CN1407137A - Bipolar type natural-circulation ion-exchange membrane electrolyzer - Google Patents
Bipolar type natural-circulation ion-exchange membrane electrolyzer Download PDFInfo
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- CN1407137A CN1407137A CN01142002.2A CN01142002A CN1407137A CN 1407137 A CN1407137 A CN 1407137A CN 01142002 A CN01142002 A CN 01142002A CN 1407137 A CN1407137 A CN 1407137A
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Abstract
A multi-electrode ion membrane electrolyzer with natural circulation is composed of electrolyzer units, semi-units of electrolyzer at ends, sealing sheets between adjacent electrolyzer units and ion exchange membrane. In anode chamber there are longitudinal and transverse guide tubes and liquid separating plate. Its advantages are high circulating effect and sealing performance, and not foaming and layering of ion membrane.
Description
(1) technical field
The present invention relates to a kind of bipolar type natural-circulation ion-exchange membrane electrolyzer, belong to the electrolyzer field in the chlorine industry in the chemical industry.
(2) background technology
At present, majority state is at the various ion-exchange membrane electrolyzers of chlorine industry in the world, and bipolar type natural-circulation ion-exchange membrane electrolyzer is a kind of low pressure reduction, low discharge, solution internal recycle electrolyzer.Existing bipolar type natural-circulation ion-exchange membrane electrolyzer mainly is made of a plurality of unit electrolytic baths, between unit electrolytic bath, be sealed with ion-exchange membrane by gasket, unit electrolytic bath by back-to-back the configuration, cathode disc that on conductive path, connects and anode disc, the framework that constitutes by four frames, be welded to the moon by the conduction gusset, negative electrode on the anode disc and anode and the moon, the gas-liquid separation box that upper portion of anode chamber is divided is formed, cathode disc and anode disc for around with the discoid component of sidewall, sidewall at cathode disc and anode disc has import and the effusive outlet of electrolysis product that the electrolysis material enters respectively, import lays respectively at the moon, on the lower wall of anode disc, outlet lays respectively at the moon, on the anode disc upper side wall, be installed with thrust-augmenting nozzle in the anodic bottom.Though the bipolar type natural-circulation ion-exchange membrane electrolyzer of this kind structure can be produced alkali lye when using, but it in use damages ion-exchange membrane easily in a short time, this is because in the electrolyzer reaction process, the anolyte compartment in below the solution rising relatively poor, the strength of solution of formation bottom is lower, cause that at 0～20cm place, distance bottom film bubbles, cause film to damage, bath voltage raises, and ion-exchange membrane is expensive, the damage of ion-exchange membrane must the rising cost, and influence is produced; On the top near the salt water inlet, because row's chlorine is not smooth, interlayer appears in ionic membrane in addition; Gas-liquid separation box rigidity is not enough, reveals easily.And this a bipolar type ion-exchange membrane electrolyzer manufacturing process complexity, the manufacturing cost height.
(3) technology contents
At the problems referred to above, the present invention designs a kind of rational in infrastructure, be easy to the bipolar type natural-circulation ion-exchange membrane electrolyzer of processing and manufacturing, it not only can make, and strength of solution is tending towards even in the anolyte compartment, prevent that the ionic membrane foaming from damaging, and guarantee that electrolyzer is not yielding, prolong the work-ing life of electrolyzer.
Bipolar type natural-circulation ion-exchange membrane electrolyzer among the present invention is mainly by unit electrolytic bath, end half-cell electrolyzer, the gasket and the ion-exchange membrane that are installed between the unit electrolytic bath constitute, the half-cell electrolyzer of unit electrolytic bath end and ion-exchange membrane are mounted to electrolyzer integral body by the sealing of fixed press device, wherein unit electrolytic bath by back-to-back the configuration, the cathode disc that on conductive path, connects, the groove frame that frame constituted around anode disc reached constitutes, anode disc and cathode disc for around with the discoid component of sidewall, anode and negative electrode are welded to respectively on anode disc and the cathode disc by the conduction gusset, in anode disc and anode, form the anolyte compartment, in cathode disc and negative electrode, form cathode compartment, sun, the top of cathode compartment has respectively and sun, the gas-liquid separation box that cathode compartment is communicated with, sidewall at cathode disc and anode disc has import and the effusive outlet of electrolysis product that the electrolysis material enters respectively, import lays respectively at the moon, on the lower wall of anode disc, outlet lays respectively at the moon, on the anode disc upper side wall, have thrust-augmenting nozzle and liquid separatnig plate in the said anolyte compartment, vertically have thrust-augmenting nozzle at anolyte compartment's entrance end, 2～15mm place, transverse distance bottom is installed with horizontal thrust-augmenting nozzle, have fluid hole below it, a side of close exit end is equipped with the thrust-augmenting nozzle longitudinally more than two or two in the anolyte compartment, liquid separatnig plate is positioned at horizontal thrust-augmenting nozzle outer lower portion near import one end, and the base of liquid separatnig plate is not less than 1.5mm far from the distance of the bottom of anolyte compartment.
