CN113026043B - Electrolysis equipment and application thereof - Google Patents

Electrolysis equipment and application thereof Download PDF

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CN113026043B
CN113026043B CN202110228369.8A CN202110228369A CN113026043B CN 113026043 B CN113026043 B CN 113026043B CN 202110228369 A CN202110228369 A CN 202110228369A CN 113026043 B CN113026043 B CN 113026043B
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power supply
electrode
voltage
waste liquid
cathode
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CN113026043A (en
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黄涛
宋东平
周璐璐
张树文
徐娇娇
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Zhejiang Huike Environmental Protection Technology Co ltd
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Changshu Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/30—Organic compounds

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Abstract

The invention discloses an electrolysis device and application thereof, wherein an electrolysis bath is coupled with a direct current power supply and a low-temperature plasma discharge power supply for use. The device has simple structure and convenient operation, and can obtain the target product only by adding the solution to be tested into the electrolytic bath for acting for a certain time. When the equipment provided by the invention is applied to the preparation of sodium hypochlorite with high effective chlorine content by using sodium chloride, the high-efficiency conversion from sodium chloride to sodium hypochlorite can be realized, and the effective chlorine content in the generated sodium hypochlorite solution meets the A-I index of sodium hypochlorite. The equipment provided by the invention is applied to purifying organic waste liquid, and can remove 99.8% of COD, 99.9% of chlorine, 99.8% of ammonia nitrogen and 99.5% of total phosphorus in the organic waste liquid to the maximum. When the equipment provided by the invention is applied to the preparation of elemental sulfur by using the sulfuric acid waste liquid, the highest conversion rate of sulfate radicals in the sulfuric acid waste liquid can reach more than 98%.

Description

Electrolysis equipment and application thereof
Technical Field
The invention belongs to the field of chemical production, and particularly relates to electrolysis equipment and application thereof.
Background
The sodium hypochlorite has better disinfection and sterilization effects, is easier to store, transport and use compared with liquid chlorine, and has better safety, so the sodium hypochlorite has wide application in the fields of water purification and sewage treatment plants, printing and dyeing industry and paper pulp bleaching. Since the outbreak of new coronavirus pneumonia, sodium hypochlorite is widely used as a bactericide and disinfectant in the lives of residents.
Currently, the preparation method of sodium hypochlorite mainly comprises 4 methods: double decomposition reaction method of bleaching powder and sodium carbonate, salt solution electrolysis method, soda solution chlorination reaction method and caustic soda chlorination method. Wherein, the sodium hypochlorite solution generated by the double decomposition reaction method of bleaching powder and sodium carbonate is easy to contain a large amount of calcium carbonate precipitate, and the preparation process needs a large amount of soda ash, thus being not suitable for industrial production. Both the soda solution chlorination reaction method and the caustic soda chlorination method are suitable for large-scale production, but chlorine is required in the preparation process, so that the potential safety hazard and the secondary pollution risk exist, and the cost is easy to fluctuate due to the change of the alkali price. The salt solution electrolysis method is a method in which chlorine gas generated by electrolysis of an aqueous sodium chloride solution is internally mixed with caustic soda and re-reacted to form sodium hypochlorite. The salt solution electrolysis method is a method for converting sodium chloride into sodium hypochlorite, other chemical reagents are not needed to be added, but the mass fraction of effective chlorine of the sodium hypochlorite prepared by the method is only 5 percent at present, and the chlorine conversion efficiency is low. Therefore, based on the above analysis, it is the key to solve the above problems to develop an apparatus and a corresponding method for preparing sodium hypochlorite with high available chlorine content using sodium chloride.
In addition, the industries of printing and dyeing, electroplating, pharmacy, food processing and the like are easy to generate a large amount of salt-containing organic wastewater, and if the salt-containing organic wastewater is directly discharged to the surrounding environment without treatment, the salt-containing organic wastewater can cause serious pollution to soil and surface and underground water bodies. The high-concentration salt-containing organic wastewater contains both high-concentration organic pollutants and a large amount of inorganic salt, so that the purification difficulty is high. For example, for wastewater containing only organic pollutants, purification of organic waste streams can often be achieved by flocculation coupled with anaerobic-aerobic biochemical processes. However, for the high-concentration salt-containing organic wastewater, the salinity of the high-concentration salt-containing organic wastewater cannot be effectively reduced through flocculation, and the high-concentration salt can inhibit the growth of microorganisms in the later-stage process, so that the treatment effect on the waste liquid is influenced.
At present, for high-concentration salt-containing organic waste liquid, a physical chemistry and biological method combined process is adopted. And the removal of salt is realized by adopting a membrane process coupled electrodialysis technology. And then the desalted organic waste liquid is treated by a biochemical (microbial) technology.
In general, the combined process can realize the treatment of the organic salt-containing waste liquid to a certain extent, but the existing combined process also has the problems of poor purification effect, more treatment links, long treatment period, high potential secondary pollution risk and the like. Therefore, if a set of equipment for disposing the high-concentration salt-containing organic waste liquid can be developed, the realization of the efficient disposal of the high-concentration salt-containing organic waste liquid is the key for solving the problems.
Furthermore, schools, especially universities, all over the country continuously generate a large amount of sulfuric acid-containing waste liquid every year during the practice of chemical experiments. Meanwhile, the sulfide metal mine can also generate a large amount of sulfuric acid-containing wastewater in the mineral exploitation, enrichment and smelting processes. For the traditional electroplating industry, wastewater containing a large amount of sulfate substances is generated in the electroplating process. If the waste water containing sulfuric acid or sulfate is directly discharged into water without proper treatment, the ecological environment of the water is seriously influenced and the water is polluted. Excessive sulfate radicals flow into the water body, so that the metabolism of anaerobic bacteria at the bottom of the water body becomes more active, and the activity of aerobic bacteria is inhibited. Meanwhile, the sulfate radical flowing into the river channel can accelerate the generation of methyl mercury in the water body and can be converted into H under the action of anaerobic bacteria2S, thereby causing serious harm to the growth and survival of various organisms such as microorganisms, algae, fishes and the like in the water body and leading the water body to gradually lose the ecological regulation function.
At present, the method for treating the waste liquid containing sulfuric acid mainly comprises an acid-base neutralization method, a chemical precipitation method and a microbial reduction method. Wherein, the acid-base neutralization method and the chemical precipitation method do not relate to the change of the valence state of sulfate radical. The microbial reduction method can convert sulfate radicals into elemental sulfur by sulfate reducing bacteria under anaerobic conditions, but the method has the problems of long action period and low sulfur conversion efficiency. Therefore, the development of a device for preparing elemental sulfur by directly utilizing sulfuric acid waste liquid and a corresponding preparation method are key for solving the problems.
The existing electrolysis equipment has a simple structure and generally consists of a direct current power supply, an electrode and an electrolysis bath. The electrodes are divided into an anode and a cathode, and the anode and the cathode are connected with a direct current power supply through leads. The waste liquid is usually placed between an anode and a cathode, and after the power is switched on, the pollutants are transferred to the direction of the electrode through the action of electromigration and electroosmotic flow, and the pollutants are converted or removed through getting lost electrons on the surface of the electrode. However, the current electrolysis device generates a large amount of hydrolysis gas (such as oxygen and hydrogen) during the electrolysis process, and a complex safety device is required to be configured for safely discharging the gas. And the current electrolytic equipment has low efficiency of disposing pollutant waste liquid and single function. For example, electrolysis of saturated sodium chloride solutions using existing electrolysis equipment can only achieve the transfer of chloride ions to the anode and then conversion to chlorine gas, which is then prepared by introducing chlorine gas into caustic soda. The method has the advantages that the utilization rate of chlorine is low, the chlorine generated in the electrolytic process cannot be fully mixed with caustic soda for reaction, the content of the effective chlorine in the prepared sodium hypochlorite is low, the oxygen generated in the electrolytic process is not fully utilized, and the oxygen in the sodium hypochlorite is required to be provided by adding the caustic soda from an external source. For another example, when the existing electrolytic equipment is used for treating the salt-containing organic waste liquid, the effective transfer and concentration of inorganic salts can be realized through electromigration, but the organic pollutants in the waste liquid cannot be effectively removed at the same time. And chlorine gas generated by anodic oxidation of chloride ions in the salt content of the electrolysis process needs additional treatment. For another example, when the waste liquid containing sulfuric acid is disposed by using the existing electrolysis equipment, the concentration of sulfate radicals at the anode can be realized, but the reduction of the sulfate radicals into elemental sulfur cannot be realized. Therefore, based on the above problem analysis, if a novel electrolysis device can be developed, different target functions can be realized and the gas generated in the electrolysis process can be recycled, which is of great significance for solving the above industrial problems.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the problems of the prior art, a first object of the present invention is to provide an electrolysis apparatus. The second purpose of the invention is to provide the application of the equipment in preparing sodium hypochlorite with high effective chlorine content by utilizing sodium chloride. A third object of the invention is to provide the use of the apparatus for purifying organic waste liquids. The fourth purpose of the invention is to provide the application of the equipment in preparing elemental sulfur by using the sulfuric acid waste liquid.
