CN85106624A - The electrolyzer of many batteries - Google Patents
The electrolyzer of many batteries Download PDFInfo
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- CN85106624A CN85106624A CN198585106624A CN85106624A CN85106624A CN 85106624 A CN85106624 A CN 85106624A CN 198585106624 A CN198585106624 A CN 198585106624A CN 85106624 A CN85106624 A CN 85106624A CN 85106624 A CN85106624 A CN 85106624A
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Abstract
The electrolyzer of many batteries is made of a plurality of elementary cell.Each elementary cell will keep in it pressing in the electrolyzer operational process and is higher than normal atmosphere.Above-mentioned multi-unit battery is coupled in series and connects power supply with polylith electric current guide plate.At assembling rigidity multiple contact electric installation between the adjacent multi-unit battery and/or between every electric current guide plate and the adjacent-cell battery, thereby setting up firm being electrically connected between the adjacent elementary cell and/or between every electric current guide plate and the adjacent-cell battery.
Description
The present invention relates to a kind of many batteries electrolyzer, the invention further relates to a kind of many batteries electrolyzer, this device is applicable to that electrolysis produces alkali metal hydroxide and chlorine from the hydrous alkali metal chloride soln, many batteries electrolyzer of the present invention is to be made of a plurality of elementary cells, each elementary cell comprises cathode compartment and the cationic exchange membrane that has an anodic anolyte compartment and have a negative electrode, and this exchange membrane is used for described elementary cell is partitioned into described anolyte compartment and cathode compartment.Each elementary cell is in the electrolyzer working process, and pressure will be kept above normal atmosphere in it.Described elementary cell is together in series and powers by a plurality of electric current guide plates, therefore assembling a kind of rigidity multiple contact electric installation between each adjacent elementary cell and/or between each electric current guide plate and this place's adjacent-cell battery, realizing being electrically connected between each adjacent unit of this device and/or between each electric current guide plate and this place's adjacent-cell battery.
Adopt this electrolyzer to come the example of electrolysis alkali metal chloride to comprise sodium-chlor, Repone K and lithium chloride, consider from the viewpoint of commerce, in all these examples, the electrolytic sodium chloride most worthy, about the electrolytic action of moisture sodium chloride solution, the present invention will elaborate hereinafter, but electrolyzer of the present invention should not a restriction be used for sodium-chlor.
As everyone knows, the electrolysis with ion-exchange film device that is used for moisture sodium chloride solution generally includes two types electrolyzer, that is: the electrolyzer of monopolar DC system and bipolar DC system.About this electrolyzer of two types, people had proposed various improvement before this.
For example, electrolyzer about bipolar DC system, the device that a kind of recommendation is arranged, thereby wherein adopt the explosive welding mode that the sidewall of adjacent elementary cell is welding together and (for example between adjacent-cell battery, realized electrical connection, can check United States Patent (USP) NO.4,111,779), also has a kind of device, wherein in electrolyzer, insert spring piece between the adjacent elementary cell, thereby provide electrical connection therebetween (for example, can check United States Patent (USP) NO.4,108,752), elementary cell is made of plastics in the another kind of recommended device, and adjacent-cell battery is (for example to realize electrical ties by means of screw bolt and nut, can check French Patent NO.2551234), also have with it similarly electrolyzer.
Electrolyzer about monopolar DC system, a kind of like this device was once proposed, in this device, a plurality of lead rods are inserted into implement distribution (for example, can check Japanese Patent Application Publication specification sheets NO.52-153877) in the electrolyzer, and another kind of electrolyzer, wherein, reduce the conductive area of electrolyzer the and directly terminal part of conducting plates and each electrode is connected and (for example, checks United States Patent (USP) NO.4,252,628).
Before this, the recommended various electrolyzers of being mentioned have carried out improving so that can be applicable to the electrolysis of salt solution intermediate ion exchange membrane.Because there are these shortcomings in they, as its device matching requirements formality complexity, between the adjacent-cell battery to electrically contact resistance bigger, the current density of electrolytic cell is inhomogeneous and to produce the expense of this device very high, so they still can not meet the demands.
In addition, it should be noted that the above-mentioned electrolyzer of mentioning commonly used owing to exist the shortcoming that alternately to exchange between monopolar type elementary cell and the bi-polar type elementary cell, therefore must prepare the elementary cell of a lot of respective type respectively according to the type of electrolyzer.
On the other hand, if the internal pressure that can keep electrolytic cell in the electrolyzer working process is during greater than normal atmosphere, the consumption that just can reduce the energy greatly (for example, can check United States Patent (USP) NO.4,105,515), if still with electrolyzer commonly used with above-mentioned various shortcomings of mentioning, although the interior pressure that keeps electrolytic cell during conduction is greater than normal atmosphere, owing to adopted boosting battery in fact can not reach gratifying effect.
Therefore, first purpose of the present invention is that a kind of many batteries electrolysis unit will be provided, in this device, contact resistance between adjacent each element cell and/or each battery guide plate and this adjacent-cell battery is littler, and the current density in these batteries equates that assembling is easy, and manufacturing cost With low.
