CN1004363B - Concurrent production of electrolytic metallic manganese and fibred electrolytic manganese dioxide - Google Patents
Concurrent production of electrolytic metallic manganese and fibred electrolytic manganese dioxide Download PDFInfo
- Publication number
- CN1004363B CN1004363B CN85104334.8A CN85104334A CN1004363B CN 1004363 B CN1004363 B CN 1004363B CN 85104334 A CN85104334 A CN 85104334A CN 1004363 B CN1004363 B CN 1004363B
- Authority
- CN
- China
- Prior art keywords
- electrolytic
- anode
- manganese
- electrolysis
- electrolyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention relates to a method for electrolyzing, smelting and producing products of manganese by using a manganese chloride solution as an electrolyte. An electrolyte, an electrolytic tank baffle and an electrolytic condition are selected. Anolyte comprises 125.8 to 188.7 g/l of manganese chloride, and catholyte comprises 88 to 151 g/l of manganese chloride, 100 to 140 g/l of ammonium chloride and an additive containing selenium. Hydrochloric acid is used for regulating acidity, an anode is from 0.1 to 0.6M, and the pH value of a cathode is from 5 to 3. A carbon rod serves as the anode, and titanium or stainless steel serves as the cathode. The current density of the anode is from 150 to 400 amperes / square meter, and the current density of the cathode is from 600 to 1200 amperes / square meter. The electrolysis temperature of the anode is from 80 to 100 DEG C, and the electrolysis temperature of the cathode is lower than 70 DEG C. The baffle is composed of an ion diaphragm material and a porous material. The present invention is suitable for simultaneously making manganese metal and manganese dioxide by an electrolysis method.
Description
The invention relates to the manganese chloride solution is that the electrolyte system electrolysis for production is produced manganese product, when negative electrode is produced electrolytic metal Mn at the method and the device of anode coproduction fibrous electrolytical manganese dioxide.
As everyone knows: the method for separating manganese metal and electrolytic manganese dioxide with electrolysis for production legal system power backup can be distinguished into two kinds of electrolyte systems such as manganous sulfate electrolyte system and Manganous chloride tetrahydrate electrolyte system according to the main component of electrolytic solution.What be widely used in suitability for industrialized production at present is the manganous sulfate electrolyte system, and the Manganous chloride tetrahydrate electrolyte system still is in the research trial stage, no matter be that manganous sulfate electrolyte system or Manganous chloride tetrahydrate electrolyte system all are to produce the one pole product, or with the negative electrode manganese metal that produces electrolysis.Or with the anode Manganse Dioxide that produces electrolysis.
The manganous sulfate electrolyte system is the system of suitability for industrialized production electrolytic metal Mn or electrolytic manganese dioxide widespread use.
Produce the electrolysis process method of electrolytic metal Mn with the manganous sulfate electrolyte system, its positive plate generally adopts alloys such as silver, tin, antimony, lead, the general stainless steel plate that consists of 1Cr18Ni9Ti or 18Cr12Ni2Mo that adopts of negative plate, electrolytic process is to make manganese be reduced into manganese metal at negative electrode in electrolytic mode, and its total reaction formula is:
Additive is generally selected sulfurous gas, selenous acid (H for use
2SeO
3), additive is to use as buffer reagent, and the composition of electrolytic solution can be according to the difference of additive and different, and referring to " table 1 ", " table 1 " is with the electrolytic solution composition of manganous sulfate electrolyte system electrolytic metal Mn, concentration and some condition.
The electrolytic condition of this system electrolysis production electrolytic metal Mn, barrier film, electrolytic production is respectively:
Electrolytic condition:
Bath voltage 4.8-5.5 volt
Cathode current density 370-400 peace/square metre
Electrolysis temperature 30-40 ℃
Diaphragm material: terylene, polypropylene fibre
Electrolysing period 24-36 hour
Negative electrode product electrolytic metal Mn composition:
The current efficiency that this electrolytic process is produced electrolytic metal Mn is * 60%, and power consumption is 8-10 thousand degree/tons, but anode is to generate oxygen, belong to useless emptying, and current efficiency is not high so power consumption is big.Negative electrode product electrolytic metal Mn contains a certain amount of sulphur, and this is incompatible to being applied to smelt the extremely low steel of sulphur content.
Electrolysis process method with manganous sulfate electrolyte system electrolysis production electrolytic manganese dioxide, its negative electrode generally adopts carbon-point, anode generally adopts materials such as carbon-point, titanium plate or lead alloy, to be the mn ion that makes divalence in electrolytic mode be oxidized to the process of Manganse Dioxide at anode to electrolytic process, and its total reaction formula is:
Electrolysis is to carry out under electrolytic solution is heated to 90-95 ℃ situation, and the composition of its electrolytic solution, concentration, condition, cycle, product situation are as follows:
Electrolytic solution is formed, concentration:
Manganous sulfate (MnSO
4) the 130-135 grams per liter
Sulfuric acid (H
2SO
4) the 30-32 grams per liter
Electrolytic condition:
Bath voltage 2-3 volt
Anodic current density 50-100 peace/square metre
Electrolysis temperature 90-95 ℃
About electrolysing period 30 days
Product composition (weight %) MnO
2〉=90%
The current efficiency that this electrolytic process is produced electrolytic manganese dioxide can reach more than 90%, and power consumption is 2.5-3 thousand degree/tons, and only anode has the electrolytic manganese dioxide product to generate, and negative electrode then generates hydrogen, belongs to useless emptying.
