WO2018044252A1 - Procédé de conversion en gaz de synthèse de déchets urbains solides et autres contenant du carbone et équipement basé sur ce procédé - Google Patents

Procédé de conversion en gaz de synthèse de déchets urbains solides et autres contenant du carbone et équipement basé sur ce procédé Download PDF

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Publication number
WO2018044252A1
WO2018044252A1 PCT/UA2017/000086 UA2017000086W WO2018044252A1 WO 2018044252 A1 WO2018044252 A1 WO 2018044252A1 UA 2017000086 W UA2017000086 W UA 2017000086W WO 2018044252 A1 WO2018044252 A1 WO 2018044252A1
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Prior art keywords
gasification
feedstock
zone
pyrolysis
residue
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PCT/UA2017/000086
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English (en)
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Sergii STRYZHAK
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Stryzhak Sergii
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Publication of WO2018044252A1 publication Critical patent/WO2018044252A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • B09B3/45—Steam treatment, e.g. supercritical water gasification or oxidation
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C11/00—Other nitrogenous fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F9/00—Fertilisers from household or town refuse
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F9/00—Fertilisers from household or town refuse
    • C05F9/02—Apparatus for the manufacture
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
    • C10B47/28—Other processes
    • C10B47/30—Other processes in rotary ovens or retorts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • 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
    • C10J3/002—Horizontal gasifiers, e.g. belt-type gasifiers
    • 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
    • C10J3/005—Rotary drum or kiln gasifiers
    • 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
    • C10J3/007—Screw type gasifiers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • C10J3/34—Grates; Mechanical ash-removing devices
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
    • F02C3/00—Gas-turbine plants characterised by the use of combustion products as the working fluid
    • F02C3/20—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products
    • F02C3/26—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products the fuel or oxidant being solid or pulverulent, e.g. in slurry or suspension
    • F02C3/28—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products the fuel or oxidant being solid or pulverulent, e.g. in slurry or suspension using a separate gas producer for gasifying the fuel before combustion
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16T—STEAM TRAPS OR LIKE APPARATUS FOR DRAINING-OFF LIQUIDS FROM ENCLOSURES PREDOMINANTLY CONTAINING GASES OR VAPOURS
    • F16T1/00—Steam traps or like apparatus for draining-off liquids from enclosures predominantly containing gases or vapours, e.g. gas lines, steam lines, containers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
    • F23G5/027—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
    • F23G5/027—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage
    • F23G5/0273—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage using indirect heating
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/20—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having rotating or oscillating drums
    • 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
    • C10J2200/158—Screws
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2220/00—Application
    • F05D2220/70—Application in combination with
    • F05D2220/75—Application in combination with equipment using fuel having a low calorific value, e.g. low BTU fuel, waste end, syngas, biomass fuel or flare gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2201/00—Pretreatment
    • F23G2201/10—Drying by heat
    • F23G2201/101—Drying by heat using indirect heat transfer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2201/00—Pretreatment
    • F23G2201/30—Pyrolysing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2201/00—Pretreatment
    • F23G2201/40—Gasification
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2203/00—Furnace arrangements
    • F23G2203/20—Rotary drum furnace
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2900/00—Special features of, or arrangements for incinerators
    • F23G2900/50201—Waste pyrolysis, gasification or cracking by indirect heat transfer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2900/00—Special features of, or arrangements for incinerators
    • F23G2900/52001—Rotary drums with co-current flows of waste and gas
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
    • 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
    • Y02E20/12—Heat utilisation in combustion or incineration of waste
    • 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
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft

Definitions

  • This invention consists of the method of thermochemical conversion into the synthesis gas of municipal solid waste (MSW) and other carbon-containing waste with large tar content into synthesis gas through the two-stage process of pyrolysis and subsequent slow fluidized- bed updraft gasification of the carbon-containing residue of the process of pyrolysis.
  • “Slow fluidized bed” is a layer of heated ground mass of carbon-containing residue of raw waste resulting from the process of low-temperature pyrolysis and fed into internal container of a gasification reactor. On the surface of this layer occurs movement of particles under the impact of gases generated in the in the zone of burning and gasification of the gasification reactor. This movement is similar to the process of slow boiling in a liquid, with the velocity of movement of generated synthesis gas over the surface of slow fluidized bed does not exceed 0.8 meters per second.
  • This invention is also a basis for a device realizing the method of thermochemical conversion into the synthesis gas of municipal solid waste (MSW) and other carbon- containing waste with large tar content into synthesis gas through the two-stage process of pyrolysis and subsequent slow fluidized-bed updraft gasification of the carbon-containing residue of the process of pyrolysis.
  • MSW municipal solid waste
  • MSW and other types of hydrocarbon materials with large amounts of tar belong to an entirely different category of fuels with high amounts of hydrocarbons in gas phase (60- 70%) and small amounts of residual carbon (30-40%), they are not suitable for traditional methods of their conversion into synthesis gas. That is to say that all current technologies attempt to convert these types of materials into synthesis gas applying those old traditional principles of gasification based on the theories of gasification oriented for the conversion of materials that have entirely different thermochemical characteristics.
  • Theory 4 a new theory (referred to further in the text as Theory 4) of gasification was developed for feedstock with high content of hydrocarbons in gaseous phase and low content of residual carbon.
  • This theory is the foundation of a new method of conversion of MSW and other types of hydrocarbon feedstock with high content of tars into synthesis gas.
  • the process consists of two-stage pyrolysis with subsequent gasification in the air-and-gas flow of slow fluidized-bed carbon residue and is called SFGP4 (Slow Fluidized-Bed Gasification Process 4). Gasification plant was developed based on this method.
  • thermochemical conversion into the synthesis gas of municipal solid waste (MSW) and other carbon-containing waste with large tar content into synthesis gas described in this application is materialized through the two-stage process of pyrolysis and subsequent slow fluidized-bed gasification of the carbon-containing residue in the air-and-gas flow using updraft process of gasification of slowly boiling layer of feedstock has enabled to develop additional technological and environmental advantages of gasification reactors using the principle of updraft gasification:
  • thermochemical conversion of MSW of different composition, fractions and highly humid, conversion of various materials that was not possible before;
  • Oxygen and steam mixture can be used instead of air;
  • Recovered synthesis gas does not contain any compounds of aromatic hydrocarbons, volatile organic compounds (VOCs) or tars, because they are destroyed in the course of thermochemical process. This simplifies significantly the system of gas cleaning and guarantees that they are not emitted in the environment;
  • Non-hazardous silica slags are formed in the process of gasification of nonorganic fractions of MSW. Heavy metals from the MSW are encapsulated within those slags, which are insoluble in water and can be used for industrial purposes.
  • Fig. 1 shows the scheme of calculation characteristics referred to in the part "Relative Calculation of the Amount of Pyrocarbon Formed in the Process of Thermal Conversion of Hydrocarbons and Tars Making Part of Pyrolysis Gases".
  • Fig. 2 shows schematic diagram of gas generator.
  • Fig. 3 shows the sketch of gas generator unit.
  • Fig. 4 demonstrates the sketch of pyrolysis part.
  • Fig. 5 shows the sketch of gasification part.
  • Fig. 6 shows configuration of gasification zone of carbon-containing residue of feedstock.
  • Fig. 7 demonstrates the scheme of computations describing the principle of operation of gas generator based on the method of thermochemical conversion into synthesis gas of MSW and other carbon-rich feedstock with high content of tars executed through two-stage process of pyrolysis and subsequent gasification in the air and gas flow of slow fluidized bed of carbon residue.
  • Fig. 8 in the form of Table 1.1 shows morphological content of solid waste used in this computation.
  • Fig. 9 in the form of Table 1.2 shows element composition of MSW.
  • Fig. 10 in Table 1.3 shows the products of the drying of feedstock.
  • Fig. 11 shows in Table 2.1 the feedstock residue after drying.
  • Fig. 12 demonstrates Table 2.2 with element composition of feedstock residue after the feedstock moisture recovery process.
  • Fig. 13 illustrates in Table 2.3 what gases are recovered in the process of moisture recovery.
  • Fig. 14 compares in Table 2.4 design data and literature data of changed elementary composition of fuel before and after the process of the recovery of moisture.
  • Fig. 15 shows in Table 3.1 of the feedstock residue entering the zone of low temperature pyrolysis.
  • Fig. 16 lists in Table 3.2 the products of low temperature pyrolysis.
  • Fig. 17 demonstrates in Table 3.3 the distribution of solid feedstock residue after the zone of low temperature pyrolysis.
  • Fig. 18 shows in Table 3.4 the part of residue of solid feedstock conveyed into the zone of high temperature pyrolysis.
  • Fig. 19 shows in Table 3.5 the part of solid feedstock conveyed into filtering zone.
  • Fig. 20 in Table 3.6 refers to the aggregate composition of gases of drying process, moisture recovering and low temperature pyrolysis conveyed into the channel of pyrolysis gases of gasification reactor.
  • Fig. 21 with Table 3.7 refers to the design and literature data of the products of low temperature pyrolysis.
  • Fig. 22 compares in Table 3.8 design and literature data on gases of low temperature pyrolysis.
  • Fig. 23 compares in Table 3.9 design and literature data on tar of low temperature pyrolysis (primary tar oil).
  • Fig. 24 in Table 3.10 gives the composition of the tar of semi-coking of the coal.
  • Fig. 25 in Table 4.1 gives aggregate composition of gases conveyed into the channel of pyrolysis gases (gases of drying, feedstock moisture and liquid release and of low temperature pyrolysis).
  • Fig. 26 in Table 4.2 lists the tars entered into the channel of pyrolysis gases.
  • Fig. 27 in Table 4.3 describes thermal conversion of primary tar oil (tar) in the channel of pyrolysis gases.
  • Fig. 28 in Table 4.4 demonstrates the gases resulting from break down of primary tar oil.
  • Fig. 29 in Table 4.5 gives the aggregate composition of tars formed in the channel of pyrolysis gases.
  • Fig. 30 in Table 4.6 quotes the data of conversion of hydrocarbons, contained in the gas mixture of the channel of pyrolysis gases.
  • Fig. 31 in Table 4.7 shows the products of conversion of hydrocarbons contained in the producer gas of low temperature pyrolysis.
  • Fig. 32 in Table 4.8 illustrates the gases after conversion in the channel of pyrolysis gases.
  • Fig. 33 in Table 4.9 shows gas mixture and pyrocarbon formed in the channel of pyrolysis gases.
  • Fig. 34 in Table 4.10 shows the tars in the channel of pyrolysis gases.
  • Fig. 35 shows in Table 5.1 solid feedstock residue conveyed into the zone of additional gasification from the zone of burning and gasification.
  • Fig. 36 in Table 5.2 shows gas mix and pyrocarbon conveyed from the channel of pyrolysis gases into the zone of additional gasification.
  • Fig. 37 demonstrates in Table 5.3 the tars conveyed from the channel of pyrolysis gases into the zone of additional gasification.
  • Fig. 38 in Table 5.4 quotes the data on thermal conversion of tars at their contact with hot burning slag residue.
  • Fig. 39 in Table 5.5 illustrates the gases resulting from the breakdown of tars.
  • Fig. 40 in Table 5.6 shows combined composition of tars in the zone of additional gasification.
  • Fig. 41 in Table 5.7 gives the data on carbon that makes part of the reactions of gasification.
  • Fig. 43 in Table 5.9 describes gas mix resulting from gasification of carbon.
  • Fig. 44 in Table 5.10 contains the data on gas mix formed in the zone of additional gasification.
  • Fig. 45 in Table 6.1 lists the products entering the zone of burning and gasification from the zone of high temperature pyrolysis.
  • Fig. 46 in Table 6.2 illustrates thermal conversion of solid carbon-rich residue at its entering the zone of burning and gasification.
  • Fig. 47 gives in Table 6.3 the data on the combustion of a part of solid carbon-rich residue.
  • Fig. 48 in Table 6.4 shows the composition of carbon-rich residue after its partial combustion.
  • Fig. 49 shows in Table 6.5 the composition of carbon residue after its partial combustion.
  • Fig. 50 describes in Table 6.6 the gas mix formed as a result of conversion of the products conveyed from the zone of high-temperature pyrolysis.
  • Fig. 51 demonstrates in Table 6.7 gas mix entering from the zone of additional gasification into the combustion and gasification zone.
  • Fig. 52 in Table 6.8 lists the tars entering from additional gasification zone into the zone of combustion and gasification.
  • Fig. 53 in Table 6.9 has the data on combustion of the tars in the zone of combustion and gasification.
  • Fig. 54 in Table 6.10 describes with the data the tar not burnt in combustion and gasification zone.
  • Fig. 55 in Table 6.11 gives the data on combustion of gases conveyed from the zone of additional gasification.
  • Fig. 56 in Table 6.12 shows the data on gases that have not burnt in the zone of combustion and gasification.
  • Fig. 57 in Table 6.13 shows gas mix formed after combustion of the products that entered from the zone of additional gasification.
  • Fig. 58 in Table 6.14 describes gas mixture formed in the zone of combustion and gasification.
  • Fig. 59 in Table 6.15 displays the data on the tar exiting zone of combustion and gasification.
  • Fig. 60 in Table 6.16 shows the total amount of air consumed.
  • Fig, 61 in Table 6.17 shows carbon residue in zone of combustion and gasification.
  • Fig. 62 in Table 6.18 shows composition of the gases of high temperature pyrolysis and gases of combustion and gasification.
  • Fig. 63 shows in Table 6.19 the mixture of the tars of high temperature pyrolysis and tars conveyed from the zone of combustion and gasification.
  • Fig. 64 demonstrates in Table 6.20 carbon residue of feedstock after high temperature pyrolysis.
  • Fig. 65 gives in Table 6.21 the data on partial decomposition of tars rising from high temperature zones.
  • Fig. 66 produces in Table 6.22 the data on the continuation of the process of high temperature pyrolysis in the zone of filtration.
  • Fig. 67 shows in Table 6.23 the data on thermal breakdown of the tar going down from the zone of filtration into the zone of high temperature pyrolysis.
  • Fig. 68 shows in Table 6.24 carbon-rich residue that participates in the reactions of gasification.
  • Fig. 69 produces in Table 6.25 the data on thermal conversion of solid carbonaceous residue.
  • Fig. 70 demonstrates in Table 6.26 the mixture of gases entering into reaction of gasification.
  • Fig. 71 displays in Table 6.27 the reactions of C0 2 .
  • Fig. 72 displays in Table 6.28 reactions of C.
  • Fig. 74 shows in Table 6.30 reactions of CH 4 .
  • Fig. 75 lists in Table 6.31 reactions of C 2 H 4 .
  • Fig. 76 describes in Table 6.32 the gas mix after gasification.
  • Fig. 77 illustrates in Table 7.1 composition of solid carbonaceous residue (semi -coke) entering the zone of high temperature pyrolysis.
  • Fig. 78 shows in Table 7.2 products of high temperature pyrolysis.
  • Fig. 79 describes in Table 7.3 relative distribution of solid residue of the feedstock in high temperature zone.
  • Fig. 80 shows in Table 7.4 the part of solid feedstock residue that goes into the zone of combustion and gasification.
  • Fig. 81 shows in Table 7.5 the part of the solid carbonaceous residue that remained in the zone of high temperature pyrolysis and is consumed in reaction of gasification.
  • Fig. 82 compares in Table 7.6 effective and literature data on the products of high temperature pyrolysis.
  • Fig. 83 makes comparison in Table 7.7 effective and literature data on the gases of high temperature pyrolysis.
  • Fig. 84 shows in Table 7.8 comparison between the effective and literature data on the tars of high temperature pyrolysis.
  • Fig. 85 compares in Table 7.9 effective and literature data on solid feedstock residue of high temperature pyrolysis (coke).
  • Fig. 86 refers in Table 8.1 the data on gas mix of the products of gasification and high temperature pyrolysis.
  • Fig. 87 contains in Table 8.2 the data on reaction of methanization.
  • Fig. 88 contains Table 9.1 with the data on tars discharged from the gasification reactor.
  • Fig. 89 produces in Table 9.1 the data on the gas mix exiting the gasification reactor.
  • Fig. 90 refers in Table 10.1 the data on slag residue discharged from gasification reactor.
  • Fig. 91 represents basic technological scheme of the process of synthesis of urea.
  • Fig. 92 presents structural scheme of technological complex.
  • carbon dioxide is a secondary product of the following oxidation of carbon oxide through reaction:
  • carbon oxide is a secondary product of the recovery of carbon dioxide by heated up carbon of the fuel as a result of reaction:
  • MSW and other carbonaceous types of waste with high tar content as a feedstock that are the types of fuel thermochemical characteristics of which correspond to high content of hydrocarbons (60-70%) in gas phase and low content of residual carbon in gasification reactors of classic design result in even higher content of C0 2 the gases thus generated. This is caused directly by the amount of carbon insufficient for the reactions of gasification.
  • thermochemical conversion of municipal solid waste (MSW) and other carbon-containing waste with large content of tars into synthesis gas through the two-stage process of pyrolysis and subsequent slow fluidized-bed updraft gasification of the carbon-containing residue in the air-and-gas flow made it possible to alter the classic scheme of gasification.
  • a new device has been created that constitutes this invention representing a new design of a gasifier, which was given a tentative name SYN1- GG (SYNTENA 1 Gas Generator). The latter makes it possible to reach the content of carbon sufficient for full scale gasification of the abovementioned types of feedstock.
  • Partial combustion of pyrolysis gases occurs because the amount of oxygen conveyed into the fuel input unit of gasification reactor is insufficient for complete burning of these gases, which is the main condition for entire process of gasification.
  • homogenous reactions of the combustion of gaseous products of pyrolysis first occur in the zone of combustion and gasification.
  • Heterogeneous reaction between oxygen and solid carbon can only be secondary.
  • the carbon resulting from a preliminary pyrolysis of the feedstock, and pyro-carbon resulting from incomplete combustion of pyrolysis gases with high calorie values, are subjected to intense heating-up during the combustion of pyrolysis gases. This causes the intensification of the "secondary" reactions of gasification (Formula 4).
  • Reactions of water gas (8) are also enhanced by high temperatures, resulting in the increase of H 2 , CO content in the gas, and respective decrease of N 2 . Because of these processes synthesis gas is formed, which in fact consists of simple combustible gases CO and H 2 , with small content of CH 4 and C x H y . Content of C0 2 remains minimal.
  • Theory 4 can be construed as a based on Theory
  • Formula 4 Three subsequent reactions (Formula 4, Formula 8 and Formula 9) are the reactions of conversion of smoke gases into conventional flammable gases CO and H 2 occurring inside a layer of red-hot carbonaceous residue.
  • Formula 8 and Formula 9 are the reactions of hydro- gasification of carbon, and Formula 4 is the reaction of the reduction of C0 2 into CO.
  • the equation of Formula 13 describes schematically the process of pyrolysis of hydrocarbon feedstock - C x H y O z .
  • the products of this pyrolysis are C0 2 , H 2 0, CO, H 2 , hydrocarbons C a H Directory and pyro-carbon C.
  • Hydrogen, carbon monoxide and hydrocarbons partially burn in the process of gasification generating carbon dioxide and water vapor. Their residues become subjects of partial thermal conversion generating hydrogen and residual pyro-carbon, as schematically described by the equation of Formula 14.
  • pyro-carbon resulting from incomplete combustion and thermal conversion of pyrolysis gases makes up for the overall deficiency of carbon in carbonaceous residue of the feedstock and is the first to enter the reactions of gasification and hydro-gasification (Formula 4, Formula 8 and Formula 9).
  • thermochemical conversion into synthesis gas of MSW and other carbon-based feedstock with high content of tars applied through the two-stage process of pyrolysis and subsequent slow fluidized-bed gasification of carbon-rich residue in the air-gas flow.
  • thermochemical conversion into synthesis gas of MSW and other carbon- based feedstock with high content of tars applied through the two-stage process of pyrolysis and subsequent slow fluidized-bed gasification of carbon-rich residue in the air-gas flow is used in the gas generator SYNl-GG, in which the entire process of generation of synthesis gas is relatively divided into the ten separate temperature zones.
  • the first three zones are the zones of low-temperature processing of the feedstock. They are located in the pyrolysis part of gas generator SY l-GG that is a specially designed rotary kiln (is referred to as SY l-RK in the description annexed to this application) slightly inclined towards the horizon. In other embodiment, it can have horizontal location. It is heated by the heat of synthesis gases resulting from the process of gasification of the feedstock.
  • the other seven zones are the zones of high temperature processing of feedstock. They are located in gasification section of gas generator SYNl-GG, which is an updraft gasification reactor (can be referred to in this description as SYNl-SFG) of special design.
  • the gasification reactor SYNl-SFG is connected to the rotary kiln SYNl-RK by a body connector or by tubes. Design of the SYNl-GG is presented in Fig. 2.
  • Zone 1 Zone of feedstock drying
  • Main feature of this zone is that during the pre-treatment of feedstock the largest part of its moisture and of the water tied in colloids are evaporated. Adsorbed gases are also released and decomposition of feedstock under these low temperatures is manifested in a weak manner, only through hardly noticeable formation of gases.
  • Zone 2 Zone of moisture removal from the feedstock
  • Zone 3 Zone of low-temperature pyrolysis
  • This zone is characterized by increased formation of gases. Gases formed here have larger content of C0 2 and of saturated and unsaturated hydrocarbons. Under the temperature of 350°C non-condensing gases start to be released. Condensing products start to be released at the same time, such as vapors of oil tar. Their amount increase and reaches maximum at the temperatures of 500° - 550°C. Large amount of the so-called pyroligneous water is also released from the feedstock, and the feedstock residue enriches significantly with carbon.
  • Zone 4 Zone of the channel of pyrolysis gases of gasification reactor
  • This zone needed to be organized because one part of burning-hot carbon from the zone of combustion and gasification, not having gasified, falls down into the slag zone from where it is removed from the gasification reactor together with the slag.
  • the main processes in this zone are partial combustion in the oxygen of air flown inside, and thermal decomposition of gaseous products of pyrolysis. There is also intense interaction between burning-hot carbonaceous residue of feedstock with oxidizing gases resulting from combustion of some part of pyrolysis gases conveyed from the zones of low- temperature processing of feedstock.
  • Zone 7 Zone of high-temperature pyrolysis of feedstock
  • Amount of carbon in feedstock residue reaches its maximal value as a result of these processes.
  • Zone 8 Zone of gas filtering
  • Hot synthesis gas is separated from slag-carbon dust.
  • the slag conveyed from the zone of additional gasification is cooled with the air flown into the gasification reactor and subsequent mechanical crushing and removal from the gasification reactor.
  • the main device is gas generator SYN1-GG, representing a device executing pyrolysis and gasification, thermochemically converting solid waste and other carbon containing feedstock with high content of tars into synthesis gas.
  • gas generator SYN1-GG representing a device executing pyrolysis and gasification, thermochemically converting solid waste and other carbon containing feedstock with high content of tars into synthesis gas.
  • Fig. 3 Detailed design of the device is presented in Fig. 3.
  • Gas generator SYN1-GG consists of two parts:
  • A. Pyrolysis unit which is a inclined rotary kiln SYN1-RK for sloping heating. It has original design shown in Fig. 4, consisting of the following devices:
  • Input unit for feeding the feedstock into the rotary kiln.
  • Gasification unit which is gasification reactor SYN1-SFG of updraft gasification of the slow fluidized-bed of feedstock, shown in Fig. 5 and consisting of the following devices:
  • Input unit conveying the feedstock into the inclined rotary kiln
  • Device that feeds the inclined rotary kiln (1) consists of the bunker 1 that has rectangular cross-section with vertical back wall and sloping side and front walls.
  • Vertical piston mechanism 2 of the loading device with hydraulic cylinder PI is fastened to the vertical back wall of the bunker 1.
  • Vertical loading channel 4 divided into the upper and lower pipes of the vertical loading channel 4 that has rectangular or round cross-section, is weld onto the lower part of bunker 1. Between these two pipes there is slide gate 3 that has hydraulic cylinder P2. Lower part of the lower pipe of vertical loading channel 4 is weld on horizontal loading channel 5 that has round or rectangular cross-section and a mounting flange at its front end.
  • horizontal piston mechanism 6 equipped with hydraulic cylinder P3 and attached to horizontal loading channel 5 with the bolt joining of coupling flange of horizontal piston mechanism 6 and horizontal loading channel 5. Operation of the loading device of the inclined rotary kiln for indirect heating
  • Pre-treated feedstock having passed through the system of feedstock pre-treatment (Fig. 3) of the technological complex SYN1-TC is conveyed by a conveyor belt to bunker 1 of the feedstock loading device (1), equipped with the vertical piston mechanism 2.
  • bunker 1 under the impact of movement of the piston of vertical piston mechanism 2, moved by hydraulic cylinder PI, the feedstock is compacted and conveyed through the vertical loading channel 4 into horizontal loading channel 5.
  • horizontal loading channel 5 under the impact of horizontal movement of the piston of horizontal piston mechanism 6, moved by hydraulic cylinder P3, the feedstock is conveyed into the tilted inclined rotary kiln of indirect heating (2).
  • Inclined rotary kiln of indirect heating (2) is presented in Fig. 4. It is used for drying, moisture recovery and low temperature pyrolysis of feedstock.
  • Inclined rotary kiln of indirect heating (2) is tilted at 2-22 degrees vis-a-vis the horizon and consists of two bodies:
  • the inner body of the inclined rotary kiln is composed of the two elements:
  • Design of the inner body of the inclined rotary kiln 7 includes round rib of the inner body 9.
  • Spiral shape outer guide vanes 11 are welded to the outer surface of the rib. They are slightly inclined towards the rib's axis.
  • Front oil seal hub 12 is welded to the front end of the rib of the inner body 9.
  • In the headstock there is a channel for the installation of the feedstock loading unit, inside which there is an oil seal.
  • In the front part of the front oil seal hub of inner body 12 there is a site for the supporting front wheel 15 bearing in its lower part on two supporting blocks 16.
  • Ring gear 20 is welded to the central part of the front oil seal hub of inner body 12. Ring gear 20 meshes with the pinion gear 21 moved by electric or hydraulic motor of the rotary kiln P4.
  • Central hub 14 is welded to the central part of the rib of the inner body 9.
  • Back hub of the inner body 13 is welded to the back end of the rib of the inner body 9. Inside the tailstock there is a site, where back supporting wheel 17 is installed. In its lower part supporting wheel bears on the two back supporting blocks 18 and the side of the back supporting wheel 17 bears on the back toe block 19.
  • Outer body of the includes rotary kiln
  • Outer body of the includes rotary kiln (2) consists of the following components:
  • Design of the outer body of includes rotary kiln
  • Design of the outer body 8 of the inclined rotary kiln includes the front rib of the outer body 22 and back rib of the outer body 29 having the heat insulation jacket of inclined rotary kiln 38 and outer coat of inclined rotary kiln 39.
  • Front flange of front rib of outer body 23 is welded to front end of front rib of outer body 22.
  • Front oil seal flange of the front rib of outer body 25 is attached to front flange of front rib 23 with the bolts.
  • Back oil seal flange of the front rib of outer body 24 is welded to back end of front rib of outer body 24.
  • Front oil seal flange of the back rib of outer body 30 is welded to the front end of the back rib of outer body 29, and at the part of back rib of outer body 29 the back flange of the back rib of outer body 31 is welded, to which the back oil seal flange of back rib of outer body 32 is attached with the bolts.
  • the hot pyrolysis gas outlet tube 33 is welded. It is equipped with the valve for emergency pressure relief 34.
  • carbonaceous residue outlet tube 35 is welded.
  • four supporting feet of the back rib of the outer body 37 are welded to the back rib of outer body 29. It is with these feet that it is attached to the frame structure of inclined rotary kiln.
  • Inclined rotary kiln for indirect heating (2) consists of rotating inner body of inclined rotary kiln 7 and of outer body of inclined rotary kiln 8 that is stationary and is fixed on the frame of its own.
  • Rotation of inner body of inclined rotary kiln 7 occurs inside stationary outer body of inclined rotary kiln 8.
  • gasproof oil seal systems located on the inner surfaces of the front oils seal flange of the front rib of outer body 25, of the back oil seal flange of the front rib of outer body 24, of the front oil seal flange of back rib of outer body 30 and of back oil seal flange of back rib of outer body 32.
  • These gasproof oil seal systems make it possible to separate working zone of inclined rotary kiln inside inner body of inclined rotary kiln 7 from gas jacket located between inner body of inclined rotary kiln 7 and outer body inclined rotary kiln 8, and insulate both these zones from the atmosphere.
  • Calculation of dimensions of inner body of inclined rotary kiln 7 and of outer body of inclined rotary kiln 8, as well as calculations of all gas zones, is based on amounts of feedstock, its composition and moisture content.
  • gas zones of inclined rotary kiln can experience either heightened or lowered pressure of gas.
  • Feedstock is fed into the inside zone of rotating inner body 7 of inclined rotary kiln for indirect heating (2) through an open end of horizontal loading channel 5 of the feeding unit (1) installed in the oil seal headstock of inner body 12.
  • Front oil seal hub of outer body 12 has gasproof oil seal hub system preventing the gases formed in the inside zone of inner body of inclined rotary kiln 7 to be released into the atmosphere through a gap between the inner wall of the front oil seal hub of inner body 12 and the outer wall of horizontal loading channel 5 of the feeding unit of the kiln (1).
  • Inner body of inclined rotary kiln 7 rotates due to the impact from electric or hydraulic engine of rotary kiln P4 conducted to inner body of inclined rotary kiln 7 via pinion gear 21 and ring gear 20. While rotating, inner body of inclined rotary kiln 7 bears with its supporting front wheel 15 on the two revolving front supporting blocks 16 and with its supporting back wheel 17 on the two back supporting blocks 18.
  • Feedstock fed into the working zone of inclined rotary kiln (2) moves in there longitudinally thanks to the 3-5 degrees inclination of inclined rotary kiln relative to the horizon and to the rotation of the inner body of inclined rotary kiln 7.
  • the feedstock is subjected to thermal processing by the heat conducted to it through the walls of the inner body of rotary kiln 7 from hot synthesis gas generated in gasification reactor (5), and moving in a gas jacket between the inner body 7 and outer body 8 of inclined rotary kiln.
  • Inner body of inclined rotary kiln 7 has on its outside external guide vanes 11 welded at some angle to inner body. They increase the area of heat transfer of the inner body of inclined rotary kiln 7 and direct the movement of hot synthesis gas in gas jacket along spiral trajectory along the surface of inner body of inclined rotary kiln 7. These two factors significantly increase heat transfer and time of contact of hot synthesis gas with inner body of inclined rotary kiln 7 and with feedstock, reducing at the same time the overall size of inclined rotary kiln.
  • Hot synthesis gas is brought at the temperature of 500-700°C into the gas jacket between inner body 7 and outer body 8 of inclined rotary kiln through the inlet tube of hot synthesis gas 26. Having moved in spiral trajectory along the surface of inner body of inclined rotary kiln 7 and having given its heat to feedstock, synthesis gas is cooled down to 120- 150°C and taken out of gas jacket through the cold synthesis gas outlet tube 27 and conveyed further through heat-insulated gas pipes into gas cleaning system.
  • the inner body of inclined rotary kiln 7 makes revolving movement inside the outer body of inclined rotary kiln 8 and with its vanes welded to the outer surface of its rib cleans the walls and all the space of gas jacket of dust residue. It also transports dust residue along the lower part of outer body of inclined rotary kiln 8 to outlet tube of dust residue 28, located in the lower down part of the front rib of outer body 22, through which dust residue is taken out of inclined inclined rotary kiln.
  • This unit operates as horizontal cyclone with mechanical cleaning of inside walls of the dust using rotation of the inside part, which is the inner body of inclined rotary kiln 7.
  • thermochemical conversion takes place that can be relatively divided into the three temperature zones:
  • Zone 1 - Zone of feedstock drying T 30 - 120°C;
  • Zone 2 Zone of moisture removal from the feedstock: T 120 - 300°C;
  • Zone 3 - Zone of low-temperature pyrolysis T 300 - 700°C.
  • hot pyrolysis gases are formed and hot carbonaceous feedstock residue, which are removed from the working zone of inner body of inclined rotary kiln 7 through outlets for pyrolysis gas and carbonaceous residue 10.
  • hot pyrolysis gases pass through gas interstice between inner body of inclined rotary kiln 7 and outer body of inclined rotary kiln 8 and are conveyed into gasification reactor (5) through the hot pyrolysis gas outlet tube 33, and hot carbonaceous feedstock residue is put into vertical channel 49 of the device feeding carbonaceous feedstock residue into the gasification reactor (4).
  • Hot pyrolysis gas outlet tube 33 has an outer heat insulation jacket. At upper end of the tube's vertical portion there is the valve for emergency pressure relief 34, through which excessive gas pressure in the working zone of the inner body of inclined rotary kiln 7 can be relieved in the atmosphere or in a separate gas channel should there be any unconventional or emergency situations during the operation of inclined inclined rotary kiln of indirect heating (2).
  • Inclined inclined rotary kiln of indirect heating (2) has thermal insulation jacket 38 and outer casing 39, minimizing heat loss into atmosphere.
  • the work of the drive of inclined rotary kiln P4 is synchronized with the work of all mechanisms of the input unit (1), of the device for unloading dust gas residue (3) and of unit for the feeding of carbonaceous feedstock residue into the gasification reactor (4). This makes it possible to manage the efficiency of gas generator SYN1-GG, make its operation uninterrupted and guarantee maximal low-temperature processing of feedstock in inclined inclined rotary kiln for indirect heating (2).
  • Device for unloading dust gas residue from inclined rotary kiln (3) presented in Fig. 4 is used for the removal of dust from the synthesis gas channel, located between inner body of rotary kiln 7 and outer body of rotary kiln 8.
  • Device for unloading dust gas residue from inclined rotary kiln (3) consists of sluice 40, equipped with upper slide gate 41, lower slide gate 42, put in motion by hydraulic cylinders P5 and P6.
  • Sluice 40 is in its upper part attached by the bolts to the flange of outlet tube for dust residue 28.
  • sluice 40 is attached by its lower flange to the flange of the pipe of vertical channel 43 with the bolted-on attachment for a pair of flanges.
  • the pipe of vertical channel 43 may have rectangular or round cross-section.
  • the lower part of the pipe of vertical channel 43 is welded to horizontal channel 44 that has round cross-section and attachment flange at its front end.
  • Dust residue of synthesis gas goes from gas jacket of inclined rotary kiln of indirect heating (2) into the device for unloading dust gas residue of rotary kiln (3) via the outlet tube for dust residue 28.
  • Upper slide gate 41 and lower slide gate 42 are in the shut position in the initial stage of loading. Because upper slide gate 41 is shut, dust residue accumulates in the outlet tube foe dust residue 28 in the amount equal or smaller than the volume of inner chamber of sluice 40.
  • upper slide gate 41 opens under the impact of the movement of hydraulic cylinder of upper slide gate P5. Dust gas residue goes down from outlet tube for dust residue 28 into the internal space of the chamber of sluice 40. After that upper slide gate 41 shuts down under the impact of hydraulic cylinder of upper slide gate P5. After it is shut, lower slide gate 42 opens under the impact of the movement of hydraulic cylinder of lower slide gate P6, and all dust residue from the inner chamber of sluice 40 is unloaded through vertical channel 43 into horizontal channel 44. From there, under the impact of spiral movement of screw mechanism 45, driven by electric or hydraulic drive P7, dust residue moves into the carbonaceous residue outlet tube 35. Afterwards this process is repeated automatically.
  • Unit for feeding of carbonaceous feedstock residue into the gasification reactor (4) outlined in Fig. 5 is used for loading into gasification reactor (5) of carbonaceous feedstock residue of MSW after thermal conversion of feedstock in rotary kiln for indirect heating (2).
  • Unit for the feeding of carbonaceous feedstock residue into the gasification reactor (4) consists of the sluice 46 equipped with upper slide gate 47, lower slide gate 48, put in motion by hydraulic cylinders P8 and P9. Sluice 46 in its upper part is attached with its upper flange by bolts to the flange of the carbonaceous residue outlet tube 35.
  • sluice 46 is attached by its lower flange to the flange of the pipe of vertical channel 49 with the bolted-on attachment for a pair of flanges.
  • Cross-section of the pipe of vertical channel 49 can have rectangular or round cross-section.
  • Lower part of the pipe of vertical channel 49 is welded to horizontal channel 50 that has round cross-section and securing flange at its front end.
  • horizontal channel 50 has securing flange, with which it is attached by the bolts to the flange of the pipe of the gasification reactor feeding unit 56.
  • screw mechanism 51 equipped with electric or hydraulic drive P10.
  • the mechanism is attached to horizontal channel 50 with the bolted-on attachment for a pair of flanges of screw mechanism 51 and horizontal channel 50.
  • upper slide gate 47 opens under the impact of the movement of hydraulic cylinder of upper slide gate P8. Carbonaceous residue goes down from carbonaceous residue outlet tube 35 into the internal space of the chamber of sluice 46. After that upper slide gate 47 shuts down under the impact of hydraulic cylinder of upper slide gate P8. After it is shut, lower slide gate 48 opens under the impact of the movement of hydraulic cylinder of lower slide gate P9, and all carbonaceous residue from the inner chamber of sluice 46 is unloaded through vertical channel 49 into horizontal channel 50. From there, under the impact of spiral movement of screw mechanism 51, driven by electric or hydraulic drive P10, carbonaceous residue moves inside gasification reactor (5) through the open end of horizontal feeding channel 50.
  • Gasification reactor (5) is schematically presented in Gig. 5. It is used for generation of synthesis gas from pyrolysis gases and carbonaceous feedstock residue, resulting from low- temperature pyrolysis of MSW in inclined rotary kiln for indirect heating (2).
  • Gasification reactor (5) consists of the body 52 with outer heat insulation jacket 58 covered by outer protective casing 59. To the lower part of the rib of the gasification reactor 52, branch pipe for the input of pyrolysis gases 55 is welded by its end. Branch pipe for installation of feeding unit 56 is welded to the central part of the rib of the gasification reactor 52.
  • Upper flange 53 is welded to the upper end of the rib of the body of the gasification reactor 52.
  • Heat-insulated lid of the body of gasification reactor 72 is attached to upper flange 53 by the flange of the lid of the body of gasification reactor 73.
  • Outlet branch pipe for hot synthesis gas 57 is welded to one side of the gasification reactor's lid 72, and the branch pipe of the mechanism of mechanical mixer 75 is welded to the lid's central part.
  • Lower flange 54 is welded to the lower end of the rib of the gasification reactor 52, and device for unloading the slag (6) from the gasification reactor (5) is welded to the lower flange 54.
  • fuel chamber 60 In the lower part of gasification reactor's body 52 fuel chamber 60 is located. It is hollow structure, the body of which consists of the inner wall of the fuel chamber 61 and its outer wall 62, connected in the lower part by concentric insert.
  • diffusors 66 are located in the upper part of the fuel chamber 60 . They are specially designed inserts, located between the inner wall of the fuel chamber 61 and the outer wall of the fuel chamber 62.
  • a cone 63 is located, representing a hollow structure, the body of which consists of the cone's inner wall 64 and outer wall 65.
  • Inner wall of the fuel chamber 61 is connected to the rib of the body of the gasification reactor 52 with the inner wall of the cone 64.
  • the upper end of the inner wall of the gasification reactor 64 is welded inside to the middle part of the rib of the body of the gasification reactor 52.
  • the lower end of the cone's inner wall 64 is welded to the upper end of the inner wall of the fuel chamber 61, whose lower end is welded to concentric insert.
  • Outer wall of the fuel chamber 62 is connected with the rib of the body of the gasification reactor 52 with the outer wall 65 of the cone and concentric insert 69.
  • the upper end of the cone's outer wall 65 is welded to the inside part of concentric insert 69, the outside part of which is welded from the inside to the middle part of the rib of the body of the gasification reactor 52.