Another object of the present invention provides a kind of many batteries electrolysis unit, can easily make this many batteries electrolysis unit with the form of ambipolar or monopole type, and used element cell is general to ambipolar or monopole type.
For foregoing of the present invention and other purposes, characteristic and advantage, the skilled work personnel in present technique field can clearly be understood in conjunction with the accompanying drawings according to following detailed working instructions and additional claim.
Fig. 1 represents the sectional view of an embodiment of the present invention, and Fig. 2 represents to be often used as the sketch into a kind of electrode vessel unit pattern of the anolyte compartment of the embodiment of Fig. 1 and cathode compartment, is the side-view that partly cuts the situation lower electrode at electrode.
Fig. 3 represents along the sectional view of Fig. 2 III-III line;
Fig. 4 (a) expression has a kind of pattern of orthographic plan of the rigid conductive thin slice of a plurality of ridges as the pad pattern;
Fig. 4 (b) presentation graphs 4(a) amplification profile of pad ridge;
Fig. 5 (a) expression has the another kind of pattern of orthographic plan of rigid conductive thin slice of the ridge of a plurality of mesoporous metal aperture plate patterns.
Fig. 5 (b) presentation graphs 5(a) part of the porous metal aperture plate skeleton view of Fang Daing;
Fig. 6 represents to be often used as the sketch of the another kind of electrode vessel unit pattern of the anolyte compartment of embodiment of Fig. 1 and cathode compartment, and this figure is that electrode part is divided the side-view when cutting;
Fig. 7 represents along the sectional view of Fig. 6 VII-VII line;
Fig. 8 represents the sectional view of another kind of electrode vessel unit pattern, and (in its edge section) has a groove on the sidewall in the electrode vessel unit, is used to install the frame shell that the synthetic resins material is made;
Fig. 9 represents the sectional view of an alternative embodiment of the invention, wherein, be equipped with rigidity multiple contact electric installation between adjacent elementary cell, and adjacent-cell battery has a kind of like this protrusion shape, this protrusion shape is to form on a sidewall surfaces of adjacent-cell battery;
Figure 10 represents the sectional view of the electrolyzer of a certain pattern of the present invention, and this electrolyzer is a kind of bipolar DC system, and assembles with the press filtration form;
Figure 11 represents the another kind of pattern of the side-view of electrolyzer of the present invention, and this electrolyzer is a kind of monopolar DC system and is to assemble with the press filtration form;
From Fig. 1 to Figure 11, represent identical parts and same section with same number without exception.And have to be noted that each parts and various piece size relationship each other not exclusively shows from Fig. 1 to Figure 11 in order to understand easily essential characteristic of the present invention, each figure is used for that present invention is described.
According to many batteries electrolysis unit provided by the present invention, it constitutes: a plurality of element cells;
Each element cell is made up of an anode chamber and a cathode chamber;
This anode chamber is by a frame shell, the plate object that metal sidewall and this frame shell are bound up and make, and the anode that the rib that can conduct electricity by polylith and sidewall weld forms;
This cathode compartment is by a frame shell, the plate object that metal sidewall and this frame shell are bound up and make, and the rib by multi-functional conduction is formed with the negative electrode of sidewall welding;
Be equipped with one deck cationic exchange membrane between the negative electrode of the anode of anolyte compartment and the cathode compartment adjacent with this anolyte compartment, therefore described anode and negative electrode all on its opposite respectively facing to this cationic exchange membrane;
Above-mentioned a plurality of elementary cells are together in series, and connect energising with polylith electric current guide plate;
Rigidity multiple contact electric installation;
Between the adjacent elementary cell and/or the rigidity multiple contact electric installation that assembles between every electric current guide plate and the adjacent elementary cell, therefore, install between a plurality of transmodulators at this and to set up fixed contact point; And, keep the interior pressure of each elementary cell to be higher than normal atmosphere wherein for making the electrolyzer operation normal.
Referring to figs. 1 through Fig. 4, expression the invention belongs to a kind of embodiment of bipolar DC system, each multi-unit battery is respectively by an anolyte compartment 14, a cathode compartment 16 and the cationic exchange membrane 12 between anolyte compartment 14 and cathode compartment 16 constitute, and anode 4 wherein and negative electrode 4 are in the face of being positioned at the cationic exchange membrane 12 on its opposite.Each anolyte compartment 14 and cathode compartment 16 be respectively by a frame shell 1, the plate object (as if Fig. 2 and Fig. 3 describe) that the metal sidewall that connects with this frame shell 12 is made and form with the electrode that sidewall 2 welds by the rib 3 that polylith can conduct electricity.Each piece conduction rib 3 has many holes 7 can make electrolyte solution and electrolysate circulation, and frame shell 1 has the inlet 5 and the outlet 6 of discharging electrolyte solution and electrolysate from the top that add electrolyte solution from the base.To electrolyte solution inlet 5 link to each other with a water supply water pipe (on figure, representing), and link to each other with header with electrolysate (on figure, not representing) by the electrolyte solution of flexible hose, in electrolyzer work, make to press in it for each elementary cell pressurization and keep greater than normal atmosphere.
