CN104388979A - Electrolytic manganese production process - Google Patents
Electrolytic manganese production process Download PDFInfo
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- CN104388979A CN104388979A CN201410698645.7A CN201410698645A CN104388979A CN 104388979 A CN104388979 A CN 104388979A CN 201410698645 A CN201410698645 A CN 201410698645A CN 104388979 A CN104388979 A CN 104388979A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 74
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000011572 manganese Substances 0.000 title claims abstract description 49
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 38
- 210000005056 cell body Anatomy 0.000 claims abstract description 102
- 238000000034 method Methods 0.000 claims abstract description 53
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 49
- 230000008569 process Effects 0.000 claims abstract description 29
- 238000004140 cleaning Methods 0.000 claims abstract description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 42
- 239000002893 slag Substances 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000003780 insertion Methods 0.000 claims description 10
- 230000037431 insertion Effects 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 6
- 239000006210 lotion Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- -1 tin anhydride Chemical class 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- 210000004027 cell Anatomy 0.000 abstract description 14
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 5
- 238000010924 continuous production Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 11
- 238000009434 installation Methods 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 238000005342 ion exchange Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 230000008439 repair process Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses an electrolytic manganese production process. The electrolytic manganese production process comprises a process of electrolyzing an electrolytic cell combination body in an electrolytic cell by using an electrolyte solution to obtain metal manganese, wherein the electrolytic cell combination body mainly consists of a combination cell body, an anode plate and a cathode plate. The electrolytic manganese production process comprises the steps of mounting the combination cell body, mounting the electrolytic cell combination body, electrolyzing, obtaining metal manganese products and preparing for continuous production. According to the electrolytic manganese production process, the clean production is realized; during operation, the hoisting of the combination tank body, the anode plate and the cathode plate is realized by a crane, the traditional manual cell cleaning manner is completely changed, and the dirty, noisy and disorder cell cleaning situation is changed; therefore, the electrolytic manganese production process is suitable for wide popularization.
Description
Technical field
The present invention is a kind of electrolytic manganese production technique, and the processing method being specifically related to use electrolyzer to carry out manganese metal in electrolytic manganese production technique and preparing, belongs to the production technical field of electrolytic manganese.
Background technology
Electrolytic metal Mn is a kind of very important industrial chemicals, iron and steel can be widely used in, non-ferrous metal, chemical industry, medicine, multiple field such as food and scientific research, its main explained hereafter flow process comprises: manganese ore raw material is added in leaching can sulfuric acid reaction through heavy metals such as deironing, regulate pH value, slagging-off and the electrolytic solution that obtains continually adds in electrolyzer, after energising electrolysis for some time, take out the negative plate with galvanic deposit manganese, through passivation, washing, dry, after divesting, obtain manganese metal finished product, in this electrolytic process, anolyte compartment is entered through barrier film, the electrolytic solution overflowing electrolyzer by the false end is more then called anolyte, this anolyte returns leaching can after collecting, for leaching manganese ore raw material.
For a long time, in electrolytic metal Mn field, there are two technical barriers of restriction electrolytic manganese technology fast development always:
One is need in electrolyzer, to add ammoniacal liquor to regulate the pH value of electrolytic solution in the process of electrolytic metal Mn, ammonia causes production on-site environment to pollute, the defect higher with electrolysis cost, such as: when electrolytic metal Mn, need in electrolyzer, to add ammoniacal liquor to regulate the pH value of electrolytic solution every for some time, ensure that the pH value of electrolytic solution is between 7 ~ 8, find that the reason that electrolyte PH value diminishes is to there is acid returning phenomenon in anode frame through studying for a long period of time of people, in order to address this problem, people improve traditional diaphragm frame, add the stopping property at the electrolyzer false end, prevent acid solution from entering into electrolytic solution from the bottom of frame, reduce the pH value of electrolytic solution, and for example patent documentation CN101608322(manganese electrolytic cell equipment, 2009.12.23) casting of disclosed use resin concrete Integratively forms the false end, by the sealing groove of false end top casting, solve cell body seepage in electrolysis process process, return the problems such as acid, through this improvement, although decrease the usage quantity of ammoniacal liquor, but in actual electrolysis production, for ensureing carrying out smoothly of electrolytic process, still need to add in the electrolytic solution ammoniacal liquor to carry out pH value and must regulate.
Two is that the electrolyzer that is spaced by multiple anode frame and negative electrode frame is after arrival certain length (4 meters), negative plate away from electrolytic solution liquid feeding end does not almost have the precipitation of manganese metal, in an electrolysing period (24 hours), the manganese metal that negative plate away from electrolytic solution liquid feeding end precipitates is few, seriously govern the output of electrolytic metal Mn, for improving the output of electrolytic metal Mn, existing patent documentation CN201296784(electrolytic metal Mn economize on electricity high-yielding electrolytic bath, 2009.08.26) disclose one and eliminate the false end, utilize the anode frame that batten replaces, in its application process, can by anode and cathode apart from shortening, obtaining electrolysis speed faster outer (that is: on negative electrode, the precipitation rate of manganese increases), also extremely economize on electricity.
