Title of Invention

CATHODE ELEMENT FOR A POT OF AN ELECTROLYTIC CELL INTENDED FOR PRODUCTION OF ALUMINIUM

Abstract

CATHODE ELEMENT FOR USE IN AN ELECTROLYTIC CELL INTENDED FOR PRODUCTION OF ALUMINIUM This invention relates to a cathode element, for use in a pot of an electrolytic cell intended for production of aluminium, comprising a cathode block (5) made of a carbonaceous material with at least a longitudinal groove along one of its side faces and a steel connection bar (6) , that is housed in the said groove such that a part of the bar emerges at one end of the block, is sealed in the groove by insertion of a conducting sealing material between the bar and the block and that includes at least one metal insert, whose electrical conductivity is greater than the electrical conductivity of the said steel. According to the invention, the insert (16) is arranged longitudinally inside the bar and is at least partly located in the segment (19) of the connection bar that is to be located outside the pot and the connection bar (6) is not sealed to the cathode block in a unsealed zone (17) with a determined surface area S located at the end of the groove at the head of the block. The presence of an insert according to the invention can simultaneously result in a very large drop in the global cathode voltage and a very strong reduction in the current density at the head of the block. Figure 2.

Full Text

CATHODE ELEMENT FOR USE IN AN ELECTROLYTIC CELL INTENDED FOR PRODUCTION OF ALUMINIUM DESCRIPTION This invention relates to the production of aluminium by fused bath electrolysis. In particular, it relates to cathode elements used in electrolytic cells intended for production of aluminium. The cost of energy is an important item in the operating costs of aluminium reduction plants. Consequently, a reduction in the specific consumption of electrolytic cells becomes very important for these plants. The specific consumption of a cell is equal to the energy consumed by the cell to produce one tonne of aluminium. It is expressed in kwh/t and, for a constant current efficiency, is directly proportional to the electrical voltage at the terminals of the electrolytic cell. The electrical voltage of an electrolytic cell can be sub-divided into several voltage drops, namely the anode voltage drop, the voltage drop in the bath, the electrochemical voltage, the cathode voltage drop and line losses. This invention relates to a reduction in the cathode voltage drop to reduce the specific consumption of electrolytic cells. The cathode voltage drop depends on the electrical resistance of the cathode element that includes a cathode block made of a carbonaceous material and one or several metal connecting bars. The materials from which the cathode blocks are made have changed in time to oppose less and less electrical resistance to current passing through them. This has increased currents passing through the cells, while maintaining a constant cathode voltage drop. In the 1970s, cathode blocks were made of anthracite (amorphous carbon). This material offered a fairly high electrical resistance. Faced with the needs of plants to increase their current intensity in order to increase their production, these blocks were progressively replaced by so-called "semi-graphite" blocks (containing between 30% and 50% of graphite) starting from the 1980s, then by so-called "graphite" blocks containing 100% of graphite grains but whose binder between these grains remains amorphous. Since the graphite grains of these blocks have a low electrical resistance, the blocks present a lower electrical resistance to current passing through them and consequently, for constant intensity, the cathode voltage drop is reduced. Finally, the most recent block generations are so-called "graphitised" blocks. A high temperature graphitisation heat treatment is carried out on these blocks, increasing the electrical conductivity of the block by graphitisation of the carbon. At the same time as these improvements to reduce the electrical resistance of materials, the current used in aluminium reduction plants for the production of aluminium increased, so as to increase their production (for constant current efficiency, the number of tonnes of metal produced by a cell is proportional to the intensity of the current that passes through it) . Consequently, since the cathode voltage drop Uc is equal to the product of the cathode resistance Re and the intensity I of the current circulating in the cathode (Uc = Re x I), cathode voltage drops are still high, typically about 300 mV. Furthermore, changes to the properties of cathode blocks have led to the emergence of new problems such as, for example erosion of cathodes. For example, it is observed that as the quantity of graphite contained in cathode blocks increases, they become more sensitive to erosion problems at the head of the block. The current density is not distributed uniformly over the entire width of the pot, and there is a peak current density at each end of the block, on the surface of the cathode. This peak current density causes local erosion of the cathode, which is particularly marked when the block is rich in graphite. These very high erosion areas can limit the life of the pot, which is a major economic problem for an aluminium reduction plant. It is known that the cathode voltage drop Uc can be reduced by using composite connection bars including a steel part and a part made of a metal with an electrical conductivity higher than steel, usually copper. Examples of patents include French patent application FR 1 161 632 (Pechiney), American patents US 2 846 388 (Pechiney) and US 3 551 319 (Kaiser) and international application WO 02/42525 (Servico). It is also known from