Describe as above-mentioned and Fig. 1, a plurality of elementary cells are together in series.Each battery is respectively the sidewall 2 of anolyte compartment 14 and the sidewall 2 of cathode compartment 16 on their two sides.Two sidewalls 2 of adjacent-cell battery are oppositely arranged by a sealing coat again each other.(that is, at the above-mentioned sealing coat of mentioning) is equipped with rigidity multiple contact electric installation between adjacent-cell battery.In this embodiment, there is the conductive foil 18 of a plurality of ridges to be used as rigidity multiple contact electric installation.Equally, for example shown in Fig. 4 (a), conductive foil 18 still can be used as pad and uses.This pad is made up of rigid metal plate 8 and some ridges 9 of forming on metal sheet 8 by for example pressure method commonly used.In the present invention, " rigidity multiple contact electric installation " this term, its connotation just is meant the device that contacts with other major parts at a plurality of somes place, this device can conduct electricity, do not have rebound resilience, this device has such rigidity so that when electric installation being clipped between the pair of metal plate and the metal sheet both sides being applied quite or less than 3 kg/cm at this
2When restraining the pressure of (0.294 milli handkerchief), this electric installation does not deform in fact, and its thickness does not change yet.Rigidity multiple contact device has a plurality of ridges.As long as this device can satisfy requirement of the present invention, their kind and shape or pattern will not be restricted.As mentioned above, have the rigid conductive thin slice (as if the pad shown in Fig. 4 (a)) and the illustrated porous metal aperture plate of Fig. 5 (a) of many ridges, all can be used as rigidity multiple contact electric installation.Or use another kind of method instead.As shown in Figure 9, rigidity multiple contact electric installation is made up of a plurality of ridge that the sidewall surfaces of at least one elementary cell in the adjacent elementary cell forms.A kind of custom design of having represented rigidity multiple contact electric installation in Fig. 9 it should be noted that especially and does not cause sidewall to break or cause many holes when forming ridge on sidewall.Under the situation of the conductive foil shown in Fig. 4 (a) and Fig. 5 (a) with a plurality of ridges, needn't give special heed to the problems referred to above, also can be easy to carry out the processing of conductive foil.Generally speaking, in rigidity multiple contact electric installation, the diameter of each ridge can be 1.4 to 4.0 millimeters, preferably 1.5 to 3.0 millimeters, and the diameter of each ridge can be 2 to 10 millimeters, preferably 3 to 5 millimeters.The spacing of ridge can be 5 to 30 millimeters, preferably 10 to 20 millimeters.Have the conductive foil (for example shown in Fig. 4 (a) and Fig. 5 (a)) of a plurality of ridges, the thickness of its thin slice can be 0.3 to 2.0 millimeter, preferably 0.5 to 1.5 millimeter.
With reference to prior figures 1,8 signs of numeral have the conductive foil (as at the pad shown in Fig. 4 (a)) of a plurality of ridges, between the adjacent-cell battery, particularly accompany a conductive foil 18 between the sidewall 2 of the sidewall 2 of cathode compartment unit 16 and unit, anolyte compartment 14 so that make adjacent-cell battery between a plurality of point of contact, keep firm rigidity contact, thereby will be together in series between the adjacent-cell battery by conductive foil 18.
Multi-unit battery and conductive foil 18 are alternately to arrange, and as illustrated in fig. 10, and multi-unit battery is with the form formation of filter press type electrolyzer.In Fig. 1 and device shown in Figure 10, electrolyzer be monopolar DC system and comprise that a pair of electric current guide plate 19,19, this a pair of electric current guide plate are separately positioned on the two ends of the multi-unit battery that arranged in series gets up.In this case, fit on conductive foil 18 between every electric current guide plate 19,19 and the adjacent with it elementary cell is therefore at every electric current guide plate 19,19 with set up between the adjacent-cell battery with it and electrically connect.
As mentioned above, the electrolyzer operational process will keep the interior pressure of two elementary cells to be higher than normal atmosphere, so two sidewalls of each elementary cell outwards expand.Because such result, can really make make by conductive foil 18 on the sidewall areas of the elementary cell that is covered with a plurality of contacts between the adjacent-cell battery and every electric current guide plate 19,19 and adjacent elementary cell between the firm rigidity of maintenance contact.In this case, electrically contact resistance and reduce to minimum, the most important thing is to strengthen their contact pressure in order to make.In the present invention, by having the rigidity multiple contact electric installation of a plurality of ridges, can realize this contact, the contact pressure that therefore increases them in point of contact is the most favourable.So not only cause between the adjacent cell and every electric current guide plate 19,19 and adjacent-cell battery between contact resistance reduce to minimum degree, and cause that its current density reaches unanimity in electrolytic cell.In addition, should notice as mentioned above that this electrolyzer has simple structure, so this device is very easy to assembling, it is low to produce cost simultaneously.