The Manganous chloride tetrahydrate electrolyte system has been a kind of electrolysis production electrolytic metal Mn of domestic and international research since 1970 and the new electrolyte system of electrolytic manganese dioxide, a series ofly studies have shown that replacing manganous sulfate electrolyte system commonly used to prepare electrolytic metal Mn with the Manganous chloride tetrahydrate electrolyte system has following advantage: reduce bath voltage, current efficiency reaches～and 80%, power consumption is few, can use the current density big 2～3 times than the manganous sulfate system.Can obtain approximately big manganese bar greater than 2 times of manganous sulfate systems, the required electrolyzer number of Manganous chloride tetrahydrate system is few under the situation of same output, for electrolyzer conveying electrolyte and the various pumps (liquid absorbing pump) that are arranged on the prefabricated workshop of electrolytic solution also correspondingly reduce, thereby reduce the floor space in the prefabricated workshop of electrolytic solution, under the situation that does not increase the electrolysis plant scale, can increase output like this, narrate respectively below with Manganous chloride tetrahydrate electrolyte system electrolytic preparation manganese metal and the method for preparing Manganse Dioxide.
Method with Manganous chloride tetrahydrate electrolyte system electrolytic preparation electrolytic metal Mn, its negative electrode is generally selected stainless steel or titanium plate for use, anode is generally selected graphite for use, and electrolyzer can use dividing plate or not use dividing plate, and separator material is generally selected vinylon, igelite or canvas etc. for use when using dividing plate.Electrolytic process is to make * be reduced into manganese metal at negative electrode in electrolytic mode, and anode is then produced chlorine or nitrogen, and its principal reaction is respectively:
When anode is put nitrogen:
(this moment, solution was not for containing NH when anode was put chlorine
4The HCl of Cl or NaCl):
Additive is generally selected sulfurous gas (SO for use
2) or selenous acid (H
2SeO
3).Its electrolytic solution composition, concentration, electrolytic condition, electrode materials, product is:
Electrolytic solution is formed, concentration:
Contain manganese 22-33 grams per liter
Contain ammonium chloride (NH
4Cl) 100-150 grams per liter
Additive (SO
2Or H
2SeO
3) 0.2 grams per liter
Electrolytic condition:
3.5 volts of bath voltages
Cathode current density 1000-1500 peace/square metre
Electrolysis temperature 30-50 ℃
Acidity pH=5-6
Electrode materials:
Negative electrode adopts stainless steel or titanium plate
Anode adopts graphite
Electrolysate:
The negative electrode manganese metal that produces electrolysis
Anode produces nitrogen (as not containing NH in the electrolytic solution
4Produce chlorine during Cl)
As " U.S. chemical abstract " 1984 the 10th) volume digest number narrates for the digest of 107124d is exactly with Manganous chloride tetrahydrate electrolyte system electrolytic preparation electrolytic metal Mn, this article translate selected passages literary composition for " in an aseptate electrolyzer, by the chloride soln electrolysis is obtained to contain:
Iron 0.001-0.01%, copper 0.0005%, nickel 0.003%, nitrogen 0.0001-0.001%, oxygen 0.01%, hydrogen 0.01% highly purified r-Mn are with a kind of manganous chloride (MnC that contains
2) be * mol and ammonium chloride (NH
4Cl) be the solution of 1 mol, adopt graphite anode and stainless steel cathode, anodic current density be the 1000-1500 peace/square metre and cathode current density be 500 peaces/square metre condition under, maximum current efficient can reach～80%.To replace stannous sulphate electrolyte commonly used with chloride electrolyte, its current efficiency can increase and can obtain the not manganese of sulfur-bearing ".The original of this piece digest is published the P66-68 page or leaf in " physical and chemical metallurgy of manganese (Φ И З И К О Х И М М Е Т А Л Л, М А Р Г А Н Ц А Р " book of publishing in Soviet Union Moscow Science Press nineteen eighty-three in full.
