US3582524A - Mercury-process electrolytic apparatus - Google Patents

Mercury-process electrolytic apparatus Download PDF

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Publication number
US3582524A
US3582524A US741109A US3582524DA US3582524A US 3582524 A US3582524 A US 3582524A US 741109 A US741109 A US 741109A US 3582524D A US3582524D A US 3582524DA US 3582524 A US3582524 A US 3582524A
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United States
Prior art keywords
mercury
denuding
electrolytic cell
pump
passageway
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Expired - Lifetime
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US741109A
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English (en)
Inventor
Hiroshi Shibata
Teruo Imai
Shigeji Kumaki
Junichi Ando
Toshio Enoki
Isao Okazaki
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Kureha Corp
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Kureha Corp
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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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/033—Liquid electrodes
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/36—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in mercury cathode cells
    • C25B1/42—Decomposition of amalgams
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features

Definitions

  • FIG.4 q 3O United States Patent 3,582,524 MERCURY-PROCESS ELECTROLYTIC APPARATUS Hiroshi Shibata, Teruo Imai, Shigeji Kumaki, Junichi Ando, Toshio Enoki, and Isao Okazaki, Iwaki-shi,
  • mercury-process electrolysis in general, mercury which has flowed through an electrolytic cell (known also as a mercurycathode cell) and become an amalgam is separated from the electrolyte and sent to a denuding tower, where the mercury is denuded by denuding water and thereby recovered. The mercury thus recovered is then first raised by a mercury pump to a hydrostatic level higher than the mercury surface level within the electrolytic cell and, from this higher level, flows into the electrolytic cell.
  • an electrolytic cell known also as a mercurycathode cell
  • the mercury which has been discharged from the denuding tower is first pumped by the mercury pump to a high level and then flows to the electrolytic tank as mentioned hereinbefore.
  • the mercury pump stops because of an abnormal occurrence such as a power failure, the mercury in the piping on the pump delivery side will fall back under its own heavy weight to the pump and create a vacuum within the piping.
  • this vacuum will cause not only the mercury in the flow path to the electrolytic cell but also the amalgam and electrolyte within the electrolytic cell to undergo a reverse flow or backflow toward and into the pump delivery circuit.
  • the upper end of the riser pipeline on the delivery side of the mercury pump is ordinarily opened to the atmosphere in a flow circuit of this character.
  • the mercury which is recovered and is separated from caustic soda in the denuding tower mixes with graphite particles arising from the disintegration of the denuding graphite granules in the tower and with caustic soda soltuion to form an emulsion.
  • the vigorous agitating action of the mercury pump causes the mercury to form, together with wash water, an additional large quantity of mercury emulsion within the pump.
  • a second object of the invention is to provide a mercury-process system wherein the closed circuit for mercury circulation is totally sealed constantly during operation thereby to prevent infiltration of air into this circuit.
  • a third object of the invention is to provide a mercuryprocess system wherein contaminants such as mercury butter formed in the electrolytic cell and graphite particles are separated from the mainstream mercury into a bypath outside of the main mercury circuit together with a small quantity of mercury separating from the mainstream mercury, and the removal of these contaminants is carried out outside of the main mercury circuit thereby to reduce the frequency of removal of contaminants, to simplify the operational procedures, and, at the same time, to improve the work environment of the electrolysis operation.
  • a fourth object of the invention is to provide, in a mercury-process system, means for causing foreign matter such as mercury emulsion formed in the denuding tower and the mercury pump, together with a small quantity of mercury, to recirculate to the denuding tower thereby to eliminate the work of removing mercury emulsion from the flow circuit upstream from the electrolytic cell.
  • a fifth object of the invention is to provide, in a mercury-process system, a closed circuit for mercury circulation which is fully sealed during operation and to provide means to prevent backilow of amalgam and 3 electrolyte within the electrolytic cell into the mercury pump pathe which backflow would otherwise occur when the mercury pump is stopped.
  • a sixth object of the invention is to provide, in conjunction With the achievement of the above fifth object, improvement in the mercury flow path from the mercury pump to the electrolytic cell.
  • a seventh object of the invention is to provide, in conjunction with the achievement of the above third and fourth objects, improvement in the separation of mercury.
  • a mercury-process apparatus of the type referred to hereinabove in which a passageway fully sealed from the outside atmosphere is used for conducting mercury amalgam from the electorlytic cell to the denuding tower, and a separation device for removing contaminants from the mercury amalgam is disposed outside of this passageway.