The technical scheme is as follows: the invention relates to an electrolysis device, which comprises an electrolytic bath, a direct current power supply and a low-temperature plasma discharge power supply; the electrolytic bath comprises a first electrode area, a high-voltage area and a second electrode area; the first electrode area is provided with a hydrogen gas exhaust port, a first electrode and a solution inlet; the high-voltage electric area is sequentially provided with a high-voltage wire, a high-voltage electrode sleeve and a grounding electrode from top to bottom, and the inside of the high-voltage electrode sleeve is sequentially provided with a high-voltage cap, a high-voltage electrode and an aeration head from top to bottom; the second electrode area is provided with an air outlet connected with the air receiving pipe and a second electrode; the gas outlet is communicated with the inner part of the high-voltage electrode sleeve through a gas connecting pipe, the high-voltage wire is connected with a high-voltage interface of the low-temperature plasma discharge power supply, and the grounding electrode is connected with a grounding port of the low-temperature plasma power supply through a grounding wire.
Further, the first electrode region is a cathode region, the second electrode region is an anode region, the first electrode is a cathode electrode, the second electrode is an anode electrode, the cathode electrode is provided with a cathode lead, the anode electrode is provided with an anode lead, the cathode lead is connected with a cathode interface of a direct current power supply, and the anode lead is connected with an anode interface of the direct current power supply.
Further, a cation exchange membrane is arranged between the cathode electrode and the high-voltage electrode sleeve, an anion exchange membrane is arranged between the anode electrode and the high-voltage electrode sleeve, a catholyte outlet is arranged in the cathode area, a solution outlet is arranged between the grounding electrode and the anode electrode, and an anolyte outlet is arranged in the anode area.
Further, the first electrode area is a cathode area, the second electrode area is an anode area, the first electrode is a cathode electrode, the second electrode is an anode electrode, the anode electrode is provided with an anode lead, the cathode electrode is provided with a cathode lead, the anode lead is connected with an anode interface of a direct current power supply, the cathode lead is connected with a cathode interface of the direct current power supply, an anode stirrer is arranged between the anode electrode and the grounding electrode, a cathode stirrer is arranged between the grounding electrode and the cathode electrode, and a slurry outlet is arranged between the grounding electrode and the cathode stirrer.
Further, the thickness of the high-voltage electrode sleeve is 0.5-2.5 cm, the high-voltage electrode sleeve is made of ceramic or quartz glass, and the vertical distance between the inner ring surface of the high-voltage electrode sleeve and the outer ring surface of the high-voltage electrode is 5-15 mm; the aeration aperture of the aeration head is 0.1-200 mu m, and the porosity of the aeration head is 35-75%.
The electrolysis equipment disclosed by the invention is applied to the preparation of sodium hypochlorite with high effective chlorine content by utilizing sodium chloride.
Further, the method for preparing the sodium hypochlorite with high effective chlorine content by using the sodium chloride through the electrolysis equipment comprises the following steps:
(A1) preparing a sodium chloride aqueous solution;
(A2) loading a sodium chloride aqueous solution into an electrolytic cell, switching on a direct current power supply, and turning on a low-temperature plasma discharge power supply to treat the sodium chloride aqueous solution;
(A3) and (4) closing the direct current power supply and the low-temperature plasma discharge power supply to obtain a sodium hypochlorite solution in the electrolytic bath.
Further, in the step (a1), the concentration of the aqueous sodium chloride solution is 5% to 25%; in the step (A2), the voltage of the DC power supply is 10-100V, and the current of the DC power supply is 100-1000A. The low-temperature plasma discharge voltage is 5-75 kV, the power is 10-100 kW, and the treatment time is 0.5-1.5 h.
The invention also discloses application of the electrolysis equipment in purifying organic waste liquid.
Further, the method for purifying the organic waste liquid by the electrolytic equipment comprises the following steps:
(B1) loading the organic waste liquid into an electrolytic bath through a solution inlet;
(B2) switching on a direct current power supply and a low-temperature plasma discharge power supply to treat the organic waste liquid;
(B3) and after the treatment is finished, disconnecting the direct current power supply and the low-temperature plasma discharge power supply, discharging the purified solution from the solution outlet, discharging the catholyte from the catholyte outlet, and discharging the anolyte from the anolyte outlet.
Further, in the step, the organic waste liquid is high-concentration organic waste liquid or salt-containing organic waste liquid, in the step, the voltage of the direct current power supply is 20-200V, the current is 100-1100A, the voltage of the low-temperature plasma discharge power supply is 5-75 kV, the power is 10-100 kW, and the treatment time is 0.2-2 h.
The electrolysis equipment disclosed by the invention is applied to the preparation of elemental sulfur by utilizing sulfuric acid waste liquid.
Further, the method for preparing the elemental sulfur by using the electrolysis equipment and utilizing the sulfuric acid waste liquid comprises the following steps:
(C1) leading the sulfuric acid waste liquid into an electrolytic cell through a solution inlet;
(C2) switching on a direct current power supply and a low-temperature plasma power supply to treat the sulfuric acid waste liquid;
(C3) starting an anode stirrer and a cathode stirrer to stir the treated sulfuric acid waste liquid, closing the anode stirrer and the cathode stirrer, and obtaining sulfur-containing slurry in an electrolytic tank;
(C4) discharging the sulfur-containing slurry from the slurry outlet;
(C5) and centrifuging the sulfur-containing slurry, and drying the solid part in vacuum to obtain elemental sulfur.
Further, in the step (C1), the sulfuric acid concentration in the sulfuric acid waste liquid is 0.5 to 17.5M; in the step (C2), the voltage of the direct current power supply is 10-100V, the current is 100-1000A, the low-temperature plasma discharge voltage is 5-75 kV, the power is 10-100 kW, the treatment time is 0.5-1.5 h, in the step (C3), the stirring time is 5-15 min, the stirring speed is 60-720 rpm, in the step (C5), the centrifugal speed is 3000-12000 rpm, the centrifugal time is 5-15 min, and the drying temperature is 50-90 DEG C
The reaction mechanism for preparing the sodium hypochlorite with high effective chlorine content by utilizing the sodium chloride is as follows: after the direct current power supply is switched on, chloride ions in the electrolytic cell migrate towards the direction of the anode electrode under the action of electromigration, and lose electrons to generate chlorine after contacting the anode electrode. Meanwhile, the surfaces of the anode electrode and the cathode electrode are hydrolyzed to respectively generate oxygen and hydrogen. Hydrogen generated by the cathode electrode is discharged into the air through the hydrogen exhaust hole, part of chlorine generated by the anode electrode is dissolved in water and hydrolyzed to generate hypochlorite, and part of chlorine and oxygen enter the high-voltage electrode sleeve through the air outlet and the connecting pipe. After a low-temperature plasma power supply is switched on, a discharge channel with high energy density is generated between the high-voltage electrode and the high-voltage electrode sleeve in the low-temperature plasma discharge process, and oxygen and chlorine are ionized and dissociated in the discharge channel to generate active particles such as chlorine free radicals, oxygen free radicals, chlorine oxygen free radicals, ozone and the like. The active particles enter the water solution in the electrolytic tank again through the aeration head, and then react with chloride ions in the electrolytic tank to generate hypochlorite, and the hypochlorite in the water solution in the electrolytic tank is combined with sodium ions to generate sodium hypochlorite.
