EP0020890B1 - Verfahren zur Entchlorung des Anolyten einer Alkalichlorid-Elektrolysezelle - Google Patents

Verfahren zur Entchlorung des Anolyten einer Alkalichlorid-Elektrolysezelle Download PDF

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Publication number
EP0020890B1
EP0020890B1 EP80101828A EP80101828A EP0020890B1 EP 0020890 B1 EP0020890 B1 EP 0020890B1 EP 80101828 A EP80101828 A EP 80101828A EP 80101828 A EP80101828 A EP 80101828A EP 0020890 B1 EP0020890 B1 EP 0020890B1
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EP
European Patent Office
Prior art keywords
anolyte
pressure
chlorine
stripping column
electrolysis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP80101828A
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German (de)
English (en)
French (fr)
Other versions
EP0020890A1 (de
Inventor
Dieter Dr. Bergner
Kurt Hannesen
Wolfgang Müller
Wilfried Schulte
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
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Hoechst AG
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Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT80101828T priority Critical patent/ATE2852T1/de
Publication of EP0020890A1 publication Critical patent/EP0020890A1/de
Application granted granted Critical
Publication of EP0020890B1 publication Critical patent/EP0020890B1/de
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes

Definitions

  • the invention relates to a process for the extensive removal of chlorine from the anolyte of an alkali metal chloride electrolysis which leaves hot and saturated with chlorine a pressure electrolysis carried out at a pressure of more than 7 bar.
  • the anolyte In the industrial processes for dechlorinating the anolyte of electrolysis cells, which operate under normal pressure, the anolyte is dechlorinated by relaxing it in a container kept under vacuum. During this spontaneous expansion, the dissolved chlorine evaporates, so that a dechlorinated anolyte remains in the vacuum container. The chlorine-containing vapors formed during the evaporation are cooled, the resulting chlorine-containing condensate is pumped back into the anolyte and the portion which is not condensed during the cooling, essentially consisting of chlorine and water vapor, is brought back to normal pressure and then dried.
  • the task was therefore to develop an economical process for processing the products, that arise in the anode compartment of an alkali chloride electrolysis cell.
  • the electrical heat loss should be used as widely as possible and the liquefaction of the chlorine should be particularly easy.
  • a process has now been found for dechlorinating and cooling the anolyte of an alkali chloride electrolysis cell by means of lowering the pressure, which is characterized in that the electrolysis is operated under a pressure of at least 8 bar in the anode compartment, and the products flowing out of the anode compartment are mechanically operated in a separator separated into anolyte and gases formed, the separated anolyte is released at a temperature which is above the boiling point of the anolyte at atmospheric pressure in a strip column to a pressure which is between atmospheric pressure and 2 bar, with the proviso that under these conditions the Anolyte boils, and then the anolyte freed from chlorine by the expansion is separated from the gas phase formed in the stripping column.
  • Pressure in the anode compartment of 8-20 bar, in particular 8-12 bar, are preferred. At pressures above about 50 bar, investment and operating costs rise sharply.
  • the boiling point of the anolyte during relaxation naturally depends somewhat on the current barometer reading ("atmospheric pressure").
  • feed temperatures into the stripping column of at least 103 ° C., preferably at least 105 ° C., in particular at least 110 ° C., are sufficient to bring the used anolyte to a boil by depressurization .
  • the feed temperature is preferably max. 140 ° C, especially max. 130 ° C.
  • the problem of the mechanical resistance of the cation exchange membrane mentioned in DE-OS 2 729 589 can be solved even at working pressures of over 8 bar.
  • the membrane can be pressed directly onto an electrode, but preferably the anode.
  • This electrode is then preferably designed openwork, for. B. made of expanded metal. In this way it is achieved that the membrane is supported by the electrode surface, but the circulation of the electrolyte is still sufficient.
  • This pressure difference should be a maximum of 5 bar, better a maximum of 3 bar, even better a maximum of 1 bar, even better a maximum of 0.5 bar, preferably a maximum of 0.1 bar. So that the membrane is pressed against the electrode, the pressure difference should, however, be at least 5 mbar, preferably at least 10 mbar.
