WO2013178803A1 - Procede et dispositif de synthèse par électrolyse du méthanol et/ou du méthane - Google Patents

Procede et dispositif de synthèse par électrolyse du méthanol et/ou du méthane Download PDF

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Publication number
WO2013178803A1
WO2013178803A1 PCT/EP2013/061303 EP2013061303W WO2013178803A1 WO 2013178803 A1 WO2013178803 A1 WO 2013178803A1 EP 2013061303 W EP2013061303 W EP 2013061303W WO 2013178803 A1 WO2013178803 A1 WO 2013178803A1
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WIPO (PCT)
Prior art keywords
electrolyte
cathode
anode
carbon dioxide
membrane
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PCT/EP2013/061303
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German (de)
English (en)
Inventor
Oliver Schael
Guido Burmeister
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Hettich Holding Gmbh & Co. Ohg
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Publication of WO2013178803A1 publication Critical patent/WO2013178803A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the invention relates to a method and a device for the electrolytic synthesis of methanol and / or methane by reduction of carbon dioxide contained in an electrolyte in the liquid phase, at the critical point or in the supercritical phase of the electrolyte.
  • photovoltaic generators By means of photovoltaic generators, it is now possible to convert sunlight into electricity with high efficiency and, after a relatively short service life, amortizing financial and energy investment. In addition, production capacities for photovoltaic generators have been installed worldwide, enabling the realization of even very large photovoltaic systems. Even with the help of wind turbines is now an implementation of
  • worldwide production capacities for wind power converters are now installed, which enable realization of very large wind farms, for example as offshore wind farms.
  • hydropower for example in wave power plants for power generation
  • the problem with the use of renewable energy sources is that it mainly takes place decentrally in often poorly developed regions.
  • the conversion into methanol and / or methane is proposed.
  • hydrocarbons are fundamentally ideal fuels. Because of the possibility of methanol either in internal combustion engines or in fuel cells, for example in fuel cells of the SOFC (Solid Oxide Fuel Cell) type or directly in fuel cells of the type
  • DMFC Direct Methanol Fuel Cell
  • Methane is the main constituent of natural gas and is an important fuel gas. Both products, methanol and methane, are also important raw materials for the chemical industry. From methanol, for example, various chemical products such as plastics, drugs or fuels can be produced.
  • methanol can also be obtained in principle by reduction electrolytically from water and carbon dioxide (CO 2 ). If the carbon dioxide is used in aqueous solution, however, only low currents can be achieved in the electrolysis, making it difficult or impossible to use the electrolysis process on a large scale.
  • CO 2 carbon dioxide
  • the electrolyte is accompanied by a conductive substance and a hydrogen-containing substance, for example hydrogen chloride or hydrogen sulfide, in order to provide protons for the reduction of the carbon dioxide on the one hand and to make the electrolyte electrically conductive on the other hand.
  • a hydrogen-containing substance for example hydrogen chloride or hydrogen sulfide
  • Methanol formed in the electrolyte and optionally further hydrocarbons are separated in a separator. This separation is complicated, since the methanol formed must be purified, inter alia, by dissociation products of the hydrogen-containing substance used, for example, chlorine-containing or sulfur-containing compounds formed.
  • the inventive method for the electrolytic synthesis of methanol and / or methane by reduction of carbon dioxide contained in an electrolyte in the liquid phase, at the critical point or in the supercritical phase of the electrolyte is characterized in that protons for reducing the carbon dioxide by a proton-conducting membrane be introduced into the electrolyte.
  • the reaction for the synthesis of methanol (H 3 COH) is split into two partial reactions.
  • the corresponding partial reactions then proceed at an anode in an anode compartment and at a cathode in a cathode compartment and are represented as follows:
  • Methane (CH 4 ) can also be formed as a competing reaction according to the overall reaction: 4H 2 + C0 2 ⁇ CH 4 + 2H 2 0.
  • the division into the partial reactions and the associated spatial separation of the partial reactions prevents mixing of the products and educts of the partial reactions at the individual electrodes, ie at the anode and at the cathode. Accordingly, the synthesized methanol can be recovered directly at the cathode without mixing the methanol with the preferably aqueous electrolyte in the anode compartment, e.g. dilute sulfuric or hydrochloric acid. Accordingly, complicated steps for separation of the methanol from the electrolyte in the anode compartment or purification of the methanol can be dispensed with.
  • this is carried out in a reactor vessel, which is subdivided by the proton-conducting membrane into an anode space and a cathode space, wherein a pressure equalization is performed to compensate for differences in pressure of the electrolyte in the anode space and in the cathode space.
  • the pressure compensation is preferably carried out automatically by a connection of the anode compartment and the cathode compartment, this connection being arranged spatially in a region of the anode compartment and the cathode compartment, in which the electrolyte is present in gaseous form.
  • the carbon dioxide-containing electrolyte is almost pure carbon dioxide.
  • This carbon dioxide-containing electrolyte is the electrolyte in the cathode compartment.
  • the concentration of carbon dioxide is maximal, which maximizes the reaction rate.
  • methanol is not soluble as a reaction product at the cathode in such an electrolyte and precipitates accordingly.
  • almost pure carbon dioxide is to be understood as meaning a carbon dioxide concentration of more than 95% and preferably of more than 99%.
  • additives may be provided in the electrolyte, which serve to increase the electrical conductivity, in particular paratoluene sulfonic acid.
  • Paratoluene sulphonic acid has The advantage, for example, of adding quaternary ammonium salts as conductivity additive is that acids release protons as conductive positive ions, which not only promotes the electrical conductivity in general, but also specifically with regard to the ions which are directly involved in the chemical reaction.
  • the method can be present as the electrolyte liquid carbon using ionic or anionic surfactants and optionally suitable emulsifiers in the form of an emulsion.
  • ionic or anionic surfactants and optionally suitable emulsifiers in the form of an emulsion.
  • the preparation of an emulsion of the product water and the educt carbon dioxide has the advantage that the current density at the cathode can be increased.
  • this is carried out continuously by passing at least the carbon dioxide-containing electrolyte past the proton-conducting membrane.
  • a continuous implementation is industrially particularly useful.
  • discontinuous process management (batch operation) is also possible.
  • a device for carrying out the aforementioned method has a pressure-resistant reactor vessel for receiving a carbon dioxide-containing electrolyte in the liquid phase, at the critical point or in the supercritical phase of the electrolyte.
  • the device is characterized in that the reactor vessel of a proton-conducting
  • Membrane is divided into an anode compartment with an anode for receiving an aqueous electrolyte and a cathode compartment with a cathode for receiving the carbon dioxide-containing electrolyte. This results in the advantages mentioned in connection with the method.
  • the anode contains platinum (Pt) and / or ruthenium (Ru) or stainless steel.
  • the cathode preferably contains magnesium (Mg), copper (Cu), zinc (Zn), aluminum (Al), nickel (Ni), iron (Fe), titanium dioxide (TiO 2 ) or ruthenium (Ru). Combinations of the mentioned materials are also possible.
  • the materials mentioned are particularly suitable electrode materials with regard to their overvoltage potential.
  • the anode and the cathode are each applied in layers on one side of the membrane, so that a membrane electrode assembly (MEA) is formed.
  • the MEA is defined between contact plates with incorporated flow channels for the electrolytes. In this way, a particularly compact construction of the device can be achieved. In addition, the largest possible and lossless power supply to the electrodes via the contact plates is given.
  • a pressure equalization arrangement is provided to compensate for differences in pressure of the electrolyte in the anode compartment and in the cathode compartment. In this way, the proton-conducting membrane is protected from pressure differences which otherwise could occur in view of the relatively high operating pressures in the liquid phase, at the critical point or in the supercritical phase of the electrolyte.
  • the pressure compensation arrangement is formed by a connection of in the anode compartment and cathode compartment, said connection being spatially arranged in a region of the anode compartment and the cathode compartment, in which the electrolyte is present in gaseous form.
  • the connection comprises a pressure compensation line and / or a pressure compensation container which has an inner membrane which allows pressure equalization without material passage.
  • an equal pressure in the anode space and in the cathode space can also be achieved by a corresponding control of inlet and outlet valves which are arranged on the rooms.
  • Fig. 1 shows a first embodiment of a device for electrolytic
  • Fig. 2 shows a second embodiment of an apparatus for the electrolytic synthesis of methanol and Fig. 3 is a phase diagram of carbon dioxide.
  • FIG. 1 shows a schematic overview of a first embodiment of a device for methanol synthesis according to the method of the invention.
  • the apparatus comprises a pressure-resistant reactor vessel 1, which is subdivided by a proton-conducting membrane 2 into two reaction chambers, an anode chamber 3 and a cathode chamber 4.
  • the anode chamber 3 and the cathode chamber 4 receive an anode- or cathode-side electrolyte during operation of the device ,
  • the reactor vessel 1 is made of a stable, in particular friction-resistant material, which is chemically inert to the reaction educts and products used, for example of a stainless steel or of inertly coated materials.
  • the proton-conducting membrane 2 is advantageously a polymer membrane, such as that marketed by the company DuPont under the trade name "Nation.”
  • both the anode and cathode chambers 3, 4 are pressurized 2 through
  • the pressure equalization line 5 is preferably arranged in an upper region of the reactor vessel 1 in order to prevent thorough mixing of the electrolytes in the two chambers 3, 4.
  • overpressure valves 6, 7 are provided here in the area of the pressure equalization line 5 and in each case separately at the spaces 3, 4.
  • the device for a discontinuous implementation of the method is set up (batch mode).
  • the reaction chambers 3, 4 of the reactor vessel 1 are first filled with the respective electrolyte and then the electrolysis process started.
  • vent valves 8 are attached to each of the spaces 3.4 in the upper region of the reactor vessel.
  • the vent valve 8 When the vent valve 8 is open, the anode chamber 3 is first filled with an aqueous electrolyte.
  • a reservoir 34 for the aqueous electrolyte is provided which communicates with the anode chamber 3 via an inlet valve 35. is bound.
  • both vent valves 8 are closed.
  • Carbon dioxide is then introduced from a reservoir 44 as a cathode-side electrolyte via an inlet valve 45 into the cathode chamber 4.
  • a reservoir 44 for example, a carbon dioxide cylinder with liquefied CO 2 is used which has a carbon dioxide lifter. Carbon dioxide can thus be released in its liquid phase.
  • the inlet valve 45 By opening the inlet valve 45, the cathode space 4 is filled with CO 2 , wherein a pressure equalization takes place via the pressure equalization line 5 to the anode chamber 3.
  • a tempering device 36 and 46 is provided to set a desired temperature for the electrolyte 3, 4.
  • aqueous electrolyte in a liquid phase in the anode compartment 3 and carbon dioxide in the cathode compartment 4 in a likewise liquid, critical or supercritical phase.
  • the inlet valve 45 is closed.
  • the electrodes Via terminals 32 and 42, the electrodes can be acted upon externally with a voltage. By applying such a voltage, a current flow between the electrodes 31 and 41 and thus the electrolysis process begins.
  • the flow of electrons within the electrolytes takes place via ionic conduction, whereby only protons, ie positively charged hydrogen ions, pass over from the anode space 3 into the cathode space 4 due to the proton-conducting membrane 2.
  • the tempering device 46 is preferably designed as a combined heating and cooling device, for example by using a Peltier element.
  • Carbon dioxide has a critical point in its phase diagram at a temperature of 31, 5 degrees Celsius (° C) and a pressure of 74 bar (see also Fig. 3). At this point, liquid CO 2 becomes a supercritical phase, in which the medium exhibits both gas and liquid properties, fluid properties. Even in the supercritical phase, the carbon dioxide concentration in the cathode chamber 4 is high, so that operation of the device can also take place in this pressure / temperature range.
  • a conductivity additive can be added thereto, for example quaternary ammonium salts, but in particular paratoluene sulfonic acid.
  • Paratoluenesulfonic acid has proved to be more suitable as a conductivity additive than quaternary ammonium salts.
  • Paratoluene sulfonic acid has the advantage over quaternary ammonium salts that acids release protons as conductive positive ions, favoring not only the electrical conductivity in general, but also specifically with respect to the ions directly involved in the chemical reaction. When these first protons released by the acid are consumed at the cathode, they are replaced by the electrical termination of the proton-conducting membrane via the acid to the cathode.
  • the liquid carbon may also be in the form of an emulsion.
  • the preparation of an emulsion of the product water and the educt carbon dioxide offers the advantage that the current density at the cathode can be increased, since in a smaller space a high conductivity of the aqueous is present in the immediate vicinity of the carbon dioxide as a reaction partner. An increase in the current density generally results in an increase in the yield
  • the cathode 41 for example magnesium can be used, which has a low overvoltage potential and thus a high efficiency for the specified reaction.
  • Alternative and usable in combination cathode materials are Cu, Zn, Al, Fe, Ni, TiO 2 or Ru.
  • the cathode material may be used in the form of a granule or colloid.
  • a carrier material may be provided, to which the (active) electron material is applied.
  • the electrode material in the form of a colloid or granulate to be formed into a carrierless electrode 41 in a sintering process.
  • platinum Pt
  • Other known materials for this reaction for example, a platinum-ruthenium (Ru) mixture can be used.
  • stainless steel can 0 as a suitable and inexpensive electrode material for the anode
  • the methanol-water mixture can advantageously be used after storage and / or transport in just this mixture as the fuel of a DMFC fuel cell, and thus be used for power generation.
  • oxygen gas is formed in the anode chamber 3 at the anode 31.
  • This oxygen gas can already be removed during operation of the device by suitable actuation of the venting valve 8 of the anode compartment 3. are left so as not to increase the pressure in the reactor vessel 1 undesirably. Due to power losses during operation of the device heat is generated at the electrodes, which is absorbed by the respective electrolyte.
  • a tempering device 36 is also provided on the anode side.
  • Fig. 2 shows another apparatus for carrying out a method for the electrolytic analysis of methanol.
  • Identical reference signs in this figure denote the same or equivalent elements as in the first embodiment of FIG. 1.
  • the device shown here is not suitable for batch operation but for a continuous implementation of the method.
  • a reactor vessel 1 which is subdivided by a proton-conducting membrane 2 into two reaction spaces, an anode space 3 and a cathode space 4.
  • a cathode 41 is arranged as an electrode, wherein each one Anoden designated. Cathode terminal 32 and 42 are guided for contacting the electrodes 31, 41 to the outside.
  • the electrodes 31, 41 with the membrane 2 are combined to form a so-called MEA (Membrane Electrode Assembly).
  • MEA Membrane Electrode Assembly
  • the corresponding electrode material in colloidal form if appropriate with a carrier substance, for example graphite in likewise colloidal form, is applied to one side of the membrane 2 in each case. This may be done, for example, after slurry in a preferably volatile liquid in a spray or screen printing process.
  • formed on the respective side of the membrane 2 is a porous, electrically conductive layer of the carrier material with embedded electrode material, which provides a large surface area of the electrochemically active electrode material.
  • this electrolyte flow is in the direction of the reactor vessel 1 by the reference numeral 33 and back to the intermediate vessel 37 by the reference numeral 33 '
  • on the cathode side is the corresponding electrolyte flow in the cathode compartment with the reference numeral 43 and back from the cathode compartment 4 with the reference numeral 43rd 'marked.
  • pumps 39 and 49 are provided both for the flow 33, 43 to the reactor vessel and for the return flow 33 ', 43'.
  • the electrolytes are preferably kept under the same pressure and temperature conditions as used in the reactor vessel 1.
  • temperature control devices 36 and 46 are arranged in the intermediate containers 37, 47.
  • temperature control devices (not shown) for the reactor vessel 1 may be present in this figure.
  • electrolytes reference is made to the statements on the first exemplary embodiment.
  • the electrolysis device resulting reaction products in particular the resulting at the cathode side methanol-water mixture is removed via further pump 49 from the cathode chamber 4 and from the intermediate container 47, which is again utilized that the methanol / water mixture has a low solubility in which liquid carbon dioxide has, which is optionally used with conductive additives, as a cathode side electrolyte.
  • the methanol-water mixture precipitates accordingly and settles in the lower region of the cathode space 3 or of the cathode-side reservoir 47. It is collected in a reservoir 53 for further use.
  • the oxygen gas accumulating on the anode side in the anode chamber 3 and in the anode-side intermediate container 37 is conducted correspondingly via anode-side pumps 39 into an oxygen reservoir 62.
  • anode-side pumps 39 into an oxygen reservoir 62.
  • pressure sensors 38 and 48 are connected, which detect the present in the respective reaction chambers 3, 4 of the reactor vessel 1 pressures during operation.
  • the measured pressures are detected in a process control device, not shown, and used to control the pumps 39 and 49 or the valves used instead.
  • the control takes place in such a way that in the anode chamber 3 and the cathode chamber 4 as much as possible the same operating pressure is present.
  • the pressure set during operation depends in turn on the phase diagram of the electrolyte used on the cathode side, such that operation with liquid C0 2 or C0 2 in a supercritical phase or C0 2 at the critical point is achieved.
  • pressure equalization lines 5 lead from the reaction chambers 3, 4 of the reactor vessel 1 to a pressure equalization tank 9.
  • the pressure equalization tank 9 has an inner membrane that allows pressure equalization without material passage in a certain pressure range.
  • the anode compartment 3 and the cathode compartment 4 are shown as open spaces in which the corresponding electrolytes can move freely.
  • flow fields flow fields
  • Different configurations of the flow fields for example meandering or harp-shaped, are possible.
  • rectified or counter-directed or crosswise directed currents can be provided on the anode and cathode sides.
  • a metal plate in which the flow channels of the flow field are incorporated, serve as a current collector for the electrodes 31, 41.
  • the reactor vessel 1 is in this case formed by two such metallic contact plates with an interposed membrane or membrane-electrode unit (MEA), wherein the two metal plates serve as anode and cathode connections 32, 42 and are electrically insulated from one another by the interposed membrane 2 - are lier.
  • MEA membrane or membrane-electrode unit
  • a plurality of such arrangements can be stacked on top of one another, wherein the contact plates in the interior of the stack are then provided with flow channels on both sides and two adjacent cells are simultaneously assigned as so-called bipolar plates.
  • a pulsed power supply may be used in which the current between two values, one smaller than the other, may be zero or even negative (reversed).
  • the pulsed power supply may on average be associated with more effective implementation and higher efficiency.
  • a brief operation of the arrangement with a reversed power supply is used for catalyst purification and / or regeneration.
  • the build-up barrier can be broken.
  • a higher efficiency is achieved.
  • the operation with reversed power supply can be done regularly or as needed. In the latter case, it may be provided to carry out a cleaning step by reversing polarity when, during operation, the values of electrolysis current and voltage indicate sinking effectiveness, for example when an increasing voltage is required to achieve a specific, predetermined current flow.
  • FIG. 3 shows a phase diagram for carbon dioxide.
  • phase boundary in the form of a solid gas 71 marks the transition from the solid to the gaseous state of aggregation up to a triple point 72.
  • a phase boundary solid-liquid 73 characterizes the transition from the solid to the liquid state of matter and a phase boundary liquid-gaseous 74 Transition from the liquid to the gaseous state.
  • the phase boundary liquid-gaseous 74 passes into a phase boundary supercritical-gaseous 76, which indicates the transition from the supercritical to the gaseous state of matter.
  • a reaction region 77 is limited.
  • reaction region 77 is the electrolyte carbon dioxide in the range according to the invention to convert it to methanol.
  • the method according to the invention and the device according to the invention can be used for the production of methanol and / or methane as energy sources and / or crude products of the chemical industry, for example by producing the mentioned products where a lot of regenerative energy from sun, wind or tides can be won.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de synthèse par électrolyse du méthanol par réduction d'un dioxyde de carbone contenu dans un électrolyte en phase liquide, au point critique ou en phase supercritique de l'électrolyte. Le procédé est caractérisé en ce que des protons sont introduits dans l'électrolyte à travers une membrane (2) conductrice de protons pour la réduction du dioxyde de carbone. L'invention concerne également un dispositif permettant la mise en oeuvre dudit procédé.
PCT/EP2013/061303 2012-05-31 2013-05-31 Procede et dispositif de synthèse par électrolyse du méthanol et/ou du méthane WO2013178803A1 (fr)

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Cited By (1)

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WO2016188829A1 (fr) * 2015-05-22 2016-12-01 Siemens Aktiengesellschaft Système d'électrolyse destiné à une valorisation du dioxyde de carbone par voie électrochimique, et pourvu d'une unité donneur de protons, et procédé de réduction

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DE102016211824A1 (de) * 2016-06-30 2018-01-18 Siemens Aktiengesellschaft Anordnung für die Kohlendioxid-Elektrolyse
DE102017201988A1 (de) 2017-02-08 2018-08-09 Siemens Aktiengesellschaft Gepulste Elektrolyse mit Bezug auf die Leerlaufspannung

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2016188829A1 (fr) * 2015-05-22 2016-12-01 Siemens Aktiengesellschaft Système d'électrolyse destiné à une valorisation du dioxyde de carbone par voie électrochimique, et pourvu d'une unité donneur de protons, et procédé de réduction
CN107849714A (zh) * 2015-05-22 2018-03-27 西门子公司 具有质子供体单元的用于电化学利用二氧化碳的电解系统和还原方法
RU2685421C1 (ru) * 2015-05-22 2019-04-18 Сименс Акциенгезелльшафт Электролизная система для электрохимической утилизации диоксида углерода с протонодонорным блоком и способ восстановления

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