EP2655552A1 - Process for the pyrolysis of organic feedstock - Google Patents

Process for the pyrolysis of organic feedstock

Info

Publication number
EP2655552A1
EP2655552A1 EP10805202.8A EP10805202A EP2655552A1 EP 2655552 A1 EP2655552 A1 EP 2655552A1 EP 10805202 A EP10805202 A EP 10805202A EP 2655552 A1 EP2655552 A1 EP 2655552A1
Authority
EP
European Patent Office
Prior art keywords
pyrolysis
reactor
gas
heated
reforming
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10805202.8A
Other languages
German (de)
French (fr)
Inventor
Prerak Goel
Christopher THANNHÄUSER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Thannhaueser Goel IP AG
Original Assignee
Thannhaueser Goel IP AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Thannhaueser Goel IP AG filed Critical Thannhaueser Goel IP AG
Publication of EP2655552A1 publication Critical patent/EP2655552A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/16—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form
    • C10B49/18—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form according to the "moving bed" type
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • 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
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • 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
    • C10J3/06—Continuous processes
    • C10J3/12—Continuous processes using solid heat-carriers
    • 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
    • C10J3/62—Processes with separate withdrawal of the distillation products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0993—Inert particles, e.g. as heat exchange medium in a fluidized or moving bed, heat carriers, sand
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/12—Heating the gasifier
    • C10J2300/1246—Heating the gasifier by external or indirect heating
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
    • C10J2300/1606—Combustion processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1625—Integration of gasification processes with another plant or parts within the plant with solids treatment
    • C10J2300/1637—Char combustion
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1853—Steam reforming, i.e. injection of steam only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1876—Heat exchange between at least two process streams with one stream being combustion gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1892—Heat exchange between at least two process streams with one stream being water/steam
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin

Definitions

  • the invention relates to a process for pyrolysis of hydrous organic feedstock, in particular of organic waste and biomass, with the following process steps: a) a lumped inert heat transfer medium circulated in the circuit is heated in a preheater, b) the heated heat transfer medium is mixed with the hydrous feedstock c) in the pyrolysis reactor, the feedstock is optionally pyrolyzed with further addition of steam, d) the mixture of pyrolysis gas and water vapor formed in the pyrolysis reactor is reformed in a reforming reactor into a product gas having a high hydrogen content (first end product), e) the pyrolysis coke formed in the pyrolysis reactor (second end product) is discharged out of the pyrolysis reactor together with the heat carrier and separated from the heat carrier, and f) the separated heat carrier is returned to the preheater.
  • Such a method is known, for example, from EP 1 337 607 and embodied in the appendix "Blauer Turm" (see www.blue-tower.de).
  • knew method is the heat carrier, the z. B. may consist of heat-resistant ceramic balls, heated in the preheater with the aid of flue gas from a furnace to about 1100 ° C and entered in this state via a solids lock in the reforming reactor located below the preheater to there the heat required for the reforming in the enter required temperature range.
  • the heat transfer medium cools down to the temperature level required for heating the pyrolysis reactor (about 750 ° C.) and is in turn introduced via a metering device into the pyrolysis reactor underneath, to which the feed material is simultaneously supplied.
  • the heat transfer medium then passes through the pyrolysis reactor together with the feedstock and, together with the pyrolysis coke produced during the pyrolysis, is discharged from the bottom of the pyrolysis reactor at a temperature of about 600.degree.
  • the heat carrier is then conveyed by means of an elevator up and entered via a lock again from above into the preheater. If the amount of water added to the hydrous feed is insufficient to reform, steam is also added to the pyrolysis reactor.
  • the system inevitably has a relatively large overall height due to the guidance of the heat transfer circuit, so that the heat transfer medium for the return to the preheater must be lifted over a relatively long conveying path, which is unfavorable both energetically and wear.
  • the heat transfer medium must be heated in the preheater up to 1100 ° C, ie up to the range of bright yellow heat, whereby the life of the one part of the heat carrier and the other part of the heat carrier leading plant parts, especially the solids sluices, can be greatly affected.
  • the invention proposes starting from the method of the type mentioned above, g) that the reforming reactor is arranged separately from the heat transfer circuit and is heated separately from this.
  • the heat transfer circuit comprises only the preheater and the pyrolysis reactor.
  • the necessary height of the plant is reduced by about the height of the reforming reactor. Because of the reduced height, the delivery path for the return of the heat carrier is shortened accordingly.
  • the reforming process can be controlled much more precisely with regard to optimized product discharge (product gas or pyrolysis coke) and optimized for the highest possible hydrogen content in the product gas.
  • a first, expedient embodiment of the invention provides that a subset of the product gas is diverted and is burned in a gas burner whose flue gas first heats the reforming reactor and then the heat carrier in the preheater.
  • the process remains energy self-sufficient and enables optimized application to pyrolysis coke. This is particularly important in locations where the pyrolysis in agriculture z. B. is needed for soil improvement.
  • a second expedient embodiment of the invention provides that the entire pyrolysis coke or a separated subset of the pyrolysis coke is incinerated in a coke furnace whose flue gas first heats the reforming reactor and then the heat carrier in the preheater. Again, the process remains energy self-sufficient and allows optimized application of hydrogen-containing pyrolysis gas. This is especially important in locations where z. B. wants to generate electricity with a gas turbine or a gas engine, z. B. to fill the power generation gaps of electricity generating solar systems.
  • the reforming process can in both cases - regardless of the particular energy source - take place in an externally heated reaction chamber of the reforming reactor. This has the advantage that the reforming process can be accomplished alone in the gas phase without interference by passing solids, if necessary in the presence of a catalyst which is located in the reaction space of the reforming reactor. Due to the presence of a suitable catalyst, it is known that the reforming process can be considerably intensified.
  • the reforming process can also be carried out in a moving bed reactor, the circulating high-temperature heat transfer medium first by the flue gas of the gas burner and / or the coke firing heated preheating and then one of them through a solids sluice separated reaction chamber, the from flows through to be reformed pyrolysis gas.
  • a catalyst which is not polluted by the feedstock and can optionally be thermally, chemically or mechanically reactivated outside the reforming reactor or can be completely or partially replaced.
  • the preheater upstream of the pyrolysis reactor is subdivided into two preheating chambers, which are successively passed through by the heat transfer medium and of which the one from the pyrolysis gas passed through and the other from the passed flue gas from the Reforming reactor is heated.
  • the preheating chamber of the moving bed reactor may also be subdivided into two preheating chambers, which are successively passed through by the high-temperature heat carrier and one of which heats the product gas passing through it and the other from the flue gas of the gas burner and / or coke firing becomes.
  • Fig. 1 Schematically the method according to the
  • a preheater with the reference numeral 1 a pyrolysis reactor with the reference numeral 2 and a reforming reactor with the reference numeral 3 are designated. Furthermore, the plant comprises a gas burner 4, a sieve 5, a product gas purification 6 and a steam generator 7.
