EP1106714B1 - Gas phase electrolytic generation of halogen - Google Patents

Gas phase electrolytic generation of halogen Download PDF

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EP1106714B1
EP1106714B1 EP00126503A EP00126503A EP1106714B1 EP 1106714 B1 EP1106714 B1 EP 1106714B1 EP 00126503 A EP00126503 A EP 00126503A EP 00126503 A EP00126503 A EP 00126503A EP 1106714 B1 EP1106714 B1 EP 1106714B1
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gas
hydrogen halide
halogen
gas phase
electrolysis
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German (de)
French (fr)
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EP1106714A1 (en
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Andreas Dr. Fischer
Hermann Dr. Pütter
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BASF SE
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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • 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
    • C25B1/24—Halogens or compounds thereof

Definitions

  • the present invention relates to a process for the production of chlorine by Gas phase electrolysis.
  • gas diffusion electrodes are used as the anode in the gas-phase electrolysis of HCl.
  • these gas diffusion electrodes are separated from the catholyte or the cathode by a solid electrolyte, in particular a polymeric solid electrolyte, such as Nafion membranes.
  • a solid electrolyte in particular a polymeric solid electrolyte, such as Nafion membranes.
  • ceramic or liquid electrolytes for example concentrated H 3 PO 4 .
  • the gas diffusion electrodes often contain a carbon black-supported finely divided catalyst, such as platinum on Vulcan carbon blacks. Further, as the catalyst materials RuO 2 or other noble metal oxides are used on carbon black carriers.
  • the gas diffusion electrodes may also be uncatalyzed, ie contain only carbon black as an electron-conducting and electrochemically active substrate.
  • the gas diffusion electrodes are highly porous and thus have a very large surface area. This surface is opened up electrochemically by impregnation with a suitable electrolyte. It must be ensured that there is no clogging of the pore system of the electrode.
  • the usually used membrane has a sufficient ionic conductivity only at an increased water content, so that a sufficient humidification of the membrane is generally necessary.
  • moistening with water it is also possible to impregnate the membrane with H 3 PO 4 .
  • the moistening can also be carried out with water formed at the cathode during the oxygen reduction.
  • external humidification is preferred because it is controllable and precisely adjustable so that substantially no excess water is in the system.
  • the membrane used is usually a Nafion membrane.
  • the humidification of the membrane for example, by loading the Reaction gases happen with water vapor.
  • the counter electrode to the gas diffusion electrode can be an oxygen-consuming or use hydrogen-developing cathode.
  • a hydrogen-developing cathode used, since it is not possible disturbing water is formed.
  • the electrode / electrolyte / electrode unit is in one with gas channels and Pantographs provided electrolysis cell block or in the case of a Series arrangement in bipolar design in an electrolytic cell stack built-in.
  • gas phase electrolysis when in a process in which HCl is obtained as a by-product in gaseous form is, as it is known for example from WO 97/24320.
  • processes for the preparation of acid chlorides or isocyanates using phosgene which in turn is made from chlorine and carbon monoxide becomes.
  • the recovered chlorine gas can be redone be used for the synthesis of phosgene.
  • An object of the present invention was now to provide a method and a Apparatus for producing halogen gas from a corresponding gaseous hydrogen halide by gas phase electrolysis to provide, by means of which at the same energy use to a higher yield Halogen gas is achieved or at the same yield of the specific Energy input is lowered.
  • a process for the preparation of at least a halogen gas using a corresponding gaseous Wasser Stammhalogenids comprising a gas phase electrolysis provided, wherein the corresponding gaseous hydrogen halide a free Oxygen-containing gas is added.
  • the gaseous hydrogen halide is selected from the Group consisting of: hydrogen fluoride, hydrogen chloride, hydrogen bromide, Hydrogen iodide.
  • hydrogen chloride for Production of chlorine gas.
  • the chlorine gas thus produced is preferably used for Production of phosgene used.
  • the produced Phosgene used for the preparation of acid chlorides and / or of isocyanates, wherein the by-produced hydrogen chloride again as Starting material is used for the inventive method. It results thus an effective closed reaction cycle.
  • the method is used for the free oxygen containing gas air.
  • air is often the easiest and least expensive.
  • HC1 gas By adding oxygen to the gaseous hydrogen halide, In particular to HC1 gas surprisingly shows a significant improvement in Current-voltage characteristic of the gas-phase electrolysis described above. This means that at a lower energy input an equal space-time yield, or with the same energy input, a higher yield of halogen gas, especially chlorine, can be achieved.
  • the process is in a process in which Hydrogen halide, in particular HCl gaseous by-produced, involved.
  • the process is incorporated in a process for the preparation of acid chlorides and / or isocyanants by means of phosgene, which in turn made of chlorine and carbon monoxide, incorporated.
  • phosgene which in turn made of chlorine and carbon monoxide, incorporated.
  • the former processes dry HCl as a by-product.
  • To the Use in the process according to the invention must be of organic Compounds are freed, preferably by means of an activated carbon treatment.
  • the recovered or recovered chlorine gas is the Synthesis of phosgene used.
  • a further advantage of the method according to the invention is the fact that the tolerance of the electrode catalysts to organic contaminants is increased by the addition of a gas having free oxygen and thus prolongs the service life of the electrodes. This is particularly advantageous since, as already mentioned, HCl is used, which may be contaminated with small amounts of organic constituents. These are oxidized by the added oxygen at elevated anodic potentials to CO 2 or other volatile oxygenates, desorbed from the electrode and can no longer block or poison the electrocatalyst.
  • HCI gas phase electrolysis is without Oxygen metering to the anode gas as a comparative example and a HCl gas phase electrolysis with oxygen dosing to the anode gas as an example of an inventive method listed.
  • Figure 1 shows the corresponding Current-voltage characteristics of electrolysis.

