EP3894352A1 - Décomposition catalytique de méthane et régénération de catalyseur, leurs procédés et utilisations - Google Patents

Décomposition catalytique de méthane et régénération de catalyseur, leurs procédés et utilisations

Info

Publication number
EP3894352A1
EP3894352A1 EP19849002.1A EP19849002A EP3894352A1 EP 3894352 A1 EP3894352 A1 EP 3894352A1 EP 19849002 A EP19849002 A EP 19849002A EP 3894352 A1 EP3894352 A1 EP 3894352A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
hydrogen
process according
previous
methane
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.)
Pending
Application number
EP19849002.1A
Other languages
German (de)
English (en)
Inventor
Adélio Miguel MAGALHÃES MENDES
Cecilia MATEOS PEDRERO
Margarida Dias Catarino
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.)
Pixel Voltaic Lda
Original Assignee
Pixel Voltaic Lda
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 Pixel Voltaic Lda filed Critical Pixel Voltaic Lda
Publication of EP3894352A1 publication Critical patent/EP3894352A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/28—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using moving solid particles
    • C01B3/30—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using moving solid particles using the fluidised bed technique
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present disclosure relates to a process to produce pure hydrogen (fuel cell grade) and carbon, an added-value product using methane as main source.
  • the disclosure also discloses a method to remove the accumulated carbon at the catalyst surface by performing in-situ carbon removal.
  • the present disclosure corresponds to a low-temperature method to decompose methane into COx-free hydrogen using an electrochemical/chemical membrane/chemical reactor.
  • the regeneration method is carried out by feeding a small fraction of the produced hydrogen to the catalyst interface yielding methane as main product, making the carbon accumulated on the catalyst surface to detach.
  • This method enables hydrogen production from methane decomposition and catalyst regeneration in a single compact device.
  • WO 93/20152 patent discloses an assisted plasma process to decompose hydrocarbons in hydrogen and carbon black with defined physical properties, at temperatures between 1000 °C and 2000 °C.
  • US 6,773,689 document is related to a process of carbon structures production from heavy hydrocarbons, characterised by a one or two-step plasma steps. Hydrogen is also formed in this method and can be used as plasma gas.
  • US 2006/0021510 patent discloses a method and apparatus for obtaining CC>2-free hydrogen from greenhouse gas saturated carbon nanotubes, at a temperature range between 527 °C and 3227 °C. Additionally, carbon nanotubes are produced during this process. [0009] These methods suffer from the main disadvantage of being carried out at very high temperatures, resulting in low efficiency and high costs.
  • US 2004/0148860 patent discloses a method and apparatus to decompose natural gas or methane directly into hydrogen and carbon using a barrier discharge non-thermal plasma application.
  • solid carbon is separated from hydrogen by filtration or by using a negatively charged electrode.
  • WO 2007/019664, US 2009/0038933 and US 8,221,689 documents are related to a process based on a cold arc discharge to decompose natural gas or methane into its gaseous constituents, mainly hydrogen and acetylene, and solid carbon.
  • the main advantage of this method is running the reactor at low temperatures ( ⁇ 200 °C).
  • WO 2011/022761 and US 2013/0153403 family disclosures disclose a non-catalytic process and an apparatus for generating hydrogen and synthetic carbon-free gas by plasma reforming of methane and other hydrocarbons. This process shows as major advantages: lower energy consumption, higher energy efficiency in production, scalability of application and high decomposition conversion. Although these methods solve the problem of using high temperature on hydrocarbon decomposition, they need hardly available apparatus which restrains their use.
  • US 6,509,000 document is related to a process for the continuous production of hydrogen from steam reforming of methane-rich hydrocarbon at low temperature (350 °C to 650 °C), using a solid catalyst comprising metal oxides from group VIII.
  • the catalyst regeneration is carried out by switching the reactor feed between hydrocarbon or steam flows.
  • the application considers two parallel reactors for the simultaneous steam reforming and regeneration steps, providing a continuous production of pure hydrogen.