We refer again to Fig. 2 and Fig. 3, usually a kind of electrode vessel that is used as anolyte compartment and cathode compartment is described, for forming inlet 5 and outlet 6, the thickness of frame shell 1 there is no particular restriction, and the frame shell has an enough intensity for this reason, but its thickness is generally 0.5 to 5.0 centimetre, preferably 1.0 to 3.0 centimetres.The starting material of the frame shell that is adopted among the present invention are not really strict, and comparatively the starting material of Shi Yonging are as zirconium, nickel, titanium and their alloy and various plastics such as polyethylene, polypropylene and polyvinyl chloride.But, in the middle of these materials,, preferably select metallic substance as preventing that from giving electrolyte solution leaks and improve the viewpoint of the physical strength of electrolyzer, the advantage that adopts these metals is because metal energy and sidewall are welded together to form whole structure.In addition, preferably select for use titanium or titanium alloy as the starting material of making anolyte compartment's frame shell.On the other hand, as the starting material of making the cathode chamber frame shell, can select to use titanium, nickel or their alloy be stainless steel for example.
Be welded in the conduction rib with sidewall 2 together, and then electrode 4 with 3 welding of conduction rib.Every inert material that is under electrolytic condition all is used as sidewall and conduction rib.For example, with regard to anode, the starting material that titanium or titanium alloy can be used as sidewall and conduction rib use.Simultaneously, with regard to cathode compartment, titanium, nickel and alloy thereof, for example stainless steel can be used as sidewall and conduction rib starting material use.
The outside surface of sidewall 2 preferably has the conductivity height, and the metallic coating that hardness is low is so that reduce the resistance that electrically contacts between sidewall and the sidewall adjacent with it and between sidewall and the electric current guide plate.This metalloid is just like copper, tin, aluminium or the like as above mentioned.When sidewall is when being made by titanium metal, the above-mentioned coating of mentioning is useful especially, because adopt this coating can give anti-titanium system sidewall generation layer oxide film.The method for preparing this type coating is very strict, and for example the technology of using usually has electroless plating, electroplates fusing spraying plating, and vapourdeposition.
Sidewall will have certain thickness, for example because the interior pressure of battery makes the suitable expansion of sidewall possibility and make sidewall more abundant with the welding of conduction rib.Preferably select its thickness to be about 1 to 3 millimeter scope in general.
Sidewall and frame shell connect each other so that make plate object.Illustrate from illustration, for example adopt welding, bolt connects, and binding agent bonding or the like can link to each other sidewall with the frame shell, preferably selects welding or binding agent bonding mode, because their advantage is to form one-piece construction.The above-mentioned material of making the frame shell by the plastics conduct of mentioning, this material is poor to electrolyte solution or electrolysate erosion resistance, when building sidewall, partly uses suitable plastic frame shell at the edge of sidewall recess, and relative section Fig. 8 in the back is described.
Have many holes 7 on conduction rib 3, these holes are that the circulation of electrolysis matter solution and electrolysate is used.Regulating does not almost have between the height (being equivalent to sidewall and distance between electrodes) of conduction rib 3 so that cationic exchange membrane 12 and the electrode 4 or does not have a space.When adjusting conduction rib 3, various factors (for example the width of frame shell 1 and packing layer 13 and 15 and the thickness of electrode 4) all to consider.From the battery top view, the position about the conduction rib preferably makes the conduction rib of anolyte compartment and cathode compartment arrange in an alternating manner.Conduct electricity rib as every of anolyte compartment conduction rib and cathode compartment every and see it is when being arranged in delegation from the apex angles of battery, if the height of rib is too big, then in a certain position, anode and negative electrode will have the danger of crushing positively charged ion alternate films, at this moment, in this position, will cause the conduction rib in the anolyte compartment to contact with the conduction rib of cathode compartment by anode exchange membrane and negative electrode, cause short circuit thus.On the other hand, when the conduction rib of anolyte compartment and the conduction rib of cathode compartment are observed from the apex angles of battery, be when arranging in the alternative mode, even the height of conduction rib is compared big slightly with desired height, and make the interval between film and the respective electrode approach zero, just the shape of electrode and/or metal sidewall need be become wavy pattern from dull and stereotyped pattern.This form can not only be eliminated near the crushed danger of film negative electrode and the anode, but and the interval convergence between the interval between film and the negative electrode and film and the anode zero.
As electrode 4, the most frequently used is porous electrode, for example by expanded metal, and perforation plate, composition such as bar-shaped, netted.The porous electroplax of being made up of perforation plate (perforation plate electrode) in the middle of them is more desirable, because the space between film and each electrode can vanishing and do not have the impaired danger of film.Perforation plate is by having many circles, ellipse, and square, rectangle, the porous plate of cruciform or shape like that is made.Normally the method with punching obtains these holes.The shape in hole is best with circle, because have circular pore volume easy-formation.The diameter in hole can be 0.5 to 6 millimeter scope, is preferably 1 to 5 millimeter.The porosity of perforation plate electrode can be 10 to 70% scope, is preferably 15 to 60%.When the diameter in hole and porosity too hour, the gas of generation is difficult to discharge.On the other hand, when the diameter in hole and porosity were too big, the current density in the cationic exchange membrane became inconsistent.
In the electrolysis of hydrous alkali metal chloride soln, use various anodes usually as electrolytic anode.For example used anode can be made up of as matrix titanium, zirconium, tantalum, niobium or their alloy, and be coated with the last layer platinum group metal oxide for example ruthenium oxide or similar substance are made a kind of anode activated coating surface on their surface.