Abstract

In the production of gaseous halogen(s) (I) by gas phase electrolysis of the corresponding hydrogen halide(s) (II), a gas (III) containing free or combined oxygen is added (II). An Independent claim is also included for electrolysis cells for this purpose with gas pipe(s) for introducing (III) on the anode side.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Chlor durch Gasphasenelektrolyse.The present invention relates to a process for the production of chlorine by Gas phase electrolysis.

Aus der US 5,411,641 ist die Gasphasenelektrolyse von HCl bereits bekannt als ein Verfahren zur Herstellung von Chlor aus gasförmigem HC1. Der Vorteil dieses Verfahrens zur Herstellung von Chlor liegt vor allem in dem im Vergleich zu einer konventionellen Salzsäureelektrolyse in wäßriger Phase geringerem Energiebedarf der Elektrolyse, d.h. die Elektrolysezelle kann ohne Ausbeuteverlust bei einer wesentlich geringeren Zellspannung betrieben werden.From US 5,411,641, the gas-phase electrolysis of HCl is already known as a process for producing chlorine from gaseous HC1. The advantage of this Process for the production of chlorine is mainly in the compared to a conventional hydrochloric acid electrolysis in aqueous phase lower Energy demand of the electrolysis, i. the electrolysis cell can without Yield loss can be operated at a much lower cell voltage.

Zudem ist es nicht mehr nötig, das hergestellte Chlor zu trocknen, wodurch sich auch eine erhebliche Zeit- und Kostenersparnis ergibt und das ganze Verfahren sich, aufgrund des fehlenden Trocknungsschrittes, wesentlich einfacher gestaltet.In addition, it is no longer necessary to dry the chlorine produced, resulting in also results in a significant time and cost savings and the whole process due to the lack of drying step, designed much easier.