  • US 2006/0257310 and US 7,767,182 documents describe a method to obtain functional nanocarbon and hydrogen from catalytic decomposition of low hydrocarbons.
  • the method considers co-feeding a gas flow comprising low concentration of an oxidising gas, reducing gas or a mixture thereof that reacts with the deposited carbon for being removed from the catalyst, making it possible to prevent the drop of conversion with time on stream.
  • US 9,061,909 document discloses a method and an apparatus for the simultaneous production of carbon nanotubes and hydrogen, using a pseudo-continuous device where the growth of carbon nanotubes, the synthesis of hydrogen, the recovery of the carbon nanotubes, and the recovery of the hydrogen are repeatedly performed.
  • the method also discloses the feeding of a gaseous stream to separate the carbon nanotubes and an oxidising gas to remove carbon remaining on the catalyst.
  • US 9,358,536 disclosure is related to a method and device for producing aromatic hydrocarbons. Additionally, carbon residues are formed as by-product which causes catalyst deactivation and fouling of reactor pipelines. This document is also related to a method for minimising the carbon deposition, by adding a small amount of carbon dioxide during the reaction, and a regeneration method comprising the replacement of the reaction feed by a regeneration gas in a cyclic way. This regeneration gas is obtained by separating the targeted hydrocarbon after the catalytic reaction, which can comprise a significant amount of hydrogen (ca. 25 vol. %). The process is carried out using two parallel reactors, conducting the reaction and the regeneration steps, at 300 °C to 900 °C and 0.1 bar to 10 bar.
  • Upham et al. (2017) disclose a process for pyrolysis of methane into hydrogen and carbon using molten metal alloy catalysts at ca. 1000 °C.
  • Metal alloys are composed by noble materials that are usually active for methane decomposition (e.g., Ni, Pt, Pd) dissolved in low-melting temperature metals (e.g., In, Ga, Sn, Pb). Catalyst deactivation due to solid carbon build-up is minimised because the carbon particles float to the surface of the molten metal and can be removed from the reactor [Upham et al., Science 358 (2017) 917-921]
  • the present disclosure relates to a process for producing pure hydrogen (fuel cell grade) and carbon, an added-value product, using methane as main source.
  • the disclosure discloses a method for methane decomposition and catalyst regeneration, in a single and compact device; the methane decomposition produces carbon that accumulates at the catalyst surface provoking its deactivation after a short time of operation, between 30 h and 500 h.
  • the present subject-matter describes a low-temperature method to decompose methane into CO x -free hydrogen using an electrochemical/chemical membrane reactor, a packed bed chemical reactor or a fluidised bed chemical reactor.
  • the regeneration method is carried out by feeding a small fraction of the produced hydrogen to convert the carbon at the interface with the catalyst to methane thus allowing the detachment of the formed carbon particles.
  • the method described in present application is performed at low temperature (same temperature to that of the reaction). In opposition to plasma assisted methods, this application is related to a method involving non expensive operation devices.
  • the present subject-matter discloses an effective regeneration method that promotes the hydrogenation of the deposited carbon using a very small fraction of the generated hydrogen (up to 5 vol. %), allowing a continuous production of hydrogen.
  • an oxidising gas such as oxygen, steam or carbon dioxide
  • the method disclosed in the present subject-matter enables hydrogen production, hydrogen purification and catalyst regeneration in a single compact device.
  • the catalyst regeneration is achieved by rising the temperature of the catalyst, ideally keeping the reactor temperature constant when methane at the inlet is replaced by hydrogen, or by electrochemically pumping hydrogen to the catalyst. Both methods allow detaching the carbon particles from the catalyst surface. The hydrogenation of carbon at the catalyst interface produces methane.
  • the catalytic decomposition of methane of the present disclosure offers the possibility of overcoming the major drawbacks of the above mentioned methods. Giving that, the temperature can be considerably decreased to about 500 to 600 °C, which leads to less energy demand and the use of reactors made of cheaper materials. However, the catalyst suffers from deactivation due to solid carbon build-up, which impairs its long-term applicability.
  • An aspect of the present disclosure relates to a low temperature method for the production of pure hydrogen using a methane rich stream as raw material, and to perform in-situ catalyst regeneration.
  • [0025] comprises the decomposition of methane into COx-free hydrogen in an electrochemical/chemical membrane/chemical reactor or chemical fluidised reactor.
  • carbon structures (whiskers) are accumulated at the catalyst surface leading eventually to its deactivation.
  • the catalyst regeneration is achieved using a small fraction of the produced hydrogen to react with carbon formed at the catalyst surface provoking the carbon detachment, thus regenerating the catalyst. This is achieved either by chemical/electrochemical methanation of carbon at the catalyst interface with hydrogen/protons or by rising the temperature of the catalyst, ideally keeping the reactor temperature constant.
  • Another aspect of the present disclosure relates to a single compact device is described, enabling the hydrogen production, hydrogen purification and catalyst regeneration.
  • An aspect of the present disclosure relates to a process for producing hydrogen comprising: feeding a methane rich stream to a chemical or electrochemical reactor; wherein the chemical reactor comprising a catalyst supported in a ceramic membrane or in a ceramic bed; contacting the methane rich stream with the catalyst at the selected temperature to produce hydrogen and solid carbon; adding a regenerating stream to react at the catalyst interface with deposited carbon for the catalyst regeneration.
  • the chemical reactor is selected from: a membrane reactor, a packed bed reactor, a fluidised bed reactor.
  • the regenerating stream is a hydrogen stream, preferably a hydrogen pure stream.
  • the process is a continuous process.
  • the molar ratio between the hydrogen pure stream and the hydrogen produce stream varies 5:95 - 15:85; 3:97 - 10:90.
  • the process further comprises a previous step of activated the catalyst by heating and reducing the catalyst at a selected temperature and atmosphere.
  • the ceramic membrane comprises:
  • porous ceramic membranes such as AI203, Si02, Ti02 and Zr02; or
  • dense ceramic membranes such as BCY, BZY and BCZY; or
  • porous or dense metallic membranes based on Pd or Pd alloys porous or dense metallic membranes based on Pd or Pd alloys.
  • the ceramic membrane further comprises a coating, preferably a coating layer comprising Ni, Fe, or mixtures thereof.
  • the reactor further comprises a proton conducting cell for electrochemical separation of hydrogen from unreacted methane.
  • the catalyst is activated with a hydrogen, methane or mixtures thereof; at a temperature between 350°C and 750°C, more preferably between 500°C and 600°C.
  • the decomposition of the methane rich stream and carbon detachment is performed in a range of temperature of 500°C and 750°C, more preferably between 550°C and 650°C.
  • the pressure is varied from 1 bar to 30 bar, preferably from 1 bar to 10 bar, more preferably from 3 bar to 6 bar.
  • the regeneration duration ranges from 10 min to 5 h, preferably 15 min - 2 h, more preferably 30 min - 1 h.
  • the methane rich stream comes from different sources such as biomass, natural gas, tail gases and livestock farming.
  • the regenerating gas is pure hydrogen recovered from the reaction step.
  • the regeneration stream comprises the downstream gas from the reaction step, comprising mostly of hydrogen and unconverted methane.
  • the hydrogen consumed for the carbon removal represents a small fraction (up to 5 vol. %) of the hydrogen produced during methane decomposition.
  • the electrochemical reactor comprises an electrocatalyst, a proton conductor membrane and a counter-electrode.
  • the catalyst of the packed bed reactor is in pellets.
  • the catalyst of the fluidised bed reactor is in pellets.
  • the chemical reactor further comprises a separation membrane.
  • the electrochemical reactor comprises an electrocatalyst, a proton conductor membrane and a counter-electrode and wherein the carbon detaching from a catalyst surface of a electrochemical reactor comprises contacting the catalyst with an inert gas flow; feeding the counter-electrode with a hydrogen pure stream for the catalyst regeneration.
  • the regenerating gas is fed directly in the catalyst side above the atmospheric pressure, at a selected temperature, to react with formed carbon yielding methane.
  • the catalyst/electrocatalyst comprises Ni, Fe, Co particles and mixture thereof.
  • the catalyst is in pellet or in a compacted form.
  • the methane rich stream comes from different sources such as biomass, natural gas, tail gases and livestock farming.
  • the pressure ranges from 1 bar to 30 bar, preferably from 1 bar to 10 bar, more preferably from 3 bar to 6 bar.
  • Figure 1 illustrates a simplified schematic diagram of a device for the production of hydrogen and carbon, with catalyst regeneration:
  • (1) - represents the electrochemical chemical reactor
  • (2) - represents the electrode that includes the catalyst
  • (3) - represents the proton conductor ceramic membrane
  • (7) - represents the inlet stream of the counter-electrode side
  • Figure 2 illustrates a simplified schematic diagram of an alternative device for the production of hydrogen and carbon, with catalyst regeneration:
  • (7) - represents the inlet stream of the permeate side of the membrane
  • (12) - represents the hydrogen permselective membrane.
  • Figure 3 illustrates a simplified schematic diagram of an alternative device for the production of hydrogen and carbon, with catalyst regeneration: (5) - represents the inlet stream of the catalyst side;
  • Figure 4 illustrates a simplified schematic diagram of an alternative device for the production of hydrogen and carbon, with catalyst regeneration:
  • Figure 5 is a graph of the hydrogen productivity and methane conversion versus time-on-stream during methane decomposition at 600°C.
  • Equation (1) solid carbon (coke) is also produced, which causes catalyst deactivation.
  • a catalyst regeneration step is required.
  • the present disclosure discloses a method for catalyst regeneration that uses hydrogen to remove coke at the catalyst interface, leading to the detachment of the carbon accumulated on the catalyst surface. Under the considered conditions mainly methane is produced, according to the next equation:
  • the method can be performed in an electrochemical/chemical membrane/bed reactor.
  • the reactor involves a Ni-based catalyst supported on a separation membrane or just a Ni-based supported catalyst, while the electrochemical reactor consists of a MEA (membrane electrode assembly) composed by a Ni-based cathode, a proton conductor membrane and a counter-electrode anode (e.g. Pt or cermet suitable for hydrogen oxidation). Methane is fed to the Ni side where it is decomposed to hydrogen and carbon.
  • MEA membrane electrode assembly
  • Methane is fed to the Ni side where it is decomposed to hydrogen and carbon.
  • the present application also describes a method for catalyst regeneration involving the hydrogenation of coke at the catalyst interface, leading to its detachment. During this step, mainly traces of methane are formed avoiding the contamination of hydrogen with undesired COx off-gases.
  • the permeation of hydrogen towards Ni interface is achieved by electrochemical pumping. A potential difference is applied between Ni and the counter electrode; protons permeate across the proton conductor membrane, reducing coke to methane at the Ni interface with electrons conducted by the external electrical circuit.
  • catalyst regeneration is achieved supplying hydrogen to the Ni side.
  • the Ni-based catalyst is supported in a membrane permeable to hydrogen or supported Ni-based catalyst pellets.
  • Selective methanation of carbon takes place at the carbon-Ni interface, making carbon particles to detach.
  • selective heating up of the metal catalyst also promotes carbon detachment upon hydrogenation of the catalyst/carbon interface.
  • the selective heating of the catalyst is achieved adding to it ceramic additives with very high relative permittivity such as calcium copper titanate (CaCu3Ti40i 2 ), barium titanate (BaTiOs) or strontium titanates (SrTiC and S ⁇ TiC ). These materials absorb microwaves allowing the selective heating upon using a microwave source.
  • the same effect can also be achieved by electrical heating the membrane or, more generally, the reactor; however, this is a less selective heating process besides being slower.
  • methane decomposition and “decomposition” are used interchangeably herein when referring to the methane cracking leading to hydrogen and solid carbon, according to Equation (1).
  • This present subject-matter discloses a method for methane decomposition and catalyst regeneration, in a single and compact device; the methane decomposition produces carbon that accumulates at the catalyst surface provoking its deactivation after a short time of operation, between 30 h and 120 h.
  • the methane decomposition is carried out in an electrochemical membrane reactor as illustrated in Figure 1.
  • This reactor (1) includes a MEA composed by a cermet cathode loaded with a Ni-based catalyst (2), a proton conductor ceramic membrane (3) and a counter-electrode (e.g. Pt or cermet suitable for hydrogen oxidation) (4).
  • the cathode electrode (2) is then fed with methane (5) which is decomposed into hydrogen and carbon at the Ni-based catalyst.
  • This reaction is performed in a range of temperature of 500 °C and 750 °C, more preferably between 550 °C and 650 °C.
  • the reactor (1) is heated by means of a temperature-controlled heating device (9).
  • the catalyst regeneration is obtained by electrochemically pumping hydrogen from the anode (4) to the cathode (2) side, which is achieved applying a potential difference to the electrodes, where the negative side is the cathode.
  • hydrogen reacts selectively with the deposited carbon, producing mostly methane, allowing its detachment.
  • examples of said dense proton conductive membrane are BCY (yttrium-doped barium cerate), BZY (yttrium-doped barium zirconate) and BCZY (yttrium-doped barium cerate-zirconate) and the cathode layer is a cermet made of a composite of these materials and the Ni-based catalyst.
  • the anode layer is made of a Pt catalyst or a cermet suitable for the hydrogen oxidation.
  • methane decomposition is carried out in a chemical membrane reactor illustrated in Figure 2.
  • This reactor (10) includes a Ni- based catalyst (11) supported on a hydrogen and methane permeable membrane (12).
  • porous and dense ceramic or metallic membranes are applied.
  • the membrane reactor (10) is fed with methane (5) which is decomposed into hydrogen and carbon on the Ni-based catalyst (11). This reaction is performed in a range of temperature of 500 °C and 750 °C, more preferably between 550 °C and 650 °C.
  • the reactor (10) is heated by means of a temperature-controlled heating device (9).
  • methane (7) is fed in the permeate side of the membrane (12) that sweeps hydrogen formed in the Ni catalyst (11) and supplies fresh methane to the reaction locus.
  • examples porous ceramic membranes are AI2O3, S1O2, T1O2 and ZrC>2.
  • hydrogen (7) is fed to the permeate side and the Ni-based catalyst (11) is heated up when methane decomposition is interrupted.
  • the regeneration of the catalyst can also be obtained using porous or dense membranes by increasing the hydrogen partial pressure or the temperature. This allows the hydrogenation of the carbon layer attached to the catalyst making the carbon particle to detach it. Carbon reduction at the catalyst interface can rely a chemical reaction with hydrogen or an electrochemical reaction with protons and electrons.
  • methane decomposition can be carried out in a packed bed reactor as illustrated in Figure 3.
  • the Ni-based supported catalyst particles (11) contact with a methane inlet flow (5) which is decomposed into hydrogen and solid carbon.
  • the decomposition reaction is performed in a range of temperature of 500 °C and 750 °C, more preferably between 550 °C and 650 °C.
  • the carbon particles detachment from the metal catalyst can be achieved by increasing the hydrogen partial pressure and/or the temperature. However, this procedure is less selective to the hydrogenation of the interfacial carbon layer, originating a higher hydrogen consumption.
  • the bed is fluidised for carbon particles removal.
  • the methane decomposition cycle is then resumed.
  • methane decomposition can be carried out in a fluidised bed reactor illustrated in Figure 4.
  • the Ni-based supported catalyst particles (14) contact with a methane inlet flow (5) which is decomposed into hydrogen and solid carbon.
  • the decomposition reaction is performed in a range of temperature of 500 °C and 750 °C, more preferably between 550 °C and 650 °C.
  • the carbon particles detachment from the metal catalyst can be achieved by increasing the hydrogen partial pressure and/or the temperature. However, this procedure is less selective to the hydrogenation of the interfacial carbon layer, originating a higher hydrogen consumption.
  • Hydrogen can be selectively removed from the reactors using dense supported or unsupported metallic membranes based on Pd or Pd alloys, such as Pd-Ag alloy (77:23 wt.%). Additionally, a proton conducting cell (PCC) can separate hydrogen from unreacted methane electrochemically and running at the same temperature of the reactor. The separation can also be performed at a different temperature from the reaction medium. Carbon particles can be removed upon decantation, such as in the case of the membrane reactors, or using a cyclone, such as in the case of the fluidised reactor.
  • PCC proton conducting cell
  • methane from different sources such as biomass, natural gas, tail gases and livestock farming, can be used to produce hydrogen.
  • hydrogen purity regarding final disclosure can be tailored based on the methane source.
  • the produced carbon particles can be reused for render back methane upon hydrogenation in a fluidised reactor operating at a pressure between 1 bar and 30 bar and temperature ranging between 500 °C and 750 °C.
  • This allows storing hydrogen, for example produced from renewable sources, which is difficult to store and to transport.
  • the use of carbon as a hydrogen carrier is preferable to the use of CO2 (e.g., methanation of CO2), since the entropy of formation of carbon is much lower than the entropy of formation of CO2. This renders the thermodynamic round-trip efficiency of storing hydrogen using carbon carrier much higher compared with using CO2.
  • the electrochemical reactor illustrated in Figure 1 was assembled with a MEA made of a cathode electrode of BCY loaded with Ni catalyst particles (2), a BCY membrane (3) and a Pt anode counter-electrode (4).
  • the assembly was placed in a temperature-controlled furnace (9) and heated up to 550 °C.
  • the cathode side (2) was then fed with pure CFU (5) (5 ml-min -1 ) and the decomposition conversion was assessed by analysing online the composition of the reactor outlet stream (6) by a CG equipped with TCD and FID detectors.
  • the Pt anode (4) was fed with ISh (7) until the CFU conversion reached a constant value.
  • the CFU stream (5) from the Ni electrode (2) was replaced by N2 and the N2 stream (7) from the Pt electrode side (4) was replaced by FI2.
  • Two approaches were considered for the Ni catalyst regeneration.
  • Figure 5 shows the evolution of the FI2 productivity and CFU conversion with time- on-stream (over 500 h) during methane decomposition
  • Example 2 [0082] In this example, CH4 decomposition and catalyst regeneration were carried out in a chemical reactor as illustrated in Figure 2. The reactor (10) assembly as for the previous example but the CH4 decomposition was carried out at 750 °C. During the regeneration step, Ni side was fed with H2 (5) and different temperature and pressure conditions were tested. On the other hand, the permeate side of the membrane was maintained under N2 atmosphere (7) during all these experiments.
  • Table 1 summarises the working conditions and main results for CH4 decomposition and catalyst regeneration steps.
  • the H2 supplied in the regeneration step represents a small fraction of the H2 produced (ca. 5 %).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé à basse température pour la production d'hydrogène pur à l'aide d'un courant riche en méthane comme matière première, et pour effectuer une régénération de catalyseur in situ. Le procédé implique la décomposition du méthane en hydrogène exempt de COx dans un réacteur électrochimique/ à membrane chimique/chimique ou un réacteur à lit fluidisé chimique. A mesure que la réaction de décomposition du méthane progresse, des structures de carbone (trichites) sont accumulées au niveau de la surface du catalyseur, conduisant à terme à sa désactivation. La régénération du catalyseur est réalisée à l'aide d'une petite fraction de l'hydrogène produit pour réagir avec le carbone formé au niveau de la surface du catalyseur provoquant le détachement du carbone, ce qui régénère le catalyseur. Ceci est obtenu soit par méthanation chimique/électrochimique du carbone au niveau de l'interface du catalyseur avec de l'hydrogène/des protons, soit par augmentation de la température du catalyseur, ce qui maintient idéalement la température du réacteur constante. Un dispositif compact unique est décrit, permettant la production d'hydrogène, la purification d'hydrogène et la régénération du catalyseur.
EP19849002.1A 2018-12-14 2019-12-16 Décomposition catalytique de méthane et régénération de catalyseur, leurs procédés et utilisations Pending EP3894352A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PT2018115211 2018-12-14
PCT/IB2019/060868 WO2020121287A1 (fr) 2018-12-14 2019-12-16 Décomposition catalytique de méthane et régénération de catalyseur, leurs procédés et utilisations

Publications (1)

Publication Number Publication Date
EP3894352A1 true EP3894352A1 (fr) 2021-10-20

Family

ID=69526289

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19849002.1A Pending EP3894352A1 (fr) 2018-12-14 2019-12-16 Décomposition catalytique de méthane et régénération de catalyseur, leurs procédés et utilisations

Country Status (2)

Country Link
EP (1) EP3894352A1 (fr)
WO (1) WO2020121287A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117902551A (zh) * 2024-03-19 2024-04-19 西南石油大学 一种甲烷无碳排放制氢的反应装置

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3222324B1 (fr) 2016-03-23 2020-05-13 Wayne State University Valproate en tant que traitement antifongique topique
EP3868708A1 (fr) * 2020-02-21 2021-08-25 L 2 Consultancy B.V. Procédé et système de décomposition thermique directe d'un composé d'hydrocarbure en carbone et en hydrogène
CN113134354A (zh) * 2021-03-09 2021-07-20 四川轻化工大学 一种高效氧还原反应催化剂的制备方法
EP4227436A1 (fr) * 2022-02-11 2023-08-16 Linde GmbH Procédé et installation d'extraction de l'hydrogène à partir du méthane
CN114870911B (zh) * 2022-03-04 2024-07-16 中化蓝天集团有限公司 一种碳载金属催化剂的再生方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO176522C (no) 1992-04-07 1995-04-19 Kvaerner Eng Fremgangsmåte ved fremstilling av karbon med definerte fysikalske egenskaper samt apparat for gjennomföring av fremgangsmåten
IN2001CN00559A (fr) 1998-09-25 2010-03-19 Kvaerner Technology & Res Ltd
US6632765B1 (en) * 2000-06-23 2003-10-14 Chervon U.S.A. Inc. Catalyst regeneration via reduction with hydrogen
US6509000B1 (en) 2000-08-31 2003-01-21 Council Of Scientific And Industrial Research Low temperature process for the production of hydrogen
ITMI20010138A1 (it) * 2001-01-26 2002-07-26 Lentek S P A Produzione di idrogeno da metano ed impianto utilizzato in tale procedimento
CA2353752A1 (fr) 2001-07-25 2003-01-25 Precisionh2 Inc. Production d'hydrogene et de carbone a partir de gaz naturel ou de methane a l'aide d'un plasma non thermique a decharge a barriere dielectrique
US7468097B2 (en) 2004-07-27 2008-12-23 University Of North Texas Method and apparatus for hydrogen production from greenhouse gas saturated carbon nanotubes and synthesis of carbon nanostructures therefrom
JP4697941B2 (ja) 2005-05-11 2011-06-08 株式会社日本製鋼所 低級炭化水素の直接分解による機能性ナノ炭素及び水素の製造方法
CA2516499A1 (fr) 2005-08-19 2007-02-19 Atlantic Hydrogen Inc. Appareil de decomposition du gaz naturel ou du methane par decharge en arc a froid
WO2011022761A1 (fr) 2009-08-25 2011-03-03 Hope Cell Technologies Pty Ltd Procédé et appareil pour la décomposition plasma de méthane et d’autres hydrocarbures
US8911596B2 (en) 2007-05-18 2014-12-16 Hope Cell Technologies Pty Ltd Method and apparatus for plasma decomposition of methane and other hydrocarbons
JP5434115B2 (ja) 2009-02-12 2014-03-05 株式会社明電舎 芳香族炭化水素製造方法及び芳香族炭化水素製造装置
US9061909B2 (en) 2009-09-10 2015-06-23 The University Of Tokyo Method for simultaneously producing carbon nanotubes and hydrogen, and device for simultaneously producing carbon nanotubes and hydrogen
US10010874B2 (en) * 2013-05-24 2018-07-03 Hindustan Petroleum Corporation Ltd. Catalytic decomposition of lower hydrocarbons to produce carbon oxides free hydrogen and bamboo shaped carbon nanotubes
US20170333889A1 (en) * 2014-10-29 2017-11-23 Flint Hills Resources, Lp Methods for dehydrogenating one or more alkanes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117902551A (zh) * 2024-03-19 2024-04-19 西南石油大学 一种甲烷无碳排放制氢的反应装置
CN117902551B (zh) * 2024-03-19 2024-05-14 西南石油大学 一种甲烷无碳排放制氢的反应装置

Also Published As

Publication number Publication date
WO2020121287A1 (fr) 2020-06-18

Similar Documents

Publication Publication Date Title
EP3894352A1 (fr) Décomposition catalytique de méthane et régénération de catalyseur, leurs procédés et utilisations
US20220073345A1 (en) Catalytic methane decomposition and catalyst regeneration, methods and uses thereof
Kyriakou et al. Methane steam reforming at low temperatures in a BaZr0. 7Ce0. 2Y0. 1O2. 9 proton conducting membrane reactor
JP5219188B2 (ja) 水素製造
JP6728226B2 (ja) 二酸化炭素および硫化水素を共処理する方法
Moon et al. Electrocatalytic reforming of carbon dioxide by methane in SOFC system
US20080283411A1 (en) Methods and devices for the production of Hydrocarbons from Carbon and Hydrogen sources
US20050089740A1 (en) Solid oxide fuel cell(SOFC) for coproducing syngas and electricity by the internal reforming of carbon dioxide by hydrocarbons and electrochemical membrane reactor system
JP2018519414A5 (fr)
US20040101472A1 (en) Method for partial oxidation of methane using dense, oxygen selective permeation ceramic membrane
WO2013180081A1 (fr) Réacteur électrochimique et procédé de production de gaz combustible
US9528190B2 (en) Method for producing liquid organic fuels and hydrogen
JP2007324120A (ja) 多孔質ニッケル皮膜を形成する方法、ならびに関連の物品および成分
JPH0696790A (ja) 生物学的原材料から電気エネルギーを生起させる方法
CA3165456A1 (fr) Methode et installation de production d'hydrogene
JP6945898B2 (ja) 電気化学触媒、集積体、電気化学反応器、炭化水素生成システムおよび炭化水素の生成方法
KR20230156935A (ko) 암모니아 탈수소화
DE10143656B4 (de) Verfahren zur Erzeugung von Energie in einem Brennstoffzellen-Gesamtsystem mit Crackreaktor und Brennstoffzelle sowie Vorrichtung zur Durchführung des Verfahrens
CN116348201A (zh) 烃制造方法
KR102168018B1 (ko) 메탄화 기능이 추가된 연료개질기와 연계된 연료전지 시스템
KR20140108461A (ko) 글라이딩 아크 플라즈마트론 및 이를 이용한 이산화탄소 저감 시스템
Khammona et al. Oxidative coupling of methane over YSZ support catalysts for application in C2 hydrocarbon production
Mazo et al. Methane oxidation catalysts based on the perovskite-like complex oxides of cobalt and nickel
JPH04321502A (ja) 燃料電池用水素製造方法及び装置並びに供給方法
Zhao et al. Protonic electrocatalytic membrane reactors

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

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

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20210706

AK Designated contracting states

Kind code of ref document: A1

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

DAV Request for validation of the european patent (deleted)
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: 20240304