  • the heat carrier 8 is formed by refractory ceramic balls, which are located for the most part in bulk in the preheater 1 and the pyrolysis reactor 2.
  • the heat transfer medium 8 is circulated continuously and moves slowly from top to bottom first through the preheater 1 and then through the pyrolysis reactor 2, then as Siebrückhalt on the screen 5 and an elevator 9 back up into the preheater. 1
  • gas-tight solids sluices 10 are provided for the passage of the heat carrier 8.
  • the heat transfer medium 8 is heated in the preheater 1 to about 800 ° C and entered at this temperature from above into the pyrolysis reactor 2. At the same time with the heat transfer medium 8 is in the pyrolysis reactor 2 via an adding device 11 to be pyrolyzed water-containing organic feedstock in the form of organic waste or biomass input.
  • air or oxygen or a mixture of air and oxygen may be introduced into the pyrolysis reactor by means of an adding device 12.
  • this feedstock On its way through the pyrolysis reactor 2, this feedstock is pyrolyzed with the addition of water vapor.
  • the energy required for the pyrolysis provides the heat transfer medium 8, which accordingly cools in the pyrolysis reactor 2 from 800 ° C to 600 ° C. If air and / or oxygen are added, a stoichiometric combustion of carbon also takes place in the pyrolysis reactor 2, whereby optionally additional heat is introduced into the pyrolysis reactor.
  • the pyrolysis coke formed during the pyrolysis is discharged together with the heat transfer medium 8 via a discharge device 14 arranged downstream of the pyrolysis reactor 2 together with the heat transfer medium 8 and applied to the screening plant 5.
  • the heat carrier 8 is retained as Siebrückhalt and fed to the elevator 9, which promotes the heat carrier 8 upwards and enters from above through the solids lock 10 in the preheater 1.
  • the pyrolysis coke separated off as a screen pass is conveyed to a product dispenser 15 where it is dispensed as the first product of the process.
  • the above emerging from the pyrolysis reactor 2 pyrolysis gas-steam mixture is entered into a heated from the outside, separate reaction chamber 16 of the reforming reactor 3 and there subjected to the reforming process.
  • the heating of the reaction chamber 16 of the reforming reactor 3 via a reaction chamber 16 surrounding the heating jacket 17 which is flowed through by the hot flue gas of about 1100 ° C of the gas burner 4 and the reaction chamber 14 is heated accordingly.
  • the product gas produced in the reaction chamber 16 by reforming is purified in the product gas purification unit 6 and sent to a product gas outlet 8 as a second process product.
  • the fuel required for the operation of the gas burner is a partial flow of the product gas which is supplied to the gas burner 4 via a gas line 19.
  • the gas burner 4 is further associated with an air supply 20, via which the gas burner is supplied with air.
  • the amount of flue gas and flue gas temperature generated in the gas burner 4 can be controlled very accurately, whereby it is possible to precisely control the heat supplied to the reaction chamber 16 of the reforming reactor 3.
  • a part of the exhaust gas stream can also be recycled into the furnace. In this way, one can advantageously return a portion of the sensible heat from the exhaust gas to the process.
  • the exhaust gas from the heating jacket 17 is supplied via an exhaust pipe 21 to the preheater 1 to its heating.
  • This exhaust still has a temperature of about 860 ° C, which is sufficient to heat the heat carrier located in the preheater 1 8 to the required about 750 ° C.
  • steam is additionally introduced into the pyrolysis reactor 2.
  • This additional steam is generated in a steam generator 7, which is expediently heated with the exhaust gas 22 from the preheater 1.
  • the additional steam generated in the steam generator 7 is input via a steam line 23 from below into the pyrolysis reactor 2.
  • the amount of steam can be controlled by the fact that the steam generator 7 via a water supply valve 24, a targeted amount of water is supplied.
  • a coke firing 34 which can be heated via a Kokstechnisch 37 with the pyrolysis or a subset of the pyrolysis coke produced.
  • the heating with product gas shown in FIG. 1 and the heating with pyrolysis coke shown in FIG. 2 can also be combined with one another so that the system can be combined with product gas, pyrolysis coke or combined heating with both heating means.
  • the reforming reactor 3 is designed as a moving bed reactor, which operates with a circulating high-temperature heat carrier 40, which consists of particularly temperature-stable ceramic balls, first in one of the flue gas of a gas burner (cf., the gas burner 4 shown in Figure 1) / or a coke-firing (cf the coke-fired furnace 34 of Figure 2) are heated and thereafter pass through a reaction chamber 42 through which the pyrolysis-gas-vapor mixture flows in order to release the heat absorbed in the preheating chamber 41, and then into the furnace via an elevator 43 Voricarmhunt 41 to be returned. Because the high-temperature heat carrier 40 comes into contact exclusively with gases here, there are hardly any disturbing solids in the moving bed reactor or at its high-temperature heat carrier 40, so that the reforming process can be controlled very precisely.
  • a gas burner cf., the gas burner 4 shown in Figure 1
  • a coke-firing cf the coke-fired furnace 34 of Figure 2
  • the flue gas used for the heating of the reforming reactor is then fed to the preheater 1 of the pyrolysis reactor 2.
  • the embodiment according to FIG. 4 additionally deals with the problem of using the sensible heat from the product gas.
  • the preheater 1 resulting from FIG. 1 has been subdivided into two preheating chambers 1a and 1b. Both preheat chambers 1a and 1b are passed through by the heat carrier 8 and are connected to each other by a solids sluice.
  • the preheating chamber 1a is - as in the embodiment of Figure 1 - heated by the flue gas from the heating jacket 17 of the reforming reactor 3.
  • the preheating chamber 1b is heated by the product gas flowing through it, which senses its sensible heat the heat carrier 8 delivers and only then the product gas cleaning 6 is supplied.
  • FIG. 5 An alternative to the use of sensible heat from the product gas is shown in FIG 5.
  • the resulting from Figure 3 preheating 41 of the moving bed reactor has been divided into two Vormérmhuntn 41 a and 41 b, which are separated from each other by a solids sluice and are traversed by the high-temperature heat transfer 40 ,
  • the preheating chamber 41a is heated by the flue gas of the coke firing 34 as in the exemplary embodiment according to FIG. 3, while the preheating chamber 41b is heated by the product gas which is supplied via a connecting line 44 between the reaction chamber 42 and the preheating chamber 41b and then via a connecting line 45 the product cleaning 6 is supplied.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

Process for the pyrolysis of hydrous organic feedstock, more particularly of organic wastes and biomass, featuring the following process steps: - a circulated inert heat-transfer medium (8) in piece form is heated in a preheater (1), - the heated heat-transfer medium (8) is introduced simultaneously with the hydrous feedstock into a pyrolysis reactor (2), - in the pyrolysis reactor (2) the feedstock is pyrolyzed, optionally with further addition of steam, - the mixture of pyrolysis gas and steam that is formed in the pyrolysis reactor (2) is reformed in a reforming reactor (3) to give a product gas having a high hydrogen content (first end product), - the pyrolysis coke (2) produced in the pyrolysis reactor is discharged from the pyrolysis reactor (2) together with the heat-transfer medium (8) and is separated off from the heat-transfer medium, and - the heat-transfer medium (8) separated off is recycled into the preheater (1). In order, in this process, to reduce the height of the plant construction and to avoid disruptively high temperatures in the region of the heat-transfer medium circuit, the invention proposes that the reforming reactor (3) is arranged separately from the heat-transfer medium circuit and is heated separately from said circuit.

