WO2016178590A1 - Réduction électrochimique du dioxyde de carbone dans un liquide ionique aqueux contenant des électrolytes - Google Patents

Réduction électrochimique du dioxyde de carbone dans un liquide ionique aqueux contenant des électrolytes Download PDF

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WO2016178590A1
WO2016178590A1 PCT/PT2016/000002 PT2016000002W WO2016178590A1 WO 2016178590 A1 WO2016178590 A1 WO 2016178590A1 PT 2016000002 W PT2016000002 W PT 2016000002W WO 2016178590 A1 WO2016178590 A1 WO 2016178590A1
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Prior art keywords
ionic liquid
electrochemical
catalytic
cathode
zinc
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PCT/PT2016/000002
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English (en)
Inventor
Tiago Da Costa Duarte Pardal
Ana Maria STAACK REIS-MACHADO
Sofia Alexandra PEREIRA MESSIAS
Margarida BUCHO NUNES DE SOUSA
Tomás Cláudio REI FERNANDES
Joana DA COSTA FRANCO AFONSO
Manuel Luís DE MAGALHÃES NUNES-DA-PONTE
Zeljko PETROVSKI
Daniela DA SILVA NUNES GOMES
Rodrigo FERRÃO DE PAIVA MARTINS
Carmen Mireya RANGEL ARCHILA
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Omnidea, Lda.
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Priority claimed from PT108442A external-priority patent/PT108442A/pt
Application filed by Omnidea, Lda. filed Critical Omnidea, Lda.
Priority to EP16726983.6A priority Critical patent/EP3292231B1/fr
Publication of WO2016178590A1 publication Critical patent/WO2016178590A1/fr

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00Electrolytic production of organic compounds
    • C25B3/20Processes
    • C25B3/25Reduction
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0668Removal of carbon monoxide or carbon dioxide
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Definitions

  • the present invent on relates to a catalytic system that is able to produce different chemical products by direct electrochemical reduction of carbon dioxide by controlling easily tunable parameters, ,soch as applied enrre tfootentiai, pressure, temperature, electrolyte composition and nature of the cathode at temperatures from room temperature up to ⁇ and pressures from atmospheric pressure up to 100 bar.
  • These chemical products are alcohols with one to ten carbon atoms, ketones op to four carbon atoms and s ngas.
  • the catalytic system comprises a catal tic cathode coupled to an ionic liquid-based electrolyte- containin water and dissolved CO2.
  • This gaseous mixture consists primarily of hydrogen, carbon monoxide and some carbon dioxide. It has approximately half of the energetic density of natural gas,
  • coal gasification was used to supply most of the syngas
  • tha was used for illumination- and heating.
  • syngas started to be used for the synthesis of fuels and chemicals.
  • Carbon monoxide is used in the chemical synthesis of several products including pharmaceutical products, in which their synthesis involves carbon yl art on and hydroformylation reaetions oreover it can be reacted- with water through the water gas shift reaction (WGS) to produce hydrogen. It has been forecasted that the world demand for carb n monoxide will increase with the development of the so called Ci chemistry. Thus, syngas composed mainly of CO and small quantities of hydrogen (i.e. low .3 ⁇ 4 €0 ratios) may also be used i such applications .
  • synga can be produced from any raw-material containing hydrocarbons including natural gas, naphtha, residual oil, petcoke, coal and iomass.
  • methanol, ethanol and 2 ⁇ propanol ail have quite high energy densities of 6.09, 8.00 and 8.58 fcW h kgl, respectively, and are comparable to hydrocarbons and gasoline, which have energy densities of 10 and 1 1 kW h kg s , respectively (YH. Chu , YG S Shuk, International Journal of Hydrogen Energy 20 i0;35: ri 23 ⁇ 4! e70).
  • ethanol can be produced directly from syngas, but it is typically indirectly produced by methanol homologation.
  • acetone is produced -mainly for use as a solvent for the production of methyl ntefhacrykte and h ' isphenol A and is also synthesized fr m fossil fttei derived products! About 6,7 million tonnes were produced worldwide in 2010 (World 3 ⁇ 4tr chemicals report, ⁇ January 2010) , Botanone is also used as a solvent, and as a plastic welding agent.
  • thermolysis thermolysis
  • thermochemicai cycles electrochemical reduction and photo-reduction.
