EP1198541A1 - Procede et appareil de gazeification des dechets - Google Patents

Procede et appareil de gazeification des dechets

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Publication number
EP1198541A1
EP1198541A1 EP00929162A EP00929162A EP1198541A1 EP 1198541 A1 EP1198541 A1 EP 1198541A1 EP 00929162 A EP00929162 A EP 00929162A EP 00929162 A EP00929162 A EP 00929162A EP 1198541 A1 EP1198541 A1 EP 1198541A1
Authority
EP
European Patent Office
Prior art keywords
gasification
reaction vessel
synthetic gas
gas
bed
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.)
Ceased
Application number
EP00929162A
Other languages
German (de)
English (en)
Inventor
Nicolas Abatzoglou
Esteban Chornet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kemestrie Inc
Original Assignee
Kemestrie Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from ES009901711A external-priority patent/ES2183662B1/es
Application filed by Kemestrie Inc filed Critical Kemestrie Inc
Publication of EP1198541A1 publication Critical patent/EP1198541A1/fr
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
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/482—Gasifiers with stationary fluidised bed
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • B01J8/002—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor with a moving instrument
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • 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
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • 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
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • C10J3/56—Apparatus; Plants
    • 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
    • C10K1/002—Removal of contaminants
    • 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
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • 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
    • C10K1/002—Removal of contaminants
    • C10K1/007—Removal of contaminants of metal compounds
    • 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
    • C10K1/026—Dust removal by centrifugal forces
    • 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
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/101—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids with water only
    • 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
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/102—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids containing free acid
    • 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
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • 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
    • C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
    • 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
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C10J2300/092—Wood, cellulose
    • 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
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • 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
    • C10J2300/0983—Additives
    • 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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1678—Integration of gasification processes with another plant or parts within the plant with air separation
    • 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
    • C10J2300/169—Integration of gasification processes with another plant or parts within the plant with water treatments
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1846—Partial oxidation, i.e. injection of air or oxygen only
    • 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]

Definitions

  • the present invention relates to synthetic fuel gas production from low cost carbonaceous materials and waste products such as biomass, municipal solid waste, plastic and rubber residues, wastewater treatment sludge, pulp and paper liquors, heavy petroleum residues. More specifically, the present invention relates to an apparatus and method for production a synthetic gas sufficiently clean to comply with current environmental regulations.
  • Synthetic gas has various uses such as:
  • Gasification is a known technique for converting carbonaceous materials to valuable combustible synthetic gas.
  • a fraction of the feedstock is oxidized thereby generating high temperatures inside the reactor (exothermic reaction).
  • the remainder of the feedstock decomposes at the high temperatures generated by the oxidation reactions generating hot combustible synthetic gas and small amounts of char
  • the reactor is constantly fed with carbonaceous material and oxygen-containing gas to keep the exothermic reaction going so as to maintain a high temperature inside the reactor.
  • the oxygen supply is about 25-30% of stochiometric values for total combustion.
  • the partial oxidation regime present in the reactor renders the process self-sufficient in energy.
  • Additional reaction processes taking place concurrently with thermal decomposition in the gasification reactor are steam reforming, the Boudouard reaction and the shift conversion reaction. The extent of these reactions determine, to a large degree, the composition of the synthetic gas produced.
  • a typical gasification reactor operates at temperatures above 700°C and pressures above 101 kPa.
  • U.S. Patent 4,968,325 discloses a biomass gasification process and plant design. This process is commercially known as BIOSYN (trademark). The process uses a fluid bed gasification reactor containing fine sand fluidized by finely dispersed bubbles, introduced through a conveniently placed grid at the bottom of the reactor, of an oxygen-containing gas. Technical viability of this process has been demonstrated for wood residues at capacities as high as 10 tones/h. Moreover, the synthetic gas resulting from wood residue gasification is not sufficiently "clean" to be used as a fuel in modern energy conversion devices. What is meant by “clean” is a synthetic gas free of harmful contaminants such as tar and particulate material including chemically aggressive species as defined by current environmental regulations.
