EP3380653A1 - Système d'électrolyse et procédé de production d'oxyde d'éthylème par voie électrochimique - Google Patents

Système d'électrolyse et procédé de production d'oxyde d'éthylème par voie électrochimique

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Publication number
EP3380653A1
EP3380653A1 EP17700962.8A EP17700962A EP3380653A1 EP 3380653 A1 EP3380653 A1 EP 3380653A1 EP 17700962 A EP17700962 A EP 17700962A EP 3380653 A1 EP3380653 A1 EP 3380653A1
Authority
EP
European Patent Office
Prior art keywords
anode
ethylene
cathode
bromine
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.)
Withdrawn
Application number
EP17700962.8A
Other languages
German (de)
English (en)
Inventor
Ralf Krause
Christian Reller
Bernhard Schmid
Günter Schmid
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.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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 Siemens AG, Siemens Corp filed Critical Siemens AG
Publication of EP3380653A1 publication Critical patent/EP3380653A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
    • C07D301/26—Y being hydrogen
    • 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
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • 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
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms

Definitions

  • the present invention relates to a process and an electrolysis system for electrochemical ethylene oxide production.
  • Ethylene oxide is a chemical substance. So far, the com flashal ⁇ ethylene oxide manufacturing a silver-gas phase epoxidation of ethylene with oxygen is known. A process based on a catalyst of a silver-supported alumina, which is operated at 270 ° C and a pressure of between 1 and 10 bar, goes back to the work of TE Lefort: In the known direct oxidation processes two technical process paths occur that about the air epoxidation and about the epoxidation with pure oxygen. While the Heilepoxidmaschinesclar is limited to very low turnover and harbor certain safety ⁇ technical risks of explosion areas, the direct reaction is run with pure oxygen in a reactor under an inert gas atmosphere.
  • Another known process for ethylene oxide production is the chlorohydrin process in which ethylene is first reacted with water and chlorine to form chlorohydrin, which is then dehydrochlorinated with calcium hydroxide in a second step.
  • this method is no longer used because of its high cost.
  • chlorine is lost in the form of calcium chloride and therefore the external base calcium hydroxide ⁇ must be continuously tracked.
  • the requirements placed on the reactor materials used represent a considerable expense.
  • one ton of ethylene oxide produced by the chlorohydrin process contains between 0.1 and 0.2 tonnes of 1,2-dichloroethane. ethane and 2 tons of calcium chloride and 40 tons of contami ⁇ nigtes water as waste products.
  • the electrolysis system according to the invention for the electrochemical Ethylenoxider Wegung comprises at least one electrolytic cell having an anode in an anode compartment and a cathode in a cathode compartment, and at least one gas separation element into ⁇ particular a membrane.
  • the cathode compartment has a first access for carbon monoxide and / or carbon dioxide and is configured to bring this incoming carbon monoxide and / or carbon dioxide into contact with the cathode.
  • the anode compartment is integrated into an anolyte circuit and the cathode compartment into a catholyte circuit, the catholyte circuit having at least one first product outlet for a reduction product.
  • This first product outlet connects to a first connection line, which again rum is connected to the anolyte circuit.
  • the anode compartment is designed such that a reduction product which has been passed to the anode compartment via this first connection conduit can be brought into contact with an oxidation product.
  • reduction product is meant a substance which is generated electrochemically in the cathodic reduction reaction.
  • fluidic connections are to be understood, ie a conduit system with at least one pump which pumps the electrolytes contained in the line system together with educts, intermediates and products through the anode compartment and cathode compartment.
  • This electrolysis system for electrochemical ethylene oxide generation has the advantage that cathode and anode reaction are used equally, which makes the system very effective.
  • the system also has the advantage that Koh ⁇ lenstoffmonoxid and / or carbon dioxide can be supplied in a chemi ⁇ rule recycling.
  • electrolysis systems for electrochemical carbon dioxide recovery should always work more efficiently. To ensure a high current density or in attempts to increase it even further, only the carbon dioxide reduction taking place on the catalytically active cathode surface has hitherto been considered.
  • Currently about 80% of the world ⁇ wide energy needs are met by burning fossil fuels whose combustion processes causes a world ⁇ wide emissions of about 34,000 million tons Kohlenstoffdi ⁇ oxide into the atmosphere per year.
  • a particular advantage is to use carbon monoxide as a reduction educt.
  • the formation of ethylene from carbon dioxide (C0 2 ) always proceeds via the intermediate carbon monoxide (CO):
  • Step 1 C0 2 -> CO + H 0 2
  • Step 2 2 CO + 2 H 2 O -> C 2 H 4 + 2 0 2
  • the substrates yield carbon dioxide and carbon monoxide in very similar current yield ethylene (see Figures 3 and 4).
  • the carbon monoxide offers to ⁇ sharmlichen advantage as starting material: The amount and produced so that the end ⁇ concentration in the product gas is at the same current yield is 50% higher than that of carbon dioxide. The reason for this is that the carbon dioxide-case transferred 12 electrons who have ⁇ , During ethylene from carbon monoxide 8 electrons are unmarried ⁇ Lich required.
  • the gas separation element separating the anode and cathode compartments is at least one mechanically separating layer, eg a separator, a membrane or a diaphragm, which initially separates the electrolysis products formed in the anode compartment and cathode compartment from one another.
  • a separator membrane or separating layer e.g. a membrane with a high bubble point of 10 mbar or greater is used.
  • bubble point is a defining variable for the inserted membrane, which describes from which pressure difference ⁇ between the two sides of the membrane a gas flow through the membrane would begin.
  • the membrane may also be a proton or cation-conducting or - gagläs ⁇ sige membrane. While molecules, liquids or gases are separated, a proton or cation flow from the anode compartment to the cathode compartment or vice versa is ensured.
  • a membrane is used which comprises sulfonated polytetrafluoroethylene, eg Nafion.
  • zirconium oxide-based separators as used, for example, in electrolysers operating in alkaline conditions.
  • a reduction product can initially be formed in the catholyte circuit, which can then be brought into contact with further reactants on the anode side or else in an external mixing unit.
  • An electrolysis system with a cell stack of several electrolysis cells can also be provided. The intermediates would then be transferred, for example, into the anode compartment or cathode compartment of the subsequent cell.
  • Cheswei ⁇ se is a mixing unit provided for this purpose in the electrolysis system, at least the comparable across the first and / or second connecting line with the catholyte and anolyte is connected.
  • a container with diaphragm can be used, which
  • the mixing unit may also include a product separation device for ethylene include, as well as a supply line to a gas diffusion anode. It does not necessarily mixed liquid and gas ⁇ to.
  • the mixing unit can also be only a pipe system with a conveyor, for example a pump, include that the mixing be acting within the electrolytic cell ⁇ .
  • the electrolysis system may also comprise a return line, via which an oxidation product from the anode compartment and / or an intermediate, which is a
  • Reaction product of at least one cathodically produced Re ⁇ production product with an anodic Oxidationspro ⁇ product is, can be returned to the catholyte cycle.
  • the electrolysis cell is designed so that the intermediate is formed in the anode compartment and this is then supplied in a further reaction in the cathode compartment, in the catholyte circulation system and / or in the mixing unit.
  • the electrolytic system in its anode chamber bromide and is configured at the anode bromide to be oxidized to bromine and the transferred to the anolyte reductive ⁇ tion product, in particular to take ethylene and brought into contact with the bromine, which ultimately leads to the reaction of the bromine with the ethylene to the intermediate bromohydrin.
  • the electrolysis system may also contain other halide ions, for example iodide or fluoride ions, which then form the intermediate with the reduction product via iodine or fluorine.
  • the gas separation element for example, a diaphragm or is designed as Diaphrag ⁇ ma.
  • the main task of the diaphragm is the separation of the gases.
  • a diaphragm offers the advantage that, for example, via a pump circuit connected to the electrolysis cell, transport of the intermediate, for example, of a halohydrin, in particular special Bromohydrin, can be done by the diaphragm from the anode into the cathode compartment.
  • the diaphragm is proton and anion permeable, so that the Ladungsaus ⁇ equal is ensured between the two cell chambers of the electrolysis cell.
  • the gas separation element is a sulfonated poly tetrafluoroethylene ⁇ on or is constituted by a zirconia-based separator.
  • the electrolysis cell is typically connected to a mixing unit with external mixing vessel, which includes a diaphragm. The transfer of the intermediate into the catholyte circuit can then be ensured via the diaphragm.
  • sulfonated polytetrafluoroethylene Nafion is preferably used, which indeed separates molecules, liquids and gases, but is permeable to protons and cations and thus again the charge balance within the
  • the electrolysis system at least one second product outlet on, which is designed a in Anolyt Vietnamese- run and / or in the catholyte out Elektrolytge ⁇ mixing bromine can be seen from this a separate Christskam- mer for chemical reconversion of the Broms supply into a bromide, which reaction chamber is connected via a further connecting line with the anode compartment, so that a fluidic connection between the reaction chamber and the anode compartment is made.
  • An electrolyte mixture is to be understood as meaning a liquid which, for example, is
  • Water, one or more different conductive salts, electrolysis educts, electrolysis products and intermediates or Ne ⁇ ben comprise. Even when using the same electric ⁇ LYTEN in the anolyte and catholyte and despite at least partial mixing of the circuits, white anolyte and
  • Catholyte in the anode compartment and cathode compartment different An ⁇ parts of their respective components.
  • the reaction chamber and the corresponding connecting line can also be configured for the reconversion of another halogen into its halide.
  • a further bromination reaction can be carried out, in which hydrogen bromide as
  • Sequence product is formed, the another imple ⁇ wetting with potassium bicarbonate or potassium hydroxide can then be supplied, which ultimately potassium bromide is formed.
  • This described embodiment of the electrolysis system with a type recycling circuit for bromine has the advantage that this can be performed in a chemical cycle, no additional bromide must be supplied from the outside, but this can always be recovered back from the by-product bromine, which means that ultimately no bromide consumption takes place.
  • the bromine could also be extracted from the electrolysis system and fed to external recycling.
  • a reduction product is fed to the anode side via ⁇ and there directly reacted with particular anodically fabric ⁇ tem oxygen.
  • the electrolysis system has an anode which comprises a catalyst and the anode space has oxygen.
  • an oxygen evolution is more preferably carried out at the anode, that the anode comprises suitable catalysts and the anolyte comprises at least water, from the oxidative Sau ⁇ erstoff can be formed at the anode.
  • Suitable catalysts are, for example, manganese, rhenium, platinum, iridium, molybdenum,
  • Niobium preferably silver but also tungsten based Katalysato ⁇ ren or their oxides, which are preferably used in supported form.
  • the catalyst supports used are TiO 2 , SiO 2 , zeolites such as TS 1 , MCM 41, SAPO 5, SAPO 34.
  • the anode is preferably designed as a gas diffusion electrode.
  • catalytically active electrode additives may be included, which include activated carbon, carbon blacks, graphites as well as Binder such as polytetrafluoroethylene or perfluorosulfonic acid and other inert polymers.
  • anode materials that are inert to the formation of metal halides are used.
  • an external supply of oxygen to the anode compartment may also be provided, e.g. via an anode designed as a gas diffusion electrode.
  • an anode designed as a gas diffusion electrode e.g., a further reaction with the anodically formed oxygen can then take place with the reduction product conducted into the anode space.
  • the electrolysis system in the cathode space has at least one suitable catalyst and suitable reducing agents in an electrolyte environment, which promote selective conversion of the carbon dioxide to ethylene.
  • the ethylene can then be übergelei ⁇ tet as a reduction product in the anode compartment.
  • the ethylene can then directly in the
  • ethylene oxide which is an even higher value chemical recyclable than the ethylene itself.
  • carbon monoxide and / or introduced carbon dioxide into a cathode chamber and ⁇ least a portion of the carbon monoxide and / or carbon stoffdioxids is reduced at a cathode to ethylene.
  • Au ⁇ ßerdem is then at least a portion of the ethylene from the catholyte through a first product outlet, and subsequent first connection line of the electrolysis transferred to the anolyte.
  • an anodic reaction can be effected or operated, thus producing a chemical valuable substance and / or an intermediate product.
  • the intermediate product typically reacts with the ethylene to form a reaction to a chemical valuable substance or to an intermediate, that is to say a further intermediate product on the way to a chemical valuable substance.
  • bromine is provided in the anode space, which is fed to the Anolyt Vietnameselauf passed ethylene for reaction to Bromohydrin and at least a portion of the resulting Bromohydrins then in a basic ambient ⁇ led exercise and dehydrohalogenated therein to ethylene oxide.
  • This alternative method has the advantage that in the
  • Process control via the Bromohydrin as intermediate no explosive mixing ratios such as in the direct ⁇ e th implementation of ethylene with oxygen, can arise.
  • the dehydrohalogenation is preferably carried out in a basic environment by adjusting the pH of the catholyte side or the pH of an external dehydrohalogenation chamber to a value of 7 or greater.
  • Under Dehydroha ⁇ logentechnik is an elimination reaction to understand where each one hydrogen and one halogen atom is split off from DER same connection, in this case in particular mostly dehydrobromination.
  • the bromine provided in the anode compartment can be generated in-situ, eg, from the oxidation reaction in a bromide ion-containing electrolyte, or the bromine can be externally provided and introduced into the system.
  • the process can also be carried out via another halohydrin, for example an iodohydrin or fluorohydrin.
  • At least a portion of the bromohydrin formed in the anode compartment is fed to the catholyte cycle and dehydrohalogenated therein to ethylene oxide.
  • the resulting ethylene oxide can then be separated from the catholyte cycle. This can ⁇ example, via a rectification column or via a distillation process.
  • a pH of 7 or less is set in the anode space in the process.
  • the acidic environment for example, suppresses the formation of oxygen at the anode and thus ensures that explosive reaction mixtures of oxygen with ethylene are avoided.
  • the low pH which can preferably also be ensured by a buffer in the anode compartment, ensures that the intermediates halohydrin or bromohydrin can not already be dehydrohalogenated in the anode compartment but can be conducted into the cathode compartment or suitable external mixing container, where then the removal of the final product ethylene oxide is provided.
  • a pH of the catholyte between 5 and 11, preferably set above 7, for example by a buffer solution.
  • the basic environment causes the dehydrohalogenation of the intermediate bromohydrin.
  • additional ADVANTAGES ⁇ le While in the substrate carbon dioxide the pH value without external constraint control always in the range of H 2 C0 3 / HC0 3 - adjusted to about 7 buffer, produced during using KOH ⁇ lenstoffmonoxid as a substrate, an additional degree of freedom in the pH. For each carbon monoxide formed
  • Ethylene produces 8 hydroxide anions (OH ⁇ ). However, only one hydroxide anion is consumed for the coupled formation of ethylene oxide via bromohydrin. Since thus hydroxide anions can accumulate, a sufficiently high pH for this process can be built up and maintained. In the carbon dioxide case, although 12 hydroxide anions would be formed per ethylene, they would immediately be neutralized by more carbon dioxide, making it impossible to build a high pH.
  • the use of a carbon monoxide / carbon dioxide mixture is of particular advantage because the pH value can be optimally adjusted here.
  • the bicarbonate formed is either removed as valuable material if the pH is around 7. At very high pH values, the valuable material carbonate is formed, provided that correspondingly small quantities of carbon dioxide have been added to the carbon monoxide, less than 30%.
  • the already described mixture of the anolyte and catholyte is also possible.
  • Carbon monoxide-carbon dioxide mixtures in the range of 0 - 100% are possible. 1 used: Particularly be ⁇ is vorzugt a mixture in the ratio.
  • the process can be used simultaneously to reduce these traces or removed by the basi ⁇ rule character of the catholyte as bicarbonate (HC0 3 ⁇ ). Traces are defined as concentrations ⁇ 1%. Preference is given to working with concentrations ⁇ 0.1%, particularly preferably ⁇ 0.01%.
  • at least part of the unused and / or liberated bromine in the electrolysis system can be taken from the electrolyte mixture and be subjected to chemical re-conversion into a bromide outside the electrolysis cell, which bromide is then returned to the electrolyte mixture.
  • a reaction of hydrogen and bromine to bromide and subsequent reaction with potassium hydrogen carbonate can take place at ⁇ potassium bromide.
  • Another example of bromine usage may be bromination of an aromatic system:
  • Aromat + Br 2-Br Aromatic + HBr
  • the method is a bromine-bromide circuit can he be supplemented ⁇ , which causes no bromide is consumed, and thus no continuous addition of bromide is necessary in the circuit. Since a thorough mixing of both circuits is effected, the bromine can be removed from the anolyte or from the catholyte circuit or, for example, from the external mixing container. However, the recirculation into the system in the form of bromide is preferably carried out selectively in the anode compartment, so that the bromide concentrated local exists locally at the anode, where the bromine cycle can then begin again on the anodic oxidation.
  • electrocatalysis offers a very good opportunity for elegant energy conversion.
  • the described sustainable synthesis route for the production of hydrocarbons is based on the one hand on the use of a low-energy source carbon dioxide, which is actually a waste product, but here as a source of carbon and on the storage of electrical energy in the form of chemical bonds.
  • electrical energy can be stored, which preferably originates from regenerative energy sources or from overcapacities, so-called excess energy.
  • the copper electrode leads carried so are mainly hydrocarbons, such as Me ⁇ than or ethylene and carbon monoxide and hydrogen.
  • the product selectivity is determined, inter alia, by the adjustable working electrode potential. Annual production of ethylene is currently 141
  • Ethylene is a chemically important raw material for a wide variety of chemicals and materials, conventionally produced by steam cracking from petroleum or naphtha, and then transported by pipeline.
  • the production of the basic chemical ethylene oxide represents a further refinement of ethylene.
  • Ethylene oxide, with an annual production of 50 Mt / a, is an important key component for the production of substances such as ethylene glycol (55%), polyols (4%), ethanolamines (7%) , Glycol ethers (12%), surfactants (12%), polyglycols (4%) and others used at a lower percentage.
  • the cathode compartment of the electrolyte used in the electrolysis cell is therefore preferably designed so that Kohlenstoffdio ⁇ xid and / or carbon monoxide preferably to hydrocarbons ⁇ , especially short-chain hydrocarbons such For example, methane CH 4 or ethylene C 2 H 4 is reduced on a catalyst.
  • Short-chain hydrocarbons are understood to mean hydrocarbon compounds C n H m with n ⁇ 6.
  • the Bromohydrin compilers be ⁇ preferably a selective reduction of the carbon dioxide and / or carbon monoxide to ethylene C 2 H 4 made. Even products could, for example, such as water ⁇ material H2 generated at the cathode.
  • a separation device is provided on the cathode space to remove by-products from the system.
  • Carbon monoxide CO and bromine Br 2 Example ⁇ example should not be merged because otherwise Br arises CO 2 that can be used in chemical syntheses, although it should be due to its toxicity, but used in close proximity to the described electrolysis system.
  • the anode chamber is preferably designed so that the re ⁇ production product of the cathodic reaction, in this case the ethylene, can be forwarded to the anode and is reacted with the in-situ generated at the anode bromine to bromohydrin.
  • the process may also be conducted over other halohydrins, which are somewhat less preferred than the bromohydrin.
  • halohydrins which are somewhat less preferred than the bromohydrin.
  • the bromohydrin thus produced at the anode then becomes active or passive, i. transferred via a bypass or via a pumping line directly into the catholyte, where it is cathodically dehydrohalogenated its basic environment.
  • the energy efficiency of the electrolysis system can taking advantage of both half-cells to produce the chemical substance ethylene oxide value of carbon monoxide and / or carbon dioxide are ⁇ be ⁇ pointing increased.
  • carbon dioxide utilization which is important for environmental reasons, has enormous economic potential.
  • electrochemically generated carbon monoxide from carbon dioxide is as a substrate or admixture helps ⁇ sant.
  • the method offers the use Various ⁇ ner carbon monoxide sources. These are, for example: - coal dust gasification: C + ⁇ O2 ⁇ * CO
  • the methods described also tolerate hydrogen in Kohlenstoffmonoxidanteil between 0 and 80%, preferably Zvi ⁇ rule 0 to 20%.
  • Ethylene oxide can then, for example via an intermediate he ⁇ follow, preferably via the formation of a halohydrin from ka ⁇ methodically produced ethylene and a halogen anodic.
  • the halohydrin is then active again transported back to the cathode to-where it is dehydrohalogenation in the basic environment of the cathode chamber and ethylene oxide is ent ⁇ .
  • the halohydrin can also be supplied in a cell stack a series cell where it is, in a basic dehydrohalogenating Conversely ⁇ advertising, eg in the cathode chamber, and
  • Ethylene oxide is formed.
  • the dehydrohalogenation requires a basic medium with a pH> 7, which is already effected locally by the cathode reaction.
  • the pH can be adjusted to a particularly suitable level by a buffer.
  • Dehydrohalogenation is dependent on the bound halogen itself and is faster for iodide than for bromide, for this in turn faster than for a chloride, and for chloride in turn faster than for a fluoride.
  • the process is, however, preferably performed so that an additional
  • the active return transport of the intermediate to the cathode can take place, for example, via the inserted diaphragm in the electrolytic cell.
  • Anolyte and catholyte are also carried out in an external container, where the gaseous products are separated over a supreme ⁇ rising gas phase and the liquid products remain in the liquid phase.
  • the technical implementation is based on the use of known membrane diaphragm electrolyzer technology.
  • Another special feature of the pre ⁇ presented electrolysis system is still in the design of the copper-based gas diffusion electrode and the so ver ⁇ -bound selective reduction of carbon monoxide and / or carbon dioxide to ethylene.
  • a special feature is that anolyte and catholyte can have the same chemical Caribbeanset ⁇ Zung and both processes by the use of a halide, particularly bromide benefit.
  • the separation of the product ethylene oxide can preferably take place via the gas phase.
  • Separation from the liquid phase is also possible by utilizing the clathrate formation by cooling the electrolyte in an external crystallization vessel or in a discontinuously operated mixer-settler device.
  • Another alternative is the use of a membrane permeation process for product separation from the electrolysis system.
  • oxygen is provided in the anode space, by means of which the ethylene introduced into the anolyte circuit is anodically epoxidized to form ethylene oxide.
  • the oxygen provided in the Anode space can be generated in situ, for example from the oxidation reaction in an aqueous electrolyte, or the oxygen can be provided externally and introduced into the system ⁇ who. The simultaneous epoxidation of ethylene to ethylene oxide thus refines a by-product of electrochemical carbon dioxide utilization.
  • a copper-based gas diffusion electrode is used on the cathode side be ⁇ vorzugt, ie, a gas diffusion electrode which has at least one copper ⁇ share, and accordingly tet ethylene selectively arbei-.
  • the gas diffusion electrode may, for example, carbon fabric or a metal mesh, on which the catalyst is applied.
  • Particularly active ethylene-developing electro-reduction catalysts are obtained by depositing the catalyst in-situ on the cathode.
  • conductive oxides may also be included as the electrically conductive material of the cathode.
  • the catalyst layer of the cathode points to the active Promoting the ethylene preferably a high wettability by the aqueous electrolyte, also an electrical contacting of the catalyst, for example by particles or catalyst centers and a possibility of arrival and Abdiffusion of gaseous educts and products, which can be ensured, for example, by the porous design of the cathode can.
  • a silver-based gas diffusion electrode is preferably used, i. a gas diffusion anode with a silver portion, at which oxygen is then formed, which further reacts with the ethylene to ethylene oxide.
  • the anode preferably has additions of activated carbon, carbon blacks, graphites or other binders, such as, for example, polytetrafluoroethylene or sulfonated polytetrafluoroethylene.
  • transition metal catalysts are also suitable for the anodic oxidation of oxygen, for example based on manganese, platinum, iridium, molybdenum, rhenium, niobium, tungsten, preferably silver or their oxides, which are preferably used in supported form.
  • the catalyst supports are Ti0 2 , Si0 2 , zeolites such as TS1,
  • the electrode should preferably be designed as a gas diffusion electrode.
  • the metals can be used as a solid material or as
  • the silver catalyst can also be deposited ex situ in situ by electrochemical deposition on a conductive carrier, for example a mesh, sheet metal or carbon fiber fabric, in an acidic pH environment.
  • a conductive carrier for example a mesh, sheet metal or carbon fiber fabric, in an acidic pH environment.
  • electrochemical deposition of the silver catalyst preference is given to a pH range between 1 and 4 and a silver nitrate solution of a concentra- tion between 0.0001 mol and 0.01 mol is recommended.
  • the silver catalyst can also be present in the oxidation states +1 or +2, ie, for example, as silver (II or I / III) oxide Ag 2 O 2 or silver (I) oxide Ag 2 ⁇ 3.
  • the number in parenthesis indicates the oxidation state.
  • the principle of anodic ethylene epoxidation is thus based on the electrocatalytic conversion of oxygen and ethylene.
  • the oxygen can be formed on the one hand in situ by the anodic decomposition of water or the electrode could also be supplied with a mixture of oxygen and ethylene directly in gaseous form.
  • the composition can be adjusted precisely and thus a safe handling of the explosive in one ⁇ chen compositions gas mixture will be ensured. This can also be ensured by first removing the oxygen formed in situ from the anolyte circuit and then metering it in, for example, in a second electrolysis cell connected in series. Especially emp ⁇ mended operating parameters can be found in Table 2 below.
  • the electrolysis system for electrochemical ethylene oxide production thus preferably has an electrolytic cell with cathode space and anode space, which are preferably separated from one another by an ion exchange membrane, typically a proton-conducting ion exchange membrane, in order to prevent mixing of the electrolytes, above all mixing prevent the anodic and cathodic products.
  • an ion exchange membrane typically a proton-conducting ion exchange membrane
  • Table 2 Highly recommended operating parameters for anodic epoxidation of ethylene.
  • a diaphragm may e.g. a ceramic or a polymer such as polypropylene, polyethylene, polyvinyl chloride, polytetrafluoroethylene have.
  • the use of composite materials in the separating layer between anode and cathode space is not excluded.
  • the carbon monoxide and / or carbon dioxide can be present in dissolved form in the electrolyte, but also in gaseous form, or can be introduced directly into the process chamber in gaseous form through the cathode gas diffusion electrode method.
  • the electrolyte used in the cathode compartment preferably has conductive salts in a concentration range between 0.1 mol and 3 mol.
  • the conductive salts used are typically alkali metal sulfates, alkali metal halides or alkali metal carbonates or alkali metal metal phosphates.
  • the pH of the catholyte is preferably adjusted between 5 and 8.
  • the pH of the electrolyte in the anode compartment is basic, ie to be selected in a pH range between 7 and 14, which is already reaction-induced in the case of in-situ generation of oxygen, in the case of external oxygen addition by a pH buffer is set.
  • ⁇ preferably is hydroxide, a 0.1 to 3 molar potassium in the epoxidation by anodically produced oxygen in the anode compartment and used a 0.1 to 1 molar potassium hydrogen carbonate solution.
  • mixtures of the mentioned Electrolytes can be used. He particularly preferably ⁇ followed by the addition of ethylene also directly over the anode gas diffusion electrode. Then, the ethylene gas addition rate is preferably set between 5 and 500 sscm per cm 2 of electrode area.
  • the presented electrochemical epoxidation from Kohlanstoffmonoxid or carbon dioxide has the advantage that the anodic nascent oxygen already activated in the electrolysis system is present, so that the process can be operated at room temperature.
  • product separation e.g. used a rectification column, unreacted ethylene, which has a boiling point of -103, 7 ° C, from the ethylene oxide, which has a boiling point at 10.7 ° C, are separated and recycled to the anode.
  • An alternative product separation of the ethylene oxide from the system is the precipitation of clathrates from the anolyte in a temperature range between 2 and 11 ° C, preferably at 11 ° C.
  • the epoxidized in the electrolysis system ethylene oxide may be mixed at 20 ° C with water. The miscibility follows directly proportional to the pressure change according to Henry's law.
  • FIG. 1 shows a schematic representation of the use of in situ generated oxygen for the epoxidation
  • FIG. 1 shows schematically the active pumping process
  • Figure 5 shows the pH profile of the electrochemical reduction of carbon dioxide and carbon mono ⁇ oxide to ethylene in the cathode space
  • FIG. 6 shows an electrolysis system for electrochemical
  • FIG. 7 shows an electrolysis system with external mixing container
  • Figure 8 shows an alternative construction of an electrolysis ⁇ systems with external mixing vessel
  • Figure 9 shows an alternative construction of an electrolysis ⁇ system with phase separator.
  • 1 shows schematically the in situ generation of oxygen O2 at the anode A, in particular at the Anodenoberflä ⁇ surface.
  • 1 shows the arrangement of cathode K and anode A of a separator S is shown greatly simplified both sides: the cathode side, the carbon monoxide CO and / or Koh ⁇ lenstoffdioxid CO2 is introduced and reduced to ethylene C2H4. This is brought to the anode side, in this case via an external connection line 1.
  • the separator S is for protons H + permeable to ensure charge neutrality in the Elect ⁇ rolysezelle EZ.
  • the ethylene C2H4 reacts on the anode side directly with anodically generated oxygen O2, which is oxidized from OH ⁇ ions of the electrolyte.
  • oxygen O2 can also be added externally.
  • a reaction of the ethylene C2H4 to ethylene oxide C2H4O with external oxygen O2 can also be carried out in the anode chamber AR in a reaction chamber separate from the electrolytic cell EZ.
  • An arrangement of anode A and cathode K is shown schematically in FIG. 2, which is intended primarily to clarify the course of the process. The reactions taking place at the anode A are separated by a diaphragm D from the reactions taking place in the cathode region.
  • Ethylene C 2 H 4 is reduced.
  • This ethylene C 2 H 4 before learning an al- extraction from the catholyte KK and To ⁇ lead in the anolyte circuit AK, preferably placed on a Ver ⁇ connecting line 1, for further reaction to the anode A.
  • the transfer of the ethylene C 2 H 4 to the anode A is again illustrated in the schematic representation of FIG. 2 by a double arrow 1 indicating the direction of flow.
  • bromide Br ⁇ are oxidized at the anode A to bromine Br 2, which then with the ethylene C 2 H 4 further reacted to Bromohydrin HOCH 2 -CH 2 Br.
  • This is, for example, transported by ⁇ means of the mixing unit 2 through the diaphragm D as ⁇ on the other side of the electrolysis cell.
  • ⁇ derum at the cathode K due to a lower pH than at the anode side, the reaction takes place to ethylene oxide iii C 2 H 4 O, water H 2 O and Br ⁇ bromide instead.
  • Fi gur ⁇ 2 is further shown that bromide ions Br- and protons H + diaphragm D pass charge balancing Kgs ⁇ NEN.
  • Another double arrow shows the removal of the
  • Cathode space KR and anode space AR of the electrolytic cell EZ are preferably separated by a diaphragm D, which prevents at least the mixing of the gases.
  • a diaphragm D can be made of a ceramic or of a polymer, such as polypropylene, polyethylene, Polyvinylchlo ⁇ chloride or polytetrafluoroethylene.
  • fiber-reinforced composite materials eg zirconium oxide ZrÜ 2 or zirconium phosphate Zr 3 (PC> 4) 4 in a polymer matrix, in the diaphragm D is not excluded.
  • Figures 3 and 4 show the Faraday efficiencies Eff in the ethylene formation C 2 H 4 of carbon dioxide CO 2 and carbon monoxide CO in comparison. Experimentally shown ⁇ to that the formation of ethylene C 2 H 4 CO carbon monoxide passes through the intermediary. Under the same reaction conditions, the substrates provide carbon dioxide CO 2 and Koh ⁇ lenstoffmonoxid CO in a very similar current efficiency Eff
  • FIG. 5 shows the pH profile of the electrochemical reduction of carbon dioxide CO 2 and carbon monoxide CO to ethylene C 2 H 4 in the cathode space KR.
  • carbon monoxide CO is used instead of carbon dioxide CO 2 as a substrate in the bromohydrin process
  • the pH value in the system also changes.
  • the pH always remains within the range of H 2 C0 without external forced control 3 / HC0 3 - Buffer at about 7.
  • the use of carbon monoxide CO as a substrate results in an additional degree of freedom in the pH: For each of carbon monoxide CO formed ethylene C 2 H 4 arise 8 hydroxide anions OH ⁇ .
  • the pH can be optimally adjusted.
  • the hydrogen carbonate formed is either removed as valuable material if the pH is around 7.
  • the valuable material carbonate is formed, provided that correspondingly low amounts of carbon dioxide below 30% are added to the carbon monoxide CO, for example by mixing the anolyte and catholyte.
  • Carbon monoxide-carbon dioxide mixtures with carbon dioxide content of from 0.01% to 30% are suitable be ⁇ Sonders.
  • potassium carbonate K2CO 3 could also be produced by the process.
  • FIG. 6 shows schematically an electrolysis plant as it can be used for electrochemical ethylene oxide production. Even if the anolyte circuit AK and the catholyte circuit KK, as described in this application ⁇ ben, are connected to each other, the anolyte side and the catholyte side is characterized in the schematic representation by two dashed framed areas of the electrolysis. Above all verdeut ⁇ light in the diagram that despite flow of technical compounds 1, 2 of the two circuits AK, KK a local pH difference AK anolyte and catholyte KK differs.
  • the electrolytic cell EZ has an anode A in an anode space AR and a cathode K in a cathode space KR, the anode space AR and cathode space KR being separated from one another or connected to one another via a membrane M.
  • the cathode K can be, for example, a gas diffusion electrode GDE, via which the carbon monoxide CO and / or carbon dioxide
  • CO2 can be introduced into the catholyte KK.
  • ⁇ de circulation systems AK KK are preferred, as in Figure 1 shown provided with pumps P, which provide the necessary circulation of the mixture of electrolytes, starting materials and products through the electrolysis system.
  • Anode A and cathode K are electrically connected to one another via a voltage supply U and via the electrolyte.
  • At least one product outlet PA1 is provided in the catholyte circuit KK, here shown for example as a gas separation chamber G, via which at least one cathodically produced electrolysis product, in particular ethylene C 2 H 4 , can be removed from the catholyte circuit KK. This is then fed via a connecting line 1 to the anode space AR.
  • the anolyte circuit AK and at least one product outlet PA3 is vorgese ⁇ hen, which in turn, as shown in Figure 6, may include a gas separation chamber G, O can be removed from the anolyte circuit AK over the anodically produced ethylene C 2 H.
  • This product outlet PA3 in the anolyte circuit AK can provide for the case I anodically produced ethylene oxide C 2 H 4 O for its extraction from the anolyte circuit.
  • this Pro ⁇ duktauslass PA3 can AK in the anolyte circuit for separating un ⁇ consumed ethylene C 2 H 4 0 upon. for the recycling of bromine Br 2 , Br ⁇ be used in the cycle.
  • an additional product outlet PA 2 is preferably provided in the anolyte circuit AK.
  • This product outlet PA2 in turn can first by means of egg ⁇ ner gas separation device G, the bromine Br 2 the Anolyt Vietnamese- Remove the run AK.
  • the bromine Br 2 can then be introduced into a reaction ⁇ chamber R where, for example a bromination is carried out to HBr and a subsequent further reaction, for example over potassium KHCO3 to potassium bromide KBr so that bromide Br ⁇ in the form of potassium bromide KBr again in the anolyte circuit AK and thus in the overall electrolysis ⁇ circuit can be initiated.
  • Potassium KHCO.sub.3 is a wide ⁇ rer recyclable material that is not consumed and therefore need not be separately led to ⁇ but is a by-product of electrolysis and supports a closed circuit.
  • the carbon monoxide CO and / or carbon dioxide CO 2 is largely in dissolved form in the electrolyte, but can also be gaseous or chemically bound the carbon monoxide CO and / or carbon dioxide CO 2 in the circulation may be present. Gaseous, it can for example be introduced directly through the cathode K when using a gas diffusion ⁇ onselektrode GDE in the process chamber KR.
  • the ethylene C 2 H 4 is also preferably introduced via a Gasdiffu ⁇ sion electrode GDE in the electrolysis system, in this case via the anode A.
  • the ethylene gas addition rate is preferably between 5 and 500 sscm per cm 2 electrode area selected; sscm is a measure of the flow rate: cm 3 per second based on standard conditions (0 ° C, 101 kPa).
  • Ethylene oxide C 2 H 4 O have very different boiling points: Ethylene C 2 H 4 already boils at -103, 7 ° C, so it is at Room temperature in gaseous form, while ethylene oxide C 2 H 4 O of 10.7 ° C. The unreacted ethylene C 2 H 4 can be recycled to the anode A.
  • Ethylene oxide C 2 H 4 O consists in the precipitation of clathrates (clathrate hydrates) from the anolyte. This is pre- ⁇ taken in a temperature range of 2 to 11 ° C, preferably at 11 ° C.
  • the clathrates contain up to 26% by weight of ethylene C 2 H 4 , which corresponds to 46 water molecules and 6.66 ethylene molecules per unit cell.
  • the clathrates can then be separated off and the ethylene C 2 H 4 be thermally released again, for example in a temperature range from 11 to 200 ° C. There is also the possibility of shortages
  • Ethylene glycol in the liquid phase are formed by hydrolysis. In a 3% mixture with water, at a pH between 5 and 9, these reach a half-life of about 20 days.
  • Bromohydrin HOCH 2 -CH 2 Br is combined from the ethylene C 2 H 4 and anodically produced bromine Br 2 .
  • Basis for this process is al ⁇ so the anodic oxidation of the bromide Br ⁇ to bromine Br 2 .
  • Al ternatively ⁇ the presented process can be driven process as a halohydrin, which means that the further Haloge ⁇ ne may be used as alternatives to bromine Br. 2
  • the bromohydrin H 2 O - CH 2 Br formed on the anode side AR is then actively pumped onto the cathode side KR in the process.
  • the mixing can be carried out both continuously and discontinuously.
  • aphragma D be circulated.
  • a bypass zwi ⁇ rule anode AR and cathode space KR may be provided in which a pump promotes mixing.
  • the mixing of anolyte and catholyte can be carried out via an external mixing container Mi. For pumping over a diaphragm D this is expedient porous.
  • the electrolytic cell EZ preferably has a membrane M.
  • This membrane M is preferably made of sulfonated polytetrafluoroethylene (PTFS), which is mostly known as Nafion.
  • PTFS polytetrafluoroethylene
  • the mixing vessel Mi has a first section Mil, which is fluidically, for example, connected via a pipe to the anode compartment AR and a second section Mi2, the flow technology, for example via a second pipe, is connected to the cathode space KR.
  • this variant of the electrolysis system is designed such that the cathode compartment comprises at least one KR to ⁇ gear GDE for carbon monoxide and / or carbon dioxide CO 2 and the anode chamber AR at least one access for ethylene C 2 H. 4
  • a mid Alkalibro-, for example potassium bromide in aqueous solution of KBr (aq) is preferably used: Then, in the anode compartment AR bromide Br ⁇ to bromine Br 2 can be oxidized.
  • the bromine Br 2 may be removed from the system then, for example, from the first region of the mixing vessel Mil Mi and is typically, as previously ⁇ be written again fed as a bromide Br ⁇ in the system.
  • the ethylene C 2 H 4 can be extracted from the second area Mi 2 of the mixing vessel Mi and the end product ethylene oxide C 2 H 4 O.
  • the structure of the electrolysis system shown in FIG. 8 is provided with an electrolytic cell EZ and an external mixing vessel Mi.
  • the electrolytic cell EZ on a membrane M, in particular a Nafion membrane and the mixing vessel Mi-E a diaphragm D for the separation of anode and cathode side or anolyte and catholyte.
  • the products from the cathodic reduction process and the anodic oxidation process are taken from the electrolysis cell EZ and combined before they are flowed into the first region Mi-AR of the mixing container Mi-E.
  • An exchange between the first chamber Mi-AR of the mixing container Mi-E and the second chamber Mi-KR of the mixing container Mi-E can take place via the diaphragm D in the mixing container Mi-E.
  • This exchange can in turn be operated via a pump, eg via a bypass system with a pump.
  • the second section Mi-Mi-KR of the mixing container e the wide implementation of the re Bromohydrins HOCH 2 -CH 2 Br then takes place to ethylene C 2 H 4 0th
  • the mixing vessel Mi-E is in this case as a second electrolytic cell Mi-E behind the first electrolysis cell EZ maral ⁇ tet.
  • the electrolysis products from the first electrolytic cell EZ are introduced into the anode space Mi-AR of the mixed electrolytic cell Mi-E.
  • the production of bromohydrin HOCH 2 -CH 2 Br in the anode space Mi-AR of the mixing cell Mi-E which then passes via the diaphragm D into the cathode space Mi-KR, takes place which prevails a pH above 7, which promotes the further reaction to ethylene oxide C 2 H 4 O.
  • the pH can be adjusted for example via a buffer.
  • the intermediate gases ethylene C 2 H 4 and bromine Br 2 are removed from the anolyte and catholyte circulation and fed to the anolyte of the active mixing cell Mi-E.
  • a configuration example with external mixing vessel MA is finally still shown that a reverse phase separator construction MA used: building the electrolysis cell EZ as ⁇ consisting of a cathode chamber KR and an anode space AR listed, which are joined together via a diaphragm D , In the cathode space KR an access for carbon monoxide CO and / or carbon dioxide CO2 and an inlet for the electrolyte (-Edukt) mixture is provided.
  • an aqueous potassium bromide solution KBr (aq) is used as the electrolyte.
  • anolyte and the catholyte are then provided, which is formed according to the method described in the cathode space KR and accordingly from the
  • a mixer separator MA is preferably used here, in which carbon monoxide CO and / or carbon dioxide CO 2, bromine Br 2 and ethylene C 2 H 4 are received and present in gaseous form in the upper volume compartment g of the mixer separator MA. From this volume g, for example, the ethylene C2H 4 is then forwarded again into the electrolyte circuit.
  • the electrolyte equilibria for bromine-containing waters differ according to the pH range.
  • the end product ethylene oxide C 2 H 4 O can be taken from the gas volume g in the mixer separator MA.
  • a retention device for gases is provided at the product outlet, which should not be present in the final product, for example, for bromine Br 2 .
  • This retention device may be pH dependent, for example.
  • the effective bromine removal is important because bromine at the cathode would be bad for efficiency.
  • the mixer separator MA may in turn have a diaphragm D. It should be avoided at all costs that gaseous reactants and products mix.
  • the mixing device MA is directed in each case thereon from to convey the bromohydrin formed on the Ano ⁇ denseite AR HOCH 2 -CH 2 Br or another halohydrin on the cathode side KR where it is dehydrohalogenated in the basic catholyte and ultimately as the ethylene oxide C 2 H 4 O is formed.
  • the process described is not limited to ethylene C 2 H 4 and ethylene oxide C 2 H 4 O. It is also possible to expand to other olefins and olefin oxides.
  • the proposed electrolysis systems and the method for producing ethylene oxide has the advantage of producing economically viable products both at the anode A and at the cathode K.
  • the combination of the two cell reactions increases the efficiency of the overall process or system.
  • the anode A is preferably a tantalum or platinum anode.
  • the anode A is designed as a gas diffusion electrode.
  • anode materials that are inert to the formation of metal halides are used.
  • electrode additives activated carbon, carbon black, graphite, and as a binder also Polytetrafluourethylen PTFE, perfluorosulfonic PFSA and other inert polymers are ⁇ sets can.
  • the cathode K copper-based Gasdiffusi ⁇ onselektroden GDE are preferably used which contain an ethylene selective catalyst.
  • the gas diffusion electrode GDE since ⁇ stand account when made of a carbon cloth or a metal mesh on which the catalyst is applied.
  • Particularly active ethylene-developing electro-reduction catalysts are created by depositing the catalyst in situ on the cathode K. But an ex situ deposition of the catalyst on the cathode fabric or network is conceivable.
  • the substrate must not necessarily ⁇ speak to a copper substrate or copper-containing substrate han ⁇ spindles. Any conductive material, in particular conductive oxides, can be used as a substrate for the gas diffusion electrode GDE.
  • By means of the configuration of the porous cathode K can be realized which is preferably used Gasdiffusionselekt ⁇ rode GDE.
  • the catalyst layer preferably fulfills the following criteria: it is wettable by aqueous electrolytes, the catalyst can be contacted electrically, especially when it consists of Kata ⁇ lysatorpumblen or catalyst centers and the arrival and diffusion away from gaseous reactants and products can be carried on the catalyst unhindered.
  • transition metal catalysts based on molybdenum, iridium, platinum, palladium, tungsten, rhenium, rhodium or Alloys of these elements can be used as a catalyst in the cathode K.
  • the metals can be used as a solid material or as a mixed metal oxide, for example as supported catalysts.
  • a preferred manufacturing method of the catalyst position via the electro ⁇ chemical deposition on a conductive support, which is in particular a net, sheet or carbon fiber cloth.
  • the electrochemical deposition of the catalyst occurs before ⁇ Trains t in the acidic pH medium in-situ.
  • the electrochemical deposition of the catalyst is particularly preferably carried out in a pH range between 1 and 4.
  • an acidic environment prevails in the anode region, i. a pH ⁇ 7 before, in the Kordoden Scheme a basic environment, i. a pH> 7.
  • Electrolytes and electrode materials The following is a reaction scheme with expiring anodic water splitting and corresponding oxygen production is shown. At the cathode K, the following reactions would initially take place: 12 C0 2 + 72 H + + 72 e 6 C 2 H 4 + 24 H 2 0
  • bromine Br 2 thus forms in the system in the event of an anodic bromide oxidation, in addition to ethylene oxide C 2 H 4 O:
  • Preferred conductive salts are alkali metal halides, alkali metal carbonates or alkali metal phosphates.
  • the pH of the catholyte, at least locally in the cathode space KR, is preferably set between 5 and 11.
  • the pH of the electric ⁇ LYTEN in the anode chamber AR is preferably set slightly acidic, that is in any case below 7, preferably below 5, so as to suppress the formation of oxygen O2.
  • the present AR electrolyte in the anode compartment is typically the same as that in the catholyte and has KK ent ⁇ speaking, a concentration of between 0.1 M and 3 M on.
  • Preferred mixtures of the electrolyte have between 0.1 M and 3 M of a metal halide, eg potassium bromide KBr, potassium chloride KCl or potassium iodide KI or an additive between 0.1 M and 1 M of a carbonate, eg potassium hydrogencarbonate KHCO 3 .
  • a metal halide eg potassium bromide KBr, potassium chloride KCl or potassium iodide KI
  • an additive between 0.1 M and 1 M of a carbonate, eg potassium hydrogencarbonate KHCO 3 .
  • the use of a three-molar potassium bromide solution KBr (aq) has proven particularly suitable, which is then preferably used as the anolyte and as the catholyte. Any bromide Br ⁇ containing electrolytes can lead to the formation of Bromohydrinen HIGH2 -CH2Br, which can be halogenated easier dehydro especially compared to chlorine compounds.
  • the described method as well as the diagnostics system described electrolyzer ⁇ offer the advantage of allowing maximum utilization of the electrical energy used by the material encryption evaluation of the cathode and the anode reaction to the known electrochemical processes. Another advantage is that are required as a reactant, ie as starting materials, only water H2O and Koh ⁇ lenstoffmonoxid CO and / or carbon dioxide CO2. In contrast to the previously known methods, no hydrogen H2 is produced as an unused waste product.
  • the bromohydrin method has the further advantage that the bromide or another halide used has a positive effect on the formation of ethylene C2H4, since the presence of a halide in the electrolyte increases the hydrogen overvoltage at the cathode K.
  • the process presented above especially due to the gas diffusion electrodes GDE used, tolerates higher temperatures than the processes hitherto known in the literature.
  • it is of great advantage that by the epoxidation of ethylene C2H4 in the proposed bromohydrin process, the formation of waste products such as calcium chloride, which is e.g. arises in the chlorohydrin process, is avoided.
  • the epoxidation described here offers the advantage of suppressing an unwanted total oxidation of ethylene C2H4. As a result, no hotspots occur, as is the case with thermally operated
  • Gas phase process arise, for example, in cavities of the catalyst bed.
  • undesirable carboxylic acids are formed, which then lead to degradation of the catalyst.
  • degradation effects such as a clogging of the catalyst pores by abrasion, poisoning of the catalyst by sulfur, corrosion or change in particle morphology, eg by
  • the presented electrochemical process basically avoids any thermally induced aging effects.

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Abstract

L'invention concerne un système d'électrolyse, p.ex., une cellule électrolytique (EZ) pourvue d'une liaison entre le circuit d'anolyte et le circuit de catholyte. Cette liaison entre le circuit d'anolyte et le circuit de catholyte permet l'introduction d'un produit intermédiaire produit côté cathode en tant qu'éduit dans le compartiment anode (AR) du système ; p.ex., du monoxyde de carbone (CO) ou du dioxyde de carbone (C02) ou un mélange des deux substrats sont réduits sur la cathode (K) pour former de l'éthylène (C2H4), lequel continue à réagir dans le compartiment anode (AR) avec un sous-produit de la réaction anodique, p.ex. bromure (Br2).
EP17700962.8A 2016-01-21 2017-01-19 Système d'électrolyse et procédé de production d'oxyde d'éthylème par voie électrochimique Withdrawn EP3380653A1 (fr)

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AU2017209876B2 (en) 2019-08-29
WO2017125469A1 (fr) 2017-07-27
DE102016200858A1 (de) 2017-07-27
CN108541277A (zh) 2018-09-14
AU2017209876A1 (en) 2018-06-21

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