CN1073171C - Multi-polar cell for recovery of metal by electrolysis of molten electrolyte - Google Patents

Abstract

The present invention relates to an electrolytic groove capable of regenerating metal from melted electrolytic liquid and an electrode assembly used in the electrolytic groove. The electrolytic groove (10) comprises the electrode assembly, and the assembly is composed of an anode (17), a cathode (19) and one or more than one bipolar electrode (18), wherein the bipolar electrode is arranged between the anode and the cathode so as to form an inter-polar clearance generating electrolytic action. In the electrode assembly, the bipolar electrode (if the number of the bipolar electrode is one) or the bipolar electrode of the innermost layer (if the number of the bipolar electrodes is more than one) basically surrounds the anode and forms a single mechanical and electrical entity. The cathode preferably surrounds one or more than one bipolar electrode, the electrode assembly comprising the cathode and the bipolar electrode is preferably made into a unit-type electrode box, and the electrode assembly as an independent self-bearing unit can be inserted into or taken from the electrolytic groove after the electrode assembly is assembled on the outer rim of the electrolytic groove. The present invention can simplify the manufacture of the electrolytic groove and can also improve the use efficiency of the electrolytic groove.

Description

With the multipole electrolyzer of molten electrolyte electrolysis with secondary metal

Technical field

The present invention relates to from molten electrolyte, produce the improved electrolyzer of metal.More particularly, the present invention relates to be used for the multipole electrolyzer of this purpose.

Background technology

United States Patent (USP) 4,604,177 and 4,514,269 have described and have a kind ofly produced the electrolyzer of metal, for example magnesium with electrolytic process, and each all has cell body this electrolyzer, and one or several electrode assemblie is housed in cell body.Include the cathode assembly that surrounds vertical cavity in each electrode assemblie, anode and one or several bipolar electrode assembly are housed in the chamber, the bipolar electrode assembly is contained between anode and the cathode assembly.In order to prevent or to stop electrolytic solution, the polylith baffle plate is housed also flowing between the adjacent cathode assembly and/or between the cell body wall of each cathode assembly and vicinity.But this cell geometry and design make this electrolyzer be difficult to make to have uniform pole clearance, and the manufacturing of this design and process cost are all very high.In addition, the stray current between electrode can cause that also current efficiency reduces.Therefore, need provide a kind of improved electrolyzer,, can also obtain the watt consumption of higher current efficiency, lower production per kilogram metal simultaneously, and make that design of electrolysis cells is compact more, cost is lower so that simplify the assembling and the method for maintaining of electrolyzer.

Summary of the invention

Therefore, the purpose of this invention is to provide the electrolyzer that improves indoor design.

Another object of the present invention provides can be simply, the electrolyzer of assembling reliably, preferably can also be simply, dismounting reliably.

A further object of the present invention provides the electrolyzer of energy economy, valid function.

One aspect of the present invention provided a kind of can be from the molten electrolyte that contains metallic compound the electrolyzer of secondary metal, this electrolyzer has cell body, include at least one inner electrolysis locellus in the cell body, each electrolysis divides the indoor electrode assemblie that has at least, this assembly comprises an anode, negative electrode and at least one are placed on the bipolar electrode between anode and the negative electrode, so that cause the pole clearance that electrolytic action takes place, this assembly also comprises the joint of carrying electric current toward electrolyzer, this electrolyzer is characterised in that, bipolar electrode, or when a plurality of each bipolar electrode, mechanically with electric on all formed an one entity, and all basically intactly round the main electrolytic surface of the bipolar electrode of main electrolytic surface of anodic or next innermost layer, its feature also is, negative electrode is basically intactly round the main electrolytic surface of bipolar electrode, perhaps there is one when above when bipolar electrode, round the main electrolytic surface of a bipolar electrode of outermost.

Another aspect of the present invention provided a kind of can be from the molten electrolyte that contains metallic compound the electrolyzer of secondary metal, this electrolyzer has cell body, comprise at least one inner electrolysis locellus in the cell body, each electrolysis divides the indoor electrode assemblie that has at least, this assembly comprises an anode, negative electrode and at least one are placed on the bipolar electrode between anode and the negative electrode, so that cause the pole clearance that electrolytic action takes place, this assembly also comprises the joint of carrying electric current toward electrolyzer, this electrolyzer is characterised in that, negative electrode is basically intactly round at least one bipolar electrode and anode, its feature also is, negative electrode and at least one bipolar electrode are fixed together forms a unit block, when the assembling electrolyzer, this assembly can be inserted in the electrolysis locellus and go.

Another aspect of the present invention has provided a kind of electrode assemblie, it can be inserted in the electrolyzer and go, this electrolyzer is to be used for from the molten electrolyte that contains metallic compound secondary metal, this electrode assemblie comprises at least one bipolar electrode and a negative electrode, it is characterized in that, each bipolar electrode all mechanically with electric on formed one entity, its feature also is, negative electrode intactly centers on basically and is fixing one or more bipolar electrodes, forms a unit block.

