WO2007112353A2 - Méthode d'amélioration de l'efficacité de gazéification grâce à l'utilisation de chaleur perdue - Google Patents

Méthode d'amélioration de l'efficacité de gazéification grâce à l'utilisation de chaleur perdue Download PDF

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Publication number
WO2007112353A2
WO2007112353A2 PCT/US2007/064934 US2007064934W WO2007112353A2 WO 2007112353 A2 WO2007112353 A2 WO 2007112353A2 US 2007064934 W US2007064934 W US 2007064934W WO 2007112353 A2 WO2007112353 A2 WO 2007112353A2
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WIPO (PCT)
Prior art keywords
steam
syngas
gasifier
generator
waste heat
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Ceased
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PCT/US2007/064934
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English (en)
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WO2007112353A3 (fr
Inventor
Philip D. Leveson
John Paul Gaus
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ZeroPoint Clean Tech Inc
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ZeroPoint Clean Tech Inc
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Publication of WO2007112353A3 publication Critical patent/WO2007112353A3/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
    • 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
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—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
    • 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
    • C10J2300/1838—Autothermal gasification by injection of oxygen or steam
    • 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
    • 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
    • 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
    • C10J2300/1892—Heat exchange between at least two process streams with one stream being water/steam
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin

Definitions

  • the present invention relates to gasifier equipment and to the process of gasification of carbon containing solids into combustible gases.
  • the improvement may be used to enrich the calorific density and hydrogen content of the produced syngas while simultaneously improving the thermal efficiency of the gasification process.
  • Gasification processes convert carbon-containing solids of liquids into combustible gases that ideally contain all the energy originally present in the feed. In reality this is not easily achieved, although with good thermal management it is possible to operate with energy efficiencies in excess of 90%.
  • the technique yields a combustible gas, which is typically rich in carbon monoxide, hydrogen and methane from a carbon containing solid.
  • Gaseous fuels have many advantages over solid fuels. They are typically cleaner burning reducing particulate carbon, hydrocarbon and carbon monoxide emissions. It is also much easier to remove sulphur, halogen and nitrogen containing volatile compounds from the syngas through scrubbing and adsorption techniques prior to combustion rather than cleaning the flue gases or the solid fuels.
  • gasification is that the gas stream produced has a relatively weak energy density.
  • the energy content per unit volume is around a fifth to a seventh that contained in natural gas and around one twentieth that of liquefied petroleum gas ("LPG").
  • LPG liquefied petroleum gas
  • This low energy density detracts from the economics of compressing the gas and transporting through pipelines to anywhere other than over short to moderate distances.
  • the gaseous fuel produced from gasification is typically used on or near the production facility.
  • biomass as a feedstock for gasification systems is becoming increasingly economically as well as environmentally attractive.
  • Potential local uses for the syngas may include, running generators to produce electrical power, using the fuel to offset natural gas in heating applications or to convert the syngas into a liquid fuel, and other uses.
  • the conversion to a liquid fuel can be readily accomplished by the catalytic reduction of carbon monoxide by hydrogen to produce methanol, ethanol or synthetic middle distillates. In this case the fuel can be readily transported to be the market place.
  • a typical biomass has an energy density around 18kJ/g on a dry basis. On a wet basis this value can be substantially less and can even be less than zero, indicating that the fuel is not capable of burning in a sustainable manner while liberating energy.
  • biomass On a dry basis biomass has a calorific value around half that of coal.
  • the low energy density, its low packing density and difficulty in handling make the economics of transporting biomass large distances unfeasible.
  • the utilization of biomass for small to medium scale distributed energy producing processes has some synergy.
  • the biomass for such a process would be sourced locally and probably within a twenty mile radius. Power may be generated and used to reverse feed already saturated power delivery lines. In such a system local communities would utilize locally grown biomass and potentially make use of some volume of waste currently being land filled to generate their own power or convert the material into fuels. In effect a community could become power and fuel self sufficient while producing no greenhouse gas emissions.
  • Biomass is a very broad term and includes all solids derived from plant matter, animal wastes as well as organic municipal waste. Suitable biomasses include, but are not limited to, sawdust, wood, straw, alfalfa seed straw, barley straw, bean straw, corn cobs, corn stalks, cotton gin trash, rice hulls, paper, municipal solid waste, barks and animal wastes. It is interesting that almost all biomass has the same ratio of carbon to hydrogen to oxygen, which is summarized as CH 1 4 O 0 O .