Description

Verfahren zur Pyrolyse von organischem Einsatzmaterial  Process for pyrolysis of organic feedstock
Die Erfindung betrifft ein Verfahren zur Pyrolyse von wasserhaltigem organischem Einsatzmaterial, insbesondere von organischen Abfällen und Biomasse, mit folgenden Verfahrensschritten: a) ein im Kreislauf gefahrener, stückiger inerter Wärmeträger wird in einem Vorwärmer erhitzt, b) der erhitzte Wärmeträger wird gleichzeitig mit dem wasserhaltigen Einsatzmaterial in einen Pyrolysereaktor eingegeben, c) in dem Pyrolysereaktor wird das Einsatzmaterial ggf. unter weiterer Zugabe von Wasserdampf pyrolysiert, d) das in dem Pyrolysereaktor gebildete Gemisch aus Pyrolysegas und Wasserdampf wird in einem Reformierungsreaktor zu einem Produktgas mit hohem Wasserstoffgehalt (erstes Endprodukt) reformiert, e) der in dem Pyrolysereaktor entstandene Pyrolysekoks (zweites Endprodukt) wird zusammen mit dem Wärmeträger aus dem Pyrolysereaktor ausgetragen und von dem Wärmeträger abgetrennt, und f) der abgetrennte Wärmeträger wird in den Vorwärmer zurückgeführt. The invention relates to a process for pyrolysis of hydrous organic feedstock, in particular of organic waste and biomass, with the following process steps: a) a lumped inert heat transfer medium circulated in the circuit is heated in a preheater, b) the heated heat transfer medium is mixed with the hydrous feedstock c) in the pyrolysis reactor, the feedstock is optionally pyrolyzed with further addition of steam, d) the mixture of pyrolysis gas and water vapor formed in the pyrolysis reactor is reformed in a reforming reactor into a product gas having a high hydrogen content (first end product), e) the pyrolysis coke formed in the pyrolysis reactor (second end product) is discharged out of the pyrolysis reactor together with the heat carrier and separated from the heat carrier, and f) the separated heat carrier is returned to the preheater.
Ein derartiges Verfahren ist beispielsweise aus der EP 1 337 607 bekannt und in der Anlage„Blauer Turm" (vgl. www.blue-tower.de) verwirklicht. Bei dem be- kannten Verfahren wird der Wärmeträger, der z. B. aus hitzebeständigen Keramikkugeln bestehen kann, in dem Vorwärmer mit Hilfe von Rauchgas aus einer Feuerung auf ca. 1100°C erhitzt und in diesem Zustand über eine Feststoffschleuse in den unter dem Vorwärmer befindlichen Reformierungsreaktor eingegeben, um dort die für die Reformierung erforderliche Wärme im erforderlichen Temperaturbereich einzutragen. Beim Durchtritt durch den Reformierungsreaktor kühlt sich der Wärmeträger bis auf das für die Beheizung des Pyrolysereaktors erforderliche Temperaturniveau (ca. 750°C) ab und wird wiederum über eine Dosiervorrichtung in den darunter befindlichen Pyrolysereaktor eingegeben, dem gleichzeitig das Einsatzmaterial zugeführt wird. Anschließend durchläuft der Wärmeträger zusammen mit dem Einsatzmaterial den Pyrolysereaktor und wird zusammen mit dem bei der Pyrolyse entstehenden Pyrolysekoks unten aus dem Pyrolysereaktor ausgetragen, und zwar mit einer Temperatur von etwa 600°C. Nach Abtrennung des Pyrolysekokses von dem Wärmeträger wird der Wärmeträger sodann mittels eines Elevators nach oben gefördert und über eine Schleuse erneut von oben in den Vorwärmer eingegeben. Falls die mit dem wasserhaltigen Einsatzmaterial zugesetzte Wassermenge für die Reformierung nicht ausreicht, wird dem Pyrolysereaktor zusätzlich noch Dampf zugeführt. Such a method is known, for example, from EP 1 337 607 and embodied in the appendix "Blauer Turm" (see www.blue-tower.de). knew method is the heat carrier, the z. B. may consist of heat-resistant ceramic balls, heated in the preheater with the aid of flue gas from a furnace to about 1100 ° C and entered in this state via a solids lock in the reforming reactor located below the preheater to there the heat required for the reforming in the enter required temperature range. As it passes through the reforming reactor, the heat transfer medium cools down to the temperature level required for heating the pyrolysis reactor (about 750 ° C.) and is in turn introduced via a metering device into the pyrolysis reactor underneath, to which the feed material is simultaneously supplied. The heat transfer medium then passes through the pyrolysis reactor together with the feedstock and, together with the pyrolysis coke produced during the pyrolysis, is discharged from the bottom of the pyrolysis reactor at a temperature of about 600.degree. After separation of the pyrolysis coke from the heat carrier, the heat carrier is then conveyed by means of an elevator up and entered via a lock again from above into the preheater. If the amount of water added to the hydrous feed is insufficient to reform, steam is also added to the pyrolysis reactor.
Beim Erprobungsbetrieb der oben genannten Anlage hat sich eine Reihe von Problemen herausgestellt. Zum einen hat die Anlage aufgrund der Führung des Wärmeträgerkreislaufs zwangsläufig eine verhältnismäßig große Bauhöhe, so dass der Wärmeträger für die Zurückführung in den Vorwärmer über einen verhältnismäßig langen Förderweg angehoben werden muss, was sowohl energetisch als auch verschleißtechnisch ungünstig ist. Zum anderen muss der Wärmeträger in dem Vorwärmer bis auf 1100°C erhitzt werden, d.h. bis in den Bereich der hellen Gelbglut, wodurch die Lebensdauer einerseits des Wärmeträgers und andererseits der den Wärmeträger führenden Anlageteile, insbesondere der Feststoffschleusen, stark beeinträchtigt werden kann. Schließlich ist bei dem bekannten Verfahren der Reformierungsprozess in Folge der im Reformierungsreaktor ständig präsenten großen Wärmeträgermasse nur noch schlecht steuerbar und somit schlecht beherrschbar. Es ist somit Aufgabe der Erfindung, das Verfahren der eingangs genannten Art dahingehend weiterzubilden, dass die Bauhöhe der Anlage verringert werden kann und störend hohe Temperaturen im Bereich des Wärmeträgerkreislaufs vermieden werden. Schließlich soll es besser möglich sein, den Reformierungs- prozess durch eine genauere Temperatursteuerung im Hinblick auf ein besseres Produktausbringen und auf einen hohen Wasserstoffgehalt im Produktgas zu optimieren. In the trial operation of the above-mentioned system, a number of problems has been found. On the one hand, the system inevitably has a relatively large overall height due to the guidance of the heat transfer circuit, so that the heat transfer medium for the return to the preheater must be lifted over a relatively long conveying path, which is unfavorable both energetically and wear. On the other hand, the heat transfer medium must be heated in the preheater up to 1100 ° C, ie up to the range of bright yellow heat, whereby the life of the one part of the heat carrier and the other part of the heat carrier leading plant parts, especially the solids sluices, can be greatly affected. Finally, in the known method of reforming process as a result of constantly present in the reforming reactor large heat transfer medium only poorly controllable and thus difficult to control. It is therefore an object of the invention to develop the method of the type mentioned in that the height of the system can be reduced and disturbing high temperatures in the heat transfer circuit can be avoided. Finally, it should be better possible to optimize the reforming process by a more accurate temperature control with a view to a better product yield and to a high hydrogen content in the product gas.