Another aspect of the present invention provided a kind of can be from the molten electrolyte that contains metallic compound the electrolyzer of secondary metal, this electrolyzer has cell body, comprise at least one inner electrolysis locellus in the cell body, each electrolysis divides the indoor electrode assemblie that has at least, this assembly comprises an anode, a negative electrode and carries the joint of electric current toward electrolyzer, this electrolyzer is characterised in that to have a structure that the liquid level of electrolyte controlling organization is housed on the negative electrode.

In electrolyzer of the present invention, anode cross section in the horizontal direction is preferably the garden cylindricality, and bipolar electrode cross section in the horizontal direction is preferably annular, but, if desired, the cross-sectional shape of these electrodes also can be without garden cylindricality and annular, and with for example avette, ellipse garden shape, square, rectangle, Polygons or the like.Why preferred garden cylindricality and annular are because can be simpler, economical when making and accurately, this will be from hereinafter seeing more obviously.Under any circumstance, the main electrolysis face of center anode (normally vertical or be vertical basically) should be fully with one heart by normally the bipolar electrode and the outermost negative electrode of corresponding geometrical shape center on.The main electrolysis face of anode, negative electrode and bipolar electrode is meant the surface-area that most electrolytic action take place thereon.Therefore, most of electrolytic action be predefined in electrode be submerged, aspectant vertical (or approximate vertical) surface goes up generation, still, some little accessory electrolytic action also may be in lower surface or the lower edge or the edge generation of electrode.In the present invention, there is no need to guarantee that bipolar electrode and negative electrode " center on " the accessory or auxiliary electrolytic surface of (promptly facing) next innermost layer electrode, though this may preferably will do in some cases.

Pole clearance between inner any two adjacent electrodes of electrolyzer basically must be all identical on all each points, and the necessary appropriateness in gap is so that efficient electrolysis (in 3 to 30mm scope, more preferably 5 to 15mm usually).

Bipolar electrode, each bipolar electrode when several preferably constitutes with one heart around anode or with one heart around the cell cube of next innermost layer bipolar electrode (that is be seen as one entity from electric and mechanical viewpoint).The surface of electrode, and anode surface itself, be preferably vertical, but also can be to interior tapered to bottom of electrolytic tank.When electrode constitutes cell cube, on the surface of electrode, can have fracture, slit, hole, crack or other discontinuities, as long as electrode in use is not subjected to the influence of these discontinuities.Even so, but consider from the physical strength and the electric property of maximum, the discontinuities that does not most preferably have this character on the electrode, and the perpendicular segment of bipolar electrode (that is have over against towards anodic surface with towards those parts on the surface of negative electrode) constitutes the unremitting surface of successive around anode or next innermost layer bipolar electrode.

Most preferably, negative electrode and bipolar electrode are consolidated and make the self-unit block that supports or the form of " box ", and it can assemble in the electrolyzer outside, prepares to put into when coming into operation electrolyzer when electrolyzer assembles then.Then, insert anode in the internal vertical axial space that the electrode box center is reserved, electrolyzer is just ready.Such cassette arrangement must be at the inner fixed one or more bipolar electrodes of living of negative electrode, and the extension of negative electrode must enough firmly so that can insert and be assembled in the electrolyzer, and can maintain the pole clearance that electrode is mutual reliably.In order to accomplish this point, (if more than one words are arranged) places dielectric isolation layer, for example similar facilities such as shim, calking piece, lath preferably between negative electrode and outermost layer bipolar electrode, and between each bipolar electrode.These sealing coats are preferably made with insulating refractories, and (though also can select other method such as gluing for use) is cemented on the electrode surface preferably to use mechanical means.Most preferably they are on the outside surface (towards the anodic surface) that is cemented in bipolar electrode.If desired, also can between innermost layer bipolar electrode and anode, place similar dielectric isolation layer, for example, before anode is inserted into electrode box, such sealing coat is placed on the anodic outside surface.

In one embodiment of the invention, also add inside extension with further reinforcing cassette arrangement in the lower end of negative electrode and interpolar electrode.These extensions are preferably substantially horizontal.The effect of supporting next innermost layer electrode can both be played in each such extension, and final anchorage force is from negative electrode, and negative electrode normally constitutes the strong metal shell of electrode box outer wall.Certainly, each electrode all can not constitute in the extension of its end (or any other parts) and electrically contacts, and therefore, mutual necessity supports should be by providing such as nonconducting sealing coats such as calking piece, shims.Such sealing coat is normally made of insulating refractories, and preferably is cemented on the surface of electrode extension.