  • the same materials that are used for the construction of normal pressure electrolysis cells can be used in the manufacture of the electrolysis cell, which works at a pressure of over 8 bar, for example titanium for the inside of the anode compartment and steel for the inside of the cathode compartment.
  • a pressure electrolysis cell which is particularly well suited for working pressures of at least 8 bar, is the subject of a parallel application with the same priority (EP-AI-0 020 887) by the applicant ("electrolysis apparatus"). It is briefly described in Example 2 (with the associated FIGS. 1 and 2a, 2b).
  • the stripping column will generally be designed as a standing cylindrical container, which can contain various internals (e.g. trays or packing layers). However, the strip column can also be designed as a horizontal container. It is only important that no backmixing can take place between the incoming and the outgoing brine and that the brine has sufficient evaporation area available. The evaporation area and the dwell time of the brine in the stripping column must be such that the majority of the chlorine in the column is removed. It is advantageous, but not necessary, to attach a droplet separator to the top of the column in order to retain entrained liquid constituents.
  • the temperature at which the anolyte leaves the anode compartment is below the boiling point at atmospheric pressure, it must be heated before it is fed into the stripping column.
  • steam can also be blown into the stripping column from below.
  • Installations e.g. floors or packing are advantageous for improving the gas exchange between boiling anolyte and steam.
  • the temperature of the anolyte in the cell is preferably at least 90 ° C., preferably 105-140 ° C., in particular 110-130 ° C.
  • a gas which mainly consists of chlorine and water vapor.
  • the condensation of the water vapor advantageously takes place on cold surfaces, i.e. H. through indirect cooling.
  • the further work-up preferably consists in adding cold (i.e. colder than the temperature of the gas phase) liquid-aqueous phase to the top of the stripping column and thus removing the main part of the remaining water vapor from the gas phase.
  • cold catholyte under reduced pressure can be used as cooling medium, which can be obtained from hot catholyte by relaxation and subsequent vacuum treatment. While the water vapor is partially condensed and the chlorine is cooled, the catholyte boils. In this way, the heat of condensation of the water vapor can be used to evaporate the catholyte.
  • the chlorine-containing condensate obtained can be used, among other things, to sprinkle the internals of the stripping column (packing, trays) from above and thus keep them moist. In this way, the salt mist that occurs when the hot anolyte relaxes is better retained.
  • the parts that are not liquefied during the condensation (chlorine, water vapor) can be compressed and e.g. B. can be returned to the separator.
  • the gas phase formed in the stripping column does not have to be freed from the main amount of water by condensation. You can . also feed directly to a neutralization column, in which hypochlorite is produced, or - in the case of smaller plants - to chlorine destruction.
  • the anolyte largely freed of chlorine in the stripping column can be introduced into a vacuum container and further expanded there.
  • the vapors obtained can be condensed by further cooling. Cooling takes place as soon as the anolyte is let down in the vacuum container. The degree of cooling depends on the level of the vacuum.
  • the vacuum container can be carried out lying or standing. It is essential that there is a sufficiently large evaporation surface and that backmixing between fresh, warm and cooled brine is avoided.
  • the chlorine- and salt-free condensate that occurs when condensing the vapors of the vacuum container can be used for many purposes. If the alkali metal chloride electrolysis is operated according to the membrane cell process, it is advantageous to add the chlorine- and salt-free condensate to the catholyte of the membrane cell, for example by introducing it directly into the cathode compartment.
  • the condensate can also be added at the salt dissolver. In both cases, the amount of soft water to be procured is reduced.
  • the latent heat of evaporation which is released during the condensation of the vapors which arise during the expansion in the vacuum container can also be used for the evaporation of the catholyte.
