DE2141143A1 - Electrolytic electrode device - Google Patents

Description

MITSUBISHI JUKOGYO KABUSHIKI KAISHA 5-1, Marunouchi 2-chome, Chiyoda-ku, Tokyo, Japan

Electrolytic electrode device

The invention relates to an electrolytic electrode device for coolers, such as those used in heating systems, chemical systems and ships and the like.

So far, most of the cooling pipes for such systems and the like have been made of corrosion-resistant copper or copper alloys been. However, they have disadvantages in that, depending on the working and environmental conditions, the same may experience corrosion, thereby reducing the life of the refrigeration system as such. In particular, if the cooler works with large volumes of sea or river water as a cooling medium for the cooling pipes, corrosion of the Cooling line break down the work of the entire system. The causes of corrosion can be numerous and different soln and this includes e.g. the voltage difference between building material and different metals, or the battery effect, which leads to local electrolysis and corrosion, dezincification, breaking up of running water, which causes breakdown corrosion results in impurities that cause attack via precipitation, as well as mechanical loads that also lead to corrosion of metals »

To report the corrosion of the species described here, is it has become known to introduce elene (II) sulfate into cooling water, whereby an anti-corrosive lining is formed on the inner wall surface of the cooling tubes, and furthermore iron ions To supply cooling water by means of electrolysis of iron using an electrifying device according to FIG.

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The former mode of operation, i.e. the formation of a protective lining from ferrous sulfate, which is introduced into the cooling water turns out to be disadvantageous, since iron (II) sulfate in the form of the anhydrous salt and many different water of crystallization Salts are present next to a heptahydrate, and all these compounds have different iron contents, and furthermore, if not closely monitored, the chemical compound to be added may not be in a correct proportion of the water volume. If the chemical content of iron is too large, the chemical compound will put in excessive Amount on the inner wall of the cooling tube, which creates an excessively thick anti-corrosive lining on a "Sufficient heat conduction is formed, or that of the cooling water added chemical compound can lead directly to corrosion.

You latter way of working, ie. the supply of iron ions into the cooling water by means of the electrolysis of iron in an electrolyzer, see FIG. 1, also has disadvantages, as explained further below. With reference to FIG. 1, the reference number 1 represents a tubular electrolytic cell, for example in the form of a cylinder with a practically vertical axis. The cell body 1 is provided with flanges 2a, 2b around the upper and lower openings. The manufacture is made of plastic or iron plates provided with a rubber lining ψ in the case of iron plates for the dual purpose of preventing corrosion and insulation. The lower flange 2b of the cell body 1 is covered with an insoluble anode plate 4 which is provided with a plurality of liquid holes 3a and a load-bearing plate 5 also with a plurality of liquid holes 3b of the same size as the liquid holes 3a, the same being fitted one on top of the other, and on the plates so arranged there is a funnel-shaped cover 6 attached thereto.

Usually the insoluble anode plate 4 is made of platinum, Lead-silver alloy, magnetic iron oxide with platinum-plated titanium or the like, and the load-bearing plate 5 is made

209808/1766

Made of plastic or the like. The funnel-shaped cover 6 is provided with an inlet pipe 7 for cooling water, as shown and indicated at the upper left part thereof, also a normally closed exhaust pipe 8 at the lower end. above the insoluble anode plate 4 is found a carbon plate 9 for protecting the anode plate. the Carbon plate 9 is provided with liquid holes 3c at positions corresponding to those of the holes 3a. Above the carbon plate or inside the electrolyte! see cell body 1 there is a plurality of scrap iron pieces 10 with a larger diameter than that of the liquid holes 3a, 3b, 3c, On the upper flange 2a of the cell body 1, a cathode plate 11 is attached, for example in the form of an iron grid, which is connected with a plurality of liquid holes is perforated and an inverted funnel-shaped cover 13 provided with an electrolytic outlet pipe 12 in the upper end is at the upper flange 2a fixed over the cathode 11. The anode plate 4 and the cathode plate 11 are in a corresponding manner connected to the positive and negative poles of the power source, not shown.

