EP0897967A2 - Procédé et appareil pour gazéifier des déchets - Google Patents

Procédé et appareil pour gazéifier des déchets Download PDF

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Publication number
EP0897967A2
EP0897967A2 EP98114660A EP98114660A EP0897967A2 EP 0897967 A2 EP0897967 A2 EP 0897967A2 EP 98114660 A EP98114660 A EP 98114660A EP 98114660 A EP98114660 A EP 98114660A EP 0897967 A2 EP0897967 A2 EP 0897967A2
Authority
EP
European Patent Office
Prior art keywords
slag
gasification
waste materials
gas
slag bath
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.)
Withdrawn
Application number
EP98114660A
Other languages
German (de)
English (en)
Other versions
EP0897967A3 (fr
Inventor
Siegmar Dr. Dipl.-Ing. Marschner
Sven Dipl.-Ing. Halang
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.)
Linde Engineering Dresden GmbH
Original Assignee
Linde KCA Dresden GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Linde KCA Dresden GmbH filed Critical Linde KCA Dresden GmbH
Publication of EP0897967A2 publication Critical patent/EP0897967A2/fr
Publication of EP0897967A3 publication Critical patent/EP0897967A3/fr
Withdrawn legal-status Critical Current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
    • C10J3/57—Gasification using molten salts or metals
    • 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
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00—Details of gasification apparatus
    • C10J2200/15—Details of feeding means
    • C10J2200/152—Nozzles or lances for introducing gas, liquids or suspensions
    • 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
    • C10J2300/0983—Additives
    • C10J2300/0993—Inert particles, e.g. as heat exchange medium in a fluidized or moving bed, heat carriers, sand
    • 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
    • C10J2300/0996—Calcium-containing inorganic materials, e.g. lime
    • 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
    • C10J2300/12—Heating the gasifier
    • C10J2300/1223—Heating the gasifier by burners
    • 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
    • C10J2300/1625—Integration of gasification processes with another plant or parts within the plant with solids treatment
    • C10J2300/1628—Ash post-treatment
    • C10J2300/1634—Ash vitrification
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S266/00—Metallurgical apparatus
    • Y10S266/90—Metal melting furnaces, e.g. cupola type
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S48/00—Gas: heating and illuminating
    • Y10S48/01—Recirculation of gases produced to lower part of fuel bed
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S48/00—Gas: heating and illuminating
    • Y10S48/02—Slagging producer
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S48/00—Gas: heating and illuminating
    • Y10S48/04—Powdered fuel injection

Definitions

  • Waste with organic admixtures may no longer be disposed of in landfills become. For this reason, thermal disposal of the Waste in the form of incineration (waste incineration) or gasification.
  • the oxygen costs for gasification are disadvantageous.
  • the gasification in the fixed-bed pressure carburetor is technically carried out.
  • This carburetor with a shaft reactor is characterized by a relatively low oxygen requirement.
  • it has the disadvantage that an addition of coarse coal is necessary in order to create a supporting structure for the waste materials.
  • a pyrolysis zone is built up in the gasifier shaft, so that the escaping gas contains typical admixtures of a pyrolysis gas (pyrolysis oils, tars), which require complex gas cleaning.
  • the gasification of waste materials in the entrained flow is known as the Noell KRC process.
  • Gas cleaning is comparatively easy here because the gas contains no hydrocarbons other than methane.
  • entrained-flow gasification requires the waste materials to be ground to a grain size of less than 0.5 mm.
  • a pyrolysis drum is therefore arranged in front of the actual entrained-flow gasifier, in which the only roughly comminuted waste is converted into a pyrolysis gas and an easily grindable pyrolysis coke.
  • the pyrolysis gas and the ground pyrolysis coke are then further split in the entrained-flow gasifier.
  • This upstream pyrolysis stage, the subsequent compression of the pyrolysis gas to the pressure of the entrained-flow gasifier and the equipment for cooling, grinding, intermediate storage and metering the pyrolysis coke are very cost-intensive.
  • Thermoselect process also precedes a pyrolysis stage for gasification.
  • the cost of processing the waste materials for gasification is very low because the waste materials are pressed into the horizontal pyrolysis shaft without any special pre-treatment.
  • the gasification process can only be operated at normal pressure because the pyrolysis shaft does not guarantee a secure sealing of the gas space.
  • the invention has for its object a method and an apparatus for gasification of waste materials that are already available at proportionate low throughputs enable economical operation.
  • this object is achieved in that the gasification in one stage in a gasifier with a liquid, rotating slag bath.
  • the process according to the invention is characterized by a one-step gasification process through which the feed into usable fission gas and an unrestricted depositable slag granulate is transferred. A complex pretreatment of the Commodities are not required.
  • a magnetic separator can be arranged to remove iron components.
  • the liquid slag bath in the gasification zone fulfills several functions. Mineral components and heavy metals in the feed are melted and adsorbed. At the same time, the slag bath serves as a heat buffer and reaction mediator and thus ensures an intensive heat and material exchange. An important function is the safe ignition and, if necessary, re-ignition of the burners.
  • excess slag together with the fission gas generated during gasification through a slag drain discharged, which protrudes beyond the slag bath and into which the slag passes a side drain opens.
  • the slag bath is preferably obtained by introducing the gasification agent tangentially and / or at least some of the waste materials are set in rotating motion.
  • at least some of the waste is in at least one solid fuel burner lumpy, with recirculated fission gas as the carrier gas to the carburetor.
  • waste materials with a diameter of up to 5 mm are expediently inserted into the carburetor above the slag bath and there will be a jet of this Waste is formed and directed to the surface of the slag bath while waste with a diameter of over 5 mm to 40 mm directly into the slag bath be entered.
  • At least one gas burner is used, which is with oxygen and during start-up with natural gas and during operation with recycle cracked gas is fed.
  • oxygen is advantageously generated by oxygen lances fed directly into the slag bath.
  • the slag bath Sand, lime and / or other substances to influence the slag melting behavior and added to the slag viscosity are added to the slag viscosity.
  • the discharged slag is expediently dropped into a water bath and transferred there into a glass-like, non-elutable state.
  • the slag bath is preferably replaced by a synthetic slag formed.
  • a device for carrying out the method has a gasification chamber for Gasification of waste materials.
  • the task is solved in that the gasification chamber Has devices for forming a rotating slag bath.
  • the gasification chamber preferably has an essentially cylindrical design with a concentrically arranged slag run through the floor.
  • the inside of the reactor jacket is expediently protected by a cooling screen, which consists of gas-tight welded fin coils with cooling water are flowed through in forced circulation.
  • the tubes are preferred on the product side donated and covered with a ceramic ramming paste.
  • One freezes on this layer Slag layer firmly and forms a thermally insulating "slag fur", the Cooling screen from the high operating temperatures as well as the direct attack by the protects liquid slag.
  • the thickness of the slag protection layer depends on the operating conditions (Temperatures, slag composition).
  • the carburetor consists of a gasification chamber 1 which is surrounded by a reactor jacket 5 and a reactor cover 7 is formed.
  • the reactor jacket 5 is through a cooling screen protected, which consists of gas-tight welded fin tube coils, through which cooling water flows in forced circulation.
  • the gas discharge at the lower part of the carburetor leads to an internal circulation of the cracked gas.
  • the swirling of the gas makes it more even the residence time and thereby achieve a more perfect balance.
  • Large quantities of slag droplets entrained in the gas hit the Carburetor wall down and flow into the slag bath 2.
  • Two types of burners are provided for introducing feed material and gasification agent into the gasification chamber 1, which are oriented obliquely downwards, tangentially to the surface of the slag bath.
  • the slag is set into a rotational movement by the transmitted impulse, as a result of which the slag bath 2 is thoroughly mixed.
  • natural gas is burned in the start-up phase and fission gas returned during operation is burned with oxygen (if necessary with the addition of steam).
  • the fine grain fraction (d ⁇ 5 mm) of the feed is burned with oxygen, with recycled cracked gas acting as the carrier gas. Small particles are already converted into entrained-flow gasification in the gas space above the slag bath 2.
  • the slag bath is expediently first formed by a synthetic slag (CaO + SiO 2 + Al 2 O 3 ).
  • a synthetic slag CaO + SiO 2 + Al 2 O 3
  • lime and sand in a ratio of approx. 0.8 to approx. 1.2 as well as a smaller proportion of Al 2 O 3 (approx. 10% by mass) are mixed and filled into the reactor.
  • the mixture is melted by the combustion of natural gas fed into the burners and brought to operating temperature.
  • the slag bath is constantly renewed by mineral components brought in with the waste.
  • the properties of the slag are determined by its composition.
  • the main components of the slag are CaO, SiO 2 and Al 2 O 3 .
  • Other slag components are metals and their oxides that are deposited with the waste. Together, the slag components form eutectics, whose melting points are significantly below the melting points of the individual components (see Pawlek; Metall prisenischen, Walter de Gruyter (1983)).
  • An important parameter for the operation of the slag bath gasifier is the viscosity of the slag.
  • the silica is formed by SiO 4 tetrahedra, in the center of which there is an Si atom which is surrounded by four O atoms. These tetrahedra form space lattices through common oxygen atoms, which remain in the liquid state as coherent complexes. The limited mobility of these large structures results in a high viscosity.
  • the Al 3+ cations are able to replace Si 4+ and in turn form AlO 4 tetrahedra, so that Al 2 O 3 has an effect similar to SiO 2 on the viscosity of a slag.
  • SiO 2 and Al 2 O 3 are so-called network formers (see Kozakevitch, Urban; viscosity and structure of liquid slags, Metz 1954). So-called network converters, such as CaO and MgO, are able to break the tetrahedron bonds of the oxygen atoms and thus lead to a reduction in the slag viscosity.
  • substances such as sand and / or lime can be added to the slag, so that the melting and viscosity behavior of the slag can be influenced within certain limits.
  • the slag run 6 is analogous to the crucible construction made of pressurized water-cooled, welded fin tubes manufactured. These are pinned on both sides and with a ceramic ramming compound busy. A slag layer freezes on the ramming mass, which closes the material from the high operating temperatures and a direct attack by the chemical protects aggressive slag.
  • the combined removal of slag and hot cracked gas keeps the slag flowable due to the high temperatures of the gas.
  • the further discharge takes place via the post-reaction room.
  • This can be designed, for example, as a port furnace or, as shown in FIG. 1, as a melting cyclone 3.
  • the slag is then refined in this way, so that possible foaming does not cause discharge problems. If the temperatures in the melting cyclone 3 are not sufficient for free flow of the slag, a burner 14 operated with recirculated fission gas and oxygen can be arranged.
  • a water bath 4 for slag granulation is flanged onto the post-reaction space.
  • the slag granulate cannot be eluted and can be deposited without restrictions.
  • the gasifier according to the invention is advantageous for a wide range of waste materials applicable.
  • the working temperature of the slag bath gasifier is set at 1600 ° C.
  • the waste gasification is carried out as an autothermal process, with the splitting of the waste materials and the amount of heat required to melt the mineral components generated by partial oxidation of the combustible components with oxygen becomes.
  • Table 1 shows the composition of standard waste according to the NRW State Environment Agency.
  • the pretreatment of the waste is limited to a rough crushing of the input material to a grain size below 40 mm. Iron can also be separated by magnetic separation.
  • the grain fraction 0 ... 5 mm is introduced into the gasification chamber via the solid fuel burner, the grain fraction 5 ... 40 mm using a screw conveyor via a nozzle.
  • Composition of a standard waste according to the NRW State Environment Agency Garbage components Dimensions-% Ash component kg / t waste C.
  • 357 M 3 iN oxygen (96 vol% O 2 ) is required for autothermal gasification of 1.0 t waste.
  • the cracked gas obtained has a high proportion of steam due to the moisture content of the feed.
  • the cracked gas has a high CO and H 2 content, so that there are sufficient energy reserves to cover any higher heat losses.
  • the ash in the waste has a high content of SiO 2 and Al 2 O 3 , which leads to a high viscosity of the slag. If this causes operational problems, adding lime through a nozzle can reduce the slag viscosity.
  • An advantageous application of the slag bath gasifier according to the invention is the gasification of old PVC, since in addition to the waste disposal, the HCl contained in the PVC can be recovered and used as HCl gas in the oxychlorination in order to ultimately produce PVC again.
  • Table 2 shows the composition of a PVC-containing waste mixture. Waste mixture with a high PVC content component Dimensions-% Pure PVC 61 Plasticizers 20th chalk 8.6 combustible waste 6.4 non-combustible waste 4th
  • an additional sifter (zigzag sifter) should be provided for the pre-treatment.
  • the heavy non-ferrous metals are separated, which are mainly converted to metal chlorides in the slag bath and would thereby reduce the HCl yield.
  • the silicates and light metals Al, Mg are desirable slag formers.
  • the possibility of using relatively coarse-grained feed material is particularly economical with PVC, since this means that comminution in a granulator is sufficient and complex and very costly low-temperature grinding is not necessary.
  • Table 3 shows that there is an oxygen requirement of 420 m 3 iN / t old PVC for autothermal gasification of the old PVC.
  • the HCl-free cracked gas is rich in CO and H 2 and can be used to generate electrical energy and process steam.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Processing Of Solid Wastes (AREA)
  • Gasification And Melting Of Waste (AREA)
  • Incineration Of Waste (AREA)
EP98114660A 1997-08-13 1998-08-04 Procédé et appareil pour gazéifier des déchets Withdrawn EP0897967A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19735153 1997-08-13
DE19735153A DE19735153C2 (de) 1997-08-13 1997-08-13 Verfahren und Vorrichtung zur Vergasung von Abfallstoffen

Publications (2)

Publication Number Publication Date
EP0897967A2 true EP0897967A2 (fr) 1999-02-24
EP0897967A3 EP0897967A3 (fr) 1999-03-24

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EP98114660A Withdrawn EP0897967A3 (fr) 1997-08-13 1998-08-04 Procédé et appareil pour gazéifier des déchets

Country Status (4)

Country Link
US (1) US6311629B1 (fr)
EP (1) EP0897967A3 (fr)
JP (1) JPH11128883A (fr)
DE (1) DE19735153C2 (fr)

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DE102012008457B4 (de) * 2012-04-24 2016-11-03 Adam Handerek Reaktor zum Vergasen und/oder Reinigen, insbesondere zum Depolymerisieren von Kunststoffmaterial, und zugehöriges Verfahren
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EP0897967A3 (fr) 1999-03-24
DE19735153C2 (de) 2003-10-16
DE19735153A1 (de) 1999-02-18
JPH11128883A (ja) 1999-05-18
US6311629B1 (en) 2001-11-06

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