  • a mercury-process apparatus of the above stated character in which the main mercury circulation system is fully sealed, and there are provided in combination therewith the above mentioned separation device, a device for preventing backflow of mercury when the mercury pump stops, and a circulation device for causing contaminants within denuded mercury to circulate, together with a part of the mercury and wash water, back to the denuding tower.
  • FIG. 1 is a flow chart indicating the essential organisation of one example of a mercury-process system constituting a preferred embodiment of the invention
  • FIG. 2 is a fragmentary perspective view, with parts cut away and with some parts in section, showing the details of the part designated by enclosure 11 in FIG. 1;
  • FIG. 3 is an elevational view, in vertical section, of the part designated by enclosure III of FIG. 1;
  • FIG. 4 is an elevational view, in vertical section, of the part designated by enclosure IV of FIG. 1;
  • FIG. 5 is a fragmentary perspective view, with parts cutaway and with parts in section, showing the part designated by enclosure V in FIG. 1.
  • the mercury in the passageway 3 is separated out from the other accompanying matter by a method wherein the mercury or mercury amalgam, contaminants, and liquid are caused to flow together through a first duct means having a length substantially greater than the width thereof, the mercury or mercury amalgam being caused to pass under and past a bafile into a further duct means which is parallel and in side-by-side disposition with the first duct means, the 'bafile forming a common, partial side wall between the ducts and having an opening thereunder and below the upper surface of the mercury or mercury amalgam so as to permit passage only of the mercury or mercury amalgam through the opening and blocking passage of the contaminants and the liquid. See our copending application No. 691,413 filed on Dec. 18, 196 7.
  • the brine and contaminants flowing along the passageway 3 ride on and are swept along by the surface flow produced by the small quantity of mercury overflowing over the weir 11, all of this brine and contaminants thereby flowing into the mercury sump 12, Accordingly, there is no possibility of contamins and brine being mixed with the mainstream mercury entering the passageway 6. Therefore, the electorlysis operation can be carried out with the electrolytic cell :1, passageway 3 and pasageway 6 in a fully sealed state.
  • the mercury sump 12 is outside of the mercury mainstream, and there is no possibility, when contaminants such as mercury butter are accumulated therein of these contaminants flowing into the passageway 6 to the denuding tower 8, it is possible to accumulate these contaminants in the sump 12 over a long period of time and to remove these contaminants thus accumulated by scooping through a small, closable scooping aperture provided above this sump.
  • a gate device as, for example, a sluice gate 18 which can be opened and closed in the vertical direction, at a point upstream from the weir 11 and to shut off the brine flow during the scooping work.
  • the small quantity of mercury which flows into the mercury sump 12, together with the contaminants is drained out of the lower part of the sump 12 in a manner to preserve the mercury hydrostatic head at a constant value and may be returned to the passageway 6 to the denuding tower without any possibility of contaminants or brine accompanying the mercury since the mercury flowrate is very low.
  • the mercury thus drained out and brine are conducted by a passageway such as passageway 13 into a contaminant separation vessel 14 as shown in FIG. 3, where the mercury is separated out and sent through a path 15 to the denuding tower 8, while the diluted brine is recirculated through a pipeline 16 to the brine dissolving process (not shown).
  • a passageway such as passageway 13 into a contaminant separation vessel 14 as shown in FIG. 3, where the mercury is separated out and sent through a path 15 to the denuding tower 8, while the diluted brine is recirculated through a pipeline 16 to the brine dissolving process (not shown).
  • Only the contamiants in a static state at an intermediate position are removed from time to time by scooping through a scooping aperture 39 or are drained out through a discharge pipe 17.
  • the chlorine can be reduced to facilitate the operators work by a suitable method such as: providing a sluice gate 18a in the passageway 13, closing this sluice gate at the time of contaminant removal to shut off the. brine, and diluting with water the chlorine in the small quantity of brine remaining in the separation vessel 14; drawing away the chlorine gas by means of a suction fan; or adding a chlorine remover such as sodium thiosulphate.
  • the entire process circulation path from the outlet of the denuding tower 8 to the electrolytic cell 1 be completely sealed. That is, in thiis circulation path, the mercury which has been sent from the denuding tower 8, through a passageway 19, and to the mercury pump is ordinarily supplied with water added thereto through an inlet 21 and is thereby washed in the pump 20 and relates piping.
  • the downstream end 23 of the riser pipe 22 on the delivery side of the pump 20 is grdinarily open to the atmosphere as mentioned hereinefore.
  • this part of the circulation path is sealed and isolated from the atmosphere but connected directly or indirectly to the denuding tower 8. More specifically, referring to FIGS. 1 and 4, the mercury which overflows from the end 23 of the riser pipe 22 flows into the space between the riser pipe 22 and an outer pipe 24, through the lower part of this pipe 24 and a pipeline 32, to the electrolytic cell 1.
