EP1106714A1 - Verfahren zur Herstellung von Halogenen durch Gasphasenelektrolyse - Google Patents
Verfahren zur Herstellung von Halogenen durch Gasphasenelektrolyse Download PDFInfo
- Publication number
- EP1106714A1 EP1106714A1 EP00126503A EP00126503A EP1106714A1 EP 1106714 A1 EP1106714 A1 EP 1106714A1 EP 00126503 A EP00126503 A EP 00126503A EP 00126503 A EP00126503 A EP 00126503A EP 1106714 A1 EP1106714 A1 EP 1106714A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gas
- hydrogen halide
- gas phase
- electrolysis
- halogen
- 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.)
- Granted
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Classifications
-
- 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.
- the gas phase electrolysis of HC1 is already known from US Pat. No. 5,411,641 a process for the production of chlorine from gaseous HC1.
- the advantage of this The process for the production of chlorine is mainly compared to that a conventional hydrochloric acid electrolysis in the aqueous phase less Electrolysis energy requirement, i.e. the electrolytic cell can without Loss of yield can be operated at a much lower cell voltage.
- gas diffusion electrodes are generally used as anode in the gas phase electrolysis of HC1.
- these gas diffusion electrodes are separated from the catholyte or the cathode by a solid electrolyte, in particular a polymeric solid electrolyte, such as, for example, Nafion membranes.
- a solid electrolyte in particular a polymeric solid electrolyte, such as, for example, Nafion membranes.
- ceramic or liquid electrolytes such as concentrated H 3 PO 4 , for example.
- the gas diffusion electrodes often contain a soot-supported, finely divided catalyst, such as platinum on Vulcan blacks. RuO 2 or other noble metal oxides on carbon black supports are also used as catalyst materials.
- the gas diffusion electrodes can also be uncatalyzed, ie only contain carbon black as the electron-conducting and electrochemically active substrate.
- the gas diffusion electrodes are highly porous and therefore have a very large surface area. This surface is developed electrochemically by soaking with a suitable electrolyte. Care must be taken to ensure that the electrode's pore system is not blocked.
- the membrane usually used only has sufficient ionic conductivity when the water content is increased, so that adequate moistening of the membrane is generally necessary. Instead of moistening with water, it is also possible to soak the membrane with H3PO 4 . Furthermore, the moistening can also be carried out with water formed on the cathode during the oxygen reduction. However, external humidification is preferred because it can be controlled and precisely adjusted so that essentially no excess water remains in the system.
- a Nafion membrane is usually used as the membrane.
- the membrane can be moistened, for example, by loading the Reaction gases happen with water vapor.
- the Reaction gases on the cathode with water vapor should be kept as dry as possible.
- An oxygen-consuming one can be used as the counter electrode to the gas diffusion electrode or use a hydrogen-developing cathode.
- a hydrogen-developing cathode is used, since there may not be any disturbing water is formed.
- the electrode / electrolyte / electrode unit is in one with gas channels and Current collector provided electrolysis cell block or in the case of a Row arrangement in a bipolar version in an electrolytic cell stack built-in.
- the product of the anode reaction is a dry chlorine gas with only low water content.
- Gas phase electrolysis proves to be particularly advantageous when it is in a process in which HCI is a gaseous by-product is, as is known for example from WO 97/24320.
- HCI is a gaseous by-product is, as is known for example from WO 97/24320.
- These processes are for example processes for the production of acid chlorides or isocyanates using phosgene, which in turn is made from chlorine and carbon monoxide becomes.
- dry HCl falls as a gas A by-product and must only be used in the electrolysis of organic Impurities are freed.
- the recovered chlorine gas can again be used for the synthesis of phosgene.
- An object of the present invention was now a method and a Device for producing halogen gas from a corresponding gaseous hydrogen halide by means of gas phase electrolysis to provide, by means of which a higher yield with the same energy input Halogen gas is reached or, with the same yield, the specific one Energy consumption is reduced.