In sum, the technical barrier existed in Process of Electrolytic Manganese is all inseparable with electrolyzer, for this reason, the present invention proposes a kind of new electrolytic manganese production technique, be starting point from the Optimal improvements of cell construction, ensureing, under the prerequisite that electrolysis production is carried out smoothly, more to overcome above-mentioned two technological difficulties, and bring rapid development for electrolytic manganese production technique, there is significant social benefit and economic worth.
Summary of the invention
The object of the present invention is to provide a kind of electrolytic manganese production technique, this technique overcomes the many deficiencies existed in existing electrolytic manganese production technique, the electrolyzer molectron adopted can realize the integration of membrane system, disassembly and assembly are convenient, can raise labour productivity, for overcoming the two large technological difficulties existed in prior art, this technique is also provided with through hole on electrolyzer molectron, this structure not only can realize the ion-exchange between anolyte and electrolytic solution, reach the object regulating electrolyte PH value, avoid adding of the acid solutions such as ammoniacal liquor, simultaneously, this structure also can improve the manganese ion concentration in electrolytic solution, improve the eduction rate of manganese metal on negative plate, in actual production process, there is cleaner production, save energy, reduce production cost, the advantage such as to raise labour productivity, great popularization.
The present invention is achieved through the following technical solutions: a kind of electrolytic manganese production technique, described production technique comprises: in electrolyzer, use electrolytic solution carry out electrolysis operation to electrolyzer molectron and obtain the process of manganese metal, described electrolyzer molectron is primarily of combination cell body, positive plate and negative plate composition, described combination cell body comprises spaced anode frame and negative electrode frame, described anode frame and negative electrode frame are all in skeleton construction, described anode frame is horizontally arranged with anode crosspiece, the upper frame of this anode crosspiece and anode frame forms the anolyte compartment holding positive plate, this anode crosspiece is provided with logical liquid bath, described anode frame is provided with the first insertion groove placing positive plate and the first through hole being communicated with electrolyzer and anolyte compartment, diaphragm bag is set with outside described anode frame, described negative electrode frame is horizontally arranged with negative electrode crosspiece, the upper frame of this negative electrode crosspiece and negative electrode frame forms the cathode compartment holding negative plate, described negative electrode frame is provided with the second insertion groove placing negative plate and the second through hole being communicated with electrolyzer and cathode compartment, in said structure, anode frame and negative electrode frame, the structure of anode crosspiece and negative electrode crosspiece is corresponding mutually, wherein, anode frame is isolated into two-layer up and down by anode crosspiece and negative electrode crosspiece respectively, upper strata is respectively anolyte compartment and cathode compartment, the positive plate (or negative plate) longitudinally inserting anode frame (or in negative electrode frame) along insertion groove can be held, anolyte in anolyte compartment flows into the lower floor of anode frame along logical liquid bath, it acts on is reclaim anolyte, anolyte is made to flow out electrolyzer by lower passage, in electrolytic process, electrolytic solution can enter in anolyte compartment from through hole, anolyte (manganous sulfate in anolyte compartment, ammonium sulfate, sulfuric acid) also there is part can infiltrate electrolytic solution from through hole, anolyte in antianode frame is recycled again, along with constantly carrying out of electrolysis, manganous sulfate in electrolytic solution is through repeatedly recycling, the concentration making to be arranged in the mn ion of electrolytic solution is below higher, can separate out on negative plate, even if reach more than 4m at electrolyzer, also can normal precipitating metal manganese on negative plate, thoroughly solve electrolyzer due to long can not the technical barrier of normal electrolytic metal Mn, greatly promote the fast development of electrolytic metal Mn technology.In actual application, diaphragm bag is set on anode frame and uses, and, also covers on the through hole of anode frame meanwhile, ensure that anolyte and electrolytic solution can carry out ion-exchange smoothly.
The production technique that the present invention relates to is for traditional technology, and have and produce the characteristics such as clean, repair maintenance is convenient, labour intensity is low, production efficiency is high, production cost is low, described production technique comprises the steps:
A: install combination cell body, anode frame is set with diaphragm bag, diaphragm bag upper end open, its opening end is fixed by the rope body be arranged at above anode frame, by negative electrode frame and the spaced permutation and combination of anode frame being set with diaphragm bag, arrange fastening piece to be fixed combination cell body, during making, the thickness of anode frame can be set to 25 ~ 40mm, the thickness of negative electrode frame can be 20 ~ 40mm, the length of the combination cell body combined is 2 ~ 5m, when reality uses, the installation of diaphragm bag, dismantle and repair all very convenient, overcome conventional membrane bag and use bottom disjunctor, top split, when the exoskeletal support of anode frame, easy appearance because of uneven or the increasing along with production and application Anodic slag of pressurized in cell liquid, negative plate adhesive diaphragm bag and the diaphragm bag that occurs is damaged, tank liquor returns acid and the situation such as manganese plate is molten.
B: install electrolyzer molectron, empty electrolyzer, combination cell body is installed in electrolyzer, insert positive plate in the anolyte compartment combining cell body after, then in electrolyzer filling electrolytic solution, add tin anhydride, then, then negative plate is inserted cathode compartment.
C: electrolysis production, electrolysis operation is started after energising, simultaneously, detect the data target in electrolytic process, due in electrolytic process, anolyte and electrolytic solution can carry out ion-exchange mutually by through hole, potential of hydrogen in electrolytic solution is stablized, therefore, do not need to add ammoniacal liquor or acid solution as traditional electrolyte device to regulate potential of hydrogen, greatly reduce production cost;
D: obtain manganese metal product, after electrolysis operation completes, takes out negative plate and cleans it, dries, peels off rear acquisition manganese metal product;
E: continue Operational preparation, after electrolysis production runs 10 ~ 15 days, successively positive plate and combination cell body are taken out and clear up, groove is repaiied to electrolyzer simultaneously, prepare with the preparation completing next round manganese metal product, wherein, the electrolytic solution in electrolyzer is changed without the need to releasing, positive plate after having cleared up and combination cell body operate according to step B again, continue the making of next round manganese metal product.
The quantity of the anode frame that the present invention relates to can be 30 ~ 60, the quantity of negative electrode frame can be 29 ~ 59, for ensureing that negative plate in each negative electrode frame can precipitating metal manganese normally, many one of the quantity of the number ratio negative electrode frame of the anode frame of described composition combination cell body.
To better implement the present invention, described fastening piece comprises the fastening press box and pull bar that are arranged at combination cell body two ends, and described fastening press box and pull bar are by the fastening locking of nut.
Positive plate of the present invention, negative plate and combination cell body are lifted by driving respectively, brightly have cleaner production, operate easy operational characteristic.
In described step e, positive plate and combination cell body are respectively by driving hanging out electrolyzer, and described positive plate is sent to slag chute and clears up, and reclaims the anode slag cleaned out, and this anode slag is MnO
2; Described combination cell body is placed in slag chute, then is transported to branch works by fork truck and clears up.
The cleaning of described combination cell body comprises the following steps:
(E.a) driving is used to tilt to sling by combination cell body, open both sides bottom cover plate, water blast gun is used to rinse, this bottom cover plate is arranged on the bottom of the fastening press box being positioned at combination cell body two ends usually, after opening bottom cover plate, lower floor's liquid chamber of combination cell body can be made to be connected with the external world, when actually operating, the anode slag of whole electrolyzer molectron bottom can be cleared, realize the efficient recovery of anode slag, convenient to operation;
(E.b) be soaked in washing lotion groove by the combination cell body after flushing, soak time >=6h, by driving hanging out, then rinses well diaphragm bag with water blast gun, after cleaning, and combination cell body for subsequent use.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) the present invention can realize the technological operation of cleaner production, operating process uses driving to realize the lifting of combination cell body, positive plate and negative plate, not only change traditional artificial clear groove mode completely, more change filthy clear channel-shaped condition, be suitable for extensively promoting the use of.
(2) vibrational power flow of the present invention is reasonable, the lower floor of electrolyzer molectron forms the liquid chamber of recyclable anolyte, in the process that combination cell body is cleared up, the labour intensity of the reduction workman of energy high degree, after opening the cover plate bottom fastening press box, carry out rinsing with water blast gun, the anode slag of whole electrolyzer molectron bottom can be cleared, realize the efficient recovery of anode slag, convenient to operation.
(3) the present invention is provided with through hole on negative electrode frame; along with constantly carrying out of electrolysis; effectively can improve the concentration of mn ion in electrolytic solution; avoid adding of ammoniacal liquor in production process; it is very reasonable to design; not only reduce the unpleasant odor in production plant, more protect production environment, there is good social benefit.
(4) diaphragm bag that the present invention relates to is set on anode frame and uses, and, also covers on the through hole of anode frame meanwhile, while ensure that anolyte and electrolytic solution carry out ion-exchange smoothly, more extend the clear groove cycle of electrolyzer, shorten the groove time clearly, add electrolysis working lipe.
(5) the electrolyzer combination physical efficiency that the present invention adopts significantly reduces production cost, reach energy-conservation, about ammoniacal liquor, save sulfuric acid, electrolysis production direct motion, improve the object of output.
(6) use of electrolyzer molectron of the present invention can reduce product abnormality in process of production, as: flake, blackout, molten, thus contribute to the realization of electrolysis later stage automation system.
(7) the electrolyzer molectron that the present invention relates to can select composite engineering plastics to be made, have corrosion-resistant, light specific gravity, intensity are high, anti-aging, be completely applicable to electrolyte medium, the advantage in more than 3 years work-ing life.
Accompanying drawing explanation
Fig. 1 is the structural representation of anode frame of the present invention.
Fig. 2 is the structural representation being provided with the anode frame of diaphragm bag of the present invention.
Fig. 3 is the structural representation of negative electrode frame of the present invention.
Fig. 4 is the structural representation of combination cell body of the present invention.
Wherein 1-anode frame, 2-negative electrode frame, 3-anode crosspiece, 4-logical liquid bath, the 5-the first insertion groove, 6-the first through hole, 7-diaphragm bag, 8-negative electrode crosspiece, the 9-the second insertion groove, the 10-the second through hole, 11-fastening press box, 12-pull bar, 13-rope body, 14-bottom cover plate.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1:
The present invention proposes a kind of electrolytic manganese production technique, this production technique is chiefly directed in electrolyzer and uses electrolytic solution carry out electrolysis operation to electrolyzer molectron and obtain the technological process of manganese metal, in actual production process, the present embodiment overcomes in traditional processing technology, many performance deficiencies in the production caused owing to using cell construction unreasonable and operating process, devise the structure of electrolyzer molectron as follows in the present embodiment, the structure of electrolyzer molectron is primarily of combination cell body, positive plate and negative plate composition, wherein, combination cell body comprises spaced anode frame 1 and negative electrode frame 2, anode frame 1 and negative electrode frame 2 are all in skeleton construction, as shown in Figures 1 to 3, anode frame 1 is horizontally arranged with anode crosspiece 3, this anode crosspiece 3 forms with the upper frame of anode frame 1 anolyte compartment holding positive plate, this anode crosspiece 3 is provided with logical liquid bath 4, described anode frame 1 is provided with the first insertion groove 5 placing positive plate and the first through hole 6 being communicated with electrolyzer and anolyte compartment, diaphragm bag 7 is set with outside anode frame 1, negative electrode frame 2 is horizontally arranged with negative electrode crosspiece 8, and this negative electrode crosspiece 8 forms with the upper frame of negative electrode frame 2 cathode compartment holding negative plate, and negative electrode frame 2 is provided with the second insertion groove 9 placing negative plate and the second through hole 10 being communicated with electrolyzer and cathode compartment.
In said structure, anode frame 1 and negative electrode frame 2, the structure of anode crosspiece 3 and negative electrode crosspiece 8 is corresponding mutually, wherein, anode frame 1 is isolated into two-layer up and down by anode crosspiece 3 and negative electrode crosspiece 8 respectively, upper strata is respectively anolyte compartment and cathode compartment, can hold and longitudinally insert in anode frame 1(or negative electrode frame 2 along insertion groove) positive plate (or negative plate), anolyte in anolyte compartment flows into the lower floor of anode frame 1 along logical liquid bath 4, it acts on is reclaim anolyte, anolyte is made to flow out electrolyzer by lower passage, in electrolytic process, electrolytic solution can enter in anolyte compartment from through hole, anolyte (manganous sulfate in anolyte compartment, ammonium sulfate, sulfuric acid) also there is part can infiltrate electrolytic solution from through hole, anolyte in antianode frame 1 is recycled again, along with constantly carrying out of electrolysis, manganous sulfate in electrolytic solution is through repeatedly recycling, the concentration making to be arranged in the mn ion of electrolytic solution is below higher, can separate out on negative plate, even if reach more than 4m at electrolyzer, also can normal precipitating metal manganese on negative plate, thoroughly solve electrolyzer due to long can not the technical barrier of normal electrolytic metal Mn, greatly promote the fast development of electrolytic metal Mn technology.In actual application, diaphragm bag 7 is set on anode frame 1 and uses, and, also covers on the through hole of anode frame 1 meanwhile, ensure that anolyte and electrolytic solution can carry out ion-exchange smoothly.
Embodiment 2:
The difference of the present embodiment and embodiment 1 is: the present embodiment, specially for the structure of electrolyzer molectron, proposes production process as follows:
(1) combination cell body is installed, anode frame 1 is set with diaphragm bag 7, diaphragm bag 7 upper end open, its opening end is fixed by the rope body 13 be arranged at above anode frame 1, by negative electrode frame 2 and the spaced permutation and combination of anode frame 1 being set with diaphragm bag 7, arrange fastening piece to be fixed combination cell body, during making, the thickness of anode frame 1 can be set to 25mm, the thickness of negative electrode frame 2 can be 20mm, the length of the combination cell body combined is 2m, when reality uses, the installation of diaphragm bag 7, dismantle and repair all very convenient, overcome conventional membrane bag 7 and use bottom disjunctor, top split, when anode frame 1 exoskeletal support, easy appearance because of uneven or the increasing along with production and application Anodic slag of pressurized in cell liquid, negative plate adhesive diaphragm the bag 7 and diaphragm bag 7 that occurs is damaged, tank liquor returns acid and the situation such as manganese plate is molten.
(2) electrolyzer molectron is installed, empties electrolyzer, combination cell body is installed in electrolyzer, insert positive plate in the anolyte compartment combining cell body after, then in electrolyzer filling electrolytic solution, add tin anhydride, then, then negative plate is inserted cathode compartment.
(3) electrolysis production, electrolysis operation is started after energising, simultaneously, detect the data target in electrolytic process, due in electrolytic process, anolyte and electrolytic solution can carry out ion-exchange mutually by through hole, potential of hydrogen in electrolytic solution is stablized, therefore, do not need to add ammoniacal liquor or acid solution as traditional electrolyte device to regulate potential of hydrogen, greatly reduce production cost;
(4) obtain manganese metal product, after electrolysis operation completes, take out negative plate and it is cleaned, dry, peel off rear acquisition manganese metal product;
(5) Operational preparation is continued, after electrolysis production runs 10 days, successively positive plate and combination cell body are taken out and clear up, groove is repaiied to electrolyzer simultaneously, prepare with the preparation completing next round manganese metal product, wherein, the electrolytic solution in electrolyzer is changed without the need to releasing, positive plate after having cleared up and combination cell body operate according to step (2) again, continue the making of next round manganese metal product.
Embodiment 3:
The difference of the present embodiment and embodiment 2 is: in the present embodiment, many one of the quantity of the number ratio negative electrode frame 2 of the anode frame 1 of composition combination cell body, the quantity of anode frame 1 is 30, the quantity of negative electrode frame 2 can be 29, the thickness of anode frame 1 is set to 28mm, the thickness of negative electrode frame 2 is set to 40mm, and the length of the combination cell body combined is 2m.
Embodiment 4:
The difference of the present embodiment and embodiment 2 is: in the present embodiment, and fastening piece comprises the fastening press box 11 and pull bar 12 that are arranged at combination cell body two ends, and as shown in Figure 4, fastening press box 11 and pull bar 12 are by the fastening locking of nut.
Embodiment 5:
The difference of the present embodiment and embodiment 2 is: in the present embodiment, positive plate, negative plate and combination cell body are lifted by driving respectively, easy to operate, especially positive plate and negative plate, driving also can be adopted to carry out polylith lift simultaneously, significantly reduce the labour intensity of workman, save labor force.
Embodiment 6:
The difference of the present embodiment and embodiment 2 is: in the present embodiment, and positive plate and combination cell body are respectively by driving hanging out electrolyzer, and positive plate is sent to slag chute and clears up, and reclaims the anode slag cleaned out, as: MnO
2; Combination cell body is placed in slag chute, then is transported to branch works by fork truck and clears up, and the cleaning of combination cell body comprises the following steps:
(5.a) driving is used to tilt to sling by combination cell body, open both sides bottom cover plate 14, water blast gun is used to rinse, this bottom cover plate 14 is arranged on the bottom of the fastening press box 11 being positioned at combination cell body two ends usually, after opening bottom cover plate 14, lower floor's liquid chamber of combination cell body can be made to be connected with the external world, when actually operating, the anode slag of whole electrolyzer molectron bottom can be cleared, realize the efficient recovery of anode slag, convenient to operation;
(5.b) be soaked in washing lotion groove by the combination cell body after flushing, soak time 6h, by driving hanging out, then rinses well diaphragm bag 7 with water blast gun, after cleaning, and combination cell body for subsequent use.
Embodiment 7:
The difference of the present embodiment and embodiment 1 is: the present embodiment, specially for the structure of electrolyzer molectron, proposes production process as follows:
(1) combination cell body is installed, anode frame 1 is set with diaphragm bag 7, diaphragm bag 7 upper end open, its opening end is fixed by the rope body 13 be arranged at above anode frame 1, by negative electrode frame 2 and the spaced permutation and combination of anode frame 1 being set with diaphragm bag 7, arrange fastening piece to be fixed combination cell body, during making, the thickness of anode frame 1 can be set to 40mm, the thickness of negative electrode frame 2 can be 40mm, the quantity of anode frame 1 is 60, the quantity of negative electrode frame 2 can be 59, the length of the combination cell body combined is 4.76m, when reality uses, the installation of diaphragm bag 7, dismantle and repair all very convenient, overcome conventional membrane bag 7 and use bottom disjunctor, top split, when anode frame 1 exoskeletal support, easy appearance because of uneven or the increasing along with production and application Anodic slag of pressurized in cell liquid, negative plate adhesive diaphragm the bag 7 and diaphragm bag 7 that occurs is damaged, tank liquor returns acid and the situation such as manganese plate is molten.
(2) electrolyzer molectron is installed, empty electrolyzer, the driving of combination cell body is lifted and is placed in electrolyzer, in the anolyte compartment of combination cell body, insert positive plate, complete installation after positive plate is lifted by polylith of driving a vehicle, after positive plate installation, filling electrolytic solution in electrolyzer, add tin anhydride, then, negative plate is inserted cathode compartment by recycling driving.
(3) electrolysis production, electrolysis operation is started after energising, simultaneously, data target in electrolytic process is detected, such as: check the situation of negative plate By Electrolysis manganese, the technical indicator of liquid level of electrolyzer, the pH value of electrolyzer electrolyte inside and the voltage of electrolyzer etc., due in electrolytic process, anolyte and electrolytic solution can carry out ion-exchange mutually by through hole, potential of hydrogen in electrolytic solution is stablized, therefore, do not need to add ammoniacal liquor or acid solution as traditional electrolyte device to regulate potential of hydrogen, greatly reduce production cost.
(4) obtain manganese metal product, after electrolysis operation completes, take out negative plate and it is cleaned, dry, peel off rear acquisition manganese metal product;
(5) Operational preparation is continued, after electrolysis production runs 15 days, driving is used successively positive plate and combination cell body to be hung out electrolyzer and clear up, groove is repaiied to electrolyzer simultaneously, electrolytic solution in electrolyzer is changed without the need to releasing, and during cleaning, positive plate is sent to slag chute and clears up, and reclaim the anode slag cleaned out, that is: MnO
2; Combination cell body is placed in slag chute, then is transported to branch works by fork truck and clears up, and the cleaning of combination cell body comprises the following steps:
(5.a) driving is used to tilt to sling by combination cell body, open both sides bottom cover plate 14, water blast gun is used to rinse, this bottom cover plate 14 is arranged on the bottom of the fastening press box 11 being positioned at combination cell body two ends usually, after opening bottom cover plate 14, lower floor's liquid chamber of combination cell body can be made to be connected with the external world, when actually operating, the anode slag of whole electrolyzer molectron bottom can be cleared, realize the efficient recovery of anode slag, convenient to operation;
(5.b) be soaked in washing lotion groove by the combination cell body after flushing, soak time 10h, by driving hanging out, then rinses well diaphragm bag 7 with water blast gun, after cleaning, and combination cell body for subsequent use.
Embodiment 8:
The difference of the present embodiment and embodiment 1 is: the present embodiment, specially for the structure of electrolyzer molectron, proposes production process as follows:
(1) combination cell body is installed, anode frame 1 is set with diaphragm bag 7, diaphragm bag 7 upper end open, its opening end is fixed by the rope body 13 be arranged at above anode frame 1, by negative electrode frame 2 and the spaced permutation and combination of anode frame 1 being set with diaphragm bag 7, arrange fastening piece to be fixed combination cell body, during making, the thickness of anode frame 1 can be set to 30mm, the thickness of negative electrode frame 2 can be 20mm, the quantity of anode frame 1 is 50, the quantity of negative electrode frame 2 is 49, the length of the combination cell body combined is 2.48m, when reality uses, the installation of diaphragm bag 7, dismantle and repair all very convenient, overcome conventional membrane bag 7 and use bottom disjunctor, top split, when anode frame 1 exoskeletal support, easy appearance because of uneven or the increasing along with production and application Anodic slag of pressurized in cell liquid, negative plate adhesive diaphragm the bag 7 and diaphragm bag 7 that occurs is damaged, tank liquor returns acid and the situation such as manganese plate is molten.
(2) electrolyzer molectron is installed, empty electrolyzer, the driving of combination cell body is lifted and is placed in electrolyzer, in the anolyte compartment of combination cell body, insert positive plate, complete installation after positive plate is lifted by polylith of driving a vehicle, after positive plate installation, filling electrolytic solution in electrolyzer, add tin anhydride, then, negative plate is inserted cathode compartment by recycling driving.