  • the upper end of the outer pipe 24 is closed and communicates through a side 25 directly (through the path of pipes 25 and 26) or indirectly (through the path of pipes 25 and 27, for example) with the denuding tower 8.
  • an automatic check valve 28 may be provided above the end 23 of the riser pipe 22 for the purpose of preventing mercury and wash water which have been caused by the delivery pressure of the pump 20 to rise rapidly up through the riser pipe 22 from flowing under their kinetic energy through a path of the side pipe 25 and into the denuding tower 8.
  • valve 28 While the pump 20 is operating, the valve 28 is pressed upward in closed position by the fluid dynamic pressure of the mercury thereby to shut off the path of the side pipe 25. When the pump 20 stops, the valve 28 is caused to drop by its own weight and a vacuum which is produced in the riser pipe 22 thereby to close the upper end 23 of the riser pipe and prevent back flow of mercury downstream from pipe 24 due to the vacuum.
  • valve 28 may be of any design suitable for its function
  • the valve 28 in the illustrated example comprises a valve body 28, a valve seat 29 supported by pipe 24 for closure seating of the valve body 28, and guide means comprising a stationary guide tube 31 and a rod fixed to and supporting the valve body 28 and slidably disposed within the guide tube 31.
  • the mercury is prevented from contacting the air of the outside atmosphere. Moreover, even if the mercury pump 20 stops suddenly because of an occurrence such as a malfunction in the electrical system, and a vacuum is created within the pipe 22, the only result is that the mercury or water and other substances in the denuding tower 8 or passageways communicating therewith (the principal substance flowing through a return pipe 35, described hereinafter, being water which has washed supply mercury for the electrolytic cell) merely undergo backflow, and there is no backfiow of the analgam and electrolyte within the electrolytic cell to the supply mercury passageway and the mercury pump 20.
  • the upper part of the outer pipe 24 is connected to the denuding tower 8
  • this upper part can be connected to a water supply pipe, in some cases, thereby to cause water to flow into the riser pipe 23 when the pump stops.
  • the mercury in the pipe 24 flows through a pipe 32 and enters a mercury separation passageway 33, where most of the mercury is separated out to flow into the electrolytic cell 1.
  • the principle of the mercury separation in the mercury separation passageway 33 as shown in detail in FIG. 5 is the same as that of the mercury separation indicated in FIG. 2. That is, the mercury separation passageway 33 may be considered to correspond to the mercury outlet passageway 3 shown in FIG. 2, and the upstream end of the electrolytic cell 1 may be considered to correspond to the separated mercury passageway 6. Further-more, the weir 34 and inlet 36 may be considered to be analogous respectively to the weir 11 and sump 12 illustrated in FIG. 2.
  • the wash water sent through the pipe 35 to the denuding tower 8 is used again as denuding water and, in the example illustrated in FIG. 1, is conducted by the pipe 35 directly to the denuding tower 8.
  • the downstream end of the pipe 35 can be connected to a part of the passageway 6 for amalgam flowing to the denuding tower 8 thereby to send the Wash water together with the amalgam to the denuding tower.
  • the upper part of this mercury may be sealed with Water, but an even more effective measure is to provide means for communicating the space above the mercury sump to the interior of the denuding tower.
  • a fully-sealed, mercury-process electrolytic apparatus comprising: an electrolytic cell; a denuding tower; a mercury pump; a sealed main circulation system for mercury through the electrolytic cell, the denuding tower, the mercury pump, and back to the electrolytic cell; overflow separation means disposed outside the main circulation system for removing contaminants from mercury amalgam; means provided in the main circulation system for preventing back-flow of mercury when the mercury pump stops; and means for causing contaminants within the denuded mercury to circulate together with a part of said mercury and mercury wash water, to the denuding tower.
  • the fully-sealed, mercury-process electrolytic apparatus as claimed in claim in which the means for pre venting backflow of mercury comprises an automatically operating valve disposed within the upper part of an elevated part of the main circulation system between the mercury pump and the electrolytic cell and operating to maintain the main circulation system. open for passage of mercury therethrough while the mercury pump is operating and to close said system against passage of mercury therethrough simultaneously with the stoppage of the mercury pump.
  • the means for preventing backfiow of mercury comprises a side pipe communicatively connecting the upper part of an elevated part of the main circulation system between the mercury pump and the electrolytic cell to the denuding tower and an automatically operating valve disposed within said elevated part and operating to close passage through the side pipe and open passage through said system while the mercury pump is operating and to open passage through the side pipe and close passage through said system promptly when the mercury pump stops.

