前苏联专利SU1665878A3 Electrolytic cell

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专利摘要:
A cell is provided having an anode and cathode separated by an ion permeable membrane or diaphragm wherein an electrode layer is bonded to or otherwise embedded in on at least one and usually to both sides of the membrane. Polarity is imparted to a bonded or embedded electrode by pressing a crinkled resiliently compressible fabric against the membrane carrying the electrode layer. This fabric is substantially coextensive with the electrode layer and is constructed so that when compressed it exerts a substantially uniform elastic reaction pressure against the membrane carrying the electrode layer or a pliable foraminous sheet, i.e. screen, interposed between the membrane carrying the electrode layer and the resiliently compressible fabric. The resiliently compressible fabric has the ability of also transmitting pressure laterally so that pressure applied may distribute across the entire area of the layer and tendency to have local areas of too low or too high pressure is minimized or reduced. Chlorine or other halogen is produced by feeding an aqueous alkali metal halide or aqueous hydrogen halide to the anode chamber. Alkali is produced in the cathode chamber and withdrawn.
公开号:SU1665878A3
申请号:SU802954174
申请日:1980-08-01
公开日:1991-07-23
发明作者:де Нора Оронцио
申请人:Оронцио Де Нора Импианти Элеттрохимиче, С.П.А. (Фирма)；
IPC主号:

专利说明:

with
with
This invention relates to electrochemical production.
The purpose of the invention is to reduce energy consumption and increase reliability.
Figure 1 shows a solid electrolyte cell having a typical electrode compressible system; Fig 2 is the same horizontal projection; FIG. 3 is the same; embodiment; figure 4 is the same vertical section.
In the device (Fig. 1), the element used in the electrolysis of sodium chloride brine has a compressible electrode or current collector associated with a vertical anode end plate 1 having a sealing surface 2 along the entire perimeter to hermetically press the edge of the diaphragm or membrane 3 with an insert, an impermeable fluid that isolates the peripheral cuff (not shown). The anodic end plate 1 also has a central, recessed surface 4 relative to said sealed surface, it extends from the bottom surface where brine is introduced, to the upper part where the spent brine is discharged and chlorine is released, and such areas are usually connected from above and below. The endplate can be made of steel, and its sides in contact with the anolyte coating are made of titanium or other passivable valve metal or they can be made of graphite or moldable mixtures of graphite and a chemically resistant resin as a binder or other anodically resistant material.
The anode should preferably consist of a titanium, niobium or other veno
about ate
00 XI 00

