CN115124118B - Thiadiazole production wastewater treatment method - Google Patents
Thiadiazole production wastewater treatment method Download PDFInfo
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Abstract
The invention relates to the field of sewage treatment, in particular to a thiadiazole production wastewater treatment method, which comprises a thiadiazole bipolar membrane electrodialysis treatment device, wherein the thiadiazole bipolar membrane electrodialysis treatment device is provided with an alkali chamber, a material chamber, an acid chamber and an electrode liquid chamber, and comprises the following steps: the method comprises the following steps: inputting thiadiazole production wastewater into a material chamber, inputting 0-0.05mol/L diluted alkali solution into an alkali chamber, inputting 0-0.05mol/L diluted acid solution into an acid chamber, and inputting 0.3-0.5mol/L sodium sulfate solution into an electrode liquid chamber; step two: electrifying the bipolar membrane electrodialysis treatment device for thiadiazole, and controlling the current density at 30-70mA/cm 2 In the middle of; step three: carrying out electrodialysis concentration on the acid solution in the acid chamber to obtain concentrated acid solution, and carrying out electrodialysis concentration on the alkali solution in the alkali chamber to obtain concentrated alkali solution; step four: and respectively carrying out evaporation concentration on the concentrated acid solution, the concentrated alkali solution and the thiadiazole-containing water solution desalted by electrodialysis. The method can recover thiadiazole, acid and alkali in the production wastewater, can eliminate the risk of salt pollution, and can also generate economic benefit.
Description
Technical Field
The invention relates to the field of sewage treatment, and in particular relates to a thiadiazole production wastewater treatment method.
Background
Thiadiazole is also called methylmercaptothiadiazole (2-mecapto-5-methyl-1, 3, 4-thiadiazaole), CAS number is 29490-19-5, molecular formula is C 3 H 4 N 2 S 2 White crystals. Thiadiazole is an important intermediate for producing medicines such as cefazolin, cefkaempferia, cefazedone, azolin cephalosporin, cefprozil, cephalosporin BL-S339, furbenazole cephalosporin and the like. In addition, the thiadiazole can be used for synthesizing antioxidants in lubricating oil, battery anode materials, coloring agents and vulcanizing agents of halogen-containing rubber.
In the process of producing thiadiazole, the produced wastewater not only has high organic matter concentration and high salt content, but also still contains a certain amount of thiadiazole, and at present, the methods for treating the wastewater mainly comprise a multi-effect evaporation method, an advanced oxidation method, a biological method and the like. The multi-effect evaporation method has high energy consumption, generates solid hazardous waste and has large subsequent treatment difficulty. The advanced oxidation method has large medicament consumption, and thiadiazole which is not completely removed in the wastewater can generate resistance genes or cause a teratogenic risk after entering a water body. The high salt content and organic thiadiazole have the inhibiting effect on the growth of microorganisms, and the biological treatment effect is poor and needs to be improved.
Disclosure of Invention
The invention aims to solve the problems and provide a method for treating wastewater generated in a thiadiazole production process and recovering beneficial substances in the wastewater.
In order to achieve the aim, the invention discloses a thiadiazole production wastewater treatment method which comprises a thiadiazole bipolar membrane electrodialysis treatment device, wherein the thiadiazole bipolar membrane electrodialysis treatment device is provided with an alkali chamber, a material chamber, an acid chamber and an electrode liquid chamber, and comprises the following steps:
the method comprises the following steps: inputting thiadiazole production wastewater into a material chamber, inputting 0-0.05mol/L diluted alkali solution into an alkali chamber, inputting 0-0.05mol/L diluted acid solution into an acid chamber, and inputting 0.3-0.5mol/L sodium sulfate solution into an electrode liquid chamber;
step two: electrodialysis of thiadiazole using bipolar membranesThe treatment device is electrified to operate, and the current density is controlled to be 30-70mA/cm 2 To (c) to (d);
step three: carrying out electrodialysis concentration on the acid liquor in the acid chamber to obtain concentrated acid liquor, and carrying out electrodialysis concentration on the alkali liquor in the alkali chamber to obtain concentrated alkali liquor;
step four: and respectively carrying out evaporation concentration on the concentrated acid solution, the concentrated alkali solution and the thiadiazole-containing water solution desalted by electrodialysis.