Zur Lösung dieser Aufgabe schlägt die Erfindung ausgehend von dem Verfahren der eingangs genannten Art vor, g) dass der Reformierungsreaktor separat vom Wärmeträgerkreislauf angeordnet ist und separat von diesem beheizt wird. To solve this problem, the invention proposes starting from the method of the type mentioned above, g) that the reforming reactor is arranged separately from the heat transfer circuit and is heated separately from this.
Beim Verfahren gemäß der Erfindung umfasst der Wärmeträgerkreislauf nur noch den Vorwärmer und den Pyrolysereaktor. Infolgedessen verringert sich die notwendige Bauhöhe der Anlage etwa um die Höhe des Reformierungsreaktors. Wegen der verringerten Bauhöhe verkürzt sich der Förderweg für die Rückführung des Wärmeträgers entsprechend. Weiterhin wird beim Verfahren gemäß der Erfindung der Wärmeträger nur noch auf die Eintrittstemperatur in den Pyrolysereaktor, d. h. auf ca. 800°C erhitzt. Hierdurch vermindert sich der Verschleiß am Wärmeträger und an den Führungs- und Transportmitteln für den Wärmeträger entsprechend. In the method according to the invention, the heat transfer circuit comprises only the preheater and the pyrolysis reactor. As a result, the necessary height of the plant is reduced by about the height of the reforming reactor. Because of the reduced height, the delivery path for the return of the heat carrier is shortened accordingly. Furthermore, in the method according to the invention, the heat transfer medium only to the inlet temperature in the pyrolysis reactor, d. H. heated to about 800 ° C. As a result, the wear on the heat transfer medium and on the guide and transport means for the heat transfer medium decreases accordingly.
Dadurch, dass beim Verfahren gemäß der Erfindung der Reformierungsreaktor separat vom Wärmeträgerkreislauf und Pyrolysekoks beheizt wird, lässt sich der Reformierungsprozess im Hinblick auf ein optimiertes Produktausbringen (Produktgas oder Pyrolysekoks) wesentlich genauer steuern und auf einen möglichst hohen Wasserstoffgehalt im Produktgas optimieren. Because the reforming reactor is heated separately from the heat transfer medium circuit and pyrolysis coke in the process according to the invention, the reforming process can be controlled much more precisely with regard to optimized product discharge (product gas or pyrolysis coke) and optimized for the highest possible hydrogen content in the product gas.
Eine erste, zweckmäßige Ausführungsform der Erfindung sieht vor, dass eine Teilmenge des Produktgases abgezweigt wird und in einem Gasbrenner verbrannt wird, dessen Rauchgas zunächst den Reformierungsreaktor und anschließend den Wärmeträger im Vorwärmer erhitzt. Hierdurch bleibt das Verfahren energieautark und ermöglicht ein optimiertes Ausbringen an Pyrolyse- koks. Das ist insbesondere an Standorten wichtig, wo der Pyrolysekoks in der Landwirtschaft z. B. zur Bodenverbesserung benötigt wird. A first, expedient embodiment of the invention provides that a subset of the product gas is diverted and is burned in a gas burner whose flue gas first heats the reforming reactor and then the heat carrier in the preheater. As a result, the process remains energy self-sufficient and enables optimized application to pyrolysis coke. This is particularly important in locations where the pyrolysis in agriculture z. B. is needed for soil improvement.
Eine zweite zweckmäßige Ausführungsform der Erfindung sieht vor, dass der gesamte Pyrolysekoks oder eine abgetrennte Teilmenge des Pyrolysekokses in einer Koksfeuerung verbrannt wird, deren Rauchgas zunächst den Reformie- rungsreaktor und anschließend den Wärmeträger im Vorwärmer beheizt. Auch hierbei bleibt das Verfahren energieautark und ermöglich ein optimiertes Ausbringen an Wasserstoff haltigem Pyrolysegas. Das ist insbesondere an Standorten wichtig, wo man z. B. mit einer Gasturbine oder einem Gasmotor Strom erzeugen will, z. B. um die Stromerzeugungslücken von stromerzeugenden Solaranlagen auszufüllen. A second expedient embodiment of the invention provides that the entire pyrolysis coke or a separated subset of the pyrolysis coke is incinerated in a coke furnace whose flue gas first heats the reforming reactor and then the heat carrier in the preheater. Again, the process remains energy self-sufficient and allows optimized application of hydrogen-containing pyrolysis gas. This is especially important in locations where z. B. wants to generate electricity with a gas turbine or a gas engine, z. B. to fill the power generation gaps of electricity generating solar systems.
Gegebenenfalls kann man auch die beiden zuletzt diskutierten Ausführungsformen der Beheizung des Reformierungsreaktors miteinander kombinieren, um je nach Bedarf und/oder Jahreszeit mehr Produktgas oder mehr Pyrolysekoks erzeugen zu können. Optionally, it is also possible to combine the two last-discussed embodiments of the heating of the reforming reactor with one another in order to be able to produce more product gas or more pyrolysis coke as required and / or season.
Schließlich kann man die Menge des entstehenden Pyrolysekokses auch dadurch beeinflussen, dass man in den Pyrolysereaktor Luft, Sauerstoff oder ein Gemisch aus Luft und Sauerstoff eingibt. Hierdurch ergibt sich in dem Pyrolysereaktor zusätzlich eine genau steuerbare unterstöchiometrische Verbrennung, die einen Teil des Kohlenstoffs vergast und zusätzlich Wärme in den Pyrolysereaktor einträgt. Finally, one can also influence the amount of pyrolysis coke formed by adding air, oxygen or a mixture of air and oxygen into the pyrolysis reactor. This results in the pyrolysis additionally a precisely controllable substoichiometric combustion, which gasifies a portion of the carbon and additionally enters heat in the pyrolysis reactor.
