CN102021600B - Method and device for producing potassium iodate through oxygen cathode non-diaphragm electrolysis - Google Patents
Method and device for producing potassium iodate through oxygen cathode non-diaphragm electrolysis Download PDFInfo
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- CN102021600B CN102021600B CN201010614643A CN201010614643A CN102021600B CN 102021600 B CN102021600 B CN 102021600B CN 201010614643 A CN201010614643 A CN 201010614643A CN 201010614643 A CN201010614643 A CN 201010614643A CN 102021600 B CN102021600 B CN 102021600B
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- oxygen
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Abstract
The invention relates to a method and device for producing potassium iodate through oxygen cathode non-diaphragm electrolysis. In the device in the invention, the mixed solution of potassium iodide and potassium hydroxide is used as electrolyte, wherein iodine ions are oxidized at the anode to generate iodate ions, oxygen is reduced at the cathode to generate hydroxyl ions; the liquid generated by electrolysis is cooled to precipitate potassium iodate crystals; and after potassium iodide and water are added in mother liquor, the mixture is send back to the electrolytic cell for electrolysis. The cathode of the electrolytic cell is an oxygen-consuming cathode and the anode is a corrosion resistant non-sacrificial anode, thus the cationic film or diaphragm is not required and the reduction of iodate ions at the cathode can be avoided. The method is obviously characterized in that the cell voltage is only about 0.6-1.0V, thus the energy consumption can be greatly reduced; the whole flow is performed circularly; and the electrolytic cell has simple structure, no ion film and low operating cost.
Description
Technical field
The invention provides method and device that a kind of electrochemical electrolysis prepares Potassium Iodate, particularly replace existing cathode for hydrogen evolution and realize that the oxidation of no barrier film anode electrochemical prepares the method and the device of Potassium Iodate with oxygen reduction cathode.
Technical background
The industrial production process of Potassium Iodate mainly comprises Potcrate oxidation style, concentrated nitric acid oxidation method, hydrogen peroxide oxidation process and electrochemical oxidation process at present.Utilizing Potcrate iodine oxide simple substance is the main flow technology that China's Potassium Iodate is produced, but because the Potcrate oxidation needs to carry out under acidic conditions, therefore equipment material is required high; In addition, the easy and iodide ion reaction generation elemental iodine of iodate causes the loss of unnecessary iodine because of elemental iodine easily distils, and reclaims the complexity that iodine has increased subsequent handling under acidic conditions; Moreover the Potcrate oxidation style can produce a large amount of chlorine, adopts caustic soda to reclaim usually, but also exists the problem of the wasting of resources and complex procedures.Patent CN1712347A directly utilizes chlorine oxidation potassiumiodide under weak basic condition to obtain Potassium Iodate, and by product is a Repone K, has simplified equipment and has reduced by product, but will use a large amount of chlorine, therefore still has safety and pollution hidden trouble.The concentrated nitric acid oxidation method can produce a large amount of obnoxious flavour nitrogen peroxide, therefore uses fewer now.Hydrogen peroxide oxidation method possesses environmental friendliness, the simple advantage of operation, but the consumption of hydrogen peroxide is big, and cost is too high.
Directly the synthetic Potassium Iodate of electrooxidation can be cut down the number of intermediate links, and improves raw material availability, and reduces the pollution to environment.In the traditional electrical solution, be reduced, must use expensive cationic membrane to suppress diffusion for the Potassium Iodate that prevents the anode surface generation diffuses to negative electrode.Patent CN101078128A provides a kind of ion-exchange membrane electrolysis paired electrolysis to prepare the method for N.F,USP MANNITOL and Potassium Iodate, can obtain N.F,USP MANNITOL at negative electrode when anode obtains Potassium Iodate, the way that obtains two kinds of products simultaneously can reduce the cost that electrolyzer uses ionic membrane to a certain extent.Patent CN1121540A provides a kind of method of utilizing liquor kalii iodide to obtain Potassium Iodate by continuous, multistage and order electrolysis for raw material, for fear of using ionic membrane, in catholyte, added the reduction that potassium bichromate suppresses iodate in this method.But potassium bichromate itself is a kind of carcinogens, very easily causes product contamination, moreover the bath voltage of this method is 2.5～3.5V, and energy consumption is higher.
