EP4001381A1 - Procédé de production de biométhane de haute pureté - Google Patents

Procédé de production de biométhane de haute pureté Download PDF

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Publication number
EP4001381A1
EP4001381A1 EP21206402.6A EP21206402A EP4001381A1 EP 4001381 A1 EP4001381 A1 EP 4001381A1 EP 21206402 A EP21206402 A EP 21206402A EP 4001381 A1 EP4001381 A1 EP 4001381A1
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EP
European Patent Office
Prior art keywords
reactor
biogas
biomethane
gaseous mixture
production
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
EP21206402.6A
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German (de)
English (en)
Inventor
Paolo Canu
Mattia PAGIN
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.)
K Inn Tech Srl
K Inn Tech Srl
Original Assignee
K Inn Tech Srl
K Inn Tech Srl
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 K Inn Tech Srl, K Inn Tech Srl filed Critical K Inn Tech Srl
Publication of EP4001381A1 publication Critical patent/EP4001381A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/106—Removal of contaminants of water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/06—Heat exchange, direct or indirect
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/26—Composting, fermenting or anaerobic digestion fuel components or materials from which fuels are prepared

Definitions

  • the present invention relates to a method for the production of high-purity biomethane from biogas.
  • high-purity biomethane is understood to mean biomethane with less than 1% hydrogen (H 2 ) by volume with less than 2.5% molar carbon dioxide (CO 2 ) and less than 0.1% molar carbon monoxide (CO).
  • the invention can be used in the industrial/chemical field in the renewable energy industry sector.
  • Biogas is a renewable energy source obtained from:
  • Biomethane is obtained from biogas by means of two successive steps:
  • anaerobic digestion is understood to mean the degradation of biomass by bacteria in the absence of molecular oxygen.
  • Biogas upgrading is a process suitable to increase the methane content in the initial biogas, obtaining biomethane which can be likened to natural gas.
  • CO 2 is generally sold to other plants/companies and/or stored, for example underground, with the technique known as Carbon Capture and Storage (CCS).
  • CCS Carbon Capture and Storage
  • CO 2 contains carbon (C) which could be usefully converted into methane.
  • the aim of the present invention is to provide a method for producing biomethane that is capable of improving the background art in one or more of the aspects mentioned above.
  • an object of the invention is to provide a method for the production of biomethane that allows full utilization of the carbon contained in the initial biogas as it is.
  • Another object of the invention is to devise a method for the production of biomethane in which CO 2 , which might not find a commercial use and would then have to be disposed of, is not produced.
  • a further object of the present invention is to overcome the drawbacks of the background art in a manner that is alternative to any existing solutions.
  • Not the least object of the invention is to provide a method for the production of biomethane that is highly reliable, relatively easy to provide and has competitive costs.
  • biomethane from biogas characterized in that said biogas is subjected to at least two steps of biogas upgrading, with intermediate removal of H 2 O, said biogas upgrading step consisting in the direct methanation reaction of the CO 2 that is present in the biogas: CO 2 + 4H 2 ⁇ CH 4 + 2H 2 O.
  • an indicated method for the production of biomethane from biogas is the one shown schematically in Figure 1 .
  • the biogas 100 is subjected to at least one biogas upgrading step, a step designated by the reference numeral 2, in Figure 1 .
  • biogas 100 is understood to reference biogas purified of contaminants, such as H 2 S (hydrogen sulfide), NH 3 (ammonia), siloxanes and/or other acid/base agents and materials that may solidify and/or affect the catalytic converters mentioned hereinafter.
  • contaminants such as H 2 S (hydrogen sulfide), NH 3 (ammonia), siloxanes and/or other acid/base agents and materials that may solidify and/or affect the catalytic converters mentioned hereinafter.
  • the step for the production of biogas 100 occurs by producing raw biogas according to a technique known per se, such as the one shown previously, and subsequently purifying it of unwanted compounds such as hydrogen sulfide (H 2 S), ammonia (NH 3 ), water H 2 O, siloxanes and chlorine (CI) compounds.
  • H 2 S hydrogen sulfide
  • NH 3 ammonia
  • CI chlorine
  • biogas upgrading step consists in the methanation reaction (MET): CO 2 + 4H 2 ⁇ CH 4 + 2H 2 O.
  • the CO 2 of which the biogas 100 is composed is converted through a methanation reaction, which consists in the catalytic hydrogenation of CO 2, , obtaining CH 4 and water (H 2 O).
  • Figure 2 is a detailed diagram of a first embodiment of the method according to the invention.
  • the method consists of two steps, which occur in two successive apparatus lines L1, L2 fluidically connected to each other.
  • Each one of the apparatus lines L1, L2 comprises respectively a reactor R1, R2 and a condenser C1, C2, as explained hereinafter, which is fluidically connected to the preceding one.
  • the two apparatus lines L1, L2 are arranged in series, as shown in Figure 2 .
  • the biogas 100, together with hydrogen (H) 101, is introduced in the first apparatus line L1, in a first reactor R1, and the mixture crosses a catalytic converter 12 contained inside the first reactor R1.
  • Figure 4 shows the first reactor R1, but this illustration also exemplifies the second reactor R2, described hereinafter, which is similar to the first one.
  • the supply of hydrogen (H 2 ) 101 to the first reactor R1 can occur, for example, by using electrolyzers, of a type known per se, and/or lines which carry H 2 from industrial production hubs.
  • the hydrogen 101 is produced by electrolyzers connected to the first reactor R1.
  • the first reactor R1 is a fixed bed reactor, made of metallic material, preferably of a metallic alloy such as one of those of the family of nickel- and chromium-based alloys known by the trade name "Inconel” and/or stainless steel.
  • the reactors R1, R2 are of the fluidized bed type.
  • the reactors R1, R2 operate at a temperature substantially comprised between 200°C and 350°C and at a pressure substantially comprised between 1 bar and 30 bars.
  • the corresponding catalytic converters 12 of the reactors R1, R2 are provided with a fine dispersion, on ceramic supports, of active metallic material, advantageously based on one or more metals of groups 8-10 of the periodic table of elements.
