EP4041939A1 - Procédé et dispositif d'électrolyse pour la production de chlore, de monoxyde de carbone et éventuellement d'hydrogène - Google Patents

Procédé et dispositif d'électrolyse pour la production de chlore, de monoxyde de carbone et éventuellement d'hydrogène

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Publication number
EP4041939A1
EP4041939A1 EP20785517.2A EP20785517A EP4041939A1 EP 4041939 A1 EP4041939 A1 EP 4041939A1 EP 20785517 A EP20785517 A EP 20785517A EP 4041939 A1 EP4041939 A1 EP 4041939A1
Authority
EP
European Patent Office
Prior art keywords
gas
cathode
catholyte
anode
carbon dioxide
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.)
Pending
Application number
EP20785517.2A
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German (de)
English (en)
Inventor
Andreas Bulan
Jürgen KINTRUP
Alexander LUEKEN
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.)
Covestro Deutschland AG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP4041939A1 publication Critical patent/EP4041939A1/fr
Pending legal-status Critical Current

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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
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    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
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    • 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
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    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the invention relates to a method and an electrolysis device for the production of chlorine, carbon monoxide (CO) and optionally hydrogen by electrochemical conversion of carbon dioxide (CO 2) and alkali chloride solution.
  • the preferred new process described below represents a particularly sustainable process for the production of isocyanates.
  • Electrolysis processes are therefore particularly suitable for producing basic chemicals such as CO in a sustainable manner.
  • electrolysis processes for the production of basic chemicals must also be developed on a large-scale industrial scale (1000t / a).
  • large-area electrolysis cells and electrolysers with a large number of electrolysis cells are necessary.
  • technical production quantities are understood to mean product quantities of more than 0.1 kg / (h * m 2 ) per electrolysis cell.
  • electrolysis cells are used with an electrode area of more than 2m 2 per electrolysis cell.
  • the electrolysis cells are combined in groups of up to 100 pieces in an electrolysis rack. Several racks then form an electrolyzer.
  • the capacity of an industrial electrolyser is currently up to 30,000 t / a of chlorine and the respective equivalents of sodium hydroxide or hydrogen.
  • GDE gas diffusion electrode
  • isocyanates usually produces hydrogen chloride which can be recycled back to chlorine by gas phase oxidation with oxygen or, after absorption in water, converted to hydrochloric acid and converted to chlorine and hydrogen or to chlorine and water by electrolysis.
  • carbon monoxide is currently produced from fossil raw materials such as natural gas or coal.
  • the CO 2 formed must be separated from the O 2 if the oxygen is to be used further.
  • the expelled CO 2 must be recycled again so that the sustainability of such a procedure is given.
  • the loss of CO 2 must generally be avoided because it is a raw material that is sometimes difficult to provide.
  • the object was to provide a process which does not have the above-mentioned disadvantages of known procedures.
  • the invention relates to a process for the production of chlorine, carbon monoxide and possibly hydrogen by electrochemical conversion of carbon dioxide and alkali metal chloride solution, characterized in that the carbon dioxide is electrochemically reduced on a gas diffusion electrode as cathode in an aqueous alkali metal chloride-containing solution as catholyte and at the same time chlorine is removed an aqueous solution containing alkali metal chloride is generated anodically as the anolyte, the alkali metal salt of carbonic acid formed in the catholyte, selected from alkali metal carbonate, alkali hydrogen carbonate or mixtures thereof, then being reacted with hydrogen chloride to form carbon dioxide and alkali metal chloride and the carbon dioxide released in the process into the cathode space to the gas diffusion electrode and the generated alkali chloride can optionally be returned to the anode compartment and / or to the cathode compartment.
  • an electrolyte containing alkali metal is used, both in the anode and in the cathode compartment.
  • Alkali chloride is understood to mean, in particular, sodium or potassium chloride, possibly also cesium chloride. Potassium chloride is particularly preferably used.
  • chlorine gas is generated from the alkali metal chloride-containing electrolyte and, at the same time, CO 2 is reduced to carbon monoxide at the cathode and, if necessary, hydrogen is generated.
  • the advantage of the new process is that no oxygen or oxygen / CO 2 mixture is produced at the anode, but rather high-purity chlorine, as is fundamentally known from chlor-alkali electrolysis.
  • the CO 2 reduction also takes place from electrolytes containing alkali metal chloride.
  • the great advantage over electrolyte systems containing carbonate or hydrogen carbonate is that, on the one hand, the electrolyte has a higher conductivity and there is no CO 2 gas at the anode is released, which disrupts the electrolysis process, i.e. leads to higher electrolysis voltages and which has to be separated again from the anode gas.