The reaction mechanism for purifying the organic waste liquid is as follows: for the high-concentration organic waste liquid, when the direct current power supply is switched on, water molecules on the surface of the anode electrode lose electrons and are hydrolyzed to generate oxygen and hydrogen ions, and water molecules on the surface of the cathode electrode are hydrolyzed to generate hydrogen and hydroxyl ions. The oxygen is communicated to the high-voltage electrode sleeve through the air outlet hole and the air receiving pipe. The hydrogen gas is discharged through the hydrogen gas discharge hole. When the low-temperature plasma discharge power supply is switched on, a discharge channel is generated between the high-voltage electrode and the high-voltage electrode sleeve, and oxygen is ionized and dissociated in the discharge channel to generate oxygen radicals and ozone. Oxygen free radicals and ozone enter the high-concentration organic waste liquid in the electrolytic bath through the aeration head, and then organic matters in the waste liquid are promoted to be mineralized and converted into carbon dioxide and water.
For the high-concentration salt-containing organic waste liquid, after a direct-current power supply is switched on, chloride ions in the waste liquid of the electrolytic cell enter into the anolyte through an anion exchange membrane under the action of electromigration, lose electrons after contacting an anode and are converted into chlorine, and water molecules on the surface of an anode electrode lose electrons and are hydrolyzed to generate oxygen and hydroxyl ions. Chlorine and oxygen are led into the high-voltage electrode sleeve through the air outlet hole and the air receiving pipe. The hydrogen gas is discharged through the hydrogen gas discharge hole. When the low-temperature plasma discharge power supply is switched on, a discharge channel is generated between the high-voltage electrode and the high-voltage electrode sleeve, and oxygen and chlorine are ionized and dissociated in the discharge channel to generate oxidation active particles such as oxygen radicals, chlorine oxygen radicals and ozone. The oxidized active particles enter the high-concentration organic waste liquid in the electrolytic bath through the aeration head, so that organic matters in the waste liquid are mineralized and converted into carbon dioxide and water, and ammonia nitrogen in the waste liquid is oxidized into nitrate. Under the action of electromigration, nitrate radical, phosphate radical, converted chloride ion and other anions in the waste liquid enter the anolyte through an anion exchange membrane, and cations in the waste liquid enter the catholyte through a cation exchange membrane.
The reaction mechanism for preparing elemental sulfur by using the sulfuric acid waste liquid is as follows: after the direct current power supply is switched on, hydrogen ions in the electrolytic cell migrate towards the cathode direction, and the hydrogen ions obtain electrons on the surface of the cathode and are converted into hydrogen. At the same time, the water on the surface of the anode loses electrons and is converted into oxygen and hydrogen ions. Oxygen generated at the surface of the anode is discharged to the air through the oxygen discharge hole. Hydrogen generated on the surface of the cathode enters the high-voltage electrode sleeve through the air outlet and the connecting pipe. After a low-temperature plasma power supply is switched on, a discharge channel with high energy density is generated between the high-voltage electrode and the high-voltage electrode sleeve in the low-temperature plasma discharge process, and hydrogen gas is ionized and dissociated in the discharge channel to generate hydrogen radicals. The hydrogen free radicals enter the water solution in the electrolytic tank through the aeration head to react with sulfate radicals to generate elemental sulfur and hydroxyl ions, and the hydroxyl ions and the hydrogen ions in the electrolytic tank generate water. After the stirrer was started, elemental sulphur was suspended in the water under the impact of the water. And opening the slurry outlet valve, and discharging the aqueous solution carrying the elemental sulfur from the slurry outlet. And centrifuging the sulfur-containing slurry to obtain elemental sulfur and an aqueous solution. And drying the elemental sulfur obtained by centrifugation to obtain the finally prepared elemental sulfur.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the invention couples the electrolytic bath with the direct current power supply and the low-temperature plasma discharge for use, has simple equipment structure and convenient operation, and can obtain the target product only by adding the solution to be tested into the electrolytic bath for acting for a certain time. The equipment provided by the invention is applied to the preparation of sodium hypochlorite with high effective chlorine content by using sodium chloride, so that the high-efficiency conversion from sodium chloride to sodium hypochlorite can be realized, the effective chlorine content in the generated sodium hypochlorite solution meets the A-I index of sodium hypochlorite, and the equipment provided by the invention is applied to the purification of organic waste liquid, so that the removal of 99.8% of COD, 99.9% of chlorine, 99.8% of ammonia nitrogen and 99.5% of total phosphorus in the organic waste liquid can be realized at most. When the equipment provided by the invention is applied to the preparation of elemental sulfur by using the sulfuric acid waste liquid, the highest conversion rate of sulfate radicals in the sulfuric acid waste liquid can reach more than 98%.
Drawings
FIG. 1 is a sectional view of an electrolytic cell of an apparatus for producing sodium hypochlorite with a high available chlorine content by using sodium chloride.
FIG. 2 is a sectional view of an electrolytic cell for purifying an organic waste liquid.
FIG. 3 is a cross-sectional view of an electrolytic cell for producing elemental sulfur from a sulfuric acid waste solution.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Application of electrolysis equipment in preparation of sodium hypochlorite with high effective chlorine content by using sodium chloride
Example 1 Effect of sodium chloride Mass concentration on the content of available chlorine
As shown in FIG. 1, the apparatus comprises an electrolytic bath 10, a DC power supply and a low temperature plasma discharge power supply; the electrolytic bath 10 comprises a first electrode area, a high-voltage area and a second electrode area; the first electrode area is a cathode area, and the second electrode area is an anode area; the upper end of the cathode region is provided with a hydrogen gas exhaust port 16 and a solution inlet 11, and the inside of the cathode region is provided with a cathode electrode 1 with a cathode lead 6; the high-voltage area is sequentially provided with a high-voltage wire 9, a high-voltage electrode sleeve 15 and a grounding electrode 4 from top to bottom, and the high-voltage cap 8, the high-voltage electrode 3 and the aeration head 5 are sequentially arranged in the high-voltage electrode sleeve 15 from top to bottom; the positive pole district upper end is equipped with the gas outlet 13 of connecting the trachea 14, the inside positive pole electrode 2 who connects positive pole wire 7 that is equipped with of positive pole district, the positive pole wire 7 that stands is connected with DC power supply's positive pole interface, gas outlet 13 is linked together through trachea 14 and high voltage electrode cover 15 are inside, high-voltage line 9 and low temperature plasma discharge power high pressure interface connection, telluric electricity field 4 is connected with low temperature plasma power ground connection port through the earth connection, negative pole wire 6 and DC power supply's negative pole interface connection. After the solution sample is loaded into the electrolytic cell 10 through the solution inlet 11, the gas generated by the electrolysis of the anode electrode 2 is introduced into the electrolytic cell 10 through the gas outlet 13, the gas receiving pipe 14, the high-voltage electrode sleeve 15 and the aeration head 5; hydrogen generated by electrolysis of the cathode electrode 1 is discharged through the hydrogen discharge hole 16.
Sodium chloride aqueous solutions having sodium chloride mass concentrations of 5%, 10%, 15%, 20%, and 25% were prepared, respectively. Opening a solution inlet valve 12, loading a sodium chloride aqueous solution into an electrolytic tank 10 through a solution inlet 11, switching on a direct current power supply and a low-temperature plasma discharge power supply to treat the sodium chloride aqueous solution, discharging hydrogen generated by electrolysis of a cathode electrode 1 into the air through a hydrogen exhaust hole 16, dissolving part of chlorine generated by electrolysis of an anode electrode 2 in the water to hydrolyze to generate hypochlorite, and enabling part of the chlorine and oxygen to enter a high-voltage electrode sleeve 15 through an air outlet 13 and an air receiving pipe 14 and then enter the solution of the electrolytic tank 10 again through an aeration head 5. After the treatment is carried out for 0.5h, the direct current power supply and the low-temperature plasma discharge power supply are disconnected, and five groups of sodium hypochlorite solutions are obtained in the electrolytic cell 10, wherein the voltage of the direct current power supply is 10V, the current is 100A, the voltage of the low-temperature plasma discharge power supply is 5kV, and the power is 10 kW.
And (3) detecting the content of available chlorine: the content of available chlorine in the sodium hypochlorite solution is detected according to the national standard of sodium hypochlorite (GB/T19106-2013).
The test results of this example are shown in Table 1.