In the above-mentioned structure, the length of liquid separatnig plate is not less than half of horizontal thrust-augmenting nozzle length.
In said structure the height of vertical thrust-augmenting nozzle of the indoor close exit end of anode be not less than the anolyte compartment vertically height 2/3.
Middle part in the anolyte compartment also is equipped with vertical thrust-augmenting nozzle, and its height is in 1/2～1/3 scope of the vertical height in anolyte compartment, and is even with liquid mixing in the enhancing anolyte compartment.
Horizontal thrust-augmenting nozzle bottom in the anolyte compartment with fluid hole be positioned near exit end one side.
For saving the distortion of precious metal material, convenient processing and minimizing cathode and anode card, side frame and bottom frame at the cathode and anode dish adopt the board plug type fixed connection structure, have plate in the middle of the trim inboard of frame appearance, the frame main body has corresponding slot, plate with wear pin after slot is seated and cooperate and form frame, fixing around the anode and cathode dish with the trim welding.
Directly welded by bending of negative electrode card and frame main body at the top of cathode compartment frame and to form, the top frame of anolyte compartment then is connected with frame main body rivet by the bending of anode card.
For rigidity and the intensity that improves the gas-liquid separation box, weld with the cathode and anode dish by the porous plate of bottom and sealing side plate at the gas-liquid separation box on cathode and anode dish top and to form.
For the chlorine that can better anode be produced is discharged, the protection ionic membrane, the present invention installs the chlorine vent pipe at the gas-liquid separation box sidepiece of anode side.
Negative electrode in the unit groove of the present invention is made after the caustic corrosion activation treatment by stainless steel substrate, with enhanced activity, and prolongs life.
The designed bipolar type natural-circulation ion-exchange membrane electrolyzer of the present invention is when using, produce the density difference that gaslift effect that gas forms and concentration difference form when utilizing itself peculiar flow-guiding structure and electrolysis, cathode and anode liquid is circulated in electrolyzer inside, and make solution even in internal mix, under low pressure reduction, low discharge situation, carry out effective electrolysis.Especially in the anolyte compartment, eliminate the bottom dead in working cycle, make anolyte all participate in circulating, the protection ionic membrane is without prejudice.
The designed bipolar type natural-circulation ion-exchange membrane electrolyzer of the present invention has following advantage:
1. unit electrolytic bath is not yielding, the quality of fit height.This is owing to adopted board plug type combination frame bar structure, not only cost is low, can solve the connectivity problem between the cathode and anode differing materials, and formed frame rigidity is stronger, in use not yielding, its trim can reach the accurate dimensions requirement by common machining, guarantees pole span size accurately;
2. each parts in the electrolyzer are easy to processing, and especially the cathode and anode dish can be shaped with general device, and are easy to install;
3. the trim sealing is reliable, is difficult for leaking;
4. the circulation of groove electrolyte inside is abundant, and the reaction dead band can not formed at the bottom, anolyte compartment, can not cause the ionic membrane bottom to bubble;
5. the gas discharge is unobstructed, can not cause ionic membrane to damage because of the long-pending dry combustion method of the gas stasis of blood.
The designed bipolar type natural-circulation ion-exchange membrane electrolyzer of the present invention is mainly used in produces high purity alkali metal oxyhydroxide.
(4) description of drawings
Fig. 1 is the structural representation of the designed electrolytic cell assembly of the present invention.
Fig. 2 is the structural representation of unit electrolytic bath among Fig. 1.