In the production process of thiadiazole, a large amount of salt is contained in the produced production wastewater, a certain amount of thiadiazole is remained at the same time, and the risk of salt pollution, organic matter pollution and resistance gene pollution caused by directly discharging water is existed. By adopting the method, the salt in the production wastewater can be recovered and converted into the corresponding acid and alkali for recovery, so that the risk of salt pollution is eliminated, and meanwhile, the thiadiazole is recovered, so that the risks of organic matter pollution and resistance gene pollution are eliminated.
The specific structure of the thiadiazole bipolar membrane electrodialysis treatment device comprises a membrane stack, the membrane stack comprises at least one membrane stack unit, bipolar membranes which are spaced from each other are arranged in the membrane stack unit, a cation exchange membrane and an anion exchange membrane are arranged, the bipolar membranes, the cation exchange membrane and the anion exchange membrane divide the membrane stack unit into an alkali chamber, a material chamber and an acid chamber which are spaced from each other in sequence, electrode plates are arranged at two ends of the membrane stack, an electrode liquid chamber is arranged between each electrode plate and the membrane stack unit, a bipolar membrane used for separating the tail end membrane stack unit from the electrode liquid chamber is arranged in the membrane stack, and the thiadiazole bipolar membrane electrodialysis treatment device further comprises a power supply used for supplying power to the electrode plates.
Regarding the termination condition of the operation of the device, between step two and step three: when the bipolar membrane electrodialysis treatment device for thiadiazole runs, a power supply continuously supplies power to the electrode plates, the conductivity of the solution in the feed liquid storage tank is monitored, and when the conductivity of the water solution containing thiadiazole desalted by electrodialysis is reduced to 5-10mS/cm, the power supply stops supplying power to the electrode plates.
Preferably, the electrode plate comprises a cathode plate and an anode plate, the cathode plate and the anode plate are respectively arranged at two ends of the film stack, the film stack unit is arranged between the anode plate and the cathode plate, the power supply is a direct current power supply, the anode of the direct current power supply is electrically connected with the anode plate, the cathode of the direct current power supply is electrically connected with the cathode plate, the film stack units are multiple, and the film stack units are sequentially arranged. The number of membrane stack units is selected according to the amount of wastewater.
Preferably, the system further comprises a solution tank, wherein the solution tank comprises an acid liquid storage tank for containing acid liquid in the acid chamber, an alkali liquid storage tank for containing alkali liquid in the alkali chamber, a feed liquid storage tank for supplying thiadiazole production wastewater to the feed chamber, an electrode liquid storage tank for supplying electrode liquid to the electrode liquid chamber, and a circulating pump for conveying the solution in the solution tank. Each solution tank is provided with a set of independent circulating pipelines, and the solutions in the solution tanks are circularly conveyed through respective circulating pumps until the conductivity of the solutions in the feed liquid storage tanks is reduced to 5-10mS/cm, and the direct current power supply and the circulating pumps finish working.
Preferably, in step one: conveying thiadiazole production wastewater into a feed liquid storage tank, conveying a sodium sulfate solution into an electrode liquid storage tank, conveying a dilute alkali liquid into an alkali liquid storage tank, conveying a dilute acid liquid into an acid liquid storage tank, and circularly conveying by a circulating pump, wherein the flow rate of a membrane surface is controlled to be 3-7 cm/s.
Preferably, the device further comprises an acid liquor electrodialysis treatment device for performing electrodialysis concentration on the acid liquor in the acid liquor storage tank, a concentrated acid liquor storage tank for collecting the concentrated acid liquor in the acid liquor electrodialysis treatment device, and an acid liquor evaporation device for performing evaporation concentration on the concentrated acid liquor in the concentrated acid liquor storage tank. And conveying the acid liquor produced in the working process of the thiadiazole bipolar membrane electrodialysis treatment device into an acid liquor storage tank, and performing electrodialysis concentration by using the acid liquor electrodialysis treatment device.