The alternate way is, also can install inside extension additional for each electrode of casket module, and provide necessary support with an insulation system, for example with one have eyelet or gap for electrolyte circulation, be cemented on the negative electrode with flat board or polylith member non-conductive but that have the material of suitable intensity to make, and across the hole of negative electrode foot.Like this, single or multiple bipolar electrodes just can be with they be placed on back up pad or the bracing member bottom, and the calking piece done of available electrically nonconducting material or shim be placed on each electrode member vertical surface between to keep suitable pole clearance.Above-mentioned flat board or member can be cemented on the negative electrode by making upholder, for example with successive horizontal direction on the negative electrode inside protruding lip or a series of inside little lug, or stretching to any fillet cross member of right opposite from any with the negative electrode lower end, flat board just withstands on above it.When using a series of fire retarding component, be to need to use this a kind of supporting type in back especially.

Should point out in passing that when electrolyzer used, owing to be immersed in the very big electrolytic solution of proportion, each bipolar electrode all had been subjected to buoyancy, therefore may no longer need much can resist the upholder that moves downward.Even so, but when making an active electrode box, the upholder that can resist gravity is provided still must for significantly each bipolar electrode.

The electrode design that use is cemented in electrode extension, flat board or member on the negative electrode is to have enough intensity and hardness, no longer require to be supported when they are inserted into electrolyzer with box lunch, and bus-bar or other fastening element that can depend merely on electrolyzer connect and can support from the bottom.

No matter how electrode box designs and be which type of supporting way in electrolyzer, final structure all must in use can make electrolytic solution circulate between each electrode member, and makes electrolyte flow even as far as possible.In addition, because electrode box uses the successive electrode surface, basically can eliminate the stray current of electrode limit portion, remaining stray current (this is meant by the electric current between the non-adjacent electrode) mainly is the bottom at electrode box, and the design of electrode box has also considered to make this stray current to reduce to minimum.

The bipolar electrode that the present invention uses is preferably made with graphite.But, can on the cathode plane (towards the face of negative electrode) of one or more bipolar electrodes, load onto the panel of steel or other suitable metal.The panel of steel can be cemented on the graphite with mechanical means, or fixed with glue or cement.The panel of steel is by the magnesium wetted, and this can play the effect that reduces polarizing voltage, thereby can improve efficiency.Metal decking can also promote that metal discharges from the surface, and this can improve current efficiency again.

Except that Steel Facing (if you are using), bipolar electrode preferably is machined to independent one with graphite block, as long as but can each bipolar electrode make (mechanically) on the structure and electric on single cell, also can be with making the suitable graphite block way glued or that be consolidated of shape.Glued useful binders is implemented, and for example uses United States Patent (USP) 4,816, the disclosed the sort of tackiness agent of 511 (Castonguay etc.), and this patent is hereby incorporated by.Screw or screw rod, pin or dowel that fixed available machining graphite becomes are realized.The pattern that can make lap joint, dovetail, screwed joint or other type fittings can be processed in connected limit, with proof strength and help forming mechanically with electric on single cell.

When negative electrode and bipolar electrode are made into boxlike, its method for supporting in electrolyzer is more convenient, also be preferred way, be depend merely on electrolyzer in the bus-bar binding of living, this is because negative electrode under any circumstance all must be electrically connected with bus-bar, and the bus-bar physical strength is big simultaneously also is supported on cell wall or other supporting frame reliably.For this purpose, on negative electrode, can do a hook-type connect elements, be installed near the cathodic bus bars, and electrode box is supported on the bus-bar, and can guarantee that negative electrode and bus-bar have reliable electrical contact.Such arrangement can sponge negative electrode and bus-bar easily because different rate of expansion and the shrinking percentage that heating causes, when electrolyzer uses, can not lean against on the negative electrode or other uses expansion pipe Anywhere and current interruptions can not take place.This mounting means also makes electrode box can be used as a use or repairs the unit and take out from electrolyzer.

By as seen above-mentioned, the present invention is at least in using the preferred embodiment of successive bipolar electrode and negative electrode basically, has started a kind of robust box structure, making it can be at electrolyzer outside assembling electrode assembly, and can be used as a unit and insert electrolyzer.This has not only guaranteed structural stability, and can make leakage current reduce to minimum, thereby improves electrolyzer efficient.

Modular electrical structure and the preferred horizontal-extending part of using negative electrode and bipolar electrode, or use the dull and stereotyped or similar upholder of bottom insulation can fundamentally reduce between the electrode by-pass flow electric current at electrode assemblie bottom and edge part.So remaining by-pass flow source is just in top of electrodes.By means of the electrolytic solution that above electrode, only keeps skim, just can increase the resistance of leakage current.Keep such thin layer can be by realizing that at the liquid level of electrolysis locellus inner control electrolytic solution a kind of preferred design arrangement is introduced in the Cathode Design.Use tank level control can make the by-pass flow electric current at electrode assemblie top reduce to minimum, therefore whole electrolyzer and electrode assemblie just can provide improved electric property.

