EP0085999B1 - Installation pour la régulation d'un groupe de cellules d'électrolyse à cathode de mercure - Google Patents

Installation pour la régulation d'un groupe de cellules d'électrolyse à cathode de mercure Download PDF

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Publication number
EP0085999B1
EP0085999B1 EP83200088A EP83200088A EP0085999B1 EP 0085999 B1 EP0085999 B1 EP 0085999B1 EP 83200088 A EP83200088 A EP 83200088A EP 83200088 A EP83200088 A EP 83200088A EP 0085999 B1 EP0085999 B1 EP 0085999B1
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EP
European Patent Office
Prior art keywords
local
anode
unit
memory
control unit
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Expired
Application number
EP83200088A
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German (de)
English (en)
French (fr)
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EP0085999A1 (fr
Inventor
Jean-Paul Detournay
Jacques Defourny
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Solvay SA
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Solvay SA
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Priority to AT83200088T priority Critical patent/ATE34782T1/de
Publication of EP0085999A1 publication Critical patent/EP0085999A1/fr
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Publication of EP0085999B1 publication Critical patent/EP0085999B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/04—Regulation of the inter-electrode distance

Definitions

  • the present invention relates to an installation for regulating a group of electrolysis cells with multiple anodes which can be displaced opposite a mercury cathode, in particular cells for the electrolysis of aqueous solutions of alkali metal halide, and more particularly of sodium chloride.
  • anode-cathode distances means that the position of the anodes in the electrolysis cells must be checked periodically and an adjustment of the anodes may be necessary. In order to obtain optimum energy efficiency, it is indeed necessary to correct the position of the anodes whose distance from the cathode would become exaggeratedly great. It should also be avoided that one or the other anode occasionally comes into contact with the mercury cathode, because the short-circuit which would result therefrom could cause serious degradation at the anode, mainly in the case of titanium anodes carrying an active coating based on noble metal oxide.
  • the causes of an untimely increase in the anode-cathode distances or of a fortuitous contact between an anode and mercury are numerous; they may reside in particular in a deformation or wear of the anode, the formation of agglomerates of large mercury (sometimes called "mercury butter") adhering to the bottom of the cell or floating on the surface of mercury, an untimely variation of the level of mercury in the cell, a fortuitous turbulence occurring in the flow of mercury.
  • Patent BE-A-668,236 (Imperial Chemical Industries Limited) describes a method for adjusting the position of an anode in a mercury cathode cell, in which the electrical conductance of the separating electrolyte layer is measured the anode of the cathode, the measured value of the conductance is compared to a set value and the position of the anode is adjusted so that these two values are equal.
  • the apparatus is programmed so as to selectively and successively scan all the anodes of the cell and execute a complete sequence of process operations, for each anode scanned.
  • the set value is a fixed value of the electrical conductance of the electrolyte layer, corresponding to a predetermined anode-cathode distance. It is generally the result of an acceptable compromise between the search for optimum energy efficiency and the search for a sufficient level of safety in the operation of the cell. It must be defined in each particular case according to the operating conditions of the cell.
  • each local unit performs a measurement of the electrical conductance of the electrolyte layer under each anode of the cell with which it is associated, it calculates a set value from local data of the operation of its cell and general data for the operation of the cell group and it compares the measured conductance value with the set value and governs the position of the anode accordingly.
  • the central unit acts as a relay between the local units, transferring the above-mentioned general data to each of them.
  • This known installation with decentralized operation has a series of disadvantages, among which a high cost of implementation, a relatively long response time of the local control units, owing to the fact that the latter must proceed with the calculation of the set values, and the impossibility of ensuring an orderly regulation of the whole group of cells.
  • the invention seeks to remedy these disadvantages by providing an installation with a function Partially centralized, which ensures automatic, rapid, orderly and reliable regulation of the anode-cathode distances of a group of electrolysis cells.
  • the anode unit can be an individual anode or a group of anodes movable together with respect to the mercury cathode, for example a group of anodes fixed together, in bypass, to a rigid and displaceable current collector.