Preferably, the device further comprises a lye electrodialysis treatment device for performing electrodialysis concentration on the lye in the lye storage tank, a concentrated lye storage tank for collecting the concentrated lye in the lye electrodialysis treatment device, and a lye evaporation device for performing evaporation concentration on the concentrated lye in the concentrated lye storage tank. And conveying the alkali liquor produced in the working process of the thiadiazole bipolar membrane electrodialysis treatment device into an alkali liquor storage tank, and performing electrodialysis concentration by using the alkali liquor electrodialysis treatment device.
Preferably, the system also comprises a thiadiazole concentrating device for carrying out evaporation concentration on the desalted thiadiazole-containing aqueous solution in the feed liquid storage tank. And carrying out electrodialysis desalination on the thiadiazole production wastewater to obtain a thiadiazole-containing aqueous solution, and then carrying out evaporation concentration on the thiadiazole-containing aqueous solution by using a thiadiazole concentration device to produce thiadiazole or recycling the thiadiazole-containing aqueous solution to form a high-value product.
Preferably, in step four; and carrying out evaporation concentration on the concentrated acid solution by using an acid solution evaporation device, carrying out evaporation concentration on the concentrated alkali solution by using an alkali solution evaporation device, and carrying out evaporation concentration on the thiadiazole-containing aqueous solution by using a thiadiazole concentration device.
In conclusion, the beneficial effects of the invention are as follows: 1. in the production process of thiadiazole, the produced production wastewater contains a large amount of salt, a certain amount of thiadiazole is remained, and the risk of salt pollution, organic matter pollution and resistance gene pollution caused by direct discharge of water bodies exists. By adopting the method, the salt in the production wastewater can be recovered and converted into the corresponding acid and alkali for recovery, so that the salt pollution risk is eliminated; and the recovered thiadiazole can eliminate organic pollution and resistance gene pollution risks. 2. The method does not need to add extra chemical substances and has mild reaction conditions. The concentrated acid and alkali can be used as the production raw materials of the thiadiazole, so that the consumption of the acid and alkali raw materials in the production process is reduced; the recovered thiadiazole can be refined to form a high-value product, and economic benefits can be generated. 3. Under the background of a novel pollutant control plan issued in China at present, the method can greatly reduce the emission of thiadiazole production wastewater, and has huge industrial application potential.
Drawings
FIG. 1 is a schematic structural diagram of a bipolar membrane electrodialysis treatment device for thiadiazole;
FIG. 2 is a schematic structural diagram of an alkali liquor electrodialysis treatment device;
fig. 3 is a schematic structural diagram of an acid electrodialysis treatment device;
FIG. 4 is a schematic view of a specific implementation process of thiadiazole production wastewater treatment;
FIG. 5 is a schematic diagram of the structure and the working principle of a bipolar membrane electrodialysis treatment system for thiadiazole production wastewater containing potassium sulfate;
FIG. 6 is a schematic diagram of a system and method for treating wastewater from thiadiazole production containing potassium sulfate;
FIG. 7 is a schematic diagram of the structure and the working principle of a bipolar membrane electrodialysis treatment system for thiadiazole production wastewater containing ammonium chloride;
FIG. 8 is a schematic diagram of a system and a method for treating wastewater from thiadiazole production containing ammonium chloride.
In the figure: thiadiazole concentrating device 1, acid liquor evaporating device 2, acid liquor storage tank 3, liquor storage tank 4, thiadiazole bipolar membrane electrodialysis treatment device 5, direct-current power supply 6, electrode liquor storage tank 7, alkali liquor storage tank 8, alkali liquor evaporating device 9, circulating pump 10, acid liquor electrodialysis treatment device 11, alkali liquor electrodialysis treatment device 12, concentrated acid liquor storage tank 13, concentrated alkali liquor storage tank 14, acid compartment 15, material compartment 16, electrode liquor compartment 17, alkali compartment 18, bipolar membrane 19, cation exchange membrane 20, anion exchange membrane 21, flowmeter 22, cathode plate 23 and anode plate 24.
