EP0866890B1 - Verfahren zur direkten elektrochemischen gasphasen-phosgensynthese - Google Patents

Verfahren zur direkten elektrochemischen gasphasen-phosgensynthese Download PDF

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Publication number
EP0866890B1
EP0866890B1 EP96938176A EP96938176A EP0866890B1 EP 0866890 B1 EP0866890 B1 EP 0866890B1 EP 96938176 A EP96938176 A EP 96938176A EP 96938176 A EP96938176 A EP 96938176A EP 0866890 B1 EP0866890 B1 EP 0866890B1
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EP
European Patent Office
Prior art keywords
gas
phosgene
bar
cathode
process according
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 - Lifetime
Application number
EP96938176A
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German (de)
English (en)
French (fr)
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EP0866890A1 (de
Inventor
Fritz Gestermann
Jürgen DOBBERS
Hans-Nicolaus Rindfleisch
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Bayer AG
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Bayer AG
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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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • 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
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms

Definitions

  • the invention relates to a process for the electrochemical conversion of hydrogen chloride to phosgene.
  • phosgene becomes catalytic generated from free chlorine.
  • the chlorine is either generated generically from one NaCl electrolysis provided, e.g. from isocyanate production originating HCl gas is processed in the form of hydrochloric acid or as Recycle chlorine recovered from the electrolysis of aqueous hydrochloric acid.
  • US 5 411 641 describes an electrochemical process for the production of chlorine described in which a dry direct oxidation in the electrochemical cell from HCl to chlorine and protons. The process runs even with cathode side aqueous electrolyte combined with hydrogen production operating voltages significantly cheaper than classic electrolysis aqueous Hydrochloric acid.
  • the invention is based on the object, starting from gaseous hydrogen chloride, according to claim 1, to produce phosgene directly by electrochemical means.
  • This object is achieved in that the anode with a proton-conducting membrane equipped electrochemical cell as Educts of dry HCl gas and dry CO gas are supplied and the at the anodic oxidation of HCl gas by chlorine radicals with the CO gas immediately react to phosgene while the protons formed simultaneously migrate through the membrane to the cathode and there when operated with aqueous HCl can be reduced to hydrogen or in the presence of oxygen to water.
  • the chlorine radicals are modeled on the anode with CO gas according to the reaction equations anodized to phosgene.
  • the process is preferably carried out in such a way that, in addition to the electrochemical anodic oxidation, an exothermic catalytic conversion of molecular chlorine with CO gas to phosgene takes place in the carbon-containing carrier material of the activated diffusion anode in accordance with the reaction equation CO + Cl 2 ⁇ COCl 2 .
  • the anodic overvoltage can be caused by the phosgene radicals that occur be lowered by 0.2 V to 0.6 V.
  • the method is advantageously carried out in such a way that to lower the Operating voltage of the electrochemical cell of oxygen at the cathode (3) is reduced and with the protons diffusing through the membrane to water reacted.
  • the method can also be carried out so that the cathode (3) operated in aqueous hydrochloric acid, with hydrogen as a by-product is produced.
  • the membrane is advantageously used to adjust its proton conductivity Supply of moist oxygen which leads to the cathode with the starting gas is additionally moistened.
  • the electrochemical reactions take place at the cathode and anode at a pressure of 2 bar to 6 bar.
  • a further development of the method according to the invention is that the Phosgene current drawn off on the anode side under the operating pressure in a recuperator cooled and liquefied and the liquefied phosgene on the secondary side in the recuperator is expanded and evaporated, the one required for liquefaction Generates cooling capacity and the primary liquefied phosgene from HCI and CO induct gas is exempted. These educt gas fractions can then be returned to the electrochemical cell.
  • the electrochemical cell is expediently used in a closed system, which also includes the recuperator at a pressure of 2 bar to 10 bar, preferably 2 bar to 6 bar, operated such that the Differential pressure between the closed system and the electrochemical Cell is approximately zero, so that the electrochemical cell even when operating below higher pressures can be operated virtually without pressure.
  • a catalytic oxygen reduction (catalyst, for example Pt, Ir, or Pd) of the supplied oxygen takes place at the cathode at the interface with the proton-conducting membrane located between the two electrodes.
  • the oxygen or the supplied oxygen-containing gas mixture (feed gas) is moistened with water, similar to a PEM fuel cell, to the saturation point.
  • the reaction follows the equation: (1) 1/2 O 2 + 2e - + 2H + ⁇ H 2 O (g)
  • the water balance of the proton-conducting membrane is pre-moistened of the feed gas taking into account the formation of water of reaction in accordance with Equation (1) controlled.
  • a single-layer proton-conducting membrane is used from fluoropolymers with protonated sulfonic acid groups in the ion transport channels as a solid electrolyte between cathode and anode.
  • the proton conductivity is, as described above, improved by moistening the cathode side.
  • the basic process is the direct oxidation of dry HCl gas to chlorine and protons, which are fed into the membrane serving as electrolyte, according to the following reaction
  • the oxidation takes place catalytically (Pt, Ir, Rh, or Pd catalyst) at the interface between the anode and the proton-conducting membrane.
  • the HCl direct oxidation delivers dry chlorine without the presence of other reactants, which immediately reacts further with the dry CO gas offered at the same time. Two reaction paths are possible, both of which are exothermic:
  • CO reacts with the anodically formed chlorine radical to form the COCl radical, which in turn reacts with another chlorine radical to form COCl 2 and diffuses out of the field of electrocatalytic analysis.
  • the reaction mechanism at the anode looks like this:
  • the hydrogen chloride oxidation is thus in both reaction steps by the CO influenced directly or indirectly.
  • the exothermic nature of the reaction steps becomes at least in part in a lowering of the activation energy of the electrochemical HCl direct oxidation implemented with the consequence of a decrease the cell voltage.
  • the chlorine radicals that have not reacted with CO or COCl radicals recombine to form Cl 2 .
  • the usual carrier material for electrochemically active catalysts integrated in the electrodes is carbon in the form of vulcanized carbon black or acetylene black, this microporous carrier layer being passed through by the product gases Cl 2 and COCl 2 coming from the electrolysis. This layer acts as an activated carbon surface, which, at the usual cell temperatures of approx. 80 ° C, is the non-electrochemical, but exothermic reaction (5) CO + Cl 2 ⁇ COCl 2 catalyzed.
  • a dry anodic product gas with the following composition is then obtained: COCl 2 + unreacted HCl gas + unreacted CO + possibly traces of Cl 2 .
  • the electrochemical cell 1 acc. 1 essentially consists of the gas diffusion anode 2, the gas diffusion cathode 3 and the one arranged between the electrodes, acting as an electrolyte proton-conducting membrane 4.
  • the anode 2 consists of a porous, catalytically activated activated carbon matrix 5, which is connected on the inside to the membrane 3 and on the outside with one from a conductive gas distributor 6, which is connected to a anodic current distributor 7 is contacted.
  • the analog cathode 3 consists of the catalytic activated carbon matrix 8, the conductive gas distributor 9 and the power distributor 10. Primarily come as catalytic material Platinum, iridium, rhodium and palladium in question.
  • Such gas diffusion anodes or cathodes are also commercially available (e.g. electrodes of the type ELAT from GDE Gasdiffusionselektroden GmbH. Frankfurt a. Main).
  • the anode 2 is in an anode gas space 11, the cathode 3 in a cathode gas space 12 arranged.
  • the two gas spaces 11 and 12 are except for the inlet and Drain pipe closed.
  • the anode gas space becomes via the feed connector 13 11 a dry educt gas mixture of HCI and CO and over the feed pipe 14 the gaseous educt gas mixture from the cathode gas space 12 Oxygen and saturated water vapor supplied.
  • the cathodic one Reduction of the resulting water vapor together with that caused by the educt gas supplied steam for sufficient moistening of the membrane 4 so that it cannot dry out.
  • unreacted oxygen can over the outlet stub 16 excess water vapor are derived.
  • phosgene (COCl 2 ) is generated according to the reaction mechanism described above, which is discharged via the product nozzle 15.
  • the electrochemical reactions at the anode and cathode are carried out at temperatures from 40 ° C to 80 ° C, at a cell voltage of 0.8 to 1.2 volts and at cell current densities of approx. 3 kA / m 2 .
  • the method can also be carried out with higher current densities.
  • the starting materials are fed in according to the above reaction equations in a stoichiometric ratio.
  • CO gas can also be supplied to the anode in a stoichiometric manner in order to suppress the formation of free chlorine.
  • FIG. 2 there is a large number of electrochemical cells 1 constructed analogously to FIG. 1 as a bipolar in series or parallel-connected cell stack 17 installed in a housing 18.
  • the enclosed pressure chamber 19 forms a gas-tight, pressure-tight, closed system, which is designed for pressures up to a maximum of 10 bar, the differential pressure from the actual process pressure being compensated for almost zero.
  • the dry educt gas mixture HCl + CO is fed to the anodes via the educt gas line 20 and the compressor 21.
  • the feed of O 2 + H 2 O on the cathode side as feed gas takes place through the feed gas line 22 and the compressor 23. With the aid of the compressors 21 and 23, the feed gas mixtures can be compressed to about 6 bar.
  • the product line 24 attached to the exit of the cell stack 17 is connected to a Phosgene recuperator 25 connected in which the phosgene generated in the cell stack 17 is liquefied by cooling condensation on the heat exchanger tube bundle 26.
  • the liquid phosgene flows through line 27 into a storage container 28.
  • the cooling capacity required for liquefaction is achieved by releasing liquid Phosgene generated from the reservoir 28 in the recuperator 25.
  • To this Purpose is the heat exchanger tube 26 via a riser 29 to the reservoir 28 connected.
  • the liquid flows directly in front of the recuperator 25 Phosgene through a relaxation throttle 31 in the riser 29. During relaxation evaporates the liquid phosgene.
  • the phosgene thus serves in this case as a refrigerant to supply the product gas consisting essentially of phosgene condense. Due to the condensation and re-evaporation, the product gas freed from unreacted HCI and CO feed gas fractions. That on this Gaseous phosgene purified in this manner is discharged through the removal line 32.
  • the relaxation takes place from the educt gas excess pressure prevailing in the cell stack 17 to about normal pressure or to that for the following ones Reactions necessary low form, so that from the electrolyser withdrawn line 32 no pressure-resistant fittings are required.
  • the enriched in the head part of the recuperator 25, consisting of HCl and CO Residual gases are recycled through the return line 33 to the anode input.
  • the cathode-side exit of the cell stack 17 is connected to an exhaust gas line 34 Removal of excess oxygen and water vapor connected.
  • the Pressure chamber 19 is supplied with an inert gas, e.g. nitrogen pressurized and maintained at about the same pressure as that with the Compressors 21 and 23 generated reactant gas pressure corresponds. Otherwise a pressure-proof design of the electrochemical cells would be required. With this encapsulation, an inerting of the reaction part is possible at the same time be monitored for starting material or product gas leakage with simple means can.

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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)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP96938176A 1995-11-23 1996-11-12 Verfahren zur direkten elektrochemischen gasphasen-phosgensynthese Expired - Lifetime EP0866890B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19543678A DE19543678A1 (de) 1995-11-23 1995-11-23 Verfahren zur direkten elektrochemischen Gasphasen-Phosgensynthese
DE19543678 1995-11-23
PCT/EP1996/004934 WO1997019205A1 (de) 1995-11-23 1996-11-12 Verfahren zur direkten elektrochemischen gasphasen-phosgensynthese

Publications (2)

Publication Number Publication Date
EP0866890A1 EP0866890A1 (de) 1998-09-30
EP0866890B1 true EP0866890B1 (de) 2000-02-09

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EP96938176A Expired - Lifetime EP0866890B1 (de) 1995-11-23 1996-11-12 Verfahren zur direkten elektrochemischen gasphasen-phosgensynthese

Country Status (13)

Country Link
US (1) US5961813A (zh)
EP (1) EP0866890B1 (zh)
JP (1) JP2000501143A (zh)
KR (1) KR19990071564A (zh)
CN (1) CN1060824C (zh)
BR (1) BR9611499A (zh)
CA (1) CA2237637A1 (zh)
DE (2) DE19543678A1 (zh)
ES (1) ES2144784T3 (zh)
HK (1) HK1018081A1 (zh)
MX (1) MX203057B (zh)
TW (1) TW420726B (zh)
WO (1) WO1997019205A1 (zh)

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KR19990076862A (ko) * 1995-12-28 1999-10-25 미리암 디. 메코너헤이 할로겐화카르보닐의 제조
WO2000078682A1 (de) * 1999-06-18 2000-12-28 Bayer Aktiengesellschaft Verfahren zum abbau organischer verbindungen in wasser
DE10149779A1 (de) * 2001-10-09 2003-04-10 Bayer Ag Verfahren zur Rückführung von Prozessgas in elektrochemischen Prozessen
CN1720633A (zh) * 2002-10-04 2006-01-11 加利福尼亚大学董事会 氟分离和生成装置
US7238266B2 (en) * 2002-12-06 2007-07-03 Mks Instruments, Inc. Method and apparatus for fluorine generation and recirculation
EP2382174A4 (en) 2009-01-29 2013-10-30 Trustees Of The University Of Princeton CONVERSION OF CARBON DIOXIDE IN ORGANIC PRODUCTS
US8845877B2 (en) 2010-03-19 2014-09-30 Liquid Light, Inc. Heterocycle catalyzed electrochemical process
US8500987B2 (en) 2010-03-19 2013-08-06 Liquid Light, Inc. Purification of carbon dioxide from a mixture of gases
US8721866B2 (en) 2010-03-19 2014-05-13 Liquid Light, Inc. Electrochemical production of synthesis gas from carbon dioxide
US8961774B2 (en) 2010-11-30 2015-02-24 Liquid Light, Inc. Electrochemical production of butanol from carbon dioxide and water
US8568581B2 (en) 2010-11-30 2013-10-29 Liquid Light, Inc. Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide
US9090976B2 (en) 2010-12-30 2015-07-28 The Trustees Of Princeton University Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction
GB2517587B (en) * 2011-12-21 2018-01-31 Xergy Ltd Electrochemical compression system
US10024590B2 (en) 2011-12-21 2018-07-17 Xergy Inc. Electrochemical compressor refrigeration appartus with integral leak detection system
US9267212B2 (en) 2012-07-26 2016-02-23 Liquid Light, Inc. Method and system for production of oxalic acid and oxalic acid reduction products
US20130105304A1 (en) 2012-07-26 2013-05-02 Liquid Light, Inc. System and High Surface Area Electrodes for the Electrochemical Reduction of Carbon Dioxide
US8641885B2 (en) 2012-07-26 2014-02-04 Liquid Light, Inc. Multiphase electrochemical reduction of CO2
US10329676B2 (en) 2012-07-26 2019-06-25 Avantium Knowledge Centre B.V. Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode
US9175407B2 (en) 2012-07-26 2015-11-03 Liquid Light, Inc. Integrated process for producing carboxylic acids from carbon dioxide
US8692019B2 (en) 2012-07-26 2014-04-08 Liquid Light, Inc. Electrochemical co-production of chemicals utilizing a halide salt
WO2014043651A2 (en) 2012-09-14 2014-03-20 Liquid Light, Inc. High pressure electrochemical cell and process for the electrochemical reduction of carbon dioxide
EP2900847B1 (en) * 2012-09-19 2021-03-24 Avantium Knowledge Centre B.V. Eletrochemical reduction of co2 with co-oxidation of an alcohol
DE102013009230A1 (de) * 2013-05-31 2014-12-04 Otto-von-Guericke-Universität Verfahren und Membranreaktor zur Herstellung von Chlor aus Chlorwasserstoffgas
US9663373B2 (en) 2013-07-26 2017-05-30 Sabic Global Technologies B.V. Method and apparatus for producing high purity phosgene
GB2550018B (en) 2016-03-03 2021-11-10 Xergy Ltd Anion exchange polymers and anion exchange membranes incorporating same
US10386084B2 (en) 2016-03-30 2019-08-20 Xergy Ltd Heat pumps utilizing ionic liquid desiccant
EP3421426A1 (de) * 2017-06-29 2019-01-02 Covestro Deutschland AG Energieeffizientes verfahren zur bereitstellung von phosgen-dampf
DE102017219974A1 (de) * 2017-11-09 2019-05-09 Siemens Aktiengesellschaft Herstellung und Abtrennung von Phosgen durch kombinierte CO2 und Chlorid-Elektrolyse
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
US11454458B1 (en) 2019-04-12 2022-09-27 Xergy Inc. Tube-in-tube ionic liquid heat exchanger employing a selectively permeable tube
WO2020216648A1 (de) * 2019-04-25 2020-10-29 Basf Se Verfahren zur herstellung von phosgen
EP3805429A1 (de) * 2019-10-08 2021-04-14 Covestro Deutschland AG Verfahren und elektrolysevorrichtung zur herstellung von chlor, kohlenmonoxid und gegebenenfalls wasserstoff

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US5411641A (en) * 1993-11-22 1995-05-02 E. I. Du Pont De Nemours And Company Electrochemical conversion of anhydrous hydrogen halide to halogen gas using a cation-transporting membrane

Also Published As

Publication number Publication date
BR9611499A (pt) 1999-07-13
CN1060824C (zh) 2001-01-17
DE19543678A1 (de) 1997-05-28
MX9803973A (es) 1998-09-30
ES2144784T3 (es) 2000-06-16
KR19990071564A (ko) 1999-09-27
WO1997019205A1 (de) 1997-05-29
CA2237637A1 (en) 1997-05-29
MX203057B (es) 2001-07-13
EP0866890A1 (de) 1998-09-30
DE59604440D1 (de) 2000-03-16
US5961813A (en) 1999-10-05
HK1018081A1 (en) 1999-12-10
JP2000501143A (ja) 2000-02-02
CN1202937A (zh) 1998-12-23
TW420726B (en) 2001-02-01

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