CN104685106A - Internal frame assembly of a cell for electrolysis of manganese, associated cell and method - Google Patents

Abstract

Internal frame assembly of a cell for electrolysis of manganese, associated cell and method. The cell comprises a plurality of anode frames, a plurality of cathode frames (64) and a plurality of diaphragms (68) interposed between each cathode frame (64) and each anode frame (66). At least one diaphragm (68) comprises a first porous wall (106A) covering a first axial opening (105A) of a cathode frame (64), a second porous wall (106B) covering the second axial opening (105B) of the cathode frame (64) and at least a connecting wall (108C, 108D) connecting the first porous wall (106A) and the second porous wall (106B) along the cathode frame (64), the first porous wall (106A), the second porous wall (106B) and the connecting wall (108C, 108D) defining an internal space (109) containing or defining the internal cathode receiving compartment (90).

Description

For the inner frame assembly of the electrolyzer of electrolytic manganese, relevant electrolyzer and method

Technical field

The present invention relates to the internal electrolytic cell framework for electrolytic manganese, described internal electrolytic cell framework expection is disposed in the cell body containing material solution, and described framework comprises:

-multiple anode superstructure;

-multiple cathode frame be arranged between anode superstructure;

-multiple barrier film be inserted between each cathode frame and each anode superstructure;

-clamp assemblies, described clamp assemblies can make cathode frame, anode superstructure and barrier film keep mutually reclining,

Each cathode frame limits one for holding the interior compartment of negative electrode, and inner cathode is held compartment and is formed with the first axially open facing the first adjacent anode superstructure and the second axially open facing the second adjacent anode superstructure vertically.

This frame assembly is used for being removably inserted in the cell body of manganese electrolytic cell (manganese electrolysic cell).

Background technology

Teaching material " operation of electrolytic manganese experimental equipment " (" Operation of Electrolytic Manganese Pilot Plant ", Boulder City Nevada, USBM Bulletin 463, pages 64and 65), in Figure 35, describe a kind of frame assembly of aforementioned type, this frame assembly has the structure of " press filtration " formula.

This frame assembly comprises cathode frame alternately and anode superstructure, and the described cathode frame that replaces and anode superstructure are each other by membranes apart.Longitudinal rod and end nut make framework and barrier film keep mutually reclining, to guarantee the good sealing between the compartment that limited by each framework.

In order to produce manganese, negative electrode is introduced in the inner cathode compartment of each cathode frame.Material solution is passed in the transverse holes manufactured in cathode frame and is carried in interior compartment.Material solution forms catholyte solution.Manganese metal is deposited on negative electrode by electrolytic process subsequently.

Due to the hydrostatic pressure that liquid level difference produces, the internal anode that catholyte solution flow into anode superstructure through barrier film holds compartment, to form anolyte solution.

At anode, a part of water (described water can obtain from anolyte solution) is decomposed to form oxygen and oxonium ion.In addition, also there is parasitic reaction (parasitic reaction) in anode place.

Particularly, can enter as cationic form the manganese of solution that flows out from negative electrode is partially oxidized to be formed solid-state form Manganse Dioxide at anode.

In order to obtain high electrolysis output, barrier film comprises filter cloth (cloths), and it is necessary that described filter cloth is separated the physics permeability produced between negative electrode accommodation compartment and anode accommodation compartment.These filter clothes slow down oxonium ion from the cathodic diffusion of anode.

In fact, the potential of hydrogen (pH) at anode place is quite low, and lower than the available pH in negative electrode place.

But any minimizing of the pH at negative electrode place all contributes to producing hydrogen when damaging manganese and producing.This causes the reduction of Current production.

Therefore, crucially, good sealing is provided, to prevent anolyte solution to be leaked in catholyte solution at barrier film and the separation surface place between cathode frame and anode superstructure.

Therefore frame assembly must carefully be assembled." press filtration " for known frame assembly designs, and is sometimes difficult to provide the mere contact guaranteeing between catholyte solution and anolyte solution to be through diaphragm filter cloth and occurs.

In addition, each frame assembly has to be taken apart by regular at production period.In fact, throw out (specifically being produced by Manganse Dioxide) is created on barrier film continuously with in anodal compartment.Have to carry out regular removing to throw out, and barrier film must be cleaned.

Therefore, when component sealing is unsatisfactory, the product production of each frame assembly is affected.

Summary of the invention

Therefore a target of the present invention is to provide a kind of framework for manganese electrolytic cell, the framework provides higher output and is still easy to assembling simultaneously when needed and takes apart.

For this reason, theme of the present invention is a kind of inner frame assembly of the above-mentioned type, it is characterized in that, at least one barrier film comprises the first porous wall, second porous wall and at least one connecting wall, described first porous wall covers the first axially open of described cathode frame, described second porous wall covers the second axially open of described cathode frame, described first porous wall is connected with described second porous wall along described cathode frame by least one connecting wall described, described first porous wall, described second porous wall and described connecting wall limit an internal space, described internal space comprises or limits described inner cathode accommodation compartment.

Frame assembly according to the present invention comprise in following characteristics one or more, described feature can by individually or may combine according to all technology Shangdis and consider:

-described first porous wall, described second porous wall and each described connecting wall limit the pocket holding cathode frame.

-described cathode frame limits the lower window of the circulation for anolyte solution, each adjacent anode superstructure limits the lower window of the described lower window facing described cathode frame, the lower window that described anode superstructure limits is for the accommodating of anolyte solution and circulation, and described first porous wall and described second porous wall limit the lower openings being oriented to face described lower window separately;

-described inner frame assembly comprises connecting frame, described connecting frame is around the described lower openings limited in described first porous wall, and around the described lower openings limited in described second porous wall, described connecting frame is connected to described first porous wall and described second porous wall hermetically, and described connecting frame is inserted in the described lower window of described cathode frame;

-described connecting wall or each connecting wall comprise with described first porous wall all-in-one-piece first side direction part and with described second porous wall all-in-one-piece second side direction part, described first side direction part and described second side direction part are placed with each other, described connecting wall comprises the attachment element between described first side direction part and described second side direction part, and described attachment element is advantageously releasable;

-described first porous wall and described second porous wall limit upper opening, and the upper opening that described first porous wall and described second porous wall limit holds in compartment for negative electrode being inserted into inner cathode;

-cathode frame limits aperture on the downside of at least one, aperture, described downside is used for the material solution containing mn ion being injected into inner cathode and holds in compartment, and described connecting wall limits the side direction window be communicated with aperture, described downside for aperture, each described downside;

-cathode frame limits at least one for discharging the aperture, upside of cathode gas, and described connecting wall limits for aperture, each described upside the side direction window be positioned at around aperture, described upside;

-described cathode frame comprises the first upper cross member and the second upper cross member, and described first upper cross member limits described first axially open up, and described second upper cross member limits described second axially open up,

Described first porous wall and described second porous wall have top attachment element separately, and described top attachment element can be bonded on around described first upper cross member and described second upper cross member respectively;

-described inner frame assembly comprises the cathode frame anode superstructure adjacent with two, each described adjacent anode framework comprises the axial vane surface be placed with respectively on described first porous wall and described second porous wall of described barrier film, each described anode superstructure comprises sealing element, and described sealing element is inserted into described axial vane surface and between the first corresponding porous wall and the second porous wall;

-described anode superstructure limits internal anode and holds compartment, described frame assembly comprises the anode be accommodated in described internal anode accommodation compartment for each described anode superstructure, described anode comprises at least one first distance piece and at least one second distance piece, at least one first distance piece described is for being pressed against described first porous wall of neighboring separators, and at least one second distance piece described is for being pressed against the second relative porous wall of relative neighboring separators;

-described inner frame assembly comprises the removable negative electrode be accommodated in described internal space for each described cathode frame, described internal space is at described first porous wall, between described second porous wall and connecting wall;

The present invention also pays close attention to a kind of electrolyzer for electrolytic manganese, and described electrolyzer comprises:

-cell body, described cell body limits the internal space for holding material solution;

-frame assembly as above, described frame assembly is disposed in described internal space.

Electrolyzer according to the present invention comprise in following characteristics one or more, described feature can by individually or may combine according to all technology Shangdis and consider:

-each described cathode frame limits at least one side opening mouth and aperture on the upside of at least one, described side opening mouth is used for the material solution containing mn ion to be supplied in described interior compartment, aperture, described upside is for discharging cathode gas, described top discharge orifice is disposed in the top of described or each side opening mouth for base feed solution, described electrolyzer comprises covering assemblies, described covering assemblies described top discharge orifice upper seal cover the internal space around described frame assembly of described cell body, described electrolyzer comprises at least one conduit, at least one conduit described is used for the emission gases of being collected by top discharge orifice described in each to clear out of described cell body,

-remove conduit to extend roughly vertically in cell body, and upwards emerge in internal space;

-described electrolyzer comprises closure member, and described closure member holds compartment to each negative electrode of the negative electrode inserted in compartment up and closes, and described closure member advantageously comprises from the axially projecting containment member of adjacent anode.

The invention still further relates to a kind of electrolyzer for electrolytic manganese, described electrolyzer comprises:

-cell body, described cell body limits the internal space for holding material solution;

-being arranged in frame assembly in described internal space, described frame assembly comprises:

* many anode superstructures;

* many are arranged in the cathode frame between anode superstructure;

* many are inserted into the barrier film between each cathode frame and each anode superstructure;

* clamp assemblies, described clamp assemblies can make cathode frame, anode superstructure and barrier film keep mutually reclining,

Each described cathode frame limits: for holding the interior compartment of negative electrode; For catholyte solution being incorporated into the aperture, top in described interior compartment; And at least one is for being supplied to the side opening mouth in interior compartment by the material solution containing mn ion;

It is characterized in that, each cathode frame limits: at least one is for discharging the aperture, upside of cathode gas, described top discharge orifice is disposed in the top of described or each side opening mouth for base feed solution, and described top discharge orifice is emerged and emerged to the outside of frame assembly in interior compartment;

Described electrolyzer comprises covering assemblies, described covering assemblies described top discharge orifice upper seal cover the internal space around described frame assembly of described cell body, described electrolyzer comprises at least one conduit, described conduit is used for the emission gases of being collected by upper gas discharge orifice described in each to clear out of described cell body

Further, remove conduit and extend vertically in cell body, and upwards emerge in internal space.

Described electrolyzer does not necessarily comprise at least one following barrier film, described barrier film comprises the first porous wall, the second porous wall and connecting wall, described first porous wall covers the first axially open of described cathode frame, described second porous wall covers the second axially open of described cathode frame, described first porous wall is connected with described second porous wall along described cathode frame by described connecting wall, described first porous wall, described second porous wall and described connecting wall limit an internal space, and described internal space comprises or limits described inner cathode accommodation compartment.

Described electrolyzer can comprise in above-mentioned feature one or more, described feature can by individually or may combine according to all technology Shangdis and consider.

The present invention also pays close attention to a kind of method for electrolytic manganese, and described method comprises:

-electrolyzer as above is provided;

-hold the material solution that compartment supply contains mn ion, to form the catholyte solution around negative electrode to the inner cathode of each cathode frame;

-on each negative electrode described in being contained in each cathode frame described, form manganese metal;

-make catholyte solution flow through the first porous wall of barrier film and the second porous wall and enter anode to hold compartment.

Accompanying drawing explanation

Read following being merely given as examples also with reference to the description that accompanying drawing carries out, the present invention will be understood better, wherein:

Fig. 1 is the schematic side elevation according to the first electrolyzer for manganese electrolysis of the present invention;

Fig. 2 is the partial top view of the electrolyzer of Fig. 1;

Fig. 3 is perspective along the transverse section III of Fig. 2 and part sectioned view;

Fig. 4 is the decomposition diagram of the inner frame assembly of the electrolyzer of Fig. 1;

Fig. 5 is the skeleton view of the cathode frame of the frame assembly of Fig. 4;

Fig. 6 is the skeleton view of the anode superstructure of the frame assembly of Fig. 4;

Fig. 7 is the skeleton view according to barrier film of the present invention;

Fig. 8 is the side-view of the barrier film of Fig. 7;

Fig. 9 is the skeleton view of the inner frame of the barrier film of Fig. 7;

Figure 10 is the cross section of the upper part around the cross bar being bonded on cathode frame of barrier film;

Figure 11 is the skeleton view for introduction into the negative electrode in cathode frame;

Figure 12 is the skeleton view for introduction into the anode in anode superstructure.

Embodiment

Fig. 1 to 12 shows according to the first electrolyzer 10 of the present invention, and described first electrolyzer 10 is for carrying out manganese electrolytic etching of metal or " MME ".

By being provided with electric current and making electric current contact with the material solution comprising mn ion Mn2+ (there is ammonium sulfate alternatively), manganese metal and being advantageously formed on multiple negative electrode.

Therefore the manganese metal formed is deposited on each negative electrode in solid form.

Electrolyzer 10 is disposed in the device of the electrolyzer 10 (such as, about 100 electrolyzers 10) comprising several series connection.

As shown in Figure 1, electrolyzer 10 comprises and limits the cell body 12 of internal space 14 and the inner frame assembly 16 of press filter type, and the inner frame assembly 16 of described press filter type is disposed in the internal space 14 of cell body 12.

According to the present invention, electrolyzer 10 comprises assembly 18 further, described assembly 18 for covering internal space 14 to catch and to transport the gas in the discharge of negative electrode place during electrolysis hermetically.

Electrolyzer 10 comprises power supply apparatus 19 and the heat exchanger 19A for cooling further, and described power supply apparatus 19 is partly visible in accompanying drawing 2 and 3, and described heat exchanger 19A is partly visible in figure 3.

Referring to figs. 1 to Fig. 3, cell body 12 is in the almost parallel hexahedral shape with longitudinal axis A-A'.Cell body comprises two end cross wall 20A, 20B, and described two end cross wall 20A, 20B are interconnected by two longitudinal walls 22, in fig 1 and 2 an only visible longitudinal wall 22.

Cell body 12 is included in the diapire 24 of closed downwards internal space 14 further.

Transverse wall 20A, 20B and sidewall 22 limit upper periphery flange, and described upper periphery flange stretches out at the circumference place in space 14.

Each sidewall 22 limits smooth upper support rim 28, and described upper support rim 28 is advantageously positioned on described flange.

Edge 28 supports upper support lath 30.

Described lath 30 supports longitudinal electrical contact 32A, 32B, and described electrical contact 32A, 32B are used for power supply apparatus 19 to be connected to anode and negative electrode respectively.

Cell body 12 comprises further: at least one is for being supplied to the conduit 34 in internal space 14 by material solution; At least one is for discharging the conduit 36 of inner frame assembly 16 and cell body 12 by anolyte solution; And at least one carries out for gas that anticathode place produces the conduit 38 removed, described gas is discharged internal space 14.

With reference to figure 1, feed conduit 34 is connected to pumping devices or gravitation device (gravity means) 40, to be supplied in cell body 12 by material solution.In the example present, advance in the top that feed conduit 34 is in transverse wall 20A in flange 26.In a remodeling, feed conduit 34 crosses transverse wall 20A in flange 26 place.

In the example depicted in fig. 1, discharge tube 36 extends through transverse wall 20A.The upstream of described discharge tube 36 is connected to frame assembly 16 by flexible hose (not shown).The downstream of described discharge tube 36 is connected to collection and processing apparatus 42, and it is outside that described collection and processing apparatus 42 are arranged in cell body 12.

With reference to figure 1, the conduit 38 for removing cathode gas is connected to the device 44 for collecting and process these gases.Avoiding problems in air cathode gas is disseminated to around cell body 12.

In the example depicted in fig. 1, remove conduit 38 extend vertically in internal space 14, and advantageously transversely wall 20A extend.

Conduit 38 is upwards formed collects aperture 46, and described collection aperture 46 is limited on the upper surface 46A of conduit 38.

Upper surface 46A is positioned in the top of the liquid level of internal space 14.Advantageously, upper surface 46A tilts along the direction at the center towards cell body 12 towards diapire 24.

The base section removing conduit 38 extends through diapire 24.

Remove conduit 38 to be defined for and to discharge the inner chamber 46B of cathode gas, it is vertical that the direction of described inner chamber 46B is roughly.

Due to this direction, all liquid or the residue that enter into inner chamber 46B naturally fall to the bottom of cell body 12 and discharge cell body 12, to prevent conduit 38 blocked.

(not shown) in a remodeling, removes conduit 38 and crosses transverse wall 20A in upper flange 26 place.Described removing conduit 38 opens wide by collecting aperture 46, and how the liquid level that described collection aperture 46 is included in the solution in internal space 14 is all positioned in the top of the liquid level in internal space 14, forever not touch liquid.

In this remodeling, collect aperture 46 can be disposed in this wall 20A near the upper corners of transverse wall 20A either side in the mode facing side spaces 60 between two parties, described side spaces between two parties 60 is between frame assembly 16 and the sidewall 22 of cell body.

Referring to figs. 1 to Fig. 4, inner frame assembly 16 is disposed in space 14.Inner frame assembly extends along axis B-B', the axis A-A of described axis B-B' and cell body 12 ' parallel or overlap.Inner frame assembly limits side spaces 60 (see Fig. 3) and between two parties axial space 62 (see Fig. 1 and Fig. 2) between two parties in internal space 14, and described axial space is between two parties positioned at end wall 20A, between 20B and frame assembly 16.

Intervening spaces 60 (Fig. 3) and intervening spaces 62 (Fig. 1) are for holding material solution.Intervening spaces 60,62 capped assemblies 18 cover, to close as hereinafter and to discharge cathode gas.

Heat exchanger 19A is disposed in intervening spaces 60, in 62.

Frame assembly 16 is placed in the internal space 14 of cell body 12 removedly.Therefore by being limited to sidewall 20A, upper channel between 20B and 22, the extracting position of frame assembly in outside, internal space 14 and for carry out electrolysis process position (be placed with in internal space 14 against diapire 24) between be removable and conveying.

This allows easily to be taken out by frame assembly 16 to carry out safeguarding and/or clean operation from cell body 12.

As mentioned above, inner frame 16 is " press filtration " formula.Therefore, with reference to Fig. 4, inner frame comprises multiple cathode frame 64, multiple anode superstructure 66 and multiple diaphragm assembly 68, and described diaphragm assembly 68 to be arranged near each cathode frame 64 and between this cathode frame 64 and each adjacent anode superstructure 66.

Advantageously, frame assembly 16 comprises dismountable clamp assemblies 72 of two end frame 70A, 70B and frame assembly 16 further, and described two end frame 70A, 70B are used for the axial end portion of laterally closed frame assembly 16.

Frame assembly 16 comprises removable negative electrode 74 (drawing in Figure 11) and removable anode 76 (drawing in Figure 12), and described negative electrode 74 is accommodated in each cathode frame 64, and described anode 76 is accommodated in each anode superstructure 66.

As shown in Figure 5, each cathode frame 64 lower crosspiece 84 of comprising two edge-on bar 80A, 80B, between two parties cross bar 82 and vertical rod 80A, 80B being linked together.

Cathode frame also comprises: the top reinforcing stull 85A that at least one (preferably two) are parallel, and 85B, described top reinforces stull 85A, and the upper end of two edge-on bar 80A, 80B is connected by 85B.

Therefore, cathode frame 64 limits interior compartment 90 for holding negative electrode 71 and lower window 92, described lower window 92 for catholyte solution with the flowing of interior compartment 90 seal isolation.

Cathode frame 64 limits for negative electrode 74 being incorporated into aperture, top 94 in interior compartment 90 further, be used for material solution to be fed to cross side aperture 96 in interior compartment 90 and according to aperture, upside of the present invention 98, aperture, described upside 98 is for discharging frame assembly 16 by cathode gas and discharging negative electrode.

This structure of cathode frame 64 allows the following flowing of material solution: namely, the driving of the gas generated by negative electrode place and the gaslift effect subsequently in interior compartment 90 (gas lift effect), described material solution is supplied aperture 96 from intervening spaces 60 through horizontal and upwards enter into interior compartment 90.Gas and liquor are discharged by from interior compartment 90 through aperture, upside 96 subsequently.

In the example present, the height of cathode frame 66 is substantially equal to the degree of depth (getting the height between the top edge of sidewall 22 and diapire 24) of internal space 14.

Vertical rod 80A, 80B extend in parallel relationship along a vertical direction.Each vertical rod 80A, 80B have side lug 100 at its upper end, and described side lug 100 laterally gives prominence to (visible in Fig. 4) relative to the longitudinal axis B-B' of frame assembly 16.

Each lug 100 limits the horizontal shoulder 101 of the Abdeckteil for holding covering assemblies 18.When inner frame 14 is disposed in the internal space 14 of cell body 12, shoulder 101 faces sidewall 22 and laterally opens wide.Shoulder 101 is positioned in the top of cathode gas discharge orifice 98.

Each side lug 100 also limits side direction recess 102, and described side direction recess 102 is in side direction upper shed and in the horizontal away from the central axis of cathode frame 64.

Recess 102 has bottom and top, and described bottom is downward-sloping when moving away the central axis of framework 64, and described top is level and perpendicular to the central axis of framework 64.

Aperture 98 is formed in recess 102.

Therefore, when frame assembly 16 being taken out from the internal space 14 of cell body 12, recess 102 is suitable for holding along framework 16 framework carrier band instrument (such as, vertical pole) extending longitudinally.

The lower end of vertical rod 80A, 80B flatly connects by lower crosspiece 84 mutually.It limits the flowing of lower window 92 for anolyte.In the example present, lower crosspiece 84 is attached to vertical rod 80A, on 80B.

(not shown) in remodeling, leg-of-mutton reinforcement distance piece can be advantageously connected to lower crosspiece 84, and is advantageously connected to vertical rod 80A, 80B at the interior corners place that vertical rod 80A, 80B and lower crosspiece 84 limit.

Cross bar 82 is arranged to be parallel to lower crosspiece 84 between two parties.Cross bar limits the top of window 92 between two parties.Cross bar limits inner cathode accommodation compartment 90 in bottom between two parties.Cross bar is added to vertical rod 80A between two parties, between 80B.Cross bar 82 is solid ground and lower window 92 and negative electrode is held compartment 90 to isolate hermetically between two parties.

Each vertical rod 80A, 80B limit vertical guiding groove 104 between two parties above cross bar 82, described vertical guiding groove laterally passes to interior compartment 90 and in opened upper end in aperture, top 94.Groove 104 guides for the anticathode 74 when negative electrode 74 being inserted into interior compartment.

Interior compartment 90 is limited in bottom by cross bar 82 between two parties and is limited by vertical rod 80A, 80B in side direction.Interior compartment on top by introducing aperture 94 and opening.

Each parallel transverse component 85A, 85B extend to the upper end of the vertical rod 80B on opposite from the upper end of vertical rod 80A.

Therefore each transverse member 85A, 85B are parallel to cross bar 82 between two parties.

A transverse member 85A is fixed on vertical rod 80A, and on an axial vane surface of 80B, and another transverse member 85B is fixed on vertical rod 80A, on the axial vane surface relative with aforementioned axial face of 80B.

Upper cross member 85A, 86B are limited to the guide path be open upwards in aperture, top 94.

Advantageously, eachly walk crosswise component 85A, 85B is made up of forked portion.Advantageously, eachly walk crosswise component 85A, 85B is made up of the material harder than the material of vertical rod 80A, 80B and/or cross bar 82,84.

In an advantageous embodiment, cross bar 85A, 85B is made of metal.Vertical rod 80A, 80B and cross bar 82,84 are made of plastics.

Interior compartment 90 is opened wide along axis B-B' and is passed to the second axially open 105B facing the second adjacent anode superstructure 66 in the first axially open 105A facing the first adjacent anode superstructure 66.

Axially open 105A, 105B are limited by vertical rod 80A, 80B in side direction, are limited by cross bar 82 between two parties in below, and are strengthened transverse member 85A by top up, and 85B limits.

In the example present, each vertical rod 80A, 80B limit a through hole 96, and described through hole 96 is for being supplied to material solution in interior compartment 90.

Each aperture 96 is horizontally through vertical rod 80A, 80B.Described aperture frame assembly 12 external open and go deep into vertical rod 80A, the thickness of 80B, described vertical rod 80A, 80B face the intervening spaces 60 between frame assembly 16 and sidewall 22.Described aperture passes to interior compartment 90 in inside.

In the example present, each vertical rod 80A, 80B comprise the aperture 96 be positioned near cross bar 82 between two parties.

In the example present, the cross section in aperture 96 is less than the maximum ga(u)ge (getting along axis BB') of vertical rod 80A or 80B.Advantageously, this cross section is circular.

As shown in Figure 5, each vertical rod 80A, 80B limit the side opening mouth 98 on the top for being vented in lug 100.The side opening mouth 98 on top is positioned in the top in each aperture 96 for base feed solution.

Advantageously, the cross section in aperture, top 98 is greater than the maximum cross-section in each aperture 96 for base feed solution.

Advantageously, the cross section in aperture, each top 98 is oval.Therefore, the height in aperture, top 98 is greater than the maximum ga(u)ge (getting along axis BB') of framework 64.The width obtained in the mode of the BB' that parallels to the axis in aperture, top 98 is less than the maximum ga(u)ge of framework 64.

In the example present, aperture, top 98 has constant cross section (described cross section obtains in the plane comprising axis B-B').Aperture 98 extends along the horizontal axis perpendicular to axis B-B'.

The upper area of interior compartment 90 is connected to the outside of frame assembly 16 by aperture, top 98.It faces sidepiece 22 for being positioned to, and is partly immersed at the most in the material solution in the internal space 14 between cell body 12 and frame assembly 12 simultaneously.

In one example, the ratio of the smallest cross-sectional of sidepiece vent ports 98 and the maximum cross-section in each aperture 98 for supplying solution is greater than 1.

There is aperture, top 98, even if therefore interior compartment 90 partly immerses material solution, also the gas contained by interior compartment 90 can be removed from interior compartment 90.

Consider the cross section in each aperture 98, cathode gas is easily discharged into the outside of frame assembly 16 from each cathode frame 94.The gas discharged does not flow through other cathode frame 64 or anode superstructure 66, but directly flows out in the side spaces between two parties 60 that aperture 98 passes to.Therefore, cathode gas is collected between cell body 12 and covering assemblies 18, and this just as will be seen below.

Only pass to interior compartment 90 for supplying the aperture 96 of solution and the aperture 98 for being vented and be positioned at the outside of inner frame assembly 16, and axially not opening wide along the axis BB' of frame assembly 16.

Particularly, aperture 96,98 obstructed athwartship planes to cathode frame 64 and not being communicated with other vent ports be formed in other cathode frame 64.

As shown in Fig. 7 to 10, each diaphragm assembly 68 comprises the first axial porous wall 106A, the second axial porous wall 106B and at least one (preferably two) side connecting wall 108C, 108D, described first axial porous wall 106A is used for the first axially open 105A of covered cathode framework 64, described second axial porous wall 106B is for covering the second axially open 105B of same cathode frame 64, first porous wall 106A is laterally connected to the second porous wall 106B around cathode frame 64 by described side connecting wall 108C, 108D.

Diaphragm assembly 68, at porous wall 106A, 106B and connecting wall 108C, limits internal space 109 between 108D, described internal space 109 is for holding cathode frame 64 and inner cathode accommodation compartment 90 thereof.

Diaphragm assembly 68 advantageously comprises connecting frame 111A, connecting frame 111A is inserted in internal space 109, to connect the first porous wall 106A and the second porous wall 106B and attachment element 111B, 111C, described attachment element 111B, 111C is used for each porous wall 106A, 106B to be attached on cathode frame 64.

In the embodiment of Fig. 7, diaphragm assembly 68 forms the pocket 110 of surrounding cathode frame 64, and described cathode frame is inserted in internal space 109.

In the example present, each free porous filter cloth 112 of the first porous wall 106A and the second porous wall 106B is made.

Filter cloth 112 has permeability.It achieves the passage towards anode superstructure 66 for holding the catholyte solution in the interior compartment 90 of negative electrode.

Filter cloth 112 is such as made up of synthetic textiles material, and the fabric advantageously matched by mechanical property and chemoresistance and its purposes is in a cell made.The permeability of filter cloth 112 is defined as: make to set up difference of altitude between catholyte solution and anolyte solution.Described difference of altitude can change according to the incrustation of filter cloth 112 and produce the flowing through filter cloth 112 from negative electrode anode of solution.

This solution flowing slow down the cathodic counter diffusion of the oxonium ion that anode place produces, and makes it possible to the pH maintaining catholyte solution.

The filter cloth 112 forming the first porous wall 106A and the second porous wall 106B is deformable.Particularly, described filter cloth is manually out of shape by user, to be inserted in internal space 109 by cathode frame 64.

When cathode frame 64 is accommodated in internal space 109, the first porous wall 106A covers the first axially open 105A completely.First axial vane surface of its also covered cathode framework 64 at least in part, comprises vertical rod 80A, 80B, upper cross member 85B and between two parties cross bar 82 and lower crosspiece 84.

First porous wall 106A is defined for the lower openings 113A by anolyte solution.Lower openings 113A is oriented to face the lower window 92 that cathode frame 64 limits.It is connected framework 111A and limits in outside.

Second porous wall 106B covers the second axially open 105B completely.Second axial vane surface of its also covered cathode framework 64 at least in part, comprise vertical rod 80A, 80B, upper cross member 85B and between two parties cross bar 82 and lower crosspiece 84, described second axial vane surface is relative with the first axial vane surface.

Second porous wall 106B is defined for the lower openings 113B by anolyte solution.Lower openings 113B is oriented to face the lower window 92 that cathode frame 64 limits, and aligns with lower openings 113A.It is connected framework 111A and limits in outside.

In the example depicted in fig. 4, lug 100 is projected into outside internal space 109.Lug 100 is not covered by the first porous wall 106A and/or the second porous wall 106B.

Get back to Fig. 7, porous wall 106A, 106B limit upper opening 114, and described upper opening 114 is for being inserted into negative electrode 74 within internal space 109 and the interior compartment 90 making it enter into cathode frame 64.

Align in the aperture, top 94 that upper opening 114 is oriented to limit with cathode frame 64.

First porous wall 106A connects together with the lateral edge of the second porous wall 106B by side connecting wall 108C, 108B respectively.

Side connecting wall 108C, 108B are along corresponding vertical rod 80A, and 80B is extending longitudinally.

The height of each side connecting wall 108C, 108B is roughly high than the height of cathode frame 64 by 20%.

Each side connecting wall 108C, the width of 108B approximates greatly the width of cathode frame 64.Therefore, the first porous wall 106A is placed with on the first axial vane surface of cathode frame 64, and the second porous wall 106B is placed with on second axial vane surface relative with the first axial vane surface of cathode frame 64.

The lower side that each connecting wall 108C, 108D limit opening between the first porous wall 106A and the second porous wall 106B is to window 115A and upper side to window 115B.

Lower window 115A is with the mode opening alignd with the side opening mouth 96 of bottom.Upper window 115B is with the mode opening alignd with transverse lugs 100.Transverse lugs 100 is projected into outside internal space 109 through upper window.

In the example depicted in fig. 7, each connecting wall 108C, 108D comprises at least one the first side plate (flap) 116A, the second side plate 116B and attachment element, described first side plate 116A and the first porous wall 106A is integral or be fixed on the first porous wall 106A, described second side plate 116B and the second porous wall 106B is integral or be fixed on the second porous wall 106B, and each or described first side plate 116A is connected with each or described second side plate 116B by described attachment element in a removable manner.

In the example depicted in fig. 7, each side plate 116A is folded into towards the second porous wall 106B and is approximately perpendicular to the first porous wall 106A.

Each second side plate 116B is folded into towards the first porous wall 106A is approximately perpendicular to the second wall 106B.Second side plate 116B is pressed on the first side plate 116A.

Attachment element is such as made up of velcro.When attachment element comes into force, each first side plate 116A is fastened on the second side plate 116B, and porous wall 106A, 106B are placed with on the relative face of cathode frame securely.

Advantageously, connecting frame 111A is made up of the filter cloth identical with porous wall 106A, 106B.Connecting frame 111A has the outer shape roughly complementary with the interior shape of lower window 92.

As shown in Figure 9, connecting frame 111A limits centre channel 117, and described centre channel 117 is for the circulation of anolyte solution.Connecting frame has the first axial vane surface 118A and the second axial vane surface 118B relative with the first axial vane surface 118A, described first axial vane surface 118A is connected to the first porous wall 106A constantly, and described second axial vane surface 118B is connected to the second porous wall 106B around window 113B constantly.

Framework 111A has continuously and the profile closed.It prevents the anolyte solution of circulation in passage 117 from entering internal space 109.

As Figure 10 paint, for each wall 106A, 106B, attachment element 111B, 111C comprises top tongue piece (tongue) 119 and releasable retaining element 120 so that top tongue piece 119 is fastened to porous wall 106A, in the inside face of 106B, described top tongue piece self can fold around upper cross member.

Tongue piece 119 advantageously with porous wall 106A, 106B is integral.The width of tongue piece 119 is less than porous wall 106A, the width of 106B, so that allowing tongue piece 116 to be inserted into is limited to transverse member 85A, in the groove between 85B.

Retaining element 120 is such as made up of velcro.Retaining element 120 makes tongue piece 119 maintain and is folded in wall 106A, and in the inside face of 106B, described wall 106A, 106B are positioned in the inside of internal space 109.

In order to install the barrier film 68 around cathode frame 64, side plate 116A, 116B is separated from one another.

Connecting frame 111A is inserted in lower window 92 subsequently, and passes the first axial vane surface of cathode frame 64 along the second porous wall 106B.

Second porous wall 106 takes out along the second side plate 116B through the relative axial vane surface of cathode frame 64 subsequently from lower window 92.

First wall 106A is placed with on the first axial vane surface of cathode frame 64, and the first side plate 106A is folded against sidepiece vertical rod 80A, 80B.

Subsequently, the second side plate 116B is folded on the first side plate 116A by towards sidepiece vertical rod 80A, 80B, and attachment element comes into force.

The top tongue piece 119 of each attachment element 111B, 111C is folded to the barrier film 68 around cathode frame 64 around corresponding upper cross member 85A, 85B subsequently.

Except sidepiece lug 100, each cathode frame 64 is almost received in the internal space 109 of barrier film 68 restriction subsequently completely.

Inner cathode holds axial window 105A, the 105B of compartment 90 by porous wall 106A, and 106B covers completely, this prevent interior compartment 90 and is directly polluted by the anolyte solution around barrier film 68.Therefore, the anolyte solution around barrier film 68 is had to through formation wall 116A, and the filter cloth of 116B enters internal space 109, and described filter cloth blocks passing through of oxonium ion.

Compared with known barrier film, be easy to assemble according to the barrier film 68 of frame assembly 16 of the present invention and very effective separation between solution around the solution provided around anode 72 and negative electrode 74.

When needed (especially as wall 106A, when 106B existing throw out), barrier film 68 is easy to be opened.

As shown in Figure 6, each anode superstructure 66 comprises two parallel vertical rod 140A, 140B and lower bottom part cross bar 142, and the lower end of vertical rod 140A, 140B connects by described lower bottom part cross bar 142.

According to the present invention, each anode superstructure 66 comprises the cross bar between two parties 146 limiting lower window 147 further.

Cross bar 146 and vertical rod 140A, 140B jointly limit top anode and hold compartment 144 between two parties.

The height of vertical rod 140A, 140B is substantially equal to the vertical rod 80A of cathode frame 64, the height of 80B.

Along with the porous wall 106A of the diaphragm assembly 68 around neighbouring cathode framework 64, the insertion of 106B, each vertical rod 140A, 140B are for corresponding vertical rod 80A, the 80B of the neighbouring cathode framework 64 that reclines.

Vertical rod 140A, 140B have side lug 148 at its upper end, and described side lug 148 is laterally given prominence to relative to axis B-B'.Each side lug 148 limits the horizontal shoulder 150 of the Abdeckteil for holding covering assemblies 18.

Each side lug 148 limits side direction recess 151 further, and the shape of described side direction recess 151 is similar with the shape of the side direction recess 102 of the corresponding of lug 100.

Lower crosspiece 142 is installed in vertical rod 140A, between 140B.The width of lower crosspiece 142 is substantially equal to the width of the lower crosspiece 84 of cathode frame 64.

In a remodeling, vertical rod 140A, 140B can be connected with lower crosspiece 142 at the lower-left corner of interior compartment 144 and lower right corner place by distance piece (not shown).

Advantageously, vertical rod 140A, 140B comprise a series of for guiding the side direction protuberance 149 of clamp assemblies 72.

Each vertical rod 140A, 140B limit vertical guiding groove 152 above cross bar between two parties, described vertical guiding groove 152 is for guiding being inserted by anode 79 within anode accommodation compartment 144.

Cross bar 146 limits at least one (preferably, multiple) vertical through channel 153 between two parties, and described vertical through channel 153 is for discharging anolyte solution and/or throw out.Passage 153 holds upward opening in compartment 144 and to lower opening in lower window 147 at anode.

Anolyte throw out is therefore, it is possible to spontaneously fall to lower window 147 from top compartment 144 under gravity.

Along with the insertion of porous wall 106A, 106B, cross bar 146 is positioned in the height identical with the cross bar between two parties 82 of neighbouring cathode framework 64 to be placed with on described cross bar 82 between two parties.

Window 147 is limited by upper cross bar 146 up, and is limited by lower crosspiece 142 in below.The lower window 92 of window 147 to the neighbouring cathode framework 64 that it faces is extended.

According to the present invention, each anode superstructure 66 comprises sealing element 153A, 153B further, and described sealing element 153A, 153B are between each axial vane surface of being inserted into anode superstructure 66 and the respective diaphragm 68 being placed with on this axial vane surface.

In embodiment disclosed in Fig. 6, each sealing element 153A, 153B make by along continuous print packing ring, and described packing ring extends on the corresponding axial vane surface of framework 66 along the first vertical rod 140A, lower crosspiece 142 and the second vertical rod 140B.

Advantageously, sealing element 153A, 153B are accommodated in corresponding groove 154A, 154B, and described groove 154A, 154B are configured in corresponding axial vane surface.

When each anode superstructure 66 is pressed against neighbouring cathode framework 64, corresponding sealing element 153A, 153B are placed with the corresponding porous wall 106A at the barrier film 68 around neighbouring cathode framework 64, on 106B.

Sealing element 153A, 153B prevent anolyte solution from negative electrode hold compartment 144 and/or from window 147 through the outside of the Clearance Flow each anode superstructure 66 and the respective diaphragm 68 being placed with on anode superstructure 66 to frame assembly 16.

With reference to figure 4, end frame 70A, 70B comprise closure panel 170 separately, and described closure panel 170 is for being placed with the interior compartment 144 of the accommodation anode faced from adjacent anode framework.Closure panel 170 comprises removable lower panel 172, and described lower panel 172 is placed with the window 92,47 faced for the circulation of anolyte solution.Removable panel 172 keeps by maintaining device 174, and described maintenance device 174 is dismountable, and described maintenance device 174 can enter and opens form to allow open to lead to respective window 92, and 147 and the entrance of bottom of compartment 144.

Comprise the pipe fitting 176 for discharging anolyte solution for each frame assembly 16, frame assembly 70A or two frame assembly 70A, a 70B, described pipe fitting 176 is for being connected to anolyte solution discharge tube 36.

Clamp assemblies 72 comprises: multiple longitudinal bar member 180 crossing frame assembly 16 and the tightening nut 182 be arranged on described rod member 180.

Rod member 180 is disposed near the side of frame assembly 16.Rod member 180 extends in the mode of the B-B' that parallels to the axis.Their edge-on bar 80A, 80B along the cathode frame 64 and edge-on bar 140A of anode superstructure 66,140B longitudinally extends.

Rod member 180 is distributed on the height of each framework 64,66.

In the example present, rod member 180 is arranged in the side direction vertical rod 114A of support frame 110, the both sides of 114B further, and not through these vertical rods 114A, 114B.

Under the Inactivation shape of clamp assemblies 72, rod member 180 is located by along cathode frame 64 and anode superstructure 66, and there is space between anode superstructure 66 and cathode frame 64.

When frame assembly 16 is assembled and clamp assemblies 72 comes into force, rod member 180 and nut 182 make cathode frame 64, anode superstructure 66 and the barrier film maintenance around each cathode frame 64 mutually recline securely.

Therefore, as shown in Figure 4, so frame assembly 16 comprises series of units assembly, described unit block comprise by barrier film 68 around cathode frame 64, anode superstructure 66 and by another barrier film 68 around another cathode frame 64.

In such configuration, the vertical rod 80A of cathode frame 64,80B and lower crosspiece 84 are placed with respectively on edge-on bar 140A, the 140B and lower crosspiece 142 of anode superstructure 66.

The porous wall 106A be made up of filter cloth 112,106B to be inserted between cathode frame 64 and anode superstructure 66 and to be maintained at vertical position.

This assembly is sane.Which ensure that internal anode holds the good sealing between compartment 144 and inner cathode accommodation compartment 90, to guarantee that the passage between these compartments described only obtains by the filter cloth 112 of porous wall 106A, 106B.In addition, it also ensures filter cloth 112 in the accurate location apart from anode and negative electrode a distance.

When assembly is necessary cleaned, described assembly is easy to dismounting, which reduces and electrolyzer 10 is resumed production the required time.

When clamp assemblies 72 comes into force, window 92,147 be oriented to mutually faced by.They limit a continuous print conduit 190 in the bottom of frame assembly 16, and described conduit 190 is for the circulation of anolyte solution and the sedimentary discharge of anolyte (see Fig. 4).

Conduit 190 is communicated with the interior compartment 144 of each anode superstructure 66 by the through channel 153 that is formed in cross bar 146 between two parties, and conduit 190 is isolated with each interior compartment 90 of cathode frame 64 by connecting frame 111A simultaneously hermetically.

As shown in Figure 11, negative electrode 74 comprises the extension bar 191B that is electrically connected of metal sheet 191A and the upper limb along metal sheet 191A, and described metal sheet 191A is inserted in the interior compartment 90 of cathode frame 64 via aperture, top 94.Each negative electrode 74 is provided with hook 160 (visible in Fig. 2) along its upper limb.

Anode 72 is inserted in the interior compartment 144 of anode superstructure 66 via aperture, top 147.Anode 72 is provided with hook 162 equally.

As shown in Figure 12, each anode 72 comprises anode sleds 192A, anode upper electrical extension bar 192B locating spacers 193A, described locating spacers 193A for making the adjacent porous wall 106A of neighboring separators 68, and 106B maintains vertically.

Advantageously, anode 72 comprises upper lateral Abdeckteil 193B further, and the horizontal Abdeckteil 193B in described portion is used for coming in top seal anodal compartment 144 and adjacent cathodic compartment 90 to Abdeckteil 193B by adjacent by touching.

Anode sleds 192A comprises multiple isolated vertical metal rod 194A, and described vertical metal rod 194A is linked together by transverse member 194B in its lower end.

Advantageously, vertical spacing part 193A is made up of electrically insulating material.Distance piece 193A extends to lower cross member 194B vertically from upper electrical extension bar 192B.Described distance piece is axially given prominence in each side of anode 72, and to contact the adjacent porous wall 106A of neighboring separators 68,106B also provides axial support for it.

When anode 72 is inserted in anode accommodation compartment 144, distance piece 193A contacts the relative porous wall 106A of neighboring separators, and 106B, to prevent described porous wall 106A, 106B enters anode and holds compartment 144 and the perpendicular orientation maintaining described porous wall 106A, 106B.

In the example present, upper lateral Abdeckteil 193B comprises the hollow tubular Abdeckteil that plastics are made, and described hollow tubular Abdeckteil limits the housing holding described bar.

Upper lateral Abdeckteil 193B axially gives prominence in the both sides of anode 72, to seal cathodic compartment 90 and to prevent the union lever 192B of anode 72 from contacting with the adjacent union lever 192A of negative electrode 74 simultaneously.

Hook 160,162 make negative electrode 74 and anode 76 can be inserted in frame assembly 16, and negative electrode 74 and anode 76 can be removed from frame assembly 16.The path 32B that negative electrode 74 and anode 76 are laid respectively at by them, 32A and be connected to power supply apparatus respectively.

According to the present invention, covering assemblies 18 is in closed upper part internal space 14, and described covering assemblies 18 faces the intervening spaces 60,62 limited by frame assembly 16.

As depicted in figs. 1 and 2, therefore covering assemblies 18 comprises side cover 200, end cap 202, described side cover 200 in closed upper part side spaces 60 between two parties, described end cap 202 for closing each axial intervening spaces 62 and advantageously,

Each side cover 200 is installed in sidewall 22 and framework 64, between 66.Side cover is advantageously received into the shoulder 101 be formed in framework 64 and 66 respectively, in 150.

Particularly, each Abdeckteil 200 is formed by the cover plate sealed.Abdeckteil 200 to be advantageously placed with on edge 202A and to be received into shoulder 101, and in 150, described edge 202A is attached to upper strip 30 securely.

Advantageously, 202 intervening spaces extensions vertically above top shoulder 26 are covered.

As shown in Figure 2, cover 202 to comprise and be placed with external portion on top shoulder 26 203 and be placed with the internal portion 204 on external portion 203, to cover axial intervening spaces 62.

External portion 203 and internal portion 204 limit pass through openings 205, and described pass through openings 205 is for inserting conduit 34 and additional conduits 205A, and described additional conduits 205A is used for heat exchanger 14A and supplies cooling fluid (such as, water).

Therefore, end cap 202 covers axial intervening spaces 62 and lateral edges 22 is connected to shoulder 26.

As mentioned above, be arranged on upper lateral Abdeckteil 193B on anode 72 contact with each other and be positioned at the top in the aperture, top 94 of cathodic compartment 94 along their sidepiece, to seal cathodic compartment 90 and to prevent the gas produced in cathodic compartment 90 from upwards revealing through aperture, top 94.

Therefore, adjacent horizontal Abdeckteil 193B limits the upper closure element 204A of cathodic compartment 90.

Therefore lid 202 and side cover 200 limit the path for collecting cathode gas, described path comprises two axial passages 210 (see Fig. 3) and public collection space 212 (see Fig. 2), described two axial passages 210 extend in the below of the side cover 200 facing aperture, each top, and the below that described public collection space 212 is positioned in end cap 202 is opened wide to face aperture 46.

The efficient recovery of cathode gas is guaranteed in the existence of passage 210 and public collection space 212, and the position of generation cathode gas regardless of cathode frame 64, and there is the minimum pressure-losses.

Particularly, the risk in blocking cathode exhaust gas aperture 98 is very limited, guarantees and cathode gas is transported to discharge tube 38 safely.

In addition, because aperture, top 94 is closed by negative electrode 74 and is partly closed component 204 close in upper part, all cathode gas are collected.Comprising when these cathode gas comprise ammonia and hydrogen, is also like this.Therefore strengthen the security of electrolyzer 10, the electrolyzer 10 that this is is particularly useful for responsive industrial environment.

Particularly, the personnel near electrolyzer 10 can not be subject to the harm of cathode gas emanation.In addition, electrolyzer 10 collects cathode gas to expect to process it, instead of by this gaseous emission in air.

The operation according to electrolyzer 10 of the present invention will be described now.

First, inner frame assembly 16 is assembled.For this reason, barrier film 68 is bonded on around cathode frame 64 as above.Cathode frame 64 and anode superstructure 66 are installed on the longitudinal bar member 180 of clamp assemblies.Barrier film 68 is inserted between each anode superstructure 64 and each cathode frame 66.

Each framework 70A, 70B are installed in the end of frame assembly 16 subsequently, and nut 182 is installed on rod member 180 to strain described assembly and to form the structure of " press filter type ".

After these are done, inner frame assembly 16 is loaded the internal space 14 of cell body 12.Described inner frame assembly leans on the diapire 24 of cell body 12.Catholyte is removed conduit 36 and is connected to framework 70A, the end pipe fitting 76 on 70B.

Anode 76 is through being inserted in interior compartment 144, and negative electrode 74 is inserted in interior compartment 90.

Therefore negative electrode 74 and anode 76 are electrically connected to path 32A, 32B respectively.

Next, the material solution containing mn ion is pumped in the internal space 14 of cell body 12 through feed conduit 34 via pumping devices 40.

The mn ion mass concentration that described material solution contains is greater than 30g/l, and especially between 30g/l to 40g/l.The mass concentration of the ammonium sulfate that material solution contains between 100g/l to 200g/l, and is advantageously about 125g/l.

The pH of material solution is adjusted to close to 7, and especially between 6 to 7.Advantageously, material solution contains sulfite ion or plasma selenium.

Material solution partly fills the internal space 14 of cell body 12.Liquid level is changed to flood sidepiece feed aperture 96 completely and not exclusively to flood upper discharge hole mouth 98.

Material solution passed be formed in the side opening mouth 96 in each cathode frame 64 and enter interior compartment 90 to contact with negative electrode 74, and therefore forming catholyte solution.

Galvanic current is provided with between negative electrode 74 and anode 76.The electronics that negative electrode 74 place provides and mn ion react, to form manganese metal according to following reaction on negative electrode:

Mn ²⁺+2e ^-→Mn

During reaction, the electronics being present in negative electrode 74 place partly reacts to form hydrogen with the oxonium ion be present in catholyte solution.

In addition, on other occasions, especially when pH reaches the value of too alkalescence, negative electrode 74 place also forms ammonia in a small amount.

The hydrogen that negative electrode 74 place is formed stirs the catholyte solution in interior compartment 90, this achieves the good distribution of the solution around negative electrode 74.

The gas (especially hydrogen and ammonia) formed is collected in subsequently in the upper part of interior compartment 90 and via closure member and is closed in compartment 90, described closure member is formed by the adjacent upper lateral Abdeckteil 193B be inserted between negative electrode 74 and anode superstructure 64 in this example, so that closed upper portion negative electrode introduces aperture 94.

The gas formed is therefore by means of only the outside drain of upper discharge hole mouth 98 towards inner frame assembly 16.

As what find out from the above, the existence of upper discharge hole mouth 98 ensure that the discharge of cathode gas, and regardless of the liquid level of the material solution be present in interior compartment 90.

Exhaust is further high uniformity and does not rely on the position of cathode frame 64 in frame assembly 16.

The gas of discharge is collected in axial passage 210 by being closed between the surface of material solution and sidepiece Abdeckteil 200 subsequently.

The path of the gas therefore collected in the outside of frame assembly 16 along frame assembly 16, in axial passage 210 along the sidewall 22 of cell body 12, towards end cross wall 20A, 20B.

Described gas is collected in the public space 212 below end cap 202 subsequently, and through collecting aperture discharge, and subsequently through removing conduit 38.

Therefore, consider the recovery of the gas collected or be discharged into after the treatment in air, the gas of collection can be drawn towards collection and treatment unit 44 subsequently.

Therefore the poisonous or hazardous gas produced in electrolytic process perfectly closed by the covering assemblies 18 of electrolyzer 10 according to the present invention.

The execution of this collection can not disturb electrolytic process, and simple and cheap.

Simultaneously, be present in a part for the catholyte solution at negative electrode 74 place in passing axial porous wall 106A, porous filter cloth 112 through barrier film 68 under the effect of fluid pressure after 106B flow in interior compartment 144, and described fluid pressure is produced by the difference of altitude between catholyte and anolyte.

Therefore described solution to penetrate in the interior compartment 144 of anode superstructure 66 and form anolyte solution.

By contact anode 76, the water existed in anolyte solution reacts to form oxygen, oxonium ion and electronics according to following reaction:

3H ₂O→1/2O ₂+2H ₃O ⁺+2e ^-

The pH of the solution at anode 76 place is therefore much smaller than the pH of the solution at negative electrode 74 place.But the filter cloth 112 of wall 106A, 106B prevents oxonium ion from advancing from the interior compartment 144 holding anode 76 to the interior compartment 90 holding negative electrode 74.This makes the pH of the solution in interior compartment 90 be maintained in required scope, to form manganese metal.

Anolyte solution flows down in lower window 147 through the passage 153 in cross bar 146 between two parties subsequently, and the conduit 190 limited through window 92,147 is subsequently towards the end tap of frame assembly 16.

Obtain perfect sealing by " press filter type " structure at frame assembly 16 place, anolyte solution is separated completely with catholyte solution during it is discharged frame assembly 16.

Next, anolyte solution upwards flows in last anode superstructure 66 adjacent with each end frame 70A, 70B, and passes end pipe fitting 176 and discharge through conduit 36 subsequently.

Hold in compartment 144 in internal anode, the existence of mn ion can cause and the parasitic reaction of water that exists in solution, thus forms manganese oxide, oxonium ion and electronics.In addition, gypsum structure can also be produced in anolyte compartment.

Therefore, the solid formed forms solid sediment, and described solid sediment is discharged downwards and is accumulated in partly in compartment 190 under its effect of conducting oneself with dignity.

Consider and keep filter cloth 112 efficiently by distance piece 193A, filter cloth 112 has flat surfaces, and described flat surfaces significantly limit gathering of solid (and the anolyte throw out especially on filter cloth 112).

In frame assembly 16 according to the present invention, therefore the incrustation of anode 76 and filter cloth 112 be postponed.This contributes to the productivity of increase electrolysis process and limits the number of times of having to the clean operation that each frame assembly 16 carries out.

During whole electrolysis process, water flows in the cooling exchanger 19A be arranged between cell body 12 and inner frame assembly 16 continuously.

When filter cloth 112 has too much incrustation or when compartment 190 is full of anolyte solution throw out, frame assembly 16 is thus lifted to the outside of the internal space 14 of cell body 12.Clamp assemblies 72 is at least partly released subsequently, to make barrier film 68 to be removed and to clean this barrier film, and need not take whole frame assembly 16 apart.

Equally, when discharge tube 190 is blocked, be positioned at end frame 70A by frame assembly 16 is taken out cell body 12 and opens subsequently, the movable closure panel at 70B place cleans this discharge tube 190 simply.Therefore frame assembly 16 according to the present invention has very favorable design, the incrustation that this design limit anolyte throw out causes, and can clean simply frame assembly 16 becoming serious once incrustation.

By taking negative electrode 74 apart and being taken out by negative electrode 74 by aperture, top 94, the manganese metal be formed on two electrodes is reclaimed simply, and need not take whole frame assembly 16 apart.

Consider that the height of the character to the solution contacted with anode 76 with negative electrode 74 specifically controls, the output of the electrolytic reaction of manganese is maximized, and impurity in the manganese formed is considerably less.

In addition, the bag shape of barrier film 68 achieves the very effective isolation of the catholyte solution of the interior compartment entering cathode frame 64, thus prevents anolyte solution anticathode electrolyte solution from polluting.

It is very effective for holding in interior compartment 90 and anode the separation obtained between compartment 144, and need not carry out complicated work in the assembling of frame assembly 16.In fact, frame assembly 16 according to the present invention is still easy to assembly and disassembly, which increases the productivity of device.

In another aspect of this invention, except remove conduit 38 configuration as unsettled the application Fig. 1 and Fig. 2 disclosed in except, identical disclosed in electrolyzer 10 and PCT patent application n ° of PCT/FR2011/051699.Remove conduit 38 to extend roughly vertically in cell body 12, and upwards emerge in internal space 14.

Claims (16)

1. the inner frame assembly (16) of the electrolyzer for electrolytic manganese (10), described inner frame assembly (16) is for being disposed in the cell body (12) containing material solution, and described frame assembly (16) comprising:

-multiple anode superstructure (66);

-multiple cathode frame (64) be arranged between described anode superstructure (66);

-multiple barrier film (68) be inserted between each cathode frame (64) and each anode superstructure (66);

-clamp assemblies (72), described clamp assemblies (72) can make described cathode frame (64), described anode superstructure (66) and described barrier film (68) keep mutually reclining,

Each described cathode frame (64) limits one for holding the interior compartment (90) of negative electrode, described inner cathode is held compartment (90) and is formed with the first axially open (105A) facing the first adjacent anode superstructure (66) and the second axially open (105B) facing the second adjacent anode superstructure (66) vertically

It is characterized in that, barrier film described at least one (68) comprises the first porous wall (106A), second porous wall (106B) and at least one connecting wall (108C, 108D), described first porous wall (106A) covers first axially open (105A) of described cathode frame (64), described second porous wall (106B) covers second axially open (105B) of described cathode frame (64), described at least one connecting wall (108C, 108D) along described cathode frame (64), described first porous wall (106A) is connected with described second porous wall (106B), described first porous wall (106A), described second porous wall (106B) and described connecting wall (108C, 108D) limit an internal space (109), described internal space (109) comprises or limits described inner cathode accommodation compartment (90).

2. inner frame assembly (16) according to claim 1, it is characterized in that, described first porous wall (106A), described second porous wall (106B) and each described connecting wall (108B, 108C) limit the pocket (110) holding described cathode frame (64).

3. inner frame assembly (16) according to claim 1 and 2, it is characterized in that, described cathode frame (64) limits the lower window (92) of the circulation for anolyte solution, each adjacent anode superstructure (66) limits the lower window (147) of the described lower window (92) facing described cathode frame (64), the described lower window (147) that described anode superstructure (66) limits is for the accommodating of described anolyte solution and circulation, described first porous wall (106A) and described second porous wall (106B) limit separately and are oriented to face described lower window (92, 147) lower openings (113A, 113B).

4. inner frame assembly (16) according to claim 3, it is characterized in that, described inner frame assembly (16) comprises connecting frame (111A), described connecting frame (111A) is around the described lower openings (113A) limited in described first porous wall (106A), and around the described lower openings (113B) limited in described second porous wall (106B), described connecting frame (111A) is connected to described first porous wall (106A) and described second porous wall (106B) hermetically, described connecting frame (116A) is inserted in the described lower window (92) of described cathode frame (64).

5. according to inner frame assembly (16) in any one of the preceding claims wherein, it is characterized in that, described connecting wall (108C, 108D) or each connecting wall (108C, 108D) comprise with described first porous wall (106A) all-in-one-piece first side direction part (116A) and with described second porous wall (106B) all-in-one-piece second side direction part (116B), described first side direction part (116A) and described second side direction part (116B) are placed with each other, described connecting wall (108C, 108D) comprise the attachment element be positioned between described first side direction part (116A) and described second side direction part (116B), described attachment element is advantageously releasable.

6. according to inner frame assembly (16) in any one of the preceding claims wherein, it is characterized in that, described first porous wall (106A) and described second porous wall (106B) limit upper opening (114), and the described upper opening (114) limited by described first porous wall (106A) and described second porous wall (106B) holds in compartment (90) for negative electrode (74) being inserted into described inner cathode.

7. according to inner frame assembly (16) in any one of the preceding claims wherein, it is characterized in that, described cathode frame (64) limits the side opening mouth (96) of at least one bottom, the side opening mouth (96) of at least one bottom described holds in compartment (90) for the material solution containing mn ion being injected into described inner cathode, described connecting wall (108C, 108D) limits for the side opening mouth (96) of each described bottom the side direction window (115A) be communicated with the side opening mouth (96) of described bottom.

8. inner frame assembly (16) according to claim 7, it is characterized in that, described cathode frame (64) limits at least one for discharging the aperture, upside (98) of cathode gas, described connecting wall (108C, 108D) limits for aperture, each described upside (98) and is positioned at aperture, described upside (98) side direction window (115B) around.

9. according to inner frame assembly (16) in any one of the preceding claims wherein, it is characterized in that, described cathode frame (64) comprises the first upper cross member (85A) and the second upper cross member (85B), described first upper cross member (85A) limits described first axially open (105A) up, described second upper cross member (85B) limits described second axially open (105B) up

Described first porous wall (106A) and described second porous wall (106B) have top attachment element (111B separately, 111C), described top attachment element (111B, 111C) can be bonded on around described first upper cross member (85A) and described second upper cross member (85B) respectively.

10. according to inner frame assembly (16) in any one of the preceding claims wherein, it is characterized in that, described inner frame assembly (16) comprises cathode frame (64) anode superstructure (66) adjacent with two, each described adjacent anode framework (66) comprises the axial vane surface be placed with respectively on described first porous wall (106A) and described second porous wall (106B) of described barrier film (68), each described anode superstructure (66) comprises sealing element (153A, 153B), described sealing element (153A, 153B) be inserted into described axial vane surface and between corresponding described first porous wall (106A) and described second porous wall (106B).

11. according to inner frame assembly (16) in any one of the preceding claims wherein, it is characterized in that, described anode superstructure (66) limits internal anode and holds compartment (144), described frame assembly (116) comprises the anode (72) be accommodated in described internal anode accommodation compartment (144) for each described anode superstructure (66), described anode (72) comprises at least one first distance piece (193A) and at least one the second distance piece (193A), at least one first distance piece (193A) described is for being pressed against first porous wall (106A) of neighboring separators (68), at least one second distance piece (193A) described is for being pressed against relative second porous wall (106B) of relative neighboring separators (98).

12. according to inner frame assembly (16) in any one of the preceding claims wherein, it is characterized in that, described inner frame assembly (16) comprises the removable negative electrode (74) be accommodated in described internal space (109) for each described cathode frame (64), described internal space (109) is positioned at described first porous wall (106A), between described second porous wall (106B) and described connecting wall (108C, 108D).

13. 1 kinds of electrolyzers for electrolytic manganese (10), comprising:

-cell body (12), described cell body (12) limits the internal space (14) for holding material solution;

-according to inner frame assembly (16) in any one of the preceding claims wherein, described inner frame assembly (16) is disposed in described internal space (14).

14. electrolyzers according to claim 13 (10), it is characterized in that, each described cathode frame (64) limits at least one side opening mouth (96) and on the upside of at least one aperture (98), described side opening mouth (96) is for being supplied in described interior compartment (90) by the material solution containing mn ion, aperture, described upside (98) is for discharging cathode gas, described top discharge orifice (98) is disposed in the top of described or each side opening mouth (96) for base feed solution, described electrolyzer (10) comprises covering assemblies (18), the upper seal ground of described covering assemblies (18) on described top discharge orifice (98) covers the internal space around described frame assembly (16) (14) of described cell body (12), described electrolyzer (10) comprises at least one conduit (38), described at least one conduit (38) is for clearing out of described cell body (12) by the emission gases of being collected by upper gas discharge orifice (98) described in each.

15. electrolyzers according to claim 14 (10), is characterized in that, described removing conduit (38) extends roughly vertically in cell body (12), and upwards emerges in described internal space (14).

16. 1 kinds, for the method for electrolytic manganese, comprising:

-provide according to claim 13 to the electrolyzer (10) according to any one of 15;

-hold the material solution of compartment (90) supply containing mn ion, to form described negative electrode (74) catholyte solution around to the inner cathode of each cathode frame (64);

-be contained in the upper formation of each negative electrode (74) in each cathode frame (64) manganese metal;

-make described catholyte solution flow through first porous wall (106A) of barrier film (68) and the second porous wall (106B) and enter anode to hold compartment (144).