Detailed Description
The following detailed description of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the description of the present application, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present application can be understood in a specific case by those of ordinary skill in the art.
The following is a description of preferred embodiments of the present invention with reference to the accompanying drawings.
The invention provides a thiadiazole production wastewater treatment system, which comprises a membrane stack system, a direct current power supply system and a waterway circulation system; the two ends of the membrane stack system are provided with a cathode plate 23, an anode plate 24 and a clamping device, and the clamping device plays a role in fixing the cathode plate 23 and the anode plate 24; a plurality of film stack units are sequentially arranged between the cathode plate 23 and the anode plate 24; a bipolar membrane 19, a cation exchange membrane 20 and an anion exchange membrane 21 are sequentially arranged in the membrane stack unit, so that an alkali chamber 18, a material chamber 16 and an acid chamber 15 are respectively formed in the membrane stack unit; the anode of the direct current power supply 6 is connected with the anode plate 24, and the cathode of the direct current power supply 6 is connected with the cathode plate 23; the water path circulating system comprises four independent water path circulating systems of an electrode liquid chamber 17, an alkali chamber 18, a material chamber 16 and an acid chamber 15; the electrode liquid circulating system comprises an electrode liquid storage tank 7, a circulating pump 10, a pipeline and an electrode liquid waterway system in the membrane stack system; the alkali liquor circulating system comprises an alkali liquor storage tank 8, a circulating pump 10, a pipeline and an alkali liquor waterway system in the membrane stack system; the feed liquid circulating system comprises a feed liquid storage tank 4, a circulating pump 10, a pipeline and a feed liquid waterway system in the membrane stack system; the acid liquor circulating system comprises an acid liquor storage tank 3, a circulating pump 10, a pipeline and an acid liquor water path system in the membrane stack system.
The thiadiazole production wastewater treatment system is communicated with the acid liquor storage tank 3; the alkali concentration system is communicated with the alkali liquor storage tank 8; and the thiadiazole concentration and crystallization system is communicated with the feed liquid storage tank 4.
Aiming at thiadiazole production wastewater containing potassium sulfate, an electrodialysis system or an evaporation system can be adopted as an acid concentration system, an electrodialysis system or an evaporation system can be adopted as an alkali concentration system, and an evaporation system can be adopted as a thiadiazole concentration crystallization system; aiming at the thiadiazole production wastewater containing ammonium chloride, an electrodialysis system or an evaporation system can be adopted as an acid concentration system, a membrane distillation system can be adopted as an alkali concentration system, and an evaporation system can be adopted as a thiadiazole concentration and crystallization system.
The invention also provides a thiadiazole production wastewater treatment method adopting the treatment system.
The thiadiazole production wastewater treatment method adopting the system comprises the following steps:
1) Injecting thiadiazole production wastewater into a feed liquid storage tank 4, and simultaneously injecting 0.5mol/L sodium sulfate solution, 0-0.05mol/L dilute alkali solution and 0-0.05mol/L dilute acid solution into an electrode solution storage tank 7, an alkali solution storage tank 8 and an acid solution storage tank 3 respectively; the added dilute alkali liquor is the dilute alkali liquor with the same cation as the salt in the thiadiazole production wastewater; the added dilute acid solution is the dilute acid solution with the same anion as the salt in the thiadiazole production wastewater.
2) Starting four independent waterway circulation systems, wherein a flow meter 22 is arranged on a pipeline, and the flow velocity of the membrane surface is set to be 5-7cm/s; the direct current at the two ends of the cathode plate and the anode plate 24 is connected, and the input current density is 30-100mA/cm 2 (ii) a Obtaining a desalted thiadiazole-containing aqueous solution in the feed liquid storage tank 4, obtaining an alkaline solution in the alkaline solution storage tank 8, and obtaining an acid solution in the acid solution storage tank 3; the solute in the alkali liquor is alkali corresponding to cations of salts in the thiadiazole production wastewater, and the solute in the acid liquor is acid corresponding to anions of the salts in the thiadiazole production wastewater.
3) After the bipolar membrane electrodialysis process is finished, a recovery step is carried out according to the adopted concentration system; (1) concentrating acid and alkali obtained by bipolar membrane electrodialysis and recycling the acid and alkali in the thiadiazole production process; (2) and (3) concentrating and crystallizing the desalted thiadiazole-containing water solution, wherein the concentration residual volume of the solution is slightly less than the completely dissolved volume of the residual salt in the thiadiazole water solution, returning the residual thiadiazole water solution to the bipolar membrane electrodialysis system after the thiadiazole is separated, and re-executing the steps 1) and 2).
The conditions for ending the bipolar membrane electrodialysis treatment process are as follows: and (3) monitoring the solution conductivity of the feed liquid storage tank 4 on line, and ending the treatment process of the thiadiazole production wastewater treated by the bipolar membrane electrodialysis when the solution conductivity of the feed liquid storage tank 4 is reduced to 5-10 mS/cm.
The reaction principle of the bipolar membrane electrodialysis treatment is as follows:
aiming at the thiadiazole production wastewater containing potassium sulfate,
a material chamber 16: k 2 SO 4 →2K + (transmembrane cation) + SO 4 2- (through the vaginal membranes);
acid chamber 15:2H + (generated from bipolar membrane 19) + SO 4 2- →H 2 SO 4 ；
Alkali chamber 18: k + +OH - (produced in bipolar membrane 19) → KOH.
Aiming at the thiadiazole production wastewater containing ammonium chloride,
a material chamber 16: NH 4 Cl→NH 4 + (Permeability to the Positive Membrane) + Cl - (through the shadow mask);
an acid chamber 15: h + (generated from the bipolar membrane 19) + Cl - →HCl；
Alkali chamber 18: NH (NH) 4 + +OH - (produced in bipolar membrane 19) → NH 4 OH；
While the thiadiazole continues to remain in the material chamber 16.
The steps 1) and 2) in the thiadiazole production wastewater treatment method can be used as a separate method for thiadiazole production wastewater treatment.
The invention also provides a bipolar membrane electrodialysis treatment method for thiadiazole production wastewater, which comprises the following steps:
1) Injecting thiadiazole production wastewater into a feed liquid storage tank 4, and simultaneously respectively injecting 0.5mol/L sodium sulfate solution, 0-0.05mol/L diluted alkali solution and 0-0.05mol/L diluted acid solution into an electrode liquid storage tank 7, an alkali solution storage tank 8 and an acid solution storage tank 3; the added dilute alkali liquor is the dilute alkali liquor with the same cation as the salt in the thiadiazole production wastewater; the added dilute acid solution is the dilute acid solution with the same anion as the salt in the thiadiazole production wastewater.
2) Starting four independent waterway circulation systems, wherein the membrane surface flow velocity is set at 5-7cm/s; the direct current at the two ends of the cathode plate and the anode plate 24 is connected, and the input current density is 30-100mA/cm 2 (ii) a Obtaining a desalted thiadiazole-containing water solution in the feed liquid storage tank 4, obtaining an alkali liquor in the alkali liquor storage tank 8, and obtaining an acid liquor in the acid liquor storage tank 3; the solute in the alkali liquor is alkali corresponding to cations of salts in the thiadiazole production wastewater, and the solute in the acid liquor is acid corresponding to anions of the salts in the thiadiazole production wastewater.
The conditions for finishing the step 2) are as follows: and (3) monitoring the conductivity of the solution in the feed liquid storage tank 4 on line, and ending the treatment process of the thiadiazole production wastewater by bipolar membrane electrodialysis when the conductivity of the solution in the feed liquid storage tank 4 is reduced to 5-10 mS/cm.
The reaction principle of the bipolar membrane electrodialysis treatment is as follows:
aiming at thiadiazole production wastewater containing potassium sulfate:
a material chamber 16: k 2 SO 4 →2K + (transmembrane cation) + SO 4 2- (transmitting the shadow mask)；
An acid chamber 15:2H + (generated from the bipolar membrane 19) + SO 4 2- →H 2 SO 4 ；
The alkali chamber 18: k + +OH - (produced in bipolar membrane 19) → KOH.
Aiming at thiadiazole production wastewater containing ammonium chloride:
a material chamber 16: NH (NH) 4 Cl→NH 4 + (Permeability to the Positive Membrane) + Cl - (through the vaginal membranes);
acid chamber 15: h + (generated from the bipolar membrane 19) + Cl - →HCl；
Alkali chamber 18: NH (NH) 4 + +OH - (produced in bipolar membrane 19) → NH 4 OH；
While the thiadiazole continues to remain in the material chamber 16.
Example 1: a BM-AM-CM three-compartment bipolar membrane electrodialysis system was used, see fig. 4. The content of potassium sulfate in the thiadiazole production wastewater adopted in the embodiment is 80g/L, the content of thiadiazole is 1.0g/L, distilled water is respectively injected into the acid chamber 15 and the alkali chamber 18, and 0.5mol/L sodium sulfate is injected into the electrode liquid chamber 17. The flow rate on the membrane surface is 5cm/s, and the current density is 50mA/cm 2 Under the operation condition, the operation is carried out in an intermittent operation mode, and after the operation is carried out for 90min, the conductivity of the solution in the feed liquid storage tank 4 is reduced to 6.96mS/cm, and the experiment is stopped. The sulfuric acid concentration in the acid liquor storage tank 3 is 0.38mol/L, the potassium hydroxide concentration in the alkali liquor storage tank 8 is 0.79mol/L,87.8% thiadiazole is retained in the feed liquor storage tank 4, the energy consumption in the feed liquor desalting process is 214w.h/mol, and the desalting current efficiency is 74.91%.
Example 2: a BM-AM-CM three-compartment bipolar membrane electrodialysis system was used, see fig. 4. The content of potassium sulfate in the thiadiazole production wastewater adopted in the embodiment is 80g/L, the content of thiadiazole is 1.0g/L, distilled water is respectively injected into the acid chamber 15 and the alkali chamber 18, and 0.5mol/L sodium sulfate is injected into the electrode liquid chamber 17. The flow rate on the membrane surface is 3cm/s, and the current density is 50mA/cm 2 Under the operation condition, the operation is carried out in an intermittent operation mode, and the conductivity of the solution in the feed liquid storage tank 4 is reduced to 5.94mS/cm after the operation is carried out for 90min, so that the experiment is stopped. The sulfuric acid concentration in the acid liquor storage tank 3 is 0.39mol/L, and the alkali liquor storage is performedThe concentration of potassium hydroxide in the tank 8 is 0.80mol/L,91.9 percent of thiadiazole is retained in the feed liquid storage tank 4, the energy consumption of the feed liquid in the desalting process is 215w.h/mol, and the desalting current efficiency is 72.90 percent.
Example 3: a BM-AM-CM three-compartment bipolar membrane electrodialysis system was used, see fig. 4. In the embodiment, the content of potassium sulfate in the thiadiazole production wastewater adopted is 80g/L, the content of thiadiazole is 1.0g/L, 0.1mol/L diluted acid and diluted alkali are respectively injected into the acid chamber and the alkali chamber 18, and 0.5mol/L sodium sulfate is injected into the electrode liquid chamber 17. The flow rate on the membrane surface is 5cm/s, and the current density is 50mA/cm 2 Under the operation condition, the operation is carried out in an intermittent operation mode, and the conductivity of the solution in the feed liquid storage tank 4 is reduced to 7.49mS/cm after the operation is carried out for 90min, so that the experiment is stopped. The concentration of sulfuric acid in the acid liquid storage tank 3 is 0.42mol/L, the concentration of potassium hydroxide in the alkali liquid storage tank 8 is 0.85mol/L,94.6% thiadiazole is retained in the feed liquid storage tank 4, the energy consumption in the feed liquid desalting process is 180w.h/mol, and the desalting current efficiency is 68.58%.