With the method for Manganous chloride tetrahydrate electrolyte system electrolytic preparation electrolytic manganese dioxide is at first to find to produce the electrolytic manganese dioxide with fibrocrystalline from the electrolysis of Manganous chloride tetrahydrate electrolyte system from Japanese scholar, is the existing more superior kind of electrolytic manganese dioxide on a kind of performance by the fibrous electrolytical manganese dioxide of Manganous chloride tetrahydrate electrolyte system electrolysis production.Mainly find expression in and can be used as High-property dry cell, the heavy current discharging time of this battery is long, thus be the problem of research always both at home and abroad for many years, but up to the present still be in the research experiment stage abroad.This electrolysis process is to be negative electrode with the carbon-point, and anode is generally then selected the carbon-point of anti-chlorine for use.Electrolytic process is to make manganese be oxidized to fibrous electrolytical manganese dioxide at anode in electrolytic mode, and negative electrode is a releasing hydrogen gas, and its principal reaction formula is:
Its electrolytic solution is formed, concentration, electrolytic condition, and product is:
Electrolytic solution is formed, concentration
Manganous chloride (MnCl
2) the 126-188 grams per liter
Electrolytic condition:
Bath voltage 2-3 volt
Anodic current density 200-300 peace/square metre
Electrolysis temperature is more than 90 ℃
Acidity (regulating) concentration 0.1-0.6 mole with hydrochloric acid
Electrolysate:
Anode produces fibrous electrolytical manganese dioxide
Negative electrode produces hydrogen
With the method for Manganous chloride tetrahydrate electrolyte system electrolytic preparation electrolytic metal Mn or electrolytic manganese dioxide with compare with the method for manganous sulfate electrolyte system electrolytic preparation electrolytic metal Mn or electrolytic manganese dioxide, the Manganous chloride tetrahydrate electrolyte system is potential many advantages really, particularly power consumption is low, and can under the situation that does not increase plant size, increase output, but the anodic product is chlorine or nitrogen when preparing electrolytic metal Mn with the Manganous chloride tetrahydrate electrolyte system, belongs to useless emptying; The product of negative electrode is a hydrogen when preparing electrolytic manganese dioxide with the Manganous chloride tetrahydrate electrolyte system, also belong to useless emptying, the effusion that will prevent chlorine from the structure of electrolyzer is than difficult, if can't prevent that the effusion of chlorine from occurring chlorine unavoidably and leaking and the situation of contaminate environment, anodic product chlorine more also is to be difficult to receive * utilize, though there is not above situation to occur when the anodic product is nitrogen.But will destroy about 0.3 ton ammonia when the electrolytic metal Mn of 1 ton of the every generation of negative electrode, this will consume a large amount of ammonium chloride (NH
4Cl), the same with the manganous sulfate electrolyte system also just unipolar with the resulting manganese product of Manganous chloride tetrahydrate electrolyte system electrolysis, and another utmost point does not have the manganese product, one utmost point of no manganese product is consume electric power in vain with regard to equaling emptying, again as replace the manganous sulfate electrolyte system to be applied to will solve on the industrial production handling problem of each relevant operation with the Manganous chloride tetrahydrate electrolyte system, because these problems are difficult to resolve and certainly cause industrial application can't realize with Manganous chloride tetrahydrate electrolyte system electrolysis production electrolytic metal Mn and electrolytic manganese dioxide, Here it is still is in the major reason in research experiment stage so far.
Manganese is material important in the metallurgical industry, and it mainly plays deoxidation, desulfurization, alloying in steel-making, improves intensity, hardness and the wear resistance of steel, also uses manganese widely in the process of ironmaking.The consumption of manganese accounts for the 3-4% of output of steel, and the impurity content that nearly 90% manganese is consumed in metallurgical industry, manganese directly influences the impurity content of iron and steel, reduce impurity content and will use the low impurity of producing with electrolysis for production, highly purified electrolytic metal Mn.Electrolytic metal Mn also is applied to producing aluminium alloy, contain the high-intensity aluminium alloy that the welding rod of low-carbon (LC), phosphorus and production can be used as the angle of rake valve of ship and contains manganese 3%, also be applied to do in the special senior alloy of jet parts, turbine and nuclear power industry simultaneously and be widely used as in recent years among the nonferrous alloy such as zinc-manganese, copper manganese of packing, electrolytic metal Mn is applied to coating on chemical industry, as siccative, be applied on the medicine industry among sterilant and the medicine in the industry such as varnish.Electrolytic manganese dioxide can be used as the depolariser of battery, can improve the discharge performance of drying battery, and along with the increase of drying battery output, the consumption of electrolytic manganese dioxide also heightens thereupon, and China this year is as with R according to estimates
6Mixing 30% electrolytic manganese dioxide in the battery calculates, need about 15000 tons electrolytic manganese dioxide, but the artificial Manganse Dioxide that comprises electrolytic manganese dioxide at present can't satisfy the demands, be at first to select rich ore for use for many years in the utilization of manganese resource, cause worldwide in recent years rich ore reserves depleted day by day, the grade of manganese ore constantly reduces, must use the manual method that comprises electrolysis for production for the grade that improves manganese ore handles low-grade manganese ore, to improve the purity of manganese ore product, but electrolysis for production need expend a large amount of electric energy, under energy-intensive situation now, should consider how to cut down the consumption of energy, so people are in to explore and a kind ofly can reduce electrolyte system that power consumption and electrolysis for production that can the production high-quality product produce manganese product in a large number replacing existing electrolyte system for many years always, not only reduce electric energy but also can roll up output and improve the method for quality to reach.
For this reason, task of the present invention is: study a kind of processing method and device of can the industrialization electrolysis for production producing manganese product, this method should be able to be produced electrolytic metal Mn and electrolytic manganese dioxide simultaneously, and can reduce power consumption significantly, and the manganese product quality of electrolysis production should high-quality.
Technical solution of the present invention in view of the above is: existing by analysis electrolysis for production legal system power backup is separated the technology of manganese metal and electrolytic manganese dioxide and the research situation of this respect, thinks that the present invention should be according to the following technical solution of what time working out.
One: consider to select the lower Manganous chloride tetrahydrate electrolyte system of power consumption as electrolyte system of the present invention from a large amount of energy-conservation angles, it is clearly that while Manganous chloride tetrahydrate electrolyte system is compared its potential advantage with the manganous sulfate electrolyte system of present industrial use.Crucial problem is how to solve that existing Manganous chloride tetrahydrate electrolyte system is existing only has a utmost point to have manganese product to generate, and another utmost point then generates the problem of chlorine or nitrogen or hydrogen and the trouble that causes therefrom.If can all there be the manganese product generation just can solve above problem in the two poles of the earth, so just should make yin, yang the two poles of the earth of Manganous chloride tetrahydrate electrolyte system possess the condition that generates electrolytic metal Mn and electrolytic manganese dioxide respectively, thus the problem more than anode coproduction fibrous electrolytical manganese dioxide fundamentally solves when negative electrode generates electrolytic metal Mn like this.
They are two years old, because simultaneously generating electrolytic metal Mn and anode at negative electrode, to generate the required separately condition of fibrous electrolytical manganese dioxide different, this just requires the condition in the two poles of the earth district should satisfy the requirement of this utmost point product respectively, should not disturb each other, the key that addresses this problem is to select suitable dividing plate that electrolyzer is separated into cathode compartment and anolyte compartment, and selected dividing plate should possess following condition according to the requirement of processing condition:
Temperature required when (1) cathodic area is with the positive column electrolysis is different, and dividing plate should have heat-blocking action.
(2) composition of yin, yang polar region solution is different, and some material that is unfavorable for that this utmost point product generates should not occur in this polar region solution, for example: ammonium ion (NH
4+) infiltrate the generation that the positive column will influence the electro-chemical properties and the Manganse Dioxide of positive column Manganse Dioxide, so dividing plate should have the ammonium ion (NH of the cathode solution of preventing
4+) infiltrate anodic dissolution and stop the interpenetrative ability of material in negative electrode, the positive column solution.
(3) in order to reduce power consumption, the resistance of dividing plate is little, just can make loss of voltage like this, thus power consumption reduced, so require dividing plate should select the low material of resistivity.
(4) cathodic area is different with the electrolytic condition in positive column, and for example the acidity in two districts requires difference, and dividing plate should have the interactional ability of two polar region electrolytic conditions that prevents.
(5) owing to contact catholyte with one side all the time at whole electrolytic process median septum, one side contacts anolyte, dipolar electrolytic solution all has certain potential of hydrogen, and electrolytic solution contains the composition of chlorine, so that dividing plate should be selected for use is acidproof, alkaline-resisting, the material of anti-chlorine.
(6) electrolysis time is longer, and electrolyzer is to use repeatedly, can not dividing plate be changed because of the end in each cycle simultaneously, so require dividing plate will have certain wearing quality to use repeatedly.
Its three: in whole electrolytic process for to make the yield of product the highest, the quality product height, but because the required condition difference of the two poles of the earth product, this just must select, take into account the situation of the two poles of the earth product when working out the electrolysis process method simultaneously, and select optimum condition on this basis, except selecting suitable voltage, electric current, potential of hydrogen, electrolysis temperature, outside the electrolyte component, also to select suitable additive amount, main additive has the function that increases current efficiency on the other hand, but growth along with electrolysis time, the content of main additive reduces gradually and causes current efficiency to descend to some extent in the electrolytic solution, should consider to add to have the supplementary additive that suppresses main additive content reduction effect and be in optimum regime to guarantee current efficiency for this reason.
Its four: selection of electrode materials should be based on drawing materials conveniently, uses current material as far as possible, and the shape of electrode is very big to the influence of current efficiency, will select rational electrode shape in view of the above.
Its five: the distribution of cathode compartment and anolyte compartment should be reasonable in the electrolyzer.
Its six: electrolysis waste solution should be able to be recycled, to reduce environmental pollution.
According to above 6 the present invention is to produce with Manganous chloride tetrahydrate electrolyte system electrolysis for production method.When negative electrode is produced electrolytic metal Mn, be to be electrode materials with the carbon material at anode coproduction fibrous electrolytical manganese dioxide, anode, anode is to be electrode materials with stainless steel or titanium, electrolyzer is separated into cathode compartment and anolyte compartment by dividing plate, from bottom continuous feeding with Manganse Dioxide (MnCl in cathode compartment of cathode compartment
2) and ammonium chloride (NH
4Cl) etc. be main cathode solution, and from the continuous effluent discharge in the top of cathode compartment, from the continuous solution that feeds based on manganous chloride in the anode chamber, bottom of anolyte compartment, and from the continuous effluent discharge in the top of anolyte compartment, anolyte compartment's liquid of discharging from upper portion of anode chamber utilizes again as the bottom feeding cathode compartment of catholyte from cathode compartment after adding some composition that lacks adjusting, in catholyte, add main additive and supplementary additive, at certain volts DS, galvanic current, potential of hydrogen, under the condition such as electrolysis temperature and concentration of electrolyte, carry out electrolysis for production production by the logical direct current of going up of electrode, when negative electrode is produced electrolytic metal Mn at anode coproduction fibrous electrolytical manganese dioxide, the process of its electrolysis for production is to make mn ion be reduced into manganese metal at negative electrode respectively in electrolytic mode, be oxidized to fiber attitude Manganse Dioxide at anode, its main reaction formula is:
Processing method of the present invention and install specific as follows:
One, the composition of electrolytic solution, concentration:
Anolyte manganous chloride (MnCl
2) the 125.8-188.7 grams per liter
Catholyte manganous chloride (MnCl
2) the 88-151 grams per liter
Ammonium chloride (NH
4Cl) 100-140 grams per liter
Main additive 0.04-0.15 grams per liter
Supplementary additive 0.1-0.5 grams per liter
Wherein main additive is selected the mixture that contains selenium compound and sulfurous gas composition for use or is selected for use separately and contains selenium compound, contains selenium compound and can select selenous acid (H for use
2SeO
3).Supplementary additive is the organism that adopts one or more, and organism can be selected for use: methyl alcohol, formaldehyde, ethanol, acetaldehyde, acetate, hydroxylammonium etc.Solvent is selected water for use.