In sum, existing electrochemical process prepares the Potassium Iodate technology, and bath voltage is high and must use ionic membrane suppressing the diffusion of iodate to the cathodic area, otherwise current efficiency will reduce, and the use of ionic membrane makes production cost remain high.
Summary of the invention
At having the shortcoming that electrochemical process prepares the Potassium Iodate technology now, the present invention is proposed.The object of the present invention is to provide a kind of less energy-consumption, pollution-free, the simple electrolytic preparation Potassium Iodate of operation method and apparatus, have bath voltage low, do not use ionic membrane, product purity height, production safety reliable characteristics.
Electrochemical preparation Potassium Iodate method of the present invention is different from prior art and is characterised in that, substitutes cathode for hydrogen evolution with oxygen reduction cathode.In the electrochemical preparation Potassium Iodate method of the present invention, it is as follows that electrochemical reaction process takes place on anode and the negative electrode in the electrolyzer:
Anode: 2I
-+ 12OH
--12e
-→ 6H
2O+2IO
3 -Φ
Θ=0.257V
Negative electrode: 3O
2+ 6H
2O+12e
-→ 12OH
-Φ
Θ=0.401V
Total reaction: 2I
-+ 3O
2→ 2IO
3 -Φ
Θ=-0.144V
The theoretical reduction potential of oxygen is higher than the iodate reduction potential, and current density reaches 4000A/m when hydrogen reduction
2Before, iodate reductive current density is compared and can be ignored, and therefore need not to use ionic membrane or barrier film can avoid iodate to be reduced at negative electrode; Consider O
2Reduction, KI oxidation need activation energy to cause cathode and anode utmost point overpotential, the solution resistance equal loss, and the actual groove pressure of electrochemical preparation Potassium Iodate is 0.6～1.0V only when using oxygen cathode, compares prior art and greatly reduces energy consumption.
The invention provides a kind of method and device of electrochemical preparation Potassium Iodate, it is characterized in that substituting cathode for hydrogen evolution with oxygen reduction cathode in the employed electrolyzer, and need not to use ionic membrane or barrier film.
The method of electrochemical preparation Potassium Iodate of the present invention is selected no diaphragm plate frame electrolyzer for use, and wherein anode is anti-corrosion non-sacrifice type anode, and material is titanium ruthenium, titanium platinum, titanium iridium, nickel ruthenium, nickel platinum, graphite or stainless steel; Negative electrode comprises existing oxygen cathode structure and other any electrode structures that can realize oxygen reduction for can realize the electrode of oxygen reduction to hydroxide ion.Existing oxygen cathode structure comprises the gentle chamber of electrode part part at least, and wherein the electrode part branch comprises eelctro-catalyst and electro-catalyst carrier, and wherein eelctro-catalyst can be Ag, Co
3O
4, MnO
2, one or more the composition in Pt and the PtNi alloy, electro-catalyst carrier can be one or more the composition in gac, acetylene black and the graphitized carbon black.
Electrochemical preparation Potassium Iodate method of the present invention specifically describes as follows:
A: the aqueous solution 1 that contains potassiumiodide 50-400g/L, potassium hydroxide 50-250g/L is preheating to the temperature identical with electrolysis temperature (25-95 ℃) in electrolytic solution reservoir 2.
B: utilize volume pump that electrolytic solution is injected in the electrolyzer 3 that keeps steady temperature (25-95 ℃) and the electrolyzer container for storing liquid 8 to hydroful by the import of electrolyzer lower end, dividing potential drop is that the oxygen of 20～50kPa is entered in the cathode air chamber spreader plate 6 by cathode air chamber upper end import, and remaining gas enters compressor from the outlet discharge and gets back to oxygen gas-holder 7.If the gas that feeds is air, then expellant gas does not need to reclaim.