The negative electrode that uses in the electrolyzer of this electrolyzer is that for example titanium, nickel or their alloy are made by metal, or makes matrix and formed with the cathodic activity coating that catalyzer nickel, thiocyanation nickel, nickel oxide or material like that constitute with these metals.
With reference to prior figures (4(a) and 4(b), as previously mentioned, the conductive foil with gasket shape is the best example with conductive foil of ridge, and this kind thin slice can be used as a type of rigidity multiple contact electric installation.Certainly, except at Fig. 4 (a) with the pad 4(b), there are various types of thin slices of many ridges to use at its one or both sides.The thickness of the conductive foil that is adopted is undemanding, but general range preferably uses porous metal aperture plate and the pad mention before this about 0.1 to 3 millimeter greatly, because they are very effective for the resistance that electrically contacts that reduces between the adjacent-cell battery and between every electric current guide plate and their adjacent-cell batteries to minimum degree.Dimensional requirement to conductive foil is undemanding, but preferably thin slice is extended to the whole zone of elementary cell sidewall 2, and its ridge preferably also requires to be distributed to the whole zone of elementary cell sidewall 2.The material that the conductive foil of many ridges is arranged can be any metal with high conductivity, for example copper, tin, aluminium, zirconium, nickel and their alloy stainless steel for example.
The liner 13 that is used for the anolyte compartment is used for sealing each electrode vessel with the liner 15 that is used for cathode compartment and leaks to prevent electrolyte solution, can rise having an even surface of cationic exchange membrane under the situation of the sealing function that gives anti-electrolyte solution leakage, generally can save one or two gasket.
Use has the liner 13 that anti-chlorine and some material manufacturings of rubber-like are used for the anolyte compartment.Optimum material is a chloroprene rubber, silicon rubber and material like that.Have second, propylene that the suitable material of the liner of using as cathode compartment 15 is worth mentioning are moulded rubber, chloroprene rubber, isobutylene-isoprene copolymer, viton and material like that.Liner 13 or 15 can be reinforced with the reinforcement fabric.
The thickness of liner that the present invention adopts to satisfy fully can hermetic electrolyte matter solution needs.Suitable thickness depends on the hardness of liner, yet general thickness is approximately 0.5 to 3 millimeter scope.
About the resinous type of cationic exchange membrane, can adopt for example mating type resin of sulfonic acid type, carboxylic acid type, sulfanilamide (SN) type and sulfonic acid and carboxylic acid.In the middle of them, the mating type resin of sulfonic acid and carboxylic acid is good especially, this resin can make some basic metal shift fast, with regard to the mating type resin, between unitary anode in anolyte compartment and the unitary negative electrode of cathode compartment, preferably assemble cationic exchange membrane, the result is coated with the Zeo-karb of last layer sulfonic acid group on one side at the anode of cationic exchange membrane, one side at the Zeo-karb that is coated with the last layer hydroxy-acid group of negative electrode.Resin matrix about cationic exchange membrane is considered from the viewpoint of anti-chlorine, adopts fluorocarbon resin the most favourable.In order to increase film strength, can use fabric, reticulation or material like that are reinforced.
With reference to Fig. 5 (a), a kind of hard conductive foil with many ridges that a kind of expanded metal is made is used in expression.Fig. 5 (b) illustrates is the part that porous metal that Fig. 5 (a) amplifies belong to the net skeleton view.The present invention preferably adopts the porous metal aperture plate, because they are very effective to reducing to electrically contact resistance.
Frame shell length of side of expression is approximately 1 meter or bigger electrode vessel unit among Fig. 6.In this case, if one of equipment strengthens rib 10 between the top margin of the centre portions of frame shell 1 and base, will help to reduce the thickness of sidewall 2 and frame shell.Expression is along the sectional view of Fig. 6 VII-VII line in Fig. 7.To strengthen that rib 10 usefulness are welded one of the top margin that maybe should be fixed by bolts to frame shell 1 and one on the base of frame shell 1.Enhancing rib 10 has many holes 7 to be convenient to electrolyte solution with water and the ionogen product passes, to get well and will not strengthen rib 10 with sidewall 2 welding, if rib 10 is welded with sidewall, because the interior pressure of elementary cell is not enough, the sidewall of elementary cell will outwards expand and cause the resistance that electrically contacts between the adjacent elementary cell and between each piece electric current guide plate and the adjacent-cell battery to increase.
The expression electrode vessel is the sectional view of another kind of form in Fig. 8, the frame shell that in electrode vessel, has plastic material to make, and the corrodibility ability of anti-electrolyte solution with water of this plastics or electrolysate is relatively poor.In this case, when building metal sidewall, be used for installing plastic frame shell (not showing) at the recess 11 of sidewall edge, the recess part of metal sidewall can adopt compacting, and method such as stretch or like that forms.
