WO2009103548A2 - Procédé de traitement de courants de gaz d'échappement lors de la production de courants gazeux biogènes - Google Patents

Procédé de traitement de courants de gaz d'échappement lors de la production de courants gazeux biogènes Download PDF

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Publication number
WO2009103548A2
WO2009103548A2 PCT/EP2009/001226 EP2009001226W WO2009103548A2 WO 2009103548 A2 WO2009103548 A2 WO 2009103548A2 EP 2009001226 W EP2009001226 W EP 2009001226W WO 2009103548 A2 WO2009103548 A2 WO 2009103548A2
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
exhaust gas
biogas
gas stream
production
Prior art date
Application number
PCT/EP2009/001226
Other languages
German (de)
English (en)
Other versions
WO2009103548A3 (fr
Inventor
Hans-Christoph Schwarzer
Hans-Georg Anfang
Original Assignee
Süd-Chemie AG
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 Süd-Chemie AG filed Critical Süd-Chemie AG
Priority to EP09713612A priority Critical patent/EP2250239A2/fr
Publication of WO2009103548A2 publication Critical patent/WO2009103548A2/fr
Publication of WO2009103548A3 publication Critical patent/WO2009103548A3/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
    • C10L3/10—Working-up natural gas or 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
    • 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
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

  • the invention relates to a process for the production of biogas from raw biogas, wherein an exhaust gas stream obtained during the treatment of raw biogas is treated with a catalyst.
  • the invention further relates to the use of a catalyst for the treatment of an exhaust gas stream resulting from the production of biogas.
  • Biogas is a mixture of the main components methane and carbon dioxide and is produced during the anaerobic fermentation of organic material. In contrast to aerobic composting, the process takes place under exclusion of air. The fermentation process takes place in nature z. B. in the rumen of cattle, moor or wetlands or rice fields instead.
  • Table 1 shows a typical composition of biogas.
  • biogas The industrial production of biogas is realized in special biogas plants. Typical starting materials for this purpose are, for. As farm manure (eg manure) and energy crops (renewable resource). The technical fundamentals for the production and use of biogas are described several times in the literature and state of the art. Good summaries are for. B. in the book “biogas practice” by Heinz Schulz (Publisher: ⁇ k ⁇ buch Verlag, ISBN-10: 3922964591 ISBN-13: 978-3922964599) to find.
  • the current main technical use is the motor conversion into electricity and heat.
  • an internal combustion engine is fed with biogas and operated with the kinetic energy generated a generator for power generation.
  • the waste heat produced in the combustion process is returned to the fermentation process as necessary process heat for fermentation and / or used in combined heat and power cogeneration systems.
  • biogas plant The current main purpose of a biogas plant is the generation of electricity and its supply to the public grid. Unlike electricity from wind and solar power plants, biogas electricity can be permanently fed into a power grid and thus cover basic loads in the electricity supply.
  • biogas energy generation in fuel cells (eg MCFC systems, "cfc-solutions") as well as the generation of syngas with on the following synthesis steps such.
  • energy generation in fuel cells eg MCFC systems, "cfc-solutions”
  • syngas with on the following synthesis steps such.
  • a methanol synthesis or a Fischer-Tropsch synthesis As a methanol synthesis or a Fischer-Tropsch synthesis.
  • a recently discussed usage path is biogas upgrading to natural gas.
  • the generated "Bicmethan"("bio natural gas”) can be decentralized connected to the natural gas network or fed and used. According to the Association Biogas e. In future, in Germany alone, up to 20% of natural gas consumption could be covered by biomethane. So that the gas can be fed into a natural gas network without any problems, other accompanying substances must be permanently separated in addition to CO 2 .
  • the quality requirements for the production of natural gas substitutes are specified in DVGW G260, 261 and 262.
  • these partial gas streams reach the atmosphere as exhaust gas. Since components of this gas stream are harmful to health and to the environment (eg methane is one of the greenhouse gases and is more harmful than CO 2 by a factor of 21), the untreated release into the environment should be avoided.
  • the exhaust gas flow through the components contained a calorific value, which would not be used for direct release into the environment.
  • EP 1 634 946 A1 describes, for example, how the proportion of methane in this exhaust gas stream can be varied by modifying the separation process.
  • the goal is to get the Adjust the flow of exhaust gas in its composition so that a combustible composition is formed, which can be used thermally (by burning), for example for the production of raw biogas (eg for heating a fermenter).
  • a disadvantage of this method is that the combustion of the exhaust gas stream produces sulfur oxides and nitrogen oxides, which are further emitted to the environment.
