CN103857832A - Internal box for an electrolytic manganese cell, provided with gas discharge openings, and associated cell and method - Google Patents
Internal box for an electrolytic manganese cell, provided with gas discharge openings, and associated cell and method Download PDFInfo
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- CN103857832A CN103857832A CN201180073449.5A CN201180073449A CN103857832A CN 103857832 A CN103857832 A CN 103857832A CN 201180073449 A CN201180073449 A CN 201180073449A CN 103857832 A CN103857832 A CN 103857832A
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- interior case
- cathode
- negative electrode
- frame
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- 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
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- 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
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a box comprising a plurality of anode frames (66), a plurality of cathode frames (64) placed between the anode frames (66) and a plurality of diaphragms (68) disposed between each cathode frame (64) and each anode frame (66). Each cathode frame (64) delimits an inner cathode-receiving compartment (90) and at least one lateral supply opening (96) for supplying a feed solution containing manganese ions to the inner compartment (90). Each cathode frame (64) defines an upper lateral opening (98) for discharging cathode gases and said upper discharge opening (98) is disposed above the or each lateral supply opening (96) for the feed solution so that the discharge opening opens at least partially above the feed solution.
Description
Technical field
The present invention relates to a kind ofly for case in the electrolyzer of manganese electrolysis, described interior case is for being placed on the groove that contains stock liquid, and described interior case comprises:
-multiple anode superstructures;
-multiple cathode frames that are placed between described anode superstructure;
-multiple dividing plates that are inserted between each described cathode frame and each described anode superstructure;
-can maintain that described cathode frame, described anode superstructure and described dividing plate abut one another and the clamp assemblies applied,
Each described cathode frame limits and holds the inner compartment of negative electrode, upper negative electrode introduction hole in described inner compartment and at least one is for being supplied to the stock liquid that contains mn ion the side opening of described inner compartment.
This chest is used for being removably inserted in the groove of manganese electrolyzer.
Background technology
Textbook " Operation of Electrolytic Manganese Pilot Plant " (the Boulder city of the state of Nevada, USBM(United States Bureau of Mines) No. 463 bulletin, the 64th page and the 65th page), a kind of chest of the structure with " pressure filter " type of the above-mentioned type has been described in Figure 35.
This chest comprises the cathode frame that replace and the anode superstructure separated from one another by dividing plate.Longitudinal rod and end nut keep abutting one another and framework and the dividing plate applied, to ensure the good sealing between the compartment being limited by each framework.
In cathode frame, be laterally formed for supplying with the side opening of the stock liquid that contains mn ion, to make each cathodic compartment be supplied to the solution being present in groove.
The upper hole upwardly opening is also set in each cathode frame and in each anode superstructure, to allow respectively the insertion of negative electrode and anode.
This chest has compact exercisable structure.But this chest is not entirely satisfactory.
Really, the electrolytic reaction of manganese produces the gas that must be discharged of some amount at negative electrode.
Especially, to occur in negative electrode although form manganese master metal by stock liquid, be present in the oxonium ion (H in cathode solution
+) reduction produce hydrogen, and be deposited on the competition of manganese metal on negative electrode.
In addition, in some cases, according to the pH of cathode solution, ammonium ion (NH in stock liquid
4 +) existence produce ammonia (NH
3) more or less obvious parasitic differentiation.
In by the described electrolyzer of USBM, these cathode gas directly, by discharging for the upper hole of inserting negative electrode, are then dispersed in the atmosphere of electrolyzer.
But, for the constraint of the existence of the environment of industrial premises, health and safety, potential poisonous or adventurous gaseous emission is produced and controlled and restriction from now on.
Summary of the invention
Therefore, the object of the invention is to obtain the interior case of manganese electrolyzer, this interior case meets environment and security constraint, meanwhile, keeps simple and processes and operation.
For this reason, theme of the present invention is a kind of interior case of the above-mentioned type, it is characterized in that each cathode frame is defined for the upper-side hole of discharge cathode gas, this upper air-vent is arranged on the top of described side opening or each side opening for base feed liquid for base feed liquid, to open above described stock liquid at least in part, and be characterised in that, described upper air-vent is opened and is led to inner compartment, and to described chest outside opening.
Interior case according to the present invention comprises one or more following features, and these features are adopted individually or according to all possible technical combinations:
The cross section of-described upper air-vent is greater than described for supplying with the side opening of electrolytic solution or each for supplying with the cross section of side opening of electrolytic solution, and advantageously, described upper air-vent has oval-shaped cross section, the oval-shaped cross section of especially extending along vertical axis.
-each described cathode frame is defined for the recess of the covering closure member that holds electrolyzer above described upper air-vent.
-each described cathode frame comprises two lateral braces and the middle transverse rod that is connected described lateral brace, and described lateral brace and described middle transverse rod limit the inner compartment of holding negative electrode, and each described upside venting hole forms through described lateral brace.
-each described cathode frame limits the sheer pole that connects described two lateral braces below described middle transverse rod, described middle transverse rod is defined for the lower window of the circulation of anodic dissolution together with described lateral brace with described sheer pole, described lower window is isolated with described inner compartment hermetically.
-each described cathode frame comprises the flange that at least one is laterally projecting, and described upper air-vent forms through described flange.
-described interior case comprises by upper patchhole and is inserted into the negative electrode in each described cathode frame, and in the time that described negative electrode is accommodated in the inner compartment of holding negative electrode, containment member sealably seals the upper introduction hole of negative electrode.
-each anode superstructure has the interior compartment that holds anode that bottom is limited by bottom bar,
Described anode superstructure has the support finger piece of multiple separation that protrude upward from described bottom bar, and the described dividing plate adjacent with described anode superstructure is laterally applied on described support finger piece.
-each dividing plate comprises the support frame of supportive grid and is applied in the net on described grid, described support frame comprises middle transverse rod, and described support finger piece is applied to the middle transverse rod of described cathode frame on the middle transverse rod of support frame of adjacent anode superstructure.
Theme of the present invention is also a kind of electrolyzer for manganese electrolysis, and the electrolyzer of described type comprises:
-be defined for the groove in the interior space that holds stock liquid,
-according to the case being placed in described interior space defined above,
-closed component, described closed component, above described upper air-vent, is sealed shut the interior space of described groove around described case;
Described electrolyzer comprises that at least one is for removing the gas discharging so that the pipeline that gas is discharged from described groove by each described upper air-vent.
Can comprise one or more following features according to electrolyzer of the present invention, these features are adopted individually or according to all technical possible combinations:
-described groove contains stock liquid, and described case is immersed in described stock liquid, and each described side venting hole is opened at least in part above described stock liquid.
-described groove comprises the sidewall extending towards each described upper air-vent, described case and described sidewall limit medial side space, described upper air-vent leads to described medial side space, described closed component comprises at least one closure member, described closure member is above each described side venting hole, from intermediate space described in upper face closure.
-described groove comprises the end wall laterally extending substantially with respect to described sidewall, and described end wall and described interior case limit axial intermediate space, and described closed component comprises from the end cap of axial intermediate space described in closed upper part.
Theme of the present invention is also a kind of method for manganese electrolysis, and the method for described type comprises:
-provide according to electrolyzer defined above;
-stock liquid that contains mn ion is provided to the inner compartment of each described cathode frame;
-on each negative electrode being contained in each described cathode frame, form manganese metal;
-in the inner compartment of each described cathode frame, generate cathode gas, especially ammonia and hydrogen;
-cathode gas is discharged from described interior case by described upper air-vent;
-cathode gas being produced by each described negative electrode outside described interior case is collected in the top of the intermediate space limiting between described groove, described case and described closed component;
-by described removing pipeline, be emitted on cathode gas collected in the top of described intermediate space.
Brief description of the drawings
Based on reading the description being merely given as examples below and with reference to the accompanying drawings, will understand better the present invention, wherein:
Fig. 1 is according to the schematic side elevation of the first electrolyzer for manganese electrolysis of the present invention;
Fig. 2 is the local top perspective of the electrolyzer of Fig. 1;
Fig. 3 is perspective and the local sectional view along the transverse plane III of Fig. 2;
Fig. 4 is the decomposition diagram of the interior case of the electrolyzer of Fig. 1;
Fig. 5 is the decomposition diagram of the cathode frame of the interior case of Fig. 4;
Fig. 6 is the local enlarged view that is marked as VI in Fig. 5;
Fig. 7 is the view that is similar to the anode superstructure of Fig. 5;
Fig. 8 is the view that is similar to the bulkhead bracket of Fig. 5;
Fig. 9 is the top view once the segmentation of the horizontal plane of the assembled interior case along Fig. 4; With
The partial view that Figure 10 obtains for the arrow X along Fig. 9.
Embodiment
Fig. 1 to Figure 10 illustrates according to of the present invention for carrying out the first electrolyzer 10 of manganese electrolytic etching of metal or " MME ".
With contain mn ion Mn
2+the situation of stock liquid contact under, selectively under the existence of ammonium sulfate, by providing electric current to form manganese metal on multiple negative electrodes.
Thereby, the manganese metal forming as deposition of solids on each negative electrode.
As shown in Figure 1, electrolyzer 10 comprises the interior case 16 of " pressure filter " type in the interior space 14 that limits the groove 12 in interior space 14 and be placed on groove 12.
According to the present invention, electrolyzer 10 also comprises assembly 18, and this assembly 18 is for sealing for catching and transport during electrolysis hermetically the interior space at the gas of cathode exhaust.
According to Fig. 1 to Fig. 3, groove 12 presents the shape of the parallelepiped substantially with longitudinal axis A-A '.Groove 12 comprises two end cross wall 20A, 20B connected to one another by two longitudinal walls 22, and only have a longitudinal wall 22 is visible in Fig. 1 and Fig. 2.
Groove 12 also comprises the diapire 24 in space 14 in downward sealing.
Advantageously, the height of transverse wall 20A, 20B is greater than the height of sidewall 22.Therefore, each transverse wall 20 defines the upper orle 26 that exceeds sidewall 22.
Each sidewall 22 defines the upper bearing edge 28 of plane.
The upper support belt 30 of edge 28 supporting.
30 supportings of upper support belt are used for longitudinal electrical contact 32A, 32B that power supply part 19 is connected with anode and negative electrode respectively.
Groove 12 also comprise at least one for stock liquid being supplied to the pipeline 34, at least one pipeline 36 for case 16 and groove 12 in anolyte is discharged in interior space 14 and at least one for removing the gas producing at negative electrode in case make gas discharge in the pipeline 38 in space 14.
According to Fig. 1, service 34 is connected with pumping parts or gravity parts 40 for stock liquid being supplied to groove 12.In this example, service 34 passes transverse wall 20A at orle 26.
In the example shown in Fig. 2, discharge tube 36 extends through transverse wall 20A.Discharge tube 36 is connected with interior case 16 by flexible hose (not shown) in upstream.Discharge tube 36 is connected with the collection and the processing element 42 that are placed on groove 12 outsides in downstream.
According to Fig. 1, be connected with the device 44 for collecting and process these gases for removing the pipeline 38 of cathode gas.This point has avoided cathode gas to spread to being arranged in groove 12 atmosphere around.
In this example, remove pipeline 38 and pass transverse wall 20A at upper orle 26.Remove pipeline 38 and open by collection hole 46, this collection hole 46 is positioned at the top of the upper limb 28 of sidewall 22, so that regardless of the level height that is included the cathode solution in space 14, all for good and all keeps not contact liq.
In this example, collection hole 46 is positioned on the both sides of transverse wall 20A, near the upper corner of this transverse wall 20A, towards the medial side space 60 between the sidewall 22 at case 16 and groove.
As specified above, interior case 16 has " pressure filter " type.Therefore,, with reference to Fig. 4, interior case 16 comprises multiple cathode frames 64, multiple anode superstructure 66 and multiple baffle assembly 68 being placed between each anode superstructure 66 and each cathode frame 64.
Advantageously, interior case 16 also comprises that two are used for laterally end frame 70A, the 70B of the axial end of fully sheathed case 16 and dismountable clamp assemblies 72 of interior case 16.
As shown in Figure 5, the sheer pole 84 that each cathode frame 64 comprises two lateral brace 80A, 80B, middle transverse rod 82 and pillar 80A and pillar 80B are linked together.
Therefore, cathode frame 64 defines inner compartment 90 for holding negative electrode and the lower window 92 for the circulation of anolyte, and lower window 92 is isolated hermetically with inner compartment 90.
In this example, the height of cathode frame 64 equals the degree of depth in interior space 14 substantially, and this degree of depth measures between the upper limb 28 of sidewall 22 and diapire 24.
Each flange 100 defines the lateral notch 101 of the closure for holding closed component 18.In the time that interior case 16 is placed in the interior space 14 of groove 12, recess 101 is laterally opened, towards sidewall 22.Recess 101 is positioned at cathode gas discharge orifice 98 tops.
Middle transverse rod 82 placement parallel with sheer pole 84.Middle transverse rod 82 defines the top of window 92.Middle transverse rod 82 defines the bottom of the inner compartment 90 of holding negative electrode.Middle transverse rod 82 is added between pillar 80A and pillar 80B.
Each pillar 80A and pillar 80B higher than middle transverse rod 82 define vertical guide path 104, and this vertical guide path 104 laterally leads to inner compartment 90 and up opens and leads to hole 94.In the time that negative electrode 74 is introduced in inner compartment 90, guide path 104 is used to guide negative electrode 74.
The bottom of inner compartment 90 is limited by middle transverse rod 82 and sidepiece is limited by pillar 80A and pillar 80B.Inner compartment 90 is upwards opened and is led to introduction hole 94.
In this example, each pillar 80A, pillar 80B define the multiple through holes 96 for cathode solution being supplied to inner compartment 90.Each through hole 96 laterally extends through pillar 80A and pillar 80B.In the outside of case 16, through hole 96 is opened the thickness that is deep into pillar 80A, pillar 80B, towards the intermediate space 60 between case 16 and sidewall 22.In inside, through hole 96 leads to inner compartment 90.
In this example, each pillar 80A, pillar 80B comprise and are positioned near the through hole 96 middle transverse rod 82 and are positioned near the through hole 96 flange 100.
In this example, the cross section of through hole 96 is less than the pillar 80A that measures along axis B-B ' or the maximum ga(u)ge of pillar 80B.Advantageously, this cross section is circular.
As shown in Figure 6, each pillar 80A, pillar 80B define in flange 100 be positioned at each through hole 96 for base feed liquid above the upper-side hole 98 for emission gases.
Advantageously, the cross section of upper-side hole 98 is greater than the maximum cross-section for each through hole 96 of base feed liquid.
Advantageously, the cross section of each upper-side hole 98 is oval-shaped.Therefore, the height of upper-side hole 98 is greater than the maximum ga(u)ge of the cathode frame 64 measuring along axis B-B '.The width of the upper-side hole 98 that the B-B ' that parallels to the axis measures is less than the thickness of framework 64.
In this example, upper-side hole 98 has constant cross section.Upper-side hole 98 extends along the horizontal axis perpendicular to axis B-B '.Upper-side hole 98 makes the upper area of inner compartment 90 be connected with the outside of case 16.Upper-side hole 98 is for arranging towards sidewall 22, and the stock liquid being partly present at the most in the interior space 14 between groove 12 and case 16 immerses simultaneously.
In example, the smallest cross-sectional of side venting hole 98 and each ratio of maximum cross-section for the through hole 96 of supplying with solution are greater than 1.
Therefore, the existence of upper-side hole 98 can be removed its contained gas from inner compartment 90, even if this inner compartment 90 is partly by stock liquid submergence.
Consider the cross section of each upper-side hole 98, cathode gas is easily discharged into the outside of interior case 16 from each cathode frame 64.The gas discharging is through another cathode frame 64 or through another anode superstructure 66, but directly flows out in the medial side space 60 that upper-side hole 98 leads to.Therefore, cathode gas is concentrated between groove 12 and closed component 18, and this names a person for a particular job and sees hereinafter.
For supplying with the through hole 96 of solution and only leading to inner compartment 90 for the upper-side hole 98 of emission gases, and open in interior case 16 outsides, and axially do not open along the axis B-B ' of case 16.
Especially, through hole 96 and upper-side hole 98 do not lead to the athwartship plane of cathode frame 64, and are not communicated with other the venting hole being formed in other cathode frame 64.
As shown in Figure 4 and Figure 8, each baffle assembly 68 comprises support frame 110 and is added to the reticulation 112 on support frame 110.
As shown in these figures, support frame 110 comprises lateral brace 114A and lateral brace 114B.From bottom to top, by sheer pole 116, middle transverse rod 118 and cross tube 120, lateral brace 114A and lateral brace 114B are connected to each other.
The height of pillar 114A, pillar 114B equals the pillar 80A of cathode frame 64, the height of pillar 80B substantially.The length of the cross bar of support frame 110 is less than the cross bar 82 of cathode frame 64, the length of cross bar 84 slightly.
Each pillar 114A, pillar 114B have side flange 121 in the top, this side flange 121 is with respect to the longitudinal axis B-B ' of interior case 16 and cross out.Each flange 121 defines the side recess 121A of the closure for holding closed component 18.
Middle transverse rod 118 defines the top of window 126.Middle transverse rod 118 is positioned at the At The Height identical with the middle transverse rod 82 of each cathode frame 64 substantially.Therefore, when dividing plate 68 nestles up adjacent cathode frame 64 and when application, sheer pole 84 and sheer pole 116 contact with each other, and middle transverse rod 82 and middle transverse rod 118 also contact with each other.
In this example, grid 122 comprises the vertical bar 128 of multiple vertical extensions between middle transverse rod 118 and cross tube 120.
The vertical bar 128 of grid 122 define between them for allowing the hole 129 by solution.The first athwartship plane 130 of the support frame 110 that the vertical bar 128 of grid 122 arranges with the anode superstructure 66 for towards adjacent flushes.
Gasket 132(Fig. 9) by second 134 supporting of support frame 110, this second 134 is positioned to contact towards adjacent cathode frame 64 and the cathode frame 64 adjacent with this.
Preferably, gasket 132 is in the periphery of grid 122, extends along pillar 114A and pillar 114B and middle transverse rod 118.
As shown in Fig. 4 and Fig. 9, along pillar 114A, pillar 114B, middle transverse rod 118 and cross tube 120, reticulation 112 is added on the first surface 130 of support frame 110.Reticulation 112 nestles up grid 122 and is employed, and advantageously, is attached on vertical bar 128.
Advantageously, with several discrete points, reticulation 112 is attached on vertical bar 128.In alternative mode, in the whole length of each vertical bar 128, attached reticulation 112.
Thisly attachedly prevent that reticulation 112 from moving towards anode superstructure.This point has prevented the contraction in the space of the discharge anode sludge causing due to reticulation 112.In addition, the attached contact having prevented between reticulation 112 and anode 76 of this reticulation 112, this is avoided in inner compartment 90, directly forming oxonium ion, and it is disadvantageous that its electric current for negative electrode produces.
For example, reticulation 112 is made up of the braided material that synthesizing, advantageously, is made up of resistance to mechanicalness and the chemical-resistant cloth with use compatibility in electrolyzer with it.In order to set up the difference of altitude between cathode solution and anodic dissolution, limit the permeability of reticulation 112.This variable difference of altitude of scaling degree according to net produce solution from negative electrode by reticulation 112 flowing to anode.This solution mobile slowed down the cathodic counter diffusion of oxonium ion generating at anode, makes to keep the pH value of catholyte.
As shown in Figure 7, each anode superstructure 66 comprises the sheer pole 142 of two parallel pillar 140A and the lower end of pillar 140B and connecting struts 140A and the lower end of pillar 140B.Sheer pole 142 defines with pillar 140A, pillar 140B the inner compartment 144 of holding anode.
According to the present invention, each anode superstructure 66 also comprises the support finger piece 146 of multiple separation that protrude upward from sheer pole 142.
The height of pillar 140A, pillar 140B equals the height of the pillar 114 of dividing plate 68 and the pillar 80A of cathode frame 64, pillar 80B substantially.
Each pillar 140A, pillar 140B are used for being used on corresponding pillar 114A, the pillar 114B of adjacent dividing plate 68.
Advantageously, in the lower right corner and the lower right-hand corner of interior compartment 144, spacing block 151 makes pillar 140A, pillar 140B be connected with sheer pole 142.
According to the present invention, each anode superstructure 66 comprises that at least two are supported finger piece 146, advantageously, comprise at least three independent support finger pieces 146.
Each support finger piece 146 is being attached at lower end 152 on sheer pole 142 and is vertically extending for reaching between the upper free end 154 of interior compartment 144.
In the time there is support finger piece 146, they arrange away from each other and away from spacing block 151.Therefore, on whole height between two adjacent support finger pieces 146, at the intermediate space 156 obtaining between lower end 152 and free end 154 at framework 66 and be completely apparent on whole width.
Therefore, support finger piece 146 and be only connected to each other by sheer pole 142, and be not connected with other elements.
The height of each upper finger tip 154 is higher than being respectively formed at the cycle window 92 in the framework 110 of cathode frame 64 and dividing plate, the height of cycle window 126.
The thickness that each support finger piece 146 obtains along axis B-B ', equals the thickness of framework 66 substantially, particularly equals the thickness of pillar 140A, pillar 140B and sheer pole 142.
In this example, support finger piece 146 is parallel to pillar 140A, pillar 140B vertically extends.
Perpendicular to axis B-B ', the width of the each support finger piece 146 obtaining along horizontal axis is less than the width of pillar.
As shown in Figure 9, while application when being close to the dividing plate 68 of anode superstructure 66 to nestle up anode superstructure 66, the either side at anode superstructure 66 along axis B-B ', the sheer pole 142 of anode superstructure 66 nestles up the sheer pole 116 of adjacent support frame 110 and is employed.
In addition, with reference to Fig. 9, be positioned at the middle transverse rod 118 of the framework 110 of the adjacent separator 68 of the either side of anode superstructure 66, advantageously near region intermediate 158 places of the support finger piece 146 free end 154 that is positioned at support finger piece 146, maintain the reticulation 112 on two relative athwartship plane 156A and athwartship plane 156B that are applied in respectively each support finger piece.
In the time that case 16 is assembled, this support has ensured the accurate location of the framework 110 of dividing plate 68.In addition, by the middle transverse rod of the framework of each dividing plate 110 118 being limited between the support finger piece 146 of adjacent anode superstructure 66 and the middle transverse rod 82 of adjacent cathode frame 64, guarantee the vertical orientation of the grid 122 of reticulation 112.
In addition, supporting finger piece 146 makes the middle transverse rod 118 of each support frame 110 near the middle transverse rod 82 of adjacent cathode frame 64.Especially by being clamped in the gasket 132 between cross bar 82 and cross bar 118, this support has ensured the abundant sealing of the inner compartment 90 of cathode frame 64.
With reference to Fig. 4, end frame 70A, end frame 70B comprise separately for towards holding the three-dimensional closure plate 170 arranging from the interior compartment 144 of the anode of adjacent anode superstructure 66.Three-dimensional closure plate 170 comprises separately for the window 92 of the circulation towards for anolyte, dismountable lower plate 172 that window 126 arranges.Dismountable lower plate 172 keeps (this maintains parts 174 and can be disassembled) by maintaining parts 174, and becomes unlimited structure, to allow to enter respectively the bottom of window 92, window 126 and compartment 144.
For each case 16, end frame 70A or end frame 70B comprise the accessory 176 for discharging anolyte, and this accessory is used for being connected with anolyte discharge tube 36.
In this example, longitudinal rod 180 is also arranged on the lateral brace 114A of support frame 110, each side of lateral brace 114B, and not through these lateral braces 114A, lateral brace 114B.
Therefore, in the invalid configuration of clamp assemblies 72, when longitudinal rod 180 is engaged by cathode frame 64 with when the anode superstructure 66, and there is gap between anode superstructure 66 and cathode frame 64 time, each dividing plate 68 is dismountable with respect to cathode frame 64 and anode superstructure 66.This can clean dividing plate 68 effectively and rapidly, and needn't take whole case 16 apart.
In the time that case 16 is assembled and clamp assemblies 72 works, longitudinal rod 180 and nut 182 firmly and hermetically maintaining near each other and application cathode frame 64, anode superstructure 66 and dividing plate 68.
Therefore, as shown in Figure 9, case 16 comprises a series of unit block that comprises cathode frame 64, dividing plate 68, anode superstructure 66 and another dividing plate 68.
In this configuration, at second 134 place, pillar 80A, pillar 80B, middle transverse rod 82 and the sheer pole of cathode frame 64 is respectively applied on pillar 114A, pillar 114B, middle transverse rod 118 and the sheer pole 116 of the framework 110 of dividing plate 68, wherein insert gasket 132, so that good sealing to be provided.
At first surface 130 places of dividing plate 68, lateral brace 114A, lateral brace 114B, sheer pole 116 and the middle transverse rod 118 of the framework 110 of dividing plate 68 is respectively applied lateral brace 140A, lateral brace 140B, the sheer pole 142 of anode superstructure 66 and supports on finger piece 146.
This assembly is firmly.This assembly has ensured holding the interior compartment 144 of anode and holding the excellent sealing between the inner compartment 90 of negative electrode, to ensure that the passage between these compartments only realizes by reticulation 112.In addition, this assembly has ensured the accurately location of reticulation 112 in a distance apart from anode and negative electrode.
But in the time that this assembly must be cleaned, it can easily be dismantled, this point has reduced for electrolyzer 10 being fed into again to the needed time in production.
In the time that clamp assemblies 72 works, window 92, window 126 are towards mutually positioning.In the lower part of case 16, window 92, window 126 define for the circulation of anolyte with for discharging the continuous pipeline 190 of the anode sludge.
Separate because support finger piece 146, therefore center-aisle 156 is completely unimpeded to move down the anode sludge towards pipeline 190 and to pass through these pipeline 190 circulating anode electrolytic solution and the discharge anode sludge.
Form negative electrode 74 by the metal sheet being inserted in by upper hole 94 in the inner compartment 90 of cathode frame 64.Each negative electrode 74 is provided with visible grapple 160 in Fig. 2 along its upper limb.
Anode is inserted in the interior compartment 144 of anode superstructure 66 by upper hole 147.Anode also has grapple 162.
According to the present invention, closed component 18 sealing surfaces are to the top in the interior space 14 of the intermediate space 60 being limited by case 16, intermediate space 62.
For example, closed component 18 comprises: for the side closure member 200 in closed upper part medial side space 60; For sealing the end cap 202 of each axial intermediate space 62; With the member 204 for sealing each upper hole 94, thus the space between the each negative electrode 74 of closed upper part and cathode frame 64.
Each side closure member 200 is arranged between sidewall 22 and framework 64,66,68.Advantageously, side closure member 200 is contained in respectively in the recess 121A in recess 101, the framework 110 being formed in framework 64, the recess 150 in framework 66.
Especially, each closure member 200 is made up of the closure plate sealing.Advantageously, closure member 200 is applied to the firm attached edge 202A of upper support belt 30 upper, is then received in recess 101, recess 150.
Advantageously, end cap 202 extends towards upper orle 26.
As shown in Figure 2, end cap 202 is hollow.End cap 202 has diapire 205, the vertical peripheral wall 206 stretching out from diapire 205 advantageously arranging with lateral edges 22 and 200 contacts of each side closure member and the upper wall 208 that peripheral wall 206 is connected with the upper limb of orle 26.
Therefore, end cap 202 covers axial intermediate space 62, and lateral edges 22 is connected with the orle 26 in the hole 46 towards for collecting gas.
For example, closure member 204 is attached at the outer of negative electrode 74 and places.Alternatively, closure member 204 comprises two anode 76 firm attached parts contiguous with each negative electrode 74 respectively.Each part is outstanding towards negative electrode 74 from anode 76,, is used on cathode frame and negative electrode 74 meanwhile.
Therefore, end cap 202 and side closure member 200 define the path for collecting cathode gas, and this path comprises two at the axial passage 210 of side closure member 200 downward-extensions towards each upper-side hole 98 and is positioned at below end cap 202 to open the public collection space 212 towards hole 46.
Regardless of the position of the cathode frame of generated cathode gas, the existence of passage 210 and public collection space 212 all guarantees to have the minimum pressure-losses by the efficient recovery of cathode gas.
Especially, the risk of stopping up cathode gas discharge orifice 98 is well limited, and this point has guaranteed cathode gas until the safe transport of discharge tube 38.
In addition, due to the top in upper hole 94 partly by negative electrode 74 and be partly closed by closure member 204, therefore all cathode gas are collected.Comprise, in the time that these cathode gas comprise ammonia or hydrogen, like this situation is exactly.Therefore, strengthened the security of electrolyzer 10, this point makes electrolyzer 10 be particularly suitable for responsive industrial environment.
Especially, appear near personnel electrolyzer 10 and be not subject to the impact of cathode gas emanation.In addition, electrolyzer 10 is collected cathode gas, processes, and cathode gas can be discharged in atmosphere with anticathode gas.
Now will describe according to the operation of electrolyzer of the present invention.
First, case 16 in assembling.For this reason, cathode frame 64, anode superstructure 66 are installed on the longitudinal rod 180 of clamp assemblies.Dividing plate 68 is inserted between each anode superstructure 66 and each cathode frame 64.
Then, end frame 70A and end frame 70B are installed in the end of case 16, and nut 182 is installed on longitudinal rod 180, for tightening assembly, form the structure of " pressure filter " type.
After in assembling, case 16 completes, interior case 16 is put in the interior space 14 of groove 12.Interior case 16 nestles up the base wall 24 of groove 12 and places.The pipeline 36 of removing anolyte is connected with the end fitting 176 on framework 70A, framework 70B.
Therefore, negative electrode 74 and anode 76 are electrically connected with path 32B, path 32A respectively.
Next,, by pumping parts 40, by service 34, the stock liquid that contains mn ion is pumped until the interior space 14 of groove 12.
This stock liquid comprises and is greater than 30g/L, especially the mn ion mass concentration between 30g/L and 40g/L.Stock liquid is included between 100g/L and 200g/L, be advantageously approximately the ammonium sulfate mass concentration of 125g/L.
Regulate the pH of stock liquid consequently close to 7, especially between 6 and 7.Advantageously, stock liquid contains sulfite ion or plasma selenium.
Stock liquid is the interior space 14 of filling slot 12 partly.Adjust level height, to flood side supply hole 96 completely, and there is no fully submergence upper air-vent 98.
By being formed on the side opening 96 in each cathode frame 64, stock liquid is incorporated in inner compartment 90, so that negative electrode 74 contacts, thereby form cathode solution.
Between negative electrode 74 and anode 76, provide the direct current for induced current DC().According to reaction below, the electronics providing at negative electrode 74 reacts with mn ion, so that on negative electrode, forms manganese metal:
Mn
2++2e
-→Mn
Between this reaction period, be present in negative electrode electronic section react with the oxonium ion being present in cathode solution so that form hydrogen.
In addition, in some cases, especially, in the time that pH reaches strong basicity value, also form a small amount of ammonia at negative electrode 74.
The hydrogen forming at negative electrode stirs the cathode solution in inner compartment 90, and solution is well distributed in around negative electrode 74.
The gas forming, especially hydrogen and ammonia, then be gathered in the upper part of inner compartment 90, and by being inserted between negative electrode 74 and cathode frame 64 so that the closure member 204 of the upper negative electrode introduction hole 94 of sealing, gas is limited in compartment 90.
Therefore the gas, forming is the outside drain towards interior case 16 by upper air-vent 98 only.
As what see hereinbefore, regardless of the level height that is present in the stock liquid in interior compartment 90, the existence of upper air-vent 98 has ensured effective discharge of cathode gas.
In addition, gaseous emission is highly uniform, and does not rely on the position of the cathode frame 64 in interior case 16.
So the gas of discharge is by being limited between the surface and side closure member 200 of stock liquid, and be collected in axial passage 210.
Their route that collected gas forms is thus: in the outside of interior case 16 along interior case 16, along the sidewall 22 of groove 12 in axial passage 210, towards end cross wall 20A, end cross wall 20B.
So gas is collected in the public collection space 212 of end cap 202 belows, by collection hole 46, then by remove pipeline 38 be discharged.
In order to make collected thus cathode gas recycle or after processing, they are discharged in atmosphere, collect and treatment unit 44 so cathode gas can be guided into.
Poisonous or the dangerous gas that therefore, can generate by electrolytic process is limited by the closed component 18 of electrolyzer 10 according to the present invention admirably.
Mode with simple cheapness is carried out this collection, and does not upset electrolytic process.
Simultaneously, after passing between the hole 129 having been limited by grid 122, a part is present in the cathode solution of negative electrode 74 under the effect of the fluid pressure being produced by the difference of altitude between catholyte and anolyte, by the perforated web 112 of dividing plate 68, flow in interior compartment 144.
Thereby this solution is penetrated in the interior compartment 144 of anode superstructure 66, has formed anodic dissolution.
According to reaction below, in the time of contact anode 76, the water being present in anodic dissolution reacts to form oxygen, oxonium ion and electronics:
Therefore, be present in the pH of solution of anode 76 more much smaller than the pH of solution that is present in negative electrode 74.But reticulation 112 stops oxonium ion to lead to from holding the interior compartment 144 of anode 76 inner compartment 90 of holding negative electrode 74.This pH that is present in the solution in inner compartment 90 that names a person for a particular job maintains in desired scope, to form manganese metal.
So anodic dissolution flow into downwards in the lower part of interior compartment 144 between support finger piece 146, then by the pipeline 190 being limited by window 92, window 126, discharged to the end of interior case 16.
By " pressure filter " structure, interior case 16 has obtained splendid stopping property, and at anodic dissolution, from interior case 16 between ejection time, anolyte fully separates with anodic dissolution.