Wie aus der WO 98/00581 bekannt, werden in der Gasphasenelektrolyse von HCl i.a. Gasdiffusionselektroden als Anode eingesetzt. Im Allgemeinen sind diese Gasdiffusionselektroden durch einen Festelektrolyten, insbesondere einen polymeren Festelektrolyten, wie beispielsweise Nafion-Membranen, vom Katholyten bzw. der Kathode getrennt. Ferner ist es auch denkbar, hier keramische oder flüssige Elektrolyte, wie beispielsweise konzentrierte H3PO4, einzusetzen. Die Gasdiffusionselektroden enthalten oft einen rußgeträgerten, feinverteilten Katalysator, wie beispielsweise Platin auf Vulcan-Rußen. Ferner werden als Katalysatormaterialien RuO2 oder andere Edelmetalloxide auf Rußträgern verwendet. Allerdings können die Gasdiffusionselektroden auch unkatalysiert sein, d.h. lediglich Ruß als elektronenleitendes und elektrochemisch aktives Substrat enthalten. Die Gasdiffusionselektroden sind hochporös und weisen somit eine sehr große Oberfläche auf. Diese Oberfläche wird elektrochemisch durch Tränken mit einem geeigneten Elektrolyten erschlossen. Hierbei muß darauf geachtet werden, daß es nicht zu einer Verstopfung des Porensystems der Elektrode kommt. Die üblicherweise eingesetzte Membran weist eine ausreichende Ionenleitfähigkeit erst bei einem erhöhten Wassergehalt auf, so daß eine ausreichende Befeuchtung der Membran i.a. notwendig ist. Anstelle einer Befeuchtung mit Wasser ist es auch möglich, die Membran mit H3PO4 zu tränken. Ferner läßt sich die Befeuchtung auch mit an der Kathode bei der Sauerstoffreduktion entstehendem Wasser durchführen. Allerdings ist eine externe Befeuchtung bevorzugt, da diese steuerbar und genau einstellbar ist, so daß im Wesentlichen kein überschüssiges Wasser im System verleibt. Als Membran wird üblicherweise eine Nafion-Membran eingesetzt.As is known from WO 98/00581, gas diffusion electrodes are used as the anode in the gas-phase electrolysis of HCl. In general, these gas diffusion electrodes are separated from the catholyte or the cathode by a solid electrolyte, in particular a polymeric solid electrolyte, such as Nafion membranes. Furthermore, it is also conceivable here to use ceramic or liquid electrolytes, for example concentrated H 3 PO 4 . The gas diffusion electrodes often contain a carbon black-supported finely divided catalyst, such as platinum on Vulcan carbon blacks. Further, as the catalyst materials RuO 2 or other noble metal oxides are used on carbon black carriers. However, the gas diffusion electrodes may also be uncatalyzed, ie contain only carbon black as an electron-conducting and electrochemically active substrate. The gas diffusion electrodes are highly porous and thus have a very large surface area. This surface is opened up electrochemically by impregnation with a suitable electrolyte. It must be ensured that there is no clogging of the pore system of the electrode. The usually used membrane has a sufficient ionic conductivity only at an increased water content, so that a sufficient humidification of the membrane is generally necessary. Instead of moistening with water, it is also possible to impregnate the membrane with H 3 PO 4 . Furthermore, the moistening can also be carried out with water formed at the cathode during the oxygen reduction. However, external humidification is preferred because it is controllable and precisely adjustable so that substantially no excess water is in the system. The membrane used is usually a Nafion membrane.

Die Befeuchtung der Membran kann beispielsweise durch Beladung der Reaktionsgase mit Wasserdampf geschehen. Vorzugsweise werden hier nur die Reaktionsgase auf der Kathode mit Wasserdampf beladen, während die Reaktionsgase auf der Anodenseite möglichst trocken gehalten werden.The humidification of the membrane, for example, by loading the Reaction gases happen with water vapor. Preferably, only the Reaction gases loaded on the cathode with water vapor while the Reaction gases are kept as dry as possible on the anode side.

Als Gegenelektrode zur Gasdiffusionselektrode läßt sich eine sauerstoffverzehrende oder wasserstoffentwickelnde Kathode einsetzen. Vorzugsweise wird hierbei eine wasserstoffentwickelnde Kathode verwendet, da dabei kein eventuell störendes Wasser gebildet wird.As the counter electrode to the gas diffusion electrode can be an oxygen-consuming or use hydrogen-developing cathode. Preferably in this case a hydrogen-developing cathode used, since it is not possible disturbing water is formed.

Die Elektrode/Elektrolyt/Elektrode-Einheit wird in einem mit Gaskanälen und Stromabnehmern versehenen Elektrolysezellenblock oder im Falle einer Reihenanordnung in bipolarer Ausführung in einen Elektrolysezellenstapel eingebaut. The electrode / electrolyte / electrode unit is in one with gas channels and Pantographs provided electrolysis cell block or in the case of a Series arrangement in bipolar design in an electrolytic cell stack built-in.

Als Produkt der Anodenreaktion erhält man ein trockenes Chlorgas mit nur geringem Wassergehalt.As the product of the anodic reaction, a dry chlorine gas is obtained with only low water content.