The sectional view of expression another kind of embodiment of the present invention in Fig. 9, wherein, the rigidity multiple contact electric installation of the present invention between adjacent elementary cell is the device in the ridge shape of a sidewall surfaces place formation of adjacent-cell battery.Owing to adopted a kind of like this structure, what therefore other just needn't be arranged has had the conductive foil device of a plurality of ridges.Make ridge 2 ' contact, set up the also similar ridge that is processed into of two sidewalls of conductive contactor battery to each other thus with opposite side wall 2.
Referring now to the sectional view of a kind of form of the represented electrolyzer of the present invention of Figure 10, this device is a bipolar DC system, and with filter die mould formula assembly construction, one side of cationic exchange membrane 12 links to each other with cathode compartment 14 by liner 13 and arranges.Another opposite side of cationic exchange membrane 12 links to each other with the anolyte compartment by liner 15 and arranges.Therefore parts 12,13,14,15 and 16 constitute three elementary cells 17.Multi-unit battery 17 is alternately arranged along with the conductive foil with many ridges, uses this distributing style, and the sidewall 2 of each anolyte compartment 16 is relative with the sidewall 2 of each cathode compartment 14.Electric current guide plate 19,19 is assembled at the two ends of the electrolyzer of arranged in series respectively, thereby and by the filter fastening framework of depressor so that vise elementary cell and the electric current guide plate constitutes the filter die mould electrolyzer of bipolar DC system of the present invention.The edge limited size of the size of electric current guide plate 19 and frame shell can be the same, reach evenly so that thereby the electric current guide plate contacts the current density that makes elementary cell with the sidewall in whole zone, coupling part 21 is connected with a rectifier by lead above the electric current guide plate.Need consider area and current density that electric current passes through,, therefore need to determine the thickness of electric current guide plate so that do not make the ohmic loss increase too big.
Can use metallic substance such as copper for the most suitable material of electric current guide plate, aluminium and suchlike material with high conductivity.
As mentioned above, electrolyzer of the present invention is when operation, and the interior pressure of each elementary cell will remain on and be higher than normal atmosphere.Method to each battery pressurization is not done special restriction.For example, but the air supply channel applying pressure variable valve of supply of hydrogen and chlorine is so that the gaseous tension that produces puts on the inside of elementary cell or supplies with the interior pressure of the circulation volume of electrolytic cell anode electrolytic solution and catholyte with suitable regulon battery with adjusting.The elementary cell pressure-controlling 0.2 to 3 kilogram force/centimetre
2The gram, be preferably 0.5 to 2.0 kilogram force/centimetre
2Gram.If the interior pressure of elementary cell is too low, between adjacent each elementary cell and the contact pressure deficiency between every electric current guide plate and the adjacent-cell battery, cause to electrically contact resistance and increase.On the other hand, if the interior pressure of elementary cell is too high, then the structure that must change electrolyzer so just causes the too high shortcoming of cost of device with anti-high pressure.
Top narration is mainly at bipolar DC system, and still, the present invention also can effectively be used for the electrolyzer of monopolar DC system, referring now to Figure 11, the figure shows the side-view of the another kind of form of electrolyzer of the present invention, this device is a monopolar DC system, builds with filter die mould assembling form.In the electrolyzer of the type, multi-unit battery 17 is alternately arranged along with being positioned over electric current guide plate 19 therebetween.Between the sidewall of a pair of anolyte compartment 17, insert electric current guide plate 19.Rigidity multiple contact electric installation is housed between each sidewall and the electric current guide plate 19 sets up electrically contacting to each other.Similarly, between the sidewall of cathode compartment, put into the electric current guide plate and set up electrically contacting each other by rigidity multiple contact electric installation.Then, electrolyzer is powered by every electric current guide plate.
As mentioned above, according to the present invention not only can reduce greatly between the adjacent-cell battery and every electric current guide plate and adjacent-cell battery between electrically contact resistance but also can make the current density of elementary cell reach even, therefore, this electrolyzer can be in current density up to 30 amperes/decimeter
2Or bigger time running.In habitual electrolyzer, be equipped with a kind of flexible contact device between the adjacent-cell battery, therefore, can not obtain high press contacts owing to shock absorption between the adjacent-cell battery, this situation with electrolyzer of the present invention is opposite.
The present invention will be described in detail according to following application example, but these examples are not construed as limiting scope of the present invention.
The example I
Many batteries of bipolar DC system electrolyzer (being similar to shown in Figure 10) is by a pair of elementary cell, cationic exchange membrane, and three multiple contact electric installation thin slices and a pair of electric current guide plate are formed.Each elementary cell comprises unit, an anolyte compartment and a cathode compartment unit, and the unitary size in anolyte compartment is identical with the unitary size of cathode compartment.Promptly be that the unitary frame shell of electrode vessel width is 2400 millimeters, highly be 1200 millimeters, and thickness is 20 millimeters.The limit of each frame shell is 20 millimeters deeply, and the unitary frame shell in anolyte compartment is to be made of titanium, and cathode compartment unit frame shell is to be made by stainless steel.Adopting height is 20 millimeters, and wide is 5 millimeters, and length is that 1160 millimeters reinforcing rib strengthens unit, anolyte compartment and unitary each the frame shell of cathode compartment.The mid-way of the internal surface on the internal surface of the top of reinforcing rib and frame shell and the base of frame shell welds together.Reinforcing rib has the hole of 10 8 mm dias, is used as and passes electrolyte solution and electrolysate.These holes vertically are arranged in and reinforce in the rib.