Two, electrolytic condition (temperature, electrolytic solution potential of hydrogen etc. when volts DS, galvanic current, electrolysis):
Voltage: 3.5-5.0 volt
Current concentration:
The 0.2-2 of anolyte compartment peace/liter
Cathode compartment 0.5-2.5 peace/liter
Current density:
Anode 150-400 peace/square metre
Negative electrode 600-1200 peace/square metre
Electrolysis temperature:
Cathodic area 80-100 ℃
The cathodic area is less than 70 ℃
The potential of hydrogen of electrolytic solution (regulating) with hydrochloric acid:
Anode solution concentration is 0.1-0.6M
Catholyte pH=5-8
Three, dividing plate: have the low feature of resistivity and have the NH that can prevent the cathodic area
4+ the ability of infiltrating the positive column and can stop the material of negative and positive two polar regions to interpenetrate.This separator material comprises ion-exchange material or poromerics two classes.Wherein, the ion-exchange dividing plate is an anion-exchange membrane, and this two classes material can individually or constitute dividing plate in the mode that overlaps each other to be used; Microporosity separator can be made by any material in pottery, plastics, diamantine, sintered glass, the bique plate, and they can individually or constitute dividing plate in the mode that overlaps each other and use; Can also constitute dividing plate in any order eclipsed mode by above ion-exchange membrane and microporosity separator uses.
Four, the arranging and shape of cathode compartment and anolyte compartment in the electrolyzer: electrolyzer can be separated into the combination that one or more have cathode compartment and anolyte compartment by dividing plate.Have one or more cathode compartment and one or more anolyte compartment simultaneously in each combination, electrolyzer, cathode compartment, anolyte compartment etc. all are the containers with three-dimensional arrangement.
Five, the shape of the material of electrode and electrode: anode is to adopt carbon or graphite or employing to contain the acid resisting material of titanium oxide, or adopts other available as the anodic material.Negative electrode is to adopt titaniferous or adopt the stainless material that contains titanium, nickel, chromium etc. simultaneously, and the shape of electrode can be selected for use: sheet, bar-shaped, tabular, hollow tubular, tooth harrow shape, spherical, hollow ball-shape etc.
Six, the repeated use of anode electrolysis effluent discharge: since in the anode electrolysis waste liquid of discharging by upper portion of anode chamber manganiferous quantity be enough to satisfy the demand of catholyte, can according to catholyte require in the anode effluent discharge add an amount of ammoniacal liquor, additive and regulate potential of hydrogen, after making its requirement of satisfying catholyte, from the bottom feeding cathode compartment of cathode compartment, use as catholyte.
Advantage of the present invention and benefit are: according to processing method of the present invention and device, can replace existing manganous sulfate electrolyte system electrolysis for production to produce manganese electrolyte system electrolysis for production fully with the manganous chloride electrolyte system and produce manganese product, the invention enables with the Manganous chloride tetrahydrate electrolyte system replaces existing manganous sulfate electrolyte system institute potential advantage to change reality into, electrolysis process method of the present invention can obtain the manganese bar bigger 2 times than manganous sulfate electrolyte system, thereby dwindled the floor space in electrolytic solution pre-preparation workshop so can reduce the quantity of various pumps in the electrolytic solution pre-preparation workshop, and can use electric current doubly than the big 2-3 of manganous sulfate electrolyte system.Output is increased, existing preparation electrolytic metal Mn and electrolytic manganese dioxide carry out in two electrolyzers respectively, during as electrolysis negative electrode generate electrolytic metal Mn then anode emit gas, belong to useless emptying, if anode generates electrolytic manganese dioxide then negative electrode is put hydrogen during electrolysis, also belong to useless emptying.In any case improve current efficiency like this, always have a utmost point not have manganese product and cause electric energy to consume in vain.And the present invention has manganese product simultaneously at the two poles of the earth, negative electrode is produced in the electrolytic metal Mn at anode coproduction fibrous electrolytical manganese dioxide in same electrolyzer, the gas that generates on the original electrode is replaced by manganese product, so trouble that does not exist the generation owing to gas to cause, bath voltage of the present invention is lower, the current efficiency of negative electrode generally can reach 70-80%, high can be greater than 80%, anodic current efficiency generally can reach 75-85%, high can be greater than 85%, utilization rate of electrical increases like this, power consumption reduce " table 2 " represented be: prior art is with 1 ton of electrolytic metal Mn of manganous sulfate electrolyte system electrolysis production and 2 tons of electrolytic manganese dioxides of electrolysis production and manganous chloride electrolyte system electrolysis production of the present invention comparison at 2 tons of fibrous electrolytical manganese dioxide institutes of anode coproduction consumed power in 1 ton of electrolytic metal Mn of negative electrode production, by the data of " table 2 " as can be known, the manganese product power saving that the present invention produces above-mentioned same quantity than existing manganous sulfate electrolyte system reaches 7-10 thousand degree, approximately saves electric energy and reaches about 60%.The manganese product that the present invention produced all belongs to high-quality product, its crystalline structure of negative electrode product electrolytic metal Mn is α-Mn, proportion is up to 7.6 gram/cubic centimetres, the proportion 6.45 gram/cubic centimetres of the electrolytic metal Mn that produce in the proportion 6.96 gram/cubic centimetres of the electrolytic metal Mn that ratio Japan produces and Xiang Tan are much bigger, heavy manganese metal helps the time can directly dropping into ladle in steel-making to be used, and can sink in the molten steel and is unlikely to float over molten steel surface to guarantee that the manganese in the steel is to distribute equably." table 3 " is the situation of negative electrode product electrolytic metal Mn of the present invention and electrolytic metal Mn standard GB-3418-82 contrast, this situation illustrates that the quality of negative electrode product electrolytic metal Mn of the present invention far surpasses GB GB-3418-82, wherein the content of manganese is up to 99.94%, content of impurities only is 0.059%, sulphur content is 0.0019%, anode product fibrous electrolytical manganese dioxide of the present invention is the fibrous texture of just having found since a kind of 1970 that has, fiber is parallel to the Manganse Dioxide of crystal growth direction, it is good that the entity battery that this Manganse Dioxide is made has a discharge performance, the sparking voltage height, advantages such as discharging current is big, and heavy current discharging time is long." table 4 " is to make R with anode product fibrous electrolytical manganese dioxide of the present invention
20The entity battery carries out the test case of 5 Europe continuous discharge secondaries, and with electrolytic manganese dioxide that Xiang Tan, Japanese Hunan the produces second test situation relatively of under same case, discharging.Situation in " table 4 " prove product of the present invention Japan, Xiang Tan, Hunan want superior many.The present invention has advantages such as a large amount of saving electric energy, output height, good product quality in summary, can replace fully existing produce the manganous sulfate electrolyte system of electrolytic metal Mn and electrolytic manganese dioxide and being applied to industrial production.
The embodiment of the invention is as follows:
Example 1: adopt five Room electrolyzers (this groove contains two cathode compartments, three anolyte compartments, and arrange with alternatively form cathode compartment and anolyte compartment, and every chamber vol is 2 liters).Add 2 liters of electrolytic solution in every chamber.Dividing plate adopts anion-exchange membrane.Negative electrode uses the titanium plate, anode is the graphite rod of 3 centimetres of diameters, the catholyte that adds contains (concentration): manganous chloride 126 grams per liters, ammonium chloride 120 grams per liters, selenous acid 0.114 grams per liter and ethanol 0.3 grams per liter, the anolyte of adding contains (concentration): manganous chloride 145.6 grams per liters.And regulate the electrolytic solution potential of hydrogen with hydrochloric acid: catholyte pH=5～7, anolyte are 0.1～0.3M.Adopt: current density is negative electrode 800 peace/rice
2, anode 250 peace/rice
2, current concentration be cathode compartment 1.5 peace/liter, anolyte compartment's 1 peace/liter, Faradaic current 6 peaces, electrolysis temperature is 45～55 ℃ of cathode compartments, 90～95 ℃ of anolyte compartments, bath voltage is 3.7 volts.After electrolysis in 24 hours, negative electrode gets electrolytic metal Mn 112.6 grams, and anode gets fibrous electrolytical manganese dioxide 204.0 grams, power consumption 0.533 degree, and current efficiency is negative electrode 76.22%, anode 87.30%.Below " example 1 table 1 " be the situation of manganous chloride change in concentration in the cathode compartment in the electrolytic process." example 1 table 2 " is the situation of the indoor manganous chloride change in concentration in anolyte compartment in the electrolytic process." example 1 table 3 " is the situation that the indoor acidity of anode changes in the electrolytic process.
Example 2, this example are that the amplification of example 1 is implemented, and adopt five identical Room electrolyzers, but the capacity of every chamber increases to 10 liters, and add 10 liters negative electrode (anode) electrolytic solution in every chamber.Dividing plate adopts anion-exchange membrane on two corundum plate therebetween.Negative electrode uses stainless steel bar, and anode is the graphite rod of 3 centimetres of diameters, and manganous chloride, ammonium chloride, selenous acid and ethanol contained in the catholyte are all identical with example 1.Contained manganous chloride is 152 grams per liters in the anolyte.The electrolysis temperature that uses is 50～60 ℃ of cathode compartments, 90～95 ℃ of anolyte compartments, and Faradaic current is 30 peaces, and bath voltage is 3.7～4.5 volts.All the other: electrolytic solution potential of hydrogen, current density, current concentration are all identical with example 1.Change electrode after electrolysis in 24 hours, negative electrode gets electrolytic metal Mn 540 grams, and anode gets fibrous electrolytical manganese dioxide 887.75 grams.Power consumption is 3.24 degree.Current efficiency is negative electrode 73.11%, anode 75.98%.Also carried out employing bique plate in this example respectively and substituted the corundum plate, adopted modes such as polylith ion-exchange membrane and polylith corundum plate to change the experiment of the combination of dividing plate, caused effect is identical.