Fig. 3 is that both sides are connected sketch with bottom frame place among Fig. 2.
Fig. 4 is that frame place, Fig. 2 middle and upper part connects sketch.
Fig. 5 is a unit electrolytic bath groove frame assembling synoptic diagram among Fig. 2.
Fig. 6 is the structure diagram of anolyte compartment's side among Fig. 2.
Fig. 7 is the chlorine vent pipe structure iron that anode gas-liquid separation box is connected among Fig. 6.
Fig. 8 is another kind of chlorine vent pipe mode of connection sketch.
Fig. 9 is a gas-liquid separation box structure diagram.
(5) embodiment
Below in conjunction with accompanying drawing embodiments of the present invention and effect thereof are further described.
The bipolar type natural-circulation ion-exchange membrane electrolyzer device that the present invention as shown in Figure 1 is designed, mainly by a plurality of unit electrolytic baths 4, the half-cell electrolyzer at two ends comprises positive pole terminal groove 5 and cathode terminal groove 2 compositions, unit electrolytic bath 4 and half-cell electrolyzer 2,5 by side lever 3 serial connections, side lever 3 is by preceding fixedly termination 1 and fixedly termination 7 fixed installations of back, be sealed and installed with ionic membrane by gasket between the adjacent unit electrolytic bath and between unit electrolytic bath and the half-cell electrolyzer, compress by the groove frame of oil gear 8 promotion activity terminations 6 unit groove, the gangway of groove frame links to each other with the manifold, forms a complete electrolyzer.
In this electrolytic cell assembly, the structure of unit electrolytic bath as shown in Figure 2, mainly by the cathode disc that on conductive path, connects 41 that disposes back-to-back, anode disc 33 and surrounding groove frame constitute, the groove frame by surrounding assembly welding frame bar 31 together as the frame main body, frame bar 31 both sides are put cathode disc 41 and anode disc 33 into, cloudy, add weldering negative electrode conduction gusset 40 and anode conducting gusset 34 on the anode disc respectively, at the moon, burn-on respectively on the anode conducting gusset negative electrode 42 and anode 35, respectively by dish, gusset, electrode is formed cloudy, the anolyte compartment, two middle many conducting platess 44 of burn-oning of dishes, conducting plates 44 is a titanium steel composite board, conducts electricity connection.Cathode compartment top is provided with catholyte gas-liquid separation chamber 43, and upper portion of anode chamber is provided with anode gas-liquid separation chamber 32, and the anolyte compartment also is provided with thrust-augmenting nozzle 36 and liquid separatnig plate 37.Cathode disc 41 can be by high chromium nickel stainless steel, the nickel panel material bending and molding of anticorrosion stress-resistant, anode disc 33 can be by titanium plate bending and molding, negative electrode 42 can be used stainless steel caustic corrosion activated cathode, and anode 35 can draw in the net plate or porous plate with the titanium that applies polynary platinum metals oxide compound such as ruthenium-iridium-tantalum zirconium; Negative electrode conduction gusset 40 can be used alkali corrosion resistance materials such as stainless steel, nickel, and anode conducting gusset 34 can be used materials such as titanium plate.Cathode disc 41 is formed cathode compartments with negative electrode 42, negative electrode gusset 40, and anode disc 33 is formed anolyte compartments with anode 35, anode gusset 34, and connection is conducted electricity by many conducting platess in centre 44 in two Room, and conducting plates 44 directly is welded on the cathode and anode dish.Cathode side trim 39 can be used alkali corrosion resistance materials such as stainless steel, nickel, and anolyte compartment's trim 38 can be used anti-crevice corrosion materials such as titanium palldium alloy plate.Cathode side trim 39 and anode side trim 38 are fixed in the side frame and the lower frame appearance of cathode and anode, its syndeton as shown in Figure 3, trim and frame adopt the socket connection mode, trim rigidly fixes with frame bar 31 with pin 62 by insertion lath 61 and is connected, be welded to connect between dish and trim, when unit electrolytic bath was squeezed, squeeze was transmitted by trim, frame bar, do not influence conduction gusset and electrode structure in the dish, make the dish inner structure more stable.This structure has not only solved the fixedly connected problem that can't weld between the unlike material, and compare with existing both sides clamp region form, reduced the precious metal usage quantity, avoid influencing weldquality because of repeating welding, make electric groove leak the problem that hidden danger increases, and make groove frame appearance more attractive in appearance.Anode seal face uses the splendid titanium palladium plate of anti-crevice corrosion, and the negative electrode trim uses the Ultralow Carbon Stainless Steel plate.Carry out the surface again behind trim and the dish assembly welding and mill processing, guarantee groove frame trim planeness.The structure of the upper side frame of cathode and anode as shown in Figure 4, directly weld fixing with frame bar 31 behind cathode disc 41 bending and moldings, anode disc 33 top bending walls adopt rivet 72 to be connected with frame bar 31, solved the connectivity problem between two kinds of unlike materials that can't directly weld, both convenient, practical again, without specific equipment processing dish, and rigidity is plugged in the Flat Steel Bar form after also being better than existing dish bending after connecting.