Example 4: a BM-AM-CM three-compartment bipolar membrane electrodialysis system was used, see fig. 4. The content of potassium sulfate in the thiadiazole production wastewater adopted in the embodiment is 80g/L, the content of thiadiazole is 1.0g/L, distilled water is respectively injected into the acid chamber 15 and the alkali chamber 18, and 0.5mol/L sodium sulfate is injected into the electrode liquid chamber 17. The flow rate on the membrane surface is 5cm/s, and the current density is 30mA/cm 2 Under the operation condition, the operation is carried out in an intermittent operation mode, and the conductivity of the solution in the feed liquid storage tank 4 is reduced to 5.53mS/cm after the operation is carried out for 150min, so that the experiment is stopped. The concentration of sulfuric acid in the acid liquor storage tank 3 is 0.38mol/L, the concentration of potassium hydroxide in the alkali liquor storage tank 8 is 0.78mol/L,87.2% thiadiazole is retained in the feed liquor storage tank 4, the energy consumption in the feed liquor desalting process is 154w.h/mol, and the desalting current efficiency is 72.79%.
Example 5: a BM-AM-CM three-compartment bipolar membrane electrodialysis system was used, see fig. 4. The content of potassium sulfate in the thiadiazole production wastewater adopted in the embodiment is 80g/L, the content of thiadiazole is 1.0g/L, distilled water is respectively injected into the acid chamber 15 and the alkali chamber 18, and 0.5mol/L sodium sulfate is injected into the electrode liquid chamber 17. The flow rate on the membrane surface is 5cm/s, and the current density is 70mA/cm 2 Under the operation condition, the operation is carried out in an intermittent operation mode, and the conductivity of the solution in the feed liquid storage tank 4 is reduced to 6.81mS/cm after the operation is carried out for 60min, so that the experiment is stopped. In the acid liquor storage tank 3The concentration of sulfuric acid is 0.38mol/L, the concentration of potassium hydroxide in the alkali liquor storage tank 8 is 0.77mol/L,91.0% thiadiazole is retained in the feed liquor storage tank 4, the energy consumption of the feed liquor in the desalting process is 293w.h/mol, and the desalting current efficiency is 75.02%.
Examples 1-5 the bipolar membrane electrodialysis treatment apparatus can also be operated in a multistage continuous mode.
The acid and alkali produced in the above examples can meet the use standard of the production raw material of thiadiazole after concentration, but example 3 is the most economical and practical example in view of the membrane stack cost and the equipment energy consumption of the bipolar membrane electrodialysis treatment device of thiadiazole.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and substitutions can be made without departing from the technical principle of the present invention, and these modifications and substitutions should also be regarded as the protection scope of the present invention.
Claims (8)
1. The thiadiazole production wastewater treatment method is characterized by comprising a thiadiazole bipolar membrane electrodialysis treatment device (5), wherein an alkali chamber (18), a material chamber (16), an acid chamber (15) and an electrode liquid chamber (17) are arranged in the thiadiazole bipolar membrane electrodialysis treatment device (5), and the thiadiazole production wastewater treatment method comprises the following steps:
the method comprises the following steps: inputting thiadiazole production wastewater into a material chamber (16), inputting 0-0.05mol/L diluted alkali liquor into an alkali chamber (18), inputting 0-0.05mol/L diluted acid liquor into an acid chamber (15), and inputting 0.3-0.5mol/L sodium sulfate solution into an electrode liquid chamber (17);
step two: the thiadiazole bipolar membrane electrodialysis treatment device (5) is electrified to operate, and the current density is controlled to be 30-70mA/cm 2 In the middle of;
step three: carrying out electrodialysis concentration on the acid solution in the acid chamber (15) to obtain concentrated acid solution, and carrying out electrodialysis concentration on the alkali solution in the alkali chamber (18) to obtain concentrated alkali solution;
step four: respectively carrying out evaporation concentration on the concentrated acid solution, the concentrated alkali solution and the thiadiazole-containing water solution desalted by electrodialysis;
the thiadiazole bipolar membrane electrodialysis treatment device (5) comprises a membrane stack, the membrane stack comprises at least one membrane stack unit, bipolar membranes (19), cation exchange membranes (20) and anion exchange membranes (21) which are mutually spaced are arranged in the membrane stack unit, the bipolar membranes (19), the cation exchange membranes (20) and the anion exchange membranes (21) divide the membrane stack unit into an alkali chamber (18), a material chamber (16) and an acid chamber (15) which are sequentially mutually spaced, electrode plates are arranged at two ends of the membrane stack, an electrode liquid chamber (17) is arranged between the electrode plates and the membrane stack unit, bipolar membranes (19) used for separating a tail end membrane stack unit and the electrode liquid chamber (17) are arranged in the membrane stack, and the thiadiazole bipolar membrane electrodialysis treatment device further comprises a power supply (6) used for supplying power to the electrode plates;
between step two and step three: when the bipolar membrane electrodialysis treatment device (5) for thiadiazole operates, the power supply (6) continuously supplies power to the electrode plates, the conductivity of the solution in the feed liquid storage tank (4) is monitored, and when the conductivity of the electrodialysis desalted thiadiazole-containing water solution is reduced to 5-10mS/cm, the power supply (6) stops supplying power to the electrode plates.