  • the syngas produced through equation 4 has a much higher energy density than air derived syngas.
  • the total energy content of the syngas is also about twice than that of the air derived product, however, the process is strongly endothermic and requires a substantial external energy input.
  • the energy can be transferred into the process through heat transfer mechanisms, which may include externally heating the gasifier through the use of heating elements within the gasifier or through passing hot inert solids into the gasification bed. Either of these techniques greatly complicates the overall design of the gasifier.
  • a second technique utilizes a large excess of superheated steam, such that the sensible heat contained in the steam is used to provide the energy for the process. However, this involves the construction of a large steam generator, thus increasing the capital expenditure of the process and generates the need for an external fuel input.
  • the present invention comprises, in one exemplary embodiment, a method which allows the waste heat generated from an external process, which is fueled by syngas, to be recycled into a gasification process to enhance the energy density of the syngas produced as well as the overall gasification efficiency of the system.
  • the invention also relates to a method of utilizing the waste heat contained in a stream exiting in the syngas-fueled process to vaporize water and produce steam.
  • the steam is then upgraded by first exchanging energy with the hot syngas exiting the gasifier and then within the gasifier itself to a temperature where significant steam gasification of the biomass occurs.
  • the process within the gasifier is driven by introducing a small amount of air into the gasifier such that some biomass is directly combusted to provide the heat required by the endothermic processes.
  • the volume of oxygen required by the process is vastly reduced and hence the volume of associated nitrogen diluent introduced is also minimized.
  • This manner of operation significantly reduces the cost of the ancillary equipment as no external steam or oxygen generator is required.
  • the method maximizes the energy content of the produced gas and under certain circumstances allows gasification efficiencies greater than 100% to be achieved.
  • the gasification efficiency is defined as the energy content of the produced gas divided by the energy content in the original biomass. The improvement becomes much increased if amounts of steam much higher than required by stoichiometry are utilized. Particularly favorable results are achieved with steam ratios in the range of 1:10 times that of stoichiometry.
  • Fig. 1 is a schematic flow diagram illustrating how waste energy from a generator powered by an internal combustion engine can be effectively recycled back to the gasification process to improve the quality of the syngas produced and improve the thermal efficiency of the gasification process
  • Fig. 2 is a schematic flow diagram illustrating how waste energy from a generator powered by an internal combustion turbine can be effectively recycled back to the gasification process to improve the quality of the syngas produced and improve the thermal efficiency of the gasification process.
  • Utilizing steam results in a syngas which has a high calorific value and is high in hydrogen and so exhibits good flame velocity attributes.
  • the gasification reactions which involve steam are highly endothermic such that external energy must be supplied to the system, either through external heating techniques, the introduction of hot inert material into the gasification bed or through the use of large volumes of excess steam such that the steam contains appreciable quantities of sensible heat. This results in a process which requires some form of external energy input and as such requires utilizing a fuel.
  • the external process that is consuming the syngas produced in the gasifier is thermally integrated with the gasification process itself.
  • waste heat from the process can be efficiently and conveniently used to enhance the gasification process to produce a syngas with a higher energy density, a higher in hydrogen concentration and in a thermally more efficient manner as compared to an air blown system.
  • the exemplary embodiment of the method described hereinbelow utilizes a gasifier operating with and without the energy recycle and discusses how the process becomes integrated within a continuous process to convert biomass into electrical power using an internal combustion engine generator and a turbine powered generator.
  • a 15cm, down-draft stratified gasifier with an integral tar cracking and hydrocarbon reforming lower chamber was used to convert biomass into syngas.
  • the biomass undergoes the decomposition process commencing with devolatization followed by flaming pyrolysis and finally char gasification.
  • the lower zone a small amount of air is introduced into the syngas such that a small fraction is further oxidized.
  • the heat liberated by this oxidation allows higher order hydrocarbons and tars to be broken down into carbon monoxide and hydrogen.
  • the result of the thermal treatment is that a syngas which is essentially free of tars and higher order hydrocarbons is produced.
  • the air flow to the gasifier was adjusted such that the maximum bed temperature was 850 0 C.
  • the syngas produced exiting the system was cooled to 40 0 C such that any condensable matter is liquefied.
  • the syngas was filtered using a 5 micron polyester filter, passed through a blower and was then used to power a 4KW YAMAHATM TRIFUELTM generator.
  • the air entering the system was preheated in a plate heat exchanger using the hot syngas exiting the gasifier, in a counter current arrangement.
  • a gas chromatograph was used to analyze the composition of the gas exiting the gasifier system.
  • a typical analysis of the syngas produced is shown below in Table 1.
  • Table 1 Gas composition produced by an air blown system
  • Table 2 Gas composition produced by an air-steam blown system:
  • Table 2 clearly demonstrates the improvements in the syngas energy density and hydrogen content that are achieved by recycling the waste heat from an external device into the gasification system.
  • Fig. 1 illustrates an exemplary, nonlimiting embodiment of a continuous process for recycling waste heat from an electricity generator powered by an internal combustion engine into a gasification system. The result is to both enrich the quality of the gas being produced there and improve the overall thermal efficiency of the gasifier.
  • Biomass 10 is fed via stream 12 into a gasification apparatus 14 known to those skilled in the art.
  • gasifier 14 volatile matter and a good fraction of the fixed carbon are converted into gaseous components.
  • the ash, non-volatiles and any unconverted fixed carbon exit via the ash outlet into a collector 16.
  • the hot syngas stream 18 exits the gasifier 14 and is partially cooled in a booster heat exchanger 20.
  • a number of heat exchangers are suitable for this operation, including, but not limited to, shell and tube, plate duct, welded plate and diffusion bonded plate heat exchangers. It may be advantageous to orientate the exchanger 20 such that the gas stream flows in a vertical plane to minimize any ash deposits occurring there to minimize fouling effects.
  • the heat exchanger 20 is used to transfer energy from the hot syngas exiting the gasifier and preheat the oxidants entering the gasifier 20.
  • the partially cooled syngas exits the heat exchanger via stream 22 and then may undergo some treatment in a syngas clean up module 24. Typically, this will involve further cooling of the syngas to allow the separation and collection of condensables followed by some method of particulate removal.
  • Cyclones, spray system, wash columns and filters are all suitable for this operation. If required or desired, volatile compounds containing sulphur, halogens or nitrogen can be removed at this stage using scrubbing and/or adsorbent-based techniques. Carbon dioxide may also be sequestered at this stage.
  • the cooled and cleaned gas then enters a generator 26 via stream 28.
  • a number of different generators are suitable to utilize syngas. Some, such as the Jenbacher range, use a compressor to increase the energy density per unit volume of the syngas.
  • the two output streams 30, 32 from the generator 28 include the electrical power 30 and the waste heat 32 contained in the cooling system and the sensible heat contained in the exhaust gases. In Fig. 1 the waste heat and sensible heat have been combined to form a combined waste heat stream 32.
  • the combined waste heat stream 32 flows into a steam generator heat exchanger 34 where the energy is used to provide the latent heat of vaporization to water 36 and convert liquid water into steam which exits the unit via stream 40. If desired some of the steam generated can be diverted as a stream 41 to ancillary equipment or processes (e.g., back to the generator 26).
  • the remaining steam is mixed with the air or oxygen from a source 42 prior to entering the booster heat exchanger 20 via stream 44.
  • the stream is superheated to a temperature close to the temperature of the syngas exiting the gasifier 20 and to a temperature above where gasification processes are initiated.
  • the superheated stream 46 exits the heat exchanger 20 and then enters the gasifier 14.
  • Fig. 2 illustrates one exemplary embodiment of a continuous process for recycling waste heat from a generator powered by some form of internal combustion turbine.
  • the system is similar to that described above with respect to the exemplary embodiment shown in Fig. 1, the difference being that only the exhaust stream 50 from a turbine 52 is utilized to convert liquid water to steam.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne une méthode de recyclage dans un procédé de gazéification de la chaleur perdue générée par un procédé externe, alimenté par du gaz de synthèse, afin d'améliorer la densité d'énergie du gaz de synthèse produit ainsi que l'efficacité globale de gazéification du système. La méthode concerne l'utilisation de la chaleur perdue contenue dans un flux sortant du procédé alimenté par du gaz de synthèse pour vaporiser de l'eau et produire de la vapeur. La qualité de la vapeur est ensuite améliorée, d'abord en échangeant de l'énergie avec le gaz de synthèse chaud sortant du gazogène, et ensuite à l'intérieur du gazogène lui-même, pour atteindre une température à laquelle la gazéification à la vapeur de la biomasse se déroule de façon significative. Le procédé à l'intérieur du gazogène est démarré par l'introduction d'une petite quantité d'air dans le gazogène pour qu'une partie de la biomasse entre directement en combustion et fournisse la chaleur requise par le procédé.
PCT/US2007/064934 2006-03-24 2007-03-26 Méthode d'amélioration de l'efficacité de gazéification grâce à l'utilisation de chaleur perdue Ceased WO2007112353A2 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US78552006P 2006-03-24 2006-03-24
US78551906P 2006-03-24 2006-03-24
US60/785,519 2006-03-24
US60/785,520 2006-03-24
US11/690,577 US20070220810A1 (en) 2006-03-24 2007-03-23 Method for improving gasification efficiency through the use of waste heat
US11/690,577 2007-03-23

Publications (2)

Publication Number Publication Date
WO2007112353A2 true WO2007112353A2 (fr) 2007-10-04
WO2007112353A3 WO2007112353A3 (fr) 2008-02-21

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