  • the catalytic converter 12 is, for example, based on ruthenium (Ru) and/or iron (Fe) and/or nickel (Ni) and/or cobalt (Co).
  • Said catalytic converter 12 is preferably based on nickel (Ni).
  • the catalytic converter 12 has a porous ceramic support, which is mechanically and thermally stable, such as alumina (Al 2 O 3 ) and/or silica (SiO 2 ) and/or titanium dioxide (TiO 2 ) and/or silicon carbide and/or other ceramic materials with a high specific surface.
  • alumina Al 2 O 3
  • silica SiO 2
  • TiO 2 titanium dioxide
  • silicon carbide silicon carbide and/or other ceramic materials with a high specific surface.
  • high specific surface is understood to mean the total surface per unit of mass of the catalytic converter, with which the gas can come in contact, by both internal and external porosity.
  • the catalytic converter 12 has a catalytic support made of alumina- ⁇ .
  • Such a catalytic converter 12 facilitates the MET reaction and limits the development of RWGS and DR reactions and therefore the production of CO.
  • the catalytic converter 12 is pretreated in a reducing environment at 600°C with H 2 , on the order of 1.9 m 3 per kilogram of catalyst.
  • the gaseous mixture obtained is made to condense in a first condenser C1, in order to remove the H 2 O that prevents the further development of the reaction toward higher purities of biomethane.
  • impure biomethane is understood to mean biomethane which has a volumetric percentage of H 2 greater than 1% and/or which does not meet the legal requirements for direct injection into the natural gas network.
  • the gaseous mixture that exits from the first condenser C1, and from the first apparatus line L1, is injected into the second apparatus line L2, into a second reactor R2, without further additions of reagents, which is similar to the first reactor R1 and in which a second methanation reaction occurs, obtaining high-purity biomethane, i.e., with H 2 lower than 1% by volume, with CO 2 lower than 2.5% molar and with CO lower than 0.1% molar.
  • the gaseous mixture that exits from the second reactor R2 is made to condense in a second condenser C2 in order to remove the H 2 O that is present.
  • Biomethane 10 that meets the purity requirements necessary for injection into the natural gas network exits from the second condenser C2.
  • the heat Q produced by the first reactor R1 can be used to:
  • auto-thermal operation in the present description, is understood to mean that the thermal energy necessary for the operation of the reactor is obtained directly from the reaction that occurs inside it, including its outward dispersions.
  • H 2 O obtained from the condensation in the first condenser C1 and in the second condenser C2 can be reused by the optional electrolyzer for the supply of hydrogen (H) 101.
  • the two apparatus lines L1 and L2 are arranged in parallel and are fluidically connected, upstream of the respective reactors R1 and R2 and downstream of the respective condensers C1 and C2, by means of two four-way valves V1, V2, respectively:
  • the two valves V1, V2 change position simultaneously, passing from the configuration shown in Figure 3a to the one shown in Figure 3b , and vice versa, depending on the production step, and in a sequential manner.
  • Such apparatus structure makes it possible to swap periodically the reactor R1 with the reactor R2, in which the first reaction, which is the most exothermic one, occurs, in order to utilize the sensible heat accumulated inside the reactor by changing the position of the first valve VI and of the second valve V2.
  • This second embodiment of the method allows therefore a reduction of the initial apparatus costs and the operating costs due to the use of service fluids.
  • the method corresponds to the one of the first embodiment described above and one obtains in output from the second condenser C2 biomethane 10 which meets the requirements for injection into the natural gas network.
  • the biogas 100 and the hydrogen 101 are then injected into the second apparatus line L2, in which the first reaction step occurs, and into the second reactor R2, in which the first methanation reaction occurs.
  • the second reactor R2 is heated more, while the second reaction step, with the second methanation reaction, downstream of the second condenser C2, which is less exothermic due to the lower concentration of reactants, occurs in the first apparatus line L1, inside the first reactor R1, which is already hot as a result of the previous configuration.
  • the gaseous mixture Downstream of the first reactor R1, the gaseous mixture is made to condense on the first condenser C1, obtaining high-purity biomethane 10 ( Figure 3b ) to be injected into the natural gas network.
  • both reactors R1 and R2 are hot, at a sufficient temperature, and it is no longer necessary to supply energy to the apparatus from the outside.
  • This apparatus structure eliminates the heat exchanges between the reactors R1, R2 of the first apparatus structure and utilizes the thermal inertia of the catalytic beds, possibly modified by using also inert fillers with high thermal capacity, such as for example silicon carbide.
  • the reactor R1, R2 is thermally insulated in order to work in adiabatic conditions with contact times comprised between 40 m 3 /(Kgcat ⁇ h) and 80 m 3 /(Kgcat ⁇ h) and a pressure comprised between 1 bar and 30 bars.
  • the method occurs substantially by means of two successive steps, each consisting of a methanation reaction and a condensation.
  • the invention achieves the intended aim and objects, utilizing the principles of the chemical equilibrium which limits the reaction in a single step, and providing a method for the production of biomethane that allows full utilization of the initial biogas.
  • the invention provides a method for the production of biomethane from biogas in which CO 2 which might not find a commercial use is not produced.
  • the invention provides a method for the production of biomethane from biogas in which all the carbon C contained in the CO 2 is converted into CH 4 .
  • the reaction is self-sustaining in the present description is understood to mean that the reaction, once triggered, releases a quantity of heat capable of sustaining the activation energy demand of the reaction itself and the residual heat dispersions.
  • the materials used may be any according to the requirements and the state of the art.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP21206402.6A 2020-11-17 2021-11-04 Procédé de production de biométhane de haute pureté Pending EP4001381A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT202000027474 2020-11-17

