EP2686464A2 - Procédé pour la conversion électrochimique sélective de co2 en hydrocarbures en c2 - Google Patents

Procédé pour la conversion électrochimique sélective de co2 en hydrocarbures en c2

Info

Publication number
EP2686464A2
EP2686464A2 EP12715237.9A EP12715237A EP2686464A2 EP 2686464 A2 EP2686464 A2 EP 2686464A2 EP 12715237 A EP12715237 A EP 12715237A EP 2686464 A2 EP2686464 A2 EP 2686464A2
Authority
EP
European Patent Office
Prior art keywords
copper
cathode
hydrocarbons
process according
carbon dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP12715237.9A
Other languages
German (de)
English (en)
Other versions
EP2686464B1 (fr
Inventor
Marta Catarina MARTINS RAMOS GONÇALVES
Tiago COSTA DUARTE PARDAL
José Augusto DÂMASO CONDEÇO
Joaquim Miguel BADALO BRANCO
Tomás Rei CLÁUDIO FERNANDES
Anabela Beatriz MADEIRA GOMES BOAVIDA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
OMNIDEA Ltda
Original Assignee
OMNIDEA Ltda
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by OMNIDEA Ltda filed Critical OMNIDEA Ltda
Publication of EP2686464A2 publication Critical patent/EP2686464A2/fr
Application granted granted Critical
Publication of EP2686464B1 publication Critical patent/EP2686464B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils

Definitions

  • the present invention relates to the field of electrochemistry and, in general, to a method of conversion of C0 2 into hydrocarbons, namely C2 hydrocarbons (ethylene and ethane) .
  • Copper is the only metallic electrode materials that yields hydrocarbons as major products (Gattrell et al., 2006, Jitaru, 2007) .
  • the mixture of hydrocarbons produced by the electroreduction of C0 2 is composed mostly of methane and ethylene.
  • the faradaic efficiency of CH 4 is commonly higher than that for C 2 H 4 .
  • Kyriacou and Anagnostopoulos (1993) reported the following formation efficiencies for the electrochemical reduction of C0 2 on copper in a 0.5 M KHC0 3 solution at 298 K: 16% for methane and 14% for ethylene.
  • Azuma et al. (1990) investigated the C0 2 reduction in a 0.05 M KHC0 3 aqueous solution at 293 K and obtained methane, ethylene and ethane with faradaic efficiencies of 17.8, 12.7 and 0.039%, respectively.
  • honeycomb-like structures were studied by Nikolic et al. (2007), namely the honeycomb-like structures. According to these authors, the main characteristics of honeycomb-like structures are the existence of two groups of craters or holes of distinct nature. They pointed out that a group of holes or craters is formed by the connection of hydrogen bubbles that resulted from an intense hydrogen evolution reaction during the deposition. The other group is originated from the agglomerates of copper grains formed in the initial stage of electrodeposition . They also referred that for longer times of deposition a third class of holes could be formed through the combination of the holes of the first two groups. Nevertheless, these authors did not refer any application of this type of electrodeposits on the electroreduction of C0 2 or any data that allowed the prediction of the behavior of this type of deposits on the referred reaction.
  • the process of this invention concerns the electrochemical conversion of carbon dioxide in aqueous solutions into hydrocarbons and, more specifically to C2 hydrocarbons (ethylene and ethane) without the formation of methane.
  • C2 hydrocarbons ethylene and ethane
  • the achievement of mixtures with a higher C2 hydrocarbons content represents an advantage in relation to the mixtures described in the prior art, since higher energetic densities are attained considering the same content of hydrogen or carbon monoxide. This advantage makes them more appropriated, for instance, to be utilized as fuels.
  • the process is carried out in an electrochemical cell wherein the cathode is a modified electrode with copper electrodeposits that increases the activity and selectivity of the method under stable CO 2 conversion.
  • the conversion of C0 2 is performed in a one step, easily scalable and can operate at ambient temperature and atmospheric pressure.
  • the number of carbon atoms in the generated hydrocarbon molecules can be controlled by the increase of copper active surface area available for CO 2 electroreduction .
  • the hydrocarbons produced can be subsequently used as industrial feedstock.
  • FIG. 1 depicts the SEM image of the electrode surface with electrodeposits having a dendritic crystal structure.
  • the deposits were obtained by an ex-situ electrodeposition of copper on a copper mesh as referred in example I.
  • FIG. 2 depicts the SEM image of the electrode surface with electrodeposits having a honeycomb-like structure.
  • the deposits were obtained by an ex-situ electrodeposition of copper on a copper mesh as referred in example II.
  • Number (1) indicates two distinct craters.
  • FIG. 3 depicts the SEM image of the electrode surface with electrodeposits having a porous 3D sponge structure. It was obtained by electrodeposition ex-situ of copper on a copper foil as mentioned in example IV. Number (2) indicates two pores in distinct layers.
  • FIG. 4 depicts a schematic drawing of an example of a laboratory-size electrochemical cell in which the process of the invention can be carried out.
  • the numbers indicate: (3) cathodic compartment, (4) anodic compartment, (5) membrane compartment (optional), (6) gas inlet, (7) reference electrode inlet, (8) gas outlet, (9) pH sensor inlet .
  • the process of this invention for the conversion of carbon dioxide into hydrocarbons, and more specifically into hydrocarbons with two carbon atoms (C2 hydrocarbons) is performed in an electrochemical cell.
  • the cell is preferentially a two compartment cell in which the cathode and the anode are separated preferentially by an ion exchange membrane .
  • the anode may be any suitable electrically conducting material appropriate for effective operation in an electrolytic cell, for example, platinum, graphite and glassy carbon.
  • the cathode material may be any suitable electrically conducting material such as copper or glassy carbon.
  • the cathode substrate may have any suitable configuration appropriate for electro-deposition, including mesh and foil configurations.
  • the cathode surface is modified by in-situ or ex-situ copper electrodeposition .
  • the ex-situ deposition is preferable to provide a stable and exclusive conversion of carbon dioxide into C2 hydrocarbons and can be performed using preferably copper sulphate as the source of copper cations and sulphuric acid to increase the acidity of the deposition bath.
  • Modified copper electrodes with good mechanical resistance and an extremely large useable surface area were used as obtained.
  • Three types of structures for the copper electrodeposits prepared by ex-situ electrodeposition are presented in Figures 1, 2 and 3.
  • the presence of the electrodeposits at the electrode surface strongly modifies the catalytic behavior of the electrodes for the conversion of carbon dioxide, consequently changing the composition of the gaseous hydrocarbon products created.
  • the catholyte may be any inorganic salt aqueous solution in which the carbon dioxide is soluble, such as KHCO3, NaHC0 3 and KC1, preferably KHC0 3 , in concentrations of around 0.0 ' 3 to 0.5 M, at a pH preferably of around 4 to 9.
  • the anolyte may be preferably the same as the catholyte.
  • a suitable ion exchange membrane that can be used may be any ion exchange membrane that allows the passage of protons, such as Nafion 117, or Nafion 417.
  • the electrochemical reduction of C0 2 to C2 hydrocarbons is achievable by using an electrochemical cell that possesses one cathode with copper electrodeposits submerged in an electrolyte in which the C0 2 is soluble.
  • any suitable shape and disposition of an electrochemical cell can be used.
  • the electrochemical reduction process can be carried out in a continuous mode (galvanostatic or potentiostatic) or in a pulsed electrolytic mode.
  • the modified cathodes presented in Figures 1 to 3 are used in the electrochemical cell for the conversion of carbon dioxide.
  • the electrodeposit at the electrode surface strongly modifies the catalytic behavior of the electrodes used for the carbon dioxide conversion, modifying subsequently the composition of the gaseous hydrocarbons (reaction products) .
  • Fig. 1 The structure shown in Fig. 1 consists of dendritic copper deposits. It was discovered that this type of electrodeposits promotes ethylene production in detriment of methane. Additionally, it was verified that the bigger the coverage of the surface electrode with dendritic copper electrodeposits, the bigger was the selectivity for ethylene .
  • the cathode modified with copper honeycomb-like structures shown in Fig. 2 promotes only the production of C2 hydrocarbons (ethylene and ethane) , not being detected methane. This result is innovative and is due to a high surface area of the electrodeposits, its morphology and structure.
  • the honeycomb-like structure of electrodeposits has a higher quantity of copper grains per volume. This configuration enhances the proximity of the active electro- catalytic sites, which results in an increased likelihood for the formations of hydrocarbons with longer chains.
  • the modified cathode illustrated in Fig. 3 is a three- dimensional copper open structure which is extremely porous. This configuration allows rapid transport of gas and liquid, and its high surface area and mechanically well-supported structure is desirable for electrochemical reactions.
  • the products are C2 hydrocarbons without formation of methane.
  • This result confirms that the availability of the copper active surface and the spatial distribution of the electro-catalytic zones are the key parameters for the conversion of carbon dioxide in hydrocarbons with two carbon atoms. Additionally it was verified that the copper electrodeposits obtained by ex-situ electrodeposition lead to the stability of the carbon dioxide reduction process, this is, to the stability of the hydrocarbon production due to the weak deactivation of the cathode.
  • the present invention and the knowledgment of the state-of- the-art indicate that the selective reduction of the carbon dioxide into C2 hydrocarbons may follow the following reaction mechanism:
  • the modified electrodes have a distinct catalytic behavior from the substrate behavior modifying the distribution of the hydrocarbons resulting from the reaction. This catalytic activity is mainly dependent on the characteristics of the electrodeposits , more specifically on the active surface area, on the morphology, and on the crystalinity (this is the structure of the copper crystals) .
  • a copper mesh cathode was modified with copper electrodeposits by ex-situ electrodeposition, having the configuration of Fig.l.
  • Potentiostatic reduction of carbon dioxide was performed in a flat cell (similar to the one depicted in Figure 4) at room temperature and atmospheric pressure, under conditions of continuous carbon dioxide flow.
  • the electrolytic solution used was of potassium bicarbonate (Merck, p. a.) with a concentration of 0.1 M.
  • a cationic exchange membrane separated the catholyte and anolyte compartments.
  • the anode was a platinum mesh.
  • the applied electrode potential was - 1.9 V, measured against a silver/silver chloride reference electrode .
  • the faradaic efficiencies of the products were calculated on the basis of the number of electrons required for the formation of one molecule of the products from carbon dioxide and water; eight for methane, twelve for ethylene, fourteen for ethane, two for carbon monoxide and two for molecular hydrogen. Only gaseous products were analyzed.
  • the utilization of electrodes with a dendritic morphology resulted in a selective production of ethylene instead of methane.
  • the electrode promotes an almost selective production of ethylene (33.3 %), being the methane production of 3.6 %.
  • Example II To confirm that the products obtained in Example II were an inherent characteristic of the electrode, different potentials and different concentrations of electrolyte were tested.
  • the CO 2 electroreduction was carried out at various cathode potentials and electrolyte concentrations.
  • the results for the potentiostatic reduction in the range -1.5 to -1.9 V in relation to Ag / AgCl are shown in Fig. 5.
  • a high selectivity to C2 hydrocarbons without production of methane was observed for all conditions tested. Only the C2 hydrocarbons composition was modified.

Landscapes

  • 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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte sur un procédé pour la conversion électrochimique sélective de dioxyde de carbone en hydrocarbures, à savoir d'hydrocarbures en C2. Le procédé est effectué dans une cellule électrochimique où la cathode est une électrode modifiée comprenant des électrodépôts de cuivre afin d'améliorer l'activité catalytique et la sélectivité du système. La formation d'un mélange d'hydrocarbures en C2 (C2H4 et C2H6) sans méthane est obtenue avec succès sur des électrodépôts de surface spécifique plus élevée. De plus, de l'éthylène est sélectivement produit au détriment de l'éthane. L'électrodépôt de cuivre ex-situ amène la régularité du procédé de réduction du dioxyde de carbone, c'est-à-dire la stabilité de la production d'hydrocarbures en raison de la faible désactivation de la cathode.
EP12715237.9A 2011-03-15 2012-03-15 Procédé pour la conversion électrochimique sélective de co2 en hydrocarbures en c2 Not-in-force EP2686464B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PT105566A PT105566A (pt) 2011-03-15 2011-03-15 Processo para a conversão electroquímica selectiva de dióxido de carbono
PCT/PT2012/000008 WO2012125053A2 (fr) 2011-03-15 2012-03-15 Procédé pour la conversion électrochimique sélective de co2 en hydrocarbures en c2

Publications (2)

Publication Number Publication Date
EP2686464A2 true EP2686464A2 (fr) 2014-01-22
EP2686464B1 EP2686464B1 (fr) 2018-11-14

Family

ID=45976495

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12715237.9A Not-in-force EP2686464B1 (fr) 2011-03-15 2012-03-15 Procédé pour la conversion électrochimique sélective de co2 en hydrocarbures en c2

Country Status (3)

Country Link
EP (1) EP2686464B1 (fr)
PT (1) PT105566A (fr)
WO (1) WO2012125053A2 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10161051B2 (en) 2013-10-03 2018-12-25 Brown University Electrochemical reduction of CO2 at copper nanofoams
US20160253461A1 (en) * 2014-10-01 2016-09-01 Xsolis, Llc System for management and documentation of health care decisions
DE102017208518A1 (de) * 2017-05-19 2018-11-22 Siemens Aktiengesellschaft Herstellung von dendritischen Elektrokatalysatoren zur Reduktion von CO2 und/oder CO
WO2020225315A1 (fr) * 2019-05-07 2020-11-12 Total Se Électrocatalyseurs synthétisés par électroréduction de co2 et procédés et utilisations associés
IT201900014580A1 (it) * 2019-08-09 2021-02-09 Laboratorio Audio Snc Di Niorettini Claudio & Doro Stefano “Procedimento per la formazione e la rigenerazione di un catodo in rame di una cella elettrochimica e cella elettrochimica per la produzione di prodotti industriali”
CN112501649B (zh) * 2020-11-22 2023-11-21 赵玉平 一种复合材料
CN112501662B (zh) * 2020-12-15 2022-03-15 中南大学深圳研究院 一种应用于高效二氧化碳还原反应生成甲烷的铜纳米片的制备方法
CN112481663B (zh) * 2020-12-15 2022-03-11 中南大学深圳研究院 一种应用于高效二氧化碳还原反应生成乙烯的铜纳米花的制备方法
CA3242900A1 (fr) * 2022-01-10 2023-07-13 Totalenergies Onetech Reduction electrochimique d'oxydes de carbone en ethylene
CN115637460B (zh) * 2022-09-28 2026-04-17 华东师范大学 一种超快速制备多孔Cu/Zn异质结电催化材料的方法及应用
WO2024184700A1 (fr) * 2023-03-08 2024-09-12 Totalenergies Onetech Catalyseur électrodéposé in situ favorisant l'électroréduction de co2 et/ou de co en produits hydrocarbonés dans des conditions acides
FR3151854A1 (fr) 2023-07-31 2025-02-07 Totalenergies Onetech Procédé de fabrication d’un carburéacteur à partir de biomasse présentant une économie d’atome optimisée

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4897167A (en) 1988-08-19 1990-01-30 Gas Research Institute Electrochemical reduction of CO2 to CH4 and C2 H4
AUPS172702A0 (en) * 2002-04-12 2002-05-23 Commonwealth Scientific And Industrial Research Organisation An electrochemical cell, a porous working electrode and a process for he conversion of a species from one oxidation state to another by the electrochemical oxidation or reduction thereof
WO2011150422A1 (fr) * 2010-05-28 2011-12-01 The Trustees Of Columbia University In The City Of New York Dendrites métalliques poreuses utilisées en tant qu'électrodes à diffusion pour une réduction aqueuse à haut rendement de co2 en hydrocarbures
IL207947A0 (en) * 2010-09-02 2010-12-30 Univ Ben Gurion Manufacturing carbon - based combustibles by electrochemical decomposition of co2

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012125053A2 *

Also Published As

Publication number Publication date
PT105566A (pt) 2012-09-17
WO2012125053A4 (fr) 2013-05-16
WO2012125053A2 (fr) 2012-09-20
EP2686464B1 (fr) 2018-11-14
WO2012125053A3 (fr) 2013-03-28

Similar Documents

Publication Publication Date Title
EP2686464B1 (fr) Procédé pour la conversion électrochimique sélective de co2 en hydrocarbures en c2
Gonçalves et al. Electrochemical conversion of CO2 to C2 hydrocarbons using different ex situ copper electrodeposits
Li et al. Effect of supporting matrixes on performance of copper catalysts in electrochemical nitrate reduction to ammonia
Yue et al. Triple-phase electrocatalysis for the enhanced CO2 reduction to HCOOH on a hydrophobic surface
EP3670701B1 (fr) Procédé de conversion de dioxyde de carbone (co2) en co par une réaction d'électrolyse
Xie et al. Efficient electrochemical CO2 reduction on a unique chrysanthemum-like Cu nanoflower electrode and direct observation of carbon deposite
Latvytė et al. A low-temperature ammonia electrolyser for wastewater treatment and hydrogen production
US9255335B2 (en) Catalysts for low temperature electrolytic CO2 reduction
CN103119017B (zh) 用于二氧化碳的电化学还原的方法和装置
Murthy et al. Metal-doped molybdenum nitride films for enhanced hydrogen evolution in near-neutral strongly buffered aerobic media
Ahangari et al. Comparing the electrocatalytic reduction of CO2 to CO on gold cathodes in batch and continuous flow electrochemical cells
US20150136613A1 (en) Catalysts for low temperature electrolytic co reduction
Xie et al. Tuning the catalytic selectivity in electrochemical CO2 reduction on copper oxide-derived nanomaterials
WO2014018091A1 (fr) Catalyseurs pour la réduction électrolytique à faible température du co2 ou du co
US6238530B1 (en) Cathode for electrolysis and electrolytic cell using the same
Kim et al. In-situ desalination-coupled electrolysis with concurrent one-step-synthesis of value-added chemicals
Yu et al. Enhanced electrochemical dechlorination of 4-chlorophenol on a nickel foam electrode modified with palladium, polypyrrole and graphene
Hasnat et al. Lean Cu-immobilized Pt and Pd films/–H+ conducting membrane assemblies: relative electrocatalytic nitrate reduction activities
Baibars et al. NiFeOxHy/Ni3Fe interface design via electropassivation for superior catalysis of HER
Piao et al. Porous dendritic BiSn electrocatalysts for hydrogenation of 5-hydroxymethylfurfural
Proietto et al. Electrochemical conversion of pressurized CO2 at simple silver-based cathodes in undivided cells: study of the effect of pressure and other operative parameters
TWI753143B (zh) 電極基材、及使用其的電極觸媒與電解裝置
Spodaryk et al. The role of malachite nanorods for the electrochemical reduction of CO2 to C2 hydrocarbons
Siltamaki et al. Synthesis and Electrochemical Study of CuAu Nanodendrites for CO 2 Reduction
Zulfiqar et al. Highly selective and corrosion resistant interconnected pNiCo@ NF electrocatalysts for methanol-assisted seawater electrolysis

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20131009

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20170515

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C25B 11/03 20060101ALI20180502BHEP

Ipc: C25D 7/00 20060101ALI20180502BHEP

Ipc: C25B 3/04 20060101AFI20180502BHEP

Ipc: C25D 7/06 20060101ALI20180502BHEP

INTG Intention to grant announced

Effective date: 20180530

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1064932

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012053450

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20181114

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1064932

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190214

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190314

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190215

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190314

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012053450

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20190815

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190315

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190315

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190315

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602012053450

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C25B0003040000

Ipc: C25B0003250000

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20120315

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181114

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20240417

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240409

Year of fee payment: 13

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602012053450

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20250315

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20251001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250315