  • These technologies may be classified as high temperature technologies (temperatures typically higher than 60 ( €, such as in thermolysis, and thermochemical cycles) and low temperature technologies.
  • Materials for reactors must comply with tight requirements and are generally expensive.
  • One of the consequences of high temperature operation is decreased life time of equipment and may lead to degradation of electrode structure- through sintering and agglomeration,
  • Electrochemical reduction of COz is an attractive technology from the point of view of its simplicity
  • the reduction is carried out in single step, and reaction products may be liberated separately in the cathodie compartment and in the anodic compartment of the electrochemical cell.
  • This type of technology is ideal for mass roduction and tor autom ti ed maintenance.
  • State-of the art electrochemical processes still present several limitations that have prevented its utilization at an industrial scale.
  • the parameters that determine the industrial applicability of this type of process are (i) &rsdaie efficiency, a measufe.of the selectivity of the process for -a certai product, (ii) current density, thai is a measure of conversion rate, (j ' ii) energetic efficiency that i a measure of the energy that is consumed for transformation, into a certain product (iv) catalytic stability and (v) process costs.
  • the first four parameters must. be simultaneously high, whilst the fifth should, be low.
  • Room temperature ionic liquids are generally defined as organic salts that are liquid at -temperatures below tCXfC.
  • the possibility of ionic liquids to absorb COj both physically ( L A . Bianchard, I>. Hancu, EJ. Beckman, j.F. Brersneeke, 1999, Nature 399, 28-29) and chemically (L. E,
  • ITS convert carbon .dioxide in another substance, when a sufficient voltage is applied.
  • One of the reactions that the sensor ca use to measure amounts concentrations of Ct3 ⁇ 4 is the reduction of € €.1 ⁇ 2 to carbon monoxide.
  • this document is not relevant t the invention, since the technological requirements for a sensor with these characteristic are quite different from th requirements that an industrial process must comply with in terms of current densities and
  • Tliese sensors utilize typically a metallic cathode and an electrolyte that can be comprised of an ionic liquid.
  • the innovative catalytic system of the present invention is no disclosed in this document. Di. Meglio e al. (I L DiMeglio and J. Rosenthal. J Am Ckem. Sew,, 2013,. 135, 8798-8801 , WO201.4/161262A.I) have reported that an economical bismuth- based material could promote the electrochemical conversion of CO 2 to CO at overpotentiais
  • GDE Gas diffusion electrodes
  • Electrochemical reduction eaci ns of carbon di xide can be written as multiple proton-etectmn reactions leadtog to several products and water; k Oz + n H : r ne ->P - mHjjO i 1)
  • the presen invention uses reaction of the type illustrated b reactions ⁇ 1-4 ⁇ coupled to water eleeuolysis to pod e the a&i ' emenhoned chemical products at the cathode.
  • Reaction 3 exemplifies die lormadon othdcohrns gsviog ethanoi as example: li.Q: ⁇ - 121-1 ⁇ c ⁇ c>H il ⁇ 3 ⁇ 4 ⁇ ;H.:0 p)
  • Reaction 4 exem li tes the ⁇ formation of ketones giving acetone as example:
  • the ener eceded for the process Is usually high, and the -current energy efficiency as well as yield of the desired product are generally low CGsitreiL y Gupta, M, (X), A I. HIeciroanaf. Chenr 206, 504, l ⁇ 19).
  • electrochemical catalysts that are able to reduce the overpotendais observed typically la electrochemical reducto tecbiti)lo y.
  • this catalytic system comprises a catalytic cathode and an electrolyte, in which the component(s) of the electrolyte allow the stabilization of the intermediary species in electrochemical reduction of CCfo thereby achieving a reduction of the activation energy of the reactions l.e in the overpotentlai .
  • thermodyn mic equilibrium potential fo a .certain reduction or osldatlon reaction and the potential at which the reaction is observed experimentally.
  • flic tents ionic liquid, or room temperature ionic liquid
  • salts or ionic compounds which form stable liqmds at temperatures lower than I ⁇ MFC.
  • deep euieehc solvents 1 ' when, used herein is to be understood as an ionic liquid that comprises a mixture forming an eutechc with a melting point lower than the melting points of the individual components.
  • regenerative system when used herein is o be understood as a electrolyse? or fuel cell that can be run in reverse mode.
  • the eiectioiysemiuei cell w3 ⁇ 4en run in the direct, or reverse mode may use the same or different electrodes.