Between adjacent unit electrolytic bath, be packaged with ionic membrane 23, its structure as shown in Figure 5, stick negative electrode caulking gum pad 22 on the cathode side trim, stick anode seal rubber sheet gasket 24 on the anode side trim, the cathode compartment of a groove frame is facing to the anolyte compartment of another groove frame, ionic membrane 23 of sandwich.When the groove frame was subjected to certain snap-in force jam-packed, groove frame trim was under the effect of anode and cathode pad, and favorable sealing property electrolyte leakage can not take place.
Anode seal 24 adopts rubber cushion and coats the gasket seal that the anticorrosion film integral sulfuration of tetrafluoro novel process is made, long service life.
Anode employing structure as shown in Figure 6 at unit electrolytic bath, anolyte inlet connection 84 has sacrificial electrode, its place, diagonal angle is an anolyte downstream end 88, and anodic dorsal part cathode compartment bottom has catholyte inlet connection 89, and its place, diagonal angle is a catholyte downstream end 81.The anolyte compartment is abundant for indoor circulation of elecrolyte, be provided with vertical thrust-augmenting nozzle 82 of 80, lower, transverse thrust-augmenting nozzles 36 of vertical thrust-augmenting nozzle at 87, middle parts of at least two vertical thrust-augmenting nozzles of right part and at least one left part, the ingress is provided with breaker plate 83, and the bottom is provided with liquid separatnig plate 37.Vertically the height of thrust-augmenting nozzle 87 is 2/3 of the vertical height in anolyte compartment, vertically the height of thrust-augmenting nozzle 80 is 1/3 of the vertical height in anolyte compartment, anode side top is provided with the gas-liquid separation box, bottom thrust-augmenting nozzle 36 is installed near 7mm place, bottom side in the bottom, anolyte compartment, the bottom thrust-augmenting nozzle is near the liquid separatnig plate 37 of burn-oning between half part of inlet side and bottom side, liquid separatnig plate 37 downsides and the about 1.5mm of bottom plate inwall.Bottom, anolyte exit is provided with two right part thrust-augmenting nozzles 87 at least, just can make the electrolytic solution internal recycle carry out fully reacting completely.
The dead band occurs in order to overcome the circulation of prior art anode electrolytic cell bottom solution, cause strength of solution on the low side, damage ionic membrane, electrolyzer adopts said structure.Because trough rim frame bottom side solution is not easy to rise, insufficient density loss that causes easily circulates, for the bottom side strength of solution is fully guaranteed, lower, transverse thrust-augmenting nozzle 36 is improved in bottom 7mm, inlet salt solution is under the effect of breaker plate 83, flowing in short range space between bottom thrust-augmenting nozzle 36 and dish, thereby improves bottom side solution.In order to make inlet salt solution fully reach the rightmost side, add one section liquid separatnig plate 37 in the lower-left side, make liquid separatnig plate 37 lower ends and chassis inwall spacing guarantee 1.5mm.In order to increase the water conservancy diversion effect of thrust-augmenting nozzle 36, on bottom thrust-augmenting nozzle 36 lower walls processing Φ 3 pod apertures 85 several, thrust-augmenting nozzle 36 interior solution sub-fractions in bottom can be mixed with bottom side solution, and this not only strengthens tank room internal recycling amount, and improves bottom solution concentration distribution homogeneity.In addition, in the anolyte exit gas outlet pipe 91 is installed also, its structure also can adopt the structure formation of gas outlet pipe 92 as shown in Figure 8 as shown in Figure 7.It is because the interior viscosity of product chlorine of anode side tank room own is strong that gas outlet pipe 91 or gas outlet pipe 92 are installed, under low internal circulating load situation, be not easy to discharge outdoor with liquid, and gas is when going out with the electrolytic solution overflow, with form discharge at intermittence, form the gas-liquid turbulence, cause top, anolyte inlet connection 84 places to form high bubble rate district easily near gas-liquid separation box place, the easy dry combustion method when high current density moves of ionic membrane this moment damages.After increasing gas outlet pipe 91, chlorine is discharged and is connected with collector tube by dedicated line, the gas-liquid separation speed and the gas velocity of discharge are accelerated, thoroughly solve high bubble rate district problem, prolong the work-ing life of film, perhaps on frame bar above the anolyte ingress, draw at least one gas outlet pipe 92, be used to guide end gas smooth and easy discharge, thoroughly solve end gas and assemble the problem that is not easy to discharge.