the international applications WO 01/63014 (Comalco) and WO 01/27353 (Alcoa), that copper inserts can be used to improve the distribution of current along the cathode block. These documents teach to enclose a copper insert in the steel connection bar and to confine the insert inside the cell in order to reduce conduction of heat out of the cell. However, these solutions are a priori expensive because copper is more expensive than steel and the copper quantities involved may be high. In the most frequently used technologies, the number of bars per electrolytic pot is usually between 50 and 100. Therefore the extra cost due to the presence of copper components can increase very quickly. Furthermore, known configurations in prior art are not fully satisfactory. These configurations cause reductions in the global cathode voltage drop (in other words including the voltage drop in the bar) of the order of 50 mV, which is too low to justify the additional investment costs, and produce relatively high peak current densities at the head of the block, namely more than about 12 kA/m2. Therefore the applicants tried to find satisfactory solutions to the drawbacks of prior art, and particularly to the problem of specific consumption. Description of the invention The purpose of the invention is a cathode element for use in a pot of an electrolytic cell intended for production of aluminium comprising: - a cathode block made of a carbonaceous material with at least one longitudinal groove along one of its side faces; - at least one steel connection bar, of which at least one part called the "external segment" will be located outside the pot, which is housed in the said groove such that a part of the bar called the "part outside the block" emerges at least at one end of the block called "block head", and which is sealed in the groove by insertion of a conducting sealing material such as cast iron or conducting paste between the bar and the block. The cathode element according to the invention is characterised in that, for each external segment: - the connection bar includes at least one metal insert with length Lc, whose electrical conductivity is greater than the electrical conductivity of the said steel, which is arranged longitudinally inside the bar and which is at least partly located in the said segment; - the connection bar is not sealed to the cathode block in at least one zone called the "unsealed" zone with a determined surface area S located at the end of the groove at the head of the block. Preferably, the insert is flush (with a defined :olerance) with the surface of the end of the said external segment. Advantageously, the said insert or each insert is made of copper or a copper based alloy. The presence of an insert according to the invention can simultaneously result in a very large drop in the global cathode voltage (for example 0.2 V for a bar with a copper insert compared with 0.3 V for an entirely steel bar) and a very strong reduction in the current density at the head of the block (at least of the order of 20%). In his research, the applicant has noted that a large part of the drop in the cathode voltage (about one third) is located in the part of the bar "outside the block" that goes out of the block. In fact, the current density in the bar increases towards the part of the bar located outside the block and reaches its maximum value at the point the bar exits the block. Consequently, over the entire part of the bar located "outside the block", a small section carries a large quantity of current, which causes a large voltage drop. The applicants had the idea of combining an unsealed zone close to the head of the cathode block, and at least one insert in each external segment of the connection bar that extends preferably over substantially the entire length of the segment. They observed that, unexpectedly, the combined effect of these characteristics very significantly reduces the peak current density that exists at the head of the block, in other words close to the ends of the block, while very significantly reducing the cathode voltage drop. In particular, they noted that the unsealed zone can significantly reduce the impact of the ridge base on the peak current density. The invention is particularly attractive when the said carbonaceous material contains graphite. A process for manufacturing a connection bar that could be used in a cathode element according to the invention, advantageously includes the formation of a longitudinal cavity - typically a blind hole - in a steel bar starting from one end of the steel bar, manufacturing of an insert made of a material with a conductivity higher than the steel from which the bar is made, with a length and a section corresponding to the length and section of the cavity, and then the introduction of the insert into the cavity. Intimate contact between the insert and the bar is usually achieved as the pot temperature increases, due to differential thermal expansion between the insert and the bar (since steel expands relatively little compared with other metals). The invention also relates to an electrolytic cell including at least one cathode element according to the invention. The invention is described in detail below with reference to the appended figures. Figure 1 shows a cross-sectional view of a traditional half-pot. Figure 2 is a view similar to Figure 1 in the case of a cell comprising a cathode element according to the invention. Figure 3 shows a bottom view of a cathode element according to one embodiment of the invention. Figure 4 shows a bottom view of a cathode element according to another embodiment of the invention. Figure 5 shows a perspective view of one end of the cathode block in Figure 3 or 4. Figure 6 shows