(3) electrolysis production, electrolysis operation is started after energising, simultaneously, data target in electrolytic process is detected, such as: check the situation of negative plate By Electrolysis manganese, the technical indicator of liquid level of electrolyzer, the pH value of electrolyzer electrolyte inside and the voltage of electrolyzer etc., due in electrolytic process, anolyte and electrolytic solution can carry out ion-exchange mutually by through hole, potential of hydrogen in electrolytic solution is stablized, therefore, do not need to add ammoniacal liquor or acid solution as traditional electrolyte device to regulate potential of hydrogen, greatly reduce production cost.
(4) obtain manganese metal product, after electrolysis operation completes, take out negative plate and it is cleaned, dry, peel off rear acquisition manganese metal product;
(5) Operational preparation is continued, after electrolysis production runs 12 days, driving is used successively positive plate and combination cell body to be hung out electrolyzer and clear up, groove is repaiied to electrolyzer simultaneously, electrolytic solution in electrolyzer is changed without the need to releasing, and during cleaning, positive plate is sent to slag chute and clears up, and reclaim the anode slag cleaned out, that is: MnO
2; Combination cell body is placed in slag chute, then is transported to branch works by fork truck and clears up, and the cleaning of combination cell body comprises the following steps:
(5.a) driving is used to tilt to sling by combination cell body, open both sides bottom cover plate 14, water blast gun is used to rinse, this bottom cover plate 14 is arranged on the bottom of the fastening press box 11 being positioned at combination cell body two ends usually, after opening bottom cover plate 14, lower floor's liquid chamber of combination cell body can be made to be connected with the external world, when actually operating, the anode slag of whole electrolyzer molectron bottom can be cleared, realize the efficient recovery of anode slag, convenient to operation;
(5.b) be soaked in washing lotion groove by the combination cell body after flushing, soak time 8h, by driving hanging out, then rinses well diaphragm bag 7 with water blast gun, after cleaning, and combination cell body for subsequent use.
Embodiment 9:
The difference of the present embodiment and embodiment 1 is: the present embodiment, specially for the structure of electrolyzer molectron, proposes production process as follows:
(1) combination cell body is installed, anode frame 1 is set with diaphragm bag 7, diaphragm bag 7 upper end open, its opening end is fixed by the rope body 13 be arranged at above anode frame 1, by negative electrode frame 2 and the spaced permutation and combination of anode frame 1 being set with diaphragm bag 7, arrange fastening piece to be fixed combination cell body, during making, the thickness of anode frame 1 can be set to 35mm, the thickness of negative electrode frame 2 can be 30mm, the quantity of anode frame 1 is 40, the quantity of negative electrode frame 2 is 39, the length of the combination cell body combined is 2.57m, when reality uses, the installation of diaphragm bag 7, dismantle and repair all very convenient, overcome conventional membrane bag 7 and use bottom disjunctor, top split, when anode frame 1 exoskeletal support, easy appearance because of uneven or the increasing along with production and application Anodic slag of pressurized in cell liquid, negative plate adhesive diaphragm the bag 7 and diaphragm bag 7 that occurs is damaged, tank liquor returns acid and the situation such as manganese plate is molten.
(2) electrolyzer molectron is installed, empty electrolyzer, the driving of combination cell body is lifted and is placed in electrolyzer, in the anolyte compartment of combination cell body, insert positive plate, complete installation after positive plate is lifted by polylith of driving a vehicle, after positive plate installation, filling electrolytic solution in electrolyzer, add tin anhydride, then, negative plate is inserted cathode compartment by recycling driving.
(3) electrolysis production, electrolysis operation is started after energising, simultaneously, data target in electrolytic process is detected, such as: check the situation of negative plate By Electrolysis manganese, the technical indicator of liquid level of electrolyzer, the pH value of electrolyzer electrolyte inside and the voltage of electrolyzer etc., due in electrolytic process, anolyte and electrolytic solution can carry out ion-exchange mutually by through hole, potential of hydrogen in electrolytic solution is stablized, therefore, do not need to add ammoniacal liquor or acid solution as traditional electrolyte device to regulate potential of hydrogen, greatly reduce production cost.
(4) obtain manganese metal product, after electrolysis operation completes, take out negative plate and it is cleaned, dry, peel off rear acquisition manganese metal product;
(5) Operational preparation is continued, after electrolysis production runs 14 days, driving is used successively positive plate and combination cell body to be hung out electrolyzer and clear up, groove is repaiied to electrolyzer simultaneously, electrolytic solution in electrolyzer is changed without the need to releasing, and during cleaning, positive plate is sent to slag chute and clears up, and reclaim the anode slag cleaned out, that is: MnO
2; Combination cell body is placed in slag chute, then is transported to branch works by fork truck and clears up, and the cleaning of combination cell body comprises the following steps:
(5.a) driving is used to tilt to sling by combination cell body, open both sides bottom cover plate 14, water blast gun is used to rinse, this bottom cover plate 14 is arranged on the bottom of the fastening press box 11 being positioned at combination cell body two ends usually, after opening bottom cover plate 14, lower floor's liquid chamber of combination cell body can be made to be connected with the external world, when actually operating, the anode slag of whole electrolyzer molectron bottom can be cleared, realize the efficient recovery of anode slag, convenient to operation;
(5.b) be soaked in washing lotion groove by the combination cell body after flushing, soak time 7h, by driving hanging out, then rinses well diaphragm bag 7 with water blast gun, after cleaning, and combination cell body for subsequent use.