The gas-liquid separation box adopts structure as shown in Figure 9 in said structure, anode disc 33, anode seal panel 112 and porous plate 113 are formed anode side gas-liquid separation box 32, and cathode disc 41, negative electrode trim side plate 115 and porous plate 116 are formed cathode side gas-liquid separation box 43.Sealing panel 112 and 115 adopts than heavy-gauge sheeting, respectively with porous plate 113 and 116 intermittent weldings after, again with anode disc 33 and cathode disc 41 overlap joints, and then mill and process trim and step 110 and 117, the gas-liquid separation box structure rigidity of this form is good, not yielding when being squeezed, good seal performance has overcome the shortcoming that prior art thin plate flexible structure in use is out of shape, is easily leaked.
When using, inject saturated brine in the anolyte ingress, salt solution is subjected to breaker plate 83 effects above inlet connection 84, to the left, upper right side, lower right side flow.Left part thrust-augmenting nozzle 82 and middle part thrust-augmenting nozzle 80 inside and outside solution are because gas-liquid distributes different, cause density different, solution density is greater than the outer solution of pipe in the pipe, solution is under the density difference effect, and solution is constantly dirty in the pipe, drives the outer solution of pipe and constantly replenishes, form left part solution internal recycle, the fresh salt solution that the left side constantly replenishes mixes with left part solution, and the left part solution density is dropped to below the prescribed value.Middle right part solution constantly mixes with fresh supplemented salt solution, and flows to the right.Top solution is because bubble rate is higher, and the inside and outside solution density difference of right part thrust-augmenting nozzle is big, in the pipe solution constantly along thrust-augmenting nozzle 87 toward dirty, manage outer certain altitude place solution and continues to flow into and replenish formation right part solution circulated.The solution that flows downward in the pipe flows out along bottom thrust-augmenting nozzle 36 and mixes with the fresh salt solution in ingress, adds reaction again.A solution part is mixed by the extremely weak solution of pod apertures 85 outflows and bottom side flowability in the bottom thrust-augmenting nozzle 36, and bottom solution is also mixed with the fresh salt solution that inlet side is come simultaneously, and bottom solution is guaranteed in certain concentration, in case form the reaction dead band.
The electrolyzer that uses the such scheme manufacturing is at current density 3.34KA/m
2, the injection brine concentration is 305g/l, pressure reduction remains on 300mmH
2Under the O situation, produce 32% caustic soda, steady running for some time, single bath voltage is stabilized in about 3.1V, the ionic membrane lower surface is not found any bubble, the bight, upper end is without any damage, electric groove stable performance.This shows that this kind design has thoroughly solved chamber frame bottom solution and crossed and cause ionic membrane a large amount of blistered problems in surface and electric groove structural distortion problem after the reaction.This invention electrolyzer is owing to use positiver sealing face structure, when compressing for a long time, thereby can not produce because structural distortion causes string on film, the pad to cause the problem of electrolyzer cisco unity malfunction, guarantee electrolyzer for a long time high quality normally move.
The foregoing description is a specific embodiments, can adjust each parameter according to practical situation.
Protection domain by claim as limiting.
