WO2016019984A1 - Procédé combiné d'utilisation de biogaz brut contenant du dioxyde de carbone, et un gaz utile - Google Patents

Procédé combiné d'utilisation de biogaz brut contenant du dioxyde de carbone, et un gaz utile Download PDF

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Publication number
WO2016019984A1
WO2016019984A1 PCT/EP2014/066860 EP2014066860W WO2016019984A1 WO 2016019984 A1 WO2016019984 A1 WO 2016019984A1 EP 2014066860 W EP2014066860 W EP 2014066860W WO 2016019984 A1 WO2016019984 A1 WO 2016019984A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkali
alkali metal
carbon dioxide
carbonate
reaction
Prior art date
Application number
PCT/EP2014/066860
Other languages
German (de)
English (en)
Inventor
Oliver Menhorn
Karl Weinberger
Original Assignee
Dennert Poraver Gmbh
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 Dennert Poraver Gmbh filed Critical Dennert Poraver Gmbh
Priority to PCT/EP2014/066860 priority Critical patent/WO2016019984A1/fr
Publication of WO2016019984A1 publication Critical patent/WO2016019984A1/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
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/104—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/306—Alkali metal compounds of potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the invention relates to a combined process for the use of raw biogas containing carbon dioxide and a useful gas, in particular methane.
  • biogas production is being strongly promoted.
  • a problem with biogas is that it has a relatively high carbon dioxide content of about 50%, so that it can not be fed directly into a gas network, in particular natural gas network, for energy supply.
  • the raw biogas Prior to this step, the raw biogas must be appropriately purified by significantly reducing the carbon dioxide content.
  • Another disadvantage of conventional biogas production is the fact that existing biogas plants have no optimized heat utilization concept, so that the overall efficiency of such plants is still in need of improvement.
  • Electricity generation could be considered on and off biogas plants with a correspondingly large gas storage. Disadvantage of this is the fact that would be necessary for efficient use uneconomically large gas storage. Also, the existing power grid in the connection of such biogas plants is usually not expanded accordingly. In addition, the efficiency is reduced even in this variant.
  • the invention has the object, a method for the use of Indicate raw biogas, which works with high efficiency and flexible to external conditions, such as energy demand peaks is customizable.
  • the use of biogas upgrading means that energy demand peaks in the power grid can be buffered.
  • the resulting in the type of use of Nutzgas holehorn alkaline bicarbonate is regenerated again to alkali carbonate, which is used in the latter type of use for the removal of carbon dioxide.
  • This can be produced with minimal use of resources from the raw biogas useful gas, such as biomethane, and fed into the gas network.
  • This also provides chemical energy in the sense of a buffering of electrical energy demand peaks, even without burdening the power grid, which can be emitted elsewhere in the case of energy demand peaks, for example by gas turbines.
  • the method steps la) to lc) of the first mode of use and the method steps 2a) to 2c) of the second mode of use can be carried out alternately in two cyclically coupled, time-separated sequence processes. This means that over a certain period, the raw biogas is utilized in the first mode of use and then over a certain period in the second mode of use, the cyclicity on the combination of both types of use by the regeneration of the alkali metal bicarbonate to alkali carbonate in the second use and its reuse in the first use is given.
  • a synchronous utilization of the raw biogas in both types of use is also conceivable.
  • the two processes are decoupled plant technology and the cyclicity is ensured by transferring the resulting in a plant for carrying out the first use type alkali metal bicarbonate in a plant to carry out the second mode of use, where then at the same time the regeneration of the alkali metal bicarbonate to alkali carbonate takes place. The latter is then continuously returned to the plant for the first use.
  • the alkali metal sodium can be used as the alkali metal sodium.
  • potassium is preferred so that potassium carbonate and potassium bicarbonate are used in one cycle.
  • the efficiency of the process can be optimized if, during the regeneration of the alkali bicarbonate, a concentrated alkali carbonate solution is prepared and provided for carbon dioxide removal.
  • the waste heat produced during the power generation of the raw biogas is sufficient to produce the corresponding temperatures for the regeneration of the alkali metal bicarbonate to alkali carbonate, that is about 200 ° C for potassium or 300 ° C for sodium as the alkali metal.
  • the inventive method for alternating use of oh biogas even act as a carbon dioxide sink.
  • FIG. 1 shows a block diagram of the sub-process for the supply of useful gas from a raw biogas
  • Fig. 2 is a block diagram of the sub-process for the conversion of
  • FIG. 3 shows a block diagram of a method composed of the two partial methods according to FIGS. 1 and 2 for the synchronous use of raw biogas
  • FIGS. 4 and 5 show a schematic representation of a rotary kiln in the different types of use
  • FIGS. 8 and 9 a schematic representation of a reaction vessel with conveyor and heat exchanger in different uses.
  • a conventional biogas reactor 1 via a biogas discharge line 2 on the one hand with a carbon dioxide (CO 2 -) absorber 3 connected, in which from the biogas reactor 1 provided raw biogas high proportion of carbon dioxide is to be removed.
  • CO 2 - carbon dioxide
  • potassium carbonate K 2 CO 3 is provided in the CO 2 absorber 3.
  • the carbon dioxide is then separated from the crude biogas from the raw biogas, essentially a mixture of CO 2 and CH 4 , according to the reaction equation K 2 CO 3 + CO 2 + H 2 O -> 2 KHCO 3 so that the useful gas CH 4 is used for feeding into a schematically indicated with 4 gas network.
  • the chemical energy inherent in the useful gas is thus temporally and locally independently retrievable as energy for power generation by means of a gas turbine.
  • the biogas reactor 1 is connected to the other via a derivative 5 with a heat engine, for example in the form of a gas engine 6 or a gas turbine, which gas engine 6 is coupled to a generator 7 for power generation on site.
  • a heat engine for example in the form of a gas engine 6 or a gas turbine, which gas engine 6 is coupled to a generator 7 for power generation on site.
  • the waste heat Q occurring during operation of the gas engine 6 is used to generate the waste heat in the CO 2 absorber 3. to regenerate potassium hydrogencarbonate according to the following reaction relationship:
  • Waste heat for example, also supplied in the form of the exhaust gas of the gas engine 6, so that in the rotary kiln 9, the regeneration of Kaliumhydrogencar- carbonate to potassium carbonate - as described with reference to FIG. 2 - takes place with release of carbon dioxide.
  • FIG. 6 An alternative to the rotary kiln 9 is shown in Figs. 6 and 7.
  • a fluidized bed reactor 10 is used, in which - as shown in FIG. 6 - in the individual fluidized bed 1 1 of the fluidized bed reactor 10 potassium carbonate is layered and raw biogas is blown from below.
  • the reaction relationship explained with reference to FIG. 1 again takes place with the formation of potassium hydrogencarbonate, and useful gas CH 4 is released.
  • the waste heat Q of the gas engine 6 for example in the form of its exhaust gases, is blown from below into the fluidized-bed reactor 10 in order to regenerate the potassium bicarbonate formed in the fluidized-bed reactor 10.
  • the reaction for the regeneration of potassium bicarbonate to potassium carbonate takes place again with the separation of water and carbon dioxide.
  • FIGS. 8 and 9 show a further plant-technical alternative for carrying out the method according to the invention.
  • a reaction vessel with a potassium carbonate solution 13 use in the back of the raw biogas is introduced.
  • carbon dioxide is removed from the crude biogas, and the potassium hydrogencarbonate which forms is precipitated on account of its lower solubility.
  • the sediment 14 thus formed in the reaction vessel 12 is conveyed via a screw conveyor 15 docked thereto to a heat exchanger 16, in which the regeneration of the potassium bicarbonate taking place with the aid of "power generation" can take place with reference to Fig. 2.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treating Waste Gases (AREA)