The above is only preferred embodiment of the present invention, and not do any pro forma restriction to the present invention, every any simple modification, equivalent variations done above embodiment according to technical spirit of the present invention, all falls within protection scope of the present invention.
Claims (7)
1. an electrolytic manganese production technique, it is characterized in that: described production technique comprises: in electrolyzer, use electrolytic solution carry out electrolysis operation to electrolyzer molectron and obtain the process of manganese metal, described electrolyzer molectron is primarily of combination cell body, positive plate and negative plate composition, described combination cell body comprises spaced anode frame (1) and negative electrode frame (2), described anode frame (1) and negative electrode frame (2) are all in skeleton construction, described anode frame (1) is horizontally arranged with anode crosspiece (3), this anode crosspiece (3) forms with the upper frame of anode frame (1) anolyte compartment holding positive plate, this anode crosspiece (3) is provided with logical liquid bath (4), described anode frame (1) is provided with the first insertion groove (5) placing positive plate and the first through hole (6) being communicated with electrolyzer and anolyte compartment, diaphragm bag (7) is set with outside described anode frame (1), described negative electrode frame (2) is horizontally arranged with negative electrode crosspiece (8), this negative electrode crosspiece (8) forms with the upper frame of negative electrode frame (2) cathode compartment holding negative plate, and described negative electrode frame (2) is provided with the second insertion groove (9) placing negative plate and the second through hole (10) being communicated with electrolyzer and cathode compartment.
2. a kind of electrolytic manganese production technique according to claim 1, is characterized in that: described production technique comprises the steps:
A: install combination cell body, anode frame (1) is set with diaphragm bag (7), diaphragm bag (7) upper end open, its opening end is fixed by the rope body (13) being arranged at anode frame (1) top, by negative electrode frame (2) and anode frame (1) the spaced permutation and combination being set with diaphragm bag (7), arrange fastening piece to be fixed combination cell body, the length of the combination cell body combined is 2 ~ 5m;
B: install electrolyzer molectron, empty electrolyzer, combination cell body is installed in electrolyzer, insert positive plate in the anolyte compartment combining cell body after, then in electrolyzer filling electrolytic solution, add tin anhydride, then, then negative plate is inserted cathode compartment;
C: electrolysis production, starts electrolysis operation after energising, detect the data target in electrolytic process meanwhile;
D: obtain manganese metal product, after electrolysis operation completes, takes out negative plate and cleans it, dries, peels off rear acquisition manganese metal product;
E: continue Operational preparation, after electrolysis production runs 10 ~ 15 days, takes out positive plate and combination cell body and clears up successively, repairing groove simultaneously to electrolyzer, preparing with the preparation completing next round manganese metal product.
3. a kind of electrolytic manganese production technique according to claim 2, is characterized in that: many one of the quantity of the number ratio negative electrode frame (2) of the anode frame (1) of described composition combination cell body.
4. a kind of electrolytic manganese production technique according to claim 2, it is characterized in that: described fastening piece comprises the fastening press box (11) and pull bar (12) that are arranged at combination cell body two ends, and described fastening press box (11) and pull bar (12) are by the fastening locking of nut.
5. a kind of electrolytic manganese production technique according to claim 2, is characterized in that: described positive plate, negative plate and combination cell body are lifted by driving respectively.
6. a kind of electrolytic manganese production technique according to claim 2, is characterized in that: in described step e, and positive plate and combination cell body are respectively by driving hanging out electrolyzer, and described positive plate is sent to slag chute and clears up, and reclaims the anode slag cleaned out; Described combination cell body is placed in slag chute, then is transported to branch works by fork truck and clears up.
7. a kind of electrolytic manganese production technique according to claim 6, is characterized in that: the cleaning of described combination cell body comprises the following steps:
(E.a) use driving to tilt to sling by combination cell body, open both sides bottom cover plate (14), use water blast gun to rinse;
(E.b) be soaked in washing lotion groove by the combination cell body after flushing, soak time >=6h, by driving hanging out, then rinses well diaphragm bag (7) with water blast gun.
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