  • the hydroxide ions produced at the cathode during the CO2 reduction react with the carbon dioxide supplied to the cathode to form the alkali salt of carbonic acid, selected from alkali carbonate, alkali hydrogen carbonate or mixtures thereof.
  • the formed alkali salt of carbonic acid is present in the catholyte in dissolved form.
  • the process parameters are designed in such a way that essentially alkali carbonate is formed, e.g. by operating the CO2 electrolysis at elevated temperature. This has the advantage of higher solubility and avoids crystallization of alkali hydrogen carbonate or alkali carbonate in the pores of the gas diffusion electrode.
  • the temperature control of the electrolytes is therefore important for a preferred method.
  • the temperature control is preferably chosen so that the temperature of the catholyte in the feed to the at least one electrolysis cell of the electrolysis device is at least 60 ° C, particularly preferably at least 70 ° C. This also increases the conductivity of the electrolytes and lowers the electrolysis voltage, which means that the process can be carried out even more economically.
  • the temperature of the catholyte in the feed to the electrochemical conversion is therefore at least 60.degree. C., in particular preferably at least 70.degree.
  • the electrochemical conversion of carbon dioxide and catholyte, in particular alkali chloride solution, at the cathode takes place in particular so that the carbon dioxide gas is electrochemically reduced on a gas diffusion electrode as cathode in the presence of catholyte and the said catholyte is guided along the surface of the gas diffusion electrode according to the principle of a falling liquid film.
  • the principle of the falling liquid film states that a liquid, here for example the catholyte, is essentially formed by the action of gravity moving film.
  • the liquid is preferably guided as a film within a gap that functions as an electrolyte space between two surfaces arranged in parallel.
  • one of these surfaces forms a gas diffusion electrode, along whose flat electrode side facing the gap the falling liquid film is guided, and the other surface forms a flat separator, in particular a membrane (preferably an ion exchange membrane or a diaphragm).
  • the catholyte is more preferably guided as a falling liquid film along the electrode surface of the gas diffusion electrode, the flow rate of the falling liquid film being able to be regulated by a means for flow braking.
  • a preferred embodiment of the new process is therefore characterized in that the hydrogen chloride is taken from a connected process for the production of isocyanates via phosgene as an intermediate product and the chlorine formed in the electrochemical conversion is returned to the phosgene production as a precursor to the isocyanate production.
  • the hydrogen formed as an optional by-product of the electrochemical conversion in the new process together with CO is separated from the mixture of hydrogen, CO and CO 2 and utilized in a preferred embodiment of the new process.
  • the hydrogen is very particularly preferably used for the production of diamines from corresponding di-nitro compounds as a preliminary stage for the isocyanate production process.
  • Another preferred embodiment of the new method is characterized in that the concentration of the alkali metal chloride solution of the anolyte and / or the catholyte is independently of one another up to 25% by weight, preferably from 15 to 25% by weight.
  • the CO2 is fed to the gas diffusion electrode via a gas space which is separated from the electrolyte space by the gas diffusion electrode.
  • the gas velocity in the gas space near the rear of the gas diffusion electrode is from 0.001 to 15 m / s, preferably from 0.01 to 10 m / s.
  • the preferred method with a gas diffusion electrode is further independently characterized in that the drift speed of the catholyte in the space between the ion exchange membrane and the gas diffusion electrode is from 0.8 to 10 cm / s.
  • the electrochemical conversion of CO2 in an electrolysis device takes place as described above on a gas diffusion electrode, which is connected as a cathode and takes place after the reaction mentioned below as an example:
  • anodes known from chlor-alkali electrolysis, preferably anodes made of titanium that have a ruthenium, titanium, or iridium oxide coating (for example DSA coating from Denora, Germany) made of an aqueous one Alkali chloride solution chlorine evolves.
  • a ruthenium, titanium, or iridium oxide coating for example DSA coating from Denora, Germany
  • a large-area gas diffusion electrode is used for the electrochemical conversion of CO2 on a production scale, and a cell construction of technical size is used to operate the gas diffusion electrode, whereby special measures may have to be taken for operation in technical electrolysis devices.
  • gas diffusion electrodes have an open-pore structure and are installed between the electrolyte space and the gas space.
  • the structure of the GDE must enable the reactant gas (here CO2) to react at the three-phase boundary between the electrolyte, catalyst and gas as close as possible to the electrolyte.
  • This boundary layer is stabilized by the hydrophobicity of the GDE material. It turns out, however, that this stabilization, which takes place solely through the surface tension of the electrolyte, only allows a finite pressure gradient between the gas side and the liquid side of the GDE. If the pressure on the gas side is too high, the gas finally breaks through the GDE and the function of the GDE is disturbed in this area, i.e.
  • the electrolysis process is locally interrupted here. If, on the other hand, the liquid pressure is too high, the three-phase boundary is shifted from the catalyst area of the GDE until the GDE is flooded with electrolyte and, if the pressure continues to increase, leads to a liquid breakthrough of electrolyte into the gas space. This also disrupts the function of the GDE.
  • the electrochemical CO2 reduction to CO or to CO / H2 mixtures differs fundamentally from the electrochemical O2 reduction.
  • hydroxide ions are formed from the oxygen gas, which means that there is a reduction in volume during the reaction.
  • the GDE consumes the oxygen, which results in a reduction in partial pressure.
  • the equimolar gas amount of product (CO or CO / H2 mixture) is created from the CO2 gas and the catholyte, and there is no reduction in the partial pressure. Under certain circumstances, this requires a special mode of operation, in particular on the cathode side of the electrolytic cell.
  • Another object of the invention is therefore an electrolysis device for the electrochemical conversion of carbon dioxide and alkali metal chloride solution, in particular according to the above-described method according to the invention, at least comprising
  • At least one source of carbon dioxide gas and (ii) at least one electrolysis cell at least comprising a cathode half-shell with a cathode, a catholyte inlet, a catholyte outlet and with a gas space which is in fluid connection with the carbon dioxide gas source via a first gas inlet and which is in fluid communication with a gas outlet for gaseous reaction product, in particular for a Gas containing carbon monoxide, unused carbon dioxide gas and optionally hydrogen, further comprising an anode half-shell, the anode half-shell having at least a second gas outlet for the anode reaction product, in particular chlorine and optionally oxygen, an anolyte feed for the introduction of an aqueous alkali metal chloride-containing solution as anolyte and an anolyte drain and an anode is provided, and a separator arranged between the anode half-shell and cathode half-shell for separating the anode compartment and cathode compartment, further
  • a preferred embodiment of the new electrolysis device is characterized in that the main vertical extension of the cathode is at least 30 cm, preferably at least 60 cm, particularly preferably at least 100 cm.
  • the cathode is a gas diffusion electrode designed to convert carbon dioxide gas.
  • the cathode contained in the at least one electrolysis cell is a gas diffusion electrode based on silver and / or silver oxide, preferably silver particles, as an electrocatalyst and with a powdery one Fluoropolymer, in particular PTFE powder, formed compacted as a non-conductive binder on a metallic or non-metallic, conductive or non-conductive carrier.
  • GDE gas diffusion electrode
  • the porosity of the catalytically active layer calculated from the material densities of the raw materials used, is in particular more than 10%, but less than 80%.
  • the GDE is specifically produced as follows:
  • the carrier element was a wire mesh made of silver with a wire thickness of 0.14 mm and a mesh size of 0.5 mm.
  • the application was carried out with the aid of a 2 mm thick stencil, the powder being applied using a sieve with a mesh size of 1.0 mm. Excess powder that protruded beyond the thickness of the stencil was removed using a scraper.
  • the carrier with the applied powder mixture is pressed using a roller press with a pressing force of 0.45 kN / cm.
  • the gas diffusion electrode was removed from the roller press.
  • the gas diffusion electrode had a porosity of about 50%.
  • the electrolysis device is preferably designed such that the gas feed line for the carbon dioxide gas leading to the cathode has a device for regulating the flow rate, e.g. B. a control valve, which controls the speed of the carbon dioxide gas in the gas space.
  • the gas velocity regulated by this device in the gas space near the rear of the gas diffusion electrode is in a particularly preferred embodiment of the aforementioned electrolysis device from 0.001 to 15 m / s, preferably from 0.01 to 10 m / s.
  • the electrolysis device is preferably designed in such a way that the drift speed of the falling liquid film of the catholyte is regulated by a means for braking the flow. It is particularly preferred if there is a means for braking the flow in the gap Catholyte flow is provided, wherein the means for flow braking is preferably designed as an electrically non-conductive, chemically inert textile fabric.
  • the drift speed of the catholyte in the space between the separator and the gas diffusion electrode which is regulated by a means for braking the flow, is in a particularly preferred electrolysis device from 0.8 to 10 cm / s.
  • the electrolysis device is particularly preferably designed in such a way that the gas feed line for the carbon dioxide gas leading to the cathode comprises a device for regulating the flow rate, which regulates the speed of the carbon dioxide gas in the gas space and that in addition to this, a means for braking the flow of the catholyte is provided in the gap, which is preferred the means for braking the flow is designed as an electrically non-conductive, chemically inert textile fabric.
  • the aforementioned preferred values for the respective speeds are particularly preferred in each case.
  • the cathode contained in the at least one electrolysis cell of the electrolysis device as a gas diffusion electrode based on silver and / or silver oxide, preferably silver particles, as an electrocatalyst and with a pulverulent fluoropolymer, in particular PTFE powder, as a non-conductive binder on a metallic or non-metallic, a conductive or a non-conductive carrier formed compacted
  • the gas supply line of the carbon dioxide gas leading to the cathode comprises a device for regulating the flow velocity, which regulates the velocity of the carbon dioxide gas in the gas space and wherein in addition to this, a means for braking the flow of the catholyte is provided in the gap, which is preferred Means for flow braking is designed as an electrically non-conductive, inert textile fabric.
  • the aforementioned preferred values for the respective speeds are particularly preferred in each case.
  • an electrolyser contains several electrolysis cells
  • the electrolysis cells are preferably installed in a bipolar arrangement so that only the respective end element is provided with a power connection.
  • Bipolar arrangement means that an anode half-shell is in contact with a cathode half-shell. The contact takes place via the metallic rear wall of the half-shells.
  • a monopolar arrangement of several electrolysis cells in one electrolyser is also conceivable, here each element has a separate power connection, the anode half-shell is connected to the positive pole of the rectifier and the cathode half-shell to the negative pole of the rectifier.
  • reaction products formed by the electrolysis can each be used as an anode reaction product and as a cathode reaction product by the previously provided defined gas discharges are taken from the electrolysis cell of the electrolysis device.
  • the first gas discharge line in the new electrolysis device is preferably connected to the upper end of the gas space and the second gas discharge line is connected to the upper end of the anode space and the first gas feed line is connected to the lower end of the gas space.
  • Another preferred embodiment of the new electrolysis device is characterized in that the second gas discharge line for the anode reaction product is connected to a second gas separation unit for separating oxygen from chlorine from the anode gas via a collecting pipe and possibly via a CO gas drying system.
  • the first gas discharge line is connected, in particular via a collecting line, to a first gas separation unit for separating carbon monoxide, hydrogen and unused carbon dioxide gas.
  • the first gas separation unit has a return line for separated carbon dioxide gas, which is connected to the first gas feed line for carbon dioxide gas, in particular via a distributor pipeline.
  • the gas separation unit has a discharge line for separated carbon monoxide, which is connected to a chemical production plant for the chemical conversion of carbon monoxide and chlorine into phosgene.
  • a particularly preferred embodiment of the new electrolysis device is characterized in that the catholyte drain and the anolyte drain are connected directly or indirectly via pipelines to an electrolyte collector, the electrolyte ammler via pipeline to a carbonate decomposition unit and the carbonate decomposition unit with at least one return for split off carbon dioxide, a controllable inlet is provided for hydrogen chloride and a return line for electrolyte and the return line is connected to both the catholyte inlet and the anolyte inlet.
  • an electrolyser see Fig. 1, electrolyser 100
  • electrolysis cells see Fig.l, electrolysis cells (Z)
  • An electrolysis cell has at least one anode half-shell and one cathode half-shell, anode and cathode, as well as educt and product lines and power connections (as is preferably shown schematically in cross section in FIG. 2).
  • the electrolysis cells are installed in a bipolar arrangement so that only the respective end element is provided with a power connection.
  • Bipolar arrangement means that an anode half-shell is in contact with a cathode half-shell. The contact takes place via the metallic rear wall of the half-shells.
  • a monopolar arrangement is also conceivable, here each element has a separate power connection, the anode half-shell is connected to the positive pole of the rectifier and the cathode half-shell to the negative pole of the rectifier.
  • the electrolysis device is able to control the temperature of the catholyte, in particular to control the temperature to at least 60.degree. C., preferably at least 70.degree.
  • the catholyte feed comprises at least one heat exchanger for temperature control of the catholyte to be fed to the at least one electrolysis cell.
  • An aqueous solution containing alkali metal chloride is fed to the anode half-shell as an electrolyte (anolyte).
  • anode half-shell chlorine is generated from the aqueous alkali chloride solution.
  • a small amount of oxygen can be formed at the anode in addition to the chlorine.
  • the pH of the alkali chloride solution that is fed to the anode half-shell is more than pH 1.5.
  • the alkali chloride in the anolyte is preferably at least one alkali chloride selected from the series: cesium chloride, sodium chloride or potassium chloride, particularly preferably selected from sodium or potassium chloride. Potassium chloride is very particularly preferably contained in the anolyte.
  • the concentration of the aqueous alkali metal chloride solution of the anolyte is up to 25% by weight, preferably from 15 to 25% by weight.
  • the concentration of potassium chloride in the aqueous alkali metal chloride solution of the anolyte is very particularly preferably up to 25% by weight, preferably from 15 to 25% by weight.
  • the chlorine gas which still contains oxygen and water vapor, is dried, for example by sulfuric acid drying, and then, depending on the oxygen content in the chlorine, fed to a chlorine gas separation. This can take place, for example, by liquefying the chlorine gas, in particular recuperatively. Accordingly, the chlorine gas can be compressed and liquefied or a chemical synthesis. Part of the chlorine is fed to the synthesis of phosgene, which is used for isocyanate production.
  • the anolyte is freed from active chlorine, i.e. chlorine with an oxidation level greater than zero.
  • active chlorine i.e. chlorine with an oxidation level greater than zero.
  • This can be done by vacuum dechlorination and / or chemical dechlorination, e.g. by adding an alkali-containing bisulfite solution or hydrogen peroxide.
  • the active chlorine content of the anolyte should in particular be less than 20 ppm.
  • the anolyte treated in this way can be combined with the catholyte freed from CO and th. This can be done either before or after the alkali carbonate decomposition.
  • potassium sulfate accumulates in the electrolyte.
  • the potassium sulfate content in the electrolyte can preferably be kept constant.
  • a maximum concentration of potassium sulfate in the electrolyte of 10 g / L is preferably not exceeded.
  • the anode and cathode half-shells are separated from one another by a separator, preferably by an ion exchange membrane.
  • a separator preferably by an ion exchange membrane.
  • perfluorinated ion exchange membranes such as membranes of the Asahi Glass F8080 type from Asahi or Chemours N2050 from Chemours
  • carbon monoxide or a mixture of carbon monoxide and hydrogen is produced from CO2 on a gas diffusion electrode, with additional hydroxide ions being produced.
  • the hydroxide ions react with excess CO2 to form carbonate ions, and in the presence of alkali ions to form alkali metal carbonate and / or alkali metal hydrogen carbonate.
  • the catholyte is led via the collecting pipe to a gas separator in which any dissolved or dispersed CO or CO / H2 gas mixture is separated from the conversion of CO2.
  • the separation can take place, for example, via a stripping column with the aid of an inert gas.
  • the stripped gas mixture is fed to an incinerator.
  • the purified catholyte is fed to an electrolyte collector or directly to an alkali carbonate decomposition unit.
  • an aqueous solution of an alkali chloride is also used as the catholyte.
  • the alkali chloride which is fed to the anode half-shell and the cathode half-shell is preferably identical. It can be sodium, potassium or cesium chloride or their Mixtures are used. Sodium or potassium chloride is preferred, potassium chloride is particularly preferred.
  • the concentration of the alkali metal chloride solution of the anolyte and / or the catholyte is particularly preferably, independently of one another, up to 25% by weight, preferably from 15 to 25% by weight.
  • the carbon monoxide and the anodically generated chlorine are preferably fed to a phosgene synthesis.
  • the phosgene produced in this way is used for the production of isocyanates, whereby it is reacted with the corresponding amine. If the amine is produced from a nitro compound, the hydrogen which may have been generated and separated off in the electrolysis can be used for its reduction.
  • the HCl gas produced during isocyanate production is produced according to the following formula conversion example and is fed in particular to the alkali carbonate decomposition unit.
  • the alkali metal carbonate formed in the cathode half-shell from hydroxide ions and the CO2 if necessary also alkali hydrogen carbonate, is converted with HCl to form alkali metal chloride, water and CO2.
  • the CO2 is then fed to the distribution pipeline for CO2.
  • the remaining solution is fed to an electrolyte collecting device where it is combined with the dechlorinated anolyte.
  • the concentration of the combined solution can be adjusted by adding water or alkali chloride salt or by dilute or concentrated solutions of alkali chloride and then returned to the anolyte and the catholyte feed to the electrolytic toe.
  • the anode or cathode half-shell is expediently charged via distributor pipelines for the anolyte and catholyte, respectively.
  • the anolyte is fed from the anode half-shell into one or more collecting pipes, whereby the chlorine generated can also be fed into the collecting pipes.
  • the gas and electrolyte are separated in the collecting pipe.
  • Fig. 1 is a schematic overview of the overall process and the for
  • FIG. 2 shows a schematic vertical cross section through an electrolysis cell Z of the
  • An electrolyser 100 is equipped with a number of 30 to 100 electrolysis cells (Z) - hereinafter also referred to simply as electrolysis cells - for each electrolyser frame.
  • An electrolysis cell Z (FIG. 2) consists of an anode half-shell 2 and a cathode half-shell 1, and these are each separated from one another by an ion exchange membrane 3.
  • the anode half-shell 2 is equipped with an anode 10 which has a commercially available coating based on a mixed oxide of ruthenium and iridium for the production of chlorine (DSA coating, Denora Germany).
  • the cathode 11 is equipped as a silver / PTFE-based gas diffusion electrode from Covestro Deutschland AG.
  • the gas diffusion electrode 11 separates the gas space 4 from an electrolyte space 12.
  • the electrolyte space 12 is delimited by the gas diffusion electrode 11 and the ion exchange membrane 3, and forms a gap 12a.
  • the gap 12a is filled with a PTFE-based fabric 24, which serves as a flow brake for the catholyte 17, which flows from top to bottom through the gap 12a filled with the fabric 24.
  • the catholyte 17 collects at the bottom of the cathode half-shell 1 and leaves it via a preferably flexible pipe connection and is fed to a collecting pipe (catholyte) 65.
  • the pipe connection is designed in such a way that it is guided immersed into the collecting pipe (catholyte) 65.
  • Anode half-shell 2 and cathode half-shell 1 are separated from one another by a separator 3, an ion exchange membrane 3.
  • a separator 3 an ion exchange membrane 3.
  • perfluorinated ion exchange membranes of the type Asahi Glass F8080 (manufacturer Asahi Glass) or Chemours N2050 (manufacturer Chemours) can be used here. This prevents the chlorine generated at the cathode 11 from being reduced again and any carbon monoxide generated at the cathode from being oxidized at the anode 10. Mixing of chlorine with hydrogen or CO is also avoided, which is necessary for safety reasons (risk of explosion of hydrogen chloride oxyhydrogen).
  • the electrical contact with a monopolar connection of the electrolysis elements to a DC voltage source takes place from the anode 10 via an electrically conductive connection 90 to the anode half-shell 2 and from the anode half-shell 2 via an anode power line 32.
  • Electrical contact is made from the cathode 11 via an elastic electrically conductive mat 36 further via an electrically conductive support structure 35 further via an electrically conductive connection 91 to the cathode half-shell 1 and from there to the direct voltage source.
  • the gas space 4 of the cathode half-shell 1 is supplied with CO2 (see FIG. 1) via a distributor pipe 44; and then unconverted CO2 and the reaction products from the Cathode half-shell 1 is supplied via a preferably flexible connection connected to outlet 6 of a collecting pipe 68 for a CO / CCh gas mixture.
  • the catholyte 14a of the collecting pipe (catholyte) 65 is fed to a gas separation unit CO2 / CO / H2 66 in order to separate the still dissolved or dispersed gases such as CO2, CO and possibly H2 from the catholyte 14a.
  • the separation can take place, for example, via a stripping column with the aid of an inert gas.
  • the stripped gas mixture 66a residual gas
  • the purified catholyte 66b is fed to an electrolyte collecting device 67 or directly to a carbonate decomposition unit 38.
  • the gas mixture removed from the gas space 4 of the cathode half-shell 1 is fed to a collecting pipe for the C0 2 / C0 / H 2 gas mixture 68. Excess or unconverted CO2 is then separated off from the gas mixture (CO2 separation 69). This can be done, for example, by amine washing.
  • the separated CO2 gas is fed back through the return line 53 to the gas space 4 of the cathode half-shell 1 via the distribution pipe CO2 44.
  • the converted CO2 is supplemented by a corresponding amount of fresh CO2 from a carbon dioxide gas source 55.
  • the anode half-shell 2 is supplied with the anolyte 15a via a distributor pipeline (anolyte) 40.
  • anode half-shell 2 chlorine is generated at the anode 10 from an aqueous alkali metal chloride solution.
  • a small amount of oxygen can be formed at the anode in addition to the chlorine.
  • the mixture of CI2, possibly O2 and the anolyte is withdrawn from the anode half-shell 2 via the outlets 7 and 9 and fed to a collecting pipe anolyte & Ch gas mixture 20.
  • the CI2 which still contains oxygen and water vapor, is taken from the collecting pipe 20 and fed to a Ch drying 22, for example by means of a sulfuric acid drying.
  • the CI2 can be fed to the Ch-gastric chloride 25 in order to separate off residues 25b of O2 with traces of chlorine. This can be done, for example, by recuperative liquefaction.
  • the chlorine can then be compressed and / or liquefied and / or fed to a chemical synthesis (e.g. phosgene synthesis 61).
  • a part of the separated CI2 25a is fed to the phosgene synthesis 61 as a precursor to an isocyanate production 60.
  • the cleaned anolyte in the collecting pipe 20 is fed to a dechlorination unit 23 for removing compounds in which chlorine is present in the oxidation state greater than zero (active chlorine).
  • a dechlorination unit 23 for removing compounds in which chlorine is present in the oxidation state greater than zero (active chlorine). This can be done either by vacuum dechlorination and / or chemical dechlorination by adding an alkaline bisulfite solution or by adding Hydrogen peroxide.
  • the active chlorine content of the anolyte should preferably be less than 20 ppm.
  • the dechlorinated anolyte is fed to the electrolyte collecting device 67.
  • the electrolytes collected in the electrolyte collecting device also contain the alkali hydrogen carbonate or carbonate formed and are fed to the carbonate decomposition unit 38.
  • the carbonate decomposition unit 38 is supplied with hydrogen chloride 62 from isocyanate production 60, the hydrogen chloride 62 reacting with the alkali carbonate or alkali hydrogen carbonate present in the electrolyte to form alkali chloride, water and CO2. If necessary, a stoichiometric excess of hydrogen chloride 62 can be added.
  • the separated CO2 is fed back to the gas space 4 of the cathode half-shell via the distributor pipe CO244 with that from the CO2 separation, the amine scrubbing 69 and the CO2 to be supplemented from a carbon dioxide gas source 55.
  • the electrolyte from the carbonate decomposition unit 38 is fed back to the anode half-shell 2 after the pH has been adjusted by means of mineral acid / alkali feed line 46, heating in the heat exchanger 42 via the distributor pipeline 40.
  • the temperature of the electrolyte fed to the anode half-shell is more than 50 ° C after the heat exchanger.
  • the pH value of the alkali chloride solution fed to the anode half-shell is between 2 and 8, the concentration of alkali chloride is 14% by weight to 23% by weight
  • the electrolyte from the CO2 carbonate decomposition unit 38 is fed back to the cathode half-shell 1 via a pH adjustment by means of a mineral acid / alkali supply line 56 and a heat exchanger 54 via the distribution channel (catholyte) 50.
  • the pH value of the electrolyte fed to the cathode half-shell 1 is between 6 and 14, and the temperature is greater than 50.degree.
  • the concentration of alkali chloride corresponds to that of the electrolyte fed to the anode half-shell.
  • the phosgene produced from the phosgene synthesis 61 is used for the production of isocyanates 60, whereby it is reacted with a corresponding, e.g., aromatic amine. If the amine is produced from an aromatic nitro compound, the hydrogen 70b generated and separated off in the CO / H2 gas separation 70 can be used for its reduction.
  • Part of the HCl gas produced in the isocyanate production 60 is fed to the carbonate decomposition unit 38.
  • the alkali carbonate formed in the cathode half-shell by the hydroxide ions and CO2 possibly also alkali hydrogen carbonate, is converted to alkali chloride, water and CO2.
  • the CO2 is fed to the distribution pipeline-C0 2 44.
  • concentration of anolyte and catholyte can be adjusted by adding water or an alkali chloride salt or by using dilute or concentrated salt solutions 18.
  • part of the electrolyte can be disposed of via a disposal line 18a.
  • An electrolysis cell Z (see FIG. 2) with an area of 2.5 m 2 , constructed from an anode half-shell 2 and a cathode half-shell 1, are separated by an ion exchange membrane 3 of the Nafion 982 WX type.
  • the anode 10 consists of a titanium expanded metal with a conventional coating equipped for chlorine production (with Ru / Ir mixed oxide) for chlorine production from Denora (DSA-Caoting).
  • the cathode a gas diffusion electrode (GDE) 11, is installed vertically in cell Z according to the principle of falling film cell technology, in which the GDE 11 rests on an elastically mounted current-carrying element 36, which in turn rests on an electrically conductive support structure 35 with openings for the Gas inlet is supported.
  • the GDE 11 is a silver- and PTFE-based GDE on a silver metal mesh from Covestrotechnik AG (corresponding to patent application EP1728896A2) for chlor-alkali electrolysis. Between GDE 11 and membrane 3, a PTFE-based flat fabric 24 was used as a flow brake, through which the catholyte 17 flows from top to bottom in free fall.
  • the current density in the electrolysis mode is 3 kA / m 2 .
  • the anode compartment 15 is 40229.02 kg / h of an electrolyte (anolyte 15a) consisting of 2.68 kg / h K 2 SO 4 , 45.8 kg / h KCl and 180.5 kg / h water with a distributor pipe pH 7 and a temperature of 80 ° C supplied.
  • an electrolyte an electrolyte 15a
  • electrolyte 15a consisting of 2.68 kg / h K 2 SO 4 , 45.8 kg / h KCl and 180.5 kg / h water with a distributor pipe pH 7 and a temperature of 80 ° C supplied.
  • the chemical dechlorination described below results in a proportion of 2.68 kg / h K 2 SO 4 in the anolyte 15a in the steady-state operation of the process.
  • the electrolyte (used anolyte) removed from the anode compartment 15 has a pH value of 3.5 and is fed to an anolyte dechlorination 23, which consists of vacuum dechlorination in a first stage, by means of which 10.3 g of the CI2 formed are removed.
  • So treated Used anolyte is fed to a second stage of the anolyte dechlorination 23 and is brought to a pH of 9 by adding 19 g of an 18% by weight potassium hydroxide solution and then to chemical dechlorination, in which the anolyte is given 0.5 g of a 38% by weight % KHSO3 solution is added.
  • the pH of the treated anolyte is lowered to 3.5 by adding 13.4 g of an 18% strength by weight hydrochloric acid.
  • the anolyte treated in this way can be fed to a storage container, electrolyte collecting device 67 or fed directly to the carbonate decomposition unit 38.
  • the anodically generated CI2 (9.92 kg / h) was, after drying 22 and removal 25 of O2, converted to phosgene together with the generated and dried CO and further CO and fed to an isocyanate production 60.
  • the HCl gas 62 separated from the isocyanate production 60 was fed to the carbonate decomposition unit 38 (10.2 kg / h).

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Abstract

L'invention concerne un procédé et un dispositif d'électrolyse pour la production de chlore, de monoxyde de carbone et éventuellement d'hydrogène par transformation électrochimique de dioxyde de carbone et d'une solution de chlorure alcalin, le dioxyde de carbone étant réduit électrochimiquement à partir d'une source de gaz carbonique (55) sur une électrode à diffusion gazeuse servant de cathode (11) dans une solution aqueuse contenant du chlorure alcalin en tant que catholyte (17) et, simultanément, du chlore étant produit anodiquement à partir d'une solution aqueuse contenant du chlorure alcalin en tant qu'anolyte (15a).
EP20785517.2A 2019-10-08 2020-10-07 Procédé et dispositif d'électrolyse pour la production de chlore, de monoxyde de carbone et éventuellement d'hydrogène Pending EP4041939A1 (fr)

Applications Claiming Priority (2)

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EP19201889.3A EP3805429A1 (fr) 2019-10-08 2019-10-08 Procédé et dispositif d'électrolyse destinés à la fabrication de chlore, de monoxyde de carbone et, le cas échéant, d'hydrogène
PCT/EP2020/078057 WO2021069470A1 (fr) 2019-10-08 2020-10-07 Procédé et dispositif d'électrolyse pour la production de chlore, de monoxyde de carbone et éventuellement d'hydrogène

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EP20785517.2A Pending EP4041939A1 (fr) 2019-10-08 2020-10-07 Procédé et dispositif d'électrolyse pour la production de chlore, de monoxyde de carbone et éventuellement d'hydrogène

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EP4310224A1 (fr) 2022-07-19 2024-01-24 Covestro Deutschland AG Production durable de composés amino organiques pour la production d'isocyanates organiques
EP4345094A1 (fr) 2022-09-30 2024-04-03 Covestro Deutschland AG Procédé de production de phosgène avec recyclage du dioxyde de carbone issu du recyclage de matière de valeur
DE102022004678A1 (de) 2022-12-13 2024-06-13 Covestro Deutschland Ag Verfahren zur Elektrolyse von Kohlendioxid mit Vorreduktion einer Silberoxid-enthaltenden Gasdiffusionselektrode

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DE19543678A1 (de) * 1995-11-23 1997-05-28 Bayer Ag Verfahren zur direkten elektrochemischen Gasphasen-Phosgensynthese
DE10333853A1 (de) * 2003-07-24 2005-02-24 Bayer Materialscience Ag Elektrochemische Zelle
DE102005023615A1 (de) 2005-05-21 2006-11-23 Bayer Materialscience Ag Verfahren zur Herstellung von Gasdiffusionselektroden
DE102008012037A1 (de) * 2008-03-01 2009-09-03 Bayer Materialscience Ag Verfahren zur Herstellung von Methylen-diphenyl-diisocyanaten
DE102010030203A1 (de) 2010-06-17 2011-12-22 Bayer Materialscience Ag Gasdiffusionselektrode und Verfahren zu ihrer Herstellung
DE102010054643A1 (de) * 2010-12-15 2012-06-21 Bayer Material Science Ag Elektrolyseur mit spiralförmigem Einlaufschlauch
DE102015212504A1 (de) * 2015-07-03 2017-01-05 Siemens Aktiengesellschaft Elektrolysesystem und Reduktionsverfahren zur elektrochemischen Kohlenstoffdioxid-Verwertung, Alkalicarbonat- und Alkalihydrogencarbonaterzeugung
DE102017204096A1 (de) * 2017-03-13 2018-09-13 Siemens Aktiengesellschaft Herstellung von Gasdiffusionselektroden mit Ionentransport-Harzen zur elektrochemischen Reduktion von CO2 zu chemischen Wertstoffen
DE102017219974A1 (de) * 2017-11-09 2019-05-09 Siemens Aktiengesellschaft Herstellung und Abtrennung von Phosgen durch kombinierte CO2 und Chlorid-Elektrolyse

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KR20220079553A (ko) 2022-06-13
US20240084462A1 (en) 2024-03-14

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