WO2015014459A1 - Procédé et dispositif d'enrichissement d'un gaz de synthèse, produit par gazéification, en hydrogène - Google Patents

Procédé et dispositif d'enrichissement d'un gaz de synthèse, produit par gazéification, en hydrogène Download PDF

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Publication number
WO2015014459A1
WO2015014459A1 PCT/EP2014/002016 EP2014002016W WO2015014459A1 WO 2015014459 A1 WO2015014459 A1 WO 2015014459A1 EP 2014002016 W EP2014002016 W EP 2014002016W WO 2015014459 A1 WO2015014459 A1 WO 2015014459A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrolysis
gas
synthesis gas
hydrogen
gasification
Prior art date
Application number
PCT/EP2014/002016
Other languages
German (de)
English (en)
Inventor
Gerald GAUBE
Dirk BAUERSFELD
Holger KITTELMANN
Original Assignee
Linde Aktiengesellschaft
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 Linde Aktiengesellschaft filed Critical Linde Aktiengesellschaft
Publication of WO2015014459A1 publication Critical patent/WO2015014459A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • 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
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/05—Pressure cells
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
    • C10J2300/1618—Modification of synthesis gas composition, e.g. to meet some criteria
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1684—Integration of gasification processes with another plant or parts within the plant with electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1846—Partial oxidation, i.e. injection of air or oxygen only
    • 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 relates to a method and a plant for enriching a synthesis gas generated by gasification with hydrogen.
  • Feedstock also referred to as gasification process for short, are known.
  • coal or biomass are used as starting material for such processes.
  • biomass gasification processes for example, used wood and forestry wood or so-called energy wood, but also agricultural residues such as straw or chaff are used.
  • synthetic biofuel can be obtained in its
  • GTL gas-to-liquids
  • CTL coal-to-liquid
  • Processes and plants for the at least partial gasification of solid, organic feedstock are also known, for example, from EP 0 745 114 B1, DE 41 39 512 A1 and DE 42 09 549 A1.
  • the present application relates in particular to such processes or plants which use a low-temperature gasifier and a
  • Biomass by partial gasification with a gasification agent at temperatures between about 300 ° C and 600 ° C to coke (so-called in the case of biomass
  • Smoldering Registration referred to as "smoldering". Smoldering is known to be characterized by a stoichiometric oxygen supply and thus an incomplete
  • Synthesis gas can also be referred to as (synthesis) raw gas at this point.
  • the synthesis gas thus produced is brought into contact with coke from the low-temperature gasifier, for example in a quench unit integrated in the high-temperature gasifier or in a quench unit connected downstream of it.
  • the coke may be previously treated separately (e.g., by grinding and sifting) and then introduced into the quench unit.
  • the latter is cooled to about 900 ° C. This causes partial conversion of the carbon dioxide to carbon monoxide.
  • the carbon monoxide-rich synthesis gas thus produced can then be further conditioned.
  • the conditioning includes, for example, another
  • Synthesis gas resulting from such gasification typically has a relatively low hydrogen to carbon monoxide ratio (H / CO ratio), typically reaching values of 0.7.
  • H / CO ratio hydrogen to carbon monoxide ratio
  • Carbon monoxide to hydrogen ratio of about 2: 1 is reached.
  • a disadvantage here is considered that in this case also resulting carbon dioxide for many subsequent processes, for example, to provide liquid
  • Hydrocarbons is not usable, and thus lost for such processes.
  • Patent claim 1 and a system with the features of claim 6.
  • the yield may be, for example,
  • Hydrocarbon products are significantly increased in subsequent processes for processing synthesis gas over conventional solutions with shift process.
  • the electrolysis is carried out as high-pressure electrolysis.
  • High-pressure electrolysis processes have a particularly high efficiency and preferably operate at pressure ratios of 3-40 bar.
  • oxygen produced during the electrolysis is used in the course of the gasification for the production of synthesis gas.
  • a usually used for the gasification air separation for oxygen production can be made smaller or completely eliminated.
  • the hydrogen-enriched synthesis gas is subjected to a Fischer-Tropsch synthesis to provide liquid hydrocarbons.
  • the Fischer-Tropsch synthesis provides a very convenient process for the heterogeneous-catalytic conversion of synthesis gas into a wide range of gaseous and liquid hydrocarbons.
  • Liquid hydrocarbons have a high energy density and can be stored in pressureless tanks. This represents a significant advantage over so-called power-to-gas concepts.
  • the non-salable or difficult to sell by-products of the Fischer-Tropsch synthesis can also be considered as stored electrical energy and stored. Because these products are easy to transport, they can also be made easier
  • liquid hydrocarbons provided are converted into electrical energy, in particular using a combustion turbine. It is conceivable, for. B. to use the mentioned by-products as fuel for a generator and to use the power thus generated in turn for the discussed electrolysis but in particular for feeding into the power grid.
  • the conversion power can be chosen to be, for example, substantially larger (for example, fifty times greater) than the
  • the invention provides a higher utilization of carbon from biogenic fuels, such as wood, in the synthesis. With the invention, a seasonal storage of electrical energy without the use of fossil carbon is possible. For storage of the hydrocarbons generated are no
  • FIG. 1 shows, in a schematic view, an exemplary system which is used for
  • Figure 2 shows a preferred embodiment of the method according to the invention in the form of a flow chart.
  • FIG. 1 schematically shows a system which is set up to carry out a preferred embodiment of the method according to the invention and designated as a whole by 100.
  • the plant 100 includes a gasification device 110.
  • the gasification device 110 may, for example, a
  • a feedstock such as biomass, such as wood or equivalent waste
  • oxygen is fed into the gasification device.
  • the line 112 is supplied with oxygen from two oxygen sources, as explained in more detail below.
  • the low-temperature gasifier is set up to blaze the solid organic feedstock.
  • the low temperature carburetor externally, for example, with waste heat of Hochtemperaturvergasers, to a suitable temperature, for example 300 ° C to 600 ° C, heated. In a start-up phase of the plant and starting torch can be used.
  • the high temperature carburetor transferred.
  • the high temperature carburetor is
  • the carbonization gas is partially oxidized with a supplied oxygen-containing gas, resulting in temperatures of, for example, 1400 ° C to 2000 ° C. As a result, a synthesis gas is obtained. The synthesis gas can then subsequently the
  • Quenchieri are supplied, where, for example, ground coke from the low-temperature carburetor is introduced (not shown). As a result of the endothermic reactions taking place in this way, the gas temperature cools to about 900 ° C. in a short time, at least partial reduction occurs.
  • Gas mixture which is a high-carbon synthesis gas in this state, can be fed to a cooler, and there, for example, cooled to a temperature of 600 ° C.
  • the synthesis gas can then be in a
  • Gas cleaning system to be cleaned.
  • gas cleaning system to be cleaned.
  • Gas purification plant is called a Reisolis, in which the synthesis gas is released from substances not required for the synthesis.
  • a gas purification system is shown schematically and designated 120.
  • the purified synthesis gas is then fed to a device for performing a Fischer-Tropsch synthesis 130.
  • the purified synthesis gas is reacted in the device 130 heterogeneously catalytically in a synthesis reaction to hydrocarbons such as paraffins, olefins and alcohols.
  • End products or the Fischer-Tropsch product are, for example, gasoline (synthetic gasoline), diesel, heating oil, as well as raw materials for the chemical industry.
  • the reaction already arrives
  • Atmospheric pressure and at a temperature of 160 to 200 ° C instead. It also higher pressures and temperatures are used.
  • Fischer-Tropsch Synthesis many different catalysts can be used.
  • transition metals such as cobalt, iron, nickel or ruthenium may be mentioned.
  • porous metal oxides with large specific surface areas are used as supports.
  • a typical Fischer-Tropsch product contains liquified gases, gasoline, kerosene (diesel oil), soft paraffin and hard paraffin. These different hydrocarbons are then separated from one another in a refining device 140 and stored in suitable storage devices 150.
  • the illustrated system further includes an electrolyzer 160 in which water is converted into oxygen and hydrogen using electrical energy (eg, from the power grid).
  • the electrolysis device 160 can be acted upon via a line 166 with electric current, from the power grid or another suitable source.
  • the hydrogen produced in this way is added to the purified synthesis gas via a line 162, so that the total hydrogen content of the purified
  • Synthesis gas is increased. Typical purified synthesis gases are included
  • Hydrogen is conveniently provided at a ratio of 2: 1.
  • the oxygen produced in the electrolysis is the gasifier 1 10 via a line 164, which opens in the line 1 12 added.
  • the oxygen can in this case be supplied to the low-temperature gasifier and / or the high-temperature gasifier. This is a very effective overall use of the electrolysis products
  • Hydrogen and oxygen provided in the context of a synthesis gas production or a Fischer-Tropsch synthesis.
  • the illustrated device additionally has an air separation device 170, which is supplied with electrical current via an electrical line 176.
  • the air separation device 170 produced oxygen is fed via a line 174, which also opens in the line 1 12, the gasification device 1 0.
  • the air separation device 170 can be dimensioned substantially smaller than conventional devices. It is also conceivable to completely dispense with the air separation device 170.
  • Hydrocarbons can now be recycled in an appropriate manner.
  • Such "hard-to-sell" products stored in the storage device 150 may be supplied, at least in part, to a combustion turbine 180 having a generator 190.
  • This electrical energy generated for example, the power grid, or the electrolysis device 160 and / or the
  • Air separation device 170 are supplied.
  • the supply of electricity in these facilities or the power grid can be variable and concrete
  • a synthesis gas is generated in a gasification device.
  • the synthesis gas is purified.
  • hydrogen is added to the purified synthesis gas by means of electrolysis.
  • Electrolyzer 160 provided oxygen, optionally with the addition of oxygen produced in the air separator 170 of the gasification device 1 10 is supplied (step 235).
  • a Fischer-Tropsch synthesis of the purified, hydrogen-enriched synthesis gas takes place.
  • the Fischer-Tropsch product is then refined in a refinery facility 140 (step 250) and subsequently stored in suitable storage facilities 150 (step 260).
  • stored refinery products are supplied to a combustion turbine 180 having a generator 190 for generating electrical energy (step 270).
  • the electrical energy thus generated can be supplied to the electrolysis device 160 or to an air separation device 170, or else to the power grid (step 280).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé et un dispositif destinés à enrichir un gaz de synthèse, produit par gazéification, en hydrogène. De l'hydrogène est ajouté par électrolyse au gaz de synthèse produit.
PCT/EP2014/002016 2013-07-30 2014-07-22 Procédé et dispositif d'enrichissement d'un gaz de synthèse, produit par gazéification, en hydrogène WO2015014459A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013012661.4A DE102013012661A1 (de) 2013-07-30 2013-07-30 Verfahren und Anlage zur Anreicherung eines mittels Vergasung erzeugten Synthesegases mit Wasserstoff
DE102013012661.4 2013-07-30

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WO2015014459A1 true WO2015014459A1 (fr) 2015-02-05

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PCT/EP2014/002016 WO2015014459A1 (fr) 2013-07-30 2014-07-22 Procédé et dispositif d'enrichissement d'un gaz de synthèse, produit par gazéification, en hydrogène

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DE (1) DE102013012661A1 (fr)
WO (1) WO2015014459A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022078915A1 (fr) * 2020-10-14 2022-04-21 Velocys Technologies Ltd Procédé de gazéification
US11753597B2 (en) 2019-11-08 2023-09-12 Expander Energy, Inc. Process for producing synthetic hydrocarbons from biomass

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070131909A1 (en) * 2005-11-04 2007-06-14 Alexandre Rojey Process for the production of synthesis gas from carbon-containing material and electrical energy
US20090235587A1 (en) * 2008-03-24 2009-09-24 Battelle Energy Alliance, Llc Methods and systems for producing syngas
EP2166064A1 (fr) * 2008-09-19 2010-03-24 Siemens Aktiengesellschaft Système pour fournir un produit chimique et procédé pour fournir un produit chimique
US20100175320A1 (en) * 2006-12-29 2010-07-15 Pacific Renewable Fuels Llc Energy efficient system and process for the continuous production of fuels and energy from syngas
DE102010028181A1 (de) * 2010-04-26 2011-10-27 Siemens Aktiengesellschaft Produktionsanlage für Chemierohstoffe oder Brennstoffe sowie ein Verfahren zum Betrieb einer solchen Produktionsanlage
US20120123000A1 (en) * 2009-07-09 2012-05-17 Areva Facility for producing synthetic hydrocarbons, and associated method
WO2012113832A1 (fr) * 2011-02-22 2012-08-30 Areva Méthode de production de méthanol ou d'hydrocarbures à partir d'une matière carbonée, avec une étape de reformage dont les conditions de fontionnement sont ajustées sélectivement

Family Cites Families (3)

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DE4139512A1 (de) 1991-11-29 1993-06-03 Noell Dbi Energie Entsorgung Verfahren zur thermischen verwertung von abfallstoffen
DE4209549A1 (de) 1992-03-24 1993-09-30 Vaw Ver Aluminium Werke Ag Verfahren zur thermischen Behandlung von Reststoffen, z.B. zur Trennung und Verwertung von Metallverbunden mit organischen Anteilen, mittels einer Kombination aus Pyrolyse und Vergasung
DE4404673C2 (de) 1994-02-15 1995-11-23 Entec Recycling Und Industriea Verfahren zur Erzeugung von Brenngas

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070131909A1 (en) * 2005-11-04 2007-06-14 Alexandre Rojey Process for the production of synthesis gas from carbon-containing material and electrical energy
US20100175320A1 (en) * 2006-12-29 2010-07-15 Pacific Renewable Fuels Llc Energy efficient system and process for the continuous production of fuels and energy from syngas
US20090235587A1 (en) * 2008-03-24 2009-09-24 Battelle Energy Alliance, Llc Methods and systems for producing syngas
EP2166064A1 (fr) * 2008-09-19 2010-03-24 Siemens Aktiengesellschaft Système pour fournir un produit chimique et procédé pour fournir un produit chimique
US20120123000A1 (en) * 2009-07-09 2012-05-17 Areva Facility for producing synthetic hydrocarbons, and associated method
DE102010028181A1 (de) * 2010-04-26 2011-10-27 Siemens Aktiengesellschaft Produktionsanlage für Chemierohstoffe oder Brennstoffe sowie ein Verfahren zum Betrieb einer solchen Produktionsanlage
WO2012113832A1 (fr) * 2011-02-22 2012-08-30 Areva Méthode de production de méthanol ou d'hydrocarbures à partir d'une matière carbonée, avec une étape de reformage dont les conditions de fontionnement sont ajustées sélectivement

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11753597B2 (en) 2019-11-08 2023-09-12 Expander Energy, Inc. Process for producing synthetic hydrocarbons from biomass
WO2022078915A1 (fr) * 2020-10-14 2022-04-21 Velocys Technologies Ltd Procédé de gazéification
US11572512B2 (en) 2020-10-14 2023-02-07 Velocys Technologies Ltd. Gasification process
US11840668B2 (en) 2020-10-14 2023-12-12 Velocys Technologies Ltd Gasification process

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