When operating the electrolysis device of the specified type, a direct current voltage is applied between the anode 4 and the cathode 11, while raw water for cooling, such as seawater, is introduced into the cell through the inlet pipe 7. The current passes through the insoluble anode 4, carbon plate 9 and the scrap iron pieces 10 to reach the cathode 11. During this period of time, the scrap iron pieces 10 are dissolved in the manner indicated by the formula A in proportion to the applied current. As a result, the Fe ⁺ -containing electrolyte flows out of the outlet pipe 12, and the inner surface of a cooling pipe made of copper or copper alloy, not shown, in connection with the outlet pipe 12 is given an anti-corrosive lining with the hydrated iron oxide (FeOOH) as shown in the following Formulas (B) and (C) are shown. The pieces of scrap iron are thus dissolved

Fe = Fe ⁺⁺ + 2e (A)

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- 4 -

2 U 1 "U 3

and as soon as the electrolyte containing Fe is removed from dt- = in cooling tube hej?

flows. surrenders

2Fe ⁺ " ¹ '+ H" 0 -13 0 "* ■ 2FgOOIJ (B)

2 FeOOH Φ Fe ₂ O, H ₂ O IC)

so that the inner surface of the cooling tubes with G.ineim ant.Jkorrof?: 'vcü film of hydrating iron oxide (FeOGII) iibeiTAitjroi tii ^f U

When working in accordance with the above-mentioned precedence ^! ; n «üJ-ei: rine Ipiri re side span, however, there is a tendency towards the inside of scale _e in the form of, for example, magnesium hydroxide (Mg (OIlK ₁ ) and

Calcium carbonate CaCO ₃ and accumulation of the l'esseJjyielnr on i-clirotteiseiistücfcen 20 _f whereby it is even possible i_r? T _f that ei « Ψ'-i I of the deposited boiler in the rooms switch? and hierdurchdie FließlranäJe bJoehiertc DiG speed _f with which the cooling water in the KWh! pipe flows thus n.immt disadvantageously from "Furthermore leads die-- El & k trelyse l-oi applying the current in the above White * ru a dissolving of the upper Surface of the scrap! Sengtüoke 10 immittc? .3bnr adjacent to the cathode 11 ₍ and thus de "F3ü;: - sigl; elrsui Acι ~ stood between the scrap iron pieces .10 and de ?: I'athc-de to, ^T .; c ™ reduces the power ''is' This n eight it with the 5N combination: resistance accumulate on the Schrotteisenstücktn 10 ¹ ©: ". boiler stone necessary to increase the current in order to form a desired amount of Fe Accordingly must the cell holder additional to electrolytic cells lle 1, as indicated by the "curve ^ Din 6r- . '£ Fig * ^! r - is increased, which results in a corresponding increase in energy consumption EeIIe I in order to maintain the desired conditions as in the case where the electrolytic device according to FIG. 1 s _c E is installed on board a ship, where vibrations cause the ship to oar and pitch _{auftreteii f} iisij- die- ΐία! £ ^? _ ίΆ'5 r ^ iode 4 also to damage thereby.

The invention is min the task sugruiide, - .. lic isit αοΐ & cJjgQh-sn- * state of the art related) U

ί-'ΐϊ: Ei: Stna & Mgsg®gmnstc: Mä consists in the ws & QBtli cli: m in _f that sin *.

2 θ 9 8 0 8/1 7 8 c * ^{> J} **

Liquid holes are formed and in the lower part of the electrolytic Cell arranged, with bar iron practically perpendicular to the anode, the cathode parts parallel and across the upper end of the bar and an arrangement is provided, through which the bar iron and the cathode parts are electrically isolated from one another, whereby an electrical Current is passed through the electrolytic cell while raw water is fed through the cell, according to the invention an electrolytic electrode device is provided, whose Energy consumption is significantly reduced due to the decrease in electrolytic cell voltage and the need for plugging the flow channels are prevented by scale emanating from the cathode, as well as the electrolytic cell is able to to be operated in a closed state for longer periods of time, even at locations that are significant Swivel movement «!! or are exposed to vibrations.

An embodiment of the invention is shown in the drawing and is described in more detail below. Show it:

Fig. 1 is a vertical section through a conventional electrolytic table Electrode device;

Fig.2 is a characteristic curve showing the changes in the electro-lytic Represents cell voltage as a function of the electrolysis time expressed in days.

Fig. 3 is a vertical section through an embodiment of the Object of invention;

4 shows a transverse section through the embodiment according to of Figure 3.

F ig, 5 ~ iiine perapoktlvlüche Ana I I; of E in-out kept the anode assembly after ο in «L * further AuiifUhrunyaform;

Fig. 6 is a cjiiier other section through ti ine further execution s shape

7 shows a vertical section through the anode arrangement of a further embodiment.

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The first embodiment of the present invention is referred to explained on Figures 3 and 4. As shown in Figure 3, reference numeral 21 indicates a tubular electrolytic cell body in the form of, for example, a cylinder with a practical vertical axis again »The cell body 21 is with corresponding flanges 22a, 22b around the upper and lower openings provided around, the same is made of plastic or iron plates, with a rubber lining in the case of the Iron plates are provided for the dual purpose of corrosion resistance or insulation, the lower flange 22b of the cell body 21 has disposed thereon an insoluble anode plate 24, for example made of platinum, which is provided with a plurality of liquid holes 23 and a load-bearing plate 25 are provided, which are flat

w be present with a plurality of flussigkeitsRöchern 23b of the same shape as the Flüsügke its holes 3a and in a coordinated this location, and a funnel-shaped cover 26 is secured to the superposed plates. The funnel-shaped cover 26 is provided with a normally closed exhaust pipe 27, and on one side of the cell body 21 an inlet pipe 28 for the raw water serving for cooling purposes is provided, e.g. at right angles to the axis of the tank body, over the insoluble anode plate 24 is a carbon plate 29 to Protect the anode plate 24 from. The carbon plate 29 is provided with liquid holes 23c at positions corresponding to those of the holes 23a above the plastic plate 29

fc is a plurality of iron bars 30 arranged in the Cell body 21 recorded v / ground. The iron rod 30 is larger in diameter than the liquid holes 23a, 23b 2 3c on.

The upper flange 2 in the cell body ^ 21 is attached to a cathode plate .31 2.B, in the form of a lüsemjittoi "; - j, which is provided with a large number of liquid holes and provides an inverted funnel-shaped leakage 1 \ with a Electrolyte outlet tube 32 at the upper end is attached to the upper flange, and a plurality of cathode rods 31a are attached to the cathode 31 and are oriented vertically downward around the iron rod 30. The lower ends of the cathode rods 31a are not in contact with the Carbon plate

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. retained and are the same with a plastic or the like isolated _f so as consumption of the Kohlenstoffρlatte 29 due to locally occurring high currents to prevent "Between the cathode rods 31a and the rod iron 30 is an insulating £ -. 'arranged 2inder 35, which at the top is open and the bottom is provided with a plurality of fluid holes 34 within the envelope. This insulating cylinder 35 is made, for example, of a plastic and protects the rod iron 30 against falling into contact with the cathode rods 31a and thus the formation of a short circuit. The anode plate 24 and the cathode plate 31 are correspondingly positive and negative Poles of a power source ,, not shown? tied together"

In the construction described here, the device operates in the following manner. Once a DC voltage zv / isehen the anode 24 and the cathode 31 beuafschlagt with simultaneous insertion of the serving for cooling the raw water, for example sea water _e into the cell through the inlet tube 28 occurs, the current through the insoluble anode 24, the carbon plate 29, the rod iron 30 and the Liquid holes 34 of the insulating cylinder 35 and reaches the cathode rods 31a “At the same time, part of the current flows through the upper opening of the insulating cylinder to the cathode 31 ) on. The electrolyte containing the iron ions according to the formula Fe -f Fe + 2e flows through the ctss outlet pipe 32 and the discharge pipe 27 from _t so that the inner wall surfaces of the cooling tubes made of copper or copper alloy, not shown, correspond to the tubes 27 _y 32 are connected, an anti-corrosive coating with hydrated iron oxide (FeOOH) out of the formulas (B) and (C) "Since the cathode has 31 via the rod iron 30 liquid ^ holes and the rod iron in turn opposite to a more" number is present in rod cathode around its circumference _B there is no possibility that a part is rapidly dissolved away of the iron in the upper part of OCE cell 21, as is the case with a conventional ropes "Overall" check solves the rods = orphans 30 evenly on , - with no significant increase in the fluid resistance © ® swisefeea of the cathode 31 nnä ä & s Änod © Zi

208808/11? ! § "Q-

occurs, as is the case with prior art devices. Further, if scale of magnesium hydroxide Mg (OH) ₂ and the like comes off the cathode, it has no effect on the liquid resistance between the bar iron 30 and the bar cathodes 31a, and the resistance remains unchanged. The use of bar iron 30 precludes clogging of the flow channel upon removal of the scale from the cathode. Thus, it is not necessary to open the electrolytic cell 21 after many hours of work to remove the fallen scale, as is required in a conventional cell. For this reason and for the reasons given above, there is no increase in the fluid resistance exhibited by the cell voltage of the electrolytic cell 21

fc thus has a lower curve E, see FIG. 2, than the comparative one Curve D of a conventional device, which indicates a significant energy saving. Providence of the insulating cylinder 35 between the cathode rods 31a and the rod iron 30 avoids short-circuiting in the event that that the bar iron should fall against the bar electrodes, thus making it possible to close the device there as well install where there is significant vibration, e.g. on board a ship. This results in very important practical ones Advantages. Furthermore, due to the electrical insulation of the free ends of the cathode rods 31, there is no local limited high currents flow between the cathode rods and the carbon plate 29, and thus the carbon

P plate 29 protected against wear caused by oxidation.

Even if platinum is used as the insoluble anode 24 in the embodiment described here, it is understood, however, that A lead-silver alloy, magnetic iron oxide, platinum-plated titanium or the like can also be used in place of platinum can. Furthermore, the inlet pipe 29 for the raw water provided for cooling purposes, which is perpendicular to the axis of the electro-Iytischen Cell 21 can also be arranged in another way, e.g. in a direction tangential to cell 21, in this case there is an additional advantage of the effective removal of the scale from the cathodes 31,31a results, due to the introduction of the raw water into the

Cell 21 such that there is a swirling flow.

In Figures 5 and 6 is a further embodiment according to the invention shown. It differs from the first embodiment in the following respects. In the Embodiments explanatory figures give the same reference numerals to the same parts, so that a renewed description unnecessary. In the second embodiment, a plurality of Iron bar groups 43, each of a plurality of iron bar members 41 connected to an insulating frame 42 has, practically perpendicular to an insoluble anode 24 by means of a carbon plate 29 between adjacent ones Liquid holes 23a of the anode 24 and anehden of clips 42b held on the bottom of the insulating frame 42. The second embodiment is briefly outlined characterized in that the bar groups 43 are fixed vertically by means of brackets 42b so that the same between the edges of the adjacent liquid holes 23a (23b, 23c) and 23a (23b, 23c) are held, as well as the cathode rod 21a are present along the liquid holes 23a, 23b and 23c, see FIG. 6. Due to which the same in their Positional insulating frames 42 cannot hold the iron bar groups 43 by tilting motion of vibration fall over and there is a greater safety factor than in the embodiment according to the first embodiment. There the cathode rod 31a along the liquid holes 23a, 23b and 23c is provided, the scale once formed on the cathode rods 31a may fall off from them is easily out of the cell through the liquid holes 23a, 23b and 23c are removed.

FIG. 7 shows a third embodiment according to the invention. A description of the parts having the same reference numerals is unnecessary here. The third embodiment is not divided differ from the others in the following respects. As bar iron 30, a plurality of iron pipes is used here, the each houses an insulating cylinder 51 which in turn contains a cathode rod 53. The insulating cylinder 51 is seen with a multitude of fluid holes 52 - /?

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and has a lower extension 51b, which is fixed in the overlying Liquid cait holes 23a, 23a and 23b of a carbon plate 29 and an insoluble anode plate 24 and a load bearing plate 25 are provided. The cylinder is open at the top and bottom.

As explained above, according to the invention there is an arrangement which essentially consists of an insoluble anode plate provided with a plurality of liquid holes and arranged in the lower part of an electric cell, bar iron that is practically perpendicular to the anode, cathode parts that parallel to and above the top of the iron bar, and an arrangement for electrically isolating the iron bar and of the cathode parts from one another, so that an electric current is passed through the electrolytic cell, while raw water is fed into the same is fed in. With this construction there is no possibility of clogging of the flow channel with scale from the The cathode has fallen off after the device has been in operation for a long time, and the electrolytic cell can be operated for a long time if it is closed will. Furthermore, the bar iron can uniformly by the action of the cathode parts, which over the length of the same and above exist, are dissolved, and thus the formation of a considerable increase in the fluid resistance between the cathode and bar iron prevented. Due to the presence of insulation between the cathode and the bar irons, whereby short-circuiting is prevented, the electrolytic electrode device according to the invention is also very well protected against the effects caused by tilting movements and vibrations.

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Claims (3)

Claims lJ Electrolytic electrode device, characterized in that that an insoluble anode plate provided with a plurality of liquid holes and arranged in the lower part of the electro-lytic Cell is present, bar iron is practically perpendicular to the anode, cathode parts parallel and above the upper end of the bar iron are present and an arrangement is provided for electrolytically isolating the bar iron of the cathode from one another are, whereby an electric current is passed through the electrolytic cell while raw water is fed into the same will. 2. Electrode device according to claim 1, characterized in that the bar iron in the form of a plurality of bar iron groups is present, each of which consists of a plurality of rod iron elements which are practically perpendicular to the insoluble anode and between adjacent liquid holes of the same with pulling isolating framework are present. 3. Electrode device according to claim 1, characterized in that that the bar iron is in the form of a plurality of iron tubes, each of which contains an insulating cylinder on in turn one of the cathode rods, the a plurality of liquid holes is formed therethrough. Dipl.-inc INSPECTED 209808/1766