Als besonders vorteilhaft erweist sich die Gasphasenelektrolyse, wenn sie in einem Prozeß, bei welchem HCI gasförmig als Nebenprodukt anfällt, eingebunden wird, wie es beispielsweise aus der WO 97/24320 bekannt ist. Diese Prozesse sind beispielsweise Prozesse zur Herstellung von Säurechloriden oder Isocyanaten mittels Phosgen, welches wiederum aus Chlor und Kohlenmonoxid hergestellt wird. In den erstgenannten Prozessen fällt trockenes HCl gasförmig als Beiprodukt an und muß zum Einsatz in der Elektrolyse nur noch von organischen Verunreinigungen befreit werden. Das wiedergewonnene Chlorgas kann erneut zur Synthese von Phosgen genutzt werden.Particularly advantageous is the gas phase electrolysis, when in a process in which HCl is obtained as a by-product in gaseous form is, as it is known for example from WO 97/24320. These processes are For example, processes for the preparation of acid chlorides or isocyanates using phosgene, which in turn is made from chlorine and carbon monoxide becomes. In the former processes, dry HCl precipitates as gaseous Beiprodukt and must for use in the electrolysis of organic Impurities are freed. The recovered chlorine gas can be redone be used for the synthesis of phosgene.

Eine Aufgabe der vorliegenden Erfindung war es nun, ein Verfahren und eine Vorrichtung zur Herstellung von Halogengas aus einem entsprechenden gasförmigen Wasserstoffhalogenid mittels der Gasphasenelektrolyse bereitzustellen, mittels derer bei gleichem Energieeinsatz eine höhere Ausbeute an Halogengas erreicht wird bzw. bei gleicher Ausbeute der spezifische Energieeinsatz gesenkt wird.An object of the present invention was now to provide a method and a Apparatus for producing halogen gas from a corresponding gaseous hydrogen halide by gas phase electrolysis to provide, by means of which at the same energy use to a higher yield Halogen gas is achieved or at the same yield of the specific Energy input is lowered.

Gelöst wird diese Aufgabe durch ein erfindungsgemäßes Verfahren gemäß Anspruch 1. Weitere vorteilhafte Ausführungsformen werden in den Unteransprüchen genannt.This object is achieved by a method according to the invention Claim 1. Further advantageous embodiments are mentioned in the subclaims.

Demgemäß wird erfindungsgemäß ein Verfahren zur Herstellung von mindestens einem Halogengas unter Einsatz eines entsprechenden gasförmigen Wasserstoßhalogenids umfassend eine Gasphasenelektrolyse bereitgestellt, wobei dem entsprechenden gasförmigen Wasserstoffhalogenid ein freien Sauerstoff aufweisendes Gas zugegeben wird.Accordingly, according to the invention, a process for the preparation of at least a halogen gas using a corresponding gaseous Wasserstoßhalogenids comprising a gas phase electrolysis provided, wherein the corresponding gaseous hydrogen halide a free Oxygen-containing gas is added.

Vorzugsweise wird das gasförmige Wasserstoffhalogenid ausgewählt aus der Gruppe, bestehend aus: Fluorwasserstoff, Chlorwasserstoff, Bromwasserstoff, Iodwasserstoff. Besonders bevorzugt verwendet man Chlorwasserstoff zur Herstellung von Chlorgas. Das so hergestellte Chlorgas wird vorzugsweise zur Herstellung von Phosgen verwendet. Weiter bevorzugt wird das hergestellte Phosgen zur Herstellung von Säurechloriden und/oder von Isocyanaten verwendet, wobei der als Nebenprodukt gebildete Chlorwasserstoff wiederum als Ausgangsstoff für das erfindungsgemäße Verfahren verwendet wird. Es ergibt sich somit ein effektiver geschlossener Reaktionszyklus.Preferably, the gaseous hydrogen halide is selected from the Group consisting of: hydrogen fluoride, hydrogen chloride, hydrogen bromide, Hydrogen iodide. Particular preference is given to using hydrogen chloride for Production of chlorine gas. The chlorine gas thus produced is preferably used for Production of phosgene used. More preferably, the produced Phosgene used for the preparation of acid chlorides and / or of isocyanates, wherein the by-produced hydrogen chloride again as Starting material is used for the inventive method. It results thus an effective closed reaction cycle.

In einer bevorzugten Ausführungsform des Verfahrens verwendet man für das freien Sauerstoff aufweisende Gas Luft. Der Einsatz von Luft ist oft am einfachsten und kostengünstigsten.In a preferred embodiment of the method is used for the free oxygen containing gas air. The use of air is often the easiest and least expensive.

Durch die Zugabe von Sauerstoff zum dem gasförmigen Wasserstoffhalogenid, insbesondere zu HC1-Gas zeigt sich überraschend eine deutliche Verbesserung der Strom-Spannungskennlinie der oben beschriebenen Gasphasenelektrolyse. Dies bedeutet, daß bei einem geringeren Energieeinsatz eine gleiche Raum-Zeit-Ausbeute, bzw. bei gleichem Energieeinsatz eine höhere Ausbeute an Halogengas, insbesondere an Chlor, erreicht werden kann.By adding oxygen to the gaseous hydrogen halide, In particular to HC1 gas surprisingly shows a significant improvement in Current-voltage characteristic of the gas-phase electrolysis described above. This means that at a lower energy input an equal space-time yield, or with the same energy input, a higher yield of halogen gas, especially chlorine, can be achieved.

In einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird das Verfahren in einen Prozeß, bei welchem Wasserstoffhalogenid, insbesondere HCl gasförmig als Nebenprodukt anfällt, eingebunden. Vorzugsweise wird das Verfahren in ein Verfahren zur Herstellung von Säurechloriden und/oder Isocyananten mittels Phosgen, welches wiederum aus Chlor und Kohlenmonoxid hergestellt wird, eingebunden. In den erstgenannten Prozessen fällt trockene HCl gasförmig als Nebenprodukt an. Zum Einsatz in dem erfindungsgemäßen Verfahren muß es von organischen Verbindungen befreit werden, vorzugsweise mittels einer Aktivkohlebehandlung.In a further preferred embodiment of the invention Procedure, the process is in a process in which Hydrogen halide, in particular HCl gaseous by-produced, involved. Preferably, the process is incorporated in a process for the preparation of acid chlorides and / or isocyanants by means of phosgene, which in turn made of chlorine and carbon monoxide, incorporated. In the The former processes dry HCl as a by-product. To the Use in the process according to the invention must be of organic Compounds are freed, preferably by means of an activated carbon treatment.

Vorzugsweise wird das hergestellte bzw. wiedergewonnene Chlorgas zur Synthese von Phosgen verwendet. Preferably, the recovered or recovered chlorine gas is the Synthesis of phosgene used.

Weiterhin vorteilhaft bei dem erfindungsgeimäßen Verfahren ist die Tatsache, daß sich durch die Zugabe eines freien Sauerstoff aufweisenden Gases die Toleranz der Elektrodenkatalysatoren gegen organische Verunreinigungen erhöht und somit die Betriebsdauer der Elektroden verlängert. Dieses ist insbesondere vorteilhaft, da, wie bereits erwähnt, HCl eingesetzt wird, welche unter Umständen mit geringen Mengen an organischen Bestandteilen verunreinigt ist. Diese werden durch den zugesetzten Sauerstoff bei erhöhten anodischen Potentialen zu CO2 oder anderen, flüchtigen Oxigenaten oxidiert, von der Elektrode desorbiert und können so den Elektrokatalysator nicht mehr blockieren oder vergiften.A further advantage of the method according to the invention is the fact that the tolerance of the electrode catalysts to organic contaminants is increased by the addition of a gas having free oxygen and thus prolongs the service life of the electrodes. This is particularly advantageous since, as already mentioned, HCl is used, which may be contaminated with small amounts of organic constituents. These are oxidized by the added oxygen at elevated anodic potentials to CO 2 or other volatile oxygenates, desorbed from the electrode and can no longer block or poison the electrocatalyst.

Weitere Vorteile und Anwendungsmöglichkeiten des erfindungsgemäßen Verfahrens werden anhand der folgenden Beispiele in Zusammenhang mit der Figur aufgezeigt.Further advantages and applications of the invention The method will be described in conjunction with the following examples Figure shown.

BEISPIELEEXAMPLES

In den folgenden Beispielen ist eine HCI-Gasphasenelektrolyse ohne Sauerstoffdosierung zum Anodengas als Vergleichsbeispiel und eine HCl-Gasphasenelektrolyse mit Sauerstoffdosierung zum Anodengas als Beispiel für ein erfindungsgemäßes Verfahren aufgeführt. Figur 1 zeigt die entsprechenden Strom-Spannungskennlinien der Elektrolyse. In the following examples, HCI gas phase electrolysis is without Oxygen metering to the anode gas as a comparative example and a HCl gas phase electrolysis with oxygen dosing to the anode gas as an example of an inventive method listed. Figure 1 shows the corresponding Current-voltage characteristics of electrolysis.