  • the organ for scanning the anode units generally consists of a logic circuit designed to connect the anode units of the electrolytic unit successively, separately and in a predetermined order, with the conductance measuring member. and with the local operating conditions detector.
  • the conductance measuring member, the transformer and the comparison circuit are coupled together and can advantageously be combined in a single device, of the type described in the aforementioned patent BE-A-668 236, comprising a device for the measurement of the intensity of the electric current passing through the scanned anode unit, a device for measuring the voltage between this anode unit and the mercury cathode, a computer coupled to these two measurement devices and designed to subtract from the voltage measured, the reversible potential of the electrolysis reaction, divide the result by the measured value of the current intensity and output a voltage signal representative of the result of the division, and a computer designed to subtract a setpoint voltage from this voltage signal and output an electrical signal representative of the result of this subtraction.
  • the motorized adjustment device generally consists of an electric motor controlled by the output signal from the comparison circuit to distance the anode unit. scrutinized from the cathode or bring it closer according to whether the instantaneous value of the conductance is higher or lower than the set value.
  • the detector may include, for example, thermocouples to measure the temperature of the electrolyte or mercury in the electrolytic unit, densimeters to measure the density of the electrolyte and thus define its concentration, flow meters to measure the flow rates of the electrolyte and mercury in the electrolytic unit, ammeters and voltmeters to measure the overall intensity of the electrolysis current in the electrolytic unit and the voltage across it.
  • the organ for scanning the local units generally consists of a logic circuit, designed to couple the local regulation units successively and separately with the central unit, in a predetermined order.
  • This circuit is also designed to transfer the signals sent by the converter from the scanned local unit into the setpoint circuit of the central unit and to transfer the setpoint signals from the central unit to the scanned local unit.
  • the setpoint circuit is used to define the setpoint value of the electrolyte conductivity for each anode unit of the electrolytic unit whose local regulation unit is scanned. It consists of an analog or digital computer which is supplied by the signals coming from the converter of the scanned local unit and which is designed to calculate, as a function of local conditions prevailing in the scanned electrolytic unit, the value of the conductance of the electrolyte layer for an imposed anode-cathode distance (conductance setpoint).
  • the local regulation units fulfill a double function: on the one hand ,. they are used to measure the electrical conductance of the electrolyte layer under each anode unit, transform this measurement into an electrical signal, compare it to a setpoint signal and activate the motorized adjustment device of the anode unit, depending the result of the comparison; on the other hand, they are used to record the local operating conditions relating to each anode unit and to convert them into electrical signals which are transferred to the central regulation unit.
  • the function of the central regulation unit is to calculate the set values of the anode units, starting from the local operating conditions recorded by the local regulation units, and to transfer these set values to the local regulation units.
  • the optimum value of the anode-cathode distance is rarely identical for all the anodes. It generally differs from one anode to another, depending in particular on the geometry of the anode, its degree, wear or its position in the cell.
  • the optimum value of the anode-cathode distances in a mercury cell is often influenced by the position of the cell among a group of cells.
  • the detector associated with each local regulation unit comprises a member for locating the position of the anode unit scanned in the electrolytic unit
  • the central regulation unit comprises a member for locating the position, in the group of cells, of the electrolytic unit associated with the scanned local unit.
  • the setpoint circuit associated with the central unit is supplied with additional signals defining the position of the scanned anode unit and of the electrolytic unit which contains it and it is thus able to make an additional correction in the definition of the set value.
  • the anode units can be divided into three categories, according to the distance which separates them from the cathode.
  • a first category includes anode units which occupy a position for which this distance is close to the ideal value and which therefore do not require an adjustment;
  • a second category of anode units consists of those which occupy a position which is excessively far from the cathode and which should be adjusted if the aim is to improve the energy efficiency of electrolysis;
  • the third category of anode units includes those which occupy a position which is excessively close to the cathode and which therefore require rapid intervention to avoid a local short-circuit and deterioration of the anode.