The unitary metal sidewall in each anolyte compartment, wide is 2400 millimeters, and height is 1200 millimeters, and thickness is 2 millimeters, and metal sidewall and frame shell is combined make plate object with the frame shell is welded together.
Many in electrode vessel unit conduction ribs and frame shells and metal sidewall are welded together, many conduction ribs are welded in after frame shell and the sidewall, the conduction rib with the minor face parallel space of frame shell in place with 12 centimetres interval, from the top view of battery, arrange placement from over-over mode as the unitary conduction rib in anolyte compartment with as the unitary conduction rib of cathode compartment.
Being used for the unitary every conduction rib height in anolyte compartment is 20 millimeters, and wide is 5 millimeters, and length is 1160 millimeters, is 22 millimeters and be used for the unitary every conduction rib height of cathode compartment, and wide is 5 millimeters, and length is 1160 millimeters, and every conduction rib has
Individual right angle is 8 millimeters hole, so that can allow electrolyte solution and electrolysate by these holes.These holes vertically are arranged on the conduction rib.
Metal sidewall and conduction rib are by making with frame shell identical materials.That is, being used for the unitary metal sidewall in anolyte compartment is to be made by stainless steel with the conduction rib.The outside surface of the unitary metal sidewall in anolyte compartment electroless plating method plated with copper.
Preparation anodic method is to adopt to hole on titanium mesh, and its aperture is 2 millimeters, the hole be arranged as zig-zag, pitch of holes is 3 millimeters, also can adopt what be made up of ruthenium, iridium, titanium and zirconium to contain the oxygen solid solution at the surface of metal titanium electric plating method.Annode area is of a size of 272 square decimeters, by many conduction ribs anode is welded with sidewall.
The method for preparing negative electrode is to adopt to hole on stainless steel plate, and its aperture is 2 millimeters, the hole be arranged as zig-zag, pitch of holes is 3 millimeters, the size of negative electrode is the same with anode.
As the rigid conductive thin slice, can adopt at the expanded metal shown in Fig. 5 (a) and Fig. 5 (b), it is made by stainless steel plate, its thickness (tg) is 1.5 millimeters, the minor axis of expanded metal (WS), major axis (WL) and highly be respectively 7 millimeters, 14 millimeters and 3 millimeters, the size of expanded metal is identical with the area of frame shell regulation.
Thickness is that 4 millimeters copper coin can be used as electric current guide plate usefulness.
As the liner of anolyte compartment with as the liner of cathode compartment is that the ethylene-propylene rubber that 0.5 millimeter viton and thickness are 2.5 millimeters prepares with thickness respectively, and the shape and size of each liner are identical with the shape and size of frame shell.
The production method of used cationic exchange membrane is as follows:
Tetrafluoroethylene and perfluor-4,7-2 oxygen-5 methyl-8-sulfonic acid fluoride nonene copolymerization, thus obtaining two kinds of polymkeric substance, that is: equivalent is that 1300 polymkeric substance 1 and equivalent are 1300 polymkeric substance 2.
It is the laminating material and thick thin slice polymkeric substance 2 laminating materials of 100 μ of thin slice of the polymkeric substance 1 of 35 μ that these polymkeric substance obtain thick through hot pressing.By teflon (tetrafluoroethylene) preparation yarn fabric is to adopt the vacuum pressing method that tetrafluoroethylene is embedded into one side of polymkeric substance 2 thin slices, the stratification goods through saponification to obtain the sulfonic acid type ion exchange membrane.This synusia is made up of polymkeric substance 1 thin slice of ion-exchange membrane, and processing makes sulfonic acid type change carboxylic acid type into thereby it is through reduction reaction, therefore can obtain cationic exchange membrane.
The device of electrolyzer is similar to form class shown in Figure 10, thereby makes cationic exchange membrane contain the carboxylic acid face towards negative electrode.
The electrolysis of sodium chloride solution is implemented as follows: thus be that the sodium chloride solution of 310 grams per liters is supplied with the anolyte compartment to make the concentration of the sodium chloride solution in exit be 175 grams per liters with concentration.On the other hand, be 30% thereby diluted sodium hydroxide solution is delivered to the weight ratio that cathode compartment makes the concentration sodium hydroxide in exit, electrolytic other conditions are as follows:
Electrolysis temperature: 90 ℃
Current density: 40 amperes/decimeter
2
The external pressure of cathode compartment: 1.82 kilogram forces/centimetre
2Gram
The external pressure of anolyte compartment: 1.46 kilogram forces/centimetre
2Gram
When electrolysis, current efficiency and cell voltage are respectively 96.0% and 6.7 volt.