Vergleichsbeispiel:Comparative Example:

In diesem Beispiel wird ein Experiment mit einer chlorentwickelnden Pt/C-Anode und einer sauerstoffverzehrenden Pt/C-Kathode (beide 1 mg Pt/cm2 aktive Elektrodenfläche), jeweils verbunden mit und voneinander getrennt durch eine Nafion 117 Membran, beschrieben. Die Zellentemperatur betrug 85°C, nur das Kathodengas Sauerstoff wurde mittels Durchleiten durch ein auf 95°C beheiztes Wassergefäß befeuchtet. Als Anodengas wurde eine Mischung aus trockenem HCI mit 20 Vol.% Stickstoff eingesetzt. Zur Vorbereitung der Messung wurde die Zelle bei einem Volt Zellspannung unter den beschriebenen Betriebsbedingungen betrieben. Anschließend wurden quasi-stationäre Strom-Spannungscharakteristiken aufgenommen, wobei jede Zellspannung für etwa eine Minute konstant gehalten wurde, bevor der Meßpunkt notiert wurde. Die Charakteristik wurde zwischen 0 und 1,8 V aufgenommen, wobei mehrfach von negativem zu positiven Potential und umgekehrt gemessen wurde. Die unter diesen Bedingungen erhaltene Strom-Spannungscharakteristik ist durch die Linie mit den kreuzförmigen Symbolen in Figur 1 dargestellt.In this example, an experiment is described with a chlorine-developing Pt / C anode and an oxygen-consuming Pt / C cathode (both 1 mg Pt / cm 2 active electrode area), each connected to and separated from each other by a Nafion 117 membrane. The cell temperature was 85 ° C, only the cathode gas oxygen was moistened by passing through a heated to 95 ° C water vessel. The anode gas used was a mixture of dry HCl with 20% by volume of nitrogen. To prepare the measurement, the cell was operated at one volt cell voltage under the operating conditions described. Subsequently, quasi-stationary current-voltage characteristics were recorded, each cell voltage being held constant for about one minute before the measurement point was noted. The characteristic was recorded between 0 and 1.8 V, whereby several times from negative to positive potential and vice versa was measured. The current-voltage characteristic obtained under these conditions is shown by the line with the cross-shaped symbols in FIG.

Beispiel:Example:

In diesem Beispiel wird ein Experiment mit dem selben Aufbau wie im Falle des Vergleichsbeispiels beschrieben. Es wurde nur als Anodengas ein Gemisch aus trockenem HCL mit 20 Vol.% Sauerstoff eingesetzt, d.h. der Stickstoff aus dem Vergleichsbeispiel wurde durch Sauerstoff ersetzt. Die unter diesen Bedingungen erhaltene Strom-Spannungscharakteristik ist durch die Linie mit offenen Quadraten in Figur 1 dargestellt.In this example, an experiment with the same construction as in the case of Comparative described. It was just a mixture of anodic gas used dry HCL with 20 vol.% Oxygen, i. the nitrogen from the Comparative example was replaced by oxygen. The under these conditions obtained current-voltage characteristic is through the line with open Squares shown in Figure 1.

Es ist deutlich zu erkennen, daß die Strom-Spannungscharakteristik nach dem erfindungsgemäßen Verfahren insbesondere bei höheren Stromdichten eine deutlich geringere Zellspannung aufweist.It can be clearly seen that the current-voltage characteristic after the inventive method, especially at higher current densities has significantly lower cell voltage.

Claims (6)

  1. A process for preparing at least one halogen gas using a corresponding gaseous hydrogen halide, comprising a gas phase electrolysis, which comprises adding a gas comprising free oxygen to the corresponding gaseous hydrogen halide.
  2. A process as claimed in claim 1, wherein the gaseous hydrogen halide is selected from hydrogen halide, hydrogen chloride, hydrogen bromide, and hydrogen iodide.
  3. A process as claimed in claim 1 or 2, wherein the gas comprising free oxygen is air.
  4. A process as claimed in any of claims 1 to 3, wherein the gaseous hydrogen halide used may be recovered from a byproduct formed in another, independent chemical process.
  5. A process as claimed in claim 4, wherein the halogen gas prepared is passed back directly or indirectly to the other, independent chemical process.
  6. A process as claimed in claim 4 or 5, wherein the other, independent chemical process is the preparation of acid chlorides and/or isocyanates by means of phosgene.
EP00126503A 1999-12-10 2000-12-08 Gas phase electrolytic generation of halogen Expired - Lifetime EP1106714B1 (en)

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DE19959683A DE19959683A1 (en) 1999-12-10 1999-12-10 Process for the production of halogens by gas phase electrolysis
DE19959683 1999-12-10

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EP1106714B1 true EP1106714B1 (en) 2005-03-16

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ES2238245T3 (en) 2005-09-01
ATE291109T1 (en) 2005-04-15

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