Claims (10)
1. bipolar type natural-circulation ion-exchange membrane electrolyzer, mainly by unit electrolytic bath, end half-cell electrolyzer, the gasket and the ion-exchange membrane that are installed between the unit electrolytic bath constitute, unit electrolytic bath, the half-cell electrolyzer of end and ion-exchange membrane are mounted to electrolyzer integral body by the sealing of fixed press device, wherein unit electrolytic bath by back-to-back the configuration, the cathode disc that on conductive path, connects, the groove frame that frame constituted around anode disc reached constitutes, anode disc and cathode disc for around with the discoid component of sidewall, anode and negative electrode are welded to respectively on anode disc and the cathode disc by the conduction gusset, in anode disc and anode, form the anolyte compartment, in cathode disc and negative electrode, form cathode compartment, sun, the top of cathode compartment has respectively and sun, the gas-liquid separation box that cathode compartment is communicated with, sidewall at cathode disc and anode disc has import and the effusive outlet of electrolysis product that the electrolysis material enters respectively, import lays respectively at the moon, on the lower wall of anode disc, outlet lays respectively at the moon, on the anode disc upper side wall, it is characterized in that: have thrust-augmenting nozzle and liquid separatnig plate in the said anolyte compartment, vertically have thrust-augmenting nozzle at anolyte compartment's entrance end, 2～15mm place, transverse distance bottom is installed with horizontal thrust-augmenting nozzle, have fluid hole below it, a side of close exit end is equipped with the thrust-augmenting nozzle longitudinally more than two or two in the anolyte compartment, liquid separatnig plate is positioned at horizontal thrust-augmenting nozzle outer lower portion near import one end, and the base of liquid separatnig plate is not less than 1.5mm far from the distance of the bottom of anolyte compartment.
2. bipolar type natural-circulation ion-exchange membrane electrolyzer according to claim 1, its feature also is: the length of liquid separatnig plate is not less than half of horizontal thrust-augmenting nozzle length.
3. bipolar type natural-circulation ion-exchange membrane electrolyzer according to claim 1, its feature also is: the height of vertical thrust-augmenting nozzle of the close exit end in the anolyte compartment is not less than 2/3 of the vertical height in anolyte compartment.
4. bipolar type natural-circulation ion-exchange membrane electrolyzer according to claim 1, its feature also is: the middle part in the anolyte compartment also is equipped with vertical thrust-augmenting nozzle, and its height is in 1/2～1/3 scope of the vertical height in anolyte compartment.
5. bipolar type natural-circulation ion-exchange membrane electrolyzer according to claim 1, its feature also is: the horizontal thrust-augmenting nozzle bottom in the anolyte compartment with fluid hole be positioned near exit end one side.
6. bipolar type natural-circulation ion-exchange membrane electrolyzer according to claim 1, its feature also is: the side frame of unit groove and bottom frame adopt the board plug type fixed connection structure, have plate in the middle of the trim inboard of frame appearance, the frame main body has corresponding slot, plate with wear pin after slot is seated and cooperate and form frame, fixing around the anode and cathode dish with the trim welding.
7. bipolar type natural-circulation ion-exchange membrane electrolyzer according to claim 1, its feature also is: directly welded by bending of negative electrode card and frame main body at the top of cathode compartment frame and form, the top frame of anolyte compartment then is connected with frame main body rivet by the bending of anode card.
8. bipolar type natural-circulation ion-exchange membrane electrolyzer according to claim 1, its feature also is: the gas-liquid separation box on cathode and anode dish top is welded with the cathode and anode dish by the porous plate of bottom and sealing side plate and forms.
9. bipolar type natural-circulation ion-exchange membrane electrolyzer according to claim 1, its feature also is: at anodic gas-liquid separation box sidepiece the chlorine vent pipe is installed.
10. bipolar type natural-circulation ion-exchange membrane electrolyzer according to claim 1, its feature also is: the negative electrode in the cathode electrode unit groove is made after the caustic corrosion activation treatment by stainless steel substrate.
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| CNB011420022A CN1189600C (en) | 2001-09-06 | 2001-09-06 | Bipolar type natural-circulation ion-exchange membrane electrolyzer |
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| CNB011420022A CN1189600C (en) | 2001-09-06 | 2001-09-06 | Bipolar type natural-circulation ion-exchange membrane electrolyzer |
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