Table 1
Example 1 table 1:
Example 1 table 2:
Example 1 table 3:
Table 2(system of the present invention and existing manganous sulfate system power consumption situation)
Table 3:(China's electrolytic metal Mn GB3418-82 standard and sample of the present invention are relatively)
Each sample of table 4(is made R
20The entity battery carries out 5 Europe continuous discharge second test situations)
Claims (41)
1, a kind of method of producing electrolytic metal Mn and fibrous electrolytical manganese dioxide simultaneously comprises with the carbon material being anode, is negative electrode with stainless steel or titanium, is that electrolytic solution carries out electrolysis with the aqueous solution of manganous chloride system, it is characterized in that,
Electrolyzer is separated into anolyte compartment and cathode compartment by dividing plate, during electrolysis, anolyte and catholyte enter and portion's discharge from it respectively from the bottom of anolyte compartment and cathode compartment respectively continuously, Manganse Dioxide and manganese metal are deposited on respectively on anode and the negative electrode, and said dividing plate has the low feature of resistivity and has the NH that can prevent the cathodic area
4+ the ability of going into the positive column and can stop the material of yin, yang two polar regions to interpenetrate.
Said electrolytic solution consists of:
Anolyte
Manganous chloride 125.8～188.7 grams per liters
Catholyte
Manganous chloride 88～151 grams per liters
Ammonium chloride 100～140 grams per liters
Main additive 0.04～0.15 grams per liter
Supplementary additive 0.1～0.5 grams per liter
Wherein, main additive is selected for use and is contained the mixture that selenium compound (as selenous acid) or it and sulfur dichloride are formed, and supplementary additive is selected from one or more in methyl alcohol, formaldehyde, ethanol, acetaldehyde, acetate and the hydroxylammonium,
Said electrolytic process adopts following condition:
3.5～5.0 volts of voltages
Current concentration
Anolyte compartment's 0.5～2 peace/liter
Cathode compartment 0.5～2.5 peace/liter
Current density
Anode 150～400 peaces/square metre
Negative electrode 600～1200 peaces/square metre
Electrolysis temperature
80～100 ℃ of positive columns
The cathodic area is less than 70 ℃
Electrolytic solution potential of hydrogen (regulating) with hydrochloric acid
Anode solution concentration is 0.1～0.6M
Catholyte pH=5～8
2, method according to claim 1, it is characterized in that the anode electrolysis waste liquid that electrolytic process is discharged makes its concentration that reaches desired each composition of catholyte and acidity scope through adding an amount of ammoniacal liquor, main additive and supplementary additive and adding hydrochloric acid to regulate potential of hydrogen, that is:
Manganous chloride 88～151 grams per liters
Ammonium chloride 100～140 grams per liters
Main additive 0.04～0.15 grams per liter
Supplementary additive 0.1～0.5 grams per liter
Acidity-basicity ph=5～8
The electrolytic solution that will meet these requirements feeds cathode compartment from the bottom of cathode compartment and utilizes again as catholyte.
3, a kind of electrolyzer that is used to implement the described method of claim 1 comprises with the carbon material being anode, is negative electrode with stainless steel or titanium, it is characterized in that,
Electrolyzer is separated into anolyte compartment and cathode compartment by dividing plate, and this electrolyzer can be made up of one or more combinations that have anolyte compartment and cathode compartment simultaneously, can have one or more cathode compartments and one or more anolyte compartment simultaneously in each combination,
Said dividing plate has the low feature of resistivity and has the NH that can prevent the cathodic area
4+ the ability of infiltrating the positive column and can stop the material of negative and positive two polar regions to interpenetrate, this separator material comprises ion-exchange material or poromerics two classes, the ion-exchange dividing plate can be anion-exchange membrane, they can use individually or in the mode that overlaps each other, microporosity separator can be made by any material in pottery, plastics, diamantine, sintered glass, the bique plate, they can use individually or in the mode that overlaps each other, or are used in any order eclipsed mode by ion-exchange membrane and microporosity separator.
The form of this electrolyzer electrode used therein can be any in sheet, rod, open tube, tooth harrow, ball and the hollow ball.
4, electrolyzer according to claim 3 is characterized in that used dividing plate is to be sandwiched between two or more than two the diamantine plate or bique plate by one or more ion-exchange membrane.
5, electrolyzer according to claim 3 is characterized in that used cathode material is a titanium.
6, electrolyzer according to claim 3 is characterized in that used anodic is shaped as the bar-shaped of 3 centimetres of diameters.
7, electrolyzer according to claim 3 is characterized in that being shaped as of used negative electrode is bar-shaped, in tubulose and the tooth harrow shape any.
