EP2089493A2 - Procédé et installation pour convertir de la biomasse solide en électricité - Google Patents

Procédé et installation pour convertir de la biomasse solide en électricité

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Publication number
EP2089493A2
EP2089493A2 EP07856169A EP07856169A EP2089493A2 EP 2089493 A2 EP2089493 A2 EP 2089493A2 EP 07856169 A EP07856169 A EP 07856169A EP 07856169 A EP07856169 A EP 07856169A EP 2089493 A2 EP2089493 A2 EP 2089493A2
Authority
EP
European Patent Office
Prior art keywords
product gas
particle
fuel cell
gas
sulfur
Prior art date
Legal status (The legal status 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 status listed.)
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Application number
EP07856169A
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German (de)
English (en)
Inventor
Serge Biollaz
Markus Jenne
Florian Nagel
Tilman J. Schildhauer
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Scherrer Paul Institut
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Scherrer Paul Institut
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Application filed by Scherrer Paul Institut filed Critical Scherrer Paul Institut
Priority to EP07856169A priority Critical patent/EP2089493A2/fr
Publication of EP2089493A2 publication Critical patent/EP2089493A2/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/2485—Monolithic reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1812—Tubular reactors
    • B01J19/1825—Tubular reactors in parallel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • 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
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • 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
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • C10K1/024—Dust removal by filtration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C01B2203/0445—Selective methanation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C01B2203/045—Purification by catalytic desulfurisation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0455—Purification by non-catalytic desulfurisation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/84—Energy production
    • 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
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • 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
    • C10J2300/0956—Air or oxygen enriched air
    • 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
    • C10J2300/1643—Conversion of synthesis gas to energy
    • C10J2300/1646—Conversion of synthesis gas to energy integrated with a fuel cell
    • 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
    • C10J2300/1671—Integration of gasification processes with another plant or parts within the plant with the production of electricity