  • each local regulation unit comprises, on the one hand, between the comparison circuit and the device motorized adjustment, a comparison memory for storing the signals coming from said comparison circuit and, on the other hand, a programmer designed to perform the operation of the local unit in two phases comprising, in a first phase, a scanning of the units anode and a coupling of the comparison circuit with the comparison memory and, in a second phase, a scanning of the anode units and a coupling of the comparison memory with an actuating member of the motorized adjustment device.
  • the first scanning phase is used to establish the comparison signals of the anode units and the second scanning phase is used exclusively for adjusting the anode units from these signals. It is possible to program the programmer so that, for example, during the second scanning phase, the anode units are scanned successively one after the other in the order of increasing anode-cathode distances.
  • the comparison memory of each local regulation unit comprises a distributor of the signals stored in an order corresponding to increasing anode-cathode distances and its programmer is coupled to the distributor so to execute the scan in the second phase, in the order of storing the signals in the comparison memory.
  • each local regulation unit comprises a memory for the storage of the setpoint signals (which, in the following, will be called “setpoint memory”), a memory for the storage of signals from the transformer (which will hereinafter be designated “conductance memory”) and a memory for the storage of signals from the converter (which will hereinafter be designated “local operating memory”);
  • the central regulation unit comprises a memory for the storage of the signals coming from the converter of the local regulation units and a memory for the storage of the signals coming from the setpoint circuit (in the following, these two memories are called respectively " local operating memory "and” setpoint memory ").
  • This embodiment of the invention allows greater flexibility in the operation of the installation, in particular allowing the local units and the central regulation unit to perform several functions simultaneously.
  • the three steps of each operating sequence can be carried out on the same local regulation unit or on separate local units, and they can be carried out simultaneously or separately, according to the constructive characteristics of the central unit.
  • the two steps mentioned in the first place above are executed on the same local regulation unit, while the third step is executed on a other local unit. It is moreover preferred that the central regulation unit executes the step cited second, after having executed the other two steps.
  • the installation according to the invention mainly in its embodiment which has just been described, has the great advantage of shortening the overall duration of the control and adjustment of the anode units and, consequently, of increasing the frequency of these checks and adjustments. It follows that under normal operating conditions of the electrolysis cells, the anode units permanently occupy positions close to the optimum and therefore require only moderate adjustments. This feature allows the use, for the motorized adjustment device, of electric motors with a slow speed of rotation and therefore of low power and small size, the cost, electrical consumption and maintenance costs of which are moderate.
  • the motorized adjustment device consists of alternating current motors of the synchronous type, possibly fitted with a speed reducer. Because they are characterized by a constant speed of rotation, the use of synchronous motors has the advantage of facilitating the control of the amplitude of movement of the anode units, by simply performing a measurement of the operating time of the motors. .
  • This variant of the invention has the remarkable advantage of allowing the adjustment of several anode units simultaneously on each electrolytic unit, since between two successive scans of an anode unit, the polling member can scan other anode units of the electrolytic unit and start, if necessary, their respective motorized adjustment devices.
  • FIG. 1 shows a group of three mercury cathode cells 1, 2, 3 for the electrolysis of aqueous sodium chloride solutions.
  • These electrolysis cells are of the horizontal mercury cathode type (J. S. Sconce, Chlorine, its manufacture, properties and uses, 1962, Reinhold Publishing Corporation, New York, pages 181 to 194). They include a movable, slightly inclined mercury cathode, above which anodes such as 4, 4 ', 4 ", 5, 5', 5" are suspended by individual support rods 6.
  • the anodes are distributed in several parallel rows of anodes coupled in bypass to current supply bus bars 7 (for example the range of anodes 4, 4 'and 4 "and the range of anodes 5, 5' and 5").
  • the support rods 6 of the anodes can be moved vertically and individually to adjust the distance between each anode and the cathode and, for this purpose, an electric motor, not shown, is associated with each anode rod 6.
  • an electric motor not shown, is associated with each anode rod 6.
  • each motor is embedded in a mass of synthetic resin poured around the motor and crossed in leaktight manner by the motor shaft.
  • the installation for regulating the group of cells 1, 2, 3 comprises three local regulation units 8, each associated with an individual electrolysis cell and a central regulation unit 9 associated with the three local units 8.
  • each local regulation unit 8 the memories 13, 16, 17 and 19 are each divided into several storage sections 13a, 13b, ..., 16a, 16b, ..., 17a, 17b, ..., 19a , 19b, ..., each storage section, in each memory, corresponding to an individual anode of the electrolysis cell associated with the local regulation unit.
  • storage sections 13a, 16a, 17a and 19a each correspond to the only anode 4 of this cell 1.
  • the memories 22 and 24 are each divided into three storage sections 22a, 22b, 22c, 24a, 24b, 24c, each section, in each memory, corresponds to an individual local unit 8.
  • Each storage section is further divided into several independent storage areas, not shown, which each correspond to an anode of the electrolysis installation.
  • the programmer 20 of the local regulation units 8 has been programmed so that the local units operate cyclically, independently of each other, each cycle comprising five successive operating phases as described below.
  • an operating cycle of the local unit 8 associated with the cell 1 comprises, in chronological order, the following five operational phases.
  • the local unit 8 of the cell 1 is scanned by the central unit 9 and the setpoint memory 17 of this local unit is coupled to section 24a of the setpoint memory 24 of the central unit 9, via a transmission circuit 27a.
  • the memory 17 stores setpoint values relating respectively to all the anodes of the cell 1.
  • the central unit 9 is disconnected from the local unit 8 associated with the cell 1.
  • the local unit 8 of cell 1 successively scans all the anodes of cell 1 in a pre-established logical order, starting for example with anode 4. While anode 4 is scanned, the detector 14 detects local data on the operation of the cell 1, such as for example the temperature and the concentration of the sodium chloride solution at the inlet and at the outlet of the cell, or at the level of the row of anodes 4 , 4 ', 4 ", the flow of mercury in the cell, the number of the scanned anode 4. These local data are transferred into converter 15 where they are each converted into a separate electrical voltage signal, which is then stored in section 16a of the local walking memory 16.
  • the measuring device 11 records the intensity 1 of the electric current in the anode 4 and the electric voltage U between the anode 4 and the floor of the cell 1, then execute the operation: in which E. denotes the reversible voltage of the electrolysis reaction for the anode considered.
  • the reversible voltage E o is a fixed datum which depends in particular on the nature of the material of the anode and the position of the latter in the cell. In the case of titanium anodes carrying an active coating formed of a mixture of ruthenium oxide and titanium oxide, E o is generally fixed between 3.10 and 3.30V, depending on the position of the anode in the cell.
  • the result of the above operation represents the conductance of the electrolyte layer under the anode 4 in the cell 1; it can be obtained in the manner described in the patents BE-A-668,236 and BE-A-695,771 cited above.
  • the comparison circuit 18 is actuated and connected to the conductance 13, reference 17 and comparison 19 memories.
  • the comparison circuit 18 subtracts the voltage signals from the memory 17 from those of the memory 13 and transfers the resulting signals (comparison signals) into the storage sections 19a, 19b, 19c, ... from the comparison memory 19.
  • the polling member 10 re-polls the anodes of the cell and, for each scanned anode, it couples the actuation circuit of the motor of the anode in section 19a, 19b, ..., of the comparison memory 19, which causes the engine to start in the required direction, until cancellation of the signal corresponding to this anode in the comparison memory 19.
  • the local unit 8 is scanned by the central unit 9 and the local operating memories 16 and 22 of these two regulation units are coupled to each other via a transmission circuit 28a, for transfer the signals from memory 116 to the storage section 22a.
  • the programmer 26 of the central unit 9 is programmed so that the latter executes a succession of operating sequences of three stages comprising a first stage corresponding to the aforementioned fifth phase of an operating cycle of a local unit 8, a second step corresponding to the second phase of an operating cycle of another local unit 8 and a third step during which the central unit 9 defines, from the information collected in the first step, setpoints relating to a subsequent cycle of operation of the local unit 8 treated in the first step.
  • the setpoint voltage is an electrical voltage value, which is representative of the setpoint value of the conductance of the electrolyte layer under the anode considered, for example the anode 4 of cell 2.
  • this value setpoint is the conductance that the electrolyte layer would have between the anode 4 of the cell 2 and its mercury cathode, under the local operating conditions detected by the detector 14, if the anode 4 occupied an ideal predetermined position .
  • the comparison memory 19 of the local units 8 comprises a distributor of the comparison voltage signals stored therein.
  • the function of the distributor is to distribute the stored signals into three categories of signals which are exemplified in the diagram in FIG. 2, in which the ordinate axis expresses the comparison voltages expressed for example in millivolts.
  • a first category comprises the comparison signals which are between two predetermined fixed limit values a and b, situated on either side of the ideal zero value and which thus correspond to the anodes occupying a position close to the optimum with respect to the cathode of their cell; the second category groups together the comparison signals which are lower than the lower limit a, for example the signal c, and which thus correspond to the anodes occupying a position excessively far from the cathode; the third category includes all the comparison signals such as d, which are greater than the upper limit b and which thus correspond to the anodes which are too close to the cathode.
  • the comparison signals are distributed in the order of their decreasing absolute values, which corresponds to a classification of the corresponding anodes in the order of decreasing anode-cathode distances.
  • the comparison signals are distributed in the order of their decreasing absolute values, which corresponds to a classification of the corresponding anodes in the order of increasing anode-cathode distances.
  • the programmers 20 of the local units 8 are by ailers programmed so that, in the fourth operational phase of the operating cycle of the local units 8, the scanning of the anodes of each cell is carried out in the order of distribution of the comparison signals in the comparison memory 19, starting with the third category of signals, then the second category.
  • This scanning order thus amounts to scanning first the anodes occupying a dangerous position, too close to the cathode, then the anodes occupying a position excessively distant from the cathode with respect to an ideal reference position.
  • the anodes of the first category are not scanned during this fourth operating phase.
  • This preferred variant of the installation according to the invention makes it possible to reduce the time allocated to the fourth operational phase of the operating cycle of the local units 8, to that which is necessary to scan and adjust only part of the anodes of each cell, because in all cases, it is the anodes whose position is the most dangerous that are adjusted first.
  • This variant embodiment of the invention thus makes it possible to shorten the duration of the operating cycles of the local units and, consequently, to increase the frequency of checks and adjustments of the anodes of the cells.
  • the anode motors are AC motors of the synchronous type and the programmer 20 of the local regulation units 8 is programmed so that during the fourth operating phase, the 'polling unit 10 operates, for each anode, a sequence of successive scans separated from each other by a constant time interval, the duration of which is at most equal to the time taken by the anode to travel an equal distance to that separating position (a) from position (0).
  • the polling member 10 operates a series of scans of neighboring anodes (for example anodes 4 ', 4 ", ).
  • the polling member 10 will, during the fourth operational phase, scan successively, first the anode 4 and start its engine in the required direction, then the anode 4 'and start its motor and finally the 4 "anode and start its motor. From this moment, the three motors of the three anodes 4, 4', 4" rotate continuously, at constant speed, so that the anodes 4, 4 ′ and 4 "are moved continuously opposite the cathode, each in a defined direction, at constant speed.
  • the scanning device 10 then returns to the anode 4 and performs a new scanning thereof: during this second scanning, the measuring device 11 reads the instantaneous value of the conductance of the electrolyte layer under the anode 4, the result is transferred, via the transformer 12, to the comparison circuit 18 and the latter sends a signal representative of the difference between the instantaneous conductance measured and the reference value which had been stored during the first operating phase described above. If the emitted comparison signal 18 does not fall below a threshold value corresponding to a correct position of the anode 4, its motor is kept running. The polling member 10 then passes to the anode 4 'then to the anode 4 "and the abovementioned operations are executed separately for each of these two anodes.
  • This cycle of scanning of the anodes 4, 4', 4" is repeated repeatedly, at regular time intervals defined above. As soon as the comparison signal 18 detected for an anode (4, 4 ′ or 4 ") falls below the aforementioned threshold value, the motor of this anode is stopped.
  • the polling member 10 then passes to a neighboring group of anodes, for example the group of anodes 5, 5 ′ and 5 ′′ and starts the same scanning sequences for them.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
EP83200088A 1982-01-28 1983-01-21 Installation pour la régulation d'un groupe de cellules d'électrolyse à cathode de mercure Expired EP0085999B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83200088T ATE34782T1 (de) 1982-01-28 1983-01-21 Vorrichtung zur regulierung einer gruppe von quecksilberkathoden elektrolysezellen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8201611 1982-01-28
FR8201611A FR2520387A1 (fr) 1982-01-28 1982-01-28 Installation pour la regulation d'un groupe de cellules d'electrolyse a cathode de mercure