The accompanying drawing summary

Fig. 1 is vertical vertical section figure of the part electrolysis locellus of the present invention's first preferred embodiment electrolyzer, and it illustrates annular electrode assemblie and structure thereof;

Fig. 2 is the horizontal vertical section figure of electrolyzer among Fig. 1, and it specifically illustrates the situation that is connected of electrode assemblie and electrolyzer bus-bar;

Fig. 3 is the horizontal sectional view at electrolytic tank electrolysis locellus top among Fig. 1, and it illustrates the concentric geometry of electrode assemblie, and integral part has: garden cylindricality anode, annular bipolar electrode, hollow cathode, negative electrode locellus baffle plate, and their joint portion;

Fig. 4 is the horizontal vertical section figure of electrolyzer among similar Fig. 1, and it illustrates the lifting gear of alternate banded method and installation or removal assembly on the electrolyzer bus-bar;

Fig. 5 is the part of horizontal sectional drawing of electrolyzer among Fig. 4;

Fig. 6 is the part vertical section figure of modification electrode assemblie of the present invention, and it illustrates the horizontal-extending part of bipolar electrode and negative electrode and the slit that electrolysis liquid flows into especially;

Fig. 7 and 8 is respectively the vertical vertical section figure and the horizontal vertical section figure of another preferred electrolyzer embodiment of the present invention, and it shows the liquid-level controller of electrode assemblie inside and supports the fire-resistant grid of bipolar electrode;

Fig. 9 is the horizontal vertical section figure of another electrolyzer of the present invention, and in the electrode assemblie shown in it, negative electrode and bipolar electrode are tapered, its objective is to assembling and installing more convenient.

Figure 10 is the horizontal vertical section figure of another kind of electrode assemblie, its utilize the refractory slab have single hole support bipolar electrode and each bipolar electrode from refractory slab distance have nothing in common with each other so that electrolytic solution can by center hole, again can be mobile by the annular space of negative electrode below or outer bipolar electrode below.

Realize optimal mode of the present invention

Fig. 1,2 and 3 illustrates first embodiment of electrolyzer 10 of the present invention, it comprises cell body 12, cell body is made of cell wall 12a and cell bottom 12b, wherein includes at least one electrolysis locellus 13 and at least one auxiliary locellus 14 (see figure 2), and the latter is called as the locellus of collecting metal.When electrolysis, the chlorine that produces in the electrolytic process is collected (and being taken away from here) on the top of electrolysis locellus 13, and resultant metal for example magnesium then is accumulated in (and finally being taken out from here) auxiliary locellus 14.Waterwall 15a, 15b that wherein also useful refractory brick is built into.Top wall 15a separates the atmosphere of two locellus.Lower walls 15b then separates the electrolytic solution of two locellus, but has hole 22,23 for the electrolyte loop circulation, also will be described below.

Generation in the pole clearance 16 that electrolytic action forms between (normally steel) negative electrode 19 of the main electrolytic surface of graphite anode 17 and one or more bipolar electrode 18 and metal.Though what draw in this embodiment is 3 bipolar electrodes, this quantity can change, but will have 1 at least usually.Anode 17, bipolar electrode 18 and negative electrode 19 are drawn in the drawings has the main electrolytic surface of vertical Cylinder shape, but they also can reduce its diameter a little equably towards bottom of electrolytic tank, thereby forms the anode assemblies of taper.

The foot of bipolar electrode 18 and negative electrode 19 has inside extension 18a and 19a, and these extensions extend in the below of anode 17 lower ends.These extensions and electrode are successive, and with relevant electrode have mechanically with electric on be connected.Inside extension 18a and 19a are level basically.

Electrolyzer shown in Fig. 1 has four independently electrode box and anode assemblies.But, within the scope of the invention, can divide indoor more or less electrode device that comprises, several such electrolysis locellus of also can in an independent electrolyzer, packing into certainly an independent electrolysis.

Carry out in the electrolytic process at utilization electrolyzer of the present invention, the metallic compound (for example magnesium chloride) that dissolves in the electrolytic solution (for example sodium-chlor and calcium chloride) is decomposed by the direct current by the bipolar electrode circulation between anode and negative electrode.Electrolysate is chlorine and fused magnesium (when metallic compound is magnesium chloride).

Chlorine is tried hard to rise to the surface of the molten electrolyte in the pole clearance 16 and is got on, and the pole clearance entrance slit 20 that to be electrode extension 18a and 19a by level constituted is connected with outside a large amount of electrolytic solution.The upward movement of gas has caused the effect of pump, orders about electrolytic solution by pole clearance 16 upwards, takes away at the chlorine of this generation and little magnesium and drips.The diameter of entrance slit 20 is inequality, the diameter maximum be on the negative electrode 19, the diameter minimum be near on the bipolar electrode of anode 17.This helps making, and to flow through between electrode the electrolytic solution in slit more even, also increases the circulation distance of stray current simultaneously, thereby reduce stray current.Slit between extension 18a and the 19a is big than slit between pole plate 18 and 19, also helps flow and evenly also can reduce by-pass current.

