CN1443874A - Green high ferrite and hypochloride double-effective electrolytic bath - Google Patents
Green high ferrite and hypochloride double-effective electrolytic bath Download PDFInfo
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- CN1443874A CN1443874A CN 02104132 CN02104132A CN1443874A CN 1443874 A CN1443874 A CN 1443874A CN 02104132 CN02104132 CN 02104132 CN 02104132 A CN02104132 A CN 02104132A CN 1443874 A CN1443874 A CN 1443874A
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Abstract
The present invention relates to an electrolytic tank capable of using electrolyte using NaCl or KCl as main component to make electrolysis to simultaneously produce perferrate solution with a certain concentration and hypochlorite solution, in which the obtained perferrate solution is a green environment-protecting high-effective water-cleaning disinfectant. Said electrolyte tank is divided into two chamber by means of ion exchange membrane, one is perferrate chamber and another is hypochlorite chamber, in every chamber a pair of cathode and anode which are made up by using special material and respectively belonged to difference power supply is inserted. After a certain time of electrolysis the perferrate solution and hypochlorite solution capable of meeting the requirements for cleaning water and disinfection can be obtained.
Description
The invention belongs to the technical field of electrochemical science and technology
Second, the technical background of the invention
The invention mainly relates to a novel electrolytic cell for ferrate and hypochlorite. Ferrate represented by sodium ferrate and potassium ferrate is a novel green high-efficiency strong oxidant developed since the 70 s of the 20 th century, and the ferrate with excellent strong oxidizing property and electron acceptor can be used as a new-generation green high-efficiency water treatment agent and a positive electrode material of a high-energy alkaline battery.
The potassium ferrate is a purple black crystal with luster, and the dried potassium ferrate can stably exist for a long time under the condition of room temperature. The very strong oxidizing properties of ferrate can be seen from its standard electrode potential in acidic and alkaline solutions.
Thus, ferrate is a stronger oxidizing agent than permanganate and rapidly oxidizes humus, organic alcohols, phenols, aldoketones, enynes, and CN in water-、S2-、NH3And the like, and simultaneously self-reduced into non-toxic and harmless Fe3+And no secondary pollution is caused, so the ferrate is a green high-efficiency water treatment agent integrating strong oxidation, flocculation, adsorption, sterilization and deodorization. In addition, the potassium ferrate has high specific capacity of 406mAh/g, which is 30 percent higher than that of Electrolytic Manganese Dioxide (EMD)313mAh/g which is generally used as a high-energy alkaline battery, and the electrode potential is constant in the reduction process of the ferrate, so the ferrate is an ideal positive electrode material of a new-generation battery. Therefore, ferrate is a new-generation green material with wide application prospect, and attracts more and more scholars to research preparation processes and application development of ferrate by using the unique water treatment function and high-energy battery materials. The synthesis of ferrate has been limited to laboratory levels. Wherein the chemical method, namely the wet method, is relatively betterMature, but the wet process is complex, has great pollution to the environment, large post-treatment workload and long aging time, so that the requirement of preparing ferrate at any time and any place can not be realized.
Hypochlorite is also a common water purifying agent for disinfection, most of hypochlorite is produced by chemical method, which is generally the product of the lower margin of chlor-alkali industry, and a part of hypochlorite is produced by electrolytic method, and the hypochlorite produced by electrolysis has wide application in the fields of water treatment, environmental protection, hygiene and epidemic prevention.
Third, the invention
The invention provides a novel electrolytic cell aiming at the prior synthesis process of ferrate and hypochlorite, which can simultaneously and conveniently produce ferrate and hypochlorite at any time and any place, thereby providing a foundation for the wide application of the ferrate. The invention is designed as follows:
the electrolytic bath is divided into a ferrate chamber and a hypochlorite chamber by a diaphragm, an anode(I) and a cathode (II) are arranged in the ferrate chamber, and the anode (II) and the cathode (I) are arranged in the hypochlorite chamber. The anode (one) is actually a soluble anode providing an iron source, and the anode (two) is an insoluble chlorine evolution electrode; the cathode (one) and the cathode (two) are actually two hydrogen evolution cathodes. They use aqueous solutions of alkali metal chlorides or hydroxides as electrolytes. These key electrodes are made of the following materials:
the anode (one) can be low carbon steel, medium carbon steel and high carbon steel.
