EP2684856A1 - Verfahren zur Methanierung des aus Gasifizierung abgeleiteten Herstellergases auf Metallkatalysatoren in Gegenwart von Schwefel - Google Patents

Verfahren zur Methanierung des aus Gasifizierung abgeleiteten Herstellergases auf Metallkatalysatoren in Gegenwart von Schwefel Download PDF

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Publication number
EP2684856A1
EP2684856A1 EP12175567.2A EP12175567A EP2684856A1 EP 2684856 A1 EP2684856 A1 EP 2684856A1 EP 12175567 A EP12175567 A EP 12175567A EP 2684856 A1 EP2684856 A1 EP 2684856A1
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EP
European Patent Office
Prior art keywords
methanation
catalyst
sulfur
reactor
metal
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EP12175567.2A
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English (en)
French (fr)
Inventor
Christian Felix Julian König
Tilman J. Schildhauer
Maarten Nachtegaal
Marcelo Daniel Kaufman Rechulski
Serge Biollaz
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Scherrer Paul Institut
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Scherrer Paul Institut
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Priority to EP12175567.2A priority Critical patent/EP2684856A1/de
Priority to PCT/EP2013/063288 priority patent/WO2014009146A1/en
Priority to EP13734007.1A priority patent/EP2870125B1/de
Priority to DK13734007.1T priority patent/DK2870125T3/en
Publication of EP2684856A1 publication Critical patent/EP2684856A1/de
Withdrawn legal-status Critical Current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
    • C10L3/102—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 (SNG).
  • SNG Synthetic Natural Gas
  • the (higher) methane content in producer gas from low temperature gasification of coal / biomass allows energetically more efficient conversion, because the extent of exothermic reactions is decreased.
  • low temperature gasification usually leads to organic sulfur compounds (e.g. thiophenes, mercaptanes), olefins and aromatic compounds in the resulting producer gas.
  • Sulfur removal which omits scrubbing and/or which is performed at temperature levels between that of the gasification and the temperature of the methanation, is desired for improvement of the overall efficiency.
  • Rabou & Bos [1] 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
  • 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.
  • 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 (C 8 H 6 S), Dibenzothiophene (C 12 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 C 8 H 6 S
  • Dibenzothiophene C 12 H 8 S
  • 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.
  • 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 oxidation is separated from a resulting product of the catalytic methanation. This feature tremendously assists the efforts of removing the sulfur content originally contained in the synthesis gas mixture.
  • 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 subsequently conveyed back to a reduction reduction or a first methanation reactor, from which it is further transferred to a second methanation reactor.
  • any further methanation reactor could be envisioned as well.
  • Another alternative can provide for the catalytic 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.
  • 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 O.
  • the catalytic reactor comprises a synthesis part (i.e. methanation), and a regeneration part. (see Fig. 3 ).
  • 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 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). This oxidizes the adsorbed or deposited carbon and sulfur species on the catalyst surface and removes them in the form of SO 2 and CO 2 to the exhaust. With an appropriate regeneration temperature, the methanation activity can be restored.
  • 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 as a circulating or bubbling fluidized bed or entrained flow, where the catalyst is fluidized and is continuously transported between the synthesis part and the regeneration part.
  • 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.
  • 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 uptake/regeneration) change over time.
  • a solid substrate such as a monolith
  • the gas feeds e.g. reducing/methanation/sulfur uptake/regeneration
  • 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 CO2.
  • 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 atmosphere (e.g. reducing/methanation/sulfur uptake/regeneration).
  • 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. Further, a combination of the above mentioned methods to achieve the change of atmosphere around the catalyst material can be applied.
  • 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.
  • gaseous or liquid peroxides or other oxidizing species e.g. hydrogen peroxide, N20
  • solid oxidizing species e.g. metal oxides
  • oxygen e.g as ion or carbonate
  • This may be accomplished by active cooling by means of heat exchangers in the methanation reactor or in the transfer lines between methanation and/or reducing steps and the regeneration steps.
  • 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.
  • 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 t1.
  • 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
  • O 2 is added, which results in generation of SO 2 (m/z 64) in response to the regeneration the methanation catalyst.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
EP12175567.2A 2012-07-09 2012-07-09 Verfahren zur Methanierung des aus Gasifizierung abgeleiteten Herstellergases auf Metallkatalysatoren in Gegenwart von Schwefel Withdrawn EP2684856A1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP12175567.2A EP2684856A1 (de) 2012-07-09 2012-07-09 Verfahren zur Methanierung des aus Gasifizierung abgeleiteten Herstellergases auf Metallkatalysatoren in Gegenwart von Schwefel
PCT/EP2013/063288 WO2014009146A1 (en) 2012-07-09 2013-06-25 A method for methanation of gasification derived producer gas on metal catalysts in the presence of sulfur
EP13734007.1A EP2870125B1 (de) 2012-07-09 2013-06-25 Verfahren zur methanierung des aus gasifizierung abgeleiteten herstellergases auf metallkatalysatoren in gegenwart von schwefel
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

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EP12175567.2A EP2684856A1 (de) 2012-07-09 2012-07-09 Verfahren zur Methanierung des aus Gasifizierung abgeleiteten Herstellergases auf Metallkatalysatoren in Gegenwart von Schwefel

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EP12175567.2A Withdrawn EP2684856A1 (de) 2012-07-09 2012-07-09 Verfahren zur Methanierung des aus Gasifizierung abgeleiteten Herstellergases auf Metallkatalysatoren in Gegenwart von Schwefel
EP13734007.1A Active EP2870125B1 (de) 2012-07-09 2013-06-25 Verfahren zur methanierung des aus gasifizierung abgeleiteten herstellergases auf metallkatalysatoren in gegenwart von schwefel

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015159044A1 (en) * 2014-04-16 2015-10-22 Johnson Matthey Public Limited Company Process
EP2977103A1 (de) * 2014-07-22 2016-01-27 Paul Scherrer Institut Herstellung von synthetischem Erdgas mit einem kohlenstoffbeständigen, promotierten und geträgerten Katalysator
CN105688919A (zh) * 2016-01-29 2016-06-22 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
CN107029726A (zh) * 2017-05-04 2017-08-11 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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WO2019170779A1 (de) * 2018-03-09 2019-09-12 Clariant International Ltd Mangandotierte nickel-methanisierungskatalysatoren mit erhoehter schwefelresistenz
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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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015159044A1 (en) * 2014-04-16 2015-10-22 Johnson Matthey Public Limited Company Process
GB2526188A (en) * 2014-04-16 2015-11-18 Johnson Matthey Plc Process
GB2526188B (en) * 2014-04-16 2016-05-11 Johnson Matthey Plc Process for preparing a methane-containing gas mixture
US9840446B2 (en) 2014-04-16 2017-12-12 Johnson Matthey Public Limited Company Process for production of methane-containing gas mixture
EP2977103A1 (de) * 2014-07-22 2016-01-27 Paul Scherrer Institut Herstellung von synthetischem Erdgas mit einem kohlenstoffbeständigen, promotierten und geträgerten Katalysator
CN105688919A (zh) * 2016-01-29 2016-06-22 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
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
CN107029726A (zh) * 2017-05-04 2017-08-11 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
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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EP2870125B1 (de) 2018-11-07
EP2870125A1 (de) 2015-05-13
DK2870125T3 (en) 2019-02-11
WO2014009146A1 (en) 2014-01-16

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