Publications (2)

Publication Number Publication Date
EP0085999A1 EP0085999A1 (fr) 1983-08-17
EP0085999B1 true EP0085999B1 (fr) 1988-06-01

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EP83200088A Expired EP0085999B1 (fr) 1982-01-28 1983-01-21 Installation pour la régulation d'un groupe de cellules d'électrolyse à cathode de mercure

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EP (1) EP0085999B1 (enrdf_load_stackoverflow)
AT (1) ATE34782T1 (enrdf_load_stackoverflow)
BR (1) BR8300399A (enrdf_load_stackoverflow)
DE (1) DE3376854D1 (enrdf_load_stackoverflow)
ES (1) ES519313A0 (enrdf_load_stackoverflow)
FR (1) FR2520387A1 (enrdf_load_stackoverflow)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IN168167B (enrdf_load_stackoverflow) * 1986-07-21 1991-02-16 Babcock & Wilcox Co
CN107195984B (zh) * 2017-06-13 2020-04-03 福建华祥电源科技有限公司 一种智能可调节储能的蓄电池

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1567955B2 (de) * 1967-07-04 1974-01-10 Bayer Ag, 5090 Leverkusen Verfahren zur Spannungsregelung und Kurzschlußbeseitigung bei Chloralkalielektrolysezellen
DE2352372A1 (de) * 1973-10-18 1975-04-24 Siemens Ag Einrichtung zur ueberwachung und anzeige der verteilung der anodenstroeme in einer chlor-elektrolyseanlage
AU1595776A (en) * 1975-08-18 1978-01-19 Olin Corp Regulating anode-cathode spacing in an electrolytic cell
DE2729732B2 (de) * 1977-07-01 1980-06-26 Hoechst Ag, 6000 Frankfurt Vorrichtung zum Regeln, Überwachen, Optimieren, Bedienen von und zur Informationsdarstellung in Chloralkalielektrolyseanlagen

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Publication number Publication date
BR8300399A (pt) 1983-10-25
EP0085999A1 (fr) 1983-08-17
FR2520387A1 (fr) 1983-07-29
ATE34782T1 (de) 1988-06-15
ES8400780A1 (es) 1983-11-01
DE3376854D1 (en) 1988-07-07
FR2520387B1 (enrdf_load_stackoverflow) 1984-03-16
ES519313A0 (es) 1983-11-01

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