TABLE 1 influence of the sodium chloride Mass concentration on the available chlorine content
Mass concentration of sodium chloride Available chlorine content Relative error
5％ 25.36％ ±0.1％
10％ 29.24％ ±0.1％
15％ 32.58％ ±0.1％
20％ 27.93％ ±0.1％
25％ 23.28％ ±0.1％
As can be seen from Table 1, when the mass concentration of sodium chloride is in the range of 5-25%, the content of available chlorine in the sodium hypochlorite solution prepared by the method is more than 22%, and the available chlorine content meets the A-I index of sodium hypochlorite, namely the available chlorine content is more than or equal to 13%.
EXAMPLE 2 Effect of DC supply Current on available chlorine content
The experimental equipment and method are the same as example 1, wherein the concentration of the sodium chloride aqueous solution is 15%, the sodium chloride aqueous solution is treated for 1h by switching on a direct current power supply and a low-temperature plasma discharge power supply, the voltage of the direct current power supply is 55V, the currents are respectively 100A, 300A, 500A, 700A, 900A and 1000A, the voltage of the low-temperature plasma discharge power supply is 40kV, the power is 55kW, and the obtained sodium hypochlorite solutions are six groups.
The content of available chlorine was measured in the same manner as in example 1, and the test results of this example are shown in Table 2.
TABLE 2 influence of DC supply Current on available chlorine content
Current of DC power supply Available chlorine content Relative error
100A 34.17％ ±0.1％
300A 41.06％ ±0.1％
500A 42.58％ ±0.1％
700A 44.25％ ±0.1％
900A 47.13％ ±0.1％
1000A 39.04％ ±0.1％
As shown in Table 2, when the current of the DC power supply is in the range of 100-1000A, the content of available chlorine in the sodium hypochlorite solution prepared by the method is more than 34%, and the available chlorine in the sodium hypochlorite solution meets the A-I index of sodium hypochlorite, namely the available chlorine is more than or equal to 13%.
EXAMPLE 3 Effect of Low temperature plasma discharge Power on available chlorine content
The experimental equipment and method are the same as example 1, wherein the concentration of the sodium chloride aqueous solution is 15%, the sodium chloride aqueous solution is treated for 1.5h by connecting a direct current power supply and a low-temperature plasma discharge power supply, the voltage of the direct current power supply is 100V, the current is 550A, the voltage of the low-temperature plasma discharge power supply is 75kV, the power is 10kW, 30kW, 50kW, 70kW, 90kW and 100kW, and the total six groups of sodium hypochlorite solutions are obtained.
The content of available chlorine was measured in the same manner as in example 1, and the test results of this example are shown in Table 3.
TABLE 3 influence of Power of Low-temperature plasma discharge Power supply on available chlorine content
Figure GDA0003409325380000081
As can be seen from Table 3, when the power of the low-temperature plasma discharge power supply is in the range of 10-100 kW, the content of available chlorine in the sodium hypochlorite solution prepared by the method is more than 41%, and the sodium hypochlorite solution meets the A-I index, namely the available chlorine is more than or equal to 13%.
Different treatment processes realize comparison of effective chlorine content of sodium hypochlorite
Example 4
The process, experimental equipment and method of the invention are the same as those of example 1, wherein the concentration of the sodium chloride aqueous solution is 15%, a direct current power supply and a low-temperature plasma discharge power supply are switched on to treat the sodium chloride aqueous solution for 1.5h, the voltage of the direct current power supply is 100V, the current is 550A, the voltage of the low-temperature plasma discharge power supply is 75kV, and the power is 100kW, so as to obtain the sodium hypochlorite solution.
Comparative example 1
The experimental equipment and method are the same as example 1, wherein the concentration of the sodium chloride aqueous solution is 15%, the sodium chloride aqueous solution is treated for 1.5h by only switching on a direct current power supply, the voltage of the direct current power supply is 100V, the current is 550A, and the sodium hypochlorite comparative solution 1 is obtained.
Comparative example 2
The experimental equipment and method are the same as example 1, wherein the concentration of the sodium chloride aqueous solution is 15%, the sodium chloride aqueous solution is treated for 1.5h only by switching on the low-temperature plasma discharge power supply, the voltage of the low-temperature plasma discharge power supply is 75kV, the power is 100kW, and the sodium hypochlorite comparative solution 2 is obtained.
Comparative example 3
The experimental equipment and method are the same as example 1, wherein the concentration of the sodium chloride aqueous solution is 15%, the sodium chloride aqueous solution is treated for 1.5h by only switching on a direct current power supply, the voltage of the direct current power supply is 100V, the current is 550A, then the direct current power supply is switched off, and a low-temperature plasma discharge power supply is switched on to treat the sodium chloride aqueous solution for 1.5h, the voltage of the low-temperature plasma discharge power supply is 75kV, and the power is 100kW, so that the sodium hypochlorite comparative solution 3 is obtained.
The effective chlorine content was measured as in example 1, example 4 and comparative examples 1 to 3, and the results are shown in Table 4.
TABLE 4 comparison of sodium hypochlorite available chlorine content by different treatment processes
Type of process Available chlorine content Relative error
Example 4 50.28％ ±0.1％
Comparative example 1 2.37％ ±0.1％
Comparative example 2 0.82％ ±0.1％
Comparative example 3 4.13％ ±0.1％
It can be seen from table 4 that, by coupling the dc electromotive discharge with the low-temperature plasma discharge, sodium chloride can be conveniently and rapidly converted into sodium hypochlorite, the available chlorine content is 50.28%, the available chlorine content meets the index of sodium hypochlorite a-I, and the effect is significantly better than the case where the dc electromotive comparative example 1 and the low-temperature plasma discharge comparative example 2 are used alone or connected in series, i.e., the comparative example 3, so that the coupling of the dc electromotive discharge and the low-temperature plasma discharge plays a role in synergy.
Second, application of electrolysis equipment in purifying organic waste liquid
The printing and dyeing waste liquid is taken from a waste liquid collecting tank of a certain Shaoxing Shangyao warp knitting and dyeing enterprise and mainly contains rhodamine B of 1789mg/LCOD and malachite green of 1542 mg/LCOD.
The landfill leachate is obtained from sanitary landfill of domestic garbage in Qingcheng mountain in Haizhou area of Hongyun harbor city. The mass concentration of COD in the landfill leachate is 2431mg/L, the concentration of ammonia nitrogen is 824mg/L, the concentration of total phosphorus is 546mg/L, and the chlorine content is 902 mg/L.
Example 5 influence of DC Power supply and Low-temperature plasma discharge on-time on purification effects of printing and dyeing waste liquid and landfill leachate
As shown in fig. 2, the apparatus comprises an electrolytic bath 10, a direct current power supply and a low temperature plasma discharge power supply as shown in fig. 1; the electrolytic bath 10 comprises a first electrode area, a high-voltage area and a second electrode area; the first electrode area is a cathode area, and the second electrode area is an anode area; the upper end of the cathode region is provided with a hydrogen gas outlet 16 and a solution inlet 11, a cathode electrode 1 with a cathode lead 6 and a cation exchange membrane 18 are arranged in the cathode region side by side, and the side surface of the lower end of the cathode region is provided with a catholyte outlet 21; the high-voltage electric area is sequentially provided with a high-voltage wire 9, a high-voltage electrode sleeve 15 and a grounding electrode 4 from top to bottom, a solution outlet 19 is arranged beside the grounding electrode 4, and a high-voltage cap 8, a high-voltage electrode 3 and an aeration head 5 are sequentially arranged in the high-voltage electrode sleeve 15 from top to bottom; the upper end of the anode region is provided with an air outlet 13 connected with an air connecting pipe 14, the side surface of the lower end of the anode region is provided with an anolyte outlet 23, and an anion exchange membrane 17 and an anode electrode 2 connected with an anode lead 7 are arranged in the anode region side by side; the anode lead 7 is connected with an anode interface of a direct-current power supply, the gas outlet 13 is communicated with the inside of the high-voltage electrode sleeve 15 through a gas connecting pipe 14, the high-voltage wire 9 is connected with a high-voltage interface of a low-temperature plasma discharge power supply, the grounding electrode 4 is connected with a grounding port of the low-temperature plasma discharge power supply through a grounding wire, and the cathode lead 6 is connected with a cathode interface of the direct-current power supply. After the solution sample is loaded into the electrolytic cell 10 through the solution inlet 11, the gas generated by the electrolysis of the anode electrode 2 is introduced into the electrolytic cell 10 through the gas outlet 13, the gas receiving pipe 14, the high-voltage electrode sleeve 15 and the aeration head 5; hydrogen generated by the electrolysis of the cathode electrode 1 is discharged through the hydrogen vent hole 16; the anion exchange membrane 17 allows only anions to pass through; the cation exchange membrane 18 allows only cations to pass through; the purified solution is discharged through a solution outlet 19; catholyte is discharged through the catholyte outlet 21; the anolyte is discharged through anolyte outlet 23.
Purifying the printing and dyeing waste liquid: the solution inlet valve 12 of the purification apparatus is opened, the printing waste liquid is loaded into the electrolytic bath 10 through the sample inlet 11, and the solution inlet valve 12 is closed. Switching on a direct current power supply and a low-temperature plasma discharge power supply, and switching off the direct current power supply and the low-temperature plasma discharge power supply after 0.2h, 0.6h, 1h, 1.4h, 1.8h and 2h to obtain six groups of purified solutions in an electrolytic tank 10, wherein the voltage of the direct current power supply is 20V, the current is 100A, the voltage of the low-temperature plasma discharge power supply is 5kV, and the power is 10 kW. The solution outlet valve 20 is opened to discharge the purified solution through the solution outlet 19, the catholyte outlet valve 22 is opened to discharge the catholyte through the catholyte outlet 21, and the anolyte outlet valve 24 is opened to discharge the anolyte through the anolyte outlet 23.
Purifying the landfill leachate: the solution inlet valve 12 of the purification plant is opened and the landfill leachate is loaded into the electrolytic cell 10 through the sample inlet 11, and the solution inlet valve 12 is closed. Switching on a direct current power supply and a low-temperature plasma discharge power supply, and switching off the direct current power supply and the low-temperature plasma discharge power supply after 0.2h, 0.6h, 1h, 1.4h, 1.8h and 2h to obtain a purified solution in an electrolytic cell 10, wherein the voltage of the direct current power supply is 20V, the current is 100A, the voltage of the low-temperature plasma discharge power supply is 5kV, and the power is 10 kW. The solution outlet valve 20 is opened to discharge the purified solution through the solution outlet 19, the catholyte outlet valve 22 is opened to discharge the catholyte through the catholyte outlet 21, and the anolyte outlet valve 24 is opened to discharge the anolyte through the anolyte outlet 23.
And (3) detecting the COD concentration: the concentration of chemical oxygen demand COD in the printing and dyeing waste liquid and the landfill leachate is measured according to the national standard bichromate method for measuring water quality chemical oxygen demand (GB 11914-;
calculation of COD removal rate: the COD removal rate was calculated according to the formula (1), wherein RCODAs the removal rate of COD, c0And ctThe COD concentration (mg/L) of the printing and dyeing waste liquid or the landfill leachate before and after purification respectively.
Figure GDA0003409325380000111
And (3) detecting the ammonia nitrogen concentration: the concentration of ammonia nitrogen in the landfill leachate is measured according to salicylic acid spectrophotometry for measuring ammonia nitrogen in water (HJ 536-2009);
calculation of ammonia nitrogen removal: the ammonia nitrogen removal rate is calculated according to the formula (2), wherein RNFor ammonia nitrogen removal, cN0The initial concentration (mg/L) of ammonia nitrogen in the landfill leachate before purification, cNtThe residual ammonia nitrogen concentration (mg/L) in the purified landfill leachate is obtained.
Figure GDA0003409325380000112
And (3) detecting the total phosphorus concentration: the total phosphorus concentration of the landfill leachate is measured according to the standard continuous flow-ammonium molybdate spectrophotometry for measuring phosphate and total phosphorus of water (HJ 670-2013).
Calculation of total phosphorus removal: the total phosphorus removal was calculated according to formula (3), where RTPAs a total phosphorus removal rate, cTP0And cTPtThe total phosphorus concentration (mg/L) of the landfill leachate before and after purification is respectively.
Figure GDA0003409325380000113
And (3) detecting the concentration of chloride ions: the content of chloride ions in the landfill leachate is measured by an ionic agent.
Calculation of chloride ion removal rate: the removal rate of chloride ions was calculated according to the formula (4) wherein RClAs a chloride ion removal rate, cCl0And ccltThe concentration (mg/L) of the chloride ions before and after purification of the landfill leachate is respectively.
Figure GDA0003409325380000121
The test results of the removal rates of COD in the printing and dyeing waste liquid and COD, ammonia nitrogen, total phosphorus and chloride ions in the landfill leachate are shown in Table 5.
TABLE 5 influence of DC power and low-temperature plasma discharge power on-time on purification effect of printing and dyeing waste liquid and garbage leachate
Figure GDA0003409325380000122
As can be seen from Table 5, when the on-time of the direct current power supply and the low-temperature plasma discharge power supply is 0.2-2 h, the printing and dyeing waste liquid and the landfill leachate can be effectively purified by using the equipment and the method, the COD removal rate of the printing and dyeing waste liquid is higher than 96%, the COD removal rate of the landfill leachate is higher than 97%, the ammonia nitrogen removal rate is higher than 95%, the total phosphorus removal rate is higher than 96%, and the chloride ion removal rate is higher than 98%.
Example 6 influence of DC Power supply voltage on purification effects of printing and dyeing waste liquid and landfill leachate
Purifying the printing and dyeing waste liquid: the experimental equipment and process were the same as example 5, in which the waste liquid was treated for 2h by connecting a DC power supply and a low-temperature plasma discharge power supply, the voltages of the DC power supply were 20V, 60V, 100V, 140V, 180V, and 200V, respectively, the current was 600A, the voltage of the low-temperature plasma discharge power supply was 40kV, and the power was 55 kW.
Purifying the landfill leachate: the experimental equipment and process were the same as example 5, in which the waste liquid was treated for 2h by connecting a DC power supply and a low-temperature plasma discharge power supply, the voltages of the DC power supply were 20V, 60V, 100V, 140V, 180V, and 200V, respectively, the current was 600A, the voltage of the low-temperature plasma discharge power supply was 40kV, and the power was 55 kW.
COD concentration detection, COD removal rate calculation, ammonia nitrogen concentration detection, ammonia nitrogen removal rate calculation, total phosphorus concentration detection, total phosphorus removal rate calculation, chloride ion concentration detection and chloride ion removal rate calculation are the same as those in example 5.
The test results of the removal rates of COD in the printing and dyeing waste liquid and COD, ammonia nitrogen, total phosphorus and chloride ions in the landfill leachate are shown in Table 6.
TABLE 6 influence of DC power supply voltage on purification effect of printing and dyeing waste liquid and garbage leachate
Figure GDA0003409325380000131
As can be seen from Table 6, when the voltage of the DC power supply is 20-200V, the printing and dyeing waste liquid and the landfill leachate can be effectively purified by using the equipment and the method, the COD removal rate of the printing and dyeing waste liquid is higher than 98%, the COD removal rate of the landfill leachate is higher than 98%, the ammonia nitrogen removal rate is higher than 99%, the total phosphorus removal rate is higher than 98%, and the chloride ion removal rate is higher than 99%.
Example 7 influence of discharge power of low-temperature plasma power supply on purification effect of printing and dyeing waste liquid and landfill leachate
Purifying the printing and dyeing waste liquid: the experimental equipment and process were the same as example 5, in which a dc power supply and a low-temperature plasma discharge power supply were connected to treat the waste liquid for 2h, the voltage of the dc power supply was 200V, the current was 1100A, the voltage of the low-temperature plasma discharge power supply was 75kV, and the power of the low-temperature plasma discharge power supply was 10kW, 30kW, 50kW, 70kW, 90kW, and 100kW, respectively.
Purifying the landfill leachate: the experimental equipment and process were the same as example 5, in which a dc power supply and a low-temperature plasma discharge power supply were connected to treat the waste liquid for 2h, the voltage of the dc power supply was 200V, the current was 1100A, the voltage of the low-temperature plasma discharge power supply was 75kV, and the power of the low-temperature plasma discharge power supply was 10kW, 30kW, 50kW, 70kW, 90kW, and 100kW, respectively.
COD concentration detection, COD removal rate calculation, ammonia nitrogen concentration detection, ammonia nitrogen removal rate calculation, total phosphorus concentration detection, total phosphorus removal rate calculation, chloride ion concentration detection and chloride ion removal rate calculation are the same as those in example 5.
The test results of the removal rates of COD in the printing and dyeing waste liquid and COD, ammonia nitrogen, total phosphorus and chloride ions in the landfill leachate are shown in Table 7.
TABLE 7 influence of discharge power of low-temperature plasma power supply on purification effect of printing and dyeing waste liquid and garbage leachate
Figure GDA0003409325380000132
Figure GDA0003409325380000141
As can be seen from Table 7, when the discharge power of the low-temperature plasma power supply is 10-100 kW, the printing and dyeing waste liquid and the landfill leachate can be effectively purified by using the equipment and the method, the COD removal rate of the printing and dyeing waste liquid is higher than 99%, the COD removal rate of the landfill leachate is higher than 99%, the ammonia nitrogen removal rate is higher than 99%, the total phosphorus removal rate is higher than 99%, and the chloride ion removal rate is higher than 99%.
Contrast of purification effects of printing and dyeing waste liquid and garbage leachate by different contrast processes
Example 8
Purifying the printing and dyeing waste liquid: the experimental equipment and process were the same as example 5, in which a DC power supply and a low temperature plasma discharge power supply were connected to treat the waste liquid for 2h, the voltage of the DC power supply was 200V, the current was 1100A, the voltage of the low temperature plasma discharge power supply was 75kV, and the power of the low temperature plasma discharge power supply was 100 kW.
Purifying the landfill leachate: the experimental equipment and process were the same as example 5, in which a DC power supply and a low temperature plasma discharge power supply were connected to treat the waste liquid for 2h, the voltage of the DC power supply was 200V, the current was 1100A, the voltage of the low temperature plasma discharge power supply was 75kV, and the power of the low temperature plasma discharge power supply was 100 kW.
Comparative example 4
Purifying the printing and dyeing waste liquid: the experimental equipment and procedure were the same as in example 5, in which the printing and dyeing waste liquid was treated for 2 hours by only switching on a DC power supply, the voltage of which was 200V and the current was 1100A.
Purifying the landfill leachate: the experimental equipment and process are the same as example 5, wherein the landfill leachate is treated for 2h by only switching on a direct current power supply, the voltage of the direct current power supply is 200V, and the current is 1100A.
Comparative example 5
Purifying the printing and dyeing waste liquid: the experimental equipment and the process are the same as those of example 5, wherein the printing and dyeing waste liquid is treated for 2h by only switching on the low-temperature plasma discharge power supply, the voltage of the low-temperature plasma discharge power supply is 75kV, and the power of the low-temperature plasma discharge power supply is 100 kW.
Purifying the landfill leachate: the experimental equipment and the process are the same as those of the example 5, wherein the landfill leachate is treated for 2 hours only by switching on the low-temperature plasma discharge power supply, the voltage of the low-temperature plasma discharge power supply is 75kV, and the power of the low-temperature plasma discharge power supply is 100 kW.
Comparative example 6
Purifying the printing and dyeing waste liquid: the experimental equipment and process were the same as example 5, wherein the printing and dyeing waste liquid was treated by switching on only the dc power supply for 2h, the voltage of the dc power supply was 200V, the current was 1100A, and then the printing and dyeing waste liquid was treated by switching on only the low temperature plasma discharge power supply for 2h, the voltage of the low temperature plasma discharge power supply was 75kV, and the power of the low temperature plasma discharge power supply was 100 kW.
Purifying the landfill leachate: the experimental equipment and the process are the same as those of the example 5, wherein firstly only a direct current power supply is connected for treating the landfill leachate for 2h, the voltage of the direct current power supply is 200V, the current is 1100A, and then only a low-temperature plasma discharge power supply is connected for treating the landfill leachate for 2h, the voltage of the low-temperature plasma discharge power supply is 75kV, and the power of the low-temperature plasma discharge power supply is 100 kW.
COD concentration detection, COD removal rate calculation, ammonia nitrogen concentration detection, ammonia nitrogen removal rate calculation, total phosphorus concentration detection, total phosphorus removal rate calculation, chloride ion concentration detection and chloride ion removal rate calculation are the same as those in example 5.
The test results of COD in the printing and dyeing waste liquid and the removal rates of COD, ammonia nitrogen, total phosphorus and chloride ions in the landfill leachate in example 8 and comparative examples 4-6 are shown in Table 8.
TABLE 8 comparison of purification effects of waste dyeing liquor and landfill leachate by different treatment processes
Figure GDA0003409325380000151
As can be seen from Table 8, the direct current electric and low temperature plasma discharge are coupled to achieve the COD removal rate of the printing and dyeing waste liquid higher than 99.73%, the COD removal rate of the landfill leachate higher than 99.69%, the ammonia nitrogen removal rate higher than 99.67%, the total phosphorus removal rate higher than 99.49%, and the chloride ion removal rate higher than 99.71%. The purification effect of the printing and dyeing waste liquid and the garbage leachate of the equipment, namely the example 8, is obviously better than that of the direct current electric, namely the comparative example 4 and the low-temperature plasma discharge, namely the comparative example 5, which are used independently or the direct current electric and the low-temperature plasma discharge are connected in series, namely the comparative example 6, so that the direct current electric and the low-temperature plasma discharge are coupled to play a role in synergy.
Application of electrolysis equipment in preparation of elemental sulfur by using sulfuric acid
Example 9 influence of sulfuric acid concentration in sulfuric acid waste liquor on sulfate conversion
As shown in fig. 3, the apparatus comprises an electrolytic bath 10, a direct current power supply and a low temperature plasma discharge power supply; the electrolytic bath 10 comprises a first electrode area, a high-voltage area and a second electrode area, wherein the first electrode area is an anode area, and the second electrode area is a cathode area; the upper end of the anode area is provided with a hydrogen gas outlet 16 and a solution inlet 11, an anode electrode 2 connected with an anode lead 7 is arranged in the anode area, and the lower end of the anode is provided with an anode stirrer 17; the high-voltage electric area is sequentially provided with a high-voltage wire 9, a high-voltage electrode sleeve 15 and a grounding electrode 4 from top to bottom, a slurry outlet 18 is arranged beside the grounding electrode 4, and a high-voltage cap 8, a high-voltage electrode 3 and an aeration head 5 are sequentially arranged in the high-voltage electrode sleeve 15 from top to bottom; the upper end of the cathode region is provided with an air outlet 13 connected with an air receiving pipe 14, a cathode electrode 1 with a cathode lead 6 is arranged in the cathode region, and the lower end of the cathode is provided with a cathode stirrer 20; the cathode lead 6 is connected with a cathode interface of a direct-current power supply, the air outlet 13 is communicated with the inside of the high-voltage electrode sleeve 15 through an air connecting pipe 14, the high-voltage wire 9 is connected with a high-voltage interface of a low-temperature plasma discharge power supply, the grounding electrode 4 is connected with a grounding port of the low-temperature plasma power supply through a grounding wire, and the anode lead 7 is connected with an anode interface of the direct-current power supply. After a solution sample is loaded into the electrolytic cell 10 through the solution inlet 11, gas generated by electrolysis of the cathode electrode 1 is introduced into the electrolytic cell 10 through the gas outlet 13, the gas receiving pipe 14, the high-voltage electrode sleeve 15 and the aeration head 5; hydrogen generated by electrolysis of the anode electrode 2 is discharged through the hydrogen discharge hole 16.
The solution inlet valve 12 is opened, and the sulfuric acid waste liquid is introduced into the electrolytic bath 10 from the solution inlet 11, wherein the sulfuric acid concentration in the sulfuric acid waste liquid is respectively 0.5M, 4M, 7.5M, 9M, 10.5M, 14M and 17.5M. And closing the solution inlet valve 12, and switching on a direct current power supply and a low-temperature plasma discharge power supply to treat the sulfuric acid waste liquid, wherein the voltage of the direct current power supply is 10V, the current of the direct current power supply is 100A, the voltage of the low-temperature plasma discharge power supply is 5kV, and the power of the low-temperature plasma discharge power supply is 10 kW. After 0.5h, the direct current power supply and the low-temperature plasma discharge power supply are disconnected, and then the anode stirrer 17 and the cathode stirrer 20 are started to stir for 5min, wherein the stirring speed of the stirrers is 60 rpm. The anode stirrer 17 and the cathode stirrer 20 were turned off to obtain a sulfur-containing slurry in the electrolytic bath 10. The slurry outlet valve 19 is opened to discharge the sulfur-containing slurry from the slurry outlet 18. Centrifuging the sulfur-containing slurry for 5min, discharging the supernatant, and vacuum drying the obtained solid part to obtain seven groups of elemental sulfur, wherein the centrifugation speed is 3000rpm, and the drying temperature is 50 ℃.