  • the system can be composed of an electrolyse*' plus- a fuel cell
  • catalytic system comprising a catalytic cathode coupled to a hydrophsSic ionic liquid-based electrolyte containing water and dissolved €02..forming ' single phase, in which the molar fraction of ionic liquid lies in the range 0, 1 -0.6 32o and eventually an additive could produce alcohols with one to ten carbon atoms, such as methanol, ethane!
  • the catalytic cathode cam comprise €, Ti, V, €r, Mix Fe, Co, Ni, €u, Zn, Zr, Mb, Mo, l u, Rh, 325 Pd, Ag, Cd, in, Sn, Bf, Ta, W, Re, Ir, Pi, Au s Ai, Si, Ti, Bi or their mixtures in -every proportions, or alloys, in particular coppcr-zirte alloys, zinc alloys, nickel alloys, copper-nickel, zinc-nickel alloy several types of stainless steel, or by their xides, mixtures of their oxides, or mixtures of metallic oxides with aforementioned metals, in the form of bulk materials, coatings, particulate materials, including nanomaterials, unsupported, or supported on conductive materials, having 330 the cathodes preferentiall high electrochemical surface areas. Copper-zinc alloys, zinc alloys, nickel alloys, copper-nickel alloys are specially preferred.
  • the ionic liquids to be used by the present invention to produce alcohols and/or ketones are currently known, ionic liquids in which carbon dioxide is soluble, or ionic liquids that will be developed.
  • the ionic liquids of the present invention are not limited to single charged ionic 335 species, they may consist of multi-charged anions and cations, where the charge of the cations and of the anions the same or different complying with molecular electro-neutrality- They include for example, cations belonging to the irnida£oi:ium family, in -particular 1,3 substituted imidazoiiu.ms with the same of different subst!tuents, pyridimom., pyrroSidi nium, phosphoniu.m, ammonium, sulphonium, cholines, acethyl cholines, prolinat.es.
  • peota-fluoro-propanoate 345 peota-fluoro-propanoate, sulfamates, carbamates, hidrogenocarbonaies, cyanides, conjugated bases of aminoacids, hetudmida ⁇ olidnt s, pyrrol ides and fiuor nated pyraaolides.
  • the organic additive may be an organic solvent, such as acetonitrile, dimethylformamide., dimethyl sulfoxide, polycarbonates, alkylcarbonates, cyclic carbonates, polyethylene glycol, and mixtures of these compounds, amines, phosphines, and in which said additive is resent In the
  • the process according to the invention ma be carried out by applying a potential more positive then the reduction potential of the compounds to be produced at the cathode.
  • the process can be carried out in continuous, semi -continuous, or in batch mode.
  • 3S5 Figure I resents a simplified schematic of the process for the production of chemical products by electrochemical reduction of €02.
  • 3 ⁇ 0 liquid products resulting from the process are Ci-Cu alcohols and ketones up to four carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol, hexano!, octanol, decanoi, or their isomers, acetone, hutanone etc.
  • the gaseous product resulting from the electrolysis Is syngas.
  • the selectivity of the electrochemical reduction of COj can be controlled by the choice of the catalytic cathode composition, electrolyte composition, temperature, pressure,
  • Another aspect of the present invention is the use of the solvent properties of snbcritieal, or supercritical carbon dioxide to promote and facilitate the separation of the electrolysis products.
  • another object of the invention is the coupling of ionic liquid extraction with high-pressure carbo dioxide extraction, exploring synergies of these two achieve a lower cost and high efficient separation of electrolysis
  • 395 alcoholic mixture is ⁇ oxidized at the anode of the fuel cell producin : electrons ' ⁇ electricity), and carbon dioxide.
  • the oxygen produced at the anode in the electrochemical reduction of € ( 3 ⁇ 4 containing eventually inert gas will be reduced at the cathode of the fuel cell producing water.
  • the €02. and water pro uced by the fuel cell are in urn, the feed of the €0 ; ⁇ , eiectroiyser.
  • the electric vehicle is supplied with alcohol, CO- produced is captured and stored in a pressure- vessel to be again converted in alcohols that can he supplied to -tank station.
  • This regenerative system allows establish, a carbon, neutral cycle in icons of carbon d oxide emission :.
  • the electrolyte is water with a supporting salt that is not an ionic liquid.
  • a supporting salt that is not an ionic liquid.
  • This application aims also at protecting the use of cathodes made of copper allo s in the referred process.
  • a synergic effect ' between copper and zinc and the electrolyte of the present invention Is not described. It is gi ven as example Faradaic efficiencies of electrolyses carried out In an electrolyte consisting of
  • thai half-cell potentials are within the range of -0,5 V to -1,3 V SHE.
  • thermodynamic equilibr um 4S0 potential of C02 ; ⁇ reduction to CO is -0. V SHE, and that the thermodynamic equilibrium potential of proton redaction to hydrogen is 0 vs. SHE the eathodie overpotential can vary with the range from 0,4 V to 1.2 V vs. SHE,
  • the present inventors observed a synergic effect in a -catalytic- system consisting of a catalytic cathode comprising an association between the catalytic cathod made- ⁇ of copper and
  • the catalytic cathode consists essentially in copper and -d and ' eventuall metallic and/or non- metallic additives In atomic percentages equal to or less than 1% generally used in commercial metallic materials, or impurities that result from their production processes, -such as So,. Pe, Pb,
  • the catalytic cathodes containing copper, and ainc may be prepared by the siate ⁇ of ⁇ the art processes, such as for example metalhirgk processes, electro-depositi n in conventional plating baths, or ionic liquids including deep entectle solvents.
  • the electrode materials may be present in the form of metallic foils, meshes, foams, solid solution, alloy, particles, including nanopartieles
  • nanopariicJes may be Cu 3 ⁇ 4% €isZn 3 ⁇ 4 or their mixtures with nanopartieies of pure copper and/or pure zinc.
  • the present invention also relates to a catalytic system for the production of syngas, i which it is possible to tune the ratio between hydrogen and carbon monoxide.
  • the tufting can be carried out, for example, by modifying the ratio between the copper and zinc c ns itu nts of the cathode, 475 electrolyte composition, applied current/potential * working pressure and/or temperature of the electrochemical reactor.
  • This catalytic system comprises a zinc-copper based ⁇ cathode with a zinc atomic percentage equal or higher than 28% and e ual or lower than: 58%, coupled: to an ionic liquid-base*, electrolyte c ntaining atef ' n which the niole fraction of ionic Liquid is in the range of 0. 1 -0. and eventually organic additives characterized b being able to produce s ngas in a 480 molar proportion Hj Cl in the range o 3 to 0.5, in which the sum of the gaseous products hydrogen and carbon monoxide are higher than 95%, with cathodic overpotential tn the range of 0.1 ⁇ to 0.7 V.
  • Another aspect of the invention relates to a catalytic cathode comprising zinc and copper with an atomic percentage of zinc equal or higher than 5S% and equal or lower than 97%, coupled to an 485 ionic liquid-based electrolyte containing water in which the mole fraction of ionic liquid is in the range of 0.1 -0 6 and eventually organic additives, characterized by being able to produce syngas in a molar proportion WCO in the range of 0.03 to 0,1 , in which the sum of the gaseou products hydrogen and carbon monoxide are higher than 95%.
  • Syngas composition mainl the ratio r /CO varies as a function of the production technology and raw-material Methane reforming yield -a Hj/CO ratio of 3-5, while ooal gasification yields H3 ⁇ 4 O ratios near unit or below one (O, I. Gl use! , A. M. esubl, A. C. Tiena, M Sudip, ChemistryFuel 49S Processing Technology, 2010, 91 136-144; B, F aigo and I A. Menende3 ⁇ 4 In: Syngas:
  • the ionic liquids to he used ' by the present invention are currently known ionic liquids in which carbon dioxide is soluble, or that will be developed that include for example, cations belonging
  • the tmidazoHirm family in particular 1 ,3 substituted imldazoliums with the same of different suhsthuents, yrSdmiunh pyrro!idierium, phosphouium, aromoniunt.. sulphomum, cholines, acetyl cholines, and the anions- that may he present combined with these cations may be tetraHnoroborate, chloride, bromide, iodine, raetahnesuiphonate, acetate, fonnia e, irifiuoroacetafe, inflate etc.
  • the organic additive may be an organic solv t, such as aeetomtri!e,
  • Another advantage of the invention is the capacity of producing syngas at a small scale. Carbon monoxide is an expensive and toxic substance. The capacity to generate only the necessary amounts Oft deman ⁇ Instead of carrying mi stoekage will reduce the costs associated to th use of €0 utilization and its safet
  • the electrochemical cell comprises the catalytic cathode of the present .invention and an anode.
  • the ⁇ ⁇ ⁇ .anode may comprise any suitable materia! know in the state-of-the art, or that will be developed, .such as for example iridium oxide, rutheftt m oxide, iron oxide, cobalt oxide, a mixed metallic oxide, nickel oxide, or platinum, titanium, or a sacrificial electrode, such as 3 ⁇ 4ine, magnesium, or aluminium.
  • the 520 anode may also be photoanode, or microbiological anode.
  • the electrochemical ceil may be an undivided; single cell, or the cathode and anode may be placed different compartments. In the latter ease the eafhoiyte and the anolyte may be separated by a. porous glass frit or other type of suitable material such as a polymeric membrane.
  • the eatholyte and the anolyte may be the same or different.
  • the anolyte can be an 525 aqueous solution containing an inorganic acid, such sulfuric acid, chloridric or phosphoric acid, ietrafiuoroborie acid, trifiuoroaeetre acid, triflic acid, or an smmwium salt, or an ionic liquid.
  • the anolyte may also contai an aqueous solution containing hydroxides, carbonates, or biearbonates of alkaline or alkaline-earth metals.
  • the electrochemical ceil or stack of cells comprises a source of electricity that powers the 530 electrodes.
  • the process according to the invention may he carried out in a continuous, semi- continuous or in batch mode
  • the cell can be pressurized with CO; or an inert gas, such as nitrogen, helium, or argon,
  • a capillary connecting both cooipartments, and/or pressure control valves avoid the huikbup of a pressure ifferenti l 535 between said compartments.
  • the oxygen may he purified to the desired degree of purity, through an additional purification step. Purification may be carried out y mijustmg the pressure and temperature of the mixture COj-Oj, so that a CO rich phase in the liquid state can be decanted from an oxygen rich gaseous 540 phase. Alternatively, another process for oxygen purification may be used, such as a membrane purification method.
  • Figure ! depicts a simplified schematic of the process for the production of chemical products by $45 electrochemical reduction of CO3 ⁇ 4
  • Figure 2 depicts a simplified schemat c of the ⁇ generative process comprising the catalytic, system of the present invention., thai is capable of produeing ' chemieal products, and when run in reverse mode electricity.
  • EMIMOTf i loliiee was used as ionic liquid. Oemineralized water was added to prepare an electrolyte with a mole fraction of EMIMOTf of 0.4. The .electrochemical cell was previously pressurized with CO? at O bar and 5*C and the electrolyte saturated in € ⁇ 3 ⁇ 4. After applying a po e tial in the range of - 580 3 ,0V a -I .8V vs, Ag Ag-s- to a bimetallic copper-zinc cathode and using a . ⁇ ⁇ sacrificial zinc anode ethanoi and acetone are produced. The Faradaie efficiency for liquid products (at room temperature and pressure) is near 100%. Ethanol and acetone are then purified in the separator
  • EMIMOTf (:l -ethyl-3-a3 ⁇ 4ethyl-in «dazolium inflate) with a purity >99% (RMN) from loiitec wa used as ionic liquid, Dernineralized water was added to prepare an electrolyte with a mole fraction of EMIMOTf of 0.4.
  • an electro-deposited copper-zinc fs!m ZmCu (50:50)% at. H a copper foil substrate with 1 cm * . geometrical area was used.
  • a catalytic system and an electrochemical process to produce high valued chemical products 595 such alcohols wit one to ten carbon atoms,, ketones op to four carbon atoms, and syngas are provided.
  • These products can find -us in application such as fuels, gasoline additives, vectors for energy storage, fuel for fuel cells, or in conventional applications as chemical, pharmaceutical and cosmetic products or as raw-materials for the production of other chemical products, it is also provided a regenerative system comprising the catalytic system of the present invention, that 600 is capable of producing chemical products, and when mn in reverse: mode electricity ,

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Abstract

La présente invention concerne un système catalytique qui est capable de produire différents produits chimiques par réduction électrochimique directe du dioxyde de carbone en régulant des paramètres réglables facilement, tels que le courant/potentiel appliqué, la pression, la température, la composition de l'électrolyte et la nature de la cathode à des températures allant de la température ambiante jusqu'à 100 °C, et à des pressions allant de la pression atmosphérique jusqu'à 100 bars. Lesdits produits chimiques sont des alcools possédant un à dix atomes de carbone, des cétones possédant jusqu'à quatre atomes de carbone et des gaz de synthèse. Le système catalytique comprend une cathode catalytique couplée à un électrolyte à base de liquide ionique hydrophile contenant de l'eau et du CO2 dissous. De préférence, l'invention envisage l'utilisation de dioxyde de carbone capturé à partir d'émissions industrielles et l'utilisation d'électricité issue de ressources renouvelables.
PCT/PT2016/000002 2015-05-06 2016-05-06 Réduction électrochimique du dioxyde de carbone dans un liquide ionique aqueux contenant des électrolytes WO2016178590A1 (fr)

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EP16726983.6A EP3292231B1 (fr) 2015-05-06 2016-05-06 Réduction électrochimique du dioxyde de carbone dans un liquide ionique aqueux contenant des électrolytes

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
PTPT108442 2015-05-06
PT108442A PT108442A (pt) 2015-05-06 2015-05-06 Sistema catalítico para produção de gás de síntese por redução electroquímica do dióxido de carbono e processo que o utilização
PTPT109188 2016-02-23
PT10918815 2016-02-23

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Cited By (12)

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CN109786962A (zh) * 2019-02-21 2019-05-21 成都形水科技有限公司 频率选择天线罩的制备方法
KR20190055431A (ko) * 2017-11-15 2019-05-23 한국과학기술연구원 이산화탄소의 전기화학적 환원반응을 통한 메탄생성방법
WO2020010296A1 (fr) * 2018-07-06 2020-01-09 University Of Kansas Conversion électrocatalytique de dioxyde de carbone dans des liquides expansés par du dioxyde de carbone
WO2019136018A3 (fr) * 2018-01-02 2020-04-02 University Of Louisville Research Foundation, Inc. Procédé et système à étapes multiples pour convertir du dioxyde de carbone en produits multi-carbone
CN110983364A (zh) * 2019-12-20 2020-04-10 湖南七纬科技有限公司 一种高亲水性电解水用隔膜及其制备方法
EP3670700A1 (fr) * 2018-12-19 2020-06-24 Paris Sciences et Lettres - Quartier Latin Procédé de conversion de dioxyde de carbone (co2) en gaz de synthèse par une réaction d'électrolyse
US10941497B2 (en) 2017-02-27 2021-03-09 Honeywell International Inc. Electrochemical carbon dioxide converter and liquid regenerator
JP2021512598A (ja) * 2018-02-12 2021-05-20 ランザテク,インコーポレイテッド 炭素変換効率を改善するためのプロセス
US20210147987A1 (en) * 2018-04-11 2021-05-20 Haskoli Islands Electroreduction of carbon dioxide on transition metal oxide catalysts
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012015921A1 (fr) 2010-07-29 2012-02-02 Liquid Light, Inc. Production électrochimique de gaz de synthèse à partir de dioxyde de carbone
WO2012177052A2 (fr) 2011-06-21 2012-12-27 한국전자통신연구원 Procédé inter-prédictions et appareil associé
US20130023404A1 (en) * 2010-03-26 2013-01-24 Dioxide Materials, Inc. Novel Catalyst Mixtures
US20140093799A1 (en) * 2010-03-26 2014-04-03 Dioxide Materials, Inc. Devices And Processes For Carbon Dioxide Conversion Into Useful Fuels And Chemicals
CN104001540A (zh) * 2014-02-12 2014-08-27 南昌航空大学 一种离子液体催化剂及其制备方法
WO2014161262A1 (fr) 2013-04-01 2014-10-09 中兴通讯股份有限公司 Procédé, dispositif et système de redémarrage après une panne d'alimentation électrique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130023404A1 (en) * 2010-03-26 2013-01-24 Dioxide Materials, Inc. Novel Catalyst Mixtures
US20140093799A1 (en) * 2010-03-26 2014-04-03 Dioxide Materials, Inc. Devices And Processes For Carbon Dioxide Conversion Into Useful Fuels And Chemicals
WO2012015921A1 (fr) 2010-07-29 2012-02-02 Liquid Light, Inc. Production électrochimique de gaz de synthèse à partir de dioxyde de carbone
WO2012177052A2 (fr) 2011-06-21 2012-12-27 한국전자통신연구원 Procédé inter-prédictions et appareil associé
WO2014161262A1 (fr) 2013-04-01 2014-10-09 中兴通讯股份有限公司 Procédé, dispositif et système de redémarrage après une panne d'alimentation électrique
CN104001540A (zh) * 2014-02-12 2014-08-27 南昌航空大学 一种离子液体催化剂及其制备方法

Non-Patent Citations (45)

* Cited by examiner, † Cited by third party
Title
A. KATOH; H. UCHIDA; M. SHIBATA; M. WATANABE, J. ELECTROCHEM. SOC., vol. 141, no. 8, 1994, pages 2054 - 2058
A. N. FRUMKIN, TRANS FARADAY SOC, vol. 55, 1959, pages 156 - 167
B A. ROSEN; A. SALEHI-KHOJIN; M. R. THORSON; W. ZHU; D. T, WHIPPLE; P. J. A. KENIS; R. I. MASEL, SCIENCE, vol. 334, 2011, pages 643 - 644
B. A. ROSEN ET AL: "Ionic Liquid-Mediated Selective Conversion of CO2 to CO at Low Overpotentials", SCIENCE, vol. 334, no. 6056, 4 November 2011 (2011-11-04), pages 643 - 644, XP055117032, ISSN: 0036-8075, DOI: 10.1126/science.1209786 *
B. FIDALGO; J. A. MENENDEZ: "Syngas: Production, Applications and Environmental Impact", 2013, NOVA SCIENCE PUBLISHERS, INC, ISBN: 978-1-62100-8, pages: 121 - 149
C. WANG; X. LUO; H. LUO; D. JIANG; H. LI; S. DAI, ANGEW. CHEM., INT. ED., vol. 50, 2011, pages 4918 - 4922
F. MARTINEZ; C. JIMENEZ; J. GARCIA; R. CAMARILLO; J. RINCON, ENVIRONMENTAL ENGINEERING AND MANAGEMENT JOURNAL, vol. 13, no. 10, 2014, pages 2477 - 2485
G. CENTI.; S. PERATHONER; WINE, G.; M. GANGERI, GREEN CHEM, vol. 9, 2007, pages 671 - 678
G. ZHAO; T. JIANG; B. HAN; Z. LI; J. ZHANG; Z. LIU; J. HE; W WU, J. OF SUPERCRITICAL FLUIDS, vol. 32, 2004, pages 287 - 291
G. ZHAO; T. JIANG; B. HAN; Z. LI; J. ZHANG; Z. LIU; J. HE; W. WU, J. OF SUPERCRITICAL FLUIDS, vol. 32, 2004, pages 287 - 291
GATTRELL, M.; GUPTA, N.; CO, A. J., ELECTROANAL. CHEM., vol. 594, 2006, pages 1 - 19
HORI, Y ET AL.: "In Mod. Aspect. E/ectroc.", vol. 42, 2008, SPRINGER, pages: 89 - 189
HU, Y, ACS SYMPOSIUM SERIES, 2010, pages 55 - 76
HUEI-RU ''MOLLY'' JHONG; SICHAO MA; PAUL JA KENIS, CURRENT OPINION IN CHEMICAL ENGINEERING, vol. 2, no. 2, May 2013 (2013-05-01), pages 191 - 199
I. ALI; N. ULLAH; S. OMANOVIC, INT. J. ELECTROCHEM. SCI., vol. 9, 2014, pages 7198 - 7205
J. D; WATKINS; A. B.. BOCARSLY, CHEMSUSCHEM, vol. 7, 2014, pages 284 - 290
J. JONES; G. K. S. PRAKASH; G. A. OLAH, ISR. J. CHEM, vol. 54, 2014, pages 1451 - 1466
J. L. DIMEGLIO; J. ROSENTHAL, J. AM, CHEM. SOC., vol. 135, 2013, pages 8798 - 8801
J. MEDINA-RAMOS; R. C. PUPILLO; T. P. KEANE; J. L DIMEGLIO; J. ROSENTHAL, J. AM. CHEM. SOC.
JOHN D. WATKINS ET AL: "Direct Reduction of Carbon Dioxide to Formate in High-Gas-Capacity Ionic Liquids at Post-Transition-Metal Electrodes", CHEMSUSCHEM, vol. 7, no. 1, 7 November 2013 (2013-11-07), DE, pages 284 - 290, XP055283865, ISSN: 1864-5631, DOI: 10.1002/cssc.201300659 *
K. CHANDRASEKARAN; J. O. M. BOCKRIS, SURF. SCI., vol. 185, 1987, pages 495 - 514
K. HARA; A.TSUNETO; A. KDO; T. SAKATA, J. ELECTROCHEM. SOC., vol. 141, no. 8, 1994, pages 2097
K. P KUHL; E. R. CAVE; D. N. ABRAM; T. F. JARAMILLO, ENERGY ENVIRON. SCI., vol. 5, 2012, pages 7050
L. E. BARROSSE-ANTLE; R. G. COMPTON, CHEM. COMMUN., 2009, pages 3744 - 3746
L. SUN; G. K RAMESHA; P. V. KAMAT; J. F. BRENNECKE, LANGMUIR, vol. 30, 2014, pages 6302 - 6308
L.A. BLANCHARD; D. HANCU; E.J. BECKMAN; J.F. BRENNECKE, NATURE, vol. 399, 1999, pages 28 - 29
M. BUDICH; G. BRUNNER, J. OF SUPERCRITICAL FLUIDS, vol. 25, 2003, pages 45 - 55
M. GANGERI; S. PERA ONER; S. CAUDO; G. CENTI; J. AMADOU; D. BEGIN; C. PHAM-HUU; M. J. LEDOUX; J. P. TESSONNIER; D. S. SU, CATAL. TODAY, vol. 143, 2009, pages 57
M. JITARU; D. A. LOWY; M. TOMA, B.; C. TOMA; L. ONICIU, J. APPLIED ELECTROCHEM, vol. 27, 1997, pages 875 - 889
M. JITARU; D. A. LOWY; M. TOMA; B. C. TOMA; L. ONICIU, J. APPLIED ELEC ROCHEM, vol. 27, 1997, pages 875 - 889
M. SEILER; C. JORK; A. KAVARNOU; W. ARLT; R. HIRSCH, AICHE./., vol. 50, 2004, pages 2439 - 2454
MAHMOOD M. N.; MASHEDER D.; HARTY C., J. J. APPLIED ELECTROCHEMISTRY, vol. 17, 1987, pages 1159 - 1170
N. HOLLINGSWORTH; S. F. R. TAYLOR; M. T. GALANTE; J. JACQUEMIN; C. LONGO; K. B. HOLT; N. H. DELEEUWAD; C. HARDACRE, FARADAY DISCUSS., vol. 183, 2015, pages 389
N. ULLAH; I. ALI; M. JANSEN; S. OMANOVIC, THE CANADIAN J. OF CHEM. ENG., vol. 93, 2015, pages 55 - 62
O. J. OLUSOLA; A. M. MESUBI; A. C. TIENA; M. SUDIP, CHEMISTRYFUEL PROCESSING TECHNOLOGY, vol. 91, 2010, pages 136 - 144
R. KORTLEVER; J. SHEN; K. J. P. SCHOUTEN; F. CALLE-VALLEJO; M. T. M. KOPER, J. PHYS. CHEM. LETT., vol. 6, 2015, pages 4073 - 4082
S. ISHIMARU; R. SHIRATSUCHI; G. NOGAMI, JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 147, no. 5, 2000, pages 1864 - 1867
S. SEO; M. A, DESILVA; J. F. BRENNECKE, J. PHYS. CHEM. B, vol. 118, 2014, pages 14870 - 14879
WENZHEN, LI., ADVANCES IN C0 CONVERSION AND UTILIZATION
WENZHEN, LI.: "Advances in CO Conversion and Utilization", 2010, pages: 55 - 76
WORLD PETROCHEMICALS REPORT, January 2010 (2010-01-01)
Y.HORI.; H. WAKEBE; T., T. TSUKAMOTO; O. KOGA, ELEC ROCHIM ACTA, vol. 39, 1994, pages 1833
YAMAMOTO, T.; TRYK, D.A.; FUJISHIMA A.; OHATA H., ELECTROCHIMICA ACTA, vol. 47, 2002, pages 3327 - 3334
YH. CHU; YG, SHUL., INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 35, 2010, pages 11261E70
ZHOU FENG ET AL: "Highly selective electrocatalytic reduction of carbon dioxide to carbon monoxide on silver electrode with aqueous ionic liquids", ELECTROCHEMISTRY COMMUNICATIONS, ELSEVIER, AMSTERDAM, NL, vol. 46, 3 July 2014 (2014-07-03), pages 103 - 106, XP029014339, ISSN: 1388-2481, DOI: 10.1016/J.ELECOM.2014.06.023 *

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