  • the anolyte which leaves the cell at a pressure of at least 8 bar, will generally not yet have reached the boiling point at atmospheric pressure.
  • the anolyte can be heated, for example, in a heat exchanger or the expansion of the anolyte in the stripping column can be supported by adding steam.
  • This process for dechlorinating the anolyte of the alkali metal chloride electrolysis by lowering the pressure is characterized in that the electrolysis is carried out under a pressure of at least 8 bar Anode compartment is operated, the products flowing from the anode compartment of the electrolytic cell are mechanically separated into anolyte and gases formed in a separator, the separated anolyte is depressurized to a pressure in a strip column at a temperature below the boiling point of the anolyte at atmospheric pressure , which is between atmospheric pressure and 2 bar, the anolyte is treated in countercurrent with steam in the strip column until it boils and the anolyte freed of chlorine by the relaxation and steam treatment is separated from the resulting gas phase. Introducing steam into the strip column causes some dilution of the anolyte. However, this measure may be desirable because water is removed from the anolyte in a membrane electrolysis cell.
  • FIG. (3) A special embodiment of the method according to the invention can be seen in the flow diagram of FIG. (3).
  • the combination of apparatuses shown there is only of exemplary importance, so that, in individual cases, a different circuit and a different embodiment of apparatuses is entirely possible, depending on the circumstances.
  • the pressure electrolysis cell (4) is divided into anode space (79) with anode (12) and cathode space (89) with cathode (16) by a membrane (14). Fermented brine is pressed into the anode compartment (79) through line (21A). A mixture of H 2 and catholyte is removed from the cathode compartment (89) through line (21C).
  • the chlorine-water vapor mixture which still has a low content of oxygen and inert gases, passes through the drip layer (51) and, under electrolysis pressure, passes through line (52) for further processing, for example drying and liquefaction.
  • the relaxed anolyte (53) obtained in (50) (saturated with chlorine in accordance with pressure and temperature) is drawn off from the separator (50) and opens via the line (54) and the expansion valve (55) in the strip column (56) relaxed a lower pressure (here: atmospheric pressure). This causes the anolyte to boil. In this way, it is completely dechlorinated in the strip column.
  • the expulsion of the chlorine in (56) can be supported by water vapor, which is supplied via line (57).
  • a particularly good contact between the relaxed anolyte and water vapor is achieved through the packing layer (58).
  • This addition of water vapor - as stated above - is particularly useful if the anolyte temperature has not yet reached the boiling point when starting up a system.
  • the upper layer of the body (59) frees the chlorine / water vapor mixture from brine droplets.
  • the chlorine-water vapor mixture leaves the column (56) via line (60).
  • Part of the steam is deposited in the condenser (61) and the condensate (62) is collected in the collecting vessel (63).
  • a cooling medium (for example cooling water or expanded catholyte which has been further cooled by vacuum evaporation) is introduced through line (64) and leaves the condenser warmed up through line (65).
  • This chlorine-containing condensate is returned to the electrolysis via line (66), pump (67) and line (68), some of which can be fed to the strip column (56) via line (69). This can ensure that the packed bed (59) of the strip column (56) remains moist and the retention of brine droplets is improved.
  • the chlorine-water vapor mixture which is not condensed in (63) is passed via line (70), into which the compressor (71) is inserted, into the separator (50).
  • Other parts can be directed via line (72) for hypochlorite production or a liquefaction plant for chlorine.
  • the brine completely dechlorinated in the strip column (56) is drawn off via line (73) and expanded into the vacuum container (75) via the expansion valve (74).
  • the level of the vacuum in the container (75) depends on the temperature at which the brine (76) concentrated there should leave the container (75), or on the amount of chlorine- and acid-free condensate which is present when the brine is concentrated should be won.
  • the brine cooled in the container (75) leaves it via the line (77). It is pumped back with the help of the pump (78) into the salt dissolver and the brine cleaning (not shown) and finally into the anode compartment (79).
  • the water vapor developed in the container (75) is freed of entrained brine droplets in the drip layer (80) and led via the line (81) to the condenser (82), where water vapor condenses.
  • the condenser (82) can be acted upon via the line (83) with cooling water which, when heated, leaves the condenser again via the line (84); However, it is also possible to use at least part of the large amount of heat obtained for the catholyte evaporation, ie for cooling in (82) lye as a coolant.
  • the condensate generated in (82) is conducted via line (85) to the condensate tank (86) and collected there.
  • the condensate (87) can be fed into the line (21B), through which the circulating catholyte is returned to the cathode chamber (89). In this way, the concentration of the catholyte can be kept constant.
  • the condensate (87) can also be fed to the salt dissolver (not shown).
  • the vacuum pump (90) via line (91) the condensate container (86) is connected, the vacuum is generated in the condensate container (86) and in the container (75).
  • Chlorine together with about 0.035 t / h Steam The condensate of the vapors of the strip column (e.g. 0.5 t / h) contains only a little chlorine dissolved and can be pumped into the salt dissolving station.
  • the brine itself leaves at boiling temperature, i.e. at approx. 107 ° C, the strip column. If a pressure of 400 mbar is maintained when the strip column is expanded into the vacuum container, the dechlorinated brine cools down to about 83'C by evaporation. Here 29 t / h Steam released; if the pressure in the vacuum container is only 520 mbar, the brine only cools down to 90 ° C and 20 t / h evaporate. Steam. The amount of heat generated in the condensation of the vapors is sufficient to evaporate the cell solution, for example from 25% by weight to 50% by weight. In this respect, the use of external steam for the concentration is made unnecessary.
  • the electrolysis apparatus has at least one electrolysis cell 4.
  • Each individual electrolytic cell 4 essentially consists of the two flange parts 1 and 2, between which the membrane 14 is sealed, and which are held together with the screws 6.
  • the flange parts 1 and 2 are electrically insulated from each other, e.g. B. by means of insulating sleeves 3.
  • the half-shells 9 and 11 are inserted, which line the flanges 1 and 2 from the inside and are pulled with their brims over the sealing surfaces of the flanges 1 and 2.
  • the sealing rings 13 and 15 provide a seal against the membrane 14.
  • the anode 12 and the cathode 16 are secured to the half-shells 9 and 11.
  • the bottoms of the half-shells 9 and 11 of adjacent cells press against one another under the internal pressure of the cells; they can be separated from one another by a film 10 (plastic or metal). Surrounding beads in the half-shells 9 and 11 cause a membrane-like behavior (not shown).
  • the spacers 17 and 18 (electrically conductive bolts), which are used for power supply and power transmission, have on their front side inside the cell power transmission elements 19 and 20, for. B. discs of insulating material, between which the membrane 14 is clamped.
  • the anode 12 and the cathode 16 are fastened to the spacers 17 and 18, respectively.
  • the anolyte and the catholyte are supplied and discharged via lines 21 which are guided radially through the flanges 1 and 2.
  • the terminal half-shells of the electrolysis apparatus are supported by pressure-absorbing organs.
  • the organs consist of the two plates 7 and the tie rods 8. Instead of the tie rods, the two plates 7 can be connected to hydraulic devices (not shown).
  • the outward-pointing half-shell 9 or 11 of the last cell 4 is supported against the internal pressure of the cell by the plate 7, which may snap into the flange 2 or 1 with a spring 22.
  • the two end plates 7 are pulled together via the tie rods 8, so that the liquid pressure on the half-shells is compensated for via the tie rods. They rest on foot elements 5.
  • threaded bolts 23 which exert pressure on the spacers 17 and 18 when screwed in.
  • the threaded bolts 23 are connected to the power supply lines 24 by means of appropriate devices 25.
  • the supply cables (not shown) are connected to these power supply lines 24 sen.
  • the individual electrolysis cells 4 are pressed together with the pressure-absorbing member and then the threaded bolts 23 are tightened, so that the electrical contacts are made through the spacers 17 and 18 through all cells.
  • the individual electrolytic cells have an essentially circular cross section, ie the cross section in the electrode plane is circular, elliptical, oval or the like.