Sulfate conversion calculation: the sulfate radical conversion rate is calculated according to the formula (1), wherein alpha is the sulfate radical conversion rate, M is the mass (g) of the elemental sulfur prepared by the invention, c is the sulfuric acid concentration (M) in the sulfuric acid waste liquid, and V is the volume (L) of the sulfuric acid waste liquid.
Figure GDA0003409325380000161
The test results of this example are shown in Table 9.
TABLE 9 influence of sulfuric acid concentration in sulfuric acid waste liquor on sulfate radical conversion
Concentration of sulfuric acid in sulfuric acid waste liquid Sulfate radical conversion Relative error
0.5M 94.32％ ±0.1％
4M 93.65％ ±0.1％
7.5M 95.06％ ±0.1％
9M 96.37％ ±0.1％
10.5M 95.28％ ±0.1％
14M 93.19％ ±0.2％
17.5M 92.84％ ±0.1％
As can be seen from Table 9, when the concentration of sulfuric acid in the sulfuric acid waste liquid is in the range of 0.5-17.5M, the sulfuric acid in the sulfuric acid waste liquid can be effectively converted into elemental sulfur by using the equipment and the method provided by the invention, and the conversion rate of sulfate radicals in the sulfuric acid waste liquid is more than 92%.
Example 10 the effect of the time for treating sulfuric acid waste liquor when the DC power supply and the low temperature plasma discharge power supply are switched on the sulfate radical conversion
The experimental equipment and method are the same as those in example 9, wherein the concentration of sulfuric acid in the sulfuric acid waste liquid is 9M. The time for disposing the sulfuric acid waste liquid by switching on the direct current power supply and the low-temperature plasma discharge power supply is 0.5h, 0.75h, 1h, 1.25h and 1.5h respectively, the voltage of the direct current power supply is 55V, the current is 550A, the voltage of the low-temperature plasma discharge power supply is 40kV, the power is 55kW, the stirring speed of the anode stirrer 17 and the stirring speed of the cathode stirrer 20 are 390rpm, the stirring time is 10min, the centrifugal speed is 7500rpm, the centrifugal time is 10min, and the drying temperature is 70 ℃, so that five groups of elemental sulfur are obtained.
The sulfate conversion was calculated as in example 9 and the results of this example are shown in Table 10.
TABLE 10 influence of the time for treating sulfuric acid waste liquid by switching on the DC power supply and the low-temperature plasma discharge power supply on the sulfate radical conversion rate
Figure GDA0003409325380000171
Figure GDA0003409325380000181
As can be seen from Table 10, when the on-time of the DC power supply and the low-temperature plasma discharge power supply is in the range of 0.5-1.5 h, the equipment and the method can effectively convert the sulfuric acid in the sulfuric acid waste liquid into elemental sulfur, and the conversion rate of sulfate radicals in the sulfuric acid waste liquid is greater than 94%.
Example 11 influence of DC supply Current on sulfate conversion
The experimental equipment and method are the same as example 9, wherein the sulfuric acid concentration in the sulfuric acid waste liquid is 9M, a dc power supply and a low-temperature plasma discharge power supply are switched on to treat the sulfuric acid waste liquid for 1h, the voltage of the dc power supply is 100V, the currents are respectively 100A, 300A, 500A, 700A and 1000A, the voltage of the low-temperature plasma discharge power supply is 75kV, the power is 100kW, the stirring speeds of the anode stirrer 17 and the cathode stirrer 20 are both 720rpm, the stirring time is 15min, the centrifugation speed is 12000rpm, the centrifugation time is 15min, and the drying temperature is 90 ℃, so as to obtain five groups of elemental sulfur.
The sulfate conversion was calculated as in example 9 and the results of this example are shown in Table 11.
TABLE 11 influence of DC supply current on sulfate conversion
Current of DC power supply Sulfate radical conversion Relative error
100A 95.24％ ±0.1％
300A 96.78％ ±0.1％
500A 96.15％ ±0.1％
700A 98.67％ ±0.1％
1000A 97.34％ ±0.1％
As can be seen from Table 11, when the DC power supply current is in the range of 100A-1000A, the sulfuric acid in the sulfuric acid waste liquid can be effectively converted into elemental sulfur by using the apparatus and the method of the present invention, and the conversion rate of sulfate radicals in the sulfuric acid waste liquid is greater than 95%.
Example 12 Effect of Low temperature plasma discharge Power on sulfate conversion
The experimental equipment and method are as in example 9, wherein the sulfuric acid concentration in the sulfuric acid waste liquid is 9M, a dc power supply and a low-temperature plasma discharge power supply are switched on to treat the sulfuric acid waste liquid for 1.5h, the voltage of the dc power supply is 100V, the current is 1000A, the voltage of the low-temperature plasma discharge power supply is 75kV, the powers are respectively 10kW, 30kW, 50kW, 55kW, 60kW, 80kW, and 100kW, the stirring rates of the anode stirrer 17 and the cathode stirrer 20 are both 720rpm, the stirring time is 15min, the centrifugation rate is 12000rpm, the centrifugation time is 15min, and the drying temperature is 90 ℃, so as to obtain seven groups of elemental sulfur.
The sulfate conversion was calculated as in example 9 and the results of this example are shown in Table 12.
TABLE 12 influence of Power supply for Low temperature plasma discharge on sulfate conversion
Low temperature plasma discharge power supply Sulfate radical conversion Relative error
10kW 94.28％ ±0.1％
30kW 96.43％ ±0.1％
50kW 98.54％ ±0.1％
55kW 98.87％ ±0.1％
60kW 97.19％ ±0.1％
80kW 96.73％ ±0.1％
100kW 98.06％ ±0.1％
As can be seen from Table 12, when the power of the low-temperature plasma discharge power supply is in the range of 10-100 kW, the sulfuric acid in the sulfuric acid waste liquid can be effectively converted into elemental sulfur by using the equipment and the method provided by the invention, and the conversion rate of sulfate radicals in the sulfuric acid waste liquid is greater than 94%.
Comparison of sulfate radical conversion rates achieved by different treatment processes
Example 13
The experimental equipment and method are the same as example 9, wherein the sulfuric acid concentration in the sulfuric acid waste liquid is 9M, the sulfuric acid waste liquid is treated by switching on a direct current power supply and a low-temperature plasma discharge power supply for 1.5h, the voltage of the direct current power supply is 100V, the current is 1000A, the voltage of the low-temperature plasma discharge power supply is 75kV, the power is 100kW, the stirring speed of the anode stirrer 17 and the stirring speed of the cathode stirrer 20 are both 720rpm, the stirring time is 15min, the centrifugal speed is 12000rpm, the centrifugal time is 15min, and the drying temperature is 90 ℃, so that elemental sulfur is obtained altogether.
Comparative example 7
The experimental equipment and method are the same as example 9, wherein the sulfuric acid concentration in the sulfuric acid waste liquid is 9M, the sulfuric acid waste liquid is treated only by switching on a direct current power supply for 1.5h, the voltage of the direct current power supply is 100V, the current is 1000A, the stirring speed of the anode stirrer 17 and the stirring speed of the cathode stirrer 20 are both 720rpm, the stirring time is 15min, the centrifugation speed is 12000rpm, the centrifugation time is 15min, and the drying temperature is 90 ℃, so that elemental sulfur is obtained.
Comparative example 8
The experimental equipment and method are the same as example 9, wherein the sulfuric acid concentration in the sulfuric acid waste liquid is 9M, only the low-temperature plasma discharge power supply is switched on to treat the sulfuric acid waste liquid for 1.5h, the voltage of the low-temperature plasma discharge power supply is 75kV, the power is 100kW, the stirring speeds of the anode stirrer 17 and the cathode stirrer 20 are both 720rpm, the stirring time is 15min, the centrifugation speed is 12000rpm, the centrifugation time is 15min, and the drying temperature is 90 ℃, so that elemental sulfur is obtained.
Comparative example 9
The experimental equipment and method are as in example 9, wherein the sulfuric acid concentration in the sulfuric acid waste liquid is 9M, the sulfuric acid waste liquid is treated by only switching on the dc power supply for 1.5h, the voltage of the dc power supply is 100V, the current is 1000A, then the dc power supply is switched off and the low-temperature plasma discharge power supply is switched on for treating the sulfuric acid waste liquid for 1.5h, the voltage of the low-temperature plasma discharge power supply is 75kV, the power is 100kW, the stirring speed of the anode stirrer 17 and the stirring speed of the cathode stirrer 20 are both 720rpm, the stirring time is 15min, the centrifugation speed is 12000rpm, the centrifugation time is 15min, and the drying temperature is 90 ℃, so as to obtain elemental sulfur altogether.
The results of the tests of example 9, example 13 and comparative examples 7 to 9 are shown in Table 13.
TABLE 13 comparison of sulfate conversion achieved by different treatment processes
Type of process Sulfate radical conversion Relative error
Example 13 98.06％ ±0.1％
Comparative example 7 12.37％ ±0.1％
Comparative example 8 38.93％ ±0.1％
Comparative example 9 64.92％ ±0.1％
As can be seen from table 13, example 13, which is the case where dc electromotive discharge and low-temperature plasma discharge were coupled, achieved a sulfate conversion of 98.06%, which was significantly superior to the case where dc electromotive discharge, comparative example 7, and low-temperature plasma discharge, comparative example 8, were used alone or both dc electromotive discharge and low-temperature plasma discharge were connected in series, comparative example 9, and it was found that coupling dc electromotive discharge and low-temperature plasma discharge had a synergistic effect.

Claims (14)

1. An electrolysis apparatus, characterized in that it comprises an electrolysis cell (10), a direct current power supply and a low temperature plasma discharge power supply; the electrolytic bath (10) comprises a first electrode area, a high-voltage area and a second electrode area; the first electrode area is provided with a hydrogen gas exhaust port (16), a first electrode and a solution inlet (11); the high-voltage electric area is sequentially provided with a high-voltage wire (9), a high-voltage electrode sleeve (15) and a grounding electrode (4) from top to bottom, and the high-voltage cap (8), the high-voltage electrode (3) and the aeration head (5) are sequentially arranged in the high-voltage electrode sleeve (15) from top to bottom; the second electrode area is provided with an air outlet (13) connected with an air receiving pipe (14) and a second electrode; the gas outlet (13) is communicated with the inside of the high-voltage electrode sleeve (15) through a gas receiving pipe (14), the high-voltage wire (9) is connected with a high-voltage interface of the low-temperature plasma discharge power supply, and the grounding electrode (4) is connected with a grounding port of the low-temperature plasma power supply through a grounding wire.
2. The apparatus according to claim 1, wherein the first electrode area is a cathode area, the second electrode area is an anode area, the first electrode is a cathode electrode (1), the second electrode is an anode electrode (2), the cathode electrode (1) is provided with a cathode lead (6), the anode electrode (2) is provided with an anode lead (7), the cathode lead (6) is connected with a cathode interface of a direct current power supply, and the anode lead (7) is connected with an anode interface of the direct current power supply.
3. The device according to claim 2, characterized in that a cation exchange membrane is arranged between the cathode electrode (1) and the high-voltage electrode sleeve (15), an anion exchange membrane is arranged between the anode electrode (2) and the high-voltage electrode sleeve (15), the cathode region is provided with a catholyte outlet, the ground electrode (4) and the anode electrode (2) are provided with a solution outlet, and the anode region is provided with an anolyte outlet.
4. The apparatus of claim 1, wherein the first electrode region is a cathode region, the second electrode region is an anode region, the first electrode is a cathode electrode (1), the second electrode is an anode electrode (2), the anode electrode (2) is provided with an anode lead (7), the cathode electrode (1) is provided with a cathode lead (6), the anode lead (7) is connected with an anode interface of a direct current power supply, the cathode lead (6) is connected with a cathode interface of the direct current power supply, an anode stirrer is arranged between the anode electrode (2) and the ground electrode (4), a cathode stirrer is arranged between the ground electrode (4) and the cathode electrode (1), and a slurry outlet is arranged between the ground electrode (4) and the cathode stirrer.
5. The equipment according to claim 1, wherein the thickness of the high-voltage electrode sleeve (15) is 0.5-2.5 cm, the high-voltage electrode sleeve (15) is made of ceramic or quartz glass, and the vertical distance between the inner ring surface of the high-voltage electrode sleeve (15) and the outer ring surface of the high-voltage electrode (3) is 5-15 mm; the aeration aperture of the aeration head (5) is 0.1-200 mu m, and the porosity of the aeration head (5) is 35-75%.
6. Use of the apparatus of claim 2 for the production of sodium hypochlorite with a high available chlorine content from sodium chloride.
7. Use according to claim 6, characterized in that it comprises the following steps:
(A1) preparing a sodium chloride aqueous solution;
(A2) loading a sodium chloride aqueous solution into an electrolytic cell (10), switching on a direct current power supply, and turning on a low-temperature plasma discharge power supply to treat the sodium chloride aqueous solution;
(A3) and (3) closing the direct current power supply and the low-temperature plasma discharge power supply to obtain a sodium hypochlorite solution in the electrolytic tank (10).
8. The use of claim 7, wherein in step (A1), the aqueous sodium chloride solution has a mass concentration of 5% to 25%; in the step (A2), the voltage of the direct current power supply is 10-100V, the current of the direct current power supply is 100-1000A, the low-temperature plasma discharge voltage is 5-75 kV, the power is 10-100 kW, and the treatment time is 0.5-1.5 h.
9. Use of the apparatus of claim 3 for purifying organic waste liquids.
10. Use according to claim 9, characterized in that it comprises the following steps:
(B1) loading the organic waste liquid into an electrolytic bath (10) through a solution inlet (11);
(B2) switching on a direct current power supply and a low-temperature plasma discharge power supply to treat the organic waste liquid;
(B3) and after the treatment is finished, disconnecting the direct current power supply and the low-temperature plasma discharge power supply, discharging the purified solution from the solution outlet, discharging the catholyte from the catholyte outlet, and discharging the anolyte from the anolyte outlet.
11. The use according to claim 10, wherein in the step (B1), the organic waste liquid is a high-concentration organic waste liquid or a salt-containing organic waste liquid, in the step (B2), the voltage of the DC power supply is 20-200V, the current is 100-1100A, the voltage of the low-temperature plasma discharge power supply is 5-75 kV, the power is 10-100 kW, and the treatment time is 0.2-2 h.
12. Use of the apparatus of claim 4 for the preparation of elemental sulphur from spent sulphuric acid.
13. Use according to claim 12, characterized in that it comprises the following steps:
(C1) leading the sulfuric acid waste liquid into an electrolytic tank (10) through a solution inlet (11);
(C2) switching on a direct current power supply and a low-temperature plasma power supply to treat the sulfuric acid waste liquid;
(C3) starting an anode stirrer and a cathode stirrer to stir the treated sulfuric acid waste liquid, closing the anode stirrer and the cathode stirrer, and obtaining sulfur-containing slurry in an electrolytic tank (10);
(C4) discharging the sulfur-containing slurry from the slurry outlet;
(C5) and centrifuging the sulfur-containing slurry, and drying the solid part in vacuum to obtain elemental sulfur.
14. The use according to claim 13, wherein in step (C1), the sulfuric acid concentration in the sulfuric acid waste liquid is 0.5-17.5M; in the step (C2), the voltage of the direct current power supply is 10-100V, the current is 100-1000A, the low-temperature plasma discharge voltage is 5-75 kV, the power is 10-100 kW, the treatment time is 0.5-1.5 h, in the step (C3), the stirring time is 5-15 min, the stirring speed is 60-720 rpm, in the step (C5), the centrifugation speed is 3000-12000 rpm, the centrifugation time is 5-15 min, and the drying temperature is 50-90 ℃.
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