Der Reformierungsprozess kann in beiden Fällen - und zwar unabhängig von der jeweiligen Energiequelle - in einer von außen beheizten Reaktionskammer des Reformierungsreaktors erfolgen. Das hat den Vorteil, dass der Reformierungsprozess allein in der Gasphase ohne Störung durch durchlaufende Feststoffe bewerkstelligt werden kann, ggf. in Anwesenheit eines Katalysators, der sich in dem Reaktionsraum des Reformierungsreaktors befindet. Durch die Anwesenheit eines geeigneten Katalysators lässt sich der Reformierungsprozess bekanntlich erheblich intensivieren. Anstelle einer von außen beheizten Reaktionskammer kann der Reformierungs- prozess aber auch in einem Wanderbettreaktor erfolgen, dessen umlaufender Hochtemperatur-Wärmeträger zunächst eine vom Rauchgas des Gasbrenners und/oder der Koksfeuerung beheizte Vorwärmkammer und danach eine davon durch eine Feststoff schleuse abgetrennte Reaktionskammer durchläuft, die vom zu reformierenden Pyrolysegas durchströmt wird. Auch in dieser Ausführungsform kann dem umlaufenden Wärmeträger ein Katalysator zugesetzt werden, der nicht vom Einsatzmaterial verschmutzt wird und gegebenenfalls außerhalb des Reformierungsreaktors thermisch, chemisch oder mechanisch reaktiviert werden kann oder ganz oder teilweise ersetzt werden kann. The reforming process can in both cases - regardless of the particular energy source - take place in an externally heated reaction chamber of the reforming reactor. This has the advantage that the reforming process can be accomplished alone in the gas phase without interference by passing solids, if necessary in the presence of a catalyst which is located in the reaction space of the reforming reactor. Due to the presence of a suitable catalyst, it is known that the reforming process can be considerably intensified. Instead of an externally heated reaction chamber but the reforming process can also be carried out in a moving bed reactor, the circulating high-temperature heat transfer medium first by the flue gas of the gas burner and / or the coke firing heated preheating and then one of them through a solids sluice separated reaction chamber, the from flows through to be reformed pyrolysis gas. In this embodiment as well, it is possible to add to the circulating heat transfer medium a catalyst which is not polluted by the feedstock and can optionally be thermally, chemically or mechanically reactivated outside the reforming reactor or can be completely or partially replaced.
Um auch die fühlbare Wärme aus dem Produktgas zu nutzen, kann weiterhin vorgesehen sein, dass der dem Pyrolysereaktor vorgeschaltete Vorwärmer in zwei Vorwärmerkammern unterteilt ist, die aufeinanderfolgend vom Wärmeträger durchlaufen werden und von denen die eine vom durchgeleiteten Pyrolysegas und die andere vom durchgeleiteten Rauchgas aus dem Reformierungs- reaktor beheizt wird. In order to use the sensible heat from the product gas, it may further be provided that the preheater upstream of the pyrolysis reactor is subdivided into two preheating chambers, which are successively passed through by the heat transfer medium and of which the one from the pyrolysis gas passed through and the other from the passed flue gas from the Reforming reactor is heated.
Zum gleichen Zweck kann alternativ hierzu oder auch zusätzlich hierzu auch die Vorwärmkammer des Wanderbettreaktors in zwei Vorwärmkammern unterteilt sein, die aufeinanderfolgend vom Hochtemperatur-Wärmeträger durchlaufen werden und von denen die eine vom durchlaufenden Produktgas und die andere vom Rauchgas des Gasbrenners und/oder der Koksfeuerung beheizt wird. For the same purpose, alternatively or in addition thereto, the preheating chamber of the moving bed reactor may also be subdivided into two preheating chambers, which are successively passed through by the high-temperature heat carrier and one of which heats the product gas passing through it and the other from the flue gas of the gas burner and / or coke firing becomes.
Um schließlich auch die fühlbare Wärme aus dem Abgas zu entnehmen, ist schließlich vorgesehen, dass mit dem Abgas aus dem Vorwärmer Dampf für die Reformierung erzeugt wird. Finally, to remove the sensible heat from the exhaust gas, it is finally provided that steam is generated for the reforming with the exhaust gas from the preheater.
Drei Ausführungsbeispiele der Erfindung werden im Folgenden anhand der Zeichnung näher erläutert. Es zeigen: Three embodiments of the invention will be explained in more detail below with reference to the drawing. Show it:
Fig. 1 : Schematisch das Verfahren gemäß der Fig. 1: Schematically the method according to the
Erfindung in einer ersten Ausführungsform; Fig. 2: schematisch das Verfahren gemäß der Invention in a first embodiment; 2 shows schematically the method according to the
Erfindung in einer zweiten Ausführungsform;  Invention in a second embodiment;
Fig. 3: schematisch das Verfahren gemäß der 3 shows schematically the method according to the
Erfindung in einer dritten Ausführungsform;  Invention in a third embodiment;
Fig. 4: schematisch das Verfahren gemäß der 4 shows schematically the method according to the
Erfindung in einer vierten Ausführungsform;  Invention in a fourth embodiment;
Fig. 5: schematisch das Verfahren gemäß der 5 shows schematically the method according to the
Erfindung in einer fünften Ausführungsform.  Invention in a fifth embodiment.
In Figur 1 der Zeichnung sind ein Vorwärmer mit dem Bezugszeichen 1 , ein Pyrolysereaktor mit dem Bezugszeichen 2 und ein Reformierungsreaktor mit dem Bezugszeichen 3 bezeichnet. Weiterhin umfasst die Anlage einen Gasbrenner 4, eine Siebanlage 5, eine Produktgasreinigung 6 und einen Dampferzeuger 7. In FIG. 1 of the drawing, a preheater with the reference numeral 1, a pyrolysis reactor with the reference numeral 2 and a reforming reactor with the reference numeral 3 are designated. Furthermore, the plant comprises a gas burner 4, a sieve 5, a product gas purification 6 and a steam generator 7.
Der Wärmeträger 8 wird von feuerfesten Keramikkugeln gebildet, die sich zum größten Teil in loser Schüttung in dem Vorwärmer 1 und dem Pyrolysereaktor 2 befinden. Der Wärmeträger 8 wird kontinuierlich im Kreislauf gefahren und wandert dabei langsam von oben nach unten zunächst durch den Vorwärmer 1 und anschließend durch den Pyrolysereaktor 2, danach als Siebrückhalt über die Siebanlage 5 und über einen Elevator 9 zurück nach oben in den Vorwärmer 1. The heat carrier 8 is formed by refractory ceramic balls, which are located for the most part in bulk in the preheater 1 and the pyrolysis reactor 2. The heat transfer medium 8 is circulated continuously and moves slowly from top to bottom first through the preheater 1 and then through the pyrolysis reactor 2, then as Siebrückhalt on the screen 5 and an elevator 9 back up into the preheater. 1
Zwischen dem Vorwärmer 1 und dem Pyrolysereaktor 2 zwischen der Siebanlage 5 und dem Elevator 9 und zwischen dem Elevator 9 und dem Vorwärmer 1 sind jeweils nicht näher dargestellte, gasdichte Feststoffschleusen 10 für den Durchtritt des Wärmeträgers 8 vorgesehen. Between the preheater 1 and the pyrolysis reactor 2 between the screening plant 5 and the elevator 9 and between the elevator 9 and the preheater 1 are each not shown in detail, gas-tight solids sluices 10 are provided for the passage of the heat carrier 8.