  • the lower end of the outer wall of the cone 65 is welded to the upper end of the inner wall of the body of the fuel chamber 62, whose lower end is welded to concentric insert.
  • Air channel 67 located between lower part of the inner wall of the rib of gasification reactor's body 52 and inner wall of air channel 68, limited at its bottom part by lower flange 54, in which there are air flange channels 83.
  • Air channel 67 in its upper part has a projection in the hollow between inner wall of the cone 64 and outer wall of the cone 65, and further between inner wall of fuel chamber 61 and outer wall of fuel chamber 62 up to concentric insert in the bottom part of the fuel chamber 60.
  • Air channel 67 ends in C-shaped branch pipes in the upper part of which there are air lances 70 located at the centre of the opening of the diffusor 66 and in their lower part welded into the bottom part of the outer wall of the fuel chamber 62.
  • a channel of pyrolysis gases 71 connected with the inlet pipe for pyrolysis gases 55 and located between the inner wall of air channel 68 at one side, and the outer wall of the cone 65 and outer wall of the fuel chamber 62 at its other side.
  • Mechanical mixer 75 is mechanical structure equipped with the shaft with blades of mechanical mixer 76, driven by a hydraulic or electric motor PI 1.
  • the gasification reactor (S) is attached to supporting structure that has the same base frame with supporting structure of inclined rotary kiln for indirect heating (2).
  • Gasification process in gasification reactor (5) occurs inside working zone of the body of gasification reactor 52.
  • Carbonaceous feedstock residue resulting from low-temperature pyrolysis of feedstock in inclined rotary kiln for indirect heating (2) is transferred inside middle part of the body of the gasification reactor 52 through open end of horizontal channel 50 of the feeding unit for carbonaceous feedstock residue (4) installed in the branch pipe for installation of gasification reactor's feeding unit 56.
  • Automatic control system maintains the level of carbonaceous feedstock in the body of gasification reactor 52 at the level of the top edge of horizontal channel 50 of the unit that feeds carbonaceous feedstock residue (4).
  • Atmospheric air pumped into the gasification reactor (5) is initially heated up in the air channel 86 of the device for unloading the slag from the gasification reactor (6), heated to 250-300°C in the air channel 66 of the gasification reactor due to the cooling of internal parts of the gasification reactor, and is channeled through air lances 70 and diffusors 66 inside fuel chamber 60.
  • pyrolysis gases formed in inclined rotary kiln for indirect heating (2) are channeled through branch pipe for the input of pyrolysis gases 55 and channel for pyrolysis gases 71 into the gasification reactor (5).
  • pyrolysis gases are additionally heated up by IR radiation of red-hot slag that there is at the bottom of the channel for pyrolysis gases 71.
  • This process is structured as a system of ejecting devices, the number of whieh is equal to number of air lances 70 and respective number of diffusors 66 in the body of fuel chamber 60.
  • Part of pyrolysis gases that have not been ejected inside fuel chamber 60 move down along outer wall of fuel chamber 62 and go inside fuel chamber 60 through the open end of the channel for pyrolysis gases 71.
  • Zone 4 Zone of the channel of pyrolysis gases of the gasification reactor: T 700 -
  • Zone 5 - Zone of additional gasification T 900 - 1350C 0 ;
  • Zone 6 Zone of gas filtration: T 700 - 900°C; Zone 7 - Zone of high-temperature pyrolysis: T 900 - 1100°C;
  • Zone 8 Zone of combustion and gasification: T 1100 - 1350°C;
  • Zone 9 - Slag zone T 150 - 900°C.
  • Zone 10 - Gas zone T 500 - 700°C;
  • maximal temperature is only developed in the central part of the fuel chamber 60 in the area of torch combustion of pyrolysis gases.
  • the hollow structures of the fuel chamber 60 and cone 63 are not overheated thanks to their inner cooling by relatively cool air passing through air channel 66.
  • Fuel chamber's internal diameter is calculated for a throughput of 500-700 kilogram of feedstock per 1 square meter of cross section of fuel chamber 60 depending on the intensity of the flow of air and intensity of boiling of the bed of carbonaceous feedstock residue, caused by the process of formation of synthesis gas.
  • Hot synthesis gas formed in the fuel chamber 60 rises to the top, to the area of broad part of the cone 63, where the zone of high-temperature pyrolysis is located.
  • hot synthesis gas is partially cooled down to the temperature T 900-1 100°C, heating to the same temperature carbonaceous feedstock residue that there is in this zone. Its high-temperature pyrolysis occurs at that time.
  • the gases of high-temperature pyrolysis are formed. They, mixed with synthesis gas, rise through the layer of slow boiling carbonaceous residue into filtration zone.
  • Filtration zone where the temperature is T 700-900°C, is located in upper part of cone 63 and partially in the zone of gasification reactor's body 52. In this zone takes place the process of the cleaning of synthesis gas of the tars of high-temperature pyrolysis. Cleaning is done by their sorbing with relatively cold carbon of feedstock residue. Lowering of the temperature in this zone occurs due to the relatively cold carbonaceous residue conveyed into filtration zone from inclined rotary kiln for indirect heating (2) through the open end of horizontal feeding channel 44 of the feeding unit that loads carbonaceous feedstock residue into the gasification reactor (5).
  • Outer diameter of the cone 63, and diameter of gasification reactor's body 52 respectively, are calculated , relative to diameter of fuel chamber 60, so that synthesis gas that has formed and perform intense boiling of the bed of carbonaceous residue in the zone of fuel chamber 60, would slow the intensity of the boiling of the layer of carbonaceous feedstock residue due to its increasing surface in the zone of high-temperature pyrolysis, and, in particular, in filtration zone.
  • Synthesis gas can get through these channels from the zone of combustion and gasification, bypassing the zone of high-temperature pyrolysis and filtration zone, directly into the gas zone. This phenomenon is called "gas breakthroughs". It negatively affects gasification process and worsens the composition of generated synthesis gas.
  • mechanical mixer 75 is located inside upper part of gasification reactor's body 52.
  • This mixer has a shaft with blades 76 that is put in motion by a hydraulic or electric motor Pl l . Making rotating movements around the shaft, the blades of mechanical mixer 76 mix the bed of carbonaceous feedstock residue, making impossible formation of vertical gas channels in it.
  • hot synthesis gas when rising, carries along a part of carbonaceous feedstock residue from the centre of gasification reactor's body 52. Hot lower layers of carbonaceous feedstock residue tend to go up together with synthesis gas. This process is interrupted by the movements of the blades of mechanical mixer 76 that throw hot layers of carbonaceous feedstock residue to peripheral area, where they are somewhat cooled by inner wall of the cone 64. The wall is cooled down from the inside by the cold air going through air channel 67. Carbonaceous feedstock residue at that time starts moving down along inner wall of the cone 64, thus circulating inside the body of the gasification reactor 52. Having passed filtration zone, synthesis gas enters free upper part of the body of the gasification reactor 52, where there is gas zone of the gasification reactor.
  • Hot slag formed in the process of gasification of carbonaceous feedstock residue in the zone of combustion and gasification, goes into the zone of additional gasification, where it is partially cooled while contacting cooler pyrolysis gases, entering this zone via lower open end of the channel for hot pyrolysis gases 71.
  • the cooling of hot slag occurs due to endothermal reactions of the interaction of hot pyrolysis gas with residual carbon in this zone, and through its cooling by the inner wall of air channel 68 cooled by colder air passing through air channel 67.
  • the slag from the zone of additional gasification goes into the slag zone located in the device for unloading of slag from the gasification reactor (6), where it is cooled even more, is crushed and unloaded through the sluice 88.
  • the gasification reactor (5) has thermal insulation jacket 58 and outer protective casing 59 that minimize heat losses into the atmosphere while gasification reactor is in operation.
  • Device for unloading the slag from the gasification reactor (6) is a part of gasification reactor (5). It is presented in general in Fig. 5 and is used to remove the slag formed during gasification of carbonaceous feedstock residue in the gasification reactor (5).
  • Device for unloading the slag (6) from the gasification reactor (5) consists of the rib of the outer body 78, inside which there is the rib of the inner body 80 and upper flange 82, to which upper part of the rib of inner body 80 and upper part of outer body 78 are welded. To the lower part of the inner body's rib 80 lower cone 81 is welded, to lower part of which the upper branch pipe of the slag unloading channel 85 is welded.
  • Both outer body 78, and the bottom 79 of the device for unloading the slag from the gasification reactor (6) can be fitted with thermal insulation jacket and protective casing.
  • a sluice 88 in the lower part of the upper branch pipe of the slag unloading channel 85.
  • the sluice 88 is equipped with the upper slide gate 89 and lower slide gate 90, driven by hydraulic cylinders P12 and P13.
  • the sluice 88 is joined in its upper part by its upper flange with the flange of the branch pipe of the slag unloading channel 85 with the bolts.
  • the sluice 88 In its lower part the sluice 88 is joined by its lower flange with the flange of the lower pipe of the slag unloading channel 91 by the bolt joining of flange pair.
  • Crushing machine 84 is placed inside the rib of outer body 80.
  • Crushing machine is equipped with the set of revolving disc mills mounted on water-cooled shafts.
  • Branch pipe of the air input channel 86 is welded tangentially to the bottom 79.
  • air channel 87 connected with gasification reactor's air channel 67 by flange air channels 83, located in upper flange 83 of the slag unloading device (6) and lower flange 54 of the gasification reactor (5).
  • Crushing machine 84 has a system of oil seals and bearings, and its own electric or hydraulic motor (not shown on the figures).
  • upper flange 82 is cooled down by supplied cold air.
  • flange air channels 83 connected with the same flange channels of lower flange 54 of the gasification reactor (5). Slightly heated air from air channel 87 of the device for unloading the slag (6) goes through flange channels 83 into the air channel 67 of the gasification reactor (5).
  • the slag formed in fuel chamber 60 becomes hot monolith silicate formation and is transferred into the slag unloading device (6), where it is crushed by the disc mills of crushing machine 84.
  • Crushed slag is dropped into lower cone 81 and the upper branch pipe of the slag unloading channel 85, where it is cooled further by supplied cold air. Then, cooled and milled slag is removed through the sluice 88 from the device for unloading the slag (6) through lower branch pipe of the channel for unloading the slag 91.
  • Crushing machine 84 of the device for unloading the slag (6) operates in sync with all the mechanisms and devices of gasification technology complex SYNl-TC. This makes it possible to manage its efficiency, operate it uninterruptedly and achieve maximal thermochemical conversion of feedstock into synthesis gas in required composition, amount and quality.
  • Technological Complex SYNl-TC (SYNTENA 1) was developed for the implementation of technology SYNTENA 1- SFGP4, using gasification process SFGP4 (Slow Fluidized-bed Gasification Process 4).
  • the main component of technological complex SYNl-TC (Technological Complex SYNTENA 1) is gas generator SYN1-GG (Gas Generator SYNTENA 1), in which phased thermochemical conversion of feedstock into synthesis gas occurs. Entire gasification process is relatively divided into ten separate temperature zones.
  • the first three zones are the zones of low-temperature processing of the feedstock.
  • Low-temperature pyrolysis of the feedstock (T ⁇ 700°C) occurs in them. They are located in the pyrolysis part of gas generator SYN1-GG, which is a specially designed inclined rotary kiln for indirect heating SY 1-RK (Rotary Kiln SYNTENA1), installed at some angle to the horizon and heated by synthesis gas resulting from gasification of the feedstock.
  • Remaining seven zones are the zones of high-temperature processing of the feedstock (T>700°C).
  • gas generator SYN1-GG which is a gasification reactor for updraft gasification of the slow fluidized bed SYN1-SFG (Slow Fluidized-Bed Gasification reactor SYNTENA1). Its design is based on the new theory of gasification (Theory 4).
  • the gasification reactor is connected with inclined rotary kiln SYN1-RK by a body junction or by tubes.
  • Zones 1, 2, 3, 4, 7 and 8 are parts of pyrolysis area, and zones 5, 6, 7, 8, 9 and 10 pertain to the area of gasification process. Zones 7 and 8 are parts at the same time the areas of both pyrolysis, and gasification processes.
  • Processes of heating, drying, low-temperature and high-temperature pyrolysis occur in gas generator SYN1-GG at the same time.
  • Gasification processes of interaction between oxidizing gases and the products of thermal break-down of the feedstock take place in it too. Division of the process of gasification into the zones is relative, as well as the subdivision of the processes that take place in these zones.
  • Many gasification processes proceed in different zones with varying intensity, so this idealization is done for the purpose of theoretical computations and better understanding of the processes, occurring inside gas generator.
  • Municipal solid waste processed in the gas generator as its feedstock are incredibly diverse and multicomponent in their organic and mineral parts, and also have varying moisture contents. These are the key aspects of their conversion, largely affecting the amount and composition of generated synthesis gas, and formation of slag residue.
  • particulate waste (dust, sand, etc.) 6,25
  • mineral part not only its composition has an effect, but also the form of inorganic components in the feedstock.
  • Two categories can be distinguished among inorganic components: mechanical inclusions, and components that are chemically related with the feedstock.
  • First category is the main one and can include 6% to 25% of inorganic components relative to the total mass of feedstock. These are mechanical inclusions such as ferrous and non-ferrous metals, ceramics, building refuse, particulate waste, glass, etc., forming its mineral part that includes such important elements as: CaC0 3 , MgC0 3 , FeC0 3 , CaSC>4, Na 2 S0 4 , FeS0 4 , FeS 2 , Si0 2 , silicates with varying content of main oxides A1 2 0 3 , S1O2, CaO, Na 2 0, K2O and small content of the oxides of other metals.
  • mechanical inclusions such as ferrous and non-ferrous metals, ceramics, building refuse, particulate waste, glass, etc., forming its mineral part that includes such important elements as: CaC0 3 , MgC0 3 , FeC0 3 , CaSC>4, Na 2 S0 4 , FeS0 4 , FeS 2 , Si0 2 , si
  • Second category includes fewer compounds and may reach from 0,47% to 2,81 ) of the total mass of the feedstock. They are present in the feedstock as components that are chemically related with the feedstock, e.g. the metals, their oxides and salts making parts of paper, cardboard. They are present in the wood, dyes in textile refuse, polymeric materials.
  • Zone 1 Zone of feedstock drying
  • Zone 1- Zone of feedstock drying is one of the zones of low-temperature processing of feedstock.
  • the temperatures in it are: T 30 - 120 °C. It is located in the first section of the inner body of the inclined rotary kiln for indirect heating SYN1-R .
  • Thermal conductivity of feedstock constantly diminishes in the process of drying. Coefficient of thermal conductivity also reduces with diminishing moisture content, starting from critical point. Moisture content reduces due to deepening of the zone of evaporation and increase of thermal resistance of the dry outer layer of feedstock. These developments worsen the heating of inside layers of the feedstock, thereby prolonging the time of complete drying of internal layers of the feedstock.
  • Adsorbed gases are also released from the feedstock during its drying. Decomposition of the feedstock is at this time manifested weakly with these temperatures, it is only expressed in hardly noticeable formation of gases.
  • the feedstock's mass reduces during the drying, but without shrinkage, that is to say that its volume does not diminish, and only its further heating causes more profound structural changes.
  • Zone 2 Zone of moisture removal from the feedstock
  • Zone 2 - Zone of the removal of moisture from the feedstock is one of the zones of low-temperature processing of the feedstock with the temperatures of T 120 - 300°C. It is located in the second section of the inner body of the inclined rotary kiln for indirect heating SYN1-RK.
  • gases start to be released from the layer of feedstock in the form of oxide, carbon dioxide and tar.
  • Methane, heavy hydrocarbon gases and hydrogen are released with further heating.
  • the gases thus formed go into the upper part of the inner body of rotary kiln, where they mix up with water vapors.
  • the amount of released gas can be 2-2,5% of the weight of the feedstock loaded into the kiln.
  • Zone 3 Zone of low-temperature pyrolysis of the feedstock
  • Zone 3 - Zone of low-temperature pyrolysis is one of the zones of low-temperature processing of feedstock.
  • the temperatures in this zone are: T 300 - 700°C.
  • Zone of low-temperature pyrolysis of the feedstock is located in the third section of the inner body of inclined rotary kiln for indirect heating SYN1-RK.
  • n and m mainly have values 1-4.
  • o Methane forms as a result of catalytic decomposition of various hydrocarbons (Formula 28). Different metals are catalysts. These metals are always present in feedstock. It also occurs because of the contact with metal walls of inner body of rotary kiln:
  • Metals and their salts contained in original feedstock and melt are incorporated into the forming carbon structure, producing significant impact on the process of pyrolysis, and later, on the process of gasification.
  • Initial temperature of decomposition of feedstock is determined mainly by its individual properties, and to some extent by the conditions in which its heating occurs.
  • Me Ca(580°C), Be, Mg(550°C), Sr(500-850°C), A1(575°C), Cu(200°C) 5 Zn(100-250°C), Cd(170-300°C), Mn(220°C), Co(170°C), Ni(230-360°C), others,
  • Me Mg (350-650°C), Pb (315°C), Be (180°C), Mn (100°C), Zn (357°C), Fe
  • Me K(500°C), Na(400°C), Li(200-400°C), and others
  • Me Fe"(700°C), Fe'"(600°C), Co(700°C), Ni(500°C), Sn(360°C), Cu(720°C), Ti(600°C), and others.
  • reactions of oxidation in the layer of feedstock intensify, augmenting temperature increase in this zone and intensifying the release of various products of destruction of feedstock, mainly such as water vapor, carbonic gas, carbon oxide, acetic acid, methyl alcohol, formaldehyde, tar, methane, ethylene, propylene and hydrogen, as well as some other products of decomposition, amounts of which depend on the morphologic composition of the feedstock.
  • Me Fe "Fe2 IM (700°C), Pb(400°C), Cu(550°C), and others.
  • Me Mn(600°-700°C), and others.
  • Me Sn(500-600°C), Pb(350°C), Cu(250°C), Cd(300°C), Mo(700°C), Co(500°C), Ni(400°C), and others.
  • Pyrolysis gas thus obtained is subjected to heating with thermal radiation coming from the wall of the inner body of inclined rotary kiln, or by direct contact with the wall.
  • the tars and particles of carbon residue deposited on the inner wall of inner body of inclined rotary kiln are removed under the impact of outside temperatures and water vapor coming from the zone of drying and zone of moisture removal, and through mechanical contact with carbonaceous feedstock residue occurring in the process of rotation of the inner body of inclined rotary kiln.
  • Gases of low-temperature pyrolysis go out of inner body of inclined rotary kiln SYN1- RK and go through a special channel into gasification reactor SYNl-SFG, where they are subjected to thermal conversion, partial combustion and further conversion into synthesis gas.
  • Zone 8 Zone of gas filtration
  • Zone 8 - Zone of gas filtration is one of the zones high-temperature processing of feedstock at the temperatures of T - 700 - 900°C.
  • Temperature in the gas filtration zone lowers to T - 700 - 900°C as compared to the temperatures of T - 900 - 1100°C in the zone of high-temperature pyrolysis mainly occurs due to relatively cold carbonaceous feedstock residue, continuously coming into this zone from the zone of low-temperature pyrolysis, situated in inclined rotary kiln for indirect heating.
  • Carbonaceous feedstock residue coming from the zone of low-temperature treatment has the structure of dry substance consisting of carbonaceous elements in various fractions. It is predominantly small fraction containing carbons in the form of semi-coke, and solid mineral elements of the feedstock.
  • Zone 7 Zone of high-temperature pyrolysis
  • the zone of high-temperature pyrolysis gasification reactor SYN1-SFG is one of the zones of high-temperature processing of the feedstock. Temperatures there vary between 900 and 1100°C.
  • Zone of high-temperature pyrolysis is formed out of solid feedstock residue transferred from inclined rotary kiln SY 1-RK in gasification reactor SY 1-SFG and heated up to the temperature of T - 900 - 1100°C due to thermal radiation coming from the zone of combustion and gasification and from the heat of hot gases rising from this zone.
  • Essential processes in this zone occur at the T - 700 - 1100°C, at this time continues the release of volatile hydrocarbons and tars, part of which, affected by high temperatures, convert into simple gases H 2 and CO. Another part is sorbed by carbonaceous residue formed in filtration zone, and a small part only gets into the gas zone. As a result of these processes the amount of carbon in feedstock residue reaches its maximum.
  • Volatile hydrocarbons and tars continue to be released from carbonaceous feedstock residue in the entire volume of the zone of high-temperature pyrolysis.
  • Predominant reactions are those, in which saturated and unsaturated hydrocarbons are formed (23) and tars with high content of the atoms of C:
  • n and m equal 4 and more.
  • Reactions of Formula 37 and Formula 38 are catalytic, the catalyzer being different metals present in carbonaceous feedstock residue.
  • Methane is formed in this process as a product of interaction of carbon with water vapor and hydrogen through the reactions:
  • This reactions is catalytic, its catalyzer, as in reactions with Formula 37 and Formula 38, are various metals present in carbonaceous feedstock residue.
  • Methane is also formed during catalytic cracking of various hydrocarbons (Formula 28).
  • the catalyzer as in reactions with Formula 26 and Formula 27, are different metals present in carbonaceous feedstock residue, for example, iron (Fe):
  • Some inorganic salts are decomposed through the reactions with Formulas 29-33. These are the salts that have not broken up in the zone of low-temperature pyrolysis with formation of respective oxides and of H 2 0, C0 2 , NO2 and O2 through the reactions with Formulas 29-33:
  • oxides of various metals are formed from the mineral part of the feedstock. These metal oxides have impurities of carbon and insignificant amounts of salts that have not yet decomposed, and some pure reduced metals. Depending on feedstock's original composition, some amount of metal alloys is formed. The basis of these alloys are iron, copper and silicon.
  • Me CdO (900°C), CuO (1026°C), and others.
  • Me Na(900-1000°C), Ca(800-850°C), Ba(1000°C), Li(800°C), Sn(800- 900°C), Cd, Mn(600°-700°C), Cd, Ni, and others.
  • Me Ti(800°C), Cr(700°C), Mo(700°C), and others.
  • Reduced metals become acceptors of oxygen in the molecules of C02 and H 2 0 in the reactions of Formulas 41-42, converting them in simple flammable gases CO and H 2 .
  • Both metal oxides and reduced metals can be a part of the cleaning of the gases obtained of such materials as HC1, H 2 S, NH and COS.
  • the metals can be both solid, or melt, or in a gas state.
  • the gases resulting from the processes of combustion and gasification are cleaned of hazardous components, and additional amounts of the CO and 3 ⁇ 4 are obtained with respective amounts of sulfides, chlorides and nitrides.
  • This process is natural, as it is caused by Archimedean force of rising gases in the layer of carbonaceous feedstock from one side, and by the force of gravitation of the Earth, from the other side.
  • chlorides are melted in this process (CaCl 2 - 787 °C, NaCl - 801 °C, and others), some carbonates (Li 2 C0 3 - 618°C, Na 2 C0 3 - 851°C, K 2 C0 3 - 89 C, and others) and some oxides (K 2 0 - 740°C, Mn0 2 - 847°C, PbO - 890°C, CdO - 900°C, SnO - 1040°C, and others).
  • Mineral components of feedstock undergo melting, both those bound with organic components (second category), and those that are mechanical impurities (first category).
  • Small mechanical inclusions of the first category, and particularly mineral components of the second category, evenly dispersed in the organic part of carbonaceous feedstock residue, are strongly shielded by carbon from the impact of high temperatures, so in the upper part of the zone of high-temperature pyrolysis they do not melt considerably.
  • the melting of some part of inorganic salts largely intensifies, this melting being caused by general rise in temperatures and reduction of the shielding of the salts by carbon. This happens due to their higher concentration provoked by the process of secondary gasification.
  • Zone 4 Zone of the channel for pyrolysis gases of the gasification reactor
  • the zone of the channel for pyrolysis gases of gasification reactor SYN1-SFG is one of the zones of high-temperature processing of the feedstock.
  • the temperatures in the zone are T 700 - 900°C.
  • Zone of the channel for pyrolysis gases of the gasification reactor is located in the inner volume of the body of gasification reactor SY 1-SFG.
  • thermochemical conversion Both hydrocarbons, and tars that they contain are subjected to this conversion.
  • High content of water vapors in the composition of low-temperature pyrolysis gases is one of the reasons for reactions of conversion of hydrocarbons in this zone.
  • Zone of combustion and gasification of gasification reactor SYNl-SFG is one of the zones of high-temperature treatment of the feedstock with the temperatures: T 1100 - 1350°C.
  • the process of gasification of carbonaceous residue is a very complex process. It is a part of high-temperature processing of the feedstock. It is executed simultaneously in all the seven zones of gasification reactor SYNl-SFG, but the main process of gasification of carbonaceous feedstock residue generating very high quality synthesis gas takes place in the zone of combustion and gasification under the temperature T 1100 - 1350°C.
  • a special feature of gasification reactor SYN1-SFG is that the hot mixture of pyrolysis gases is conveyed into the space under the lances of fuel chamber from the channel for pyrolysis gases and from the zone of additional gasification.
  • This mixture contains large amounts of simple hot gases H 2 , CO, and CH 4 , and certain portion of hydrocarbon gases and tars with high calorie value.
  • Gas mixture entering the fuel chamber, also contains water steams 3 ⁇ 40 and carbon dioxide gas C0 2 . These actively participate in gasification process and themselves lower the temperature of combustion of gas mixture. This make it possible to control the temperature in the fuel chamber either through the general moisture content of loaded feedstock, or by feeding additional amounts of H 2 0 or C0 2 into the gasification reactor. Due to the high velocity of the air flow a "zone of combustion of pyrolysis gases" and a “zone of gasification of carbonaceous feedstock residue" are formed in front of the air lances. Their general configuration is presented in Fig. 6.
  • Combustion process is distributed evenly in the zone of combustion of pyrolysis gases and gasification process is distributed evenly in the zone of gasification of carbonaceous feedstock residue thanks to the large number of air lances and high speed of the air blown through them.
  • the not melted inorganic particles or the drops of melted slag can be transferred into the central part of the zone of combustion of pyrolysis gases, thus forming a slag cone in its centre (3).
  • Partial combustion of pyrolysis gases in the bed of carbonaceous feedstock residue occurs in the zone of combustion of pyrolysis gases. Combustion occurs under the impact of oxygen of the air, conveyed into the fuel chamber of the gasification reactor that represents a system of torch combustion of gases shown in Fig. 6.
  • Partial combustion of pyrolysis gases occurs due to the fact that the amount of air oxygen supplied into the fuel chamber of the gasification reactor is insufficient for complete burning out of these gases, the latter being key precondition for entire process of gasification.
  • the dynamic of reactions of combustion is branching-chain with progressing self- acceleration owing to the heat released in exothermal reactions, and the volume of air oxygen conveyed into the fuel chamber is calculated on the basis of thermal energy needed to maintain temperature regime in all the zones of the gasification reactor, and for generation of synthesis gas of best possible composition and amounts.
  • Equations of Formula 10 and Formula 13 may also be presented as a complex interaction of simple reactions of oxidation (Formulas 14-18), and of reactions of dehydration (Formula 11 and Formula 12):
  • combustion and gasification hot air is conveyed at high speed into combustion and gasification zone. This air is heated as a result of the cooling of the components and parts of gasification reactor. If need be, water steam (H 2 0) and/or carbon dioxide (C0 2 ) may be fed into this zone.
  • High speed of the air exiting air lances permits to loosen the carbonaceous feedstock residue mass in entire span of the fuel chamber, and in particular, in the area of the band of air lances. It makes possible to create in this zone a powerful effect of "boiling" of carbonaceous feedstock residue in the volume of gases formed in the process.
  • Air oxygen in the process of combustion is virtually totally expended in the reactions of oxidation of a part of pyrolysis gases, in which mostly carbon dioxide, water steam and pyro-carbon are released. These then become the main agents together with carbonaceous feedstock residue in the process of gasification.
  • the nitrogen (N) and sulphur (S) are oxidized to the oxides NO x and S0 2 . Their amount depends on initial content of these elements in the feedstock and on the gas dynamic during diffusion combustion of the part of pyrolysis gases inside fuel chamber.
  • Gasification of carbonaceous feedstock residue is executed in the zone of gasification of carbonaceous feedstock residue. This process constitutes the conversion of combustion gases C0 2 and H 2 0 into the simple combustible gases H 2 and CO due to their restoration in the fluidized bed of carbonaceous feedstock residue.
  • Reactions of Formula 4, Formula 8 and OopMyjia 9) primarily occur at a boundary of the process of torch combustion of pyrolysis gases in the bed of carbonaceous residue and at the periphery of this process.
  • Hot gases resulting from the process of gasification move upwards, thus towards a layer of carbonaceous feedstock residue moving down from the zone of high-temperature pyrolysis, heating it and setting it in motion in the form of suspension layer. At this time the temperature in the upper part of the zone of combustion and gasification rises to T - 1100 - 1200 °C.
  • the hot synthesis gas is additionally cooled to T 700 - 1100°C, heating to the same temperature carbonaceous feedstock residue in this zone, subjecting it to partial gasification and high-temperature pyrolysis.
  • gasification reactor SYN1-SFG and gasification process SYN1- SFGP4 in general are well correlated for the processing of various types of feedstock with high content of hydrocarbons and chars in gas phase, and with low content of residual carbon. Municipal solid waste is exactly this kind of feedstock.
  • Reactions of Formula 37 and Formula 38 are catalytic, the metals in carbonaceous feedstock residue serving as catalyzers.
  • H 2 and CO and fine-dispersed pyro- carbon are formed as a result of the thermal conversion of carbons and tars going into the zone of combustion and gasification from the channel for pyrolysis gases as a part of gases of low-temperature pyrolysis and carbons and tars of high-temperature pyrolysis sorbed by carbonaceous residue.
  • Inorganic ingredients of the feedstock come into the zone of combustion and gasification from high-temperature pyrolysis zone in the state differing from initial as a result of thermochemical transformation they have undergone in the zones preceding combustion and gasification zone.
  • Me Ca(900-1200°C), Na(1000°C), K(1200°C), Ba(1000°C), Li(730-1230°C), and others;
  • Cleaning of generated gases of HC1, H 2 S, NH 4 and COS can be executed with metal oxides and reduced metals.
  • the metals can be solid, melted or gaseous.
  • Generated gases are also cleaned of vapors of metals, including heavy metals, during the process of their transformation into respective sulfides, chlorides and nitrides that are resistant to destruction by temperature and subsequently become part of the slags.
  • these additives can be metal oxides, their salts and hydrates of oxides, and silicon dioxide.
  • Inorganic constituent of carbonaceous feedstock residue undergoes cardinal chemical and structural transformations in the zone of combustion and gasification, being at the same time a catalyst of gasification and an acceptor. It takes active part in production of synthesis gas in large amounts and of great quality, and in its cleaning of hazardous impurities of heavy metals, compounds of sulfur and chloride, transforming them into an inactive, insoluble form representing in their major part compounds of silicon slag.
  • the main process of formation of the slag corresponds to a reaction of interaction of some metal oxides with silicon oxide (Formula 49):
  • the temperature of slag formation also directly depends on the components of inorganic constituent in carbonaceous residue, therefore the temperature of slag formation can be changed with special inorganic additives to the feedstock in the form of metal oxides, their salts, hydrate oxides and silicon dioxide.
  • the slag As a result of the processes occurring in the zone of combustion and gasification, the slag is formed, the main components of which are metal and non-metal oxides, sulphides, chlorides, fluorides, inclusions of metal alloys and unreacted carbon.
  • the slag thus formed represents complex amorphous-crystalline form of the silicates with variable composition with some mechanical inclusions.
  • the structure of the slag formation in the zone of combustion and gasification is a slag cone with a peak (3) in Fig. 6, located in the centre of fuel chamber at the level of air lances. Slowly cooling melt of the slag descends along the cone's slopes.
  • Slag cone's solid foundation is formed by unmelt inorganic inclusions (of the first category) of various sizes transferred into the central part of fuel chamber under the impact of high velocity of torch jets.
  • the slag then goes down into the slag zone, where it is transformed as it cools into a single mass of slag of a complex amorphous-crystalline form.
  • Zone 5 - zone of additional gasification of gasification reactor SYN1-SFG is one of the zones of high-temperature processing of the feedstock at the temperatures T 900 - 1100°C.
  • Additional gasification zone is situated inside the inner volume of the body of gasification reactor SYN1-SFG.
  • Main gasification process in gasification reactor SY 1-SFG occurs in the zone of combustion and gasification, and in high-temperature pyrolysis zone. But beneath the zone of combustion and gasification in this gasification reactor there is a zone of additional gasification. This zone needed to be organized because one part of burning-hot carbon from the zone of combustion and gasification, not having gasified, can fall down into the slag zone from where it is removed from the gasification reactor together with the slag.
  • this carbon part of hot gas of low-temperature pyrolysis is conveyed into the zone of additional gasification through an open ingress of the channel for pyrolysis gases of the gasification reactor.
  • This part of hot gas contains large portion of water steam and certain amount of C0 2 .
  • Carbonaceous feedstock residue that has not been gasified in the zone of combustion and gasification undergoes final gasification under the impact of water steam and C0 2 once it is in the zone of additional gasification.
  • thermochemical transformations of pyrolysis gases continue in this zone, the main reactions now being the reactions of dehydration (25) and (26) mentioned earlier in the text;
  • the slag comes into this zone mostly in liquid form, descending along the slopes of the slag cone, but also in the form of some solid formations, and more rarely in the form of slag masses.
  • the slag is affected by:
  • the slag slowly cools after some time to the temperature of T 900 - 1100°C, turning into a complex amorphous-crystalline form of the silicates of variable composition with some mechanical inclusions.
  • the slag is conveyed into the slag zone of gasification reactor SYN1-SFG from the zone of additional gasification, its temperature being T - 900°C, in the form of monolithic hot slag, but some part of it can also be in liquid form, and some amount of slag may have a shape of separate solid formations.
  • the slag is slowly cooled under indirect impact of cold atmospheric air pumped into the gasification reactor, then it is mechanically crushed in an impact crusher by means of disc cutters and subsequently removed from the gasification reactor through a sluice device into a receiving bunker.
  • the cooling of the slag is slow due to its large thermal capacity, which, in its turn, causes the need for a large volume of the slag zone, where the slag has to be kept for long periods of time.
  • the slag cools down to the temperature T - 300°C and acquires complex amorphous-crystalline form that depends on the conditions of the cooling, on initial morphological composition of the feedstock, its moisture content and possible inorganic additions to the feedstock, and on possible additional supply of water or water steam into this zone.

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Abstract

L'invention concerne un procédé et un dispositif de conversion thermochimique en gaz de synthèse d'une charge d'alimentation riche en carbone de déchets urbains, solides et autres, présentant une teneur élevée en goudrons. La conversion est réalisée lors d'un processus de pyrolyse en deux étapes (zones 1-3, 7) et de gazéification à tirage ascendant consécutive (zones 4-6, 8-10) de lit fluidisé de résidu de charge d'alimentation carbonée dans un flux air et gaz lent. Les zones 1-3 sont des zones de traitement de charge à basse température et sont situées dans la partie pyrolyse du dispositif. Les zones 4-10 sont des zones de traitement de charge à haute température et sont situées dans la partie gazéification du dispositif. La partie pyrolyse du dispositif est constituée d'un dispositif de chargement de charge d'alimentation (1), d'un séchoir rotatif à chauffage indirect (2) et d'un dispositif d'évacuation de résidu gazeux de poussière (3). La partie gazéification du dispositif est constituée d'un gazéifieur (5), d'une unité d'acheminement de résidu de charge d'alimentation carbonée dans le gazéifieur (4) et d'une unité de déchargement des scories (6). La présente invention utilise également un gaz de synthèse dans les modes de réalisation présentés ici.
PCT/UA2017/000086 2016-09-05 2017-08-23 Procédé de conversion en gaz de synthèse de déchets urbains solides et autres contenant du carbone et équipement basé sur ce procédé WO2018044252A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107120656A (zh) * 2017-05-09 2017-09-01 周冲 一种间接热裂解及灰渣燃烧熔融炉及其处理方法
CN108728140A (zh) * 2018-08-13 2018-11-02 湖南叶林环保科技有限公司 有机危废低温热解发电系统
CN109163330A (zh) * 2018-10-10 2019-01-08 永清环保股份有限公司 一种生活垃圾热解气化处理系统、处理方法及发电系统
CN112377914A (zh) * 2020-10-09 2021-02-19 江苏朗誉环保设备有限公司 一种危废炉渣等离子焚烧炉及其焚烧方法
EP4008798A1 (fr) * 2020-12-04 2022-06-08 HBI Srl Procédé d'extraction de métaux à partir d'une masse humide de déchets

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
UA66822U (uk) * 2011-04-26 2012-01-25 Национальный Университет Кораблестроения Имени Адмирала Макарова Спосіб утилізації органічних відходів - екопірогенезіс
KR20120131817A (ko) * 2011-05-26 2012-12-05 한국에너지기술연구원 폐감귤을 이용하여 건조 유동층 방식으로 열분해 가스화한 합성가스 생산장치 및 생성방법
RU136799U1 (ru) * 2013-05-15 2014-01-20 Федеральное государственное бюджетное учреждение науки Объединенный институт высоких температур Российской академии наук (ОИВТ РАН) Комплекс энерготехнологический многофункциональный переработки биомассы
US8790428B2 (en) * 2008-03-18 2014-07-29 Karl-Heinz Tetzlaff Method and device for producing synthesis gas from biomass
GB2529053A (en) * 2014-07-03 2016-02-10 Dps Bristol Holdings Ltd Waste processing apparatus
UA110956C2 (uk) * 2013-07-29 2016-03-10 Термоселект Актіенґезелльшафт Спосіб виробництва сечовини зі сміття будь-якого складу переважно побутових відходів

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8790428B2 (en) * 2008-03-18 2014-07-29 Karl-Heinz Tetzlaff Method and device for producing synthesis gas from biomass
UA66822U (uk) * 2011-04-26 2012-01-25 Национальный Университет Кораблестроения Имени Адмирала Макарова Спосіб утилізації органічних відходів - екопірогенезіс
KR20120131817A (ko) * 2011-05-26 2012-12-05 한국에너지기술연구원 폐감귤을 이용하여 건조 유동층 방식으로 열분해 가스화한 합성가스 생산장치 및 생성방법
RU136799U1 (ru) * 2013-05-15 2014-01-20 Федеральное государственное бюджетное учреждение науки Объединенный институт высоких температур Российской академии наук (ОИВТ РАН) Комплекс энерготехнологический многофункциональный переработки биомассы
UA110956C2 (uk) * 2013-07-29 2016-03-10 Термоселект Актіенґезелльшафт Спосіб виробництва сечовини зі сміття будь-якого складу переважно побутових відходів
GB2529053A (en) * 2014-07-03 2016-02-10 Dps Bristol Holdings Ltd Waste processing apparatus

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107120656A (zh) * 2017-05-09 2017-09-01 周冲 一种间接热裂解及灰渣燃烧熔融炉及其处理方法
CN107120656B (zh) * 2017-05-09 2020-12-22 无锡爱普特设备科技有限公司 一种间接热裂解及灰渣燃烧熔融炉及其处理方法
CN108728140A (zh) * 2018-08-13 2018-11-02 湖南叶林环保科技有限公司 有机危废低温热解发电系统
CN108728140B (zh) * 2018-08-13 2024-02-06 湖南叶林环保科技有限公司 有机危废低温热解发电系统
CN109163330A (zh) * 2018-10-10 2019-01-08 永清环保股份有限公司 一种生活垃圾热解气化处理系统、处理方法及发电系统
CN112377914A (zh) * 2020-10-09 2021-02-19 江苏朗誉环保设备有限公司 一种危废炉渣等离子焚烧炉及其焚烧方法
EP4008798A1 (fr) * 2020-12-04 2022-06-08 HBI Srl Procédé d'extraction de métaux à partir d'une masse humide de déchets

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