a segment of a connection bar fitted with an insert with a circular section. Figure 7 shows a segment of a connection bar fitted with an insert with a circular section in a lateral groove. Figure 8 shows cathode current distribution curves along a cathode block. As illustrated in Figure 1, an electrolysis cell 1 comprises a pot 10 and at least one anode 4. The pot 10 comprises a pot shell 2 whose bottom and sidewalls are covered with elements made of a refractory material 3 and 3'. Cathode blocks 5 are supported on the bottom refractory elements 3. Connection bars 6, usually made of steel, are sealed into the lower part of the cathode blocks 5. The seal between the connection bar (s) and the cathode block 5 is usually made by using cast iron or conducting paste 7. As illustrated in Figures 3 to 5, the cathode blocks 5 are substantially parallelepiped in shape with length Lo, in which one of the side faces 21 has one or several Longitudinal grooves 15 in which the connection bars 6 tfill be housed. The grooves 15 open up at the head of the block and generally extend from one end of the block to the other. The length of the so-called " part outside the block" 22 of the bar 6 that emerges from the cathode block 5 is E. The cathode blocks 5 and the connection bars 6 form cathode elements 20 that are usually assembled outside the pot and are added to it during the formation of its inner lining. An electrolytic pot 10 typically comprises more than about 10 cathode elements 20 arranged side by side. A cathode element 20 may include one or several connection bars passing through the block from side to side, or one or several pairs of half-bars typically in line, that extend only on a part of the block. The function of the connection bars 6 is to collect the current that passed through each cathode block 5 and to direct it to the conductor network located outside the pot. As illustrated on Figure 1, the connection bars 6 pass through the pot 10 and are typically connected to a connecting conductor 13, usually made of aluminium, through a flexible aluminium fitting 14 connected to the segment(s) 19 of the bars that come out of the pot 10. During operation, the pot 10 contains a pad of liquid aluminium 8 and an electrolytic bath 9 above the cathode blocks 5, and the anodes 4 dip into the bath 9. A solidified bath ridge 12 usually forms on the side linings 3'. A part 12' of this ridge 12, called the "ridge base" can project over the upper lateral surface 28 of the cathode block 5, The ridge base electrically isolates the cathode and increases the peak current density at the block head. Figure 2 shows an electrolytic cell 1 for the production of aluminium in which the same elements are denoted using the same references as above. As illustrated in Figure 2, each end of the connection bar 6 is fitted with a metal insert 16, preferably made of copper or a copper alloy, extending on a length Lc, typically starting substantially from the end or each outer end of the bar 6. The insert 16 is at least partly located in the external segment or each external segment 19 of the connection bar 6 that will be located outside the pot 10. The insert or each insert 16 is preferably housed in a cavity forming a blind hole inside the bar 6. This variant can avoid exposure of the insert to possible bath or liquid metal infiltrations. The cavity may be a groove on a side face of the bar as illustrated in Figure 7 . The insert preferably occupies at least 90% of the length Le of the external segment or each external segment 19 of the connection bar 6 in which it is housed to optimise the reduction in the voltage drop obtained according to the invention. The end surface 24 which will be outside the pot 10 is usually substantially vertical when the cathode element 20 is installed in a pot. According to one advantageous variant of the invention, the insert or each insert 16 is substantially flush, with a determined tolerance, with the surface 24 of the end of the external segment 19 of the bar 6. The said determined tolerance is preferably less than or equal to ± 1 cm. According to another advantageous variant of the invention, the external end of each insert 16 is set back by a determined distance from the surface 24 of the end of the external segment 19 of the bar 6. The said determined distance is preferably less than or equal to 4 cm. The cavity formed by setting back the insert may advantageously contain a refractory material to prevent heat loss by radiation and / or convection. The length Lc of the insert 16 is typically between 10 and 300%, preferably between 20 and 300%, and more preferably between 110 and 270%, of the length E of the "part outside the block" 22 of the bar 6 that emerges from the cathode block 5 and in which the insert is housed. The longer the insert, the lower the cathode voltage drop. However, the applicant noted that, when the insert is longer than 270% of the part 22 of the bar outside the block, increasing of the insert length only has a small effect on the value of the cathode voltage drop. As illustrated in Figure 2, at least one zone 17 located between the bar 6 and the cathode block 5 does not contain any sealing material. This zone called the "unsealed" zone is advantageously completely or partly filled with an electrically insulating material such as a refractory material, typically in the form of fibres or fabric; this material is inserted between the bar 6 and the cathode block 5, in the unsealed zone 17 as illustrated in Figure 5. The unsealed zone or each unsealed zone 17 is located close to the end 25 of the cathode block 5 called the "block head" from which the bar emerges and covers a determined surface area S. Preferably, the unsealed zone or each unsealed zone 17 is flush with the surface 27 of the block head 25 from which the bar 6 emerges. Figures 3 and 4 illustrate two particular embodiments of the cathode element 20 according to the invention. In the example in Figure 3, the cathode element includes two parallel connection bars that pass through the cathode block from side to side. Each bar then includes two parts outside the block 22 and two external segments 19. In the example in Figure 4, the cathode element includes four connection bars (also called "half-bars") each of which projects at one end of the block. Each bar then comprises a single part outside the block 22 and a single external segment 19. In both examples, a conducting sealing material 7 is inserted between the block 5 and each bar 6, except in areas located at the ends of the block 5 where there are unsealed zones 17 that can be filled with refractory materials. The total area A of the determined surface(s) S of the unsealed zone(s) 17 of each connection bar 6 is typically between 0.5 and 25%, and preferably between 2 and 20%, and more preferably between 3 and 15%, of the area Ao of the surface So of the bar 6 that may be sealed, called the "sealable zone". The sealable surface So is the surface of the part 23 of the bar 6 that faces the internal surfaces of the groove 15 in the block 5. When the connection bar or each connection bar 6 passes through the cathode block 5 from one side to the other as illustrated in Figure 3, the area Ao of the sealable surface So is typically equal to Lo x (2 H + W) , where H is the height of the bar and W is its width. In this case, since each connection bar 6 has an unsealed zone 17 at each end 25, the total area A is equal to the sum of the areas of each determined surface S. When the connection bars 6 are interrupted towards the centre of the block to form two half-bars in line with each other as illustrated in Figure 4, the area Ao of the sealable surface So of each half-bar is typically equal to Li x (2 H + W) , where H is the height of the bar and W is its width. In this case, since each connection half-bar 6 has an unsealed zone 17 at a single end, the total area A is equal to the area of the determined surface S of this unsealed zone. However, the applicant has observed that when the discontinuity of the bar close to the centre of the block is relatively short, which is usually the case, this has little effect on the distribution of the current and the voltage drop, such that the area A can be determined as if the bars were continuous from one end to the other. The determined surface S is typically a simple shape to facilitate formation of the unsealed zone 17. In the case illustrated in Figures 2 to 4, in which the unsealed zone 17 is formed by the lack of sealing over a length Ls, starting from the surface 27 of the block head 25, the area of the determined surface S is typically equal to Ls x (2H + W). In this case, the length Ls of each unsealed zone 17 is preferably between 0.5 and 25%, and preferably between 2 and 20%, and more preferably between 3 and 15%, of the half-length Lo/2 of the block. The section of the insert 16 also affects the reduction of the cathode voltage drop. Advantageously, the cross section of each insert is between 1 and 50%, and preferably between 5 and 30%, of the cross section of the bar 6. For values of insert section greater than 30% of the total section, the additional conducting quantity significantly increases the cost without increasing performances very much. The insert 16 is typically in the form of a bar. The shape of the cross section of the insert 16 is free, this shape possibly being rectangular (as illustrated in Figure 5), circular (as illustrated in Figure 6 or 7) , or ovoid or polygonal. However, it is advantageously circular in order to facilitate manufacturing of the connection bar, and particularly manufacturing of the cavity in which the said insert will be housed. The applicant has carried out digital calculations to evaluate the distribution of the cathode current at the surface 28 of the cathode block obtained with configurations according to prior art and according to the invention. Figure 8 shows the results of a calculation corresponding to the dimensions of the connection bar and a current intensity typical of existing electrolytic cells. The curves correspond to the current density J at the upper surface 28 of the block, expressed in kA/m2 as a function of the distance D from the end of the block. The cell comprises 20 cathode elements arranged side by side and each comprising two connection bars as illustrated in Figure 3. The total intensity is 314 kA. The length of the connection bars L is equal to 4.3 m, the height H is equal to 160 mm and the width W is equal to 110 mm. The length E of the connection bars extending outside from the cathode blocks is 0.50 m. Curve A, applicable to prior art, corresponds to an all-steel connection bar. The cathode voltage drop is 283 mV (between the centre of the liquid metal pad and the anode frame of the downstream pot). Curve B, applicable to prior art, applies to a steel bar with the same dimensions as in case A, but comprising a copper cylindrical insert with a length equal to 1.53 m and a diameter equal to 4.13 cm. The insert is placed along the longitudinal axis of symmetry of the bar and extends substantially from the centre of the bar (in other words substantially from the central plane P of the pot) to about half the thickness of the lining of the side 3' of the cell. The cathode voltage drop is 229 mV. The reduction in the cathode drop is about 19% less than in case A, and the reduction in the peak current density is about 18%. Curve C relating to the invention corresponds to a steel bar with the same dimensions as in case A, but with a copper cylindrical insert with length Lc equal to 1.30 m and with a diameter equal to 4.5 cm (corresponding to a copper volume identical to that in case B) . The insert is placed along the longitudinal axis of symmetry of bar and, as in Figure 2, extends from the outer end of the bar to the inside of the cell. The length of the unsealed zone is 0.18 m and it covers the three normally sealed faces of the bar. The cathode voltage drop is 190 mV. The reduction in the cathode voltage drop is about 32% less than in case A, and the reduction in the peak current density is about 37% less than in case A. The distribution of the cathode current is significantly more uniform than in cases A and B. CLAIMS 1. Cathode element (20), for use in a pot (10) of an electrolytic cell (1) intended for production of aluminium, comprising: a cathode block (5) made of a carbonaceous material with at least one longitudinal groove (15) along one of its side faces (21); at least one steel connection bar (6), of which at least one part called the "external segment" (19) will be located outside the pot (10) , which is housed in the said groove (15) such that a part (22) of the bar called the "part outside the block" emerges at least at one end (25) of the block called "block head", and which is sealed in the groove (15) by insertion of a conducting sealing material (7) such as cast iron or conducting paste between the bar and the block, and characterised in that for each external segment (19): - the connection bar (6) includes at least a metal insert (16) with length Lc, whose electrical conductivity is higher than the electrical conductivity of the said steel, which is arranged longitudinally inside the bar and which is at least partly located in the said segment (19); - the connection bar (6) is not sealed to the cathode block (5) in at least a zone called the "unsealed" zone (17) with a determined surface area S located at the end of the groove (15) at the head of the block. 2. Cathode element (20) according to claim 1, characterised in that each insert (16) is made of copper or a copper based alloy. 3. Cathode element (20) according to either of claim 1 or 2, characterised in that the length Lc of each insert (16) is between 10 and 300% of the length E of the "part outside the block" (22) of the bar (6) in which the insert is housed. 4. Cathode element (20) according to either of claim 1 or 2, characterised in that the length Lc of each insert (16) is between 20 and 300% of the length E of the "part outside the block" (22) of the bar (6) in which the insert is housed. 5. Cathode element (20) according to either of claim 1 or 2, characterised in that the length Lc of each insert (16) is between 110 and 270% of the length E of the " part outside the block" (22) of the bar (6) in which the insert is housed. 6. Cathode element (20) according to any one of claims 1 to 5, characterised in that the cross section of each insert (16) is between 1 and 5 0% of the cross section of the bar (6). 7. Cathode element (20) according to any one of claims 1 to 5, characterised in that the cross section of each insert (16) is between 5 and 30% of the cross section of the bar (6). 8. Cathode element (20) according to any one of claims 1 to 7, characterised in that the total area A of the determined surface(s) S of the unsealed zone(s) (17) of each connection bar (6) is between 0.5 and 25% of the area Ao of the surface So of the bar (6) that may be sealed. 9. Cathode element (20) according to any one of claims 1 to 7, characterised in that the total area A of the determined surface (s) S of the unsealed zone (s) (17) of each connection bar (6) is between 2 and 20% of the area Ao of the surface So of the bar (6) that may be sealed. 10. Cathode element (20) according to any one of claims 1 to 7, characterised in that the total area A of the determined surface (s) S of the unsealed zone (s) (17) of each connection bar (6) is between 3 and 15% of the area Ao of the surface So of the bar (6) that may be sealed. 11. Cathode element (20) according to any one of claims 1 to 10, characterised in that an electrically insulating material is inserted between the connection bar (6) and the cathode block (5) in the unsealed zone or each unsealed zone (17). 12. Cathode element (20) according to any one of claims 1 to 11, characterised in that each insert (16) is flush, with a defined tolerance, with the surface (24) of the end of the external segment (19) of the bar (6). 13. Cathode element (20) according to claim 12, characterised in that the said determined tolerance is less than or equal to i 1 cm. 14. Cathode 'element (20) according to any one of claims 1 to 11, characterised in that the external end of- each insert (16) is set back by a determined distance from the surface (24) of the end of the external segment (19) of the bar (6). 15. Cathode element (20) according to claim 14, characterised in that the said determined distance is less than or equal to 4 cm. 16. Cathode element (20) according to claim 15, characterised in that the cavity formed by setting back the insert contains a refractory material. 17. Cathode element (20) according to any one of claims 1 to 16, characterised in that the cross section of each insert (16) is circular. 18. Cathode element (20) according to any one of claims 1 to 17, characterised in that each insert (16) is housed in a cavity forming a blind hole inside the bar (6) . 19. Cathode element (20) according to any one of claims 1 to 18, characterised in that the said carbonaceous material contains graphite. 20. Electrolytic cell (1) intended for the production of aluminium, characterised in that it comprises at least a cathode element (20) according to any one of claims 1 to 19.

Documents:

4029-CHENP-2006 CORRESPONDENCE PO.pdf

4029-CHENP-2006 AMANDED CLAIMS 17-12-2009.pdf

4029-CHENP-2006 AMANDED PAGE OF SPECIFICATION 17-12-2009.pdf

4029-chenp-2006 claims-03-07-2009.pdf

4029-CHENP-2006 CORRESPONDENCE OTHERS 18-12-2009.pdf

4029-chenp-2006 correspondence others-03-07-2009.pdf

4029-CHENP-2006 EXAMINATION REPORT REPLY RECIEVED 17-12-2009.pdf

4029-CHENP-2006 FORM-1 17-12-2009.pdf

4029-chenp-2006 form-26-03-07-2009.pdf

4029-CHENP-2006 FORM-3 17-12-2009.pdf

4029-CHENP-2006 OTHER PATENT DOCUMENT 17-12-2009.pdf

4029-chenp-2006-abstract.pdf

4029-chenp-2006-claims.pdf

4029-chenp-2006-correspondnece-others.pdf

4029-chenp-2006-description(complete).pdf

4029-chenp-2006-drawings.pdf

4029-chenp-2006-form 1.pdf

4029-chenp-2006-form 18.pdf

4029-chenp-2006-form 26.pdf

4029-chenp-2006-form 3.pdf

4029-chenp-2006-form 5.pdf

4029-chenp-2006-pct.pdf