WO2014009146A1 - Procédé pour la méthanation de gaz de gazogène issu de gazéification sur des catalyseurs métalliques en présence de soufre - Google Patents

Procédé pour la méthanation de gaz de gazogène issu de gazéification sur des catalyseurs métalliques en présence de soufre Download PDF

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Publication number
WO2014009146A1
WO2014009146A1 PCT/EP2013/063288 EP2013063288W WO2014009146A1 WO 2014009146 A1 WO2014009146 A1 WO 2014009146A1 EP 2013063288 W EP2013063288 W EP 2013063288W WO 2014009146 A1 WO2014009146 A1 WO 2014009146A1
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WIPO (PCT)
Prior art keywords
methanation
catalyst
sulfur
reactor
metal
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PCT/EP2013/063288
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English (en)
Inventor
Serge Biollaz
Marcelo Daniel Kaufman Rechulski
Christian Felix Julian König
Maarten Nachtegaal
Tilman J. Schildhauer
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Paul Scherrer Institut
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Priority to DK13734007.1T priority Critical patent/DK2870125T3/en
Priority to EP13734007.1A priority patent/EP2870125B1/fr
Publication of WO2014009146A1 publication Critical patent/WO2014009146A1/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
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/103—Sulfur containing contaminants
    • 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
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/104—Carbon dioxide

Definitions

  • Catalytic conversion of producer gases from gasification of solid feedstocks usually requires desulfurization in order to protect catalysts in downstream processes such as state-of the-art Fischer-Tropsch synthesis or methanation for production of Synthetic Natural Gas
  • Rabou & Bos describe the use of a commercial molybdenum based hydrodesulphurization (HDS) catalyst to convert thiophenes etc. to hydrogen sulfide (H 2 S) which is followed by H 2 S removal by means of a metal oxide bed (ZnO) and subsequent methanation over a nickel catalyst.
  • HDS molybdenum based hydrodesulphurization
  • ZnO metal oxide bed
  • Catalysts for sulfur tolerant methanation are for instance molybdenum sulfide or vanadium sulfide [2b, 2c] .
  • Li et al . [4] describe the regenerative desulfurization of producer gas from coal or biomass gasification over metal based absorber materials.
  • Carr et al. [8] describe a method of regeneration of sulfur poisoned hydrocarbon cracking catalysts consisting of several cycles of oxidation and subsequent reduction.
  • the catalyst used is based on Co, Ni, W, Cu, Mo, Cr, Mn, V or their oxides while the temperature for oxidation is between 900 - 1100 ° F.
  • Aguinaga & Montes [9] describe the regeneration of nickel catalysts by a sequence of oxidation- and reduction steps at constant temperature between 200°C and 500°C.
  • the catalysts were poisoned by thiophene and the regeneration procedure with very low O 2 concentration (0.05 vol-%) removed up to 80% of the sulfur in 26 minutes.
  • Li et al [10] describe the regeneration of sulfur-poisoned nickel steam reforming catalysts with an oxidation- and a reduction step.
  • the proposed temperatures are > 750°C for the oxidation in diluted oxygen, and > 850 °C for the regeneration in inert gas and subsequent reduction in diluted hydrogen which is far above the temperature limit for a typical methanation catalyst.
  • the methanation catalyst is a metal, a metal oxide, a metal sulfide or a mixture of metals, metal oxides or metal sulfide/nitride/phosphide on a support;
  • said metal or metals are selected from a group
  • the metal or metals can be promoted by one or more of the following elements: K, P, Na, Ba, Ni, Ru, Rh, Co,
  • This method provides for the methanation of a producer gas proposing a simplified process as compared to the prior art.
  • the method achieves a nearly complete methanation of CO in the presence of both organic and inorganic sulfur compounds, as well as olefins, tars etc., combined with an at least partial uptake of sulfur followed by a relatively fast oxidative regeneration of the methanation catalyst (bed material) and sulfur release, preferably at a temperature level near the methanation temperature.
  • sulfur species present in the synthesis gas mixture include, but are not limited to, one or more of the following compounds: hydrogen sulfide (H 2 S) , carbonyl sulfide (COS) , carbon disulfide (CS 2 ) , thiophene (C 4 H 4 S) , Benzothiophene (CsH 6 S) , Dibenzothiophene (Ci 2 H 8 S) and their derivates.
  • H 2 S hydrogen sulfide
  • COS carbonyl sulfide
  • CS 2 carbon disulfide
  • thiophene C 4 H 4 S
  • Benzothiophene CsH 6 S
  • Dibenzothiophene Dibenzothiophene
  • a fast regeneration of the methanation catalyst is achieved when the regeneration of the methanation catalyst is performed by oxidation of the methanation catalyst in the presence of an oxidizing agent, preferably when the regeneration of the methanation catalyst is performed by oxidation of the catalyst with a gaseous oxidizing agent.
  • said gaseous oxidizing agent may be air, air diluted with inert gas or air diluted with product gas after the methanation step. From the energetic point of view, suitable reaction
  • conditions can be achieved when the methanation and the regeneration are performed at different temperatures between 300°C and 1100°C, thereby preferring for the methanation step a range between 300°C and 450°C.
  • the methanation and the regeneration may be performed at the same temperature between 300°C and 700°C, preferably in the range from 300°C and 450°C.
  • a further preferred embodiment of the present invention can be achieved when a resulting product of the catalyst
  • the catalytic methanation can be performed in a fluidized bed reactor or an entrained flow reactor, from which a part of the catalyst can be conveyed to another fluidized bed reactor or another entrained flow reactor, in which the methanation catalyst can be oxidized and subsequently conveyed back to said methanation reactor.
  • the catalytic methanation can be performed in a fluidized bed reactor or an entrained flow reactor, from which a part of the catalyst can be conveyed to another fluidized bed reactor or another entrained flow reactor, in which the methanation catalyst can be oxidized and
  • Another alternative can provide for the catalytic reaction
  • methanation being performed in one or more fixed bed
  • reactors of which at least one is temporarily disconnected from a feed of the synthesis gas mixture thereby being subject to an exposure to a gaseous oxidizing agent.
  • another advantageous feature of a preferred embodiment of the present invention provides for controlling the temperature in the catalytic methanation by means of internal heat exchangers or external heat exchange in a recycle stream or in a transfer line between methanation part and regeneration part.
  • the temperature control for the catalytic methanation can be supported or achieved by controllable insertion of the reactant gases and/or by several feeding points and/or by cross flow and/or flow reversal .
  • the catalyst support can be modified to minimize the adsorption of sulfur or carbon species.
  • Fig. 1 a biomass methanation method as described by
  • Fig. 2 a simplified biomass methanation process
  • Fig. 3 a simplified scheme of the combined sulfur removal and methanation process
  • Fig. 4 measured signal at the outlet of the methanation reactor at constant temperature of 430°C versus time for diverse reactants .
  • the present invention for the process of the methanation of producer gas proposes a simplified process (see Fig. 2) with nearly complete methanation of CO in the presence of both organic and inorganic sulfur compounds, olefins, tars etc. combined with an at least partial uptake of sulfur followed by a relatively fast oxidative regeneration of the bed material and sulfur release at a temperature level near the methanation temperature.
  • the present invention comprises continuous methanation, catalyst regeneration and sulfur removal and therefore leads to less unit operations.
  • the catalyst regeneration can be performed at relatively high oxygen partial pressures, which allows performing the regeneration much faster.
  • the catalyst reduction can be performed in the methanation reactor and does not require, but may have a specific reduction reactor.
  • the product gas, coming from a low temperature gasifier is sent into a catalytic reactor, where H 2 and CO form CH 4 and H 2 0. (see Fig. 2) .
  • the catalytic reactor comprises a
  • the sulfur species e.g. H 2 S, COS, C 4 H 4 S, thiophene-derivates , benzothiophenes , dibenzothiophenes
  • carbon species e.g. C 2 H 4 , aromatics and other unsaturated hydrocarbons
  • the catalyst looses its activity for the synthesis, while sulfur and/or some carbon adsorb or deposit on the catalyst, thereby removing the sulfur and/or carbon species from the gas stream.
  • the inactive catalyst is regenerated in the
  • the regeneration part of the reactor in presence of an oxidant such as diluted oxygen (e.g. air mixed with oxygen-depleted flue gas, but also peroxides, N20 or metal oxides) .
  • diluted oxygen e.g. air mixed with oxygen-depleted flue gas, but also peroxides, N20 or metal oxides
  • This oxidizes the adsorbed or deposited carbon and sulfur species on the catalyst surface and removes them in the form of S0 2 and C0 2 to the exhaust.
  • the regenerated catalyst is fed back to the synthesis part where it catalyses the desired reactions (methanation etc.) until the catalyst is deactivated again.
  • Both parts of the reactor can be operated at different temperatures, where the synthesis part is operated at preferentially around 300 °C, and the temperature in the regeneration part is > 300°C (see Fig. 3) .
  • Both parts of the reactor can be operated at the same temperature, especially in the range of 400 - 450°C.
  • the reactor can be designed
  • the reactor can be designed as a swing reactor, where the fuel gas and the oxygen-containing gas are switched between two or more packed bed reactors, e.g. when the catalyst activity drops below a certain limit.
  • the catalyst can be mechanically transported in a moving bed design between the synthesis reactor and the regeneration reactor.
  • the regeneration of the catalyst may take place in a certain zone of a combined reactor .
  • the poisoned catalyst can be transported from a first methanation reactor where it is exposed to sulfur- laden synthesis gas to the regeneration reactor, and from said regeneration reactor to a second methanation reactor which is placed downstream of said first methanation reactor, where the catalyst is exposed to a sulfur-depleted synthesis gas which had been at least partially converted to methane. From said second methanation reactor, the catalyst can be then transported to said first methanation reactor or to said oxidation reactor. Further, it is possible to introduce a solid adsorber bed such as ZnO between the first and the second methanation reactor to further deplete the gas in sulfur before it enters the second methanation reactor downstream.
  • a solid adsorber bed such as ZnO
  • the catalyst can be deposited on a solid substrate, such as a monolith, where one or more monoliths are exposed to sulfur-laden synthesis gas while one or more monoliths are exposed to oxidizing conditions, and the gas feeds (e.g. reducing/methanation/sulfur
  • the catalyst may be suspended in a liquid (e.g. ionic liquid), which may have additional useful absorption capacity for sulfur species, nitrogen species, ions, salts, tars, olefins and/or C02.
  • a liquid e.g. ionic liquid
  • the reactions are then carried out in three phase flow such as a bubble column.
  • the change of atmosphere around the catalyst material may then be achieved either by change of the gas composition fed, by addition of liquid or solid oxidants or by transporting the liquid phase with the suspended catalyst between one or more reactors fed with differing gas
  • the catalyst may be connected to a moving part (similar to a recuperator, e.g. in form of a spinning monolith) which is moved or turned between reactors or reactor parts with the differing gas atmosphere.
  • a moving part similar to a recuperator, e.g. in form of a spinning monolith
  • the addition of the oxidant to the regeneration step may take place by addition of (diluted) air or oxygen containing (flue) gas, by addition of gaseous or liquid peroxides or other oxidizing species (e.g. hydrogen peroxide, N20) , by addition of solid oxidizing species (e.g. metal oxides), by transport of oxygen (e.g as ion or carbonate) through a membrane or by a combination of them.
  • oxygen containing gases or species that may split off oxygen are fed on the retention side of the membrane.
  • gas and/or liquid and/or solids may be taken out and cooled externally, followed by recycle to the methanation/reducing steps.
  • cooling may be achieved by evaporation of a liquid in the reducing/methanation step or in the transfer lines, by latent heat uptake in a solid or liquid or by coupling with an endothermic reaction.
  • temperature control may be achieved or supported by suitable addition of the reactant gases, e.g. several feeding points, cross flow, flow reversal etc.
  • the catalyst is preferably a supported Ru catalyst or Ru containing catalyst, which may contain species supporting the sulfur uptake and/or the methanation reaction. Further, a combination or common transport of species or materials supporting the sulfur uptake and/or the methanation reaction may be applied. It is advantageous to choose the support and the regeneration conditions such that adsorption of sulfur species (e.g. H2S, S02) on the support and subsequent release and spill-over on the catalyst in any further step is minimized. Besides the choice of non-acidic supports (e.g. carbides, nitrides or phosphides), this may be accomplished or supported by modification of the (surface) properties of the support.
  • sulfur species e.g. H2S, S02
  • Fig. 4 shows the measured signal at the outlet of the reactor at constant temperature of 430°C versus time.
  • H 2 (m/z 2) starts flowing through the reactor at time tl.
  • CO is added at time t2, which is reflected by the increasing methane signal (m/z 15) .
  • H 2 S/COS/C 4 H 4 S/Ar are added at time t3.
  • COS m/z 60
  • C 4 H 4 S (m/z 84) are

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention porte sur un procédé pour la production catalytique d'un mélange de gaz riche en méthane à partir de gaz de synthèse contenant du soufre avec élimination simultanée au moins partielle de soufre, comprenant : a) la production d'un mélange de gaz de synthèse ; et b) la mise en contact dudit mélange de gaz de synthèse avec un catalyseur de méthanation, ce qui désactive de cette manière en continu le catalyseur de méthanation par le soufre et éventuellement les espèces carbonées comprises dans le mélange de gaz de synthèse dans une partie du processus de méthanation, alors qu'une partie dudit catalyseur de méthanation appauvri est simultanément régénérée par oxydation dans une partie différente du processus : c) le catalyseur de méthanation étant un métal, un oxyde métallique, un sulfure métallique ou un mélange de métaux, d'oxydes métalliques ou de sulfure/nitrure/phosphure métallique sur un support ; d) ledit métal ou lesdits métaux étant choisis dans un groupe comprenant Ni, Ru, Mo, Co, Fe, Rh, Pd, Pt, Ir, Os, W et V, le support étant un oxyde choisi dans un groupe comprenant Al2O3, SiO2, TiO2, CeO2, ZrO2, les carbures, les nitrures, les phosphures ou les mélanges de ceux-ci et e) le métal ou les métaux pouvant être activés par un ou plusieurs des éléments suivants : K, P, Na, Ba, Ni, Ru, Rh, Co, Pt, Pd, Ir, W, Os, V ou Mn. Le procédé permet de réaliser une méthanation presque totale du CO en présence de composés aussi bien organiques qu'inorganiques du soufre, tels que des oléfines, des goudrons, etc., combinée avec une capture au moins partielle du soufre suivie d'une régénération par oxydation relativement rapide du catalyseur de méthanation (matériau en lit) et d'une libération du soufre, de préférence à un niveau de température proche de la température de méthanation.
PCT/EP2013/063288 2012-07-09 2013-06-25 Procédé pour la méthanation de gaz de gazogène issu de gazéification sur des catalyseurs métalliques en présence de soufre WO2014009146A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DK13734007.1T DK2870125T3 (en) 2012-07-09 2013-06-25 Process for methanization of gasification-derived generator gas on metal catalysts in the presence of sulfur
EP13734007.1A EP2870125B1 (fr) 2012-07-09 2013-06-25 Procédé destiné à produire un mélange gazeux riche en méthane à partir de gaz de synthèse contenant du soufre provenant d'une gazéification

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EP12175567.2 2012-07-09
EP12175567.2A EP2684856A1 (fr) 2012-07-09 2012-07-09 Procédé destiné à produire un mélange gazeux riche en méthane à partir de gaz de synthèse contenant du soufre provenant d'une gazéification

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN111819163A (zh) * 2018-03-09 2020-10-23 科莱恩国际有限公司 具有提高的耐硫性的锰掺杂的镍甲烷化催化剂
CN115216347A (zh) * 2022-06-24 2022-10-21 沈阳航空航天大学 一种流化床气化与固定床甲烷化耦合系统及方法

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GB201406890D0 (en) * 2014-04-16 2014-05-28 Johnson Matthey Plc Process
EP2977103A1 (fr) * 2014-07-22 2016-01-27 Paul Scherrer Institut Production de gaz naturel de synthèse à l'aide d'un catalyseur résistant au carbone, promoté et supporté
CN105688919B (zh) * 2016-01-29 2018-04-03 太原理工大学 一种沉淀燃烧法制备的浆态床镍基甲烷化催化剂及其应用
CN107029726B (zh) * 2017-05-04 2019-09-13 太原理工大学 一种纳米镍基co甲烷化催化剂的制备方法及应用
CN108855230A (zh) * 2018-06-20 2018-11-23 杭州同久净颢科技有限责任公司 一种涂覆型脱硝催化剂及其制备方法
CN110152651A (zh) * 2019-05-17 2019-08-23 太原理工大学 应用于合成气甲烷化的耐硫催化剂及其制法和应用

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Publication number Priority date Publication date Assignee Title
CN111819163A (zh) * 2018-03-09 2020-10-23 科莱恩国际有限公司 具有提高的耐硫性的锰掺杂的镍甲烷化催化剂
CN115216347A (zh) * 2022-06-24 2022-10-21 沈阳航空航天大学 一种流化床气化与固定床甲烷化耦合系统及方法

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EP2870125B1 (fr) 2018-11-07
EP2684856A1 (fr) 2014-01-15
DK2870125T3 (en) 2019-02-11

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