2. The thiadiazole production wastewater treatment method according to claim 1, wherein the electrode plates comprise a cathode plate (23) and an anode plate (24), the cathode plate (23) and the anode plate (24) are respectively positioned at two ends of the membrane stack, the membrane stack unit is positioned between the anode plate (24) and the cathode plate (23), the power supply (6) is a direct current power supply, the anode of the direct current power supply is electrically connected with the anode plate (24), the cathode of the direct current power supply is electrically connected with the cathode plate (23), and the membrane stack unit is provided with a plurality of membrane stack units which are sequentially arranged.
3. The thiadiazole production wastewater treatment method according to claim 2, further comprising a solution tank comprising an acid solution storage tank (3) for containing an acid solution in the acid chamber (15), and an alkaline solution storage tank (8) for containing an alkaline solution in the alkaline chamber (18), and a feed solution storage tank (4) for supplying thiadiazole production wastewater to the feed chamber (16), and an electrode solution storage tank (7) for supplying an electrode solution to the electrode solution chamber (17), and further comprising a circulation pump (10) for delivering the solution in the solution tank.
4. The thiadiazole production wastewater treatment method according to claim 3, wherein in the first step: conveying the thiadiazole production wastewater into a feed liquid storage tank (4), conveying a sodium sulfate solution into an electrode solution storage tank (7), conveying a dilute alkali solution into an alkali solution storage tank (8), conveying a dilute acid solution into an acid solution storage tank (3), and circularly conveying the dilute acid solution by a circulating pump (10), wherein the membrane surface flow velocity is controlled to be 3-7 cm/s.
5. The thiadiazole production wastewater treatment method according to claim 3, further comprising an acid electrodialysis treatment device (11) for performing electrodialysis concentration on the acid in the acid storage tank (3), a concentrated acid storage tank (13) for collecting the concentrated acid in the acid electrodialysis treatment device (11), and an acid evaporation device (2) for performing evaporation concentration on the concentrated acid in the concentrated acid storage tank (13).
6. The thiadiazole production wastewater treatment method according to claim 5, further comprising a lye electrodialysis treatment device (12) for performing electrodialysis concentration on the lye in the lye storage tank (8), a concentrated lye storage tank (14) for collecting the concentrated lye in the lye electrodialysis treatment device (12), and a lye evaporation device (9) for performing evaporation concentration on the concentrated lye in the concentrated lye storage tank (14).
7. The thiadiazole production wastewater treatment method according to claim 6, further comprising a thiadiazole concentration device (1) for performing evaporative concentration on the desalted thiadiazole-containing aqueous solution in the feed liquid storage tank (4).
8. The thiadiazole production wastewater treatment method according to claim 7, wherein, in step four; the concentrated acid solution is evaporated and concentrated by the acid solution evaporation device (2), the concentrated alkali solution is evaporated and concentrated by the alkali solution evaporation device (9), and the thiadiazole-containing aqueous solution is evaporated and concentrated by the thiadiazole concentration device (1).
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