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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 Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Sampling And Sample Adjustment (AREA)
EP80101828A 1979-04-12 1980-04-05 Verfahren zur Entchlorung des Anolyten einer Alkalichlorid-Elektrolysezelle Expired EP0020890B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80101828T ATE2852T1 (de) 1979-04-12 1980-04-05 Verfahren zur entchlorung des anolyten einer alkalichlorid-elektrolysezelle.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2914870 1979-04-12
DE19792914870 DE2914870A1 (de) 1979-04-12 1979-04-12 Verfahren zur entchlorung und kuehlung des anolyten der alkalihalogenid- elektrolyse

Publications (2)

Publication Number Publication Date
EP0020890A1 EP0020890A1 (de) 1981-01-07
EP0020890B1 true EP0020890B1 (de) 1983-03-23

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ID=6068172

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80101828A Expired EP0020890B1 (de) 1979-04-12 1980-04-05 Verfahren zur Entchlorung des Anolyten einer Alkalichlorid-Elektrolysezelle

Country Status (14)

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US (1) US4251335A (pt)
EP (1) EP0020890B1 (pt)
JP (1) JPS55141581A (pt)
AR (1) AR227391A1 (pt)
AT (1) ATE2852T1 (pt)
AU (1) AU531558B2 (pt)
BR (1) BR8002280A (pt)
CA (1) CA1165273A (pt)
DE (2) DE2914870A1 (pt)
ES (1) ES490264A0 (pt)
FI (1) FI65820C (pt)
IN (1) IN152456B (pt)
NO (1) NO801059L (pt)
ZA (1) ZA802175B (pt)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8612627D0 (en) * 1986-05-23 1986-07-02 Ici Plc Dechlorination of aqueous alkali metal chloride solution
US5607619A (en) * 1988-03-07 1997-03-04 Great Lakes Chemical Corporation Inorganic perbromide compositions and methods of use thereof
US5620585A (en) * 1988-03-07 1997-04-15 Great Lakes Chemical Corporation Inorganic perbromide compositions and methods of use thereof
US5112464A (en) * 1990-06-15 1992-05-12 The Dow Chemical Company Apparatus to control reverse current flow in membrane electrolytic cells
US5385650A (en) * 1991-11-12 1995-01-31 Great Lakes Chemical Corporation Recovery of bromine and preparation of hypobromous acid from bromide solution
US5616234A (en) * 1995-10-31 1997-04-01 Pepcon Systems, Inc. Method for producing chlorine or hypochlorite product
EP4083257A1 (de) * 2021-04-27 2022-11-02 Siemens Energy Global GmbH & Co. KG Verfahren zum entgasen von aus einem elektrolyseur abgeleiteten flüssigkeitsströmen

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE160450C (pt) *
GB1095324A (pt) * 1965-02-16
SE432447B (sv) * 1974-03-09 1984-04-02 Asahi Chemical Ind Sett att utfora elektrolys i en elektrolyscell
US3988235A (en) * 1974-07-26 1976-10-26 Kureha Kagaku Kogyo Kabushiki Kaisha Vertical diaphragm type electrolytic apparatus for caustic soda production
JPS534796A (en) * 1976-07-05 1978-01-17 Asahi Chem Ind Co Ltd Electrolysis of pressurized alkali halide
US4176023A (en) * 1978-10-05 1979-11-27 Desal-Chem, Inc. Delsalinization and chemical extraction process

Also Published As

Publication number Publication date
NO801059L (no) 1980-10-13
JPS6340872B2 (pt) 1988-08-12
FI65820C (fi) 1984-07-10
DE3062405D1 (en) 1983-04-28
IN152456B (pt) 1984-01-21
CA1165273A (en) 1984-04-10
ES8100679A1 (es) 1980-12-01
AR227391A1 (es) 1982-10-29
ZA802175B (en) 1981-05-27
FI801144A (fi) 1980-10-13
AU5737980A (en) 1980-10-16
EP0020890A1 (de) 1981-01-07
ATE2852T1 (de) 1983-04-15
BR8002280A (pt) 1980-12-02
JPS55141581A (en) 1980-11-05
FI65820B (fi) 1984-03-30
DE2914870A1 (de) 1980-10-30
US4251335A (en) 1981-02-17
ES490264A0 (es) 1980-12-01
AU531558B2 (en) 1983-08-25

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