Composition of anode (ii): graphite or metal ruthenium-titanium electrodes or platinized titanium-based electrodes.
The cathode (I) and the cathode (II) can be made of common carbon steel or nickel-plated metal wires (sheets), graphite and other materials.
The anode (I) and the cathode (I) are connected with the anode and the cathode of the power supply (I), and the anode (II) and the cathode (II) are connected with the anode and the cathode of the power supply (II). The power supply (II) can be formed by shunting or dividing the power supply (I) through a simple circuit.
The power supply of the electrolytic cell adopts direct current as the power supply, and the power supply consists of two relatively independent power supplies, namely a power supply I and a power supply II. Wherein, the power supply (I) supplies power to the cathode (I) and the anode (I) electrode pair, and the power supply (II) supplies power to the cathode (II) and the anode (II).
The direct current can be constant-current direct current or sinusoidal pulse direct current, the frequency range of the sinusoidal direct current is 1-100 HZ, and the optimal frequency range is 10-60 HZ.
The diaphragm of the electrolytic cell can be a common mechanical membrane or an ion exchange membrane. The general mechanical film can be a polyvinyl chloride woven film or a asbestos film or a microporous rubber sheet and the like. We have found in experiments that the use of cation exchange membranes enables higher concentrations of ferrate and hypochlorite solutions to be obtained. Wherein, the effect of the strong acid polytetrafluoroethylene ion exchange membrane is the best, and other cation exchange membranes also have certain effect.
The electrolyte solution of the invention is divided into an electrolyte (I) in a ferrate chamber and an electrolyte (II) in a hypochlorite chamber. The electrolyte (I) can be one or more of chloride or hydroxide of alkali metal. The weight ratio of the components is as follows:
NaCl：0～26.2％， KCl：0～15％，
LiCl: 0-15%, NaOH or KOH: 0 to 40 percent. The optimal concentration (weight ratio) of the electrolyte is as follows:
(1)NaCl：10～15％，KCl：1～5％，NaOH：3～8％
(2) NaCl: 1-3%, KCl: 1-3%, NaOH or KOH: 25-40%. Wherein NaCl serves to support the electrolyte and activate the soluble iron anode. The electrolyte (II) is prepared by dissolving one or more alkali metal chlorides in water. The weight ratio of the components is as follows:
NaCl: 0-26.2%, KCl: 0-25%, LiCl: 0 to 20 percent. Wherein the optimal electrolyte (weight ratio) comprises the following components: NaCl: 2-11%, KCl: 0 to 2 percent.
When the electrolyzer is powered on, the electrolyzer performs the following electrochemical reactions, the reaction principle of which can be expressed as follows:
anode (i): --------------------------(1)
cathode (i): ----------------------------------(2)
anode (ii): -------------------------------------(3)
cathode (ii): ----------------------------------(5)
it is known that in neutral or alkaline solutions, OH-Is the fastest ion for electromigration, and FeO4 2-The electromigration rate is only OH-While the electrolyte (one) can actually use very low NaOH concentration, the cathode (two) makes OH in the electrolyte (one) react through hydrogen evolution-The concentration is increased, and a certain concentration of Cl is simultaneously added into the solution-Can activate soluble iron anode to oxidize iron anode into FeO4 2-And dissolved out. In the ferrate chamber, we make the electrode surface of the anode (one) and the cathode (two)The area ratio is 5-20: 1, so that under high cathode current density, FeO is obtained4 2-The cathode is reduced to diffusion control, the cathode hydrogen evolution becomes the main reaction, and the OH generated by the cathode hydrogen evolution reaction-And is an anode FeO4 2-Provides conditions for the generation of (c). OH produced by the cathode (one) in the hypochlorite chamber-Cl generated by the anode (II)2Conversion to ClO-And Cl-. After one hour of electrolysis, we can obtain ferrate solution and hypochlorite solution from the ferrate chamber and hypochlorite chamber, respectively.
Compared with the prior electrolytic cell, the electrolytic cell has the following advantages:
1. one electrolytic cell produces two effective substances, ferrate and chlorine-containing hypochlorite, simultaneously, which cannot be realized by the prior single electrolytic cell.
2. The ferrate electrolytic cell avoids the production of ferrate by using strong corrosive 30-50% concentrated sodium hydroxide. The novel double-effect electrolytic cell can generate ferrate meeting the requirements of disinfection, water purification and sterilization in electrolyte mainly containing NaCl or KCl.
3. The double-effect electrolytic cell can conveniently use a small storage battery as an electrolytic power supply to be made into a small electrolytic cell to produce ferrate and hypochlorite anytime and anywhere, thereby meeting the sterilization and disinfection requirements of people in the field, families and industrial and mining enterprises.
4. The ferrate solution generated by the electrolysis of the electrolytic cell is safer and more convenient to store than the chlorine, chlorine dioxide and other gases used by people in the past, and is non-toxic and pollution-free.
5. The electrolytic cell generates hypochlorite solution while producing ferrate, avoids certain occasions that ferrate cannot be used for disinfecting and purifying water caused by single electrolysis to generate ferrate in the prior art, and enlarges the application range of the electrolytic cell.
Through the comparison, the novel double-effect electrolytic cell has greater advantages than the prior single electrolytic cell.
Therefore, we can see that the invention has wide application prospect, and can conveniently and simultaneously produce green high-efficiency ferrate and conventional hypochlorite disinfection water purifying agent. The novel electrolytic cellwidens the way and the mode for synthesizing ferrate, so that the synthesis of the ferrate is not limited to the synthesis range of the current laboratory, and can be popularized to the field, families and industrial and mining enterprises, thereby providing a source for the wide application of the ferrate as a new generation of green high-efficiency water purifying agent.
Inventive example 1
A rectangular electrolytic tank made of polytetrafluoroethylene plastic is internally divided into a ferrate chamber and a hypochlorite chamber by a asbestos membrane. Placing an anode (I) and a cathode (II) in a ferrate chamber in parallel (wherein the area ratio of the two is 10: 1); an anode (II) and a cathode (I) are arranged in the hypochlorite chamber in parallel, and the electrodes are led out by a lead. The cathode (I) and the anode (I) are respectively externally connected with a 6V lead storage battery as an electrolysis power supply (I); the anode (II) and the cathode (II) are respectively externally connected with a 4V lead storage battery as an electrolysis power supply (II).
The composition of the matrix material of each electrode is as follows:
anode (i): a low carbon steel sheet containing 0.2% by weight of carbon;
cathode (i): plating a nickel common carbon steel sheet;
anode (ii): a pure graphite plate impregnated with liquid paraffin;
cathode (ii): and plating a nickel-black wire mesh.
The two electrode chambers were loaded with 20% NaCl + 5% NaOH (ferrate chamber) and 8% NaCl (hypochlorite chamber) by weight, respectively. The cathode (II) is at 300mA/cm2Electrolyzing for 5min at current density, and switching on the power supply (I) to obtain current density of 28mA/cm2(relative to the area of the anode I), 3.1g/l of sodium ferrate and 8g/l of sodium hypochlorite solution which meet the requirements of disinfection and purification can be obtained after electrolysis for 1 h.2. Example 2
A rectangular electrolytic tank made of polyvinyl chloride plastic is divided into a ferrate chamber and a hypochlorite chamber by a polytetrafluoroethylene cation exchange membrane. Placing an anode (I) and a cathode (II) in a ferrate chamber in parallel; an anode (II) and a cathode (I) are arranged in the hypochlorite chamber in parallel, and the electrodes are led out by a lead.
The cathode (I) and the anode (I) are respectively externally connected with a 6V nickel-hydrogen storage battery as an electrolysis power supply (I); the anode (II) and the cathode (II) are respectively externally connected with a 4V lead storage battery as an electrolysis power supply (II).
The composition of the matrix material of each electrode is as follows:
anode (i): a common medium carbon steel sheet;
cathode (i): nickel-plated stainless steel sheets;
anode (ii): a ruthenium titanium metal anode;
cathode (ii): a nickel alloy wire mesh.
The two electrode chambers were loaded with 3.6% NaCl + 25% NaOH (ferrate chamber) and 10% KCl (hypochlorite chamber) by weight, respectively. Simultaneously connecting the power supply I and the power supply II, wherein the current density of the cathode II is 350mA/cm2The current density of the anode (I) is 26mA/cm2After electrolysis for 1.2h, 3.8g/l of sodium ferrate and 9.5g/l of potassium hypochlorite solution which meet the requirements of disinfection and water purification can be obtained.
Claims (10)
1. The invention relates to a novel electrolytic cell for ferrate and hypochlorite. The novel electrolytic bath is composed of an electrolyte solution mainly containing chloride, two pairs of cathodes and anodes and two corresponding relatively independent power supplies and diaphragms.
2. The electrolytic cell of claim 1, wherein the electrolyte solution is one or more of alkali metal chloride or hydroxide such as LiCl, NaCl or KCl, and is dissolved in water.
3. The power supply for electrolysis cell of claim 1, which can supply direct current to the electrolysis cell, or sinusoidal pulse direct current, the frequency range of the sinusoidal pulse direct current is 1 to 100Hz, and the optimum frequency range is 10 to 60 Hz. The two pairs of cathodes and anodes are respectively a cathode (I), an anode (I), a cathode (II) and an anode (II), and the two pairs of electrodes are respectively powered by the power supply (I) and the power supply (II).
4. The cathode (I), anode (I), cathode (II), anode (II) according to claim 3. The electrode material of the anode (I) can be made of low carbon steel, medium carbon steel and high carbon steel; the electrode material of the anode (II) can be made of graphite, metal ruthenium titanium or platinized titanium; the cathode (I) and the cathode (II) can be made of one of common carbon steel, nickel-plated metal wires (sheets), graphite and the like.
5. The electrolyte solution of claim 2, which is divided into a ferrate compartment electrolyte (one) and a hypochlorite compartment electrolyte (two).
The electrolyte (I) can be one or more of chloride or hydroxide of alkali metal. The weight ratio of the components is as follows:
NaCl：0～26.2％， KCl：0～15％，
LiCl: 0-15%, NaOH or KOH: 0 to 40 percent.
The electrolyte (II) is prepared by dissolving one or more alkali metal chlorides in water. The weight ratio of the components is as follows:
NaCl：0～26.2％，KCl：0～25％，LiCl：0～20％。
6. the electrolyzer diaphragm of claim 1 which can be a common mechanical membrane or an ion exchange membrane.
7. The mechanical membrane of claim 7, which may be a woven membrane of polyvinyl chloride or an asbestos mesh or a microporous rubber diaphragm.
8. The ion exchange membrane of claim 7, which is a polytetrafluoroethylene cation exchange membrane or other type of cation exchange membrane.
9. The electrolyte solution of claim 5, which comprises the following components in an optimal weight ratio:
electrolyte (one) NaCl: 10-15% of electrolyte (II) NaCl: 2 to 11 percent
KCl：1～5％ KCl：0～2％
NaOH：3～8％
10. The electrolyzer of claim 1 whose power sources can be two relatively independent power sources or an equivalent power source (two) formed by dividing a power source (one) and a power source (one) through a simple circuit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 02104132 CN1443874A (en) | 2002-03-08 | 2002-03-08 | Green high ferrite and hypochloride double-effective electrolytic bath |
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| CN 02104132 CN1443874A (en) | 2002-03-08 | 2002-03-08 | Green high ferrite and hypochloride double-effective electrolytic bath |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732903A (en) * | 2004-01-16 | 2012-10-17 | 巴特尔纪念研究所 | Methods and apparatus for producing ferrate (vi) |
| CN105734608A (en) * | 2016-02-26 | 2016-07-06 | 武汉大学 | Synchronous production process for manganese metal and chlorine disinfectant through electrolytic cell |
-
2002
- 2002-03-08 CN CN 02104132 patent/CN1443874A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732903A (en) * | 2004-01-16 | 2012-10-17 | 巴特尔纪念研究所 | Methods and apparatus for producing ferrate (vi) |
| CN105734608A (en) * | 2016-02-26 | 2016-07-06 | 武汉大学 | Synchronous production process for manganese metal and chlorine disinfectant through electrolytic cell |
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