  • the object of the present invention is therefore to provide a method in which the exhaust gas stream is freed from harmful components and, in addition, the energy contained in the exhaust gas stream can be utilized.
  • the object is achieved by a method for the production of biogas from raw biogas, comprising the steps of
  • the provision of the raw biogas can be carried out by the methods known in the art, for example anaerobic fermentation in an industrial biogas plant.
  • the exhaust gas stream is treated with a catalyst. This means that the exhaust gas stream is passed over the catalyst, resulting in a heat of reaction which can be reused.
  • the catalyst used is an oxidation catalyst.
  • the catalyst may consist of one or more layers, which may be the same or different.
  • the oxidation catalyst is preferably a monolithic catalyst, for example with metal and ceramic honeycombs.
  • the catalyst is a foam or a bulk material catalyst, for example a shell catalyst, a solid material or an extrudate, wherein a wide variety of geometric shapes and dimensions are possible.
  • the catalysts may be coated with one or more washcoat layers and contain one or more noble metals and / or metal oxides and / or mixtures thereof as active components.
  • the catalyst is designed so that a catalytically active compound is present as a coating on a suitable support.
  • the catalytically active layers are preferably based on aluminum, cerium, tungsten, titanium, iron, silicon and zirconium oxide, or combinations of the abovementioned, which additionally comprise catalytically active noble metals and / or catalytically active metals.
  • Suitable noble metals are preferably selected from the group comprising platinum, palladium, rhodium, copper, silver and ruthenium.
  • the catalytically active layer is preferably applied in the form of a washcoat by impregnation, spraying or vacuuming (incipient wetness method), which contains the catalytically active substances, in particular the metals.
  • the metals are usually applied in the form of their nitrates, chlorides, sulfates, sulfites, acetates, etc., or complex compounds of these metals.
  • the corresponding oxides in the form of slurries are also usable.
  • a drying or calcining step is typically carried out, whereupon metal or noble metal doping of the washcoat surface is additionally carried out with further catalytically active metals or their compounds, such as nitrates, chlorides, sulfates, sulfites, acetates or complex compounds can.
  • the oxidation catalyst may be a zeolite or a zeolite-like material, or a support material may be coated with the zeolite or zeolite-like material.
  • a support material may be coated with the zeolite or zeolite-like material.
  • the zeolite is preferably selected from a group of zeolites having the topologies AEL, BEA, CHA, EUO, FAO, FER, KFI, LTA, LTL, MAZ, MOR, MEL, MTW, LEV, OFF, TON and MFI.
  • zeolite is used in the context of the present invention as defined by International Mineralical Association (DS Coombs et al., Canadian Mineralogist, 35, 1979, 1571) a crystalline substance from the group of aluminum silicates having a spatial network structure of the general formula
  • the zeolite structure contains voids, channels that are characteristic of each zeolite.
  • the zeolites are classified into different structures according to their topology.
  • the zeolite framework contains open cavities in the form of channels and cages that are normally occupied by water molecules and additional framework cations that can be exchanged.
  • An aluminum atom has an excess negative charge which is compensated by these cations.
  • the interior of the pore system represents the catalytically active surface. The more aluminum and the less silicon a zeolite contains, the denser the negative charge in its lattice and the more polar its internal surface.
  • the pore size and structure is determined by the Si / Al ratio, which is the major part of the catalytic character of a zeolite, besides the parameters of manufacture, ie, use, or type of template, pH, pressure, temperature, presence of seed crystals accounts.
  • the presence of divalent or trivalent cations as a tetrahedral center in the zeolite framework gives the zeolite a negative charge in the form of so-called anion sites, in the vicinity of which the corresponding cation positions are located.
  • the negative charge is compensated by the incorporation of cations in the pores of the zeolite material.
  • the zeolites are mainly distinguished by the geometry of the cavities formed by the rigid network of SiO 4 / AlO 4 tetrahedra.
  • the entrances to the cavities are formed by 8, 10 or 12 rings, the expert speaks here of narrow, medium and large pore zeolites.
  • Certain zeolites show a uniform structure structure, e.g. For example, the ZSM-5 or the MFI topology, with linear or zigzag running channels, in others close behind the pore openings larger cavities, eg. As in the Y or A zeolites, with the topologies FAO and LTA.
  • the zeolite is a metal-exchanged zeolite, more preferably a Fe zeolite.
  • the zeolite or zeolite-like material may be further coated or doped with a noble metal. Suitable noble metals are also preferably selected from the group comprising platinum, palladium, rhodium, copper, silver and ruthenium.
  • the production processes for metal-exchanged zeolites, for example via solid or liquid phase exchange, are known to the person skilled in the art.
  • methods for coating or doping zeolites with noble metals are known to those skilled in the art.
  • the present invention thus describes a combined process for the production of biogas from raw biogas, which consists of a separation process and a downstream process, wherein in the downstream process harmful and environmentally hazardous components of the exhaust gas Removed stream from the separation process by catalytic oxidation and wherein the released during the oxidation heat is available for further use.
  • FIG. 1 A schematic overview of the method according to the invention can be seen in FIG. 1
  • the exhaust gas contains less harmful components
  • the catalyst serves as a heat storage to compensate for these cyclical fluctuations (minimum regulation requirement).
  • the catalysts defined above can also be used to purify the exhaust gas streams produced during the use of the biogas produced (for example during combustion in a gas engine) and thus also to remove harmful and environmentally hazardous components.
  • the above-defined catalysts can also be used to purify the exhaust gas streams produced during the production of the raw biogas (for example heating of the fermentation) and thus likewise to remove harmful and environmentally hazardous components.
  • the catalysts defined above may also be used to purify the exhaust streams produced during the generation, purification or use of a biogenic gas (for example, by gasification of organic (bio) mass) and thus also to remove harmful and environmentally hazardous components.
  • a biogenic gas for example, by gasification of organic (bio) mass
  • a biogas plant which is suitable for carrying out the process according to the invention and comprises at least one catalyst as described above.
  • the catalyst is arranged in the exhaust gas line of the waste gas produced during the treatment of the raw biogas.
  • a further catalyst is arranged in an exhaust gas line of an exhaust gas obtained in the fermentation in the bioreactor (for example, waste gas produced during fermentation or biogenic waste gas produced during fermentation).
  • an additional catalyst is arranged in an exhaust gas line of an exhaust gas resulting from the use of the generated biogas (combustion).
  • the methane content is based on geothermal or biogas operated stationary engines (eg in combined heat and power plants) typically below 3000 ppm (corresponds to about 0.3% by volume).
  • the oxygen content is about 8-12 vol .-%.
  • sufficient oxygen is available for the catalytic or thermal total oxidation.
  • a catalyst which consists of a ceramic and / or metallic support which comprises a washcoat layer based on alumina and platinum as the active component.
  • the platinum concentration is preferably in the range of 1.0 to 1.5 g / l honeycomb volume.
  • CO reductions in exhaust gas can be achieved from 70% to over 90%.
  • the catalysts for the respective exhaust gas strands may be the same or different. However, the catalysts are preferably adapted to the respective use.
  • the catalyst which is located in an exhaust line of the exhaust gas produced when using the generated biogas (combustion) is preferably high-temperature stable, since the heat generated during the combustion of biogas can produce an exhaust gas with a temperature of more than 400 ° C.
  • the combination of several catalysts ensures that sufficient thermal energy is always available for biogas production. Excess thermal energy, which is obtained by the use of one or more catalysts, can be collected for example in hot water tanks or used for other purposes (eg for power generation).
  • Example 1 Example 1 :
  • Catalyst composition for the purification of the partial gas flow occurring in the production of biogas exhaust gas flow
  • a catalyst was used with a ceramic support coated with an alumina-based washcoat layer containing platinum and palladium as active components.
  • the total precious metal concentration was 3 g / l, 4 g / l and 5 g / l honeycomb volume.
  • Catalyst composition for the purification of the partial gas flow occurring in the production of biogas exhaust gas flow
  • a metallic support catalyst coated with a washcoat layer based on alumina with platinum and palladium as the active component was used.
  • the total precious metal concentration was 3 g / l, 4 g / l and 5 g / l honeycomb volume.
  • Catalyst composition for the purification of an exhaust gas stream which occurs during the combustion of biogas in a stationary engine :
  • a catalyst was used with a ceramic support comprising a washcoat based on alumina and platinum as the active component.
  • the platinum concentration was in the range of 1.0 and 1.5 g / l honeycomb volume.
  • Catalyst composition for the purification of a waste gas stream, which occurs during the combustion of biogas in a stationary engine :
  • a metallic support catalyst comprising a washcoat layer based on alumina and platinum as the active component was used.
  • the platinum concentration was in the range of 1.0 and 1.5 g / l honeycomb volume. Thus, CO reductions in the exhaust gas of 90% could be achieved.

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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)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de production de biogaz à partir de biogaz brut, caractérisé en ce qu'un courant de gaz d'échappement se formant lors de la production de biogaz brut est traité par un catalyseur. L'invention concerne en outre l'utilisation d'un catalyseur pour le traitement d'un gaz d'échappement se formant lors de la production de biogaz.
PCT/EP2009/001226 2008-02-21 2009-02-20 Procédé de traitement de courants de gaz d'échappement lors de la production de courants gazeux biogènes WO2009103548A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09713612A EP2250239A2 (fr) 2008-02-21 2009-02-20 Procédé de traitement de courants de gaz d'échappement lors de la production de courants gazeux biogènes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008010329A DE102008010329A1 (de) 2008-02-21 2008-02-21 Verfahren zur Behandlung von Abgasströmen bei der Aufarbeitung biogener Gasströme
DE102008010329.2 2008-02-21

Publications (2)

Publication Number Publication Date
WO2009103548A2 true WO2009103548A2 (fr) 2009-08-27
WO2009103548A3 WO2009103548A3 (fr) 2010-01-14

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PCT/EP2009/001226 WO2009103548A2 (fr) 2008-02-21 2009-02-20 Procédé de traitement de courants de gaz d'échappement lors de la production de courants gazeux biogènes

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EP (1) EP2250239A2 (fr)
DE (1) DE102008010329A1 (fr)
WO (1) WO2009103548A2 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010018703A1 (de) * 2010-04-29 2011-11-03 Messer Group Gmbh Verfahren zum Betreiben eines Verbrennungsmotors und Verbrennungsmotor
EP4086514A1 (fr) * 2021-05-05 2022-11-09 MEGTEC Systems AB Système synergétique et procédé de traitement de déchets

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4142399A1 (de) * 1991-12-20 1993-06-24 Linde Ag Verfahren zur entschwefelung von h(pfeil abwaerts)2(pfeil abwaerts)s-haltigem biogas
DE19840691A1 (de) * 1998-08-24 2000-03-09 Wolfgang Tentscher Produktion von verkaufsfähigen Gasen aus Biogasen und Deponiegasen mittels anaerober Fermentation von Reststoffen aus Landwirtschaft, Kommune, Industrie und Gewerbe und von Ganzpflanzen oder Teilen derselben
EP1634946A1 (fr) * 2004-09-13 2006-03-15 RÜTGERS CarboTech Engineering GmbH Procédé de production de gaz naturel biologique en respectant l'environnement

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT55555B (de) * 1910-03-03 1912-09-25 Lualdi & C Fa Kehrichtbehälter mit durch Drehen des Tragbügels sich öffnendem und schließendem Deckel.
DD219952A1 (de) * 1983-09-30 1985-03-20 Claus Elle Verfahren zur partiellen reinigung von gasen
DE10356276A1 (de) * 2003-11-28 2005-06-30 Tentscher, Wolfgang, Dr. Reinigung von Kohlendioxid aus Biogas von störenden Begleitstoffen während und nach der Aufbereitung mit der nassen Druckgaswäsche
EP1754695A1 (fr) * 2005-08-17 2007-02-21 Gastreatment Services B.V. Procédé et appareil pour la purification de courants de gaz riche en méthane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4142399A1 (de) * 1991-12-20 1993-06-24 Linde Ag Verfahren zur entschwefelung von h(pfeil abwaerts)2(pfeil abwaerts)s-haltigem biogas
DE19840691A1 (de) * 1998-08-24 2000-03-09 Wolfgang Tentscher Produktion von verkaufsfähigen Gasen aus Biogasen und Deponiegasen mittels anaerober Fermentation von Reststoffen aus Landwirtschaft, Kommune, Industrie und Gewerbe und von Ganzpflanzen oder Teilen derselben
EP1634946A1 (fr) * 2004-09-13 2006-03-15 RÜTGERS CarboTech Engineering GmbH Procédé de production de gaz naturel biologique en respectant l'environnement

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Publication number Publication date
WO2009103548A3 (fr) 2010-01-14
DE102008010329A1 (de) 2009-09-03
EP2250239A2 (fr) 2010-11-17

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