Publications (1)

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EP4001381A1 true EP4001381A1 (fr) 2022-05-25

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EP21206402.6A Pending EP4001381A1 (fr) 2020-11-17 2021-11-04 Procédé de production de biométhane de haute pureté

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014001933A1 (de) * 2014-02-12 2015-08-13 Michael Niederbacher Verfahren und Anlage zum Erzeugen von Biomethan
WO2021234073A1 (fr) * 2020-05-20 2021-11-25 Tma-Process Procede de methanation de l'hydrogene h2 et du dioxyde de carbone co2 ou de l'hydrogene h2 et du monoxyde de carbone co en vue de la production de methane ch4

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014001933A1 (de) * 2014-02-12 2015-08-13 Michael Niederbacher Verfahren und Anlage zum Erzeugen von Biomethan
WO2021234073A1 (fr) * 2020-05-20 2021-11-25 Tma-Process Procede de methanation de l'hydrogene h2 et du dioxyde de carbone co2 ou de l'hydrogene h2 et du monoxyde de carbone co en vue de la production de methane ch4

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
ADNAN ET AL: "Technologies for Biogas Upgrading to Biomethane: A Review", BIOENGINEERING, vol. 6, no. 4, 2 October 2019 (2019-10-02), pages 92, XP055644058, DOI: 10.3390/bioengineering6040092 *
CURTO DIEGO ET AL: "Renewable based biogas upgrading", JOURNAL OF CLEANER PRODUCTION, vol. 224, 20 March 2019 (2019-03-20), pages 50 - 59, XP085670709, ISSN: 0959-6526, DOI: 10.1016/J.JCLEPRO.2019.03.176 *
MUÑOZ RAÚL ET AL: "A review on the state-of-the-art of physical/chemical and biological technologies for biogas upgrading", REVIEWS IN ENVIRONMENTAL SCIENCE AND BIO-TECHNOLOGY, KLUWER, DORDRECHT, NL, vol. 14, no. 4, 26 September 2015 (2015-09-26), pages 727 - 759, XP035930331, ISSN: 1569-1705, [retrieved on 20150926], DOI: 10.1007/S11157-015-9379-1 *
NATALIA ALFARO ET AL: "Evaluation of process performance, energy consumption and microbiota characterization in a ceramic membrane bioreactor for ex-situ biomethanation of H2 and CO2", BIORESOURCE TECHNOLOGY, vol. 258, 23 February 2018 (2018-02-23), AMSTERDAM, NL, pages 142 - 150, XP055701493, ISSN: 0960-8524, DOI: 10.1016/j.biortech.2018.02.087 *
NATURAL GAS AND BIOMETHANE FOR USE IN TRANSPORT AND BIOMETHANE FOR INJECTION IN THE NATURAL GAS NETWORK, December 2016 (2016-12-01)

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