Definitions

  • the invention relates to a method and a plant for highly efficient power generation from biomass according to claim 1 and the claim.
  • the plant concept combines the technologies of «biomass gasification» and «solid-ceramic fuel cells», revealing new solutions especially in the areas of heat integration, controllability and system simplicity.
  • Gasification is a relatively old technology that was initially explored for coal as a fuel. Depending on the desired plant size and intended use as well as the desired purity of the product gas produced, many different types of gasifier were developed.
  • the gasification is usually introduced from above into the carburetor.
  • the gasification medium usually air
  • the product gas is led out of the upper part of the gasification space.
  • the advantage of this reactor type is that the process works even with very humid gasified material.
  • the reactor design is very simple and easy to scale. captively.
  • the temperature of the product gas is in the range between 150 0 C to 650 ° C.
  • these carburetors have the disadvantage that the product gas is very heavily tar-charged, these being primarily tar primary species. Typical values for this are 50 to 200 g / m.sup.n 3 . These are usually oxygenated.
  • Sulfur compounds are also contained in the product gas in organic form, which is why conventional sulfur absorbers do not show the desired cleaning effect.
  • the gasification is usually introduced from above into the carburetor.
  • the gasification medium mostly air, we also injected from above into the gasification room.
  • the product gas is led out of this in the lower part of the gasification space.
  • the advantage of this type of reactor the product gas is almost free from tar with Teerbeladungen to 0:05 to 0:25 g / m n. 3
  • the process is very sensitive to the moisture of the gasification product and its geometry. This is because the gasification material can not rest on a supporting grate but rather is held by controlled bridging. This is due to the high temperatures in the lower part of the gasification chamber, which make the use of a grate impossible.
  • the reactor design is not easily scalable.
  • the temperature of the product gas is in the range between 650 ° C. and 1050 ° C.
  • Sulfur compounds are generally present in the product gas in an inorganic form, which is why conventional sulfur absorbers can be used.
  • problems can occur in the fixed-bed gasification of heavily ash-containing gasification material.
  • Fluidized bed gasifiers have been developed to avoid these problems. They are almost unlimited in terms of plant size. At the moment, fluidised bed gasifiers are the most widely used types of gas generators for power generation from biomass. They have moderate Teerbeladitch to 15 g / m 3 n and are relatively insensitive to variations in feed moisture. adversely is that the reactors and the process control are relatively complex.
  • the product gas from the biomass gasification contains numerous impurities such as sulfur compounds and tarry compounds and particles. In general, these substances are removed in process steps at relatively low temperatures up to a maximum of 200 0 C from the product gas. This makes sense, since the working machines used in the prior art (gas engines and gas turbines) require low gas inlet temperatures to achieve high efficiencies.
  • washing in appropriate scrubbers various washing liquids can be used, such as water or diesel.
  • Sulfur species are less of a problem for gas turbines and gas engines.
  • Sulfur absorber materials that can be used at temperatures between room temperature and 200 0 C are known from steam reforming processes. Publications are known with regard to the product gas purification of organic sulfur compounds: WO 2005/007780 A2 [16] discloses a two-stage desulfurization unit in which the main portion of organic sulfur compounds can be absorbed in the first desulfurization stage by means of a zeolite (available from Südchemie). The absorber materials used initially crack organic sulfur compounds and also absorb some of them. The absorber materials used can be regenerated. In the second desulfurization step, the residual organic sulfur compounds are removed by a non-regenerable sulfur absorber. Between the two desulfurization stages, a gas-liquid separation takes place, as a result of which organic sulfur compounds are concentrated in the liquid phase. - A -
  • WO 02/22763 A1 [17] describes a fluidized bed desulphurisation unit for the adsorption of organic sulfur compounds from common fuels, such as e.g. Diesel.
  • the composition of the raw gas as well as the type and design of the fuel cell charged with it determine the required degree of product gas conditioning. Particular attention must be paid to the longevity and efficiency of the fuel cell.
  • Hydrogen is the preferred fuel for fuel cells.
  • the production of hydrogen of sufficient purity as fuel is laborious and costly.
  • centrally produced hydrogen is difficult to store and transport. This involves dangers such as high risk of explosion [I].
  • R & D therefore goes in the direction of system-integrated hydrogen production from fossil and renewable hydrocarbon sources.
  • Hydrogen can be obtained from hydrocarbons through the following processes:
  • the poisoning of STR catalysts is a problem because the gases to be reformed usually have small amounts of sulfur. Sulfur chemisorbs at appropriate temperatures on any metallic surface, thus blocking active sites of metallic catalysts. The form in which the sulfur is present is secondary. Therefore, the STR process is usually preceded by a desulfurization stage.
  • Non-Catalytic PO and Catalytic Partial Oxidation CPO The PO or CPO is an alternative to STR. Hydrocarbons, which may also contain oxygen, are degraded to a mixture of hydrogen and carbon monoxide. The reaction follows the given stoichiometry: C x H y O z + (0.5xz) O 2 ⁇ xCO + 0.5y H 2 ( ⁇ H R > 0) The generated carbon monoxide is converted to hydrogen via the likewise exothermic WGS.
  • PO reactors are preferably used for hydrogen production from liquid hydrocarbon mixtures (gasoline, diesel etc.), since the process heat in the reactor can be used for evaporation.
  • the reactors are also characterized by their compactness, which is why they are also suitable for mobile applications.
  • a very important advantage of the PO is that no de-ionized water is needed. Thus it can be dispensed with the appropriate apparatus or exhaust gas recirculation.
  • EP 0 576 096 A2 discloses a process for preparing a catalyst which catalyzes the partial oxidation of hydrocarbons.
  • ATR Autothermal reforming ATR
  • STR and CPO The combination of STR and CPO is called ATR.
  • ATR uses molecular oxygen and water vapor as the source of oxygen.
  • the reaction follows the stoichiometry: C x H y O z + 0.5 * (0.5xz) O 2 + 0.5 * (xz) H 2 O ⁇ x CO + 0.5 * (x + yz) H 2 (- ⁇ H> 0)
  • the ATR requires less steam than the conventional STR.
  • the required process heat is generated by the exothermic partial oxidation, which makes the heat management of the ATR much easier than with the STR [8].
  • Solid oxide fuel cells produce electricity through spatially separated chemical reactions in which, similar to batteries, there is an electron flow between the reaction spaces.
  • the core of the fuel cell is the electrolyte, which is the two
  • the conversion of the fuel to electricity is thus without any rotating parts or generators.
  • ZrO 2 Zirconium oxide
  • the efficiency of fuel cells is basically not limited by the Carnot efficiency.
  • SOFCs have the highest efficiencies in the conversion of fuel gas to electricity [9].
  • SOFCs can be operated in a wide temperature range between 500 0 C to 1000 0 C [10].
  • the high operating temperatures of SOFCs and the typically incomplete fuel utilization of SOFCs offer high potential for use in hybrid systems [9].
  • the waste heat generated in the SOFC at a high temperature level allows the use of gas and steam circuits as a "bottoming" cycle. As a result, otherwise lost waste heat can be harnessed.
  • Thermodynamic calculations have shown that pressurized systems are likely to increase efficiency even further.
  • the pollutant emissions of such hybrid systems are expected to be low because the main fuel conversion is done electrochemically. The same applies to the carbon dioxide emissions, which correlate directly inversely proportional to the system efficiency.
  • the high operating temperatures of SOFCs allow the use of cheap catalyst materials compared to low and medium temperature fuel cells.
  • SOFCs use nickel as the anode catalyst.
  • platinum is used in polymer electrolyte membrane fuel cells [10].
  • SOFCs have a high degree of flexibility with regard to the composition of the fuel gas, because in addition to hydrogen they can also electrochemically convert carbon monoxide and even hydrocarbons [10].
  • the high operating temperatures and the catalyst materials used allow thermally integrated STR and WGS of fuel gases.
  • the conversion of the fuel gases can either be done outside of the fuel cell in a separate reactor, which receives the required process heat from the fuel cell, or within the fuel cell.
  • the endothermic character of the STR can be used to chemically cool the fuel cell, thus reducing the amount of waste heat and subsequently increasing efficiency [2].
  • the steam required for the STR is continuously produced by the exothermic electrochemical reactions. The efficiency-optimal proportion of internal reforming depends on numerous factors.
  • the SOFC technology is relatively easy to adapt in systems in the power range from a few watts to several megawatts [9].
  • the SOFC technology is not mature yet.
  • the current status of technology development ranges from basic research mainly in the field of materials science to the operation of pre-commercial systems and the development of market entry strategies.
  • the heat integration between the high-temperature fuel cell used is carried out via a catalytic combustion of the anode exhaust gas, which is passed directly from the fuel cell in the coal gasifier.
  • the catalytic combustion takes place in a reactor housing located within the coal gasifier.
  • the released combustion heat is used directly to support the endothermic gasification reactions.
  • the patent does not elaborate on controllability of the system and gas purification steps.
  • US 2002/0194782 Al is directed to heat integration between a high temperature fuel cell and a biomass fluidized bed gasifier.
  • This has a special feature that the combustion part, in which unreacted carbon is burned and thus an inert bed material is heated, is located inside the gasification part.
  • the heat exchange between the combustion and gasification part is thus carried out by convection and heat radiation between the reactor walls and on the inert circulating bed material.
  • the heat integration of the high-temperature fuel cell via the combustion of unreacted anode gas in the combustion part of the carburetor.
  • the combustion gas from the Combustion part is supplied to the cathode of the high-temperature fuel cell.
  • the object of the present invention is to provide a method and a plant for the generation of solid biomass via a gasification fuel cell coupling, which combines several process units in a holistic manner.
  • Figure 1 Schematic representation of the system
  • Figure 2 Schematic representation of the particle filtration unit with integrated catalyst monoliths for the realization of a variably adjustable proportion of catalytically reacted product gas.
  • FIG. 1 The plant for the thermal and control integration of high-temperature fuel cells and biomass gasification is shown in FIG. 1:
  • the biomass 61 is introduced from above into the carburetor 1. There, the biomass 61 with preheated air 82 into a mixture of particles, steam, hydrogen, carbon monoxide,
  • the proportion of condensable species in crude product gas 62 is high and accounts for approximately 25% of its calorific value.
  • the existing tar compounds in the crude product gas 62 are usually oxygenated and are due to the temperature of the product gas of about 600 0 C in the gas phase. At this temperature, alkalis and heavy metals usually condense on larger particles. If the temperature of the product rises above the evaporation temperature of heavy metals and alkalis, it can be cooled by adding water. Sulfur compounds are usually organic in nature.
  • the product gas contains almost no (higher) hydrocarbons, so chemical cooling of the downstream fuel cell by internal steam reforming is limited.
  • the crude product gas 62 is then passed in an apparatus 2 for removing particles, see also FIG. 2.
  • the apparatus 2-also called particle separator 2 in this document- consists essentially of the two separate chambers 201 and 202: raw gas chamber 201 and clean gas chamber 202.
  • the particles with the alkalis and heavy metals condensed on them are prevented from passing from the raw gas chamber 201 into the clean gas chamber 202 by high-temperature resistant filter elements 203 and deposited as filter cakes on the filter elements.
  • the filter cake is cyclically depending on the resulting pressure loss across the filter elements by pressure surges with particle-free product gas of the
  • Filter elements detached and discharged from the apparatus Within the filter elements 203 catalytically coated monoliths 205 are housed fixed or movable.
  • the monoliths 205 correspond to catalytic reactors in which condensable species can be post-gasified and / or the abovementioned reversible reactions steam reforming, water gas conversion and methanation can proceed.
  • the position of the monolith By the position of the monolith, the proportion of the raw particle-free product gas that can flow through the monolith can be adjusted. This is made possible in particular by the homogeneous pressure distribution within the filter elements.
  • FIG. 2 shows by way of example 3 different positions of the catalyst monolith. In case A, the monolith 205 is in the idle position.
  • the raw particle-free product gas is passed together with its high load of oxygen-containing tar compounds and organic sulfur compounds in the clean gas chamber 202 and then leaves the particle 2 as clean gas 63.
  • case B is the monolith 205, see. Figure 2, in full load position.
  • the crude particle-free product gas is passed completely over the catalytically coated or active monoliths. There, almost all aromatic and oxygen-containing tar compounds are degraded to hydrogen and carbon monoxide. Furthermore, own measurements have shown that almost all organic sulfur compounds are converted to hydrogen sulphide.
  • the pure product gas 63 leaves the apparatus 2 as stream 63.
  • case C about half of the crude product gas is passed over the monolith. The catalytically reacted product gas then mixes with the crude product gas.
  • the mixture has a lower loading of hydrocarbon compounds than the crude product gas and leaves the apparatus 2 as clean gas 63.
  • the methane content may have increased, allowing for chemical cooling of the downstream fuel cell by internal steam reforming.
  • the amount of air, hydrogen and / or water vapor required for the catalytic conversion is adjusted on the basis of the temperature in the monolith and thus always enables optimum conditions for the catalytic conversion.
  • the pre-heated amount of air, hydrogen and / or water vapor 83 is introduced into the interior of the filter elements via a lance 204, which is passed through the monolith, where it mixes with the crude product gas. The mixture is then passed through the catalytic monolith.
  • the filter elements prevent backmixing with the crude product gas outside the filter elements.
  • the particle-free and completely, partially or not catalytically reacted product gas 63 is then passed into a heat exchanger where it is cooled down to temperatures of about 650 0 C to 850 ° C to 400 0 C: cooled product gas 64.
  • cooled product gas 64 After cooling, flows through the gas is a zinc oxide bed with upstream dechlorination (second sulfur absorber 3). Measurements have shown that at this temperature, the hydrogen sulfide concentration in the gas can be lowered below 1 ppm, without exceeding the thermal stability of the absorber material used.
  • the low-sulfur product gas 66 contains more or less organic sulfur compounds depending on the proportion of catalytic conversion. In the standard case, the entire product gas is fed to the catalytic conversion. Require
  • the low-hydrogen sulfide product gas 66 still contains a certain amount of organic sulfur compounds.
  • the product gas 66 is passed into the first sulfur absorber 4, where the organic
  • Sulfur compounds are absorbed at temperatures between 600 0 C and 800 0 C of a (eg perovskitischer) absorber material.
  • the now particle-free, completely, partially or non-catalytically reacted and completely desulfurized product gas 67 is then passed into a second heat exchanger 12, in which the heated desulfurized product gas 68 is heated by the hot anode exhaust gas 69 to almost the operating temperature of the anode 5.
  • the anode exhaust gas 69 is used to heat the desulfurized product gas 67 and is then passed into a burner 7 where it is burned with the already cooled cathode exhaust gas 80.
  • the hot flue gases 71 are expanded in a turbine 8, which drives a generator 16 and a compressor 9 via a common shaft.
  • the expanded flue gases 72 are used in a further heat exchanger for preheating the air compressed in the compressor 9 76 before they are used in a steam cycle to generate additional electricity 92 (electrical energy) and useful heat 93.
  • the air 75 sucked in by the compressor 9 is divided into two parts after compression and preheating.
  • the stream 77 is passed into a third heat exchanger 13, where it is brought by the cathode exhaust gas 79 almost to the operating temperature of the cathode 6. This corresponds to the temperature of the anode 5.
  • the second portion of the compressed preheated air 81 is again divided into two parts.
  • Stream 82 is introduced as gasification medium 82 in the carburetor 1. Air can be introduced into the particulate filter system 2 with integrated catalytic conversion in which it serves as part of the reaction medium 83 at most.
  • the proposed invention combines several process units known per se into an overall system whose properties are superior to the sum of all individual process units.
  • the hydrocarbon compounds contained in the product gas and partially oxygen-containing can be used for internal reforming with low carbon deposition risk in the SOFC. This chemically cools the SOFC, resulting in lower amounts of waste heat.
  • the hydrocarbon compounds can be hydrogenated and carbon monoxide as needed at the desired high operating temperatures be implemented.
  • the chemical cooling of the SOFC is hardly possible, which has a negative effect on the overall efficiency of the system.
  • the production of hydrocarbon compounds (eg methane) from hydrogen and carbon monoxide is possible at appropriate operating temperatures by means of catalytic methanation.
  • the condensable tar compounds contained in the product gas from biomass gasification are converted to hydrogen and carbon monoxide by catalytic conversion (e.g., autothermal reforming).
  • catalytic conversion e.g., autothermal reforming
  • the integration of the corresponding monoliths in the filter elements of the particle filtration system makes it possible to make the proportion of oxygen-containing hydrocarbon compounds variable.
  • the ATR corresponds in the broader sense of a second gasification stage, which can be switched on continuously. This makes it possible, the respective optimal proportion of internal
  • Biomass gasification and SOFC are thermally integrated via air preheating.
  • reaction medium 83 preheated air; reaction medium

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Fuel Cell (AREA)
  • Industrial Gases (AREA)
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Abstract

L'invention concerne un système complet utilisé pour produire de l'énergie électrique (92) à partir de biomasse (61), par gazéification. Ledit système comprend plusieurs unités de traitement (1, 2, 3, 4, 17) combinées en un tout, de sorte que les propriétés d'ensemble soient supérieures à la somme des propriétés individuelles des unités de traitement (1, 2, 3, 4, 17).
EP07856169A 2006-11-09 2007-10-24 Procédé et installation pour convertir de la biomasse solide en électricité Withdrawn EP2089493A2 (fr)

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EP07856169A EP2089493A2 (fr) 2006-11-09 2007-10-24 Procédé et installation pour convertir de la biomasse solide en électricité

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EP06023301 2006-11-09
EP07856169A EP2089493A2 (fr) 2006-11-09 2007-10-24 Procédé et installation pour convertir de la biomasse solide en électricité
PCT/EP2007/009213 WO2008055591A2 (fr) 2006-11-09 2007-10-24 Procédé et installation pour convertir de la biomasse solide en électricité

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WO2008055591A3 (fr) 2008-07-17
BRPI0718697A2 (pt) 2014-02-18
CA2668952C (fr) 2012-05-15
US8535840B2 (en) 2013-09-17
WO2008055591A2 (fr) 2008-05-15
CA2668952A1 (fr) 2008-05-15
US20090305093A1 (en) 2009-12-10

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