WO2020121287A1 - 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 Download PDF

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WO2020121287A1
WO2020121287A1 PCT/IB2019/060868 IB2019060868W WO2020121287A1 WO 2020121287 A1 WO2020121287 A1 WO 2020121287A1 IB 2019060868 W IB2019060868 W IB 2019060868W WO 2020121287 A1 WO2020121287 A1 WO 2020121287A1
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catalyst
hydrogen
process according
previous
methane
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Adélio Miguel MAGALHÃES MENDES
Cecilia MATEOS PEDRERO
Margarida Dias Catarino
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Pixel Voltaic Lda
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Priority to EP19849002.1A priority Critical patent/EP3894352A1/fr
Priority to US17/413,408 priority patent/US20220073345A1/en
Publication of WO2020121287A1 publication Critical patent/WO2020121287A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • 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 %).

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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.
PCT/IB2019/060868 2018-12-14 2019-12-16 Décomposition catalytique de méthane et régénération de catalyseur, leurs procédés et utilisations WO2020121287A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10617659B2 (en) 2016-03-23 2020-04-14 Wayne State University Valproate as a topical anti-fungal treatment
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
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
CN114870911A (zh) * 2022-03-04 2022-08-09 中化蓝天集团有限公司 一种碳载金属催化剂的再生方法
EP4227436A1 (fr) * 2022-02-11 2023-08-16 Linde GmbH Procédé et installation d'extraction de l'hydrogène à partir du méthane

Families Citing this family (1)

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

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993020152A1 (fr) 1992-04-07 1993-10-14 Kvaerner Engineering A.S. Reacteur de decomposition
EP1227062A1 (fr) * 2001-01-26 2002-07-31 LENTEK S.p.A. Procédé et dispositif pour la production d'hydrogène à partir d'un hydrocarbure gazeux
US6509000B1 (en) 2000-08-31 2003-01-21 Council Of Scientific And Industrial Research Low temperature process for the production of hydrogen
US6632765B1 (en) * 2000-06-23 2003-10-14 Chervon U.S.A. Inc. Catalyst regeneration via reduction with hydrogen
US20040148860A1 (en) 2001-07-25 2004-08-05 Fletcher David E. Production of hydrogen and carbon from natural gas or methane using barrier discharge non-thermal plasma
US6773689B1 (en) 1998-09-25 2004-08-10 Kvaerner Technology Research Ltd. Carbon media for storage of hydrogen
US20060021510A1 (en) 2004-07-27 2006-02-02 University Of North Texas Method and apparatus for hydrogen production from greenhouse gas saturated carbon nanotubes and synthesis of carbon nanostructures therefrom
US20060257310A1 (en) 2005-05-11 2006-11-16 The Japan Steel Works, Ltd. Method for producing functional nanocarbon and hydrogen by direct decomposition of lower hydrocarbon
WO2007019664A1 (fr) 2005-08-19 2007-02-22 Atlantic Hydrogen Inc. Decomposition de gaz naturel ou de methane par decharge d'arc froide
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
US20130153403A1 (en) 2007-05-18 2013-06-20 Hope Cell Technologies Pty Ltd Method and apparatus for plasma decomposition of methane and other hydrocarbons
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
US20160129424A1 (en) * 2013-05-24 2016-05-12 Hindustan Petroleum Corporation Ltd. Catalytic Decomposition of Lower Hydrocarbons to Produce Carbon Oxides Free Hydrogen and Bamboo Shaped Carbon Nanotubes
US9358536B2 (en) 2009-02-12 2016-06-07 Meidensha Corporation Method for producing aromatic hydrocarbon and apparatus for producing aromatic hydrocarbon
US20170333889A1 (en) * 2014-10-29 2017-11-23 Flint Hills Resources, Lp Methods for dehydrogenating one or more alkanes

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993020152A1 (fr) 1992-04-07 1993-10-14 Kvaerner Engineering A.S. Reacteur de decomposition
US6773689B1 (en) 1998-09-25 2004-08-10 Kvaerner Technology Research Ltd. Carbon media for storage of hydrogen
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
EP1227062A1 (fr) * 2001-01-26 2002-07-31 LENTEK S.p.A. Procédé et dispositif pour la production d'hydrogène à partir d'un hydrocarbure gazeux
US20040148860A1 (en) 2001-07-25 2004-08-05 Fletcher David E. Production of hydrogen and carbon from natural gas or methane using barrier discharge non-thermal plasma
US20060021510A1 (en) 2004-07-27 2006-02-02 University Of North Texas Method and apparatus for hydrogen production from greenhouse gas saturated carbon nanotubes and synthesis of carbon nanostructures therefrom
US7767182B2 (en) 2005-05-11 2010-08-03 The Japan Steel Works, Ltd. Method for producing functional nanocarbon and hydrogen by direct decomposition of lower hydrocarbon
US20060257310A1 (en) 2005-05-11 2006-11-16 The Japan Steel Works, Ltd. Method for producing functional nanocarbon and hydrogen by direct decomposition of lower hydrocarbon
WO2007019664A1 (fr) 2005-08-19 2007-02-22 Atlantic Hydrogen Inc. Decomposition de gaz naturel ou de methane par decharge d'arc froide
US20090038933A1 (en) 2005-08-19 2009-02-12 Boutot Tobie Jean Decomposition of Natural Gas or Methane Using Cold Arc Discharge
US8221689B2 (en) 2005-08-19 2012-07-17 Atlantic Hydrogen Inc. Decomposition of natural gas or methane using cold arc discharge
US20130153403A1 (en) 2007-05-18 2013-06-20 Hope Cell Technologies Pty Ltd Method and apparatus for plasma decomposition of methane and other hydrocarbons
US9358536B2 (en) 2009-02-12 2016-06-07 Meidensha Corporation Method for producing aromatic hydrocarbon and apparatus for producing aromatic hydrocarbon
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
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
US20160129424A1 (en) * 2013-05-24 2016-05-12 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

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
BOUSQUET, P.TYLER, S. C.PEYLIN, P.VAN DER WERF, G. R.PRIGENT, C.HAUGLUSTAINE, D. A.DLUGOKENCKY, E. J.MILLER, J. B.CIAIS, P.WHITE, : "Contribution of anthropogenic and natural sources to atmospheric methane variability", NATURE, vol. 443, no. 7110, 2006, pages 439 - 443
LEWIS, S. L.: "The Paris Agreement has solved a troubling problem", NATURE, vol. 532, no. 7599, 2016, pages 283
LUA, A.C.WANG, H.Y.: "Decomposition of methane over unsupported porous nickel and alloy catalyst", APPLIED CATALYSIS B: ENVIRONMENTAL, vol. 132-133, 2013, pages 469 - 478
SHAH, N.PANJALA, D.HUFFMAN, G.P.: "Hydrogen Production by Catalytic Decomposition of Methane", ENERGY & FUELS, vol. 15, no. 6, 2001, pages 1528 - 1534
UPHAM, D.C.AGARWAL, V.KHECHFE, A.SNODGRASS, Z.R.GORDON, M.J.METIU, H.MCFARLAND, E.W.: "Catalytic molten metals for the direct conversion of methane to hydrogen and separable carbon", SCIENCE, vol. 358, no. 6365, 2017, pages 917 - 921, XP055463666, DOI: 10.1126/science.aao5023

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10617659B2 (en) 2016-03-23 2020-04-14 Wayne State University Valproate as a topical anti-fungal treatment
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
CN114870911A (zh) * 2022-03-04 2022-08-09 中化蓝天集团有限公司 一种碳载金属催化剂的再生方法

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