Molten mixture 11 is walked out pole clearance 16 at the electrode box top, and here overflow in the chlorine top of passing through electrolysis locellus 13, and molten electrolyte is then wrapped up in to drip with little magnesium and left away and admission passage 21, and this passage is to be included in the external structure of negative electrode 19.Liquid finally is discharged in the locellus 14 of collecting metal by the gangway on waterwall 15a, the 15b 22 then, drips at this little magnesium and goes up the surface, and electrolytic solution then sinks to passing through the gangway 23 of waterwall 15b bottom and turns back to the ingress of tank room.

Anode 17 stretches out on the electrolyzer cover plate and electric being attached on the gripping unit 25, and gripping unit is a water-cooled, and with good electrical contact between holding anode and the gripping unit, gripping unit constitutes supplies with the Faradaic current lead-in wire.Jaw carriage also is used for supporting anodes 17 on the electrolyzer cover plate, the anode that supports with this way keeps leaving the extension 18a certain spacing of bipolar electrode lower end.In addition, available insulated fireproof sealing coat (not drawing among the figure) comes holding anode to be in the central position of innermost layer bipolar electrode 18.Between cover plate 24 and anode 17 sealing-ring 26 is housed also on the electrolyzer, in case air is invaded, because electrolysis locellus 13 is generally being worked so that extract chlorine product out under the pressure below atmospheric pressure slightly, if packing less words, air will be invaded.

Negative electrode 19 carries out with being electrically connected by inverted pocket member or hook 28 of cathodic bus bars 27, and hook card jail is on the 27a of the extension of cathodic bus bars 27.Extension 27a and cathodic bus bars 27 meet at right angles, both or constitute L shaped section, perhaps constitute tee-section, decide on the position in the electrolyzer.In assembling during electrolyzer, the self-supporting electrode box of being made up of negative electrode 19 and bipolar electrode and extension thereof is by means of hook 28 being dropped on the 27a of bus-bar extension and installing.The smooth internal surface of hook 28 is connected electrically on the negative electrode, has just constituted with the extension of cathodic bus bars low-impedancely to electrically contact.This connection does not need welding or fastener, and therefore the entire electrode box can be removed after use.In addition, there is not welding to mean that the thermal expansion that causes when the electrolyzer heating can be absorbed.In illustrated embodiment, hook 28 provides whole support and location at electrolysis branch chamber interior counter electrode box, breaks away from because the lower end of electrode box is a fire-resistant diapire with the inner lining cutting of electrolyzer.

The electrolysis locellus of another kind of pattern is shown in Fig. 4 and Fig. 5.This is the distortion of garden shown in Figure 2 cylindrical electrode device.The arrangement of negative electrode 19 and four bipolar electrodes 18 basically with Fig. 2 in identical.Outer periphery around negative electrode 19 is equipped with flat board 30 level or that tilt a little.Flat board is square or rectangle, and it becomes in the tank room dividing plate of horizontal direction substantially, in order to prevent effusively from the electrode device top to contain the bottom that electrolytic solution that magnesium drips directly is back to electrolysis locellus 13.This device has played the same effect of passage 21 among Fig. 2.Cathodic bus bars 27 is conductors of a rectangular cross section, passes cell wall 12a and enters inside.Tee-section or L shaped section 27b are made in the bus-bar termination.

The last angle 27c of T shape or L shaped section splays a little, as shown in the figure.The plate 31 that stretches out downwards is consolidated into the right angle with dull and stereotyped 30, and in the time of in electrode device is packed electrolyzer into, plate 31 contacts with the medial surface 27d of T shape or L shaped section.The auxiliary plate that stretches out downwards 32 is cemented on dull and stereotyped 30, and is splayed to match with bevel 27c on the bus-bar.When packing electrolyzer into, the weight of electrode device is the hook 28 that constitutes by the part by member 31,32 and dull and stereotyped 30 and finally being born by bus-bar 27,27b.Dull and stereotyped 30 can be close to cell wall, but are not supported on the wall.In order to simplify the mounting or dismounting of electrode device, hook 33 is housed on the neighboring of negative electrode 19.Engageable these hooks of lifting gear (that is showing picture among lift-Tu) are arranged and the entire electrode device is raised up.

Fig. 6 is similar to Fig. 1 to 5 but the partial cross-section enlarged view of the electrode device of slight change.In this embodiment, the horizontal-extending part 18a of bipolar electrode 18 and negative electrode 19 and the slit between the 19a, and the slit between the bottom surface 17a of innermost layer bipolar electrode and anode 17, and the hole 18b and the 19b at extension 18a and 19a center, their size will be done so that preferably that the cross-sectional area that electrolysis liquid flows to pole clearance 16 can promote the major portion of entire electrode device all to have uniform electrolyte flow rate.The upper face 18c of the horizontal-extending part 18a of bipolar electrode 18 preferably has the gradient at such as shown downward a little oblique center, and preferably stamp open-work 18d in case sludge (mainly being MgO) gathers, if not, sludge may block electrolyte flow and may cause short-circuit cycle.

In electrolyzer utilization operation of the present invention, it is very important making the electrolytic solution degree of depth of top of electrodes (shown in figure 2 11) keep as far as possible for a short time, can prevent by-pass current like this, simultaneously can also guarantee to take place effectively chlorine/magnesium and be separated into and reach this purpose, the tank level control facility of electrolytic solution may be installed in electrolyzer.United States Patent (USP) 4,518,475 (O.Sivilotti) have been described the method and apparatus that is suitable for, and the content that is incorporated herein this patent as a reference.

Fig. 7 and Fig. 8 illustrate the another kind of fluid level control system of available of the present invention.On aforesaid conventional cathode 19, install a cell 40 additional as reservoir.Electrolytic solution turnover cell has hole 41 in the cell bottom, so that can be introduced rare gas element (for example argon) toward the top 42 of cell.By means of introducing or enter the liquid level of rare gas element with regard to may command electrolytic solution by pipe 43 pressurization, this is because the indifferent gas physical efficiency substitutes out more from reservoir 40 or fewer electrolytic solution and make it to enter electrolysis locellus 13.This reservoir device not only is specially adapted to the described electrode assemblie type of this specification sheets, and as pack into the surrogate that also can be used as the huge and complex control apparatus of traditional type in the negative electrode of plain electrolysers and particularly useful of this reservoir.

Everybody can notice, has inside extension the embodiment before the bipolar electrode 18 in Fig. 7 and Fig. 8 does not resemble.In the case, bipolar electrode supports by the fire-resistant grid 45 of insulating, has suitable hole on the grid and can allow fused electrolytic solution flow in the pole clearance 16.The extension 19a (as preceding) of level is housed, in order to support and to clamp fire-resistant grid on the negative electrode.With such way, electrode device still can be formed an independently electrode box like before, and is inserted into or takes out electrolyzer as a unit.Because the termination frame of negative electrode and bipolar electrode is on the insulation grid, the stray current of electrolysis bath of liquid must therefore just make distance more elongated, thereby stray current also can be littler by refractory slab and intermediary's electrolytic solution.

A kind of modification of the design of Fig. 1 to Fig. 5 is shown in Fig. 9.In this embodiment, anode 17, bipolar electrode 18 and negative electrode 19 are garden cylindricalitys, but tapering is arranged.The tapering of each electrode is all consistent, to guarantee the pole clearance unanimity.The design also is equipped with bus-bar 27, this is the same with the design that has rectangular extension 27a, but in the present embodiment, the extension 27a of bus-bar is a ramped shaped, the angle of gradient is identical with the tapering of negative electrode 19, therefore when electrode box be inserted into electrolyzer and by hook 28 fix in position after, electrically contacting between cathodic bus bars and the negative electrode is good.Hook 28 is splayed, and can install and remove in electrolyzer easily so that have the electrode assemblie of slope shape or conical surface.

Another modification of the design of Fig. 7 and Fig. 8 is shown in Figure 10.The lower end of electrode assemblie shown in the figure comprises anode 17, three bipolar electrodes 18 and negative electrodes 19.A refractory slab 45 is arranged among the figure, and its center is porose 50, and the hole is concentric with anode and other electrode.Refractory slab 45 is to use along several places on the end periphery under the negative electrode the L shaped ear handle 19c that inwardly stretches to support downwards, but will allow under the negative electrode most of area of end periphery not interrupted.Therefore electrolytic solution can be by uncrossed area around the negative electrode lower end.Also upwards enter electrode assemblie by hole 50 by all pole clearances 16.Innermost layer and outermost bipolar electrode are to keep leaving the certain distance of refractory slab 45 with little spacing block 51, also the local extension on the avaivable electrode partly keeps this distance, and the electrolytic solution of below, respective electrode lower end is almost unhinderedly flowed.The intermediary bipolar electrode then directly is supported on the refractory slab 45.Anode 17 is remained on last from the bigger distance of PLASTIC LAMINATED 45 than innermost layer bipolar electrode by its external bracing (among the figure draw).Similarly, the continuous periphery of negative electrode lower end also stops in the more eminence of outermost layer bipolar electrode lower end.Do like this, just by means of making the bypass distance expand the by-pass current that maximum (the bypass distance is meant the path that electrolytic solution passes through between the non-nearest neighbour utmost point) reduces electrode resistor bottom effectively to.Final simple fire-resistant design cost is not high.

In fact, complete assembly of the present invention is made fairly simple also relatively more cheap.For example, graphite bi-polar electrode 18 can be with the independent diffusing piece of mach suitable shape, with screw, pin, dowel or similarly link material link together with mechanical means and make mechanically with electric one electrode member.Also can adopt lap joint, screwed joint or dovetail.Graphite loose also available cement of piece or tackiness agent gluing for example use in the United States Patent (USP) of mentioning previously 4,816,511 disclosed program to do.When using the horizontal-extending part of electrode, also available similar way gets on the vertical section that the extension is bonded to electrode.

Before point out that bipolar electrode (and peripheral negative electrode) can have any shape easily on horizontal slice.But garden cylindricality or annular are preferred.Concerning these two kinds of shapes, graphite bi-polar ring and anode can be made (for example on vertical boring mill with an independent graphite, Workpiece Rotating, and machinery tools comprise that the thickness of cutter head and handle of a knife is slightly smaller than the material that is gone out by Xuan, and this thickness is exactly typical desired pole distance).The graphite bi-polar electrode can be made with one or more vertical graphite section with same diameter, preferably process with other bipolar electrode as described above with an independent graphite, loose mail after making can be glued or be linked together the example of mechanical means such as above-mentioned linking with screwed joint with mechanical means.With such method, can assemble high 2 meters or above, pole clearance greatly to 5 to 7mm bipolar electrode, this pole clearance is exactly the joint-cutting of milling machine operation.

As mentioned above, electrode assemblie of the present invention preferably is assembled into boxlike.Because design of the present invention, electrode box can assemble in the electrolyzer outside, inserts electrolyzer as independent full unit then.Can use the cathode shell (all sealing this structure) of metal, then horizontal-extending part (or the fire-resistant grid of insulating) and bipolar electrode be inserted in the cathode shell successively, can use the fire-resistant sealing coat of insulating simultaneously when needed.If what use is the successive cathode shell, even the available loose mail that is not consolidated into modular construction is made bipolar electrode, that is those loose mails be not mechanically with electric on single entity, the time in position load onto the fire-resistant sealing coat of insulating again in assembling, to support these electrode loose mails.Do so still and can be installed in electrode assemblie in the electrolyzer as one entity.But, having maximum intensity and secular electrical integrity in order to make electrode assemblie, preferred bipolar electrode still is (or process with an independent raw material, or connect or the independent structure of glued one-tenth with mechanical means) of independent modular construction.Electrode box is all to assemble and the electrolyzer of can packing into, can keep its integrity when enlarging operation, and can be used as independent unit and take out from electrolyzer.Anode is then separately and exclusively installed and is taken out.

Embodiment

Built the electrolyzer of a full size, it designs as shown in Figure 1, 2, 3, and turns round 600 days.This electrolyzer resemble expectation successfully work, bath voltage is 13.5 to 14.2 volts, current efficiency is between 75% and 80%.This current efficiency is higher by 5% to 10% than the electrolyzer without the boxlike electrode assemblie of traditional design.

Claims (25)

1. the electrolyzer of energy secondary metal from the molten electrolyte that contains metallic compound, this electrolyzer has cell body (12), include at least one inner electrolysis locellus (13) in the cell body, each electrolysis divides the indoor electrode assemblie that has at least, this assembly comprises an anode (17), a negative electrode (19) and at least one are placed on the bipolar electrode (18) between anode and the negative electrode, so that cause the pole clearance (16) that electrolytic action takes place, this assembly also comprises the joint (25 of carrying electric current toward electrolyzer, 27), this electrolyzer is characterised in that, bipolar electrode (18), or when a plurality of each bipolar electrode, mechanically with electric on all formed an one entity, and all basically intactly round the main electrolytic surface of the bipolar electrode (18) of the main electrolytic surface of anode (17) or next innermost layer, negative electrode (19) is basically intactly round the main electrolytic surface of bipolar electrode (18), perhaps there is one when above when bipolar electrode, round the main electrolytic surface of a bipolar electrode of outermost (18).

2. the electrolyzer of claim 1 is characterized in that, negative electrode (19) mechanically with electric on consist of one entity.

3. claim 1 or 2 electrolyzer is characterized in that, negative electrode (19) and the bipolar electrode of at least one are fixed together forms a unit block, and this assembly can be used as one unit and is inserted in the electrolysis locellus (13) and goes.

4. the electrolyzer of claim 3 is characterized in that, this unit block also can be used as one unit and takes out from electrolysis locellus (13).

5. claim 1,2 or 4 electrolyzer is characterized in that negative electrode (19) has open lower end and has the supporting structure of inside stretching, extension, and this supporting structure provides support at least one bipolar electrode (18) when the assembling electrolyzer at least.

6. the electrolyzer of claim 5, it is characterized in that, this supporting structure comprises from local outstanding extension, the open lower end of negative electrode (19), and supported bipolar electrode (18) is to be supported on this extension by the sealing coat of one deck electrical isolation at least when the assembling electrolyzer at least.

7. the electrolyzer of claim 6, it is characterized in that having a plurality of bipolar electrodes (18), the open lower of each bipolar electrode all partly inwardly is extruded with extension (18a), except that the extension of innermost layer bipolar electrode, other each extension all provides support to next internal layer bipolar electrode (18) by one deck dielectric isolation layer at least during electrolyzer in assembling at least.

8. the electrolyzer of claim 5 is characterized in that, this supporting structure is an insulation system, and electrolytic solution can enter pole clearance (16) by this structure, and the anchorage force of this supporting structure (19a) is born by negative electrode.

9. the electrolyzer of claim 8 is characterized in that, insulating supporting structure is the flat board (45) of a perforate.

10. claim 1,2,4,6,7,8 or 9 each electrolyzer, it is characterized in that, said at least one bipolar electrode (18) is to be boundary with the opposite electrolytic surface towards anode and negative electrode of direction, and their horizontal slice shape all is circular, oval, square, rectangle, Polygons or avette separately.

11. the electrolyzer of claim 10 is characterized in that, said at least one bipolar electrode system is a boundary with the opposite electrolytic surface towards anode and negative electrode of direction, and their horizontal slice shape all is circular separately.

12. the electrolyzer of claim 10 is characterized in that, the horizontal slice shape of negative electrode (19) is identical with said at least one the shape of bipolar electrode (18).

13. the electrolyzer of claim 11 is characterized in that, the horizontal slice shape of negative electrode (19) is an annular.

14. claim 1,2,4,6,7,8,9,11,12 or 13 electrolyzer is characterized in that, said at least one bipolar electrode (18) is that the graphite with monolithic forms through machining.

15. claim 1,2,4,6,7,8,9,11,12 or 13 electrolyzer is characterized in that, said at least one bipolar electrode (18) is made with loose mail gluing of polylith graphite or mechanically connect together.

16. claim 1,2,4,6,7,8,9,11,12 or 13 electrolyzer, it is characterized in that, a plurality of bipolar electrodes (18) are arranged, and these bipolar electrodes draw out by means of milling machine operation that joint-cutting constitutes pole clearance (16) with monolithic graphite and machining is finished.

17. the electrolyzer of claim 15, it is characterized in that, each bipolar electrode (18) is to make with the upright circular segments of stacking of polylith, these circular segments are glued or machinery connects together and constitutes single electric going up and entity mechanically, and each circular segments all forms through machining with monolithic graphite.

18. the electrolyzer of claim 17, the bipolar electrode (18) that it is characterized in that having the upright circular segments of stacking of a plurality of usefulness to make, it is further characterized in that, these circular segments draw out by means of milling machine operation that joint-cutting constitutes pole clearance (16) with monolithic graphite and machining is finished.

19. claim 1,2,4,6,7,8,9,11,12,13,17 or 18 electrolyzer, it is characterized in that, said at least one bipolar electrode (18) is to make and at the panel that steel is housed on the anodic surface with graphite, and this Steel Facing is by means of gluing or mechanically connect and be fixed to graphite and get on.

20. the electrolyzer of claim 3 is characterized in that, has at least a joint (28) to be used for being connected on the cathodic bus bars (27a) on the negative electrode (19), this joint is supported on this unit block on the bus-bar.

21. claim 1,2,4,6,7,8,9,11,12,13,17,18,19 or 20 electrolyzer is characterized in that, in negative electrode inside the liquid level of electrolyte controlling organization are housed.

22. the electrolyzer of energy secondary metal from the molten electrolyte that contains metallic compound, this electrolyzer has cell body (12), include at least one inner electrolysis locellus (13) in the cell body, each electrolysis divides the indoor electrode assemblie that has at least, this assembly comprises an anode (17), a negative electrode (19) and at least one are placed on the bipolar electrode (18) between anode and the negative electrode, so that cause the pole clearance (16) that electrolytic action takes place, this assembly also comprises the lead-in wire (25 of carrying electric current toward electrolyzer, 27), this electrolyzer is characterised in that, negative electrode (19) is basically round said at least one bipolar electrode (18) and anode (17), negative electrode (19) and the bipolar electrode of at least one (18) are consolidated and consist of unit block, and this assembly can be used as a unit and is inserted in the electrolysis locellus (13) when electrolyzer is installed.

23. cell electrode assembly that can insert electrolyzer, electrolyzer is to be used for from the molten electrolyte that contains metallic compound secondary metal, this cell electrode assembly comprises at least one bipolar electrode (18) and negative electrode (19), it is characterized in that, each bipolar electrode (18) consist of mechanically with electric on single entity, negative electrode (19) is basically round the main electrolytic surface of bipolar electrode and fix bipolar electrode as a single cell.

24. the assembly of claim 23 is characterized in that, negative electrode (19) mechanically with electric on consist of one entity.

25. the electrolyzer of energy secondary metal from the molten electrolyte that contains metallic compound, this electrolyzer has cell body (12), include at least one inner electrolysis locellus (13) in the cell body, each electrolysis divides the indoor electrode assemblie that has at least, this assembly comprises an anode (17), a negative electrode (19) and carries the lead-in wire (25,28) of electric current toward electrolyzer, this electrolyzer is characterised in that to have a structure that liquid level of electrolyte controlling organization (40) are housed on the negative electrode (19).

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