8, according to claim 3 or the described electrolyzer of claim 7, it is characterized in that the bar-shaped or tubulose of being shaped as of used negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85104334.8A CN1004363B (en) | 1985-06-06 | 1985-06-06 | Concurrent production of electrolytic metallic manganese and fibred electrolytic manganese dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85104334.8A CN1004363B (en) | 1985-06-06 | 1985-06-06 | Concurrent production of electrolytic metallic manganese and fibred electrolytic manganese dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85104334A CN85104334A (en) | 1986-09-03 |
| CN1004363B true CN1004363B (en) | 1989-05-31 |
Family
ID=4793776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85104334.8A Expired CN1004363B (en) | 1985-06-06 | 1985-06-06 | Concurrent production of electrolytic metallic manganese and fibred electrolytic manganese dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1004363B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835195A (en) * | 2017-02-26 | 2017-06-13 | 桂林理工大学 | A kind of method for adding low selenium composite additive electrolytic manganese |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037620C (en) * | 1995-03-17 | 1998-03-04 | 贵州省新材料研究开发基地 | Compound alloy anode for electrolytic production of metal manganes and its preparation method |
| CN102502925B (en) * | 2011-11-29 | 2013-11-13 | 浙江大学 | Device capable of generating electric energy and simultaneously removing metal ions and method of device |
| CN102703926B (en) * | 2012-05-19 | 2014-11-26 | 湘西自治州矿产与新材料技术创新服务中心 | Selenium-free additive for high-efficiency production of electrolytic manganese |
| CN106319562B (en) * | 2015-07-02 | 2018-11-13 | 阿克陶科邦锰业制造有限公司 | Electrolytic manganese buffer solution and its application process |
| CN106319561A (en) * | 2015-07-02 | 2017-01-11 | 阿克陶科邦锰业制造有限公司 | Additive with impossibility of anode mud generation in anode zone and application thereof |
| CN105734608B (en) * | 2016-02-26 | 2019-03-19 | 武汉大学 | The synchronous production technique of manganese metal and chlorhexidine-containing disinfectant is carried out using electrolytic cell |
| CN105624727B (en) * | 2016-04-08 | 2017-07-28 | 吉首大学 | The method for producing electrolytic manganese metal and electrolytic manganese dioxide in same electrolytic cell simultaneously |
| CN109112569B (en) * | 2018-09-19 | 2023-07-25 | 兰州交通大学 | Production method for simultaneously preparing manganese metal and manganese dioxide by ion exchange membrane electrolysis method |
| CN109020596A (en) * | 2018-09-25 | 2018-12-18 | 湖南科嘉新材料有限公司 | A kind of carbon-carbon composite and preparation method thereof and the application in electrolytic manganese dioxide production |
-
1985
- 1985-06-06 CN CN85104334.8A patent/CN1004363B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835195A (en) * | 2017-02-26 | 2017-06-13 | 桂林理工大学 | A kind of method for adding low selenium composite additive electrolytic manganese |
| CN106835195B (en) * | 2017-02-26 | 2018-11-06 | 桂林理工大学 | A method of the low selenium composite additive electrolytic manganese of addition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85104334A (en) | 1986-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1004363B (en) | Concurrent production of electrolytic metallic manganese and fibred electrolytic manganese dioxide | |
| CA1335974C (en) | Electrolyzing method | |
| CN1880512A (en) | Trivalent chromium electroplating solution in sulfate system and method for preparing same | |
| US5004527A (en) | Continuous electrolytic production of alkali metal perchlorates | |
| CA2265183A1 (en) | Magnesium metal production | |
| Natarajan | Electrobioleaching of base metal sulfides | |
| CN1005920B (en) | Method for prolonging operating life of hydrogen-releasing electrode | |
| CN108486606A (en) | A kind of cyclone electrolytic cell step recycles the method and products thereof of copper, selenium and tellurium | |
| US4295943A (en) | Process for the electrolytic production of manganese dioxide | |
| US3074860A (en) | Electrolytic process for the production of metallic titanium from aqueous solution of titanium compounds | |
| CN110184631B (en) | Cyanide-free gold plating electroplating solution and preparation method and electroplating process thereof | |
| CN107475539B (en) | A kind of method that gaseous state electrochemistry prepares Titanium | |
| CN114182301A (en) | Method for preparing metal beryllium by electrolyzing beryllium oxide through fluoride molten salt | |
| KR20010062509A (en) | Electrode and electrolyte for use in preparation of nitrogen trifluoride gas, and preparation method of nitrogen trifluoride gas by use of them | |
| JPS6133918B2 (en) | ||
| US4595466A (en) | Metal electrolysis using a low temperature bath | |
| WO2021085845A1 (en) | Surface treatment metal electrode bar for electropolishing | |
| US5534131A (en) | Process for heavy metals electrowinning | |
| CN109306502B (en) | Manganese electrolyte additive and using method thereof | |
| CN118028904B (en) | Method for leaching noble metal by thiosulfate electrochemical oxidation | |
| JPS6442592A (en) | Production of copper oxide powder by electrolysis | |
| JPS57181385A (en) | Production of quaternary ammonium hydroxide by electrolysis | |
| US4582584A (en) | Metal electrolysis using a semiconductive metal oxide composite anode | |
| KR100198193B1 (en) | Manufacturing method of methanesulfonic acid | |
| CA1120423A (en) | Electrowinning of metals |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |