WO2014207279A1 - Procédé d'obtention de gaz de synthèse - Google Patents

Procédé d'obtention de gaz de synthèse Download PDF

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Publication number
WO2014207279A1
WO2014207279A1 PCT/ES2014/070470 ES2014070470W WO2014207279A1 WO 2014207279 A1 WO2014207279 A1 WO 2014207279A1 ES 2014070470 W ES2014070470 W ES 2014070470W WO 2014207279 A1 WO2014207279 A1 WO 2014207279A1
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electrochemical cell
conductor
alcohol
gaseous
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Spanish (es)
Inventor
Antonio DE LUCAS CONSUEGRA
Jesús GONZÁLEZ COBOS
José Luís VALVERDE PALOMINO
Carmen JIMÉNEZ BORJA
Nuria GUTIÉRREZ GUERRA
José Luís ENDRINO ARMENTEROS
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Abengoa Research SL
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Abengoa Research SL
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using oxygen; using mixtures containing oxygen as gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • 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
    • 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
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a process for obtaining synthesis gas (H 2 / CO) with a controllable ratio by means of a catalytic and electrochemical process using an electrochemical cell formed by anionic or cationic conductive solid electrolytes.
  • the control of the H 2 / CO ratio is carried out in a single stage under constant operating conditions, that is, at a constant temperature of the electrochemical cell and constant conditions of composition and concentration of the input current.
  • the present invention is encompassed in the technical field of synthesis gas production and for its use in the petrochemical industry or in the production of fuels.
  • the synthesis gas (mixture of H 2 / CO) is known to have a wide variety of applications in the petrochemical industry.
  • synthesis gas can be used in the production of ammonia or methanol.
  • synthesis gas can be used as an intermediate product in the production of synthetic gasolines, for use as fuel or lubricant through the Fischer-Tropsch synthesis.
  • the required H 2 / CO ratio is typically 2.
  • processes within the petrochemical industry such as oxo-synthesis processes that require lower H 2 / CO ratios, between 1 and 2, or even pure carbon monoxide (CO), as occurs in carbonylation processes.
  • hydrogen (H 2 ) of high purity is required, such processes are for example reactions of hydrogenation, interesting in this case to obtain an H 2 / CO ratio greater than 2, as high as possible.
  • the synthesis gas is generally obtained at the industrial level by catalytic processes of reforming or partial oxidation of hydrocarbons, mainly from methane (EP0168892 A2). This type of process allows obtaining a fixed H 2 / CO ratio and typically of 3. In order to obtain a different H 2 / CO ratio, additional purification, separation and conversion steps are necessary, such as: water displacement reactions in gaseous state ( denominated in English water gas shift), processes of adsorption under pressure or preferential oxidation of CO. These additional stages, prior to the synthesis process, imply a greater complexity of the process as well as higher production costs of the final product.
  • H 2 / CO ratio can be controlled in these processes by adjusting the operating conditions such as the temperature at which the synthesis is carried out or the relationship between the starting hydrocarbon and the added O 2 .
  • the complexity and costs of these processes are high because the temperatures used are usually high, greater than 1000 ° C and reactors of two gas inlets and two gas outlets are required to work in double atmosphere [US47993904].
  • the present invention relates to a process for obtaining synthesis gas (H 2 / CO) with a controllable ratio by means of a catalytic and electrochemical process using an electrochemical cell formed by ionic, anionic or cationic conductive solid electrolytes.
  • the control of the H 2 / CO ratio is carried out under constant conditions of operation, that is, at constant temperature of the electrochemical cell and constant conditions of composition and concentration of the input current.
  • the inlet stream is selected from a gaseous stream of light hydrocarbons together with a stream of water vapor, or a gaseous stream containing at least one (C 1 -C 3) alcohol.
  • light hydrocarbons are meant those organic chemical compounds formed solely of hydrogen and carbon (C1-C4), including natural gas.
  • Natural gas is a combustible gas that comes from geological formations, which is why it constitutes a non-renewable energy source.
  • natural gas can contain carbon dioxide, ethane, propane, butane and nitrogen, among other gases.
  • the light hydrocarbons are selected from the list comprising methane, ethane, propane, butane, natural gas or any combination thereof.
  • the solid electrolyte conductor is an anionic conductive material, for example oxygen ion conductor (O 2 " ), in the present invention it comprises at least one electrode selective for the electrolysis of the water and at least one selective counter electrode to the reforming reaction and to the partial oxidation of the input current of the electrochemical cell.
  • O 2 " oxygen ion conductor
  • the addition of gaseous streams of humidified hydrocarbons or of alcoholic gas streams, together with or without a stream of water vapor, will allow in addition to the synthesis gas obtained by conventional catalytic reforming in the electrochemical catalyst will produce additional electrocatalytic processes that allow to control the final H2 / CO ratio under constant conditions, that is, at constant temperature of the electrochemical cell and constant conditions of composition and concentration of the input current.
  • the electrochemical cell when the electrochemical cell is at a temperature between 300 ° C and 980 ° C, and under constant conditions of composition and concentration of the input current, the catalytic process of reforming on the selective counter electrode takes place. process. Additionally, under the application of electric current, the electrolysis reaction occurs with the consequent production of H 2 .
  • the O 2 ions generated in the electrochemical reaction are transported by the solid electrolyte conductor to the counter electrode that acts as a catalyst for the electrocatalytic oxidation of the inlet current and CO with the consequent production of synthesis gas (H 2 / CO
  • the counter electrode that acts as a catalyst for the electrocatalytic oxidation of the inlet current and CO with the consequent production of synthesis gas (H 2 / CO
  • synthesis gas H 2 / CO
  • the CO can be oxidized to CO 2 by electrochemical oxidation, which allows a net control of the H 2 / CO ratio of the synthesis gas produced by controlling the speed of each of the processes with the electrical intensity. It is the intensity of applied voltage that allows controlling the electrochemical speed of the mentioned processes.
  • the solid electrolyte conductor is a cationic conductive material, for example sodium ion conductor Na + and potassium K +
  • it comprises a selective catalyst electrode to the process of reforming the inlet current of the cell electrochemistry and a metallic counter electrode. This configuration allows the process of reforming the input current to be promoted electrochemically, by sending promoter ions from the cationic conductive material to the selective electrode of the reforming process.
  • the presence of electro-positive ions for example of Na + and K + ions in the catalytic electrode favors chemisorption of electronegative molecules such as water versus hydrocarbon or alcohol that form the input stream.
  • the controllable adsorption of the inlet current is carried out by varying the electric potential that varies the content of the promoter sent to the catalyst electrode, making it possible to control the degree of decomposition of the inlet current and the degree of the reforming process, with it the H 2 / CO ratio of the resultant synthesis gas obtained.
  • a solid cationic electrolyte conductor Na + or K + conductor
  • the final adjustment of the H 2 / CO ratio is produced by the sending of ionic promoters (Na + or K + ) by current electrical to the catalytic electrode that modify the adsorption of water in the active centers and with it the kinetics of the catalytic process. This occurs under a constant concentration of the input current and a specific operating temperature of the electrochemical cell.
  • the main advantages with respect to conventional reforming techniques is, firstly, that it is not necessary to incorporate a pure 0 2 current in the electrochemical cell since it is produced in situ during the electrolysis process, avoiding this mode additional pre-stages such as for example the additional preliminary separation of N 2 from the air.
  • the electrochemical cell that can be used is simple, does not require complex atmospheric separation chambers.
  • the control of the H 2 / CO ratio is carried out by means of a variation of the voltage applied to the electrodes that allows the control of the electrochemical processes.
  • the operating conditions are constant, the synthesis is carried out at a constant temperature and at a low temperature in comparison with those used in conventional techniques.
  • the inlet stream is not only limited to wet gaseous light hydrocarbons, gaseous streams of pure or moist alcohols can also be used.
  • a first aspect of the invention relates to a process for producing synthesis gas, of controllable H 2 / CO ratio, comprising the passage of an input current selected from a gaseous stream of light hydrocarbons and a stream of water vapor, or a gaseous stream containing at least one (C1-C3) alcohol to an electrochemical cell which is at a temperature between 300 ° C and 980 ° C, characterized in that said electrochemical cell contains a solid electrolyte conductor ion to which a potential between -3 and +3 volts is applied.
  • electrochemical cell in the present invention a device capable of transforming an electric current into a chemical oxidation-reduction reaction that does not occur spontaneously.
  • the electrochemical cell also refers in the present invention to an electrochemical reactor suitable for industrial use in any configuration known to any person skilled in the art, such as, for example, an electrochemical reactor with a tubular or monolithic configuration.
  • the inlet stream does not contain pure O2.
  • the inlet stream is diluted in an inert gas stream, where the inert gas is selected from the list comprising nitrogen (N 2 ), helium (He), neon (Ne), argon (Ar), krypton (Kr). ) and xenon (Xe).
  • the inert gas stream is N 2 .
  • the inlet stream can be diluted up to 98% by volume in said inert gas stream.
  • the electrochemical cell is at a temperature between 500 ° C and 900 ° C.
  • the applied potential is between -2.5 and +2.5 volts. More preferably, between -2 and +2 volts.
  • the gaseous light hydrocarbons are selected from the list comprising methane, ethane, propane, butane, natural gas or any combination thereof.
  • the light hydrocarbon is a combination of light hydrocarbons comprising at least methane.
  • the light hydrocarbon is natural gas.
  • the proportion of light hydrocarbon and water vapor depends on the hydrocarbon used, for example, in case the hydrocarbon is methane, the preferred ratio will be about 1: 3.
  • the alcohol is selected from the list comprising methanol, ethanol, propanol or any combination thereof. More preferably, the alcohol is methanol or ethanol.
  • the alcohols can be bioalcohols obtained by the action of a microorganism or by some other biotechnological process.
  • alcohols can be used from residual streams of alcohols with high graduation, up to 90 ° C.
  • a stream of water vapor is added.
  • gaseous inlet streams of hydrocarbons or of alcohol and water vapor can be mixed before passing into the electrochemical cell or they can pass without previously mixing.
  • gaseous hydrocarbon or alcohol streams and the water vapor stream are mixed before passing to the electrochemical cell.
  • the solid ionic electrolyte conductor is an anionic conductor that conducts oxygen ions (O2 " ).
  • the anionic conductor comprises a solid electrolyte selected from zirconium oxide, titanium oxides, yttrium oxide stabilized with zirconium oxide, zirconium oxide stabilized with calcium, perovskites with mixed conductivity or any combination thereof .
  • the anionic conductor comprises at least one electrode selective to the electrolysis of water and at least one counter-electrode selective to the reforming reaction and to the process of partial oxidation of the Input current.
  • the electrode selective to the electrolysis of water is platinum (Pt).
  • the selective counter-electrode to the reforming reaction of the input stream is selected from nickel (Ni), platinum (Pt), palladium (Pd) or any combination thereof.
  • the electrochemical cell containing an anionic conductor as described above is at a temperature of between 700 and 900 ° C when the inlet stream is a gaseous stream of light hydrocarbons and a stream of water vapor.
  • the electrochemical cell containing an anionic conductor as described above is at a temperature of between 500 and 750 ° C when the inrush current is a gaseous stream containing at least one (C1-C3) alcohol.
  • the solid ionic electrolyte conductor is a cationic conductor.
  • the inlet stream in this case is also formed by a gaseous stream of light hydrocarbons and a stream of water vapor, or a gaseous stream containing at least one alcohol (dC 3).
  • the gas stream containing at least one (C1-C3) alcohol must also contain a stream of water vapor.
  • the cationic conductor conducts sodium ions Na + or potassium K + .
  • the cationic electrolyte is selected from Na- ⁇ -0 2 0 3 , ⁇ - ⁇ - ⁇ 2 0 3 , NASICON, LISICON or any combination thereof.
  • the cationic conductor further comprises at least one metal electrode selective to the process of reforming the inlet stream and at least one metal counter electrode.
  • the metallic electrode selective to the process of reforming the input current is platinum (Pt).
  • the metal counter electrode is gold (Au).
  • the electrochemical cell containing a cationic conductor as described above, is at a temperature between 700 and 900 ° C when the inlet current is a gaseous stream of light hydrocarbons and a stream of water vapor .
  • the electrochemical cell containing a cationic conductor as described above, is at a temperature between 500 and 750 ° C when the inlet current is a gas stream containing at least one (C1-C3) alcohol ) and that adds a stream of water vapor.
  • the voltage source used to apply the aforementioned voltage to the electrochemical cell can be a conventional source with fossil or nuclear energy origin or a renewable source using, for example, hydraulic, solar, wind, geothermal, marine and / or biomass energy .
  • the method uses a conventional or renewable source for the application of the potential. More significantly, the procedure uses a conventional source.
  • FIG. one Representation of an electrochemical cell that uses an ionic solid electrolyte conductor, which can be both anionic and cationic.
  • FIG. 2 Schematic representation of a solid electrolyte conductor acting as an anionic conductor comprising an anionic solid electrolyte, an electrode selective to the electrolysis of water and a counter electrode selective to the reforming reaction and to the partial oxidation of the input current.
  • FIG. 4 Dynamic graph showing the different H 2 / CO ratios obtained according to the applied potential in a given period of time
  • FIG. 5 Schematic representation of a solid electrolyte conductor acting as a cationic conductor comprising a cationic solid electrolyte, a metal electrode selective to the process of reforming the input current and a metal counter electrode.
  • FIG. one shows the configuration of a laboratory electrochemical cell that uses ionic solid electrolyte conductors, both anionic (9) and cationic (10).
  • This cell consists of the following elements:
  • the anionic (9) and cationic solid electrolyte conductors (10) are inside the quartz tube (8) that limits the area where the H 2 / CO controlled synthesis gas is produced and the additional electrocatalytic processes in phase soda.
  • This quartz tube (8) is closed by a metal cover (4) that couples a perforated alumina tube (6).
  • the working electrode (1) and the counter electrode (2) are connected with the anionic (9) or cationic (10) solid electrolyte conductors through this perforated alumina tube (6), the potential is applied to these electrodes (1 ) and (2).
  • the different temperatures that are reached in the cell electrochemistry are achieved by the cooling coil (5) coupled to the metal cover (4) and by gold wires (7) that act as thermal conductors and that are introduced into the cell through the alumina tube.
  • the input current is introduced through the gas inlet (11) and the synthesis gas produced is collected through the gas outlet (3).
  • Selective counter electrode to the reforming process and partial oxidation of the input current is platinum (Pt)
  • FIG. 2. shows a schematic representation of an anionic conductor comprising an anionic solid electrolyte which acts as a YSZ-type conductor of O 2 " ions and which further comprises a working electrode selective to the electrolysis of water (13) and a selective counter-electrode to the reforming reaction and partial oxidation of the input stream (12).
  • Both electrodes are connected to a power supply that allows the application of electrical intensity to the system and, therefore, allows the control of the composition of the synthesis gas under fixed conditions of operation (operating temperature of the electrochemical cell) and reaction (composition and concentration of the input current of the electrochemical cell).
  • the coupling of the electrolysis process to the catalytic reforming process allows to carry out the additional production of H 2 as well as the partial oxidation of the hydrocarbon (and therefore the adjustment of the ratio) without the need to feed pure oxygen to the electrochemical reactor (avoiding previous stages). of separation of the same from the air).
  • the 0 2 is generated in-situ in the process itself, which allows the presence of secondary reactions of total and partial oxidation.
  • FIG. 4. shows the ratios of H 2 , CO and C 0 2 versus the time obtained using the configuration of the electrochemical cell described in this example.
  • OCP refers to the state of the open circuit in which the electrochemical cell is located when no potential is applied.
  • the H 2 / CO ratio remains practically constant.
  • an immediate response is observed, less than 5 minutes, which corresponds to the drastic increase in the H2 / CO ratio as a function of the applied voltage.
  • an electrochemical cell is used as shown in FIG. one . with a solid cationic electrolyte conductor as shown in FIG. 5. to produce synthesis gas.
  • the cationic solid electrolyte shown in Figure 5 consists of the following elements:
  • Electrode working platinum selective to the process of reforming the input current for example CH 4 + H 2 0 ⁇ H 2 , CO, C0 2 )
  • FIG. 5. shows a schematic representation of a cationic solid electrolyte (17) which acts as conductive type Na-p-AI 2 03 Na + and comprising a selective electrode reforming process stream inlet (15) and Au counter-electrode (16).
  • the electrodes are connected to a power supply that allows the application of the electrical intensity to the system and, therefore, allows the control of the composition of the synthesis gas under fixed conditions of operation (temperature of operation of the electrochemical cell) and reaction (composition and concentration of the input current of the electrochemical cell).
  • the control of the quantity of sodium ions Na + promoters sent to the catalyst electrode is carried out by means of the controlled application of electric current that allows to control the adsorption of the species that participate in the catalytic process and therefore the ratio of synthesis gas produced .
  • FIG. 6 The variation of the H 2 / CO ratio is shown as a function of the applied potential for different reaction temperatures from a humidified methane stream. This figure shows that the voltage variation allows control of the H 2 / CO ratio.
  • the H 2 / CO ratio values obtained in this electrochemical cell comprising a solid cationic electrolyte conductor range between 6 and 30 for a temperature range between 450 ° C and 550 ° C.
  • an electrochemical cell is used as shown in FIG. one . with the solid anionic electrolyte conductor that is described in example 1 and is depicted in FIG. 2 to produce synthesis gas.
  • FIG. 7 It can be observed how the H 2 / CO ratio obtained can be varied depending on the potential and the different reaction temperatures applied. This figure shows that the voltage variation allows control of the H 2 / CO ratio.
  • the H 2 / CO ratio values obtained in this electrochemical cell comprising an anionic solid electrolyte conductor range between 2.4 and 9.13 for a temperature range between 500 ° C and 600 ° C. Examples 1 to 3 provided by way of illustration are not intended to be limiting of the present invention. Although they refer to a laboratory-sized electrochemical cell, this cell could be replaced by tubular configurations or monolithic reactor-type configurations (called Monolithic Electro-promoted reactor) on an industrial scale.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Electrochemistry (AREA)
  • Automation & Control Theory (AREA)
  • Hydrogen, Water And Hydrids (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 d'obtention de gaz de synthèse (H2/CO) à rapport ajustable au moyen d'un processus catalytique et électrochimique qui utilise une cellule électrochimique formée par des électrolytes solides conducteurs ioniques, anioniques ou cationiques. L'ajustement du rapport H2/CO est réalisé en une seule étape dans des conditions constantes de fonctionnement, c'est-à-dire, à température constante de la cellule électrochimique et dans des conditions constantes de la composition et de la concentration du flux d'entrée. Selon la présente invention, le flux d'entrée est sélectionné entre un flux d'hydrocarbures légers et un flux de vapeur d'eau ou un flux gazeux qui contient au moins un alcool (C1-C3).
PCT/ES2014/070470 2013-06-28 2014-06-06 Procédé d'obtention de gaz de synthèse Ceased WO2014207279A1 (fr)

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ESP201330975 2013-06-28
ES201330975A ES2525957B1 (es) 2013-06-28 2013-06-28 Procedimiento de obtención de gas de síntesis

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Citations (6)

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US4793904A (en) 1987-10-05 1988-12-27 The Standard Oil Company Process for the electrocatalytic conversion of light hydrocarbons to synthesis gas
US6287432B1 (en) * 1987-03-13 2001-09-11 The Standard Oil Company Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions
US20040180249A1 (en) * 2003-03-12 2004-09-16 The Regents Of The University Of California System for the co-production of electricity and hydrogen
US20070131909A1 (en) * 2005-11-04 2007-06-14 Alexandre Rojey Process for the production of synthesis gas from carbon-containing material and electrical energy
WO2008033452A2 (fr) * 2006-09-13 2008-03-20 Ceramatec, Inc. Appareil et procédé de co-génération d'hydrogène de haute pureté et d'énergie électrique

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Publication number Priority date Publication date Assignee Title
US5714091A (en) * 1987-03-13 1998-02-03 The Standard Oil Company Process for the partial oxydation of hydrocarbons
ID20211A (id) * 1997-04-29 1998-10-29 Praxair Technology Inc Metoda produksi hidrogen dengan menggunakan membran elektrolit padat

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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