  • U.S. Patent 4,448,588 relates to a synthetic gas conditioning process. What is meant by “conditioning” is the treatment of the synthetic gas prior to its use as a fuel or other intended use. The process shows the use of the carbon-rich solids, i.e. char, resulting from gasification to remove organic vapors from the synthetic gas.
  • a related object is to provide synthetic gas conditioning steps and related apparatus for purifying the synthetic gas and minimizing the final effluents to be disposed of.
  • the present invention provides improvements relating to a gasification reaction vessel for converting carbonaceous feedstock to synthetic gas.
  • the reaction vessel being of the type having a bottom portion with a grid for retaining a bed of fluidizable and heat-retaining particulate material.
  • the latter is most preferably silica sand of average diameter of 200 to 700 ⁇ m.
  • the bed is fluidized by a stream of oxygen-containing gas fed through the grid tuyeres, the bottom portion also being adapted to receive, laterally, a feed of carbonaceous material to be gasified, the reaction vessel further having a top portion for recovering and evacuating the synthetic gas produced in the bottom portion.
  • the improvements generally consisting of: a top portion of the reaction vessel having an enlarged average internal cross-sectional area compared to the average cross-sectional area of the bottom portion so as to facilitate disengagement and removal of said synthetic gas from the bed of particulate material.
  • the present invention also provides an improved gasification process using a reaction vessel containing a fluidized bed for receiving a carbonaceous material feedstock for gasification and a fluidizing gas, the improvement in the gasification process consisting of: providing as the fluidization gas an oxygen-enriched air containing up to 50%, preferably 30 - 40%, oxygen to said reaction vessel (percentages based on volume).
  • the present invention also provides an improved conditioning process for the hot synthetic gas exiting the reaction vessel.
  • the conditioning process provides a clean, cold synthetic gas ready for use in various applications such as a fuel for boiler furnaces, internal combustion engines, gas turbines, etc.
  • the process improvements consisting of : subjecting the synthetic gas to a sequential treatment in at least one cyclone to remove particulate material therefrom, followed by a treatment in at least one counter-current wet- scrubber tower to cool said gas and solubilize or entrain further pollutants, followed by a treatment in at least one venturi scrubber to remove further pollutants, followed by treatment in a at least one demister to remove residual liquid droplets.
  • Optional additional conditioning treatments are also provided. Recycling steps are also described and are aimed at revealing means to increase energy efficiency and minimize by-product generation.
  • FIG. 1 represents the gasifier, in accordance with the invention.
  • FIG. 2 is a schematic representation of the process of the present invention
  • Figure 3 shows the cooling tower of the gas scrubbing system of this invention
  • Figures 4J-4.5 present the composition of the producer gas as function of the oxygen content of the gasifying agent
  • Figure 4.6 gives the producer gas flow rate as function of the oxygen content of the gasifying agent
  • Figure 4.7 gives the gasification temperature as function of the oxygen content of the gasifying agent
  • Figure 4.8 presents the HHV of the gas as function of the gasifying agent
  • Figure 4.9 presents the cold gas efficiency as a function of the percentage of oxygen content of the gasifying agent
  • Figures 5J-5.5 present the composition of the producer gas as function of the oxygen content of the gasifying agent
  • Figure 5.6 gives the producer gas flow rate as function of the oxygen content of the gasifying agent
  • Figure 5.7 gives the gasification temperature as function of the oxygen content of the gasifying agent
  • Figure 5.8 presents the HHV of the gas as function of the gasifying agent
  • Figure 5.9 presents the cold gas efficiency as a function of the oxygen content of the gasifying agent
  • Figure 5J 0 presents the tar by-product generation as a function of the oxygen content of the gasifying agent.
  • the invention proposes a process to convert organic-rich wastes into a clean synthetic gas using an atmospheric or pressurized bubbling fluid-bed gasification reactor.
  • the gasification is followed by gas conditioning which, will yield cold clean gas for use as a fuel in boilers, internal combustion engines, etc.
  • the present invention can advantageously be used to convert various forms of refuse rich in carbonaceous material.
