WO2014207703A1 - Ensemble pour la production de méthane à partir du gaz de sol émis par des zones de dégazage - Google Patents

Ensemble pour la production de méthane à partir du gaz de sol émis par des zones de dégazage Download PDF

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Publication number
WO2014207703A1
WO2014207703A1 PCT/IB2014/062635 IB2014062635W WO2014207703A1 WO 2014207703 A1 WO2014207703 A1 WO 2014207703A1 IB 2014062635 W IB2014062635 W IB 2014062635W WO 2014207703 A1 WO2014207703 A1 WO 2014207703A1
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WO
WIPO (PCT)
Prior art keywords
soil gas
methane
production
suited
assembly
Prior art date
Application number
PCT/IB2014/062635
Other languages
English (en)
Inventor
Paolo DEIANA
Claudia BASSANO
Vincenzo Barbarossa
Giuseppina VANGA
Original Assignee
Agenzia Nazionale Per Le Nuove Tecnologie, L'energia E Lo Sviluppo Economico Sostenibile (Enea)
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 Agenzia Nazionale Per Le Nuove Tecnologie, L'energia E Lo Sviluppo Economico Sostenibile (Enea) filed Critical Agenzia Nazionale Per Le Nuove Tecnologie, L'energia E Lo Sviluppo Economico Sostenibile (Enea)
Publication of WO2014207703A1 publication Critical patent/WO2014207703A1/fr

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Classifications

    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention concerns an assembly for the production of methane from soil gas emitted by terrestrial or marine degassing zones.
  • soil gas we mean a gas produced by natural degassing zones.
  • some dormant volcanic areas are characterised by a more or less continuous emission of soil gas from the ground, consisting mainly (90 to 99% vol.) of carbon dioxide (CO 2 ) ⁇
  • the soil gas emitted comprises, in addition to CO 2 , also nitrogen, water vapour, hydrogen sulphide, methane and, to a lesser extent, other components.
  • the gaseous emissions are associated with faults that run through structural highs of buried carbonate rocks with aquifers below.
  • the CO 2 content in these areas can reach values in the order of 50,000 g/m 2 /day.
  • the electric accumulation systems can be defined as systems that store the electric energy converting it into another form of energy (chemical, mechanical, electrostatic, electromagnetic) .
  • the most widespread energy storage systems are electrochemical accumulators, also known as batteries; said systems allow medium-term storage ( ⁇ 1 day) with use limited by their low energy, power density and duration.
  • Other systems include pumping stations and hydroelectric production.
  • the object of the present invention is to provide a solution with technical characteristics such as to meet the needs relative both to the emissions of CO 2 from the ground and storage of the energy from renewable sources.
  • the subject of the present invention is an assembly for the production of methane from soil gas emitted by the ground, the essential characteristics of which are described in claim 1, and the preferred and/or auxiliary characteristics of which are described in claims 2-6.
  • a further subject of the present invention is a method for the production of methane, the essential characteristics of which are described in claim 7, and the preferred and/or auxiliary characteristics of which are described in claims 8 and 9.
  • the number 1 indicates as a whole an embodiment of the assembly subject of the present invention.
  • the assembly 1 comprises collection means for collecting the soil gas from the ground 2, a treatment device for treating the soil gas 3, generation means for generating electric energy from renewable sources 4, an electrolyzer device 5, a methanation section 6 and a treatment device for treating the methane produced 7.
  • the collection means for collecting the soil gas from the ground 2 are produced with systems that provide for containment of the gaseous flow from natural degassing phenomena from the ground in a confined environment.
  • Said collection means preferably comprise a layer of material permeable to the soil gas, a layer of material impermeable to the soil gas arranged above the permeable layer and suited to prevent outflow of the soil gas, and a suction system arranged to act directly on said permeable layer and suited to guarantee both the progress of the soil gas through the permeable layer and draw-off of said soil gas.
  • the suction system is arranged either across the layer of material impermeable to the soil gas or where said impermeable layer is not present in order to act directly on the layer of material permeable to the soil gas without the interposition of the layer of impermeable material.
  • the material permeable to the soil gas comes from the group consisting of stones, gravel, sand, natural fibre fabrics such as cotton, jute and wood fibres whereas the impermeable material consists of clay, synthetic materials such as rubber sheaths, plastic materials and cementitious material .
  • the soil gas thus drawn off is conveyed into the soil gas treatment device 3, the main job of which is to remove from the soil gas the sulphuric compounds in order not to jeopardise the subsequent methanation step by deactivation of the catalyst.
  • the sulphuric compounds can be removed via technologies which entail wet absorption or adsorption on sorbents at high temperature.
  • the wet desulphurization entails washing with water or with 3 ⁇ 4S-selective solvents based on soda or amines, which remove the sulphuric compounds by absorption in the liquid medium.
  • the absorption is performed in packed towers or columns and is favoured by low temperatures in the order of the ambient temperature and pressures which according to the type of absorption - chemical or physical - can range from the ambient pressure to higher pressures.
  • Wet absorption comprises a solvent regeneration section with consequent energy expenditure and recirculation of the regenerated solvent to the absorber.
  • the soil gas treatment device 3 performs desulphurization at high temperature, offering the advantages connected with the possibility of treating solids and non- liquids with obvious simplification in running and costs.
  • the desulphurization at high temperature is based on the adsorption of H 2 S on alkaline and transition metal oxides, capable of removing the sulphides up to parts per million and which can be regenerated via oxidisation with air.
  • the main distinction between the two types of oxides is the possibility or otherwise of regenerating the sulphide that forms.
  • the non-regenerable adsorbents contain alkaline metals (Ca, Ba, Sr) including limestone and dolomite.
  • the regenerable adsorbents contain transition metals (Fe, Zn, Mn, Cu, Ni, etc.) and can be based on single oxides, combination of different oxides and combinations of oxide and aggregates.
  • the pure oxide phase is confined on supports that increase the surface area and reduce the tendency to sinter.
  • reaction occurs above 250°C while the regeneration occurs in nitrogen dilution air atmosphere or in a vapour current and develops in the temperature range of 500°C-900°C with the following reaction:
  • the presence of the means for generation of electric energy from renewable sources 4 is an option that may not be provided if the assembly 1 is directly interfaced with the electric grid.
  • the production of electric energy from renewable sources has the function of covering the electrical requirement of the assembly 1 as a whole. In particular, this refers mainly to the electrical requirement of the electrolyzer and, secondarily, the electrical consumption of auxiliaries, e.g. water recirculation pumps, compressors, suction units and controls.
  • the generation means for generating electric energy from renewable sources 4 can preferably comprise a photovoltaic plant sized in order to cover internal uses or larger in the case of feeding of the surplus electric energy into the grid. This type of plant is immediately available on the market. A small to medium-sized wind generation plant could also be used in said system.
  • the assembly 1 can be connected directly to the electric grid in order to absorb the production surplus at reasonable costs (application as energy storage) .
  • the electrolyzer device 5 can be of alkaline type which uses an aqueous solution of a hydroxide-based alkaline electrolyte with concentration between 25% and 35%.
  • the conventional alkaline electrolyzers operate at a pressure near to ambient pressure and with operating temperatures varying between 70°C and 90°C and a cell voltage ranging from 1.8 to 2.25 V.
  • the consumption relative to the production of 1 Nm 3 of hydrogen is around 4-6 kwh/Nm 3 H 2 with efficiency between 60 and 70%.
  • this type of electrolyzer can produce hydrogen at pressures in the order of 1 to 30 bar.
  • the electrolyzer device 5 can be of the type with polymer electrolyte membrane (PEM) cells.
  • PEM polymer electrolyte membrane
  • This type of electrolyzer allows much higher energy density and power to be achieved but requires catalysts in the platinum group and therefore has higher costs than the alkaline electrolyzers.
  • the values of the energy required in kwh by the process for producing one Nm 3 of 3 ⁇ 4 in the case of electrolyzers with PEM technology are 4-5 kwh/Nm 3 H 2 .
  • the presence of the electrolyzer device 5 in the assembly 1 allows the system to receive the variable supply of electric power.
  • the hydrogen produced (with a 99% degree of purity) is sent to a storage tank (known and therefore neither described nor illustrated for the sake of simplicity) which allows decoupling of the discontinuous operation of the electrolyzer from the continuous operation of the plant.
  • a storage tank known and therefore neither described nor illustrated for the sake of simplicity
  • the oxygen produced by the electrolyzer device having a high degree of purity (99.5%vol), can be advantageously utilised by the market.
  • the methanation section 6 consists of one or more reactors in series/parallel and provides the catalytic conversion of CO 2 into CH .
  • the main reactions involved in the process are listed below.
  • catalysts are used. Many catalysts have been tested (Ni, Cu, Ir, Co, Fe, Pt, Pd, Mo, W , Ru and Rh, all with different supports like AI 2 O 3 , Ti0 2 , Ce0 2 , -MgO-, -MgAl 2 0 4 -, -K 2 0-MgAl 2 0 4 - , Si0 2 , -Cr 2 0 3 , ksr, -MgO- ksr, Zr0 2 , Al 2 0 3 -CaO , La 2 0 3 ) but the most active are those based on nickel and nickel oxides (70 ⁇ 80 %) and A1 2 0 3 oxides (30 ⁇ 20%) .
  • the nickel and nickel oxide catalysts are poisoned by the sulphuric compounds and by the arsenic and therefore the soil gases must be pre-treated to remove the sulphuric compounds.
  • the reaction temperature is maintained around 300°C and, given the exothermicity of the reactions, the temperature in the reactor must not rise above 430°C otherwise the catalytic activity will be reduced.
  • the reaction occurs with reduction in the number of moles, it is possible to operate at a pressure ranging from a few bars up to 60 bars.
  • the fixed bed technology is used (catalyst bed shaped into cylinders or pellets) equipped with pressure, temperature and composition controls.
  • the soil gas supplied is heated to approximately 250°C and sent to the reactor, adjusting the flow rate so that the temperature does not rise beyond the desired values.
  • the methane produced is cooled and sent to the treatment device 7 provided to eliminate its water content.
  • the methane is then compressed to the pressure necessary for the specifications of the network into which it will be fed or to the storage specifications in the case of local consumption.
  • the condensed water downstream of the methanation is subsequently conveyed to the electrolyzer 5 by means of a dedicated transport line 8.
  • the assembly and the method subject of the present invention offer the significant advantage of converting the CO 2 emitted from the ground into methane via a process that uses the hydrogen produced by the electrolysis which in energy terms is supplied by renewable sources. In this way a gas is produced, with zero emissions, which substitutes the natural gas.
  • the particular advantage of the solution of the present invention is the generation of a standardised product, i.e. the methane, which can be fed into the network or stored for local use.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fertilizers (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Cette invention concerne un ensemble pour la production de méthane comprenant au moins un réacteur de méthanation (6) conçu pour convertir le dioxyde de carbone en méthane au moyen d'une hydrogénation catalytique, un dispositif de type électrolyseur (5) conçu pour produire l'hydrogène nécessaire qui sera introduit dans le réacteur de méthanation (6), un moyen de collecte (2) pour collecter à partir de zones de dégazage un gaz de sol comprenant du dioxyde de carbone, et un dispositif de traitement (3) pour désulfurer le gaz de sol collecté par le moyen de collecte (2) et conçu pour purifier le dioxyde de carbone qui sera introduit dans le réacteur de méthanation. Le dispositif de type électrolyseur (5) est alimenté par une énergie électrique provenant de sources renouvelables.
PCT/IB2014/062635 2013-06-26 2014-06-26 Ensemble pour la production de méthane à partir du gaz de sol émis par des zones de dégazage WO2014207703A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITRM2013A000367 2013-06-26
IT000367A ITRM20130367A1 (it) 2013-06-26 2013-06-26 Gruppo per la produzione di metano da gas emesso dal suolo

Publications (1)

Publication Number Publication Date
WO2014207703A1 true WO2014207703A1 (fr) 2014-12-31

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IT (1) ITRM20130367A1 (fr)
WO (1) WO2014207703A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017009575A1 (fr) * 2015-07-16 2017-01-19 Engie Dispositif et procédé de production de gaz de synthèse
FR3081471A1 (fr) * 2018-05-22 2019-11-29 Arkolia Energies Installation de production de methane
WO2021099695A1 (fr) * 2019-11-19 2021-05-27 Arkolia Energies Installation de production de méthane

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2448685A (en) * 2007-04-23 2008-10-29 David Andrew Johnston Carbon dioxide absorbed from air and hydrogen from electrolysis of water, for production of carbon monoxide, alcohols, Fischer-Tropsch hydrocarbons & fuels
WO2011003081A1 (fr) * 2009-07-02 2011-01-06 The University Of Chicago Procédé et système de conversion d'électricité en ressources d'énergies alternatives
WO2012047443A2 (fr) * 2010-10-04 2012-04-12 University Of Southern California Recyclage du dioxyde de carbone par capture et stockage temporaire pour produire des combustibles renouvelables et des produits dérivés
US20120091730A1 (en) * 2009-04-09 2012-04-19 Zentrum Fuer Sonnenenegie-und Wasserstoff-Forschun g Baden-Wuertlemberg Energy Supply System and Operating Method
EP2532729A2 (fr) * 2011-06-10 2012-12-12 SolarFuel GmbH Procédé de préparation d'un mélange gazeux injectable dans un réseau de gaz et installation à cet effet
FR2977089A1 (fr) * 2011-06-17 2012-12-28 Laurent Jean Serge Zibell Stockage et restitution de masse d'electricite sous forme chimique comprenant des etapes d'electrolyse, de methanisation et d'oxycombustion.
US20130041051A1 (en) * 2009-12-23 2013-02-14 Solar Fuel Gmbh Method for producing a methane-rich product gas and reactor system usable for that purpose
WO2013029701A1 (fr) * 2011-08-29 2013-03-07 Ostsee Maritime Gmbh Installation d'alimentation en énergie, destinée notamment au domaine des technologies domestiques

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2448685A (en) * 2007-04-23 2008-10-29 David Andrew Johnston Carbon dioxide absorbed from air and hydrogen from electrolysis of water, for production of carbon monoxide, alcohols, Fischer-Tropsch hydrocarbons & fuels
US20120091730A1 (en) * 2009-04-09 2012-04-19 Zentrum Fuer Sonnenenegie-und Wasserstoff-Forschun g Baden-Wuertlemberg Energy Supply System and Operating Method
WO2011003081A1 (fr) * 2009-07-02 2011-01-06 The University Of Chicago Procédé et système de conversion d'électricité en ressources d'énergies alternatives
US20130041051A1 (en) * 2009-12-23 2013-02-14 Solar Fuel Gmbh Method for producing a methane-rich product gas and reactor system usable for that purpose
WO2012047443A2 (fr) * 2010-10-04 2012-04-12 University Of Southern California Recyclage du dioxyde de carbone par capture et stockage temporaire pour produire des combustibles renouvelables et des produits dérivés
EP2532729A2 (fr) * 2011-06-10 2012-12-12 SolarFuel GmbH Procédé de préparation d'un mélange gazeux injectable dans un réseau de gaz et installation à cet effet
FR2977089A1 (fr) * 2011-06-17 2012-12-28 Laurent Jean Serge Zibell Stockage et restitution de masse d'electricite sous forme chimique comprenant des etapes d'electrolyse, de methanisation et d'oxycombustion.
WO2013029701A1 (fr) * 2011-08-29 2013-03-07 Ostsee Maritime Gmbh Installation d'alimentation en énergie, destinée notamment au domaine des technologies domestiques

Non-Patent Citations (1)

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Title
"Biogas Digest Volume II Biogas -Application and Product Development Information and Advisory Service on Appropriate Technology", 1 January 1999 (1999-01-01), XP055102956, Retrieved from the Internet <URL:http://www2.gtz.de/dokumente/bib/04-5365.pdf> [retrieved on 20140218] *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017009575A1 (fr) * 2015-07-16 2017-01-19 Engie Dispositif et procédé de production de gaz de synthèse
FR3038912A1 (fr) * 2015-07-16 2017-01-20 Engie Dispositif et procede de production de gaz de synthese
CN107922862A (zh) * 2015-07-16 2018-04-17 前苏伊士环能集团 生成合成气的装置和方法
CN107922863A (zh) * 2015-07-16 2018-04-17 前苏伊士环能集团 生成合成气的设备和方法
FR3081471A1 (fr) * 2018-05-22 2019-11-29 Arkolia Energies Installation de production de methane
WO2021099695A1 (fr) * 2019-11-19 2021-05-27 Arkolia Energies Installation de production de méthane

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