Next, anodic dissolution upwards flows into the last anode superstructure 66 of contiguous each end frame 70A, end frame 70B, by end fitting 176, be then discharged by pipeline 36.
In the interior compartment 144 that holds anode, the existence of mn ion can cause the parasitic reaction with the water existing in solution, so that forms manganese oxide, oxonium ion and electronics.In addition, the formation of gypsum also may appear in anodal compartment.
The solid that formed has thus formed solid mud, and this solid mud is discharged downwards under the effect of their weight, and is partly stored in compartment 190.
Consider by grid 122 and effectively fix reticulation 112, reticulation 112 has and limits significantly solid, the especially plane of the accumulation of the anode sludge in reticulation 112.In addition, separate owing to supporting finger piece 146, between them, provide apparent intermediate space 156 to make the anode sludge very effectively discharged to the pipeline 190 of discharge and storage mud therefore from top to bottom, and in the whole length of anode superstructure 66, support finger piece 146.
Therefore,, in interior case 16 according to the present invention, postpone to make dirty anode 76 and reticulation 112.This contributes to increase the productivity of electrolysis process, and contributes to limit the number of times of the cleaning operation that must carry out for each interior case 16.
During whole electrolysis process, water continuously flows in the cooling exchanger 19A being arranged between groove 12 and interior case 16.
In the time that reticulation 112 is too dirty, or in the time that compartment 190 has filled up negative electrode mud, interior case 16 is raised from the interior space 14 of groove 12.Then, partly unclamp clamp assemblies 72, to dividing plate 68 is taken out, clean, and must the whole interior case 16 of dismounting.
Equally, in the time that discharge tube 190 is blocked, can be by case 16 in taking out from groove 12, then by opening the closure panel 172 of the movement that is positioned at end frame 70A, end frame 70B place, and pipe blow-through 190 simply.Therefore, interior case 16 according to the present invention has very favorable design, this design limit made dirty by the anode sludge, and become too obvious once dirt, this design allows to clean simply interior case 16.
By dismounting negative electrode 74, by take out negative electrode 74 from upper hole 94, reclaim and be formed on two manganese metals on electrode simply.
Consider that the output of the electrolytic reaction of manganese is maximized to specifically controlling with the height of the character of negative electrode 74 solution with contacting with anode 76 that contact, and the amount of impurity in formed manganese is low-down.
Claims (14)
1. the interior case (16) of the electrolyzer for manganese electrolysis, described interior case (16) is for being arranged on the groove (12) that contains stock liquid, and described interior case (16) comprising:
-multiple anode superstructures (66);
-multiple cathode frames (64), described cathode frame (64) is arranged between described anode superstructure (66);
-multiple dividing plates (68), described dividing plate (68) is inserted between each described cathode frame (64) and each described anode superstructure (66);
-clamp assemblies (72), described clamp assemblies (72) can maintain described cathode frame (64), described anode superstructure (66) and described dividing plate (68) near applying each other,
Each cathode frame (64) be defined for hold the inner compartment (90) of negative electrode, for negative electrode being incorporated into the upper hole (94) of described inner compartment (90) and at least one is for being supplied to the stock liquid that contains mn ion the side opening (96) of described inner compartment (90);
It is characterized in that, each cathode frame (64) is defined for the upper-side hole (98) of discharge cathode gas, described upper discharge orifice (98) is positioned in the top of described side opening (96) or each side opening for base feed liquid (96) for base feed liquid, so that at least in part at described stock liquid upper opening
And be characterised in that, described upper air-vent is opened and led to described inner compartment (90), and open to described interior case (16) outside.
2. interior case according to claim 1 (16), it is characterized in that, the cross section of described upper air-vent (98) is greater than described for supplying with the side opening (96) of electrolytic solution or each for supplying with the cross section of side opening (96) of electrolytic solution, advantageously, described upper air-vent (98) have oval-shaped cross section, especially along vertical axis extend oval-shaped cross section.
3. interior case according to claim 1 and 2 (16), is characterized in that, each cathode frame (64) is defined for the recess of the covering closure member that holds electrolyzer in the top of described upper air-vent (98).
4. according to interior case in any one of the preceding claims wherein (16), it is characterized in that, each cathode frame (64) comprises two lateral brace (80A, 80B) be connected described lateral brace (80A, middle transverse rod (82) 80B), described lateral brace (80A, 80B) and described middle transverse rod (82) limit the inner compartment of holding negative electrode, each upside venting hole (98) forms through lateral brace (80A, 80B).
5. interior case according to claim 4 (16), it is characterized in that, each cathode frame (64) is limited to two lateral brace (80A of connection of described middle transverse rod (82) below, sheer pole (84) 80B), described middle transverse rod (82) and described sheer pole (84) and described lateral brace (80A, 80B) be defined for together the lower window (92) of the circulation of anodic dissolution, described lower window (92) is isolated with described inner compartment (90) hermetically.
6. according to interior case in any one of the preceding claims wherein (16), it is characterized in that, each cathode frame (64) comprises at least one side flange crossing out (100), and described upper air-vent (98) forms through described side flange (100).
7. according to interior case in any one of the preceding claims wherein (16), it is characterized in that, described interior case (16) comprises by upper patchhole (94) and is inserted into the negative electrode (74) in each cathode frame (64), in the time that described negative electrode (74) is accommodated in the described inner compartment (90) of holding negative electrode, containment member (204) sealing is for inserting hermetically the upper hole of negative electrode.
8. according to interior case in any one of the preceding claims wherein (16), it is characterized in that, each anode superstructure (66) has the interior compartment (144) being limited by bottom bar (142) for holding anode, bottom,
Described anode superstructure (66) has the support finger piece (146) of multiple separation that protrude upward from described bottom bar (142), and the described dividing plate (68) adjacent with described anode superstructure (66) is laterally applied on described support finger piece (146).