  • wood residue, refuse derived fuel « RDF » from municipal solid waste, plastic and rubber residues, wastewater treatment sludge as well as residues from various industrial operations such as pulp and paper black liquors, petroleum heavy residues altogether with other non dangerous carbonaceous materials are examples of gasifiable residual streams.
  • These carbonaceous feedstocks may be predried or preheated in order to increase the efficiency of the overall process. Typically their moisture content does not exceed 20 wt% of the feedstock.
  • the non-condensable portion of the synthetic gas is a mixture of CO, H 2 , C0 2 , N 2 , H 2 0 and light hydrocarbons of up to 7 carbon atoms.
  • the relative concentration of each constituent depends on the feedstock but it is a strong function of the gasification agent (percentage of oxygen in the oxygen-containing gas fed to the gasification reactor), the ratio of gasification agent to feedstock, and the extent of reactions taking place in the freeboard of the reactor.
  • the synthetic gas entrains small particles, known as particulate matter, and contains low amounts of higher molecular weight hydrocarbons in the gaseous phase, known in the literature as tar.
  • the particles come from two sources: the inorganic matter present in the feedstock and hydrocarbons condensation reactions responsible also for the formation of tar present in the synthetic gas. The latter reactions lower the carbon conversion of the process thus decreasing its total energetic efficiency. Appropriate conditions are used as function of the feedstock to minimize the condensation reactions.
  • the hot gas exiting the gasification reactor after passing through a cyclone system (typically one or two cyclones) is sent to a wet scrubbing apparatus, generally multi-step, for gas cooling and conditioning.
  • a wet scrubbing apparatus generally multi-step, for gas cooling and conditioning.
  • the purpose of the wet scrubbing is to remove the particulate and the condensable species present in the synthetic gas.
  • gasifier (10) is a cylindrical reaction vessel internally lined with appropriate insulation and refractory material layers, generally referred to as insulation (12). Gasifier (10) may operate either under atmospheric or above atmospheric pressure.
  • the bottom section of gasifier (10) is equipped with an oxygen-rich gas distribution grid (14).
  • Above the grid (14) there is the section known as the fluidization bed (16) which is advantageously filled with silica sand or alumina sand.
  • the fluidization bed (16) which is advantageously filled with silica sand or alumina sand.
  • the mean size of the granular material used in the bed will vary between 200 and 700 ⁇ m.
  • One skilled in the art will readily appreciate that the final choice will depend on carbonaceous feedstock reactivity, oxygen content fed to the gasification reactor, operation pressure and reactor geometry (defining the fluid-dynamics and the residence-time distributions).
  • the height of bed at rest (16) is between 1 ,5 and 2 times the internal cross- sectional area of the gasifier (10).
  • Gasifier (10) is preferably cylindrical. However, one skilled in the art will readily appreciate that gasifier (10) may be conical, pyramidal, square or rectangular or other suitable shapes.
  • the lower section (18) is designed to be filled almost entirely by the expanded fluid bed (16) during gasification.
  • the upper section, i.e. the freeboard, (20) will advantageously have an enlarged internal cross- sectional area when compared to the lower section (18), in the case of a cylindrical gasifier (10), it will have up to about 1 ,5 times the cross-sectional area of the lower section (18).
  • conical or pyramidal gasifier (10) In the case of conical or pyramidal gasifier (10), it would be installed with the wider portion on top.
  • the larger cross-sectional area at the top favors an appropriate disengagement of the gas from the fluidized bed of granular solids and thus results in a shorter vessel than a reactor having an identical diameter in both the fluidization and the freeboard sections for the same levels of disengagement.
  • the relative heights of the two sections (18) and (20) of the gasifier (10) will depend on feedstock physico-chemical properties and several other parameters among which gasification fluid-dynamics and kinetics as well as the desired synthetic gas composition.
  • Coarse solids, not entrained by the synthetic gas exiting the gasifier (10) remain in the fluid bed and can be removed continuously from the bottom of gasifier (10).
  • the separation of the coarse solids from the bed material i.e. silica sand or alumina
  • particulate matter of low inorganic content material has lower density than sand and tends to stay at the top of the expanded bed. This leads to higher attrition rates which gradually decrease the size of these particles and facilitate the 'washing' of these solids off the fluid bed.
  • high density inorganic material accompanies the feedstock it may be removed from the bottom of the bed through appropriately designed exit ports.
  • Total residence times of the synthetic gas evolved in gasifier (10) is about 10 to 20 seconds, usually half of it in the lower section (18) of the reactor.
  • the ratio of lower section (18) height to top section (20) height is between 2 to 1 and 3 to 1.
  • the gasifier (10) advantageously operates at gas velocities ranging between 5 and 20 times the minimum fluidization velocity (as defined in standard fluidization engineering literature).
  • gasifier (10) requires essentially no external heating or cooling.
  • gasifier (10) will require preheating. This is preferably done with a gas burner to reach a temperature of about 500°C.
  • steady state temperature inside gasifier (10) is set by a combination of the following parameters: reactor geometry; operation pressure; insulation and refractory lining thermal properties; fluid-bed material and size; feedstock nature, physico-chemical properties (composition, humidity, size) and input rate; • oxygen-containing gas composition, velocity and flow rate.
  • One key and surprising feature of the present invention is the discovery that the use of an oxygen-enriched fluidizing gas vastly improves the properties of the resulting synthetic gas. More specifically, it was discovered that using oxygen-enriched air, of about 30 to 50%vol of oxygen, preferably 30 - 40 % vol. oxygen as a fluidizing agent greatly improves the key gasification parameters: cold gas efficiency, lower tar production and higher calorific values of the synthetic gas. Supporting data is found in Figures 4J to 5J 0 and in Tables 1 to 7 herein below
  • the temperature is dependent upon the equivalence ratio used
  • a lines Gasification results from mass and energy balances 2.
  • B lines SG composition
  • the remaining apparatus and process steps relate to gas conditioning of the synthetic gas evolved from gasifier (10). These conditioning steps will now be described in greater detail.
  • the synthetic gas exiting gasifier (10) passes through cyclones (22) and (24) connected in series.
  • the number of cyclones requires will depend on the cleaning strategy.
  • cyclones (22) and (24) will generally retain between 90 and 95% of the total amount of particles entrained by the synthetic gas as fly ash.
  • Modern cyclones are indeed able to cut out of the synthetic gas stream 99% of particles with mean particle size higher than 10 ⁇ m. This means that the remaining particles in the synthetic gas, estimated between 1000 and 2000ppm/v, have a mean particle size of less than 10 ⁇ m.
  • the particles removed through cyclone (22) are split into two streams : C9 and C10.
  • C9 is the solids purge of the gasification process while C10 is recycled back to the gasifier to increase the carbon conversion of the system.
  • the ratio of these two streams (or expressed differently the recycle ratio) is a function of the carbon content of the particles removed by cyclone (22). These particles may eventually be mixed with any solids purged directly from the gasifier.
  • stream C9 may be partially directed to water treatment column (26) for use as an absorbent as described herein below.
  • the carbon in the particles has specific surface area and adsorption features resembling those of activated carbon.
  • the proposed process utilizes this carbon-containing particle (also known as ash) together with activated carbon to treat, through adsorption, the wastewater purge. Upon saturation of the carbon by adsorption, part of the solids are recycled back to the gasifier to increase the carbon conversion while decreasing the amount of solids to be disposed of.
  • the hot gas conditioning module consists of a mobile granular filter and a multitubular fixed-bed tar catalytic reforming reactor.
  • the mobile granular filter and the catalysts are proprietary inventions of the applicants and described in separate patents and/or applications.
  • Particles removed by cyclone (24) are fed to water treatment system (26) as shown by stream C36. These particles are characterized by sufficient surface area to be used as adsorbent. Nevertheless, additional amounts of activated carbon, stream C37, are necessary for compliance with environmental regulations for disposal of treated water effluent, stream C38. As will be apparent from the following description, water treatment system (26) is used to treat the water used to scrub remaining pollutants from the synthesis gas exiting cyclone (24), stream C7.
  • the process includes the use of a three stage wet (water) scrubbing module comprising water spray column (28), venturi scrubber (30) and cyclonic separator (32).
  • the synthetic gas stream C7 enters water spray column (28).
  • Column (28) is illustrated in greater detail in Fig.3.
  • Column (28) is a water-spray column preferably counter-current, cylindrical and with a conical bottom.
  • Column (28) is used as a first stage scrubber for (a) cooling the synthetic gas down to about 90°C, b) removing about half of all remaining particles (targeting those comprised between 2 and 10 ⁇ m) and c) condensing all tarry compounds having boiling points higher than 100°C (excluding some volatile organic compounds (VOCs)).
  • VOCs volatile organic compounds
  • water stream W1 enters from the top of column (28), under pressure, and is dispersed using screw-shaped nozzles (34) producing wide angle sprays (36).
  • Water stream W1 is the scrubbing/quenching solution.
  • the pH of the scrubbing/quenching solution is adjusted in accordance with the carbonaceous feedstock and the pollutants contained in the synthetic gas.
  • Acid gases are removed through alkaline scrubbing.
  • Ammonia is removed through acidification of the scrubbing water.
  • Volatile metals and salts are removed through quenching.
  • Alkaline and acidic scrubbing produces environmentally neutral rejects.
  • Condensed metals are subdivided into two categories : 1) alkali and alkaline earth metals giving non polluting salts and 2) heavy metals under their elemental form or as oxides if present in the gasified feedstock .
  • the latter being essentially insoluble in water, as shown in metal distribution studies, precipitate and can be recovered and removed from the process , streams C19 and C28.
  • contaminated water stream C15 exists column (28) and is routed to heat exchanger (38) for further cooling to about 30°C.
  • stream C1 7 enters decanter/skimmer tank (40) to remove precipitated material.
  • tank (40) the heavier inorganics (and the organics sticking to the inorganics organics) decant and can be removed. Meanwhile the lighter organics float at the water surface and are removed by skimming.
  • the scrubbed synthetic gas, stream C16, still containing micronic particles, water and tar droplets, VOCs and some very volatile metals enters the second stage scrubbing process, namely venturi scrubber (30).
  • Venturi (30) is preferably designed to operate at gas velocity range of 80-100m/s and give a total pressure drop between 0,07 and 0J 5 atm. These conditions give a near micronic dispersion of the water stream entering the throat of the cyclone. This provides an appropriate removal of the remaining particles with an efficiency of near 99% for particles of size as low as OJOm. Ignoring the humidity of the synthetic gas, in this venturi scrubber, the ratio gas/water used is about 1 to 1 w/w. During the contact time (usually of less than 2s) the synthetic gas is cooled to about 35-40°C without significant temperature increase of the water stream.
  • the synthetic gas enters the third and last stage of the scrubbing module, namely cyclonic separator (32).
  • the water leaving the bottom of the gas-liquid cyclonic separator, stream C24 is fed into a second decanting/skimming tank (42) much like tank (40).
  • Tank (42) is of significantly smaller size due to the lesser amounts of water involved in this recycle loop.
  • streams C27 and C28 of Fig. 2 are pumped out to join the analogous streams C18 and C19 of tank (40).
  • the cyclonic separator is a high velocity design unit able to remove droplets of mean size 5 ⁇ m with an efficiency of about 80%. This means that the global separation efficiency is higher than 95%. Nevertheless smaller droplets are still present in the exiting gas stream (Fig. 2, stream C23) and require further removal.
  • Filter (44) is a high efficiency demister for completing droplet removal. Commercially available viscous filters as well as corrugated plate coalescers can be used to accomplish this task. Filter (44) can efficiently remove residual aromatics present in minute quantities (ppm or ppb). Removal is generally performed with a bed of activated carbon which also removes residual organic vapors. Once saturated the spent activated carbon may be recycled back to gasifier (10).
  • dehumidification unit (46) depends on specifications imposed by the synthetic gas end-use devices.
  • the synthetic gas leaving the filter/demister will have an average temperature of about 25°C and will be saturated with water. This means that it will contain between 2 and 3%w/w of water. Usually this level of humidity is not prohibitive for final synthetic gas use in commercial burners/boilers, internal combustion engines and gas turbines.
  • Dehumidification units (46) work by adsorption, for example by passing over a bed of alumina, and can reduce the moisture content of the gas to the desired levels.
  • the runs have taken place in a Process Development Unit (or pilot plant).
  • the gasification reactor is a 4 m high refractory-lined cylinder having 60 cm as outside diameter in the lower section, expanded to 74 cm in the upper section.
  • the inner diameters are 30 cm and 45 cm, respectively.
  • Fluidizing gas enters the reactor through a distribution grid formed by an assembly of 9 tuyeres.
  • the grid of proprietary design, also serves as support for the sand bed.
  • the gasifier is fed from a 1.3 m3 live-bottom hopper by a system consisting of a transfer screw, a chute and an injection screw which can be located in either one of two ports situated at 48 cm or 29 cm above the grid.
  • Air (or oxygen-enriched air) is supplied by a compressor.
  • the main flow (about 80%) enters the reactor through the grid.
  • the rest (20%) is directed to the feeding system to prevent back flow of gases from the reactor to the hopper.
  • the sand (Si0 2 ) bed height (at rest) has been varied between 60 and 45 cm.
  • the average diameter of the sand particles is 0.5 mm (2.6 kg/I as density).
  • Fluidizing velocities are comprised between 0.3 and 0.75 m/s.
  • the biomass solids in the bed are estimated at less than 10% of the total bed solids.
  • the volumetric bed capacity is 1 J 2 tones of biomass • h)-
  • a bypass system permits to either send the entire gas produced to a granular filter and then to the flare, or go directly to the flare.
  • Char and ash are collected in two reservoirs connected to the cyclones as well as in the filter media used.
  • the installation is equipped with more than 40 thermocouples and 20 pressure transducers. Air and producer gas flows are measured by thermal dispersion and orifice flow meters, respectively.
  • the waste feed rate is monitored by a system of 3 load cells.
  • the feed rate is adjusted by the rotation of the screws at the bottom of the hopper.
  • Each isokinetic gas sampling probe has a heated filter, a water/tar/VOCs condensing heat exchanger/collector, a gas impact demister, a drierite gas dryer, a regulated pump, a dry gas flow meter and an appropriate orifice/manometer arrangement insuring isokinetic conditions.
  • Oxygen content of the fluidizing air was 20,9; 30; 40; and 50%vol. for the four runs respectively.
  • Figures 4J-4.5 present the composition of the producer gas as function of the oxygen content of the gasifying agent. We can conclude that as oxygen content.
  • the fluidizing gas increases the inert gases N 2 and Ar are decreasing while all other gases coming from organic matter gasification increase.
  • Figure 4.6 presents the synthetic gas flow rate as function of the oxygen content of the gasifying agent. As expected the gas flow rate is decreasing. It is preferably for the commercialization of the technology to have flow rates as low as possible in order to decrease the cost associated with gas conditioning, piping and handling in general. Moreover, for the same gasification reactor, lower gasifying agent and producer gas flow rates lead to lower linear velocity profiles and higher residence times in the fluid- bed gasification vessel. This in turn leads to lower particle entrainment (carry-over) and allows heavy tar gasification and CO shift reactions to proceed at higher conversion rates.
  • Figure 4.7 presents the gasification temperature as function of the oxygen content of the gasifying agent. As the available heat is transferred to a smaller gas flow rate the temperature increases nearly linearly with the oxygen content.
  • Figure 4.8 presents the HHV of the synthetic gas as function of the gasifying agent. It is also an increasing function. Values between 9 and 12 MJ/Nm 3 are obtained. Such values classify the synthetic gas as a medium calorific value gas and render its use in end-use devices easier and more efficient than low calorific value producer gas.
  • Oxygen content of the fluidizing air was 20,9; 30; and 40%v/v for the three runs respectively.
  • Figures 5J-5.5 present the composition of the producer gas as a function of the oxygen content of the gasifying agent. We can also conclude, as in the wood case, that as oxygen content increases in the fluidizing gas the inert gases N 2 and Ar are decreasing while all other gases coming from organic matter gasification increase.
  • Figure 5.6 gives the producer gas flow rate as a function of the oxygen content of the gasifying agent. The trend and the comments are the same as in the wood case.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Industrial Gases (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

L'invention porte sur des améliorations apportées à une cuve à réaction (10) de gazéification servant à la conversion d'apports carbonés en gaz de synthèse, ladite cuve étant du type à section inférieure munie d'une grille destinée à retenir un lit d'un matériau (16) fluidifiable particulaire conservant la chaleur. Les améliorations consistent d'une manière générale à accroître la section transversale intérieure moyenne de la partie supérieure (20) de la cuve (10) par rapport à celle de la partie inférieure (18) pour faciliter le dégagement et l'extraction du gaz de synthèse du lit de matériau particulaire. L'invention porte également sur une amélioration du procédé de gazéification par utilisation d'un fluidifiant enrichi en O, faisant passer la teneur volumique en O à environ 25-35 %, ou de préférence à 30-40 %; elle porte en outre sur un processus de traitement du gaz de synthèse chaud sortant de la cuve (10), fournissant un gaz de synthèse froid et épuré prêt à l'emploi pour différentes applications, telles que du fioul pour chaudières, pour fours industriels, pour moteurs à combustion interne, etc.
EP00929162A 1999-05-14 2000-05-11 Procede et appareil de gazeification des dechets Ceased EP1198541A1 (fr)

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CA2272038 1999-05-14
CA2272038 1999-05-14
ES9901711 1999-07-29
ES009901711A ES2183662B1 (es) 1999-05-14 1999-07-29 Recipiente de reaccion de gasificacion y procedimiento correspondiente
PCT/CA2000/000552 WO2000069994A1 (fr) 1999-05-14 2000-05-11 Procede et appareil de gazeification des dechets

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US10011792B2 (en) 2010-08-16 2018-07-03 Nikhil Manubhai Patel Sandwich gasification process for high-efficiency conversion of carbonaceous fuels to clean syngas with zero residual carbon discharge
BR112013010886A2 (pt) 2010-11-05 2016-08-02 Thermochem Recovery Int Inc sistema de circulação de sólidos e processo para captura e conversão de sólidos reativos
AU2012315914B2 (en) 2011-09-27 2015-07-09 Thermochem Recovery International, Inc. System and method for syngas clean-up
JP6139845B2 (ja) * 2012-10-09 2017-05-31 三菱日立パワーシステムズ株式会社 炭素系燃料のガス化システム
CN105588127B (zh) * 2015-12-29 2019-04-26 广州市祈雅典环保科技有限公司 采用生物质气化装置的锅炉燃烧系统
ES2940894T3 (es) 2016-02-16 2023-05-12 Thermochem Recovery Int Inc Sistema y método de generación de gas producto de energía integrada de dos etapas
EP4119637A1 (fr) 2016-03-25 2023-01-18 ThermoChem Recovery International, Inc. Système de génération de produit gazeux intégré en énergie à trois étapes
US10364398B2 (en) 2016-08-30 2019-07-30 Thermochem Recovery International, Inc. Method of producing product gas from multiple carbonaceous feedstock streams mixed with a reduced-pressure mixing gas
US9920926B1 (en) 2017-07-10 2018-03-20 Thermochem Recovery International, Inc. Pulse combustion heat exchanger system and method
US10099200B1 (en) 2017-10-24 2018-10-16 Thermochem Recovery International, Inc. Liquid fuel production system having parallel product gas generation
US20200080011A1 (en) * 2018-09-12 2020-03-12 Monte Cristo Gasifiers LLC Enriched Air Gasifier
US11555157B2 (en) 2020-03-10 2023-01-17 Thermochem Recovery International, Inc. System and method for liquid fuel production from carbonaceous materials using recycled conditioned syngas
US11466223B2 (en) 2020-09-04 2022-10-11 Thermochem Recovery International, Inc. Two-stage syngas production with separate char and product gas inputs into the second stage

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