Abstract

Procédé cyclique d'utilisation alternée de biogaz brut, comprenant deux modes d'utilisation, notamment aux fins de fourniture de gaz utile et de conversion en électricité, et comprenant les étapes consistant à : - selon un premier mode d'utilisation aux fins de fourniture de gaz utile, =1a) prendre l'alcali-carbonate, =1b) éliminer le dioxyde de carbone du biogaz brut en faisant réagir le dioxyde de carbone avec l'alcali-carbonate afin d'obtenir du carbonate alcali-hydrogène conformément à l'équation gaz utile + alcali2CO3 + H2O + CO2 gaz utile + alcali HCO3 ainsi que =1c) dissociation du carbonate alcali-hydrogène et fourniture du gaz utile; et - selon un deuxième mode d'utilisation aux fins de conversion en électricité, =2a) procéder à la combustion du biogaz brut dans un moteur thermique (6) avec production d'énergie électrique et de chaleur perdue, =2b) utiliser la chaleur perdue pour la régénération du carbonate alcali-hydrogène conformément à l'équation 2 alcaliH2CO3 alcali2CO3 + H2O + CO2 et =2c) recycler le carbonate alcali ainsi généré à l'étape 1a).
PCT/EP2014/066860 2014-08-05 2014-08-05 Procédé combiné d'utilisation de biogaz brut contenant du dioxyde de carbone, et un gaz utile WO2016019984A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2014/066860 WO2016019984A1 (fr) 2014-08-05 2014-08-05 Procédé combiné d'utilisation de biogaz brut contenant du dioxyde de carbone, et un gaz utile

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2014/066860 WO2016019984A1 (fr) 2014-08-05 2014-08-05 Procédé combiné d'utilisation de biogaz brut contenant du dioxyde de carbone, et un gaz utile

Publications (1)

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WO2016019984A1 true WO2016019984A1 (fr) 2016-02-11

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1207132A1 (fr) * 1999-07-09 2002-05-22 Ebara Corporation Procede et appareil de production d'hydrogene par gazeification de matiere combustible, procede de generation electrique utilisant des piles a combustible, et systeme de generation electrique utilisant des piles a combustible
US20100325958A1 (en) * 2009-06-30 2010-12-30 Jennifer Lynn Molaison Method and Apparatus for Removal of Carbon Dioxide from Pre-Combustion Syngas
US20120060686A1 (en) * 2010-09-09 2012-03-15 Exxonmobil Research And Engineering Company Mixed Amine and Non-Nucleophilic Base CO2 Scrubbing Process for Improved Adsorption at Increased Temperatures
WO2013034947A1 (fr) * 2011-09-08 2013-03-14 Cellennium (Thailand) Company Limited Valorisation de biogaz en méthane purifié commercialisable exploitant la culture de microalgues
US20140030177A1 (en) * 2012-07-30 2014-01-30 Exxonmobil Research And Engineering Company High cyclic capacity amines for high efficiency co2 scrubbing processes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1207132A1 (fr) * 1999-07-09 2002-05-22 Ebara Corporation Procede et appareil de production d'hydrogene par gazeification de matiere combustible, procede de generation electrique utilisant des piles a combustible, et systeme de generation electrique utilisant des piles a combustible
US20100325958A1 (en) * 2009-06-30 2010-12-30 Jennifer Lynn Molaison Method and Apparatus for Removal of Carbon Dioxide from Pre-Combustion Syngas
US20120060686A1 (en) * 2010-09-09 2012-03-15 Exxonmobil Research And Engineering Company Mixed Amine and Non-Nucleophilic Base CO2 Scrubbing Process for Improved Adsorption at Increased Temperatures
WO2013034947A1 (fr) * 2011-09-08 2013-03-14 Cellennium (Thailand) Company Limited Valorisation de biogaz en méthane purifié commercialisable exploitant la culture de microalgues
US20140030177A1 (en) * 2012-07-30 2014-01-30 Exxonmobil Research And Engineering Company High cyclic capacity amines for high efficiency co2 scrubbing processes

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