9. interior case according to claim 8 (16), it is characterized in that, each dividing plate (68) comprises the support frame (110) of support grid (122) and is applied in the reticulation (112) on described grid (122), described support frame (110) comprises middle transverse rod (118), and described support finger piece (146) is applied to the middle transverse rod of described cathode frame (64) (82) on the middle transverse rod (118) of described support frame (110) of adjacent anode superstructure (66).
10. the electrolyzer for manganese electrolysis (10), the electrolyzer (10) of described type comprises:
-be defined for the groove (12) in the interior space (14) that holds stock liquid,
-according to the interior case (16) being arranged in described interior space (14) in any one of the preceding claims wherein,
-closed component (18), described closed component (18), in the top of described upper air-vent (98), is sealed shut the interior space (14) of described groove around described interior case (16);
Described electrolyzer (10) comprises that at least one is for removing the gas discharging so that the pipeline (36) that described gas is discharged from described groove (12) by each upper air-vent (98).
11. electrolyzers according to claim 10 (10), is characterized in that, described groove (12) contains stock liquid, and described interior case (16) is immersed in described stock liquid, and each side venting hole (98) is opened at least in part above described stock liquid.
12. according to the electrolyzer described in claim 10 or 11 (10), it is characterized in that, described groove comprises the sidewall (22) extending towards each upper air-vent (98), described interior case (16) and described sidewall (22) limit medial side space (60), described upper air-vent (98) leads to described medial side space (60), described closed component (18) comprises at least one closure member (200), described closure member (200) is in each side venting hole (98) top, in intermediate space described in closed upper part (60).
13. electrolyzers according to claim 12 (10), it is characterized in that, described electrolyzer comprises the end wall (20A laterally extending substantially with respect to described sidewall (22), 20B), described end wall (20A, 20B) limit axial intermediate space (62) together with described interior case (16), described closed component (18) is included in described in closed upper part the axially end cap (202) of intermediate space (202).
14. 1 kinds of methods for manganese electrolysis, the method for described type comprises:
-provide according to claim 10 to the electrolyzer (10) described in any one in 13;
-provide to the inner compartment (90) of each cathode frame (64) stock liquid that contains mn ion;
-at the upper manganese metal that forms of each negative electrode (74) being contained in each cathode frame (64);
-generation cathode gas, especially ammonia and hydrogen in the inner compartment (90) of each cathode frame (64);
-cathode gas is discharged from described interior case (16) by described upper air-vent (98);
-cathode gas being produced by each negative electrode (74) outside described interior case (16) is collected in the top of the intermediate space (60) limiting between described groove (12), described interior case (16) and described closed component (18);
-by described removing pipeline (36), be emitted on cathode gas collected in the top of described intermediate space (60).
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/FR2011/051699 WO2013011203A1 (en) | 2011-07-15 | 2011-07-15 | Internal box for an electrolytic manganese cell, provided with gas discharge openings, and associated cell and method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103857832A true CN103857832A (en) | 2014-06-11 |
Family
ID=44503975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180073449.5A Pending CN103857832A (en) | 2011-07-15 | 2011-07-15 | Internal box for an electrolytic manganese cell, provided with gas discharge openings, and associated cell and method |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN103857832A (en) |
| UA (1) | UA110726C2 (en) |
| WO (1) | WO2013011203A1 (en) |
| ZA (1) | ZA201400295B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109844474A (en) * | 2016-09-30 | 2019-06-04 | 菲兹克斯公司 | Method and apparatus for analyzing fine definition electromagnetic wave |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1738372A (en) * | 1927-11-04 | 1929-12-03 | Edgeworth-Johnstone Robert | Electrolytic cell |
| US2543059A (en) * | 1948-07-19 | 1951-02-27 | William T Rawles | Apparatus for electrowining or electroplating of metals |
| FR2169710A1 (en) * | 1971-12-23 | 1973-09-14 | Pechiney Saint Gobain |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR951725A (en) * | 1944-11-16 | 1949-11-02 | Electrolytic cell, and method of using said cell to recover manganese | |
| US4107023A (en) * | 1976-07-09 | 1978-08-15 | Hooker Chemicals & Plastics Corporation | Filter press halate cell |
| US4533455A (en) * | 1980-10-14 | 1985-08-06 | Oronzio De Nora Impianti Elettrochimici S.P.A. | Bipolar separator plate for electrochemical cells |
| FI122595B (en) * | 2009-02-03 | 2012-04-13 | Outotec Oyj | Method of recycling metal by electrolysis and electrolysis system |
-
2011
- 2011-07-15 CN CN201180073449.5A patent/CN103857832A/en active Pending
- 2011-07-15 WO PCT/FR2011/051699 patent/WO2013011203A1/en active Application Filing
- 2011-07-15 UA UAA201401449A patent/UA110726C2/en unknown
-
2014
- 2014-01-14 ZA ZA2014/00295A patent/ZA201400295B/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1738372A (en) * | 1927-11-04 | 1929-12-03 | Edgeworth-Johnstone Robert | Electrolytic cell |
| US2543059A (en) * | 1948-07-19 | 1951-02-27 | William T Rawles | Apparatus for electrowining or electroplating of metals |
| FR2169710A1 (en) * | 1971-12-23 | 1973-09-14 | Pechiney Saint Gobain |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109844474A (en) * | 2016-09-30 | 2019-06-04 | 菲兹克斯公司 | Method and apparatus for analyzing fine definition electromagnetic wave |
| CN109844474B (en) * | 2016-09-30 | 2021-10-15 | 菲兹克斯公司 | Method and apparatus for analyzing high-definition electromagnetic waves |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013011203A1 (en) | 2013-01-24 |
| ZA201400295B (en) | 2014-10-29 |
| UA110726C2 (en) | 2016-02-10 |
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