the electrolytic anode area and the electrolytic cathode area;
the oxidation-reduction potential detection device is used for detecting the oxidation-reduction potential of the liquid in the electrolysis anode area and controlling the process;
the electrolytic power supply is provided with a current regulator, or a current regulator is additionally arranged to regulate the current output by the electrolytic power supply or control the on/off of the electrolytic power supply.
8. A solution oxidising treatment unit according to claim 7, characterised in that a gas delivery device is provided, the gas delivery device being arranged to deliver oxygen to the anolyte and/or catholyte.
9. The solution oxidation treatment apparatus according to claim 7, wherein the electrolysis separator is an anionic membrane or a bipolar membrane, and the electrolysis separator is a composite electrolytic tank formed by combining two layers of anion exchange membranes or a bipolar membrane and an anion exchange membrane, and comprises an electrolysis anode area, an electrolysis cathode area and an electrolysis buffer area between the electrolysis anode area and the electrolysis cathode area.
10. A solution oxidising treatment unit according to claim 9, wherein a make-up fluid reservoir is provided for holding a make-up fluid for the catholyte or anolyte or buffer to facilitate make-up additions to the catholyte or anolyte or buffer.
CN202021916363.7U 2019-09-05 2020-09-04 Solution oxidation treatment device Active CN214880478U (en)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
CN2019214651701 2019-09-05
CN201921465170 2019-09-05
CN2019215434942 2019-09-17
CN201921543494 2019-09-17
CN2019222641877 2019-12-12
CN201922264187 2019-12-12
CN202020180146X 2020-02-18
CN202020180146 2020-02-18

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