C: close electrolytic solution feed liquor volume pump, electrolytic solution carries out internal recycle in electrolyzer 3 He in the container for storing liquid 8, and circulation velocity is 5～50L/ (minm
2), on negative and positive the two poles of the earth, to switch on, current density is 500-4000A/m
2Under carry out electrolysis, 20%～40% KI is converted into KIO in the groove electrolyte inside
3Open the feed liquor volume pump then fresh electrolyte is entered in the electrolyzer, electrolyzer contains KIO simultaneously
3, KI, KOH electrolytic solution enter after the electrolysis in the reservoir 9 by upper end outlet.
D: the electrolytic solution of reservoir 8 changes KIO over to after utilizing volume pump with electrolysis
3Crystallisation by cooling separator 10, cooling temperature is-5～10 ℃, the white KIO that separates out
3Crystal is transferred to KIO
3In the fine seperator 11.KIO in the fine seperator
3Solid transfer after the frozen water washing is to KIO
3In the hold-up vessel, and the washing mother liquor is got back to KIO
3In the crystallisation by cooling separator 10.
E: contain KOH, KI, KIO by what Crystallization Separation device 10 obtained
3Mother liquor be back in the electrolytic solution reservoir 2, and add KI, KOH and less water at this, keep in the electrolytic solution reservoir 2 concentration of electrolyte within the required range.
The said process circulation is carried out, and can constantly obtain product solid K IO
3
Compare with existing electrochemical method, electrochemical preparation Potassium Iodate method and apparatus of the present invention has following advantage: owing to adopt cathodic oxygen reduction to replace cathode hydrogen evolution, bath voltage is reduced to 0.6～1.0V by 2.5 original～3.5V, greatly reduces energy consumption; In addition, need not to use ionic membrane or add potassium bichromate, can avoid the reduction of iodate ion, reduced production cost effectively, improved production efficiency at cathode surface.
Description of drawings
Fig. 1 is the device and the schematic flow sheet thereof of the alkaline aqueous solution electrolysis production Potassium Iodate of potassiumiodide of the present invention.
Wherein: 1, the KI and the KOH aqueous solution; 2, electrolytic solution feed liquor storage tank; 3, electrolysis slot number chamber; 4, anode; 5, negative electrode; 6, cathode air chamber; 7, oxygen or air gas tank; 8, electrolytic solution internal recycle container for storing liquid; 9, electrolytic solution fluid storage tank; 10, KIO
3Separating tank; 11, KIO
3Smart separating tank; 12, KIO
3The product jar.
Specific embodiment
For technical characterictic of the present invention is described better, describe below by specific embodiment, embodiment 1-example 3 is the electrolysis in batches of the little electrolyzer in laboratory, and embodiment 4, example 5 are the continuous cyclic electrolysis of amplification test.
Use sheet frame type electrolyzer, anode titanium ruthenium, negative electrode oxygen cathode, cathod catalyst are cobalt oxide, the electrode useful area is 20cm
2, preparation KI 100g/L, KOH 80g/L electrolytic solution 100ml, 45 ℃ of electrolyte temperatures, cathode air chamber aerating oxygen, current density 100mA/cm
2, electrolysis time 5h, average cell voltage 0.675V.
Electrolytic solution heating after the electrolysis is concentrated the postcooling crystallization, with the filtering solid drying that obtains, with the KIO of gained
3Solid crude product merges coarse crystallization and the two-part mother liquor of recrystallization with frozen water flushing recrystallizing and refining, and titrimetry gets KIO in the mother liquor
3Quality is 2.15g, solid K IO
3Quality is 10.38g, analyze purity 99.78%.Whole KIO
3Yield 97.2%, solid K IO
3Yield 80.52%, unit K IO
3Electrolytic power consumption 0.539kwh/kg.
Use sheet frame type electrolyzer, anode titanium ruthenium, negative electrode oxygen cathode, cathod catalyst are Co
3O
4, the electrode useful area is 20cm
2, preparation KI 180g/L, KOH 100g/L electrolytic solution 200ml, 75 ℃ of electrolyte temperatures, cathode air chamber aerating oxygen, current density 200mA/cm
2, electrolysis time 9h, average cell voltage 0.714V.
Electrolytic solution heating after the electrolysis is concentrated the postcooling crystallization, with the filtering solid drying that obtains, with the KIO of gained
3Solid crude product merges coarse crystallization and the two-part mother liquor of recrystallization with frozen water flushing recrystallizing and refining, and titrimetry gets KIO in the mother liquor
3Quality is 7.08g, solid K IO
3Quality is 38.14g, analyze purity 99.46%.Whole KIO
3Yield 97.44%, solid K IO
3Yield 82.18%.Unit K IO
3Electrolytic power consumption 0.568kwh/kg.
Use sheet frame type electrolyzer, anode nickel ruthenium, negative electrode oxygen cathode, cathod catalyst are Ag, the electrode useful area is 20cm
2, preparation KI 160g/L, KOH 100g/L electrolytic solution 200ml, 75 ℃ of electrolyte temperatures, cathode air chamber aerating oxygen, current density 200mA/cm
2, electrolysis time 8h, average cell voltage 0.764V.
Electrolytic solution heating after the electrolysis is concentrated the postcooling crystallization, with the filtering solid drying that obtains, with the KIO of gained
3Solid crude product merges coarse crystallization and the two-part mother liquor of recrystallization with frozen water flushing recrystallizing and refining, and titrimetry gets KIO in the mother liquor
3Quality is 6.71g, solid K IO
3Quality is 33.62g, analyze purity 99.92%.Whole KIO
3Yield 97.76%, solid K IO
3Yield 81.5%, unit K IO
3Electrolytic power consumption 0.606kwh/kg.
Use sheet frame type electrolyzer, anode titanium ruthenium, negative electrode oxygen cathode, cathod catalyst are Ag, the electrode useful area is 20dm
2, configuration KI 180g/L, the electrolytic solution 10L of KOH 120g/L, 75 ℃ of electrolyte temperatures, the cathode air chamber aerating oxygen, after the storage of electrolyzer electrolyte inside was full, electrolytic solution internal recycle flow velocity was 1L/min, current density 25A/dm
2, behind the 20min, fresh electrolyte enters electrolyzer with the flow velocity of 140～160ml/min, and electrolyzer contains KIO simultaneously
3, KI, KOH electrolytic solution enter in the electrolysis fluid reservoir by upper end outlet, carry up to 10L electrolytic solution and finish.Electrolysis total consuming time 70min, the reasonable opinion of actual electrolysis electricity electric weight 33.45%, average cell voltage 0.843V.
Liquid in the electrolysis fluid reservoir enters KIO
3Cooling separator 10.Crystalline KIO
3Solid transfer is to KIO
3In the smart separating tank 11, frozen water washing back purified KIO
3Solid enters in the product jar 12.Obtain KIO
3Solid oven dry back weighing is 644.32g, analyzes to such an extent that purity is 99.92%.The washing mother liquor is got back to KIO
3In the crystallisation by cooling separator 10, the mother liquor of merging 10 and 11 enters in the electrolytic solution feed liquor container for storing liquid 2, and final mother liquor is 9.53L, contains KI 127.02g/L, KIO
312.26g/L.Current efficiency 98.09%, solid K IO
3Yield 83.01%, unit K IO
3Electrolytic power consumption 0.646kwh/kg.
Above-mentioned mother liquor is added the about 500g of KI solid, and add water and be settled to 10L, the circulation of beginning next round.
Embodiment 5
Use sheet frame type electrolyzer, anode titanium ruthenium, negative electrode oxygen cathode, cathod catalyst are Ag, the electrode useful area is 20dm
2, configuration KI 160g/L, the electrolytic solution 10L of KOH 120g/L, 75 ℃ of electrolyte temperatures, the cathode air chamber aerating oxygen, after the storage of electrolyzer electrolyte inside was full, electrolytic solution internal recycle flow velocity was 0.5L/min, current density 20A/dm
2, behind the 25min, fresh electrolyte enters electrolyzer with the flow velocity of 100ml/min, and electrolyzer contains KIO simultaneously
3, KI, KOH electrolytic solution enter in the electrolysis fluid reservoir by upper end outlet, carry up to 10L electrolytic solution and finish.Electrolysis total consuming time 102min, the reasonable opinion of actual electrolysis electricity electric weight 43.87%, average cell voltage 0.908V.
Liquid in the electrolysis fluid reservoir enters KIO
3Cooling separator 10.Crystalline KIO
3Solid transfer is to KIO
3In the smart separating tank 11, frozen water washing back purified KIO
3Solid enters in the product jar 12.Obtain KIO
3Solid oven dry back weighing is 769.12g, analyzes to such an extent that purity is 99.85%.The washing mother liquor is got back to KIO
3In the crystallisation by cooling separator 10, the mother liquor of merging 10 and 11 enters in the electrolytic solution feed liquor container for storing liquid 2, and final mother liquor is 9.27L, contains KI 89.80g/L, KIO
312.31g/L.Current efficiency 97.56%, solid K IO
3Yield 84.99%, unit K IO
3Electrolytic power consumption 0.682kwh/kg.
Above-mentioned mother liquor is added the about 700g of KI solid, and add water and be settled to 10L, the circulation of beginning next round.
Claims (4)
1. the method for an electrolytic preparation Potassium Iodate, it is characterized in that wherein substituting cathode for hydrogen evolution with oxygen reduction cathode in the electrolyzer, specifically comprise: with the mixing solutions of potassiumiodide and potassium hydroxide as electrolytic solution, wherein iodide ion forms iodate ion in anodic oxidation, oxygen forms hydroxide ion in cathodic reduction, reaction solution is separated out the Potassium Iodate crystallization through cooling, carries out electrolysis and mother liquor returns electrolyzer after adding potassiumiodide and water.
2. the method for electrolytic preparation Potassium Iodate as claimed in claim 1, wherein electrolytic solution by handling equipment from bottom of electrolytic tank enter, the top flow out to form and to circulate.
3. the method for electrolytic preparation Potassium Iodate as claimed in claim 1, wherein the electrolyzer feed liquor consists of potassiumiodide 50-400g/L, and concentration of potassium hydroxide is 50-250g/L, and electrolysis temperature 25-95 ℃, current density is 500-4000A/m
2
4. used device of electrolytic preparation Potassium Iodate method as claimed in claim 1, it is characterized in that electrolyzer adopts undivided cell, wherein anode is anti-corrosion non-sacrifice type anode, and material is a kind of in titanium ruthenium, titanium platinum, titanium iridium, nickel ruthenium, nickel platinum, the graphite; Negative electrode is an oxygen reduction electrode, comprises oxygen cathode eelctro-catalyst and electro-catalyst carrier, and wherein eelctro-catalyst is Ag, Co
3O
4, MnO
2, one or more the composition in Pt and the PtNi alloy, electro-catalyst carrier is one or more the composition in gac, acetylene black and the graphitized carbon black.
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|---|---|---|---|
| CN201010614643A CN102021600B (en) | 2010-12-21 | 2010-12-21 | Method and device for producing potassium iodate through oxygen cathode non-diaphragm electrolysis |
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|---|---|---|---|
| CN201010614643A CN102021600B (en) | 2010-12-21 | 2010-12-21 | Method and device for producing potassium iodate through oxygen cathode non-diaphragm electrolysis |
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| CN102021600B true CN102021600B (en) | 2011-12-28 |
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| CN108505062B (en) * | 2018-05-04 | 2019-07-23 | 厦门大学 | A kind of method that electro-catalysis reduction oxygen generates hydrogen peroxide |
| CN109055966A (en) * | 2018-09-13 | 2018-12-21 | 北京化工大学 | A kind of chemical combined method for preparing chlorine dioxide of electrochemistry- |
| CN112030179B (en) | 2019-06-04 | 2022-06-17 | 泰安汉威集团有限公司 | Environment-friendly production process of iodate |
| RU2732691C1 (en) * | 2019-12-06 | 2020-09-22 | Федеральное государственное автономное образовательное учреждение высшего образования «Северный (Арктический) федеральный университет имени М. В. Ломоносова» | Method of obtaining potassium iodate from iodine |
| CN111394746B (en) * | 2020-04-10 | 2021-06-08 | 山东博苑医药化学股份有限公司 | Electrochemical co-production method of potassium iodate and hydroiodic acid |
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| CN101078128B (en) * | 2007-06-30 | 2010-08-18 | 广西壮族自治区化工研究院 | Method and device for preparing mannitol and potassium iodate by electrolysis in pairs |
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