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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)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Drying Of Solid Materials (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US741109A 1967-11-24 1968-06-28 Mercury-process electrolytic apparatus Expired - Lifetime US3582524A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP7537267 1967-11-24
JP7537367 1967-11-24
JP7537467 1967-11-24

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US3582524A true US3582524A (en) 1971-06-01

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US741109A Expired - Lifetime US3582524A (en) 1967-11-24 1968-06-28 Mercury-process electrolytic apparatus

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US (1) US3582524A (da)
BE (1) BE717966A (da)
CH (1) CH486916A (da)
CS (1) CS166685B2 (da)
DE (1) DE1800140A1 (da)
DK (1) DK123016B (da)
ES (1) ES356648A1 (da)
FR (1) FR1582595A (da)
GB (1) GB1223296A (da)
NL (2) NL6811478A (da)
NO (1) NO120678B (da)
SE (1) SE354263B (da)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2737345A1 (de) * 1976-08-20 1978-03-09 Canon Kk Halbleiterlasermodul

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1462830A (en) * 1974-11-19 1977-01-26 Ici Ltd Operation of mercury-cathode cells

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2737345A1 (de) * 1976-08-20 1978-03-09 Canon Kk Halbleiterlasermodul

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SE354263B (da) 1973-03-05
DK123016B (da) 1972-05-08
ES356648A1 (es) 1970-05-01
NL134491C (da)
CS166685B2 (da) 1976-03-29
NL6811478A (da) 1969-05-28
FR1582595A (da) 1969-10-03
NO120678B (da) 1970-11-23
GB1223296A (en) 1971-02-24
DE1800140A1 (de) 1969-08-14
CH486916A (fr) 1970-03-15
BE717966A (da) 1968-12-16

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