Der Wärmeträger 8 wird im Vorwärmer 1 auf etwa 800°C erhitzt und mit dieser Temperatur von oben in den Pyrolysereaktor 2 eingegeben. Zugleich mit dem Wärmeträger 8 wird in den Pyrolysereaktor 2 über eine Zugabevorrichtung 11 das zu pyrolysierende wasserhaltige organische Einsatzmaterial in Form von organischen Abfällen oder Biomasse eingegeben. Außerdem kann, um die entstehende Menge von Pyrolysekoks zu beeinflussen, mittels einer Zugabevorrichtung 12 Luft oder Sauerstoff oder ein Gemisch aus Luft und Sauerstoff in den Pyrolysereaktor eingegeben werden. The heat transfer medium 8 is heated in the preheater 1 to about 800 ° C and entered at this temperature from above into the pyrolysis reactor 2. At the same time with the heat transfer medium 8 is in the pyrolysis reactor 2 via an adding device 11 to be pyrolyzed water-containing organic feedstock in the form of organic waste or biomass input. In addition, in order to influence the resulting amount of pyrolysis coke, air or oxygen or a mixture of air and oxygen may be introduced into the pyrolysis reactor by means of an adding device 12.
Auf seinem Weg durch den Pyrolysereaktor 2 wird dieses Einsatzmaterial unter Zugabe von Wasserdampf pyrolysiert. Die für die Pyrolyse erforderliche Energie liefert der Wärmeträger 8, der sich dementsprechend im Pyrolysereaktor 2 von 800°C auf 600°C abkühlt. Falls Luft und/oder Sauerstoff zugegeben werden, findet in dem Pyrolysereaktor 2 außerdem eine unterstöchiometrische Verbrennung von Kohlenstoff statt, wodurch gegebenenfalls zusätzlich Wärme in den Pyrolysereaktor eingetragen wird. On its way through the pyrolysis reactor 2, this feedstock is pyrolyzed with the addition of water vapor. The energy required for the pyrolysis provides the heat transfer medium 8, which accordingly cools in the pyrolysis reactor 2 from 800 ° C to 600 ° C. If air and / or oxygen are added, a stoichiometric combustion of carbon also takes place in the pyrolysis reactor 2, whereby optionally additional heat is introduced into the pyrolysis reactor.
Das im Pyrolysereaktor 2 gebildete Pyrolysegas-Wasserdampf-Gemisch verläset, wie durch den Pfeil 13 angedeutet, den Pyrolysereaktor 2 mit etwa 630°C in Richtung auf den Reform ierungsreaktor 3 und wird dort weiter behandelt, wie weiter unten noch erläutert wird. The pyrolysis gas-steam mixture formed in the pyrolysis reactor 2, as indicated by the arrow 13, leaves the pyrolysis reactor 2 at about 630 ° C. in the direction of the reforming reactor 3 and is further treated there, as will be explained below.
Der bei der Pyrolyse gebildete Pyrolysekoks wird zusammen mit dem Wärmeträger 8 über eine nach dem Pyrolysereaktor 2 angeordnete Austragsvorrichtung 14 zusammen mit dem Wärmeträger 8 ausgetragen und auf die Siebanlage 5 aufgegeben. Dort wird der Wärmeträger 8 als Siebrückhalt zurückgehalten und dem Elevator 9 zugeführt, der den Wärmeträger 8 nach oben fördert und von oben über die Feststoffschleuse 10 in den Vorwärmer 1 eingibt. Der als Siebdurchlauf abgetrennte Pyrolysekoks wird demgegenüber zu einer Produktausgabe 15 gefördert und dort als erstes Produkt des Verfahrens ausgegeben. The pyrolysis coke formed during the pyrolysis is discharged together with the heat transfer medium 8 via a discharge device 14 arranged downstream of the pyrolysis reactor 2 together with the heat transfer medium 8 and applied to the screening plant 5. There, the heat carrier 8 is retained as Siebrückhalt and fed to the elevator 9, which promotes the heat carrier 8 upwards and enters from above through the solids lock 10 in the preheater 1. In contrast, the pyrolysis coke separated off as a screen pass is conveyed to a product dispenser 15 where it is dispensed as the first product of the process.
Das oben aus dem Pyrolysereaktor 2 austretende Pyrolysegas-Wasserdampf- Gemisch wird in eine von außen beheizte, separate Reaktionskammer 16 des Reformierungsreaktors 3 eingegeben und dort dem Reformierungsprozess unterzogen. Die Beheizung der Reaktionskammer 16 des Reformierungsreaktors 3 erfolgt über einen die Reaktionskammer 16 umgebenden Heizmantel 17, der vom etwa 1100°C heißen Rauchgas des Gasbrenners 4 durchströmt wird und die Reaktionskammer 14 entsprechend beheizt. Das in der Reaktionskammer 16 durch Reformierung erzeugte Produktgas wird in der Produktgasreinigungsanlage 6 gereinigt und an eine Produktgasausgabe 8 als zweites Verfahrensprodukt weitergeleitet. The above emerging from the pyrolysis reactor 2 pyrolysis gas-steam mixture is entered into a heated from the outside, separate reaction chamber 16 of the reforming reactor 3 and there subjected to the reforming process. The heating of the reaction chamber 16 of the reforming reactor 3 via a reaction chamber 16 surrounding the heating jacket 17 which is flowed through by the hot flue gas of about 1100 ° C of the gas burner 4 and the reaction chamber 14 is heated accordingly. The product gas produced in the reaction chamber 16 by reforming is purified in the product gas purification unit 6 and sent to a product gas outlet 8 as a second process product.
Der für den Betrieb des Gasbrenners benötigte Brennstoff ist ein Teilstrom des Produktgases, welcher dem Gasbrenner 4 über eine Gasleitung 19 zugeführt wird. Dem Gasbrenner 4 ist weiterhin eine Luftzuführung 20 zugeordnet, über die der Gasbrenner mit Luft versorgt wird. Über eine genaue Steuerung der Luft- und Gaszufuhr des Gasbrenners 4 kann die in dem Gasbrenner 4 erzeugte Rauchgasmenge und Rauchgastemperatur sehr genau gesteuert werden, wodurch es möglich ist, auch die der Reaktionskammer 16 des Reformierungs- reaktors 3 zugeführt Wärme genau zu steuern. Zum gleichen Zweck kann auch ein Teil des Abgasstroms in die Feuerung recycelt werden. Auf diese Weise kann man vorteilhafterweise einen Teil der fühlbaren Wärme aus dem Abgas in den Prozess zurückführen. The fuel required for the operation of the gas burner is a partial flow of the product gas which is supplied to the gas burner 4 via a gas line 19. The gas burner 4 is further associated with an air supply 20, via which the gas burner is supplied with air. By precise control of the air and gas supply of the gas burner 4, the amount of flue gas and flue gas temperature generated in the gas burner 4 can be controlled very accurately, whereby it is possible to precisely control the heat supplied to the reaction chamber 16 of the reforming reactor 3. For the same purpose, a part of the exhaust gas stream can also be recycled into the furnace. In this way, one can advantageously return a portion of the sensible heat from the exhaust gas to the process.
Das Abgas aus dem Heizmantel 17 wird über eine Abgasleitung 21 dem Vorwärmer 1 zu dessen Beheizung zugeführt. Dieses Abgas hat immer noch eine Temperatur von ca. 860°C, was ausreicht, den im Vorwärmer 1 befindlichen Wärmeträger 8 auf die erforderlichen ca. 750°C zu erwärmen. The exhaust gas from the heating jacket 17 is supplied via an exhaust pipe 21 to the preheater 1 to its heating. This exhaust still has a temperature of about 860 ° C, which is sufficient to heat the heat carrier located in the preheater 1 8 to the required about 750 ° C.
Weil die dem Pyrolysereaktor 2 zusammen mit dem Einsatzmaterial zugeführte Wassermenge bisweilen nicht ausreicht, eine für die Reformierung ausreichende Wasserdampfmenge zur Verfügung zu stellen, wird weiterhin in den Pyrolysereaktor 2 zusätzlich Dampf eingegeben. Dieser zusätzliche Dampf wird in einem Dampferzeuger 7 erzeugt, der zweckmäßig mit dem Abgas 22 aus dem Vorwärmer 1 beheizt wird. Der im Dampferzeuger 7 erzeugte zusätzliche Dampf wird über eine Dampfleitung 23 von unten in den Pyrolysereaktor 2 eingegeben. Die Dampfmenge kann dabei dadurch gesteuert werden, dass dem Dampferzeuger 7 über ein Wasserzuführungsventil 24 eine gezielte Menge Wasser zugeführt wird. Because the amount of water supplied to the pyrolysis reactor 2 together with the feed material is sometimes insufficient to provide a sufficient amount of steam for reforming, steam is additionally introduced into the pyrolysis reactor 2. This additional steam is generated in a steam generator 7, which is expediently heated with the exhaust gas 22 from the preheater 1. The additional steam generated in the steam generator 7 is input via a steam line 23 from below into the pyrolysis reactor 2. The amount of steam can be controlled by the fact that the steam generator 7 via a water supply valve 24, a targeted amount of water is supplied.
Beim Ausführungsbeispiel der Figur 2 tritt an die Stelle des Gasbrenners 4 eine Koksfeuerung 34, die über eine Koksleitung 37 mit dem Pyrolysekoks oder einer Teilmenge des erzeugten Pyrolysekokses beheizt werden kann. Die in Figur 1 gezeigte Beheizung mit Produktgas und die in Figur 2 gezeigte Beheizung mit Pyrolysekoks können im Bedarfsfall auch miteinander kombiniert werden, so dass man die Anlage je nach Bedarf mit Produktgas, Pyrolysekoks oder auch mit beiden Heizmitteln kombiniert beheizen kann. Erforderlichenfalls können auch Heizmittel verwendet werden, die nicht aus der Anlage stammen. Letzteres ist aber nur sinnvoll, wenn solche Heizmittel kostengünstig zur Verfügung stehen. In the embodiment of Figure 2 occurs in the place of the gas burner 4, a coke firing 34, which can be heated via a Koksleitung 37 with the pyrolysis or a subset of the pyrolysis coke produced. If necessary, the heating with product gas shown in FIG. 1 and the heating with pyrolysis coke shown in FIG. 2 can also be combined with one another so that the system can be combined with product gas, pyrolysis coke or combined heating with both heating means. If necessary, it is also possible to use heating means that are not from the plant. The latter is only useful if such heating means are available at low cost.
Beim Ausführungsbeispiel gemäß Figur 3 ist der Reformierungsreaktor 3 als Wanderbettreaktor ausgebildet, der mit einem umlaufenden Hochtemperatur- Wärmeträger 40 arbeitet, der aus besonders temperaturstabilen Keramikkügelchen besteht, die zunächst in einer vom Rauchgas eines Gasbrenners (vgl. den in Figur 1 dargestellten Gasbrenner 4) und/oder einer Koksfeuerung (vgl. die Koksfeuerung 34 von Figur 2) beheizten Vorwärmkammer 41 aufgeheizt werden und danach eine vom Pyrolysegas-Wasserdampfgemisch durchströmte Reaktionskammer 42 durchwandern, um dabei die in der Vorwärmkammer 41 aufgenommene Wärme abzugeben, und anschließend über einen Elevator 43 in die Vorwärmkammer 41 zurückgeführt zu werden. Dadurch, dass der Hochtemperatur-Wärmeträger 40 hier ausschließlich mit Gasen in Berührung kommt, gibt es kaum störende Feststoffe in dem Wanderbettreaktor oder an dessen Hochtemperatur-Wärmeträger 40, so dass sich der Reformierungsprozess sehr genau steuern lässt. In the embodiment according to Figure 3, the reforming reactor 3 is designed as a moving bed reactor, which operates with a circulating high-temperature heat carrier 40, which consists of particularly temperature-stable ceramic balls, first in one of the flue gas of a gas burner (cf., the gas burner 4 shown in Figure 1) / or a coke-firing (cf the coke-fired furnace 34 of Figure 2) are heated and thereafter pass through a reaction chamber 42 through which the pyrolysis-gas-vapor mixture flows in order to release the heat absorbed in the preheating chamber 41, and then into the furnace via an elevator 43 Vorwärmkammer 41 to be returned. Because the high-temperature heat carrier 40 comes into contact exclusively with gases here, there are hardly any disturbing solids in the moving bed reactor or at its high-temperature heat carrier 40, so that the reforming process can be controlled very precisely.
Auch hier wird das für die Beheizung des Reformierungsreaktors verwendete Rauchgas anschließend dem Vorwärmer 1 des Pyrolysereaktors 2 zugeführt. Again, the flue gas used for the heating of the reforming reactor is then fed to the preheater 1 of the pyrolysis reactor 2.
Das Ausführungsbeispiel gemäß Figur 4 befasst sich zusätzlich mit dem Problem der Nutzung der fühlbaren Wärme aus dem Produktgas. Hierzu ist der aus Figur 1 hervorgehende Vorwärmer 1 in zwei Vorwärmkammern 1a und 1 b unterteilt worden. Beide Vorwärmkammern 1a und 1b werden vom Wärmeträger 8 durchlaufen und sind durch eine Feststoffschleuse miteinander verbunden. Die Vorwärmkammer 1a wird - wie beim Ausführungsbeispiel gemäß Figur 1 - vom Rauchgas aus dem Heizmantel 17 des Reformierungsreaktors 3 beheizt. Die Vorwärmkammer 1b wird demgegenüber vom durchströmenden Produktgas beheizt, welches seine fühlbare Wärme an den Wärmeträger 8 abgibt und erst danach der Produktgasreinigung 6 zugeführt wird. The embodiment according to FIG. 4 additionally deals with the problem of using the sensible heat from the product gas. For this purpose, the preheater 1 resulting from FIG. 1 has been subdivided into two preheating chambers 1a and 1b. Both preheat chambers 1a and 1b are passed through by the heat carrier 8 and are connected to each other by a solids sluice. The preheating chamber 1a is - as in the embodiment of Figure 1 - heated by the flue gas from the heating jacket 17 of the reforming reactor 3. In contrast, the preheating chamber 1b is heated by the product gas flowing through it, which senses its sensible heat the heat carrier 8 delivers and only then the product gas cleaning 6 is supplied.
Eine Alternative zur Nutzung der fühlbaren Wärme aus dem Produktgas zeigt Figur 5. Dort ist die aus Figur 3 hervorgehende Vorwärmkammer 41 des Wanderbettreaktors in zwei Vorwärmkammern 41a und 41b unterteilt worden, die voneinander durch eine Feststoff schleuse getrennt sind und vom Hochtemperatur-Wärmeträger 40 durchlaufen werden. Dabei wird die eine Vorwärmkammer 41a wie beim Ausführungsbeispiel gemäß Figur 3 vom Rauchgas der Koksfeuerung 34 beheizt, während die Vorwärmkammer 41 b vom Produktgas beheizt wird, welche über eine Verbindungsleitung 44 zwischen der Reaktionskammer 42 und der Vorwärmkammer 41b zugeführt wird und danach über eine Verbindungsleitung 45 der Produktreinigung 6 zugeführt wird. An alternative to the use of sensible heat from the product gas is shown in FIG 5. There, the resulting from Figure 3 preheating 41 of the moving bed reactor has been divided into two Vorwärmkammern 41 a and 41 b, which are separated from each other by a solids sluice and are traversed by the high-temperature heat transfer 40 , The preheating chamber 41a is heated by the flue gas of the coke firing 34 as in the exemplary embodiment according to FIG. 3, while the preheating chamber 41b is heated by the product gas which is supplied via a connecting line 44 between the reaction chamber 42 and the preheating chamber 41b and then via a connecting line 45 the product cleaning 6 is supplied.

Claims

Patentansprüche claims
1. Verfahren zur Pyrolyse von wasserhaltigem organischem Einsatzmaterial, insbesondere von organischen Abfällen und Biomasse, mit folgenden Verfahrensschritten: a) ein im Kreislauf gefahrener, stückiger inerter Wärmeträger wird in einem Vorwärmer (1) erhitzt, b) der erhitzte Wärmeträger (8) wird gleichzeitig mit dem wasserhaltigen Einsatzmaterial in einen Pyrolysereaktor (2) eingegeben, c) in dem Pyrolysereaktor (2) wird das Einsatzmaterial ggf. weitere unter Zugabe von Wasserdampf pyrolysiert, d) das in dem Pyrolysereaktor (2) gebildete Gemisch aus Pyrolysegas und Wasserdampf wird in einem Reformierungsreaktor (3) zu einem Produktgas mit hohem Wasserstoffgehalt (erstes Endprodukt) reformiert, e) der in dem Pyrolysereaktor (2) entstandene Pyrolysekoks (zweites Endprodukt) wird zusammen mit dem Wärmeträger (8) aus dem Pyrolysereaktor (2) ausgetragen und von dem Wärmeträger (8) abgetrennt, und f) der abgetrennte Wärmeträger (8) wird in den Vorwärmer (1) zurückgeführt, 1. A process for pyrolysis of hydrous organic feedstock, in particular of organic waste and biomass, comprising the following process steps: a) a cycled lumped inert heat transfer medium is heated in a preheater (1), b) the heated heat transfer medium (8) is simultaneously c) in the pyrolysis reactor (2), the feed material is optionally pyrolyzed further with the addition of steam, d) the mixture of pyrolysis gas and water vapor formed in the pyrolysis reactor (2) is mixed in a pyrolysis reactor (2) Reforming reactor (3) to a product gas with a high hydrogen content (first end product) reformed, e) in the pyrolysis reactor (2) resulting pyrolysis (second end product) is discharged together with the heat carrier (8) from the pyrolysis reactor (2) and from the heat carrier (8) separated, and f) the separated heat transfer medium (8) is returned to the preheater (1),
d a d u r c h g e k e n n z e i c h n e t, g) dass der Reformierungsreaktor (3) separat vom Wärmeträgerkreislauf angeordnet ist und separat von diesem beheizt wird. characterized, g) that the reforming reactor (3) is arranged separately from the heat transfer circuit and is heated separately from this.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass eine Teilmenge des Produktgases abgezweigt wird und in einem Gasbrenner (4) verbrannt wird, dessen Rauchgas zunächst den Reformierungsreaktor (3) und anschließend den Wärmeträger (8) im Vorwärmer (1 ) beheizt. 2. The method according to claim 1, characterized in that a partial amount of the product gas is diverted and is burned in a gas burner (4), the flue gas first the reforming reactor (3) and then the heat carrier (8) in the preheater (1) heated.
3. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass der Pyrolysekoks oder eine abgetrennte Teilmenge des Pyrolysekokses in einer Koksfeuerung (34) verbrannt wird, deren Rauchgas zunächst den Reformierungsreaktor (3) und anschließend den Wärmeträger (8) im Vorwärmer (1 ) beheizt. 3. The method according to claim 1, characterized in that the pyrolysis or a separated portion of the pyrolysis coke is burned in a coke furnace (34), the flue gas first the reforming reactor (3) and then the heat carrier (8) in the preheater (1) heated.
4. Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass in den Pyrolysereaktor (2) zusätzlich Luft, Sauerstoff oder ein Gemisch aus Luft und Sauerstoff eingegeben werden. 4. The method according to one or more of claims 1 to 3, characterized in that in the pyrolysis reactor (2) additionally air, oxygen or a mixture of air and oxygen are entered.
5. Verfahren nach den Ansprüchen 1 oder 2, dadurch gekennzeichnet, dass der Reformierungsprozess in einer von außen beheizten Reaktionskammer (14) des Reformierungsreaktors (3) erfolgt. 5. Process according to claims 1 or 2, characterized in that the reforming process takes place in an externally heated reaction chamber (14) of the reforming reactor (3).
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass der Reformierungsprozess in der Reaktionskammer (16) des Reformierungsreaktors (3) in Anwesenheit eines Katalysators erfolgt. 6. The method according to claim 5, characterized in that the reforming process in the reaction chamber (16) of the reforming reactor (3) takes place in the presence of a catalyst.
7. Verfahren nach Anspruch 2 und/oder 3, dadurch gekennzeichnet, dass der Reformierungsprozess in einem Wanderbettreaktor erfolgt, dessen umlaufender Hochtemperