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WO2018210393A1 - Procédé et système de production d'un gaz combustible chaud à base de combustibles solides - Google Patents

Procédé et système de production d'un gaz combustible chaud à base de combustibles solides Download PDF

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Publication number
WO2018210393A1
WO2018210393A1 PCT/DK2018/050114 DK2018050114W WO2018210393A1 WO 2018210393 A1 WO2018210393 A1 WO 2018210393A1 DK 2018050114 W DK2018050114 W DK 2018050114W WO 2018210393 A1 WO2018210393 A1 WO 2018210393A1
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WIPO (PCT)
Prior art keywords
stage
gas
partial oxidation
ash
fuel
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Ceased
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PCT/DK2018/050114
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English (en)
Inventor
Jens Dall Bentzen
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Dall Energy Holding ApS
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Dall Energy Holding ApS
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Priority to DKPA201970772A priority Critical patent/DK201970772A1/en
Publication of WO2018210393A1 publication Critical patent/WO2018210393A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
    • 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
    • C10J3/22—Arrangements or dispositions of valves or flues
    • 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
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/52—Ash-removing devices
    • 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
    • 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
    • C10J3/723—Controlling or regulating the gasification process
    • 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
    • C10J2300/09—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
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas

Definitions

  • the invention relates inter alia to a method and a system for producing hot burnable gas with a low content of NOx, dust and tar as well as clean ash with a low carbon content by means of a stage-divided thermal reactor.
  • the conversion process of the solid fuel takes place in separate vertical stages (from below and up) : ash burn-out, char oxidation and gasification, pyrolysis, drying and a partial oxidation stage wherein a part of the gas from the gasifier is oxidized.
  • the stages: ash burn-out, char oxidation and gasification, pyrolysis and drying comprise part of an updraft gasifier.
  • the partial oxidation stage functions both as:
  • the hot burnable gas can be used for several purpose e.g. for combustion for production of hot water, steam or heating thermal oil, or it can be cooled and cleaned and used as gas in a gas engine or gas turbine, or it can be synthesized into liquid products, or it can be distributed to end users further away.
  • WO/2010/022741 which relates to a thermal reactor in which solid fuel can be converted into a clean hot flue gas with a low content of volatile organic compounds (VOC's), NOx and dust, and clean ash with a low carbon content by means of a stage-divided thermal reactor, where the conversion process of the solid fuel is in separate vertical stages (from below and up) : ash burn-out, char oxidation and gasification, pyrolysis, drying, and a gas combustion stage where gas from the gasifier is combusted.
  • VOC's volatile organic compounds
  • WO 01/68789 Al A staged gasification process and system for thermal gasification of special waste fractions and biomass, e.g.
  • wood comprising a drier in which the fuel is dried upon contact with superheated steam.
  • the dried fuel is fed into a pyrolysis unit to which superheated steam is also supplied.
  • the volatile tar, containing components produced in the pyrolysis unit is passed to an oxidation zone in which an oxidation agent is added so as to cause a partial oxidation, whereby the content of tar is substantially reduced.
  • the solid fuel components from the pyrolysis unit may be fed into a gasification unit to which hot gases from the oxidation zone are supplied. In the gasification unit the solid fuel components are gasified or converted to carbon.
  • the gas produced in the gasification unit may be burnt in a combustion unit, such as a combustion engine.
  • WO 2008/004070 Al A method of controlling an apparatus for generating electric power and apparatus for use in said method, the apparatus comprising : a gasifier for biomass material, such as waste, wood chips, straw, etc.. Said gasifier being of the shaft and updraft fixed bed type, which from the top is charged with the raw material for gasification and into the bottom of which gasifying agent is introduced, and a gas engine driving an electrical generator for producing electrical power, said gas engine being driven by the fuel gas from the gasifier.
  • a gasifier for biomass material such as waste, wood chips, straw, etc.
  • Said gasifier being of the shaft and updraft fixed bed type, which from the top is charged with the raw material for gasification and into the bottom of which gasifying agent is introduced, and a gas engine driving an electrical generator for producing electrical power, said gas engine being driven by the fuel gas from the gasifier.
  • Solid fuel is usually converted into a burnable gas (gasification) or into a flue gas (combustion) in a moving bed or a fluid-bed reactor.
  • Moving-bed reactors are typically divided into following categories: updraft (air/gas goes up and fuel down); downdraft (air and fuel go down) or
  • grate/stoker-based system moving grate, vibrating grate, stoker
  • fuel moves horizontally (often with a slope downwards).
  • Fluid-bed reactors are typically divided into the following categories: bubbling fluid bed (BFB), circulating fluid bed (CFB) or entrained flow (EF).
  • BFB bubbling fluid bed
  • CFB circulating fluid bed
  • EF entrained flow
  • Fresh solid fuel such as biomass or waste has very different properties compared to coal. Especially the content of volatiles and water is much higher in biomass and waste. In coal, the volatile content is normally below 30%, whereas for biomass and waste the volatile content is normally above 65% (dry ash free weight basis). Further, the content of water in fresh biomass and waste is often above 20%, and even often above 50%, so drying of the fuel is often a very important issue in biomass and waste reactors. Further, the content and the composition of the ash can be very different for coal and biomass/waste. Also the content of alkali metals (Na, Ka), Chlorine, Potassium, Silica etc. may be much higher, and ash melting points of biomass and waste are known to be much lower than in coal.
  • Feeding systems are normally screw or push type or pneumatic "spreader stoker" feeders.
  • grate systems the fuel is transported by the grate. In most cases, combustion air is led through the grate. These systems may have several problems including hot spots on the grate, uneven air distributions, ash/char falling through the grate, controlling the stages on the grate etc.
  • fluid-bed systems the fuel is mixed with the bed material. The fluid-bed systems may have problems with separating the bed material from the ash, and with separating the different process steps as fluid beds are normally well-stirred reactors.
  • Updraft gasifiers are not often used, as the amount of tars (longer gaseous molecules that condensate while cooled) is very high. Updraft gasifiers were earlier used for production of town gas, but these sites have caused
  • Lately updraft gasifiers have been used also for gas-engine operation with extensive tar removal systems, such as described in WO 2008/004070 Al and for full combustion of solid fuels as in WO/2010/022741.
  • Updraft gasification technology is known as a simple and robust technology.
  • updraft gasifiers there is a simple feeding and transporting mechanism, both into the reactor and out of the reactor, where the ash can be removed in a cold state.
  • the gasification agent In updraft gasifiers, there is a simple feeding and transporting mechanism, both into the reactor and out of the reactor, where the ash can be removed in a cold state.
  • the gasification agent When the ash layer is in the bottom of the reactor, the gasification agent
  • updraft gasifiers convert the fuel very well and that there is very little carbon in the ash.
  • the updraft gasification technology has some disadvantages such as ⁇
  • ⁇ The produced gas has a high content of tars, which are difficult to clean up when syngas production is the aim of the gasifier
  • WO 2007/036236 Al describe a solution to this problem : If the combustion unit is designed for wet fuels and receives a dry fuel then the lack of water in the fuel can be compensated for by adding water to the fuel or into the thermal reactor, so the drying zone doesn't become too hot, thus resulting in NOx formation and/or overheating materials. Tars and Partial oxidation of tars
  • the allowable tar levels are about 50.5 and 1 mg/Nm for gas engines, gas turbines and fuel cells, respectively. There is though a large uncertainty
  • Cracking of tars can be done by partial oxidization : Oxygen (0 2 ) reacts with the condensable tar molecules and decompose the tar molecules into small gaseous molecules, that are not condensable. With partial oxidation at temperatures around 600-900°C and with an air ratio above 0.2 the tar content of the gas can be reduced 90 - 95% or more, maybe even 98-99 %. Partial oxidation is especially efficient at temperatures of 800-900°C.
  • Typical amount of Tar from an updraft gasifier - without partial oxidation - is about 5-10 g/Nm3 gas.
  • the dust level out of the thermal reactor is more than 500 mg/Nm3. Therefore, extensive filtering is normally necessary. Only very few types of reactors (for instance updraft gasifiers) have a dust level below 100 mg/Nm3. Such reactors may not need filtering.
  • NOx is causing acid rain and there are therefore strict limitations on NOx levels from thermal reactors.
  • Fuel NOx is formed from the nitrogen in the fuel when oxygen is added to the fuel and the fuel is heated and chemical reactions occur.
  • Thermal NOx is formed in the gas combustion stage and is mainly dependent on the temperature. The higher the temperature is, the higher NOx formation, but also the higher the oxygen content is, the more NOx is formed. The NOx formation is moderate when the temperature is below 1100°C, but NOx formation accelerates when the temperature gets above 1100°C.
  • NOx level from state of art thermal reactors are 200 mg NOx/m3 or above.
  • the NOx level in gases can be reduced if the gases are in reduced atmosphere (No or very little content of 02). Especially, if the temperature is between 600-900°C and the retention time is 1 second or longer, the NOx reduction is considerable.
  • NOx can also be reduced for instance by Selective catalytic reduction (SCR) or Selective non-catalytic reduction (SNCR).
  • SCR Selective catalytic reduction
  • SNCR Selective non-catalytic reduction
  • the SCR process use a catalyst to convert NOx into diatomic nitrogen, N 2 , and water, H 2 0.
  • the SNCR method is used to reduce NOx emissions in thermal plants using solid fuels such as biomass, waste and coal.
  • the process involves injecting either ammonia or urea into the hot flue gas where the temperature is between 750°C and 1100°C to react with the nitrogen oxides formed in the combustion process.
  • the resulting product of the chemical redox reaction is nitrogen (N 2 ), carbon dioxide (C0 2 ), and water (H 2 0).
  • An important parameter for combustion plants is the oxygen content in the flue gas. The lower the oxygen content, the better.
  • the excess air is more than 5%, such as 7% (dry basis), which corresponds to a lambda (stoichiometric ratio) of 1.3 or more.
  • Normally untreated air is used for combustion, but the properties of the air can be improved by adding steam and/or oxygen to the air.
  • the carbon content of the ash is often 10% or more. This leads to an efficiency and environmental problem :
  • the carbon contains valuable energy, which is not utilised, and it also contains environmentally unfriendly substances, such as PAH (Polycyclic aromatic hydrocarbons).
  • the char content is often high, such as 10% or above.
  • the ash removal systems are costly and complicated, as the ash removal system is operating at temperatures above 300 C.
  • Ash-removal systems of updraft gasifiers can be made simple, as the temperature in the ash removal system is below 300 C.
  • the fuel is moved from the inlet to the ash outlet by a grate.
  • this grate is made of high-grade steel, which is both costly and also needs replacement.
  • a part of the grate is replaced at least every year, and costs related to downtime, materials and labour may be very high.
  • Fluid-bed reactors and updraft gasifiers are typically round, whereas grate systems are typically rectangular.
  • the round shape in typical updraft gasifiers results in a maximum size of about 10 MW thermal.
  • a typical key figure of updraft gasifiers is 1 MW/m2 of char gasification reactor.
  • the diameter is then more than 3 m and, due to the grate design, the flow may become uneven if the plant is much bigger. Therefore, it is recognized that app. 10MW is the maximum input of round updraft gasifiers. Size of plants
  • Combustion plants are made in very small scale, such as stoves of 5 kW and even below, or in very large scale, such as coal-fired power plants, which can be several hundred MW.
  • a typical turn-down ratio of grate systems and fluid beds is about 1 : 2, whereas updraft gasifiers may have a turn-down ratio of 1 : 10 or even 1 : 20.
  • the present invention provides an improved method and an improved system or installation for gasification of biomass and waste.
  • Various aspects, features and embodiments of the invention will be presented in the following .
  • the present invention may be viewed as using the updraft gasification principle followed by a partial oxidation stage.
  • An updraft gasifier utilizes gravity to move solid matter between process stages. Thus, directional wording such as up and down and top and bottom is to be interpreted in the normal way with respect to gravity.
  • the fuel is fed into the top of the fuel bed and converted into a burnable gas in the following successive stages (from top and down) : a drying stage, a pyrolysis stage, a char gasification and an oxidation stage and an ash burn out stage.
  • updraft gasifier oxygen is added to the gas from the updraft gasifier and so the tars from the updraft gasifier are cracked (by partial oxidation) into non-condensable gases, and heat from exothermal reactions of the partial oxidation is transferred to the top layer of fuel in the updraft gasifier, which hereby effectively dries and pyrolyses the fuel.
  • the present invention provides, in a first aspect, a method for converting a solid carbonaceous fuel into burnable gas and ash, said method preferably comprises stages, where the fuel may be heated to temperatures causing the fuel to decompose into gaseous and solid components, and a partial oxidation stage, where the gaseous components produced are partially oxidised, the stages taking place inside a thermal reactor and preferably comprises:
  • the fuel at the pyrolysis stage is heated by means of the gases formed in the gasification and oxidation stage and the partial oxidation stage, the drying stage, the pyrolysis stage, the gasification and oxidation stage and the ash burn-out stage form an updraft gasifier and are carried out in an updraft moving bed reactor,
  • the partial oxidation stage takes place above the pyrolysis stage, where the gases from the updraft gasifier are partially oxidized, and heat from the partial oxidation is transferred to the top layer of fuel in the updraft gasifier.
  • the stages are not provided by mechanical dividing elements, such as horizontal wall elements.
  • stage is preferably used to designate a specific region or zone within a chamber, which chamber being defined by wall elements.
  • a stage is preferably defined as a region or zone in which a given process is taken place.
  • the stages comprised in the updraft gasifier e.g. drying, pyrolysis, char gasification and partial oxidation, ash burn out
  • the stages are separate stages in the sense that the different processing of the fuel are carried out in separate stages.
  • the stages are successive in the sense that fuel goes directly from one stage to another.
  • Each of the stages may also be characterized as being coherent, typically in the sense that the stage is a zone in which a particular process is taken place.
  • the partial oxidation stage is also a stage that is separate from the other stages and where processes involving gas from the updraft gasifier take place.
  • gases from the updraft gasifier are partially oxidized preferably means that the gases from the updraft gasifier are burned to provide a partial oxidation of the gases. As presented herein, burned is preferably not considered to be a complete oxidation.
  • the partial oxidation stage may be closer than 4 m to the top of the solid fuel or even closer than 2 m to the top of the solid fuel.
  • the temperature in the partial oxidation stage may be between 550 - 950°C, preferably between 750 - 900°C.
  • the gas leaving the thermal reactor (gas produced in the reactor) may have a heating value of 2-5 MJ/Nm 3 , wherein the heating value may be controlled at least by the water content of the carbonaceous fuel.
  • the tar content of the gas from the updraft gasifier may be reduced by 90 - 99% in the partial oxidation stage preferably by controlling the oxygen injected into the partial oxidation.
  • gas from the partial oxidation stage may be cooled preferably either within the thermal reactor or downstream from the thermal reactor.
  • the oxygen required for the partial oxidation in the partial oxidation stage may be supplied as air, oxygen enriched air or pure oxygen.
  • the oxygen injected into the partial oxidation stage may be injected horizontally or in a direction pointing downwards.
  • the partial oxidation stage may be followed by a gas combustion stage such that the gases from the updraft gasifier pass through the partial oxidation stage before they go into the gas combustion stage, where gas from the gasifier is combusted.
  • the gas combustion stage may be downstream from the thermal reactor.
  • the gas combustion stage may be inside the thermal reactor.
  • the gas combustion stage may be supplied with air and/or flue gas.
  • the gas combustion stage may be followed by an SNCR stage such that the gases from the updraft gasifier pass through the partial oxidation stage and the gas
  • the gas from the updraft gasifier may be converted into liquid fuel in a gas synthesis stage.
  • the partial oxidation may be provided to have a retention time of the gas in the partial oxidation stage of more than 1 second, such as more than 2 seconds and provide a temperature in the partial oxidation stage between 500-1000°C, such as between 600-900°C thereby producing NOx content in the gas leaving the thermal reactor below 200 mg/Nm3, such as below 150 or even below 100 mg/Nm3.
  • oxygen such as air
  • the temperature in partial oxidation stage may be between 500-1000°C, such as between 600-900°C and the retention time in the partial oxidation stage may be more than 1 seconds, such as more than 2 seconds, thereby preferably providing a tar content in the gas leaving the thermal reactor below 0.5 g/Nm 3 , such as below 0.1 g/Nm 3 , or even below 0.05 g/Nm 3 .
  • the flow of gas upwardly through the top layer solid fuel may be controlled so as to keep the amount of dust, below 500 mg/Nm3, such as below 100 or event below 50 mg/Nm3 in the gas leaving the thermal reactor (1).
  • method is controlled, preferably be controlling, inter alia, the amount of in-feed of carbonaceous fuel into the reactor, so that the retention time in the ash burn-out stage (6) is at least one hour, such as at least two hours, such as at least 4 hours, thereby providing a carbon content in the ash after burn-out less than 10%, such as less than 5%, such as less than 1%, or even less than 0.5% based on weight.
  • the invention in a second aspect, relates to a system for converting a solid carbonaceous fuel into burnable gas and ash said system preferably comprising a thermal reactor, said thermal reactor comprising stages for conversion of solid carbonaceous fuel into a burnable gas, said stages being separate process stages preferably comprising :
  • said thermal reactor may further comprise means adapted to controlling the oxygen amount to be led to the ash burn-out stage and the partial oxidation stage so that the gases produced may be converted into burnable gas with low emissions (NOx, CO) and with low excess oxygen content and preferably high steam content, and where further said partial oxidation stage may be providing heat to the pyrolysis and drying stages by radiation and convection.
  • the system may comprise a reactor wall of the thermal reactor preferably extending from fuel inlet to ash outlet in a horizontal or sloping direction so that fuel moves towards the ash outlet by gravitational force.
  • system may further comprise means, such as one or more nozzles, to inject oxygen into the partial oxidation stage, preferably horizontally or in a direction pointing downwards.
  • means such as one or more nozzles, to inject oxygen into the partial oxidation stage, preferably horizontally or in a direction pointing downwards.
  • system may further comprise a gas combustion stage in the thermal reactor where gas from the gasifier may be combusted.
  • system may further comprise an SNCR stage.
  • the system may further comprise means, such as one or more nozzles, to inject urea or ammonia into the SNCR stage.
  • the system may further comprise a gas synthesis stage, wherein gas from other process stages may be converted into liquid fuel.
  • the fuel is transported into the thermal reactor, preferably by screws, pushers, spreader stokers or other transporting means.
  • the gasifier does not need any transporting mechanism inside the reactor besides the ash removal system.
  • Fresh fuel is transported into the reactors drying stage.
  • the water in the fuel evaporates.
  • Fuels may have a very little water content, such as a few %, or fuels may have high water content, such as 60% (weight basis) or higher.
  • At atmospheric pressure drying happens when the fuel is heated to e.g. 100°C. The higher the temperature is, the faster is the drying process.
  • the energy for the drying process comes from two internal processes:
  • the drying reaction time in this reactor is short: Fuels with a high moisture content above 40% water, can dry in around 1 hour while dryer fuel can dry much faster such as below 5 minutes, thus resulting in a very compact drying stage.
  • the solid organic fuel is heated to a temperature between app. 300° and 900° C and decomposed into a solid component containing char and ash and a gaseous component containing organic components including tars, methane, CO, C02, H2 and H20 etc.
  • the energy for the pyrolysis process comes primarily from two other internal processes:
  • the solid component produced in the pyrolysis stage is converted into a burnable gas and a carbon-rich ash.
  • Gasification reactions (mainly C02+C -> 2 CO and H20 + C -> CO + H2) are endothermal (energy consuming).
  • Gasification agent is the gas produced by the oxidation.
  • the temperature in the gasification and oxidation stage is between 600°C-1100°C.
  • "gasification” is often named "reduction”.
  • the carbon that is not gasified in the gasification stage is oxidized/burned by use of oxygen.
  • oxygen also steam and nitrogen can be added as dry air, moisturized air, and steam can also be let to the oxidation stage.
  • the temperature in the oxidation stage is between 700-1100°C. The ash layer.
  • the ash layer Below the char oxidation and gasification stage is the ash layer.
  • the oxidation agent (air) and possibly steam are let into the ash layer.
  • the temperature of air/steam is low, such as below 300°C or even below 100°C.
  • inert ash is cooled, resulting in a cold ash, such as below 300°C, or even below 200°C.
  • the ash can be removed by an ash removal system, such as ash screws or other means.
  • the updraft gasifier produces a combustible gas containing H20, H2, CO, C02, CH4 and higher hydrocarbons.
  • a typical gas composition just above the bed when a fuel with 50% water content used is:
  • H20 41%, H2: 12%, CH4: 2%, CO: 18%, C02: 4%, N2: 21%, higher
  • H20 33%, H2: 11%, CH4: 0%, CO: 4%, C02: 13%, N2: 39%, higher
  • the partial oxidation process is carried out near the bed surface, such as 4 metres or below, and hereby the top of the bed is heated by the partial oxidation stage mainly by radiation, but also somewhat by convection.
  • the heat transfer from the partial oxidation to the updraft gasifier bed results in a colder flame, and hereby is the NOx and soot level low.
  • the amount of oxygen can be regulated : More oxygen will increase the temperature and vice versa.
  • cooling items can be inserted such as steam super heater or other types of superheaters i.e. helium based superheaters for use in Stirling engines. Dust
  • an updraft gasifier where the speed of gas through the top layer of the solid fuel is below 2 m/s or even below 1 m/s, which result in a very low-dust gas leaving the updraft gasifier.
  • the nozzles can be placed in a uniform height or in various heights, and
  • the nozzles point horizontally or even a bit downwards, e.g. in an angle of 0-20 degrees in such a way and in such a height that heat transfer to the bed below is optimized.
  • the nozzles shall, or may, not point into the fuel layer, as this will increase dust emissions.
  • the dust level of current invention be very low: such as below 100 mg/Nm3 or even below 50 mg/Nm3.
  • the walls of the thermal reactor are shaped in such a way that there is some back mixing/recirculation of the flue gas which will improve NOx reduction and tar reduction.
  • the walls can be placed in an angle so that radiation from the hot walls to the top layer of the fuel is increased.
  • Moisturized air can be used for the partial oxidation as moisturized air reduce soot and NOx formation, and increase overall efficiency when condensing of the gas is used.
  • the nozzles are designed to give the right mixing of air and gasification gas.
  • the nozzle speed (speed of gas out from the nozzle) will, or could, be between 20-40 m/s at full load.
  • the temperature in the partial oxidation stage is typically between 550-950°C. Water content in fuel
  • a gasification unit according to the present invention can use a wide spectrum of fuels, such as wet fuels with a low heating value or dry fuels with a high heating value. This is possible by adjusting the amount of air used for partial oxidation.
  • a system that adds water to the system can ensure a very stable temperature, independently of the fuel heating value in the thermal reactor, and hereby stable and low emissions.
  • the gas produced according to the invention can be used to several purposes:
  • the gas can be combusted in a combustion chamber and the hot flue gas can heat up water, thermal oil, steam or the like
  • the gas can be cooled and cleaned and used in internal combustion
  • the gas can be converted into liquid fuel by condensing and/or synthesis.
  • Fuel-NOx is formed when there is an over stoichiometric air-fuel ratio in the fuel. In the present invention, there is very limited or even no excess air in the char oxidation stage as the present invention uses the updraft gasification principle.
  • Thermal-NOx is formed when temperatures are high, such as over 1100C. As preferred temperatures are 800-950C, very small amounts of thermal NOx are produced.
  • a main chemical reaction path for reducing NOx is that CO react with NOx and form free N2 at temperature between 600-900C.
  • the present invention may result in a gas with a very low NOx such as below 200 mg/Nm3, or even below 150 mg/Nm or even below 100 mg/Nm3.
  • Preferred embodiments of controlling to accomplish the above may be
  • the retention time is typically provided by the size of the thermal reactor, and the temperature is controlled by the amount of oxygen/air introduced into the partial oxidation stage, since more oxygen/air provides a higher temperature.
  • a SNCR method can be used, for instance, urea can be injected.
  • a main advantage in the present invention is that the content of tars is limited. As previously described is the typical amount of tar from an updraft gasifier in the range of 5-10 g/Nm3. According to preferred embodiments of the present invention - with a partial oxidation stage after an updraft gasifier - will the tar amount be reduced at least 90% (to 0,5-1 g/Nm3), and possibly even as low as below 0,2 g/Nm3 (tar reduction of 96-98%).
  • Such very low tar level is achieved due to good (intimately) mixing, the right amount of oxygen (to provide a partial oxidation), sufficient retention time (such as more than 1 seconds, such as more two seconds) and temperature of partial oxidation stage such as between 500-1000°C, such as between 600-900°C.
  • Partial oxidation (secondary air) while drying and pyrolysis are driven by energy from radiation from the partial oxidation and convection from the hot gas in the char gasifier.
  • each active oxygen molecule is used either for burning out de-volatilized char or for oxidizing gas components, such as the tars.
  • an updraft gasification principle is used for converting char into burnable gas and ash.
  • the retention time of the final carbon burn-out in the ash burn-out stage may be several hours which is much more than in for instance in grate furnaces, which have a retention time of about 10 minutes in the final carbon burn-out stage. This results in a high char burn-out, thus a low carbon content in the ash, in the present invention :
  • the carbon content in the ash is, or may be, less than 10%, or even below 5% or 1%.
  • moisturized air can be used, or steam can be added in the bottom of the thermal reactor.
  • Ash removal system
  • Another main advantage of the invention is, or may be, the simplicity of removing the ash.
  • the ash removal systems are costly and complicated, whereas according to this invention the ash removal system is technically easy to embody and cheap.
  • the ash can easily be removed by a round grate system or simply by one or several screws.
  • Standard screws remove materials from one end, so if screws are used they must have, or may have, a special design so the ash is removed in an even layer.
  • a major advantage of the present invention is that there is no moving parts placed in warm stages, such as the drying, pyrolysis, char oxidation and char gasification stages.
  • the system consists of the following moving parts:
  • Air blower (below 100°C).
  • the thermal reactor is divided into stages in the vertical direction.
  • the various stages include (from below and up) :
  • Partial oxidation The partial oxidation stage functions both as tar reduction and heat source for the top layer of the updraft gasifier.
  • the stages can be partly horizontally divided, i.e. the drying section could be close to the feeder, and the pyrolysis stage could be horizontally away from the feeder.
  • the drying section could be close to the feeder
  • the pyrolysis stage could be horizontally away from the feeder.
  • Such a shape will keep pyrolysis gases away from the feeder, and it will keep the feeder section cool (such as below 200°C).
  • the height of the thermal reactor may differ from a few metres for small plants to more than 8 metres, such as more than 10 metres for large plants.
  • the thermal reactor is preferably round or rectangular.
  • the solid bed as well as the partial oxidation stage may have different dimensions
  • the bottom part of the thermal reactor may have one diameter, and higher up in the drying/pyrolysis region, it may be wider, and above in the partial oxidation stage, the thermal reactor may be even wider.
  • a plant may comprise components or stages, which are located outside of the thermal reactor and such that the gasses produced in the thermal reactor pass through those components or stages subsequently, i.e. after leaving the thermal reactor. Such components or stages are said to be located downstream from the thermal reactor. Size of plants
  • these types of plants will be between 1-50 MW thermal input, but they may be both smaller and larger.
  • a typical design parameter is, or may be, that there shall be about lm2/MW fuel input in the gasification section and about 1-2 seconds retention time in the partial oxidation stage; the retention time may be determined as the volume of the partial oxidation stage divided by the volume flow through the partial oxidation stage.
  • the invention can be used to design thermal reactors with a turn-down ratio of 1 : 10 or even below e.g. 1 :20.
  • a registration system of the bed height may preferably be installed and the registration system may preferably interact with the feeding system.
  • the bed height can be registered by sensors such as radar, ultrasonic or gamma measurements.
  • the bed height will, or may be, typically be between 1-3 meters.
  • the ash In the bottom of the gasifier, the ash is removed, and oxygen (air) is injected into the ash layer.
  • the ash removal system is activated when the ash is with a minimum of ash, as only by then is the temperature of the ash low.
  • the ash layer contains char
  • the char will oxidize, and the ash will be warm.
  • the char When the char is fully burned, the ash will be cold.
  • temperature measurements right above the oxygen (air) inlet can indicate if the char is fully burned and then activate the ash removal system. Oxygen for gasification and for partial oxidation
  • the stoichiometric ratio for the thermal reactor is app. 0.5-0.9.
  • a typical gas composition is: H20: 33%, H2: 11%, CH4: 0%, CO: 4%, C02: 13%, N2: 39%, higher hydrocarbons (Tars) : 0-1% (by volume).
  • the heating value of gas produced in the thermal reactor will, or may, be between 2-5 MJ/Nm3 (higher heating value at 25C).
  • the main influence of the heating value is the water content of the fuel. The drier the fuel is, the higher the heating value is.
  • the oxygen supply for the partial oxidation may preferably be controlled by a temperature sensor and/or by a sensor that measures CO and/or H2 content.
  • the updraft gasifier stage operates, or may operate, with a stoichiometric ratio of 0.2-0.25, so about 20-40% of the oxygen is led to the ash burn-out stage and the rest to the partial oxidation stage.
  • water can be used for temperature control of the gas combustion stage.
  • the system offers a number of advantages compared to state-of-the-art gasification technologies. It could therefore be expected that the system will be expensive and complicated. However, the simplicity and the compactness of the system is a main advantage of the invention.
  • the pressure of the system will be atmospheric, but the system can be built for both underpressure and overpressure.
  • Fig. 1 schematically illustrates how the basic process steps of the thermal reactor according to the invention interact.
  • Fig. 2 schematically illustrates an energy plant producing heat and power.
  • Fig. 3 shows an energy-mass balance of the energy plant illustrated in Figure 2.
  • Fig. 4 shows the flow lines of the air added to the partial oxidation reactor 13, and to the combustion chamber in the plant illustrated in Figures 2 and 3.
  • Fig. 5 shows the velocity lines in the partial oxidation reactor and in the
  • Fig. 6 shows a schematic diagram of the updraft ash system and the updraft gasification part illustrated in Figures 2, 3, 7, 8 and 9; in fig. 6, upper part, the view is illustrated in a side view to show the interior of the thermal reactor, the lower part of fig. 6 is illustrates the ash screws as seen in an end view.
  • Fig. 7 shows schematically a thermal reactor with an updraft gasifier and a partial oxidation zone, and downstream from the thermal reactor: a zone for gas combustion and a boiler.
  • Fig. 8 shows the system depicted in fig. 7 in use
  • Fig. 9 illustrates another embodiment of an energy plant producing heat and power
  • Fig. 10a and 10b shows temperature distribution and flow velocities during use of a thermal reactor according to a preferred embodiment of the present invention, DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION
  • Fig. 1 is a unit or reactor to which fuel and oxygen is added and a burnable gas with low dust and low tar content is produced (in fig. l, the gray-shaded box framing : Drying, Pyrolysis, Char gasification and oxidation, Ash burn-out and Ash Layer is only for illustrating the updraft gasification stages) :
  • the fuel is converted thermally by addition of air (and/or oxygen).
  • a burnable gas, 14, with a low dust and a low tar content is produced in the thermal reactor 1.
  • the fuel added to unit 1 is solid, e.g. biomass, waste or coal.
  • the fuel is fed by a feeder 2, and converted to a gas in the bottom of the reactor, which is an updraft gasification process, comprising drying process 3, pyrolysis process 4, char gasification and oxidation process 5, ash burn out process 6, an ash layer 7, an ash removal system 8, one or several gasification agents 9 and one of several sensors SI.
  • an updraft gasification process comprising drying process 3, pyrolysis process 4, char gasification and oxidation process 5, ash burn out process 6, an ash layer 7, an ash removal system 8, one or several gasification agents 9 and one of several sensors SI.
  • the gasification agents 9, can be 02, C02 and/or H20 or a mix hereof.
  • a preferred mix is moisturized air, with 0.2 kg H20 per kg dry air.
  • Another preferred mix is recirculated flue gas that is mixed with fresh air, so the mix has an 02 content of 10-13%.
  • the temperature of the gasification agent is preferably between 80-150C.
  • SI is the sensor that activates the ash removal system.
  • SI is preferably one or several temperature sensors that register the temperature of the ash layer.
  • the setpoint of SI is preferably between 80-120C. When the temperatures are below the setpoint, the ash layer is thick, SI registers a low temperature, and some ash can be removed by the ash removal system 8.
  • the temperature sensor SI When ash is removed the solid stages above will move downwards due to gravity, including the ash burnout stage, which has a temperature of 300-800 C. Following this, the temperature sensor SI will register a higher temperature and the ash removal system will stop and await further ash removal until the temperature is again below the setpoint.
  • the ash can be removed by several types of ash removal systems including screws. When screws are used they preferably must have, or may have, a special design so ash is removed in an even layer - see also fig. 6, fig. 7 and fig. 8.
  • the cross sectiona area of the updraft gasification part is approximately 1 m2/MW thermal input of fuel.
  • the height of the updraft gasification bed is about 1-3 m.
  • the gas composition of the updraft gasification part depend on the fuel.
  • a typical gas composition using biomass with 50% moisture is :
  • H20 41%, H2: 12%, CH4: 2%, CO: 18%, C02: 4%, N2: 21%, higher
  • the cross sectional area of the updraft gasification part is approximately 1 m2/MW thermal input of fuel.
  • the gas production of the updraft gasification part at full load is about 0.15-0.2 kg/s/MW, which equals 0.15-0.2 kg/s/m2 which equals a gas speed of app. 0.3- 0.4 m3/s. Due to this very low gas speed through the updraft gasifier, very little dust (below 100mg/Nm3) is carried on to the partial oxidation process.
  • the updraft gasifier fuel bed is the partial oxidation stage 10: Oxygen, 13, is added to the gas (e.g. by introducing air), and the gas is hereby partially oxidized and the temperature of the gas is increased due to exothermic reactions of the gas with oxygen. Also the gas composition is changing as the tars
  • the temperature of the partial oxidation stage is preferably between 750C-950C. If air is used an approximate gas composition after partial oxidation is, or may be: H20 33%, H2 11%, CH4 0%, CO 4%, C02 13%, N2 39%, higher hydrocarbons (Tars) 0%
  • the inlet of the oxygen for the partial oxidation process is placed above the inlet of the fuel for the updraft gasifier. Preferably the inlet for the oxygen is 1-4 m above the inlet of the fuel.
  • the partial oxidation is carried out above the top of the fuel bed, and here the partial oxidation also functions as an extra heat source for the drying and pyrolysis stages, and the fuel bed in the updraft gasifier can be as low as 1-3 m in height.
  • the temperature and gas composition of the partial oxidation stage can be controlled and optimized in various ways, depending on the purpose of the plant:
  • One or several sensors S2 can measure temperature and/or gas components such as e.g. CO, H2, CH4, C02, H20, NOx.
  • the exit temperature can be controlled by the amount of oxygen added and/or amount of water, 12, added : More oxygen increases the temperature, whereas more water decreases the temperature.
  • the gas composition can also be adjusted by the amount of oxygen and/or amount of water added.
  • the amount of NOx can further be reduced by injection of urea, 12, or other SNCR catalyst. Feeding system 2 and control of bed height S3
  • the feeding of the fuel is adjusted according to the thermal output of the plant and the bed height of the updraft gasifier.
  • the Sensor S3 measures the bed height.
  • the sensor S3 is preferably a radar, but it can also be other systems such as ultrasonic, IR camera, etc. When the bed height is too large less fuel is feed into the gasifier, and eventually more gasification agent 9 is added, and vice versa.
  • Gas cooler 11 When the bed height is too large less fuel is feed into the gasifier, and eventually more gasification agent 9 is added, and vice versa.
  • the gas can be cooled in one or several gas coolers 11, which can be integrated in the thermal reactor 1 or in following stages.
  • a colder gas, 15, is produced.
  • the gas cooler(s) 11 are typically considered optional, not mandatory in connection with the present invention.
  • FIG. 2 an energy plant, producing heat and power, is schematically illustrated.
  • the items with reference numerals A00-AFR-A07, F00-F09 and W00-W12 are explained in fig. 3.
  • OCR CYCLE in fig. 2 refers to Organic Rankine Cycle.
  • A06 is the air for the updraft gasifier which is first preheated by the gasification reactor then, moisturized in the "Gasification Humidifier". Hereafter it is named A07. The air is then heated in drawing by external heat jacket of the "gas combustion”. Hereafter it is named A07 and this moisturized and dry air is then lead to the blower (the arrow) and pushed into the air inlet of the gasifier. It is noted, that this process involving the Gasification Humidifier may be considered optionally.
  • moisturized and preheated air 13 (A04) is partially oxidizing the gases produced in the updraft gasifier, and that water 12 (Wll) is supplied to the partial oxidation stage.
  • the water is in this case quench water and carrying particles collected in the quench to the thermal reactor.
  • the produced gas 14 may be lead to a combustion chamber where the gas is combusted to a flue gas consisting of N2, C02, H20 and 02.
  • combustion chamber is very low (below 10 mg/Nm3). Due to the low velocity of the gas leaving the updraft gasifier the dust content is very low (below 100 mg/Nm3)
  • the flue gas from the combustion chamber may be cooled in several stages:
  • the flue gas is cooled in thermal oil heat exchangers in the ORC cycle which is producing electricity and heating.
  • the flue gas is cooled in the Quench and in the Flue gas scrubber.
  • the Quench function as cooler before the flue gas- scrubber and as particle removal system.
  • the flue gas scrubber function both as a cooler of the flue gas and as a heater of the condensate water.
  • the energy of the hot water produced in the Flue gas scrubber is transferred to the district heating water through the heat exchanger "Scrubber heat recovery".
  • the gasification air used in the updraft gasifier is moisturized in the Gasification Humidifier, and subsequently heated and dried before it is lead to the updraft gasifier.
  • the air used for the partial oxidation and for the gas combustion chamber is moisturized in the Combustion Humidifier, and subsequently heated and dried before it is lead to the reactor 1, and to the combustion chamber.
  • the produced condensate is filtered in a filter before excess condensate water is lead to the sewer system or used as process water somewhere else.
  • this system only has one stream of solid particles, namely the bottom ash 8, of the updraft gasifier.
  • Water and particles collected in the Quench is used to moisturize the bottom ash.
  • Fig. 3 shows an energy-mass balance of the energy plant illustrated in Figure 2.
  • the Energy-mass balance is based on 2500 kg/hour of biomass with ⁇ 1% ash and 30% water. This is equivalent to approximately 8.697 MW thermal input to the plant (Based on Lower heating value of the fuel).
  • the high efficiency (above 100%) is possible due to the fact the energy input is measured as low heating value, and the flue gas condensation system converts the water vapours in the flue gas into energy in terms of hot water.
  • Fig. 4 shows the flow lines of the air added to the partial oxidation stage 10 and to the combustion chamber 16 in the plant illustrated in Figures 2 and 3.
  • Fig. 4 also illustrates by numeral 17, openings used for oxygen and/or air into the gas combustion stage.
  • Fig. 5 shows the velocity lines in the partial oxidation reactor and in the
  • Fig. 6 shows a schematic diagram of the updraft ash system and the updraft gasification part illustrated in Figures 2 and 3.
  • Six air nozzles 9 are placed between each of the seven ash screws 8, so there is a total of thirty-six air nozzles in the ash layer.
  • the size of the reactor is: Width : 3 m, depth : 3 m, which results in 9 m2. As the fuel input in the reactor is app 8.7 MW the specific load approximates 1 MW/m2.
  • Each air nozzle supplies 0.25 m2 of ash-layer with air.
  • thermo-couples SI are placed in the ash layer between each ash screw to monitor the temperature of the ash layer. So in total there are eighteen
  • thermocouples are thermocouples.
  • the shaft of the screws is conical. This is to ensure that ash is removed in an even layer. It is seen that the screws have an angle of app. 25 degrees downwards from the feed to the ash system. This is to ensure an even height of the fuel layer, as the fuel in the top will approximately have such angle. See also figure 4 and 5. It is seen that the gasification reactor has refractory lining in a least two qualities. The inner lining has high temperature and chemical resistance while the outer lining has good insulation properties.
  • Fig. 7 shows schematically a thermal reactor with an updraft gasifier and a partial oxidation zone, and downstream from the thermal reactor: a zone for gas combustion and a boiler (thermal oil heater).
  • Fig. 8 shows the system depicted in fig. 7 in use,
  • Fig. 9 illustrates another embodiment of an energy plant producing heat and power.
  • An explanation as to the reference numerals A00-AFR-A07, F00-F09 and W00-W12 can be found in fig. 3.
  • the basic operations of the plant shown in fig. 9 is as illustrated in fig. 3, and fig. 9 can be viewed as a more complete illustration of the plant shown in fig. 3.
  • Fig 10a shows temperature distribution within a thermal reactor according to the preferred embodiment illustrated in fig. 8. Please observe that the vertical and horizontal planes in which the temperatures are shown, are not physical planes but imaginary planes at which the temperatures are determined.
  • Fig. 10b shows the flow lines of the air added to the partial oxidation stage 10 and to the combustion chamber 16 and of the gases therein of the preferred embodiment illustrated in fig. 8.
  • thermal reactor With reference to fig.s 4, 5 and 10, please observe, that the lower part of the thermal reactor is not illustrated, and the lower boundary in the illustration of the thermal reactor is the top of the bed.
  • the thermal reactor may be as illustrated in fig.s 7 and 8. Please observe that dimensions given in the drawings are not to be construed as limiting for the scope of the invention, since they refer to a preferred
  • oxygen/air is preferably used for referencing air, such as atmospheric air, oxygen enriched air and/or pure oxygen

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  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne un procédé et un système de production de gaz combustible chaud présentant une faible teneur en NOx, en poussières et en goudron et des cendres propres à faible teneur en carbone au moyen d'un réacteur thermique divisé en étages. Dans le réacteur thermique divisé en étages (gazéifieur à courant ascendant), le processus de conversion du combustible solide est effectué dans des étages verticaux séparés (de bas en haut) : la combustion de cendres, l'oxydation de résidus de carbonisation et la gazéification, la pyrolyse, le séchage et un étage d'oxydation partielle dans lequel une partie du gaz provenant du gazéifieur est oxydée. L'étage d'oxydation partielle fonctionne à la fois comme étage de réduction de goudron et comme source de chaleur pour le séchage et la pyrolyse de la couche supérieure du gazéifieur à courant ascendant.
PCT/DK2018/050114 2017-05-19 2018-05-18 Procédé et système de production d'un gaz combustible chaud à base de combustibles solides Ceased WO2018210393A1 (fr)

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EP4151706A1 (fr) * 2021-09-15 2023-03-22 Bios Bioenergiesysteme GmbH Procédé et dispositif de fabrication d'un produit de gaz à faible teneur en goudron et en poussières

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US20110146155A1 (en) * 2008-08-30 2011-06-23 Dall Energy Holding Aps Method and system for production of a clean hot gas based on solid fuels
US20110250661A1 (en) * 2010-04-13 2011-10-13 Bhagya Chandra Sutradhar Methods for gasification of carbonaceous materials

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US20110146155A1 (en) * 2008-08-30 2011-06-23 Dall Energy Holding Aps Method and system for production of a clean hot gas based on solid fuels
US20110250661A1 (en) * 2010-04-13 2011-10-13 Bhagya Chandra Sutradhar Methods for gasification of carbonaceous materials

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4151706A1 (fr) * 2021-09-15 2023-03-22 Bios Bioenergiesysteme GmbH Procédé et dispositif de fabrication d'un produit de gaz à faible teneur en goudron et en poussières

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