Example 2
The actual form class with example 1 of the electrolytic process of sodium chloride solution seemingly, unless replace expanded metal as the inflexible conductive foil with the pad shown in Fig. 4 (a) and Fig. 4 (b).This pad comprises 0.8 mm thick (t
1) stainless steel plate 8(many ridges 9, its diameter (w are arranged on its one side
1) be 3 millimeters, the degree of depth (H
1) be 2 millimeters).Arrangement pitches (d between the ridge
1) be 20 millimeters and spacing (d
2) be 17.5 millimeters, the sharp-crested diameter of each ridge is 1 millimeter.
When electrolysis, current efficiency and cell voltage are respectively 96.0% and 6.6 volt.
Claims (5)
1, many batteries electrolyzer is characterized in that comprising:
A plurality of elementary cells;
Each elementary cell is made up of unit, an anolyte compartment and a cathode compartment unit;
This unit, anolyte compartment is by a frame shell, the plate object that metal sidewall and this frame shell are bound up and make, and form by many ribs and the anodes that are welding together of described sidewall that can conduction;
This cathode compartment unit is by a frame shell, metal sidewall and this frame shell be bound up the plate object made and by many can conduction ribs and the negative electrode that described sidewall is welded together form;
Load onto a kind of cationic exchange membrane between unitary anode in anolyte compartment and the unitary negative electrode of cathode compartment adjacent with this unit, anolyte compartment, therefore, anode and negative electrode are all faced described cationic exchange membrane respectively;
Above-mentioned multi-unit battery is together in series and switches on the connection of polylith electric current guide plate;
Rigidity multiple contact electric installation;
Be equipped with rigidity multiple contact electric installation between the adjacent elementary cell and/or between every electric current guide plate and the adjacent elementary cell, therefore firmly contacting setting up between many point of contact near this device; And wherein for making the electrolyzer operation normally will keep the interior pressure of each elementary cell to be higher than normal atmosphere.
2, according to the electrolyzer of claim 1, many protruded objects that wherein said rigidity multiple contact electric installation is formed by the surface of at least one sidewall of elementary cell are formed.
3, according to the electrolyzer of claim 1, wherein above-mentioned rigidity multiple contact is led device and is made up of the rigid conductive thin slice pattern with many ridges.This rigid conductive thin slice is to be clipped between the adjacent-cell battery and/or to be clipped between each electric current guide plate and the adjacent-cell battery.
4, according to the electrolyzer of claim 3, wherein said rigid conductive thin slice with many ridges can be the pattern of pad or expanded metal.
5, according to the electrolyzer of any one claim of claim 1 to 4, wherein, the internal pressure that keep each elementary cell be 0.2 to 3 kilogram force/centimetre
2Gram.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP145821/85 | 1985-07-04 | ||
| JP60145821A JPS627885A (en) | 1985-07-04 | 1985-07-04 | Multipair electrolytic cell for alkali chloride using ion-exchange membrane method |
| JP60-145821 | 1985-07-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85106624A true CN85106624A (en) | 1987-04-29 |
| CN85106624B CN85106624B (en) | 1988-12-07 |
Family
ID=15393909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85106624A Expired CN85106624B (en) | 1985-07-04 | 1985-09-02 | Multi-cell electrolyzer |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS627885A (en) |
| CN (1) | CN85106624B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103384732A (en) * | 2011-02-25 | 2013-11-06 | 旭化成化学株式会社 | Large electrolytic vessel and electrolysis-stopping method |
| CN104005045A (en) * | 2014-06-11 | 2014-08-27 | 北京首位能源科技有限公司 | Extendable combined multi-polar electrolytic bath |
| CN109154090A (en) * | 2016-05-26 | 2019-01-04 | 卡勒拉公司 | Anode unit piece installing, contact band, electrochemical cell and its use and manufacturing method |
| CN110607533A (en) * | 2018-06-14 | 2019-12-24 | 松下知识产权经营株式会社 | Electrochemical hydrogen pump |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316063C (en) * | 2004-04-09 | 2007-05-16 | 阜新竞欣电化有限责任公司 | Press filter type multi-electrode ion film unit electrolytic tank |
-
1985
- 1985-07-04 JP JP60145821A patent/JPS627885A/en active Pending
- 1985-09-02 CN CN85106624A patent/CN85106624B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103384732A (en) * | 2011-02-25 | 2013-11-06 | 旭化成化学株式会社 | Large electrolytic vessel and electrolysis-stopping method |
| CN104005045A (en) * | 2014-06-11 | 2014-08-27 | 北京首位能源科技有限公司 | Extendable combined multi-polar electrolytic bath |
| CN109154090A (en) * | 2016-05-26 | 2019-01-04 | 卡勒拉公司 | Anode unit piece installing, contact band, electrochemical cell and its use and manufacturing method |
| CN109154090B (en) * | 2016-05-26 | 2021-08-06 | 卡勒拉公司 | Anode assembly, contact strip, electrochemical cell, and methods of use and manufacture thereof |
| US11142834B2 (en) | 2016-05-26 | 2021-10-12 | Calera Corporation | Anode assembly, contact strips, electrochemical cell, and methods to use and manufacture thereof |
| CN110607533A (en) * | 2018-06-14 | 2019-12-24 | 松下知识产权经营株式会社 | Electrochemical hydrogen pump |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS627885A (en) | 1987-01-14 |
| CN85106624B (en) | 1988-12-07 |
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