with
a metal in the form of a gas permeable screen 5 and an electrolyte coated with a non-passivable material resistant to electrolysis, for example, a precious metal and / or oxides and mixtures of oxides of metals of the platinum group or other electrocatalytic coatings that serve as the anode surface, when placed on an electrically conductive substrate. The anode is hard, and the screen is thick enough to carry the current of electrolysis from the ribs 6 without significant loss of resistance. It is necessary that a flexible screen with small cells, which could be made of the same material as screen 5, be positioned on the surface of screen 5 to ensure good contact with the membrane with a density of 30 or more, and preferably 60-100 contact points on 1 cm2 of the membrane surface. with small cells, it can be fixed by T9-spot welding to screen 5 or inserted by screen 5 and a membrane. The fine screen is coated with precious metals or conductive oxides resistant to anolyte.
The vertical cathode face plate 7 has on its inner side a central zone 8, recessed relative to the peripheral sealed surface 9, said zone 8 being flat, so that it has no ribs and is parallel to the sealing surface. The pressing element, made in the form of an elastic mesh of spiral or bonded wire 10, is made of a nickel alloy and is installed within the specified zone of the caddy end plate. In the device, the cathode 11 is a wire helix or several interconnected coils, and these coils can be hooked onto the membrane directly. However, the cathode 11 must be positioned between the wire spiral 10 and the membrane 3 so that the spiral and the screen engage each other and the membrane.
The space between adjacent spirals must be large enough to allow gas or electrolyte to flow or move between spirals, for example, inwards and outwards of the central area, closed by a spiral. Such spaces are usually large, often 3-5 times larger than the diameter of the wire. The thickness of the uncompressed wire helix is 10-60% greater than the depth of the central zone 8 relative to the plane of the sealing surfaces. During assembly of the element, the helix shrinks from 10 to 60% of its original thickness, due to which elastic
reactive force, preferably in the range of 80 UOg / cm2 surface,
The cathode end plate 7 can be made of steel or any other electrically conductive material that is resistant to caustic and hydrogen. Membrane 3 must be liquid-tight and semi-permeable to cations, as well as ion-exchangeable. The cathode 11 is usually made of nickel mesh from wire or other material that is resistant to corrosion under cathode conditions. While the screen may be rigid, it is desirable that it be flexible and non-rigid in such a way that the perceived irregularities of the cathode surface of the membrane can be easily bent. Such irregularities may be in the very surface of the membrane, but more often occur due to irregularities in the more rigid anode, in which the membrane abuts.
The size of the cathode holes may be smaller than the size of the holes between the spirals in the conductor. Screens with apertures of 0.5-3 mm in width and length can be used, although screens with smaller apertures are preferred. . The spiral net, since it is electrically conductive, has an active electrode surface, and also serves to prevent damage to the membrane with a spiral or other squeezed element, and when the electrode presses the screen in a limited area, the screen helps distribute pressure across the membrane surface between adjacent pressure points and also prevents penetration of the broken part of the helix into the membrane.
During electrolysis, hydrogen and alkali metal hydroxide are released to the screen and usually to some or all of the helix. When the helical spirals are compressed, their back surfaces, i.e. those that are removed or displaced from the membrane surface reach the screen and the membrane, and the greater the degree of compression, the smaller the average space of the spirals from the membrane and the more electrolysis occur at least during the cathodic polarization of the surface of the spiral. Thus, the compression effect increases the total effective cathode surface.
Compressing the electrode effectively reduces the total voltage required to provide a current of 1000A per meter of active membrane surface and more. At the same time, the compression should be limited so that the compressible electrode remains open to the flow of electrolyte and gas. The spirals (Fig. 4) remain open.
to provide central vertical channels through which electrolyte and gas can pass. In addition, the spaces between the spirals remain to facilitate the access of the catholyte to the membrane and sides of the spirals. The wire helix usually has a diameter of 0.05-0.5 mm. Although it is possible to use a larger wire, this leads to greater rigidity and lower compressibility, so that wire over 1.5 mm is rarely used.
In the assembled state (Fig. 2), the end plates 1 and 7 are clamped, due to which the helix 10 or grid 10 is pressed to the electrode 11. During the operation of the element, the anolyte consisting, for example, of saturated sodium chloride brine, circulates through the anode chamber, although it is more desirable to supply fresh anolyte through the inlet pipe (not shown) near the bottom of the chamber and release the used anolyte through the exhaust pipe (not shown) near the upper part of the chamber along with the release of chlorine.
The cathode chamber is fed with water or alkali diluted with water through an inlet pipe (not shown) in the lower part of the chamber, while the alkali is discharged as a concentrated solution through an outlet pipe (not shown) in the upper part of the cathode chamber. The hydrogen obtained from the cathode can be removed from the cathode chamber either together with the concentrated caustic solution or through another exhaust pipe in the upper part of the chamber.
The anodic and cathode end plates are appropriately connected to an external current source and the current passes through a series of ribs 6 to the anode 5. The ionic conductivity is observed mainly through the ion-exchange membrane 3, while the current passes due to migration of sodium ions through the cationic membrane 3 from the anode 5 to the cathode 11 of the element. Electrodes provide multiple contact points on the membrane.
After the element is assembled, the current collector is in a compressed state, when deformation is noted by about 10-60% of the original thickness of the spirals or folds, thereby creating an elastic force on the surface of the cathode 11 and, therefore, on the confining surface, which is represented by a relatively rigid, nondeformable anode or anode current collector. Such an elastic force provides the required pressure on the contact points between the cathode and the membrane.
Since the helical spirals and the screen are movable relative to each other and relative to the membrane, as well as the rear carrier wall, the absence of mechanical limitations for differential elastic deformation between adjacent spirals or adjacent folds of the elastic electrode allows it to be adjusted horizontally to obtain minor deviations from flatness or parallelism between the planes. mi represented by the anode and the bearing surface of the cathode part, respectively. Such minor deviations are usually observed in the standard process and, therefore, are largely compensated.
The advantages of the elastic electrode are fully realized in industrial electrolyzers of the press filter type, which contain large numbers of elementary elements clamped together in series, forming high-capacity modules. In this case, the end plates of the intermediate elements are represented by the surfaces of bipolar separators carrying an anode and cathode current collector on each surface. Bipolar separators, while acting as the confining walls of the electrode chambers, electrically connect the anode of each element to the cathode of the adjacent element with the cathode of the adjacent element in series.
Due to the increased deformability, the elastic compressible electrodes make it possible to more evenly distribute the clamping force of the filter press module of each element, and this is true when the opposite side of each membrane is rigidly fixed with a relatively rigid anode. In such series-connected elements, the use of elastic seals on the sealing surfaces of the elements is recommended to prevent the elasticity of the compressed module from being limited to membrane elasticity. A great advantage can be obtained with the elastic deformation of the elastic collectors inside each element of the series.
A corrugated fabric of interconnected wires is used as a compensating element of the electrode instead of spirals (Fig. 3), with an additional electrolyte channel provided for the circulation of electrolyte. As can be seen from the diagram, the element contains anodic 1 and cathodic 7 end plates mounted in the the tical plane, wherein each end plate has a channel with lateral
Tanks, covering the anode and cathode space.
The anode contains a relatively rigid compressible sheet of expanded titanium, whether another perforated anodic-resistant substrate with a non-passivable coating, for example, from metal or acid, or a mixture of platinum-group oxide metal. Such a sheet is sized to fit into the side walls of the anode plate 10 and is held by rigidly spaced electrically conductive metal or graphite fins that are attached to or protrude from the base of the anode end plate. 15 The spaces between the ribs provide a free flow of anolyte, which is fed from below and stretches from above such spaces. The entire face plate and the fins may be made of graphite or 20 of titanium-clad steel, or other suitable material. The ends of the ribs carrying the anode sheet may not be coated, although, for example, platinum coating is possible to improve electrical contact, and the anode sheet may also be welded to the edges. The anodic rigid perforated sheet is held firmly in a vertical position. Such a sheet may be an expanded metal 30 having upward inclined holes directed from the membrane (Figure 4) in order to deflect the rising gas bubbles to the membrane space.
It is necessary that a flexible screen with small cells of titanium or other valve metal coated with an non-resorbable layer, which is predominantly a precious metal or conductive, oxides with a low overpotential during the anodic reaction (for example, release chlorine), located between the rigid perforated sheet and the membrane.
On the cathode side, the ribs extend outward from the base of the cathode face stina over a distance that is part of the entire depth of the cathode space. Such fins are distributed throughout the cell to provide parallel gaps for electrolyte flow. As in the described embodiment of the device, the cathode end plate and the ribs can be made of steel or nickel alloy with iron or other alloys that are resistant to cathode exposure. A relatively rigid plate is welded on the conductive ribs, which is perforated and allows easy circulation through one side of the electrolyte. Usually such holes or
the louvres are inclined upward from the membrane —or from the compressible electrode in the direction of the cathode space (FIG. 4). The pressure plate is electrically conductive and serves to create the polarity of the electrode and the pressure applied to it, and it can also be made of expanded metal or a heavy screen of steel, nickel, copper or their alloys.
The grid (Fig. 3) is compressed or is a fabric of a wire with small cells, which is open, and where the strands of wire are twisted into a relatively flat fabric with interconnected loops. Such fabric is then corrugated so that the folds are located closer, for example, at a distance of 0.3-2 cm, and the total thickness of the fabric is 5-10 mm. The folds may have a zigzag pattern, and the tissue cells are larger, for example, have a larger pore size than the screen.
Between zero compression and compression up to 4 mm, the voltage drop is 5-150 mV. The element voltage remains almost constant up to a pressure of 2 mm, and then begins to rise. A value of 2 mm corresponds to 30% of the original fabric thickness. This allows you to save 5% and higher energy during brine electrolysis.
During operation of the device, a saturated aqueous solution of sodium chloride is fed into the lower part of the element and passes upward through the channels or spaces between the ribs, and the diluted brine and the chlorine released are discharged from the upper part of the element. Water or dilute sodium hydroxide is supplied to the lower part of the cathode chambers and lifted through the channels, as well as through the voids of the compressed sheet, hydrogen and alkali are poured from the upper part of the element. Electrolysis takes place at a constant current between the anodic and cathodic end plates.
As can be seen from the vertical flow diagram in the element (figure 4). at least the upper openings in the pressure plate provide, as a blind, an inclined outlet to the outside of the fabric, through which some of the hydrogen and / or electrolyte is released to the rear chamber. Consequently, the vertical spaces at the back of the pressure plate and the space occupied by the compressed screen provide for the upward flow of catholyte and gas.
With the help of two such cameras you can
reduce the gap between push
plate and membrane and increase the compression
sheet, leaving the sheet open for
jTOTOKa fluid that serves to increase
total effective surface of the active parts of the cathode.
PRI me R 1. The first experimental element A was made in accordance with FIGS. 3 and 4. Electrode width 500 mm, height 500 mm, cathode face plate, cathode ribs and cathode pressure perforated plate made of steel with electroplated coating nickel The pressure plate was obtained by a longitudinal section of a 1.5 mm thick steel plate, in which the holes were made 12 and 6 mm in size. The anodic end plate is made of titanium-coated steel, and the anode ribs are made of titanium.
The anode contains a coarse, rigid metallic titanium screen obtained by cutting a titanium plate 1.5 mm thick with 10 and 5 mm holes, and a fine titanium screen is obtained by cutting a titanium plate 0.20 mm thick with 1.75 holes and 3.00 mm and fixed by spot welding on the inner surface of the coarse screen. Both screens are covered with a layer of a mixture of ruthenium oxide and titanium, corresponding to a load of 12 g of ruthenium (as metal) per 1 m of surface.
The cathode contains three layers of corrugated nickel-wire fabric forming an elastic mesh, with a nickel wire diameter of 0.15 mm. The fabric has a herringbone pattern with a wave amplitude of 4.5 mm and a step between the peaks of 5 mm. After the three layers of corrugated fabric are subjected to pressure in the order of 100-200 g / cm, the mesh has a thickness of 5.6 mm. After the pressure is removed, the mesh acquires the same thickness due to the elasticity. The cathode also contains a 20 mesh nickel screen formed from 0.15 mm diameter nickel wire, whereby the screen has about 64 contact points per 1 cm2 of the membrane surface, which is determined by the method of applying pressure-sensitive paper. The membrane is a 0.6 mm thick hydrated film from Nafion 315, cation exchange, i.e. Perfluoric sulfonic acid type membrane.
The reference test element B, of the same size, has electrodes made in the usual way, with two rigid screens directly resting on opposite membrane surfaces without using a small screen and without uniformly compressing (i.e. without a grid). . The current tests are similar to those shown in FIG. one.
Performance data: incoming brine concentration 300 g / l NaCI; 180 g / l effluent brine concentration
NaCl; anolyte temperature 80 ° C; anolyte pH 4; caustic concentration with catholyte 18% by weight of NaOH; current density 3000 A / m2.
Experimental element A is in operation when the grid is strongly compressed, as a result of which the following characteristics of the element are obtained: the element voltage and current depend on the degree of compression of the grid. The cell voltage decreases as the mesh compresses up to a thickness corresponding to 30% of the original thickness. After such a compression, the voltage of the element begins to increase somewhat.
By reducing the degree of compression of the mesh to a thickness of 3 mm, the operation of element A is compared with what was obtained in parallel on element B, taken as a standard. The following results were obtained:
To obtain the dependence of the cell voltage on the effect of the bubbles, the cells were rotated 45 ° and then 90 ° from the vertical position, while the anode remained horizontally above the membrane. The following performance data was obtained:
Tilt, .Napr Out-O2 to CI2
hail.Vtoku,%
453,385 4.4
453.6585 4.4
Horizon3,386 4.3
- z.b85 4,5
The voltage of element A in a horizontal position begins to rise slowly and stabilizes at 3.6 V. The voltage of element B in a horizontal position jumps abruptly to 12 V and the electrolysis stops. These results were explained as follows: when the elements are rotated from the vertical position to the horizontal, the influence of the bubble effect on the voltage of the element decreases in element B, while in element A this does not occur due to the insignificance of its effect, which is partially explained a lower voltage of element A relative to element B; when the horizontal position is reached, hydrogen begins to accumulate under the membrane and to a greater extent isolates the active surface of the cathode screen from ionic current conduction through the catholyte in the reference element B, while the same effect is significantly less pronounced in element A,
This can be explained only by the fact that a significant part of the ionic conductivity is limited within the thickness of the membrane and the cathode provides sufficient contact with the mono-exchange group on the surface of the membrane to effectively maintain electrolysis.
With a significant decrease in the density and frequency of contact points between the electrodes and the membrane by replacing small screens with coarse screens, element A mode more closely resembles the mode of reference element B. In addition, the elasto compression of the cathode layer ensures that the membrane surface is covered with densely distributed contact points. 90, er more often on 98% of all surfaces, even in the presence of significant deviations from flatness or parallelism of the pressure plates.
EXAMPLE 2. To verify the obtained results, element A is modified by replacing all the anode structures made of titanium with the same structures made of nickel-coated steel (anode end plate and anode ribs) and pure nickel (coarse screen). and shallow screen) 0.3 mm thick membrane, cation exchange, Nafion 120 (manufactured by DuPont de Nemours).
Pure, double distilled water, having a resistivity of more than 200,000 ohms cm, circulates in the cathode and anode chambers. An increase in the potential difference is applied to the two end plates of the cell and the electrolysis is accompanied by the release of oxygen on the nickel screen of the anode, and hydrogen is released on the nickel screen of the cathode. After several hours of work, the following results were obtained:
Density of flow temperature, ° C ka, A / mmenta, V

2.7 3.5 5.1
65 65 65
The conductivity of electrolytes is negligible and the element works as a system with solid electrolyte.
By replacing the small electrode screens with coarse ones, thereby reducing the density of contacts between the electrodes and the membrane surface from 100 to 16 points per 1 cm2, a sharp increase in the cell voltage is obtained.
Voltage is evil Temperature, ° C ment, V
8,865
12,265
50
50
50
five
0
five
It is possible to increase the density of contact points between the electrodes and the membrane using various methods. For example, a small cell electrode screen can be sprayed with metal particles through a plasma setup, or the metal wire forming the membrane contact surface can be chemically treated to increase the density of the contact points. The design should be flexible enough to ensure even contact distribution over the entire surface of the membrane.
As described in Example 1. The small sieves have about 64 contacts / cm. By replacing the small sieves with much more coarse sieves, the electrochemical behavior of cell A is closer to the behavior of cell B.
Using a series of special observations with different deviations to use the gas phase as an electrical path interrupter. It has been established that the number of contacts should be at least 30 per 1 cm2. Based on the evaluation of prints of sieves under pressure on sensitive paper, the ratio should be 0.25-0.40.

权利要求:
Claims (1)
[1]
An electrolyzer for electrolysis of an aqueous solution of sodium chloride, comprising an anode and a cathode, between which there is a diaphragm or membrane, electrolyte input and output connections, an element to press one of the electrodes to the diaphragm or membrane, anode and cathode current leads. Made in the form of metal blocks, and one of the electrodes is made in the form of a plate placed on a conductor, characterized in that, in order to reduce power consumption and increase reliability of operation, the other electrode is made in The form of a flexible metal mesh of wire, the pressing element is made in the form of an elastic metal mesh of spiral or connected wire with an area equal to that of the electrode, and is placed between the current lead and the metal mesh electrode, the number of mesh contacts with the membrane or diaphragm is 30-64 per cm2, and the ratio of the contact area to the area of the membrane or diaphragm is 0.25-0.40
Z / d / dU
Г11 П11 .Ч -Ц -Щ .Х1 1Ч.-Ч К, -ч D.L. l, y
4 Mn4 K «Ntl iie ft il i f4 fl 6rflPi lf
SO
/
8189991
№ / Ј 4

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法律状态:

优先权:

申请号 | 申请日 | 专利标题

IT24919/79A|IT1122699B|1979-08-03|1979-08-03|RESILIENT ELECTRIC COLLECTOR AND SOLID ELECTROLYTE ELECTROCHEMISTRY INCLUDING THE SAME|

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