- a method for the production of at least a halogen gas using an appropriate gaseous Hydrogen halide comprising gas phase electrolysis provided, wherein a free or the corresponding gaseous hydrogen halide bound oxygen-containing gas is added.
- the gaseous hydrogen halide is preferably selected from the Group consisting of: hydrogen fluoride, hydrogen chloride, hydrogen bromide, Hydrogen iodide.
- Hydrogen chloride is particularly preferably used Production of chlorine gas.
- the chlorine gas thus produced is preferably used for Production of phosgene used.
- the one produced is more preferred Phosgene used for the production of acid chlorides and / or isocyanates, the hydrogen chloride formed as a by-product in turn as Starting material is used for the inventive method. It results thus an effective closed reaction cycle.
- the method is used for the free or bound oxygen containing gas air.
- air is often the easiest and cheapest.
- the process becomes a process in which Hydrogen halide, especially gaseous HC1, is obtained as a by-product, involved.
- the process is a manufacturing process of acid chlorides and / or isocyanants by means of phosgene, which in turn made from chlorine and carbon monoxide.
- phosgene which in turn made from chlorine and carbon monoxide.
- the first mentioned processes produce dry HC1 as a by-product.
- To the Use in the process according to the invention must be organic Compounds are freed, preferably by means of an activated carbon treatment.
- the chlorine gas produced or recovered is preferably used Synthesis of phosgene used.
- Another advantage of the method according to the invention is the fact that the addition of a free or bound oxygen-containing gas increases the tolerance of the electrode catalysts to organic contaminants and thus extends the operating time of the electrodes.
- HCl is used, which may be contaminated with small amounts of organic constituents. These are oxidized by the added oxygen at increased anodic potentials to CO 2 or other volatile oxigenates, desorbed by the electrode and can therefore no longer block or poison the electrocatalyst.
- the invention further relates to an electrolysis cell for producing at least one halogen gas using a corresponding gaseous one Hydrogen halide using the method of gas phase electrolysis, the Electrolysis cell has at least one gas channel on the anode side Supply of a gas containing free or bound oxygen suitable is.
- HCl gas phase electrolysis is without Oxygen metering to the anode gas as a comparative example and HC1 gas phase electrolysis with oxygen metering to the anode gas as an example for an inventive method listed.
- Figure 1 shows the corresponding Current-voltage characteristics of electrolysis.
- This example describes an experiment 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 one another by a Nafion 117 membrane.
- the cell temperature was 85 ° C, only the cathode gas oxygen was moistened by passing it through a water vessel heated to 95 ° C.
- a mixture of dry HCl with 20 vol.% Nitrogen was used as the anode gas.
- the cell was operated at a volt cell voltage under the operating conditions described. Quasi-stationary current-voltage characteristics were then recorded, with each cell voltage being kept constant for about one minute before the measurement point was noted. The characteristic was recorded between 0 and 1.8 V, whereby measurements were taken several times from negative to positive potential and vice versa.
- the current-voltage characteristic obtained under these conditions is represented by the line with the cross-shaped symbols in FIG. 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims (8)
- Verfahren zur Herstellung von mindestens einem Halogengas unter Einsatz eines entsprechenden gasförmigen Wasserstoffhalogenids umfassend eine Gasphasenelektrolyse,
dadurch gekennzeichnet, daß
dem entsprechenden gasförmigen Wasserstoffhalogenid ein freien oder gebundenen Sauerstoff aufweisendes Gas zugegeben wird. - Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das gasförmige Wasserstoffhalogenid gewählt ist aus der Gruppe, bestehend aus: Fluorwasserstoff, Chlorwasserstoff, Bromwasserstoff, Iodwasserstoff.
- Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das freien oder gebundenen Sauerstoff aufweisende Gas Luft ist.
- Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das eingesetzte gasförmige Wasserstoffhalogenid aus einem bei einem anderen unabhängigen chemischen Prozeß entstehenden Nebenprodukt gewinnbar ist.
- Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß das hergestellte Halogengas direkt oder indirekt wieder dem anderen unabhängigen chemischen Prozeß zugeführt wird.
- Verfahren nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß der andere unabhängige chemische Prozeß die Herstellung von Säurechloriden und/oder Isocyanaten mittels Phosgen ist.
- Elektrolysezelle zur Herstellung von mindestens einem Halogengas unter Einsatz eines entsprechenden gasförmigen Wasserstoffhalogenids durch Gasphasenelektrolyse, wobei die Elektrolysezelle anodenseitig mindestens einen Gaskanal aufweist, der zur Zuführung von einem freien oder gebundenen Sauerstoff aufweisenden Gases geeignet ist.
- Verwendung von Chlorgas zur Herstellung von Phosgen, dadurch gekennzeichnet, daß das Chlorgas mittels eines Verfahrens nach einem der Ansprüche 1 bis 6 hergestellt wurde.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19959683 | 1999-12-10 | ||
DE19959683A DE19959683A1 (de) | 1999-12-10 | 1999-12-10 | Verfahren zur Herstellung von Halogenen durch Gasphasenelektrolyse |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1106714A1 true EP1106714A1 (de) | 2001-06-13 |
EP1106714B1 EP1106714B1 (de) | 2005-03-16 |
Family
ID=7932209
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00126503A Expired - Lifetime EP1106714B1 (de) | 1999-12-10 | 2000-12-08 | Verfahren zur Herstellung von Halogenen durch Gasphasenelektrolyse |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1106714B1 (de) |
AT (1) | ATE291109T1 (de) |
DE (2) | DE19959683A1 (de) |
ES (1) | ES2238245T3 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109468658A (zh) * | 2018-12-11 | 2019-03-15 | 浙江巨圣氟化学有限公司 | 一种碳酰氟的制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5871380A (ja) * | 1981-10-21 | 1983-04-28 | Agency Of Ind Science & Technol | 電解水素の製造法 |
WO1997024473A1 (en) * | 1995-12-28 | 1997-07-10 | E.I. Du Pont De Nemours And Company | Production of carbonyl halide |
WO1997024306A1 (en) * | 1995-12-28 | 1997-07-10 | E.I. Du Pont De Nemours And Company | Production of ethylene dichloride by direct chlorination and production of vinyl chloride monomer using chlorine recycle |
-
1999
- 1999-12-10 DE DE19959683A patent/DE19959683A1/de not_active Withdrawn
-
2000
- 2000-12-08 EP EP00126503A patent/EP1106714B1/de not_active Expired - Lifetime
- 2000-12-08 ES ES00126503T patent/ES2238245T3/es not_active Expired - Lifetime
- 2000-12-08 AT AT00126503T patent/ATE291109T1/de not_active IP Right Cessation
- 2000-12-08 DE DE50009777T patent/DE50009777D1/de not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5871380A (ja) * | 1981-10-21 | 1983-04-28 | Agency Of Ind Science & Technol | 電解水素の製造法 |
WO1997024473A1 (en) * | 1995-12-28 | 1997-07-10 | E.I. Du Pont De Nemours And Company | Production of carbonyl halide |
WO1997024306A1 (en) * | 1995-12-28 | 1997-07-10 | E.I. Du Pont De Nemours And Company | Production of ethylene dichloride by direct chlorination and production of vinyl chloride monomer using chlorine recycle |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 007, no. 161 (C - 176) 15 July 1983 (1983-07-15) * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109468658A (zh) * | 2018-12-11 | 2019-03-15 | 浙江巨圣氟化学有限公司 | 一种碳酰氟的制备方法 |
CN109468658B (zh) * | 2018-12-11 | 2020-10-30 | 浙江巨圣氟化学有限公司 | 一种碳酰氟的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DE19959683A1 (de) | 2001-06-13 |
ATE291109T1 (de) | 2005-04-15 |
DE50009777D1 (de) | 2005-04-21 |
ES2238245T3 (es) | 2005-09-01 |
EP1106714B1 (de) | 2005-03-16 |
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