DE2546688A1 - METHOD AND DEVICE FOR MANUFACTURING ACCUMULATOR TUBE PLATES - Google Patents

Description

Date:

CHLORIDE GROUP LIMITED
London, UK

Method and device for the production of accumulator tube plates

The invention relates to the production of accumulator plates, preferably of accumulator tube plates, in particular the pulling of the plate tubes, a new device for implementation of the process as well as new muddy active masses.

The casing tubes of the tubular plates can consist of a wide variety of materials and be arranged in different ways. The jacket pipes can for example be connected to one another, or it can be separate jacket pipes that are separated on the pens or souls are arranged.

An example of such a separate jacket pipe arrangement exists in that one uses fabric jacket pipes with a thin outer plastic sheath, the perforations with about 1 to 2 mm in diameter at intervals of about 1 to 2 mm. The plastic cover has a diameter of about 0.1 to 0.2 mm.

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Although the invention is not limited to such arrangements is, their description is given in particular with regard to casing pipe arrangements, in which the casing pipes represent a single, preformed production part, as this is the arrangement of the Casing pipes on the plate cores made easier.

A conventional method of making tubular sheets is to impregnate jacket tubes with a resin, in order to make them stiff and still permeable, the casing pipes are applied to a series of lead alloy cores, respectively a soul for each jacket pipe, and the space between the inside of the jacket pipes and the souls with active Material, e.g. B. lead oxide powder, by means of a funnel, and the arrangement shakes to the powder in the jacket pipes to condense. This method poses significant problems, e.g. B. regarding the waste of lead oxide powder, the unevenness of the filling weight and the unevenness the filling, whereby there is easily a stronger compression in that part of the casing pipes which is below during filling, however, when using the tube plates it is up.

To reduce these problems, it is known from GB-PS 947 796, a pasty active material which is a water-soluble Contains thickener to extrude into the casing pipes under high pressure. However, this procedure results in tubular plates, which have unpredictably variable electrical properties. Furthermore, there is a tendency for the paste to to change and lose their fluidity under pressure and continue to get stuck in the processing machines if there are interruptions or delays in the production process.

It is also known from DT-AS 2 243 377, a measured Volume corresponding to the internal volume of the tubular plate, of an acidic accumulator paste within a very short period of time, for example in less than 1.5 seconds, in press in the casing pipes. To do this, the paste is given a

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additional amount of water incorporated. According to DT-AS 2 243 377 - a suspension is to be created here; in fact it is However, the mixture is a thick fast that is not self-leveling. Contain the pastes described 3 parts of gray lead oxide, 1 part of red lead oxide, 2.96 parts by weight of oxides per 1 part by weight of acid and water, and 0.06 parts by weight of sulfuric acid with a specific gravity of 1.4 per 1 part by weight of oxide, i.e. 12.6 percent of the gray lead oxides are sulfated. According to the description, the pastes have dynamic viscosities in the range of 3000 up to 4000 cP, whereby it is not specified which measuring methods or measuring devices are to be used.

In the work carried out in the context of the invention, the viscosity of the paste described above was the DT-AS 2 243 377 measured by means of a rotary vane viscometer. This rotary vane viscometer and the measuring method are described below.

During the measurements it was found that the paste described had a rotary vane viscometer torque value of 107 g.m (0.775 lbs.ft.). The paste is not self-leveling that is, if you put a chunk of mass on a flat surface applies, the clot does not spread or run within 24 hours, although there is a small amount of liquid separate from the solids during this period.

This method has the disadvantages that an accurate It is necessary to measure the volume of the paste to be pressed in, and the paste is so viscous that it can be pressed in under high pressure the casing pipes must be pressed in.

This requirement for the application of high pressures leads to density differences of the paste in accordance with the length of the casing pipes, the paste tending to overcompress at the inlet ends of the casing pipes, which, in use, are the lower end or represent the ground. In addition, it is difficult to do that

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To transport paste over the full length of the casing pipes, especially with deep plates. This imposes a serious limitation on the size of the plates that can be filled and brings with it further problems in the production of accumulators from this paste and in the use of these accumulators themselves.

It has been found that this alleviates the aforementioned problems or can be avoided by using a fundamentally different mass, device and method, in which a pourable, liquid sludge of very low viscosity is poured under the force of gravity into the casing pipes pours or introduces and, after the casing pipes are filled, preferably by increasing the pressure or counterpressure condensed. By controlling the pressure value to which the pressure is allowed to rise, the degree of compression can be changed as desired become ^ and very even densities can be achieved.

In the following, the term "tube plate" is used for the case used where the individual cores or discharge pins are each separated or connected by a jacket tube, are encased, while the term "armor plate" is not limited to the case of the tubular plate; rather, the around the souls arranged casing have any shape.

The invention thus provides a method for producing armor plates for accumulators by introducing a active, water-containing mass in the porous envelope of the plate when the envelope is on the conductive element of the Plate is arranged, which is characterized in that an active mass is used with such a water content that active material is filtered out through the porous envelope and a bed of active material is built up in the envelope, the bed, starting from the end opposite the feed of the mass, back to the end of the feed

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the mass builds up, and liquid passes through the walls of the enclosure during the period of bed build-up.

The active material is preferably lead oxide active material and the weight ratio of pesticides to water in the mass is preferably 2.5: 1 down to 0.4 ί 1 ·

The term "enclosure" includes both arrangements of separate Casing pipes as well as arrangements of casing pipes that are connected to one another or made of flat material are. Any coverings come into consideration, provided that these are a bag or a pocket around the one or more conductive ones To form elements of the plate around and to filter out active material as a bed around the etrome-conducting element (s) capital.

In a preferred embodiment, the invention relates to a method for producing armor plates, preferably tubular plates, for accumulators, preferably lead accumulators, by introducing an active material into the porous envelope of a coated plate, for example the casing tubes, if the Jacketed pipes on the conductive element of the plate, for Example, the cores or discharge pins, are arranged, which is characterized in that the active mass is in the envelope feeds as aqueous sludge when the casing is oriented in a substantially vertical plane so that the solids can settle down to the bottom of the casing under the force of gravity, the aqueous sludge having a weight ratio- nis of active material to water in the range of 2.5! 1 to 0.4! 1 possesses, the material of the envelope is selected so that that it filters out active material while passing liquids through, thereby removing the solids at least in part are held within the envelope and the liquid at least partially exit through the walls of the envelope able, and the feeding of the sludge into the casing continues until the casing with active

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Material is filled, whereupon the pressure in the feeder can be seen. for wrapping to a value of more than 0.35 kg / cm (0.35 atü), but not more than 7 kg / cm (7 atü ) _f and then brings about a pressure release.

In the following, the method of the invention is described essentially with reference to the manufacture of tubular plates.

The ratio of the volume of sludge that is fed into the tubes is, to the total inner free volume of the tubes in the plate is preferably at least 2: 1, in particular at least 3: 1> 4: 1 or 5: 1 »where a range from 5: 1 to 15: 1 is preferred and a range from 6: 1 to 10: 1 is particularly preferred.

The inner free volume of the tube is the volume within the inside diameter of the tube, that is not occupied by the conductive elements.

The aqueous sludge is a mixture of water and particulate! active material. It can turn out to be here sludge to which no acid has been added and which is essentially free of sulfate.

The preferred weight ratio of solids to liquid to be used in the sludge within the aforesaid Moved area depends on the active material used and the permeability or permeability of the tubes to be filled.

Preferably the aqueous sludge is a mixture of particulate active material, for example Lead oxide and water in a weight ratio in the range from 0.5: 1 to 1.5: 1 or 2.0: 1, in particular 1: 1 to 1.8: or about 1.5: 1.

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Sludge with oxide ratios of 0.1: 1, 0.5: 1, 1 * 1 » 1.5: 1 x and 2.0: 1 have densities of 1.1, 1.4, 1.7, 2.15 and 2.35 g / ml, respectively. Preferably the slurry has a density of less than 2.5 g / nu.

The pesticide particles in the mud are so large that less than 1 percent by weight a size of over 200 u, less than 1 percent by weight a size of less than 0.001 u and 95 percent by weight have a size of less than 50 ρ. The particle sizes are determined by means of sieve analysis.

In the case of the non-woven or non-woven type described below Material is preferred to be acid-free slurries with a solids to liquid ratio of 2.0: 1 to 0.5: for example 1.5 ϊ 1 to 0.7: 1 to be used.

In particular, in the case of acid-free sludges, such sludge compositions are used preferred, the gray lead oxide or red lead oxide or mixtures of gray lead oxide and red lead oxide with Contains up to 70 percent red lead oxide. Mixtures of gray lead oxide and red lead oxide with weight ratios are preferred from 66: 34 to 33 ί 67.

In the spunbond material described below, it is preferred to use acid-free slurries with a ratio of Solids to liquid from 2.5: 1 to 1: 1 to be used.

For the woven material described below, it is preferred acid free slurries with a solids to liquid ratio greater than 2.0: 1, for example in the range from 2.4: 1 to 2.5: 1 to be used.

The slurries or suspensions suitable according to the invention have viscosities which essentially correspond to the viscosity of water. Herein lies a fundamental difference to conventional Akkumulatorpasten and pastes used in the DT-AS 2,243,377. The viscosities of the

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According to the invention suitable sludge can not be measured with a Brookfield viscometer, since the solids wean when left standing.

The sludge suitable according to the invention can be easily poured, and the solids settle out of the liquid phase quickly, that is, in less than 15 minutes on standing.

The compositions used according to the invention are thus characterized in that they have a rotary vane viscometer torque value (see description below) of less than 0.83 g. m (0.006 lbs. ft), preferably no more than 0.55 g. m (0,004- lbs. ft), measured at 20 ⁰ C, hold.

The suspension half-life (as described below) of the slurry is preferably no greater than 15 minutes and is preferably in the range of 1 to 10 minutes.

The viscosities of the slurry are essentially independent of the shear rate, that is, it is not a question around thixotropic gels, and although there is a decrease in viscosity with increasing shear rate, this decrease is not pronounced and ee no gel forms when the shear force is removed .

The slurries can contain conventional fillers and additives for the active material, such as hydrophobic or hydrophilic Silicon dioxide or silica gel, for example in amounts of 0.1 to 0.5 percent by weight, based on the oxide. Bringing in The sludge into the tubes is preferably carried out under the force of gravity, that is, at a pressure or overpressure of 0 or below 0.35 kg / cm, until the tubes are filled with the mass. Then the pressure or overpressure is left up to a value of not more than 7 kg / cm rise and then leads to « send a pressure relief.

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In one embodiment, the filling of the tubes is carried out in the essential by gravity. A pressure build-up is then allowed to take place in order to put pressure on the active material Exercise the filled tube, for example, for a fraction of the time it takes to fill the tube is. For example, a pressure in the range of 0.35 to 3.5 kg / cm, for example 0.7 to 2.1 kg / cm, for example for Can be used 1/10 to 1/2 the time, or the same amount of time, it takes to fill the tube. if For example, it takes 5 to 15 seconds to fill the tube If necessary, the pressure is applied for a period of 1 to 5 seconds, for example.

In a further embodiment, the pressure is applied over a longer period of time. Here you guide the filling The tubes pass essentially under gravity by pushing the sludge into the tubes under a back pressure of 0 pumped in. When the tubes are full, pumping continues and the back pressure is allowed to reach a value of do not rise above 4.9 kg / cm. The pressure can therefore be

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ranging from 0.35 to 3 »5 kg / cm, for example 0.7 to 2.1 kg / cm, lie. The weight of the oxide in the tubes can be controlled by regulating the pressure build-up, as in the examples emerges. In general, the pressure is only allowed to rise up to a fixed value and then the pressure is released come here.

Surprisingly and in contrast to the prior art, where the entire filling process is carried out under high pressure, which is reflected in a layering of the active material, the paste in the vicinity of the inlet opening has a greater compression, the arrangement according to the invention enables a uniform increase in the Density of the active material over the entire jacket tube without stratification.

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As stated above, the material of the tube or jacket tube is selected so that it has a piling effect on the active material used. However, this does not mean that all of the active material is removed from the liquid that exits through the casing pipes, but only that a part is retained in and by the casing pipes.

As stated above, the active material to liquid ratio to be used will depend on a variety of factors including the nature of the material from which the casing pipes are made.

According to the invention, a compromise has to be made between the requirement of the material to have high water permeability to ensure good conductivity when using the battery, and the requirements for the material, to have a good filtering effect, so that the filling process can be carried out quickly, and the active material that should remain in the jacket pipes for a long period of use and under shock and vibration loads. A suitable material consists of a non-woven wadding made of polyester fibers with a thickness of 0.5 to 0.7 mm and a weight from 120 to 160 g / cm. This material does not have any perforations, but derives its porosity from the natural ones Gaps that exist between the fibers that make it up. It has nitrogen permeability (as below described) of 8.0 liters / cm / min and a water permeability (as described below) of 1.5 liters / cm / min.

In general, it is preferred to use a material with a nitrogen permeability in the range from 0.5 to 20, in particular 1 to 10, and particularly preferably 3 to 9 liters / cm / min to be used. This material preferably has water permeability of at least 0.01, in particular 0.1 or 0.5 to 1, 2 or 5 »liters / cm / min or more.

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As described below, it is preferred to use a slurry in which the violets of the active material have an average particle size in the range of 5 to 20 µm.

However, it can also contain material with a mean particle size in the range from 1 to 30 or 50 or 10Ou can be used with the same advantage, as long as the jacket pipe material is still sufficient Has a filtration effect. It can also use active material with a larger particle size, such as granulated material, for example with a particle size of 0.1 to 1.0 mm can be used, and optionally mixtures can also be used made of active material of different particle sizes are used.

Depending on the specific accumulator to be produced, it can be any active material. Although the invention is described in connection with lead-acid batteries, the teaching of the invention, the requirements of the active Describes mass and the material for the envelope, thereby achieving a filtration filling and a bed of active Material from the bottom of the enclosure (the top end in use) is built up onto other electrochemical systems Find application.

With respect to lead storage batteries, substantially all of the lead oxide particles have particle sizes below 100µ, for example less than 1 percent by weight have diameters greater than 200µ. In addition, less than 1 percent have diameters less than 0.001 p. Typically at least 50 weight percent, for example 95 weight percent, is less than 50 microns in size, 50 weight percent is less than 10 microns in size, and 5 weight percent is less than 1 micron in size. The oxide can be a mixture of gray lead oxide with an average particle size of 20 microns and red lead oxide with an average particle size of 5 to 10 microns. The ratio of gray to red lead is, for example about 95: 5 to 5: 95, preferably 90: 10 bie 50: 50, with a ratio

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of about 33 to 67 is particularly preferred.

Preferably, the casing tubes are clamped at the upper and lower ends so that liquid from the entire surface of the Casing pipes can escape.

Preferably, a supply of the sludge is continuously mixed during filling, while a small part of the sludge supply is mixed is filled from this continuously mixed supply into the casing pipes.

The sludge supply is preferably conveyed by a pump, which ensures a uniform delivery and the state of suspension of the mud. During the pauses between the filling of the tube plates, the sludge is removed from the The outlet end is circulated to the inlet end of the pump, for example via a circulation line. This circulation line is with the Pump outlet and a stirred storage tank connected from which a feed line leads to the pump inlet.

In a first embodiment of the method, the sludge fed by a pump into a tubular plate. If the Plate is filled, there is continuous circulation from pump outlet to pump inlet, whereupon the feed of the Sludge is carried out in another tube plate.

The apparatus for performing the method of the invention preferably includes at least one filling station with means for holding the envelope of a plate that is on the Conductive element arranged in a substantially vertical plane is, and a filling distributor device for feeding of sludge in the envelope of a plate which is arranged in the holder, and further a sludge storage tank with stirring devices for receiving a supply of active material sludge, and dispensing devices for dispensing the sludge from the storage tank to the distribution device of a selected filling station.

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The delivery devices preferably contain circulation devices to circulate the sludge to the storage tank when the sludge is not being delivered to a filling station.

The dispensing devices can be a pump with a supply line, which is in communication with the storage tank, and valve means contain, wherein a circulation valve which is connected to the Pump outlet communicating mud from the pump outlet, preferably selectively, to a filling station, or if more than a filling station is used, leads to a selected filling station, or circulates the sludge to the storage tank.

The devices for holding the plates are preferably designed and included for holding tubular plates a frame which is firmly connected to the filling manifold and includes upper and lower jaws for reversibly clamping the panels to the frame.

The gripping jaws can be toothed and the outer surface profile the top and bottom of the tube plate to be adapted.

At least the upper gripping jaw is preferably provided with an elastic, sealing covering provided.

The distributor device is preferably adapted to the use of tubular plates and then preferably has one Outlet nozzle arrangement, consisting of rigid filling tubes, which are arranged at a certain distance in a straight line, wherein the filling tubes are centered with respect to the jacket tubes of the plate and have outer diameters which are the inner ones Correspond to the diameters of the plate tubes. Thus are located the tubes are preferably arranged vertically so that the sludge can be filled at the top of the tubes.

The filling tubes can pass through an elastic seal, the dimensions of the frame in relation to the plate

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/ are matched that the end of the plate inevitably against or is pressed into the seal to secure the plate in the holder.

Preferably there is a pressure sensitive valve in cooperation with the inlet side of each fill manifold.

Per pump and sludge storage tank there are preferably at least two filling stations are provided, the circulation valve being a three-way valve.

The or each pressure-sensitive valve can be arranged so that an automatic changeover of the circulation valve or of the valve devices that connect the or each distributor device to the common feed line, on urawalt pitch takes place, and to bring about a pressure relief of the plate as soon as the predetermined pressure value is reached.

The pump preferably consists of a rotor designed as a single-thread screw, which is arranged in a cylindrical housing which is designed as a two-start screw thread, the screw of the housing having twice the pitch as owns the rotor screw. The rotor rotates around its own axis in one direction, while the axis of the rotor rotates around the The axis of the cylinder housing revolves at the same speed, but in the opposite direction of rotation.

The method of the invention is not limited to pulling tubular plates. Sheaths of other shapes can also be used, for example envelope-like sheaths, in which case the grid need not be in the form of a pen comb; Rather, it can be a conventional cast grid or a net-like grid, for example an extensive metal grid or a flat material or a plate with punched openings. Even the use of a fixed disk would be possible as long as the required power storage function is sufficient

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Scope is guaranteed.

■ The wrapping can be flexible or rigid or stiff material. At least in the case where the envelope is flexible, it is preferred during the filling process a support using porous support devices, for example by means of rigid, porous flat materials, Make sieves or grids so that the plate remains substantially parallel-sided while liquid exit.

With this arrangement, the inlet manifold must also do so be modified that instead of a series of tubes that fitted into the ends of the individual jacket tubes of the envelope are a single or double tubular cut or slot for fitting into the open lower end of the envelope is provided. A double slot arrangement that nests over the end of the grid and a pair of slots provided along both sides of the grille and can be clamped to this, can have advantages over a single schiit own z arrangement.

The end of the wrapper can be lengthened after filling Bottom rod to be closed. This can consist of an inner pin, which grips the end of the grille, and an outer pin Clamp or an integral jaw are made on the tenon to grip the exterior of the enclosure and hold it against the tenon to keep.

In a further embodiment, instead of an inlet manifold of fixed tube outlet openings or fixed slots or incisions an array of retractable Fill tubes extending down into the envelope may be used. With this arrangement one begins like this that the filling tubes extend in their full length down into the covering on the souls (which here no Zeiltrierrippen must have, as the filling tubes these

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Function). As the active material leaks from the ends of the tubes, the tubes become along the envelope pulled out, finally stopped at the top open end of the envelope where they can be momentarily clamped, and then taken away to finish filling the plate.

It is obvious that this arrangement is more complicated than the arrangement in which the sludge is simply poured into the upper ones Tube ends is fed. This simple arrangement is therefore particularly preferred.

The invention is described below with reference to the drawings, which represent preferred embodiments of the invention. Show it:

Figure 1 is a schematic side view of a device according to the invention,

Figure 2 is an enlarged schematic perspective view of the filling box shown in Figure 1,

Figure 3 is a schematic partial view of the lower gripping jaw shown in Figure 2 in the open position, only a few plate tubes are shown,

Figure 4 is a cross-sectional view along the line IV-IV of figure 3 »

Figure 5 is a partial cross-sectional view of the upper gripping jaw in the open position, as in Figure 3,

FIG. 6 a general front view of the rotary vane viscometer, which is used to measure the viscosity of the sludge used according to the invention,

Figure 7 is a front detailed view of the wing assembly of Viscometer of Figure 6,

Figure 8 is a plan view of the container for use

with the viscometer of Figure 6 to record the sample whose viscosity is to be measured,

FIG. 9 is a plan view, in the form of an optical microphotograph, to a non-woven material, NW, which is used in the examples and

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further inks is described,

Figure 10 is a front view of a preferred embodiment of a satellite fill station for use in a variant of the method in which a central sludge processing station has several satellite filling stations supplied with mud,

FIG. 11 is a side view of the satellite filling station of FIG. 10,

FIG. 12 is a plan view of the satellite filling station of FIG. 10,

FIG. 13 is a plan view of the central sludge processing station, which is mentioned in connection with Figure 10,

Figure 14 is a side view of the station shown in Figure 13,

FIG. 15 shows a front view of a preferred embodiment of a filling distributor with an upper gripping jaw, as used in the filling station shown in Figure 10,

Figure 16 is a plan view of the filler manifold shown in Figure 15,

FIG. 17 shows a cross-sectional view along the line XVII XVII of FIG. 15,

FIG. 18 shows a front view of a preferred embodiment of a lower gripping jaw as in the one in FIG Figure 10 used filling station shown, and

19 shows a longitudinal section along the line XIX-XIX in FIG.

The device consists of a sludge tank 10 in which the sludge to be filled into the plate tubes is stored. Of the The tank is equipped with a stirring blade 11, at the bottom of the tank, which can be controlled by means of a drive belt 12 from a motor 13 Speed is driven. A vertical feed pipe 15 leads from a point immediately above the stirring blade 11 to the inlet opening of a feed pump 16, which is also controlled by a drive belt 17 from a motor 18 with. ·

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Speed is driven. The outlet of the pump 16 is via a vertically downward conveying pipe 19 with a Plate filling station 20 connected. The conveyor pipe 19 leads over a pressure gauge 22, a two-way valve 23 and a fishtail distributor 24. The valve 23 can be set so that the sludge flows vertically downwards to station 20. In another position, the mud is over a Circulation line 26, which extends down to a point immediately above the agitator blade 11, fed back into the tank 10. The lines 15 and 26 preferably have the same cross section.

The mass of the sludge supply is preferably maintained at about 150 kg, generally about 100 to 200 kg. The ones in each tube plate The amount of sludge fed in, the individual filling weight, is in the range from 400 to 1000 g. In general that lies Weight ratio of active material, for example 75 kg, in the continuously mixed sludge supply, to the individual fill weight in the range of 200: 1 to 25: 1, for example 160 ι 1 to 100: 1.

The station 20 consists of a frame 29 which is rigidly fixed with respect to the manifold 24 and upper and lower Gripping jaws 30 and 31 has.

The gripping jaws 30 and 31 are toothed and correspond to the outer one Surface profile of the lower and upper end of the tubular plate, since the plate is inserted into the gripping jaws with its open lower end facing the distributor 24. The distributor has an outlet nozzle assembly consisting of 6.4 mm long copper tubing or other rigid esophagus, wherein the outer diameters are the inner diameters of the plate tubes correspond. These esophagus are arranged at a certain distance from each other in a straight line, whereby the middle of the esophagus is aligned with the middle of the plate tube.

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Thus, the open ends of the plate tubes are snugly placed on the esophagus and are held in this state by the upper gripping jaw 30, which with an elastic Sealing lining can be equipped.

The lower gripping jaw 31 holds the plate in position and presses the tubes against a thickened end portion of the diverter pins or souls. The surfaces of the plate are completely free.

The souls are made of a conventional lead alloy a conventional structure and are arranged on a guide rod so that their centers are the centers of the tubes with which they are used. The cores are preferably equipped with short axial ribs as spacers, which serve to center the souls in the jacket pipes and a bending of the souls during handling before the Prevent filling

The station 20 is described in detail below with reference to FIGS.

As stated above, the station 20 includes a frame 29 which is rigidly attached in relation to the manifold 24. This frame consists of two parts 32 and 33 $ which are mutually pivotally connected to each other around the left edge. Part 33 is rigidly connected to distributor 24. The upper

the
and / lower jaws each consist of two parts 30 A and 30 B and 31 A and 31 B. The parts 30 A and 31 A are carried by the movable part 32 of the frame 29, and the parts 30 B and 31 B are supported by the fixed part 33 of the frame.

The fixed part 33 also carries the upper and / or lower Locking levers 36 and 37 'which are arranged to fit into the upper and lower handles 38 and 39 of the movable frame member 32 intervene and thus close the filling station.

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The fixed part 33 of the frame 29 also carries a lower support rod 42 of a recess 43t through which the flag 44 passes a plate 45 passes through it, and which at the same time facilitates the insertion of the plate into the filling station.

the
The upper and / or lower gripping jaws 30 and 31 have toothed profiles which correspond to the outer envelope dimensions of the plate, and the two parts of each gripping jaw define a series of cylindrical holes 48 which are interconnected by cavities 49 when closed. These cavities 49 have twice the thickness of the material 47 of the casing, so that the casing is prevented from being cut or crushed by the gripping jaws.

The lower gripping jaw 31 presses the fabric or fleece 47 of the envelope against the widened shoulders 51 of the souls 52 of the Plate, so that a good seal is guaranteed (compare Figures 3 and 4)

FIG. 5 shows the casing pipes used in the distributor. A distributor plate 54 has a number of feed tubes 55 which lead downward through it, with tapered ends 56 which lead through openings in a rubber seal 58. This seal is elastic and can only be compressed with the fingers up to about half of the uncompressed starting thickness, which is about 3 »2 mm. Figure 5 shows the sheath or tube soyi ^ & iir position over the ends 56 of the supply tube. In fact, however, the arrangement is such that the gasket 58 must be compressed to about 1.6 mm by the forcibly inserted sheath 50 in order to bring the guide rod of the panel onto the support rod 42 of the frame. (This compression is not shown in the drawing). The jaw 30 presses the fabric or fleece 47 (Sig. 4 ·) of the casing around the ends 56 of the supply tubes 55 so that a good seal is achieved at the upper end. The casing pipes are therefore filled with a vertical arrangement, with the guide rod at the lower end.

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16

The pump / is one under the trade name Monopurap well-known pump, which ensures an even supply or Guaranteed delivery and contains a rotor equipped as a single-start screw, which is arranged in a cylindrical housing which is designed as a two-start screw thread, the screw of the housing having twice the pitch as owns the rotor screw. The rotor rotates around its own axis in one direction, while the axis of the rotor rotates around the The axis of the cylinder housing revolves at the same speed, but in the opposite direction of rotation. When using this Pump gives you a positive delivery rate with a steady flow, with the separation of liquid or solids in the mud is prevented.

In another embodiment (not shown), the filling station 20 is designed as a twin distributor arrangement, each distributor being fed by the pump 16. The two-way valve 23 is replaced by a three-way valve, and each line leading from the valve 23 to a manifold contains a pressure-sensitive valve 70.

This valve 70 is preferably a pressure reducing valve, that on every desired pressure, to the

clearance 1.05 kg / cm, can be adjusted. If this value is reached, the valve keeps the pressure at 1.05 kg / cm until it is actuated, for example manually.

The procedure would then be to insert a plate into a manifold and the valve 23 from either the recirculation or the other distributor. After the plate has been filled, for example in 5 seconds, the pressure is released

1 »05 kg / cm and then holds at this value for 5 seconds. During this time the filled plate is removed from the other manifold and replaced with a new plate. The valve 23 can then be switched over so that either a temporary circulation or the filling of the new plate takes place immediately.

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In a further embodiment, the pressure reducing valve is 70 arranged so that a circulation of the pump supply and a pressure release with respect to the plate takes place as soon as the set pressure has been reached.

During operation, the filling process takes place as follows: The sludge becomes the desired one in the tank 10 by means of the agitator blade 11 Recycled composition. Then a thistle plate 50, aligned so that the nonwoven material tubes 47 are over the metal cores 52, and against the Jaws 30 B and 31 B placed in the station 20, with the open, lower ends up against the seal 58 and over the Ends 56 of the feed tube 55 of the manifold 24 are pressed. After the one by folding the part 32 of the frame Has closed jaws 30 and 31, the locking levers 36 and 37 are placed over the handles 38 and 39. While using the stirring blade 11 keeps in operation, the valve 23 is on circulation division brought, whereby the pump 16 is connected to the pipe 28. After the pump 16 has been switched on, it is circulated for as long as until a steady flow is reached. During the circulation, the pressure gauge 22 shows the pressure value zero.

The valve 23 is then actuated in such a way that the pump 16 is connected to the distributor 24. The mud enters the Station 20, with part of the active material settling inside the jacket tubes, while excess liquid and active material emerge through the fabric or fleece 47 of the jacket pipes and drip into the tank 10. The valve 23 is held in this position until the casing pipes are filled with active material. At this time the pressure gauge indicates a relatively sudden increase in pressure. The valve 23 is then operated so that the sludge over the pipe 26 is returned to the tank 10.

After the jaws 30 and 31 have been opened, the filled plate is removed and further processing steps, such as introduction of the bottom rod, pickling, drying and electrolytic processing

60981 8/099 «

Formation, subject.

The excess sludge contained in the manifold falls into the tank 10.

In the case of continuous operation, the pressure increase indicated by the pressure gauge 22 can be used to control the filling cycle are, for example, to operate the valve 23, opening the jaws 30 and 31 to release the manifold 24 and the Attach a new panel in a stapled arrangement. One could provide limit switches in such a way that these through the new plate are triggered, causing the manifold 24 to reset the valve 23 to the filling position.

In the embodiments of FIGS. 10 to 19, two or more, for example three, satellite fill assemblies, as in FIGS Figures 1 to 5 shown, supplied with sludge from a central Schlamrareservoir and treatment tank, which is on a Scale is mounted so that it can be weighed continuously. The reservoir is continuously stirred and is with equipped with a flow-controlled water supply so that the sludge volume remains constant. You go with a mud an oxide / water ratio of 1.5 ϊ 1. Any satellite fill assembly is fed with sludge by means of a variable speed pump. Once the weight of the reservoir to about 550 kg and the oxide / water ratio 1.2 t 1 has fallen, the pumps of the satellite stations are switched off. Then 362 kg of red oxide and 181 kg are added gray oxide too. As a result, the oxide / water ratio falls into the satellite stations to about 1: 1. When the supply from the reservoir to the satellite stations is resumed, the solid / liquid ratio is restored .

In this arrangement, it is preferred to increase the volume of the tank in the satellite fill arrangement so that if the supply from the main tank is switched off during the renewal, the

609818/099 «

Oxide / water ratio does not drop too much. The amount of sludge is preferably kept in the range of 500 to 625 kg, and thus the weight ratio of active material in the sludge to the individual fill weight is (e.g. 200 to 1200 grams) in the range of 1300: 1 to 200: 1, for example 1000: 1 to 250: 1. Mixing of the sludge in the reservoir continues during the oxide addition and when it stops the pumps belonging to the satellite stations are switched on again.

The central sludge processing station 100 is shown in FIGS. A preferred form of satellite filler 130 is shown in FIGS. 10 to 12 and 15 ″ to 19.

Three such identical filling devices 130 are preferably fed through the central station 100 via a pump-operated supply line 101 and a pump operated or gravity return line 102.

The central station includes a circular mud tank 103 »which is on a base plate 104 using a load cell 105 and a pair of cross spring bearings 106 is mounted. The load cell and the cross spring bearings are at the corners arranged in an equilateral triangle. A vertical stirrer 107 is horizontal for rotation about a vertical axis Placed level at the bottom of the tank 103 and is driven by a motor 108 so that the solids in the tank 103 remain in suspension. The tank has a lid 109 with a jacketed or covered opening 110 (not shown), through the powder by means of a powder feed device 111 can be fed into the tank 103.

The powder feeding device 111 consists of an elevator 112 with a frame 113 »which are used to lift a drum with active material along a circular path, whereupon it is poured into the tank in position 115, as.

6 0 98 1 - 87 0 9 9 * 8

represented by the broken lines in FIG. The device 11 is located in a casing 116, such as indicated by the broken lines in FIG. The tank 103 is opened with the aid of a float tap or valves 117 refilled with water.

The preferred embodiment of the filling device of the figures 10 to 12 is very similar to the device shown in FIGS. 1 to 5; for the same parts will be the same Reference numbers used.

The sludge tank is equipped with a stirrer 11, which located at the bottom of the tank and driven via a gearbox 131 by a motor 13 with adjustable speed will. A vertical feed line 15 with a filter 140 at the lower end leads from a point immediately above the Stirrer n to the inlet opening of a feed pump 16 (monopump), which is driven by a motor 18 with adjustable speed.

The outlet 132 of the pump 16 is connected to an ordinary supply line 133 which, after a pair of inlet valves 134 and 135 to a pair of filling manifolds 136 and 137 to a circulation line 138 leads, which extends down to the mud tank 10.

The valve 134 is under the control of a pneumatic cylinder 141 with crank or lever 142 and is arranged so that it is always open with respect to the distributor or the bypass flow. The valve 135 is similarly arranged. This valve 135 is under the control of a similar cylinder 143 with a crank or lever 144.

Valves 134 and 135 supply manifolds 136 and 137 via lines 146 and 147 which lead from the valves to the manifolds so that any settling in these lines takes place in the area of the valves 134 and 135 so that the sediment can be easily flushed out. The pressure gauges I48

609818/09 9 ^ 8

and 149 are located in lines 146 and 147 and are connected to pressure cut-off devices so that as soon as the pressure reaches the predetermined value in line 146 or 147, which can be determined as desired, the cylinder 141 or 143 is automatically actuated, the output from the pump is directed into the bypass flow and via the lines 133 and 138 to the Tank 10 is returned.

Cylinders I41 and 143 are still under control switches operated by gate 150 (although this can be bypassed if necessary). If the gate has a distributor, for example 151 in Figure 12, is closed, it switches the valve 134 from bypass flow to supply, so that the sludge to the distributor 136 is transported. When the pressure rises and breaks, the gate can be swiveled to the other side to avoid the Actuate valve 143 for the other filling manifold 137.

The fill manifolds I36 and 137 are connected to lower jaws 152, only one of which is shown in FIG. The manifolds and lower jaw are on a rear wall 155 mounted (see Figure 11), which, deviating from the vertical is slightly inclined backwards, so that the introduction of the plates into the jaws and prevents the plates from falling out before the jaws are closed.

The filling manifolds are shown in detail in FIGS. 18 and 19 shown.

In FIGS. 15 to 17 the distributors consist of a distributor body 160 which is screwed to the mounting plate 155 and has a right-angled, horizontal sludge distribution hollow Forms space 161, which is fed from the rear through a central opening 162 which is connected to the line 146 or 147. In the middle of the upper surface of the cavity 161 is an opening 163 in which the pressure gauge I48 or 149 is arranged is.

609818/099 $

A series of nozzles 167 extend out from and over the bottom surface of cavity 161 in body 160 short nozzles, the jacket pipe is pulled and clipped on. Clamping is carried out by a movable front jaw surface 170, which is attached to the body 160 by means of vertical screws 171. The inner surface of the jaw 170 is supported by a frame worn, which consists of a series of rounded teeth, as in Figure 5t. However, the teeth are beveled, as in figure 17 indicated by the reference number 172.

The toe 170 cooperates with a movable heel 175 and the two jaws are actuated by a pair of pneumatic cylinders 176 mounted on pistons 177 which in turn are attached to the toe 170.

The cylinders 176 are attached to the heel 175. If it is operated to extend the piston 177, then so move the jaw side 175 backwards against the mounting plate 155 and at the same time move the front jaw forward. That The extent of this shift can be regulated by means of adjustable stops 178. The jaw 175 has a rounded, serrated upper edge I80, which clings the rear edge of the fabric or fleece to the nozzles 167, and this edge is I80 also beveled slightly, as can be seen from FIG. The jaw 175 also has a grooved edge I8I around the To facilitate holding the plate in the jaw. Thus, the plate can be held in the correct grooves on the edge 18I and then pushed up into the jaws.

In FIGS. 18 and 19, the lower jaw 152 consists of a rear frame 190 which is screwed to the mounting plate 155, but is separated therefrom by a spacer 191 so that liquid escaping from a plate in the jaw can flow off to the rear . A pair of side flanges 192 are bolted to the rear frame 190 and a front frame 193 is pivotable by pivot pins 194

60 $ 98.18 / 099

connected to these flanges. Furthermore, at least one of these splashes carries a stop 195 »for a larger movement of the front frame 193 as 90 degrees, starting from the closed Position to prevent. The front frame is locked in the closed or open position by an end position spring lock with a spring 197 on each side of the jaw from a pin 198 on the front frame to a pin 199 on the rear Framework leads.

The outer top edge of the front frame has a handle 200. The opposite inner top edges of the rear Frame 190 and the front frame 193 have coordinated round-toothed jaws 202 and 203, both of which have beveled upper inner edges, as indicated in 204 and 205. The jaws are dimensioned so that the tissue or Fleece of the jacket tube is pressed firmly against the widened shoulders of the Btromleitenden souls.

A horizontal rod or protrusion 208 extends outwardly below the jaw 203 and serves to support the guide rod a plate. It also has a recess through which the flag of the plate fits.

Each satellite filler comes with a workbench 220 and equipped with a receiving basin in the vicinity of the tank 10. Part of the workbench 220 is on the right side of the tank can be seen in Figure 10. This provides an area where the workforce can insert a floor stick into the open End of each plate can insert, for example a conventional stopper made of plastic, for example polyethylene, the is hammered on the ends of souls. Furthermore, a Scales may be provided in order to enable the working personnel to check the filling weight of the plates.

A pump (monopump) 230 (not shown) is under the Workbench in the supply line 101, which leads from the tank 103 to the tank 10, is provided. The pump power is designed so that about.

609818/0998

45 liters (10 gallons) of mud per minute can be pumped into tank 10, which has a capacity of approximately 135 liters. The return line 102 is a gravity line and the filler 130 is therefore in operation Raised about 30 cm above ground level. If necessary, can however, the recirculation can also be done by pumping.

If necessary, a larger tank, for example with a capacity of 225 liters, can be used. The sludge in the tank 10 is thus preferably renewed every 5 to 15 minutes, for example every 10 minutes.

The use of the device is described below.

The sludge is prepared in the tank 103 with the desired composition and then continuously via the line 101 pumped into satellite tanks 10 by pump 230. From there the circulation takes place via an overflow line arrangement 231 » which is connected to the return line 102.

The sludge weight in the tank 103 becomes continuous or periodic is measured by the load cell 105 and when there has been a drop to a set value, a warning signal is given submitted.

The sludge in the tanks 10 is continuously mixed by the pump 16 and pumped through the circuit, line 15 »pump 16, line 132, valve 134 in the bypass flow, valve 135 in the bypass flow and line 133.

609818/0998

A plate of material tubes that are placed on the conductive Souls are arranged and have suitable dimensions for the upper bracket and lower bracket used, is shown in a fill manifold such as 136 is used. Then be the upper bracket and the lower bracket closed. The gate 150 is then closed, and if the automatic one Arrangement is in operation, the cylinder 141 sets the valve 134 so that the pump 16 is connected to the fill manifold 136. The plate fills, the pressure in the distributor cavity 161 rises and, when the set value is reached, releases the Pressure gauge 148, which in turn actuates the cylinder 141, which then sets the valve 134 back to bypass flow division.

Once the gate 150 is closed, another plate can be inserted into the manifold 137. Thus, as soon as the first plate is filled, the filling of the next plate can be started, either before or after removal of the first plate. The cycle can then continue until tank 103 needs to be refilled, and this can be done by another facility if necessary.

609818/0 99 8

At the end of a working period or when the filling station is to be shut down, it is advisable to pour the sludge from the tank 10 into the Pump back tank 103, thoroughly clean the filling station and rinse the associated lines with water.

The invention has been described above with reference to the preferred embodiment described in which the plates are arranged substantially in a vertical plane. While this vertical Arrangement of the plates shown in Figures 1 to 5 can be shown in Figures 10 to 19 and, as shown in Figure 11, the plates are well filled even if they deviate from the vertical by an angle of about 5 degrees.

Provided the uniform structure of a bed made of active material from the end opposite the inlet end is possible, with the cavity between the core and the casing on both sides are filled essentially evenly, so that the electrical properties are not impaired, the exact angle of the plate arrangement during the filtration filling does not play a special role.

It is therefore useful to align the plate as vertically as possible; however, there is enough room for deviations. The tolerable angle varies depending on the length and diameter of the plate and the size of the cores or Conductor pins. Even when filling a very narrow annular gap, there are no significant adverse effects on the evenness of the infill can be expected as long as the maximum horizontal distance from side to side across the sloping casing pipe not a multiple, for example ten times, is the minimum transverse dimension of the jacket pipe or sheath.

Thus it may generally be possible to fill the casing pipes if they are inclined up to 60 degrees from the vertical, although inclines up to only 20 degrees are probably more appropriate to the vertical "

609818/0998

The invention extends to further additional aspects with respect to the general inventive concept of the device.

In one embodiment, at least two filling stations are provided for each pump and each sludge storage tank, and the Distributors are fed by a common feed line that leads from the outlet of the pump to the circulation valve. Furthermore are Valve means are provided for selectively connecting each manifold to the supply line.

In another embodiment, the upper jaw includes a fixed toothed surface and a movable, cooperating therewith serrated surface which is arranged so that it can be removed from the fixed surface as it passes through pneumatic or hydraulic devices, this is held in parallel. They are also used to aid the flow of fluids of the tubes at least one, and preferably both, of the opposing faces of the lower edge of the upper jaw or the leading edge of the lower jaw, or preferably both jaws, beveled.

The rear surface of the upper jaw preferably carries a grooved or ribbed portion for ease of retention a plate in the cheek.

In a further embodiment, the lower jaw has a front jaw surface that can be pivoted downwardly with a rear jaw surface is connected, wherein adjusting means are provided and arranged so that the front plate is brought into either the closed position or the fully open position.

The invention also relates to a system for filling covered accumulator plates, which has a central sludge processing station and at least one filling device in accordance with the above description, as well as devices for

609818/0998

includes the supply of sludge from the central station to the filling device.

The devices for supplying sludge preferably comprise devices for the continuous supply of sludge to the or each filling device and return means for returning the sludge to the central station, whereby the sludge is continuous can be circulated.

The sludge treatment station preferably contains a tank, weighing devices for determining the tank weight, stirring devices, to keep the sludge in suspension, as well as devices for the supply of active material and liquids.

The weighing device is preferably a load cell which is attached under the tank.

The stirring device is preferably a stirrer or a stirring blade that rotates at the bottom of the tank. The invention further relates to the use of the plant, whereby sludge is continuously added from the central processing tank each filling device and back to the central tank is transported at such a speed that the contents of the sludge tank of the filling device are at least hourly, preferably is replaced at least every half hour, especially every 5 to 15 minutes.

In a further embodiment (not shown) the three filling devices (those around the central sludge processing station are arranged around) arranged in a straight line, with the central station either at the end of the Line or in the line between adjacent filling devices. Up to six filling devices can be made from a single one Central station to be fed with sludge. The feed line or supply line 101 and the return line 102 are in this If both are equipped with a pump (e.g. monopump),

609818/0998

these are hoses or pipes with an internal diameter of 25 mm can act.

The examples illustrate the invention.

Rotary vane viscometer torque values are used in the examples (and in the description) for the characterization of easily pourable sludges with low viscosity. Both The values given in Tables IV, VII, X and XV are the read values and not the torque values, which are used to characterize the preferred slurries. For converting the torque values read from the tables IV, VII, X and XV on the torque values used for definition is the background value of 0.55 g «m (0.004 lbs. ft) to be deducted from the measured values. In certain examples, e.g., Examples 2 and 24 in Table IV, and in In Examples 17, 26, 34, 54, 55 and 56 in Table XV, the sludge has the same viscosity value as the background value. Thus, the measured or read torque value is not greater than the background value for the performed Measurement, and these slurries thus meet the preferred viscosity properties, i.e. they have a torque value less than 0.83 m »g (0.006 lbs.ft).

609818/0998

example 1

This example describes plate making using the device shown in Figures 1 to 5.

There are positive plates with 15 casing pipes each 22.9 cm length used. The jacket pipes are made of non-woven Polyethylene terephthalate fibers. The production is as follows:

A thin layer (1.5 m wide) of fibers with a middle Length of 11.4 cm is made using the crimping technique. then About 10 layers are placed on top of one another in such a way that an endless non-woven fleece (also 1.5 m wide) is created.

The fibers generally extend longitudinally in the non-woven material, which is folded in a zigzag manner when it is moved by a conveyor belt running in the longitudinal direction of the non-woven material runs towards a tape running at right angles to this, is removed. Thus, the fibers extend substantially across the Longitudinal direction of the nonwoven material, however, due to the running direction of the second belt, the fibers are in adjacent layers inclined opposite at a small angle to the transverse direction.

The material obtained is then subjected to impregnation with a 50 percent strength by weight polyacrylic resin binder. It is 0.5 to 0.7 mm thick and weighs 120 to 160 g / cm.

This material is then processed into a casing pipe arrangement, by running two layers of the material through a multiple sewing machine to make the layers along parallel lines Lines (for example at a distance of about 25 mm) together

609818/0998

associate. This creates pockets or tubes in a conventional manner.

The material is then dipped into a phenolic resin and then dried. Here the phenolic resin absorption is approximately 30 percent, based on the dry weight of the fleece material. After cutting the material to length, mandrels are used circular cross-section of 7 »3 mm in diameter between the Rows of stitches introduced to form the pockets. The material has an air permeability of 8.0 liters / min / cm and a water permeability of 1.5 liters / min / cm. Its structure is shown in FIG. 9.

FIG. 9 shows that this nonwoven material consists of randomly entangled individual fibers. The fibers have a diameter of about 25 microns, the range generally being from 20 to 50 microns . The gaps between individual fibers generally have a size of less than 250 u, mostly less than 100 u. In addition, the material with a thickness of 0.5 to 0.7 mm has a three-dimensional structure, which allows the overlapping of numerous individual fibers with any passage, from one side to the other, allowed by the fleece material. This material has an excellent filtering effect for the purposes of the invention. While it allows the passage of both liquids and solids in a tubular shape, it fills rapidly with active material when it is placed or poured into the tubes under gravity.

The measurement of air permeability is done as follows: A sample 2.8 cm in diameter (6.16 cm effective cross-sectional area) is clamped in place. The time is then measured which is required for 50 liters of dry nitrogen to pass through the sample at 20 ^° C. with a pressure difference of 1.5 cm water column.

Because of the high permeability, the material is measured by means of mercury porosimetry or air flow

609818/0998

- yf -

not accessible through a sample saturated with alcohol.

It is known, however, that air permeability is a good measure of a material's ability to pile up. The ones that are suitable according to the invention Materials can thus be characterized by measuring their air permeability.

The measurement of the water permeability is carried out in this way . .that the time

with 1 liter volume

is measured, which initially requires a 42 cm high water column /, to flow through the sample under gravity.

After shielding the bottom of the column under the sample, water is fed over the sample, and then the lower end under the sample is opened to the atmosphere.

The sludge used in Example 1 is a mixture of 1 part by weight of gray lead oxide (mean particle size 20 yes) and 2 parts by weight of red lead oxide (mean particle size 5 to 1Op.), Mixed with water in a weight ratio of 1.5 : 1 (main amount of water) represent.

Tank 10 holds 150 kg of sludge, the agitator 11, 76.2 χ 3.8 cm, rotates at 30 to 70 rpm to keep the pests in suspension. The pump 16 is set so that the throughput volume is 9.5 liters / min, generally 4 to 10 liters / min. During the circulation, the pressure gauge 22 shows the value zero. The valve 23 is now brought to the filling position under the same stirring and pumping conditions. The pressure gauge 22 shows the pressure zero for a period of 5 seconds and a pressure of 1.05 kg / cm after a further second when the valve 23 is brought to the circulation position again. The inner volume of the tubes is 105 ml.

609818/099 «

-46 -

The volume of the soles transported through the plate is Oy8 liters, that is, the ratio of sludge volume to internal Disk volume "is 7» 6: 1.

It has been found that flow rates of less than 4 liters / min result in rather slow pull speeds, which degrades the productivity of the process. At flow velocities of over 13 liters / min., with these specific cells, fairly low filling weights for the plates are obtained.

While the sludge is thus introduced into the upper ends of the casing pipes, these fill from the bottom to the top, with A uniform oxide layer builds up in the jacket pipe and water and some oxide through the pipe material, mainly in Height of the upper surface of the active material in the tube, exiting. However, liquid also occurs over the entire filling height of the Casing pipe, and it can be assumed that further liquid is pressed out over the entire length of the casing pipe, as soon as the counterpressure builds up.

After drying, the plates are weighed. The panel weight is 450 ± 20 grams. The plates are then subjected in a conventional manner a pickling (pickling).

Numerous panels are made in the manner described. Some are taken apart and weighed, taking there is no significant difference in weight between the top, middle, and bottom of the tubes. From other panels the electrical properties are measured and made from the same active material using the powder vibration method produced panels compared. These comparison plates are hereinafter referred to as standard plates.

The plates produced according to the invention have essentially the same discharge duration for the first and also for the tenth discharge according to a standard charge / discharge process as the standard plates.

609818/0998

Flatten with different inner jacket tube volumes in the range of 50 to 250 ml can easily be filled.

As stated above, it was found that the degree of compaction and thus the total dry filling weight of the jacket pipes can be regulated by controlling the pressure, which one after Can build up completion of the filling period.

Using the same slurry and tubes as described above, it was found that increasing the pressure to as little as 0.35 or 0.49 kg / cm the weight is 420 grams - $ 5. let the If the pressure rises to 1.05 kg / cm, the weight is 450 grams - $ 5 »and with a pressure increase of up to 2.45 kg / cm the weight is 500 grams ί 5 ^

In all cases the tubes are filled evenly without stratification.

With a filling weight of 450 grams, the active material in the tubes has a density of 4.3 grams / ml.

This example is carried out using a paste containing 3 parts of oxide per 1 part of water (the mixture has a density of of 3 »5 g / ml), repeated. This material is essentially squeezed into the tubes, which fill in less than 1 second. No significant amount of liquid occurs here through the tubes. The investigation shows that the panels obtained have a considerable stratification with respect to the Have density in the tubes.

Examples 2 to 27

These examples are carried out according to Example 1 using the device described in FIGS. 1 to 5.

609818/09 9 * 8

The casing pipes are produced according to Example 1, but the length is 36.9 (instead of 22.9) cm.

These non-woven tubes of Example 1 are used for certain Examples used. This is followed by the letters I A and I B, and II A and II B in the following tables NW pointed out. In addition, two other pipe materials are used.

One is a spun-woven material (in Tables I A and I B and II A and II B below denotes the letter SW), which has an air permeability (see Example 1) of 6.0 liters / cm / min .. It contains 17 wefts / cm and 22 warps / cm. Own the warp threads a diameter of about 250 p, and the weft threads a diameter of about 375 p. The microscopic examination shows that the gaps between adjacent warp threads and adjacent weft threads amount to a maximum of about 250 χ 250 ρ. These However, gaps are crossed by numerous loose strands protruding from the threads. In this way the filtering capacity becomes of the material greatly improved.

The second material is a woven material (in Tables I A and I B and II A and II B denoted by the letter W), the one. Air permeability (see Example 1) of 15.2 liters / cm / min.

It contains 18 weft threads / cm and 22 warp threads / cm. The warp and weft threads have a diameter of about 250 μ. The microscopic examination shows that the gaps between neighboring warp threads and neighboring weft threads are about 250 χ 250 ρ and are not crossed or divided by fibers that protrude from the threads. The filtering capacity of this material is so with substantially less than that of the spin-woven material.

The masses used are given in Tables IA and IB and II A and II B.

609818/09 9-8

The sludge is made from mixtures of gray lead oxide (mean particle size 20 μ) and red lead oxide (mean particle size 5 to 10 p.), Which are mixed with water (main amount) in various weight ratios.

Of the pesticide particles in the sludge, less than 1 percent by weight a size greater than 200 microns, less than 1 percent by weight a size of less than 0.001 u, and 95 percent by weight a size of less than 50 p. The determination of these particle sizes takes place by means of sieve analysis.

The tank 10 contains 150 kg of sludge, the stirrer, 76.2 χ 3.8 cm, rotates at 30 to 70 rpm to keep the solids in suspension. The pump 16 is set so that the in the tables I A and II A specified throughput volumes can be achieved. During the circulation, the pressure gauge 22 shows a value from zero. Using the same stirring and pumping conditions, the valve 23 is switched to the filling position. The length of time during which the pressure gauge 22 shows the pressure zero, is noted, and the total time after which the valve 23 again is switched to circulation position and the maximum pressure are also noted. The results are in Tables I A and II A indicated. The total internal free volume of the jacket pipes is 170 ml.

In Table III are the results of some examples relating to the stratification of the filling and the measurements of the porosity of the active material.

In Tables I to III, Example 7 relates to woven tube W. Examples 6, 9, 12, 15, 16, 19, 22 and 23 relate to the spun-woven tube SW, and the remaining examples the non-woven tube NW. The filling of the tubes in all the examples it is carried out in the same way as described in example 1, that is, the solids are filtered out and the level of solids gradually rises in the tubes, with most of the liquid coming out of the

609818/0993

Tubes at the level of the solids level emerges, which is resistant migrates upwards.

6 0 9 8 1 8/0 9 9 ^l 8

Table I A

O CD CO

at
game Gray Fixed
material Sulfa
tie Tube
small NW Pumped
Schwin— Pump
volu time to
to be Calculated
Pumping volume total time
until duration
the 19th 2327 35 16 Pressure at
Conclude 2546688 River
sig
speed tion of the typ
gray
Oxide η age men
ml /
lake start of
pressure
construction,
lake until the Be
start of
Press
construction
ml end of
Pressure
rose,
t ₂
lake pressure
to whom
manure
t ₂ - U ₁
lake 17th 2082 30th 13th of the valve,
Overpressure
kg / cm 2 33:67 1.49: 1 O dd O 33 - - 20th - 23 2817 33 10 0.56 3 η 1.46: 1 O η O dd 23 759 31 8th 16 1960 24 8th 1.61 4th " 1.44: 1 O SW 40 122.5 - - 7th - 50 6125 65 15th 0.28 VJl η 1.42: 1 O W. η η 8th 980 12th 4th 27 3307 45 22nd 2.8 6th η 1.37: 1 O NW dd N 30th 3675 40 10 65 7962 110 45 1.4 7th η 1.35: 1 O SW η no filling, as solids are not from the
Mud filtered out - 8th dd 0.89: 1 O NW π 122.5 JZ
2.45 C ^ 9 η 0.87: 1 O NW ft N 2.1 10 η 0.36: 1 O SW dd η 2.8 11 dd 0.71: 1 O NW dd π 2.8 12th η 0.70: 1 O NW dd η 0.49 13th ft 0.48: 1 O dd η 2.38 14th It 0.31: 1 O ft κ 1.05

For example, gray red game

Table I B

Water Acid Moisture Pa- PiItrate- Settling Half-life Ste in the weight of the sample plate be suspension

Weaning half-life of the Piltrattrat suspension

ml

3 4th 5 6th 7th 8th

S 9 cd 10

<b 11

12th

13th
14th

18000 37000 55000

51784 50884 50189 48444 47634 47634 46708 45969 45049 44141 43505 20665

37000

35391

"

"

¹¹

"

53391

^M.

"

63391

ⁿ

91391

67340

739 920 908 636 886 747

7.6

7 days)

23.1

(7 days)

CJ) CJ) CO CD

Table II A.

O CD CD OO

at
game Gray Fixed
fabrics Sulfa
tie Tubular
small Pumping
Schwin- Pump—
volu time to
to be Calculated
Pumping volume Total time duration
until the pressure
to whom
manure
t ₂ -t ₁
lake Pressure at
Conclude Oil EOT " River
sig
speed tion
of
gray
Oxide
% ■ byp age men
ml /
lake start of
pressure
construction,
lake until the Be
start of
Press
construction
ml end of
Pressure
rose,
t ₂
lake 6.0 of the valve,
Overpressure
kg / cm CO
cn
OO
CD 15th 66:34 2.49: 1 mm SW 40 122.5 2.0 245 8.0 - 2.1 16 66:34 2.45: 1 - SW 40 122.5 1.5 184 - - 0.14 17th 66:34 2.00: 1 - NW 40 122.5 3.0 368 - - 0.07 18th 66:34 1.97: 1 - NW 40 122.5 - - 7.5 - 2.1 19th 66:34 1.94: 1 - SW 40 122.5 - - 7.0 - 2.1 20th 66:34 1.11: 1 - NW 40 122.5 6.0 735 10.5 - 2.45 21 66:34 1.08: 1 - NW 40 122.5 7.0 858 - 9 0.07 "£ { 22nd 66:34 1.07: 1 - SW 40 122.5 12th 1470 21 - 2.1 23 66:34 1.05: 1 - SW 40 122.5 11.7 1433 - 13th 0.07 24 66:34 0.54: 1 - NW 40 122.5 14th 1715 27 - 2.03 25th 66:34 0.53: 1 - NW 40 122.5 11.7 1433 - 4.2 0.07 26th 100: 0 1.65: 1 - NW 40 122.5 4th 490 8.2 - 2.45 27 100: 0 1.60: 1 - NW 40 122.5 4th 490 - .0, P7 •

For example, gray red game

S g

Table II B

Water acid humidity Pa- filtrate settling half-life settling half-life Ste in the weight of the sample of the sample of the filtrate plate be suspension trats suspension

ml ml gg # min 4>

15th
16
17th

18th

S 20

21

σ 23

co 24

25th

26th

27

64333 63427 61660

60025 59075 57240

54931

54269

53384

52751

51333

33000

30428

25879

25879

30879

30403

30403

51403

50758

50758

50758

97758

96929

20000

19005 ο

906 520 685 950 965 957 662 885 633 970

1009 120 284

332 747

1504

93

68

78

48

31

2.5

674 - 523 86 463 73

12th

19th

22nd

12th

5.5

0.5

0.5

CD tD CO OO

Gray : 34 Pests Sulfa above Table III below A-D With- 1 2 3 4th With Deviation at ϊίοΤ " : 34 liquid tie Layering (Floor) tel chung, tel chung, game : 34 tion D. center A. i ° i ° p 34 of : 34 gray C B ι 34 Oxides, 271 279 66 ί 0 2.49: 0 291 288 + 8 274 + 2 272 280 279 276 277 + 2 15th 66 1.97 : 0 299 268 277 295 - 3 291 + 1 288 299 295 289 293 ± ² 18th 66 1.44 y 0 309 288 295 290 - 4th 295 + 1.5 296 299 299 296 298 + 0.7 19th 66 1.11 i 0 278 290 294 276 - 19th 299 + 3 299 302 307 298 302 ± ¹ > ⁷ 20th 66 1.07 i 0 314 305 293 289 - 2 279 + 1 280 281 282 282 281 + 0.4 22nd 66 0.54! 0 283 282 279 273 - 25th 301 + 4 300 307 303 302 303 + 1.3 24 100 1.65 y 0 304 296 - 10 279 + 2 280 282 281 280 281 + 0.4 26th 280 278 : 1 ι 1 ί 1 : 1 ! 1 ; 1 - 1

Comments on Tables I A and IB. II A and II B and III

1.) Solid / liquid ratios

A) The weight of the solids removed with the samples of the filtrates is neglected as the weight of these samples is relatively low and there is no easy way to increase the solids to liquid ratio in the filtrates determine.

B) When calculating the ratios is the amount of liquid disregarded that is removed in the paste in the jacket pipes. These ratios therefore mean a bit too small Value related to the solids content of the sludge.

2.) Gray / red ratios

It is assumed that the ratio is constant remains, with the exception of the cases where gray or red oxide is additionally added.

3 ..) Wet paste in the plate

The weight of the jacket pipe, the lead elements and a ground rod is 645 grams is the weight of the damp, filled plate plus a loose floor stick minus 645.

.4.) , Settling the sample (percent)

This is the height A of the solids in the container divided by the height B of the liquid from the bottom of the tank Container, expressed as a percentage after the sample has been thoroughly shaken for 0.5 minutes and then in an upright position Has been left to stand for 24 hours.

The container is a test tube with a round bottom and 1.5 cm inside diameter. The mud filling is at least 9 cm.

5 ») Half-life of the suspension

This indicates the time that the solids level of the

609818 / 099B

- 4f-

Sample in the container, as specified under 4.), is required in order to drop halfway between B and A.

The test is carried out by holding a rubber band with the lower edge at the halfway level, i.e. (B + A) / 2 cm from The bottom of the test tube, shake the test tube vigorously for a period of at least 0.5 minutes or so long until all solids are removed from the bottom of the test tube, then align the test tube and take the time from this Measure the point in time up to the point in time when the light under the rubber band is first visible.

6.) Pump / speed

This is purely a setting value. This measures the volume of sludge that is passed through the distributor is pumped through at various settings by collecting the sludge that emerges from the manifold. For every Pump setting, two measurements are made. The sludge volume is determined from this.

Then, in the form of a graph, the pump volume setting values are displayed (0, 20, 30 and 40) plotted against time in seconds using a stopwatch. Here receives get a satisfactory straight line.

7.) Time until the start of pressure build-up, t ..

This is the length of time between the opening of the inlet valve and the point in time when the pointer of the pressure gauge actually begins to display (and not just flutters).

8.) Calculated pump volume up to the start of pressure build-up This is the time given in the eighth column from the left of Tables IA, II A, XI A, XII A and XIII A, multiplied by the volume value given in the seventh column from the left of the aforementioned tables. It is a purely arithmetical value.

60981 8/099 «

9.) Layering (Table III)

The Bestimmiong is such that the plates are dried for 6 hours in sulfuric acid of a density of 1.40 g / ml is immersed (pickling), and then for 12 hours at 82 ⁰ C.

The guide rod and the bottom rod are then cut from the plate; the rest is divided into four equal horizontal strips, namely A, B, C and D cut with the strip A coming from the lower end of the plate. Then the Strips weighed. These horizontal strips are then cut into four sections of three tubes, each being fourth tube is omitted, which are designated with the numbers 1 to 4, with section 1 from the flag side originates from the plate. Then the four sections 1 of each horizontal strip are weighed; the value is in Table VI below 1 specified. The other vertical sections 2, 3 and 4 are weighed in the same way.

10.) Pencil porosity (Table V)

This value is determined using the known method of mercury introduction porosimetry. The determination is carried out on the same samples as used in Table III, carried out. Details of this method are given in GB-PS 1,331,257. The rotary vane viscometer values for some of the slurries used in the above examples are shown in Table IV.

The viscometer used is described in FIGS. 6, 7 and 8.

The viscometer consists of a frame 110 with an electric motor 111 which drives an agitator assembly 120 through a gear box 112 and a torque converter 119. The speed in the gear box 112 is scanned by a tachometer generator 113, the output line of which with a digital voltmeter 113 A is connected. That produced by the torque converter The voltage signal is fed into a recorder 114,

609818/09 9 * 8

the one with variable speed and variable Scale is equipped.

A sample container 130 is clamped to an adjustable table 115 by means of a pneumatic cylinder 117 can be raised and lowered on guides 116.

The sample container 130 has a removable cover 131 which is attached above the stirrer assembly 120. The lid can be attached to the container by means of an external bayonet lock (not shown).

The agitator assembly 120 is releasable on the output shaft 118 of the Gear box 112 attached, and consists of a central Rod 121 with a protrusion 122 at the lower end, which in use engages a hole 132 in the bottom of the container 130. The rod 121 has a diameter D 5 of 1.3 cm and carries three pairs of stirrers 123, 124 and 125. The stirrers 123 and are in the same plane, at right angles to the stirrers 124. All the stirring blades of the stirrers are vertical, and thus aligned parallel to the axis of the rod 121. the Stirrers are carried by arms 126, 127, and 128. The distance D 6 from the center of the arm 126 to the projection 122 is 6.5 cm, the distance D 7 from the center of the arm 1 - 7 to the projection 122 3 »9 cm, and the distance from the center of the arm 128 to the protrusion 122 1.6 cm. The width of each stirrer D 3 is 1.2 cm, with a height D 2 of 1.2 cm and a thickness of 0.1 cm. The distance D 4 from the inside edge of each stirrer to the surface of the rod 121 is 1.5 cm.

The distance D 1 between the outer edges of the stirrers in a stirrer pair is 6.8 cm.

The internal height of the container 130 is 8.2 cm with an internal one 8.8 cm in diameter. There are four inner baffles 135, which at the diameter ends, each at right angles to one another, are arranged. The thickness D 10 of each baffle 135 is

609818/09 98

carries 0.30 cm, whereby these baffles protrude inwards by an amount of D 9 = 0.5 cm. The distance D 11 of the guide plates on the diameter is 7 _f 65 cm. Each baffle extends the full height of the container. The container and the baffles are made of smooth, stainless steel.

The use of the device happens as follows: The container is to a depth of 8.2 cm with the to be tested Material filled, lifted into position, clipped to table 115 and closed with lid 131.

After operating the pen 114, the motor 111 becomes employed, with the gear unit providing a low shear rate, for example 6 rpm. The output torque and the existing torque are determined by the torque converter 119. Engine and writer become like this operated for a long time until a steady torque value has been registered for a period of at least 2 minutes. this then represents the constant torque value. This continuous torque is indicated, and if there was an initial peak this fact is also indicated. The sample is then removed, shaken, measuring the amount of material, and then the container is refilled. The measurement is then repeated at a higher shear rate, for example! 8 rpm This The cycle is repeated as required depending on the desired shear rates.

The underground torque value, i.e. the one when the container is empty 130 is found is 0.55 g. m under all in Shear rates given in Table II. The same value is obtained when the container is filled with water.

In the case of the rotating vane viscometer — torque— defined here ment value is that value of the continuous torque value of the sample that is determined in the aforementioned manner by means of the aforementioned device at a shear rate of

6098 18/0 9 98

6 rpm is measured at room temperature (20 ⁰ C), minus the background value at 20 ⁰ O.

609818/0998

. example

CD CD OO

Oxide, solids gray / red liquid

Table IV

SuIfation of the gray oxide, i>

Rotary vane viscometer

Comparison., (Example 1 of DT-AS 2 243 377)

17 24 26

75 33

66

66

100

25 67

34

34

2.90:

1.49:

2.00:

0.54:

1.65:

Shear rate, rpm

Torque, g. m

Peak

107 Yes 0.69 no 0.55 no 1.11 no 0.55 no 0.83 no 0.69 no 0.69 no

with regard to the viscosity values, see general remarks of Example 1

CD O CO OO

CD CD CO GO

example - 50 18th Pores, - 25th porosity 100 · - 12.5 0.9 50 - 6.4 0.8 25th - 3.2 0.2 12.5 - 1.6 0.2 6.4 - 0.8 0.1 3.2 - 0.4 0.4 1.6 - 0.2 0.2 0.8. - 0.1 1.3 0.4 ■ - 0.05 3.3 0.2 ■ - 0.035 5.5 0.1 ■ , 035 3.3 0.05 - Total porosity 0.8 below 0 apparent density 2.1 eff. density 19.1 5.5 6.8

Table V

20 24 due to pores of the specified size

0.7 0.6

0.4 0.4

0.1 0.2

0.1 0.2

0.1 0.1 0.3

0.1 0.5

1.1 2.3 4.9 4.9 4.6 4.1

3.2 3.6 0.9 0.9 1.0 1.2

17.5
5.6
6.7

19.0 5.4 6.7

It has been found that at ratios of oxides to water of over 2.5: 1 the piltration process does not take place, and in addition, the process is much more difficult to control. There is thus a tendency for the panels to overfill, excessively Compression and uneven filling of the jacket pipes, which can lead to the formation of large pockets and gaps and low density areas continue to be unevenly distributed across the plate.

With ratios of oxides to water below 0.4 ϊ 1 the time required to fill the panel becomes excessively long, and the weight of oxide placed in the casing drops to unacceptably low levels.

It is thus preferred that the weight of the wet paste be in the plates used in Examples 2 to 27 is at least 800 grams, preferably 800 to 950 grams.

As can be seen from Table IV, the viscosities of the aqueous slurries used in the present invention are all very low. Compared to the viscosity of conventional accumulator pastes and the paste described in Example 1 of DT-AS 2 243 377, these aqueous slurries have practically the same viscosity as water. In comparison to a rotary vane viscometer torque value for the paste of DT-AS 2 243 377 of 107 g. m, typical pourable, self-leveling slurries of the invention have torque values of less than 0.83 gm, especially not more than 0.55 g. m.

Comparative Examples 28 to 33

These are highly viscous mixtures which do not fall within the scope of the invention and are only given for comparison purposes.

Masses with rotating vane viscometer torque values are used of 0.83 g. m and above. the

6098 18/0998

Comparative Examples 28 to 32 were made with the device of Figures 1 to 5 performed. The comparative example / was carried out with the device of FIGS. 10 to 19. Latter Device differs from the first mentioned only in the delivery speed of the pump (monopump), the use a pressure-sensitive selector switch that automatically switches off the sludge supply as soon as the pressure in the supply lines to the distributor has reached a specified value, and in certain implementation characteristics. The jacket pipes used have a total internal free volume of 105 ml.

The amounts or proportions of the ingredients and the conditions used in these comparative examples are given in Table VI A and VI B below.

The viscosities of the compositions used are given in Table VII below. The results of the investigation regarding the layering for Example 33 are summarized in Table VIII.

None of the aforementioned masses can be filled in using the filtration filling process; there is always filling from the inlet end downwards. Some masses, for example as in Example 30, are so thick that they cannot be pumped into the casing pipes. In Example 31, not all of the gas tubes are filled. As can be seen from Table VIII, the density of the active material in the plate of Example 33 varies considerably, namely by + 20 $, compared to a maximum deviation in Table III of + 4 $

It has also been found that the use of these higher viscosity pastes easily leads to problems with regard to occasional blockages in the machines or devices used.

609818/0998

Table VI A

For- Pest- Sulpha- Tube- Pump- Pump- Time until Calculated total time Duration play Gray matter deepen
Red whisper typ
sig- des
horror
Oxides,
1 °

Schwin- volu- to loading Pump volume up to
Density men from the beginning to the end of the
Start of pressure build-up, pressure increase,
t «baus t _o

ml /
lake

lake

ml

lake

the

Pressure application t ₂ - t see

overpressure when closing the valve

kg / cm *

28 75:25 3: 1 O 29 66:34 2.57: 1 O cn 30th 75:25 2.86: 1 3.75 O
CO 31 75:25 0.70: 1 9 OO 32 66:34 0.73: 1 9 OO 33 100: 0 0.9: 1 17th O CD CD OC

122.5 1 to 2 2.1

122.5 2 245 6.0 4.0 2.8

- too thick, does not go into the jacket pipe

- - 9 3.5

122.5 3 368 9 6 2.8

1 3 2 1.4

- 57 -

CD O CD OO

00 \ O CO CO OO

Gray 66384 Red water acid Table VI B. * Half-life
time of
Rehearsal
pension - Sit down
of the PiI
trats Half-life
the piltrat
suspension at
game G G ml ml Humidity
Fast
in the
plate Piltrate settling
weight of the pro
be mm min 7.5 min 42388 _ β G 98 28 25879 - _ - 10 29 45000 15000 20000 1000 1089 228 not self-assured
constantly - - 30th 58428 2000 - - - - - 31 35669 18266 71996 2000 567 - 76 - - 32 87131 90900 7000 661 - 91 - - 33 272 -

07

r-o cn .tr- (T)

cn

OO

CO

example

Oxide, solids gray / red liquid

Table VII

SuIfation
of the gray
Oxides, <f °

Rotary vane viscometer

Shear rate, RPM

Torque, g. m

Peak

OO __i

"^ O CD CO

Comparison, (example 1 of DT-AS 2 243 377) 28 29 30 31 32 33

25 25 34 25 25 34 0

2.90 3.30 2.57 2.86 0.70 0.73 0.90

12.6

3.75

9
17th

107 1.94 2.36 9.15 1.66 1.39 1.39

no

for viscosity values see
general remarks from example 1

I. H m φ approx νονό φ T-CVJ • Η CO CO · Η O Φ h M + I in ■ ** ■ cr> ro ro O CVJ in o> ω CJ • Η § ro Φ ο in H VO I. Φ • Η COO S. P.
• + I ι ti Φ in α) »ϋ in + * ο ti W T-
CVJ —Ι
H
H α ;> -P φ Φ γ { in H O
, J H VO H Φ O CO ti τ- Ct) Φ VO O O ά I tt £ in <Η Φ C • Η 3 «A- CO P. H φ Φ «Η «Η T- O -P approx approx approx • Ρ CQ H T- Φ Pm ·· L. fo CT * ι-ί Φ O I. • Η O ■ Η Ρ « O Φ ta O PQ ro ro

25A6688

609818/0998

25,6688

As already mentioned, other electrochemically active substances besides active lead material are also suitable for the process of Invention suitable.

Of course, the components used in such alternative embodiments must be compatible with one another. If, for example, alkaline, negative active material is to be used, the cores are preferably made of a metal which has sufficient chemical corrosion resistance in an alkaline environment. Examples of this are steel discharge pins with a round or strip-shaped cross-section, which can be nickel-plated. Instead of the polyester jacket pipes, jacket pipes made of polyamides or nylon can be used, for example. Preferred examples of the alkaline electrochemically active material are nickel hydroxide for the positive plate and cadmium hydroxide for the negative plate. These typically contain a proportion of electrically conductive material, for example sufficient amounts of graphite, to ensure appropriate conductivity. Preferably about 5 to 15 weight percent graphite is used. Steel can be used as an electrically conductive element and in a suitable porous form to ensure the piltration filling. Another example of the alkaline electrochemically active material is iron oxide for the negative active material. ^v

The nickel hydroxide may also contain particles or flakes of nickel in a dispersed form to improve conductivity. The iron oxide can also contain conductive material to improve conductivity.

Aqueous potassium hydroxide containing a small amount of lithium hydroxide is typically used as the electrolyte can.

A variety of electrochemically active lead material

is already mentioned, including gray lead oxide and red

609818/0998

254668a

Lead oxide. Gray lead oxide exists in a wide variety of forms with different levels of lead and lead monoxide (PbO) and varying particle sizes depending on the manufacturing method. Hardinge oxide, which is obtained by grinding lead grains in a ball mill, has a lead- hold from about 20 to 40? pounds, for example 30 #, and a PbO content from about $ 80 to $ 60, for example $ 70.

The material is then subjected to an air classification, the coarser particles being returned to the grinding. The material has an average particle size of 15 up to 25 yes, preferably 20 α.

Tudor oxide is another oxide that is obtained by grinding · However, this material does not undergo any air classification and has an average particle size of 30 to 50 p., preferably 40 u.

Oxide obtained after the roasting process, for example so-called Barton oxide, has an average particle size of 12 to 15 u.

According to the invention, the use of chemically inert casings is possible. However, this includes the filling of the casing pipes metallic forms of the active material and their chemical or electrolytic conversion into the electrochemically active Shape within the envelope. The invention thus also encompasses such embodiments.

Accordingly, the term "active mass" also includes such material that is inside the porous envelope, either before or after assembly into plate sets into which electrochemically active form can be converted.

There are numerous other electrochemically active combinations, which are suitable for use in accumulators.

609818/0998

The method has so far been described in connection with secondary or rechargeable systems. However, it is the same— painted applicable to primary accumulator systems where the active ones Materials or one of them enclosed in a porous envelope and in the envelope as a liquid, suspended, preferably aqueous, sludge can be introduced.

The liquid used as a suspending agent for the sludge In the simplest case, it is water (or aqueous solutions), which for several reasons, such as costs, safety and inertness, is clearly preferred. However, if the If the use of an aqueous carrier would cause problems, it could be replaced by another liquid carrier appropriate for the active material used.

Examples of other battery systems for which the method of the invention can be used are compiled in Table IX below.

The active materials listed below become particulate with suitable particle sizes used to make a filtration fill with the porous envelope used reach.

6 0 9 8 18/0998

Battery positive negative system electrode electrode

Table IX Electrolyte Primary

or

Secondary

Remarks

^ O. CD CD CD CD

Zinc zinc

zinc

money

Money,

catalyzed with precious metals or base metals such as copper

Manganese oxide / charcoal mixtures with a charcoal collector lamella

Ammonium chloride or potassium hydroxide primary

Ammonium chloride

zinc η Kai lumhydr oxi d Zinc- Graphite, cataly
sated with preciousness
tallen or base
metals such as copper η iron like E like E cadmium η η magnesium Manganese dioxide / carbon
Mixtures with a
Coal collector orla-
melle Potassium hydroxide
Potassium chromate
Potassium chlorate Mercury
ber- (I) -
oxide (HgO) cadmium aqueous potassium
hydroxide

Secondary
Primary

like E

Air is sent through the negative electrode, during which ionization occurs,

like E

It

Battery positive negative system electrode electrode

Table IX, continued electrolyte

Primary
or

Secondary

Remarks

nickel

Graphite, catalyzed with precious metals or base metals such as copper

Potassium hydroxide

O CO CO OO Secondary The electrodes are in place in a tightly closed container that is saturated with hydrogen gas. The electrodes consume hydrogen during discharge and release hydrogen while charging.

cn

Experiments have found that non-woven tubes after the filtration fill process, using either positive alkaline active material or negative alkaline active material can be filled.

It has been found that conventional negative alkaline active material (composition in weight percent: 76 $ cadmium hydroxide, 5 i ° metallic cadmium, 15 $ iron oxide, 2 $ Graphit'und 2 <fo paraffin) woven non-alone in the same under gravity (NW) casing pipes can be introduced as used in Examples 2-27. It has further been found that a ratio of active material to water in the range from 0.75: 1 down to 0.2: 1 results in sludges which cause a filling from the lower or bottom end of the casing pipes upwards to the inlet opening, wherein a good even distribution of the active material in the jacket pipes is achieved. The solids in these slurries settle out relatively quickly, similar to the lead oxide slurries described above. In all cases the liquids are easily pourable.

Similarly, conventional positive alkaline active Masses (the 85 percent by weight nickel hydroxide and 15 percent by weight graphite (a mixture of powdered graphite and Graphite flakes) contain) 'when used in equal proportions of solids to liquid to slurries, the cause a filling from the lower end of the jacket pipes up to the inlet openings, with a good even distribution of the active material in the jacket pipes is achieved.

With these sludges, too, the solids settle out relatively quickly, similar to the above

oxxd
wrote Bleljschlämmen. Here, too, it is in all of them

Cases around easily pourable liquids.

Experiments with the application of pressure on the mud have shown that the amount of active introduced into the jacket pipes

609818/0998

--ββ -

Material can be increased by the application of pressure in a manner similar to that described above in connection with active Lead oxide material is described.

Another consideration which must be taken into account in order to carry out a successful filtration fill is the relationship between the sludge particle size and the permeability, structure and pore dimensions, i.e. the filtering capacity, of the material from which the porous envelope is made. For example, when using a highly porous cover, such as the woven cover described in connection with Examples 2 to 27, in particular Example 7 *, and a 33 J 67 cream mixture of Hardinge gray oxide and red lead oxide, the relatively small one Particle size, with a solids / liquid ratio of only 1.35: 1 »as in Example 7, is not possible to fill the woven jacket tubes, since no bed of active material builds up within the jacket tubes. If, however, 100 i * of gray Tudor oxide with an average particle size of 40 u is used, then with solid / liquid ratios in the range from 2.5: 1 to 2.0: 1 using these woven jacket pipes (W) very possible to effect a satisfactory filtration fill. Using these solid / liquid ratios, these jackets can also be satisfactorily filled using slurries in which the ratio of Tudor oxide to red lead oxide is, for example, 80:20, 60:40, 40:60 or 20:80.

With these solid / liquid ratios, these casing pipes can also be filled with Hardinge oxide and an 80:20 mixture of Hardinge oxide and red lead oxide.

The invention has heretofore been described in connection with acid-free lead oxide active material. However, lead oxide active material to which acid has been added to cause at least partial sulfation can also be used.

609818/0 998

ta

It has been found that the addition of acid has a marked effect on the viscosity of the sludge within a certain range Exerts degrees of sulfation.

The reason for this effect is not known with certainty. Without wishing to be bound by any theory, it is believed that this is due to changes in the degree of hydration and thus intramolecular or intraparticulate interactions depending on the amount of intermediate sulfate compounds that may be present in the acidified slurries. The numerical values given in Table X below for the rotary vane viscometer torque clearly show this dependence of the viscosity on the degree of sulfation.

609818/0998

cn σ co co

co co co

Table X

Sludge, solids- water- I ^ SO.-volume solids SuIfatie-viscosity (g. M)

Example weight no.

volume _{(1f4g / ml)} ml ml

liquid

tion,

at 20 ^° C

X = 6

and X o / min
X = 24 X = 42

10.1 10.2 10.3 10.4 10.5 10.6

2000 2000 2000 2000 2000 2000

667 0 536 152 410 306 284 458 160 612 134 764

With regard to the viscosity values, see general remarks from Example 1. The amount of water added is the water present in the sulfuric acid and that caused by the reaction of HpSO ₄ with PbO to form PbSO. resulting water is taken into account

3: 3 3 3 i 3! 3 " , 1 : 1 ί 1 : 1 s 1 i 1

0 1.52 20th 123 40 360 60 505 80 74.6 100 48.8

Peak

yes yes yes yes yes

"254668a

Care must therefore be taken to use a system in which the solid / liquid ratio is sufficiently low so that the degree of sulfation applied "when using the specific Wrapping material will not cause the filtration fill to fail.

It has further been found that at least "when using the non-woven material NW described above within a broad range of lead oxide slurries, those slurries which have a rotary vane viscometer torque value (see Example 1) of less than 0.83 mg at 20 ^° C., give a usable filtration charge, while slurries with a torque value of 0.83 mg and above are suitable for the injection charge. Thus, while the invention is not limited to the use of slurries with torque values below 0.83 mg, the use of these slurries however, it is particularly preferred.

In the following examples 34 to 42 there are some recipes indicated for acidic sludge, which is suitable for the filtration filling suitable.

1 gram of gray lead oxide requires 0.4 ml of sulfuric acid one Density of 1.4 g / ml to achieve 100 percent sulfation.

When using gray lead oxide, which contains 30 %> lead and 70 % lead oxide, the degree of sulfation, i.e. the percentage of lead sulfate, is Y by the equation

Y _ 216.4 x volume of H ₃ SO ₄ (density 1.4) in liters

Weight of the gray lead oxide given in kg.

Examples 34 to 42

These examples are carried out using the device described in FIGS.

609818/09 98

The amounts or ratios and conditions used and the results obtained are shown in the tables below XI A and XI B indicated. All examples are 100 percent Hardinge oxide at solid / liquid ratios from 1.28: 1 down to 0.43 s 1 »and non-woven jacket pipes used.

It can be seen that when using this acid-containing slurry, somewhat lower values are obtained for the wet paste in the plate compared to the acid-free slurries of Examples 1 to 27 _y . However, as can be seen from Table XIV below, this is only due to a lower density of the active material in the jacket tubes. There is good distribution and, in particular, no harmful stratification.

The viscosities of the slurries used in Examples 34 and 38 are given in Table XV.

609818/0996

Tatelle XI A

CD O CO OO

co co οό

at
game Gray Fixed
fabrics Sulfa
tie Tubular
small Pumpge
Schwin Pump
volu time to
to be Calculated
Pumping volume total time
until duration
the Overpressure
at the EOT " River
sig
speed tion
* ■ typ age men
ml /
lake start of
pressure
construction,
lake until the Be
start of
Press
construction
ml end of
Pressure
rose,
* 2
lake pressure
to whom
manure
lake Conclude
of the Ven
tils
kg / cm 34 100/0 1.28: 1 1.5 NW 40 122.5 3 348 7th 4th 2.80 35 100/0 1.24: 1 1.5 NW 40 122.5 3 368 - - 0.07 36 100/0 0.82: 1 1.5 NW 40 122.5 4th 490 12th 8th 2.66 37 100/0 0.79: 1 1.5 NW 40 122.5 4th 490 - - 0.07 38 100/0 0.47: 1 1.5 NW 40 122.5 7th 858 19th 12th 1.68 39 100/0 0.46: 1 1.5 NW 20th 78 12th 936 30th 18th 2.10 40 100/0 0.44: 1 1.5 NW 20th 78 12th 936 - - 0.07 41 100/0 0.43: 1 4.0 NW 40 122.5 6th 735 14.5 8.5 2.45 42 100/0 0.42: 1 4.0 NW 20th 78 10 780 25th 15th 2.24

Example gray game

Red

Table XI B

Water acid moisture filtrate settling half-life settling half-life

Paste is weighted in proportion to the weight of the filter in the filtrate the be sample stock suspension Platte pension

ml

ml min

min

34
35
36
37
38
39
40

29796 27809 25181 24898 24374 2318O 22319 21826 20702

23005 200 892 - 79.6 22186 200 489 83 79.6 31313 200 883 - 68.4 31313 200 524 366 68.4 51313 200 779 - 57.6 50439 200 861 - ' 57.6 50439 200 493 1948 57.6 50439 200 720 2190 59.6 49703 200 732 2156 _

56.0 47.6

32.8 25.0 29.3

Examples 43 to 50

These examples are carried out using the apparatus described in FIGS.

The amounts or ratios and conditions used and the results are given in Tables XII A and below XII B compiled. In these examples, high levels of red lead at solid / liquid ratios of about 1.6: 1, as well as non-woven jacket pipes NW used.

The layering results are given in Table XIV.

The viscosities of those used in Examples 44 »47» 48 and 50 Slurries are summarized in Table XV.

The degree of sulfation shown in Table XII A became simple obtained by replacing the weight of gray lead with the weight of red lead. The slurries of Examples 47 to 50 were made by adding gray lead oxide to the Example 46 sludge.

609818/09 9 ^λ 8

Example gray
SoF "

Plague sulphate raw materials type

Liquid

tion

Table XII A

Pump- Pump- Time to Calculated total duration of the Schwin- voIu- to the Pump- Pump volume time to the Density of the beginning of to the end of printing-printing— start of user expansion, Print imprint

- 74 -

Overpressure "at

Closing the valve

ml / see

lake

construction

ml

rose,
* 2 ² - *1 kg / c; sec sec 1.40 44.5 16, 5 - 26.5 - 0.35 66 22nd 1.05 47.5 30, 5 1.40 26.5 18 5 2.10 12th 7th 2.10 12th 7th 2.80 15th _

CD CO 00

43
44
45
46

47 48

49
50

0/100
0/100
0/100
0/100

1.63: 1 0.07

1.59: 1 0.18

1.55: 1 0.18

1.50: 1 0.77

9.9 / 90.1 1.62: 1 0.72 18.6 / 81.4 1.68: 1 0.72 18.6 / 81.4 1.63: 1 0.72 18.6 / 81 , 4 1.59: 1 0.72

NW NW NW NW NW NW NW NW 40 40 40 40 40 40 40 40

122.5 122.5 *) 122.5 122.5 122.5 122.5 122.5 122.5

3430

4165

2083

980

613

613

*) no pressure build-up

Example gray game

Red

Table XII B

Water acid moisture piltrate settling half-life settling half-life
Paste weight of the proton of the pil- der filtrate in the sample suspension
Plate pension

ml

ml

min

43 - 44 - 45 - cn
O 46
47 3000 Around*
CO 48 5799 _A
OO 49 5241 O 50 5107 CO
CO
cö

31334 19263 10 882 - 62 30452 19263 25th 528 - - 28734 18509 25th 799 - - 27935 18509 100 717 - - 27218 18509 100 788 3055 73 25398 18509 100 784 2202 87 22954 17186 100 723 - - 22365 17186 100 818 _

9 15.7

Examples. 51 to 56

These examples are carried out using the apparatus described in Figures 10-19.

The amounts or ratios and conditions used and the results are given in Tables XIII A and below XIII B. These examples show high levels of gray lead oxide and a higher degree of sulfation than used in Examples 34-42. Non-woven casing pipes are used.

The stratification results are shown in Table XIV. The viscosities of the slurries used in Examples 51-54-55 and 56 are given in Table XV.

60981 8 / 099B

Table XIII A

at
game Gray : 0 pest
fabrics Sulfa
tie Tube
chen Pumpge
Schwin Pump
volu time to
to be Calculated
Pumping volume total
time to duration
the overpressure
at the EöT " : 0 River
sig
speed tion Type age men start of
pressure
construction,
*1 until the Be
start of
Press
construction to the end
of
Pressure
rose,
4th pressure
to whom
manure
* 2- * 1 Conclude
of the Ven
tils : 0 ml /
lake lake ml * 2
lake lake kg / cm 51 100 : 8th 0.49: 1 16.7 NW 40 200 - - 5 5 1.40 cn 52 100 «15, 0.48: 1 16.7 NW 20th 150 4th 600 6th 2 1.54 co 53 100 : 44, 0.48: 1 16.7 NW 0 100 - - 5-10 - 1.40 CD 54 92 0.50: 1 16.6 NW 0 100 - 5-10 - 1.40 co 55 84.5 5 0.52: 1 16.1 NW 0 100 - - 5-10 - 1.40 O
co
co
co 56 55.5 5 0.78: 1 10.6 NW 0 100 5 - 7th 2 1.40 - <-
eat

r-o cn

CD OD CD

Example gray game

Red

Table XIII B

Water acid moisture filtrate settling half-life settling half-life Paste weight of the proton of the pil- der filtrate in the sample suspension Plate pension

ml ml i $

min

51 44737 - 90900 3500 270 52 43636 - 90900 3500 295 53 43048 - 90900 3500 293 co 54 41857 3630 90900 3500 305 O
CD 55 39685 7250 90900 3500 309 OO 56 39485 31645 90900 3500 356 OO Ό998

73

72
72
66

CJ) CD CO OD

• η ω

■ PH • rl Φ

ro

CO

• Η Φ

-PH -H Φ

CO CO

ιη

ιη

T ο + 15- +3.5 + 6-9 + 5-6 T-
VO + 3-4 τ-
VO
CO CO
ιη
CO ιη
CO in
C- in in
C- in
CvJ CM CO
CM CO
CO ιη
ro Vk
ro in
ro a in
in 262 O
ιη
CO in in in 262 OO
ιη
CM ιη
CO in
ro ro ro
ro VO
ro CM
in C-
O CO
C- Γ
ΟΟ in
ro ro 37.5 T-
Vf 56.5 ο O
τ- ιη in in , 63: , 59: οο
CM vo
ro VO
ro C-
ro CM
Vf in
in ιη in in in CO
ro C-
ro VO
ro in
ro Vf Vk
in
in τ- + 10-24 + 15-26 + 23-29 + 14-19 + 20-24 in
CM in in
C- C-
in in
in ro
in C-
in Vf
C- ro
τ— CM in C-
CO cn CvJ
ro 243 ro in
in vo
in in
VO in
VO Vf
00 244 C-
Vf ro
VO τ-
VO in
VO Vf
VO ro
CO 240 C- C-
VO ro
VO VO
Vf ro
in O
C- ο
ro
CJ ro ro CO
ro VO
Vf C-
in O C- C- C- VO VO "*" VO VO VO
τ- VO
τ-
τ- ViT
T-
T- O CO , 49: co , 48: , 50: CM
in 00
C-
Vl

Or- T-OOOO O O

τ- ο ·· vf ο O O ·· in ·· in

·· O vo · »·· ·· ·· co in ·» in ·>

O * - · "- ■ O O O ··» in »vf O "ooco OO OCO vft- invf T-Qr- T-r-T-CT \ CO in N ro O T-COrOvftn

vfvfin ininininin

vo in

609818/0998

Oxide, Fixed Tabel Rotary vane viscometer. at grey Red fabrics Sulfa Shear Rate, Torque, Peak game River
sig
speed tie Rpm g. m tion

100: 1 1.28: 1 1.5 6

29 42 100: 1 0.47: 1 1.5 6

24 42 100: 1 0.43: 1 4.0 6

24 42 0: 100 1.59: 1 0.18 6

24 42 9.9: 90.1 1.62: 1 0.72 6

24 42 18.6: 81.9 1.68: 1 0.72 6

24 42 100: 0 0.49: 1 16.7 6

24 42 92: 8 0.50: 1 16.6 6

24 42 84.5: 15.5 0.52: 1 16.1 6

24 42 55.5: 44.5 0.78: 1 10.6 6

24 42

1.11 no 1.11 no 0.97 no 0.69 no 0.69 no 0.83 no 0.55 no 0.55 no 0.55 no 0.55 no 0.69 no 0.69 no 0.55 no 0.69 no 0.69 no 0.55 no 0.55 no 0.55 no 0.69 no 0.69 no 0.69 no 0.83 no 0.55 no 0.55 no 0.97 no 0.69 no 0.69 no 0.83 no 0.69 no 0.69 no

^r ) Regarding the viscosity values, see general remarks from Example 1

809818/0998

By comparing the results with respect to the stratification in Tables VIII and XIV it is clear that the means Sheets obtained by filtration filling (Table XIV) have a considerably lower degree of stratification than those obtained by injection filling (Table VIII) obtained plates.

Comments on Tables XI A and XI B to XIII A and XIII B 1.) Sulphation

It is believed that all of the acid will be absorbed and react with the excess oxide by the time the first addition takes place. Thus, the percentage sulfation remains constant until a further addition of acid takes place, that is, a Part of the acid is removed along with each paste sample removed.

2.) Solid / liquid ratio

The calculation takes into account any acid that

is added as a liquid.

The effect of presulphating the active lead material has been described with reference to three ranges of the possible theoretical scope of the sludge compositions. This is a 100 % gray oxide with solids / liquid ratios of 1.3 s 1 to 0.4: 1 and degrees of sulfation in the range from 1.5 to 4.0 % (Examples 34 to 42); 0: 100 to 20:80 mixtures of gray to red with solid / liquid ratios in the range from 1.5: 1 to 1.7: 1 and degrees of suI fatigue in the range from 0.05 to 0.8 # ( Examples 43 to 50); and 100: O to 55: 45 mixtures from gray to red at solid / liquid ratios ranging from 0.4: 1 to 0.8: 1 and at suif ierungsgraden 10-17 f <> (Examples 51 to 56).

It is believed that there are numerous other presulfated lead active material formulations suitable for filtration fill. It is to the skilled person due to the

609818/0998

information given regarding the influence of the acid on the viscosity and the influence of the change in the ratio from pesticides to liquid, the influence of acid on viscosity and the influence of changing ratios from gray oxide to red oxide, as well as the influence of the change in the permeability of the porous envelopes easily possible to select suitable formulations and suitable material for the porous envelope.

Claims

6098 18/09 9 8

Claims (52)

Claims 1. Process for the production of accumulator armor plates by introducing an active, liquid-containing mass into the porous envelope of the plate, if the envelope is arranged on the conductive element of the plate, characterized gekennzei chnet that one uses an active mass with such a liquid content that active material through the porous envelope filtered out and a bed of active material is built up in the envelope, the bed starting out from the end opposite the feed of the mass, back to the end of the feed of the mass, and Liquid passes through the walls of the enclosure during the period of bed construction. 2. Process for the production of accumulator armor plates by introducing an active material into the porous envelope of the plate, when the envelope is arranged on the electrically conductive element of the plate, characterized in that, that one feeds the active mass into the envelope as an aqueous sludge when the envelope in substantially vertical plane is aligned so that the solids to the bottom of the envelope under gravity can settle, the aqueous sludge having a weight ratio of active material to water in the range of 0.4: 1 to 2.5: 1, the material of the envelope is selected to filter out active material while Liquids are allowed to pass through, whereby the solids are at least partially held within the enclosure are and the liquid is able to escape at least partially through the walls of the envelope, and the The sludge continues to be fed into the casing until the casing is filled with active material, whereupon the pressure in the feeder to the envelope is on ρ ρ a value of more than 0.35 kg / cm, but not more than 7 kg / cm, can rise and then brings about a pressure release .. 609818/09 9 8 3. The method according to at least one of claims 1 and 2, characterized in that an arrangement of casing pipes is used as the casing, which side by side on one
Conductive element, a pin in each jacket tube, are arranged. 4 · The method according to claim 3 »characterized in that there is a ratio of sludge volume that is in the casing pipes
is fed to the total inner free volume of the casing pipes in the plate of at least 2: 1. 5. The method according to claim 4 »characterized in that a ratio of 3: 1 to 15: 1 is used» 6. The method according to at least one of claims 1 to 5, characterized in that an aqueous sludge is used which is an aqueous mixture of particulate! active material and liquids, the weight ratio of the solids to the liquids in the
Range from 1: 1 to 1.8: 1. 7. The method according to at least one of claims 1 to 6, characterized in that there is a sludge with a density of less than 2.5 g / ml used. 8. The method according to at least one of claims 1 to 7, characterized in that a sludge with a Rota— vane viscometer torque value of less than 0.83 m. g used at 20 ^° C. 9. The method according to at least one of claims 1 to 8, characterized in that after filling the envelope allows the counter pressure in the sludge feed to the envelope to rise to a value in the range from 0.35 to 3.5 kg / cm. 10. The method according to claim S _9, characterized in that a period of time during which the pressure is allowed to rise, 6098 18/099 8 1/10 of the time it takes to pull the casing, up to a time equal to the filling time of the envelope. 11. The method according to claim 10, characterized in that the envelope is filled in 5 to 15 seconds and the pressure allowed to increase for a period of 1 to 15 seconds. 12. The method according to at least one of claims 1 to 11, characterized characterized in that a wrapping material with a nitrogen permeability in the range of 0.5 to 20 Liters / cm / min used. 13 · The method according to claim 12, characterized in that a wrapping material having a nitrogen permeability in the range of 3 to 10 liters / cm / min is used. 14. The method according to claim 13 »characterized in that one a non-woven material is used as the wrapping material Polyester fibers with a thickness of 0.5 to 0.7 mm and a weight of 120 to 160 g / cm, with a nitrogen permeability of 8.0 liters / cm / min and a water permeability of 1.5 liters / cm / min. 15. A method according to any one of claims 1 to 14, characterized in that one uses an acid-free mass, the gray lead oxide and red lead in weight ratios of 66: 34 to ^33: contains 67 wherein the weight ratio of Peststoffen to liquid in the range of 2.0: 1 to 0.5: 1. 16. The method according to claim 15 »characterized in that one employs a pesticide to liquid weight ratio in the range of 1.5 * 1 to 0.7: 1. 17. The method according to at least one of claims 1 to 13 »thereby characterized in that one is used as the wrapping material 6098 18/099 8 . 25A6688 spun-woven material with 15 to 25 wefts / cm and 15 to 25 warp threads / cm and a nitrogen permeability of 5 liters / cm / min is used. 18. The method according to claim 17 _f, characterized in that an acid-free sludge is used, the gray lead oxide
and red lead oxide in weight ratios of 66: 34 to 33 J 67, the weight ratio of pesticides to liquid in the range of 2.5 1 to 0.9: 1
lies. 19. The method according to at least one of claims 1 to 18, characterized characterized in that the active material is an active Lead material is used, which is at least partially sulfated before it is introduced into the porous envelope of the plates has been subjected. 20. The method according to claim 19 »characterized in that
an active material with a degree of sulfation of
used below 17 weight percent. 21. The method according to claim 20, characterized in that an active material with a degree of sulfation in the range from 0.05 to 16.7 percent used. 22. The method according to claim 19 »characterized in that the active material is gray lead oxide with a degree of sulfation of up to 4 percent and a ratio of pesticides to liquid in the range from 1.3: 1 to 0.4: 1
applies. 23. The method according to claim 19, characterized in that the active material used is gray lead oxide, which is up to
Contains 45 percent by weight red lead oxide, and a degree of sulfation in the range of 10 to 17 percent, as well as a
Apply a pesticide to liquid ratio of less than 0.8: 1. 609818/09 98 24 · The method according to claim 19 »characterized in that red lead oxide is used as the active material, which is up to Contains 20 percent by weight of gray lead oxide, and a degree of sulfation of up to 0.8 percent, as well as a ratio from solids to liquids not exceeding 1.7! 1 applies. 25 · The method according to at least one of claims 1 to 24, characterized characterized in that an active material having an average particle size in the range from 1 to 100 ii used. 26 · The method according to claim 25, characterized in that an active material with an average particle size in Used range from 5 to 20 yu. 27 · The method according to at least one of claims 2 to 26, characterized in that the cover is at the top and the lower end while the sludge is fed into the envelope so that liquid over the entire surface the envelope can escape. 28. The method according to at least one of claims 2 to 27, characterized characterized in that a sludge supply is continuously mixed during filling and a smaller one Feeds part of this continuously mixed supply into each plate envelope. 29. The method according to claim 28, characterized in that one a weight ratio of active material in the continuous applies mixed sludge supply to the individual fill weight in the range of 1300: 1 to 25: 1. 30. The method according to at least one of claims 2 to 29, characterized in that the sludge supply from a stirred sludge supply in a storage tank by a pump to a filling distributor , which feeds a plate, wherein 609818/09 9 8 _ ββ - - ■ a pump is used that ensures an even delivery and holding the sludge in suspension, and the sludge, during the periods between feeding into a wrapped plate over the fill manifold, from the outlet the pump via a urine circulation line, which is connected to the pump outlet from there let is connected, circulates to the storage tank and / via a feed to the pump inlet. 31. Device for filling accumulator armor plates, marked by at least one filling station with devices for holding the envelope of a plate, which on the electrically conductive element is arranged in a substantially vertical plane, and a filling distributor device for feeding sludge into the envelope of a plate which is arranged in the holder, and furthermore one Sludge storage tank with stirring devices for receiving a supply of active material sludge, as well as dispensing devices for dispensing the sludge from the storage tank to the distribution device of a selected filling station. 32. Apparatus according to claim 31 »characterized in that the delivery devices are circulating devices for circulation of the sludge to the storage tank when the sludge is not being delivered to a filling station. 33 device according to at least one of claims 31 or 32, characterized in that the dispensing devices leading to the distribution devices include a pump with a supply line, which is in communication with the storage tank and includes valve means, wherein a circulation valve which is in communication with the pump outlet, Directs sludge from the pump outlet to a filling station, or circulates the sludge to the storage tank. 34 · Device according to at least one of claims 31 to 33 »characterized in that the devices for holding the plates are designed as holders for tubular plates 60981 8/0998 and include a frame that is integral with the fill manifold and upper and lower jaws for reversible plague clamping of the panels to the frame contains. 35 «Device according to claim 34» characterized in that the gripping jaws serrated and adapted to the outer surface profile of the lower and upper ends of the tubular plate are. 36. Device according to at least one of claims 34 and 35 »characterized in that at least the upper jaw with is provided with an elastic, sealing covering. 37 device according to at least one of claims 31 to 36, characterized in that the distributor device for adapting to the use of tubular plates comprises an outlet nozzle arrangement, consisting of rigid filling tubes that are arranged in a straight line at a certain distance, contains, wherein the filling tubes are centered with respect to the casing tubes of the plate and have outer diameters, which correspond to the inner diameters of the casing pipes. 38. Apparatus according to claim 37 »characterized in that the filling tubes pass through an elastic seal, the dimensions of the frame in relation to the plate are adjusted so that the end of the plate inevitably is pressed against and into the seal, and so an attachment of the plate in the holder takes place. 39. Device according to at least one of claims 3I to 38, characterized in that a pressure sensitive valve interacts with the inlet side of each filler manifold is available. 40. Device according to at least one of claims 31 to 39 » characterized in that per pump and sludge storage tank 60 9818/0998 at least two filling stations are provided, and the circulation valve is a three-way valve. 41. The device according to at least one of claims 31 to 39 _f ', characterized in that at least two filling stations are provided per pump and sludge storage tank, and the distribution devices are fed by a common feed that leads from the outlet of the pump to the circulation line, and Valve devices are provided for selectively connecting each manifold device to the supply line. 42. Device according to at least one of claims 39 to 41 _f, characterized in that the pressure-sensitive valve is a pressure reducing valve. 43 «Device according to at least one of claims 39 to 41» characterized in that the or each pressure sensitive valve is arranged to allow automatic changeover of the circulation valve or valve devices that the or each distributor device with the common Feed line, connect, takes place on urawalting division, and the pressure in the feed line on the plate is released once the set pressure is reached. 44. Device according to at least one of claims 31 to 43, characterized in that the pump contains a rotor equipped as a single-thread screw, which is in a cylindrical Housing is arranged, which is designed as a two-start screw thread, the screw of the housing has twice the pitch of the rotor screw, and the rotor rotates around its own axis in one direction rotates, while the axis of the rotor around the axis of the cylinder housing at the same speed, but opposite Direction of rotation, circling. 45. Device according to at least one of claims 34 to 44, characterized in that the upper jaw has a fixed one 609818/09 9 8 toothed surface and a cooperating movable has serrated surface which is arranged so that it can be removed from the fixed surface while it, is held in parallel by pneumatic or hydraulic devices. 46. Device according to at least one of claims 34 to 45, characterized in that at least one of the opposite faces of the lower edge of the upper jaw or the upper edge of the lower jaw is beveled. 47 · Device according to at least one of Claims 34 to 46, characterized in that the rear surface of the upper Baking carries a grooved or ribbed part to improve the plate support in the baking. 48. Device according to at least one of claims 34 to 47, characterized in that the lower jaw has a front jaw surface which is pivotally connected to a rear jaw surface downwardly, adjusting means being provided and arranged so that the front plate is brought into either the closed position or the fully open position. 49. Device for filling covered accumulator plates, characterized by a central sludge processing station. tion and at least one filling device according to one of claims 31 to 48, as well as devices for the sludge supply from the central station to the filling facilities. 50. Apparatus according to claim 49, characterized in that the means for supplying sludge include means for continuously supplying sludge to the or each filling device and return means for returning the sludge to the central station, whereby the sludge can be continuously circulated. 609818/0998 51. Device according to at least one of claims 49 and 50, characterized in that the sludge processing station a tank, weighing devices to determine the tank weight, stirring devices to keep the sludge in suspension as well as facilities for the supply of active material and liquids. 52. Apparatus according to claim 51, characterized in that the weighing device consists of a load cell which under the tank. 53 · Device according to claim 51, characterized in that the stirring devices consist of a stirrer or stirring blade that rotates at the bottom of the tank. 54 · Use of the device according to one of claims 49 to 53 for filling accumulator armor plates, characterized in that one continuously sludge from the central processing tank to each filler and back to the central tank at such speed transported that the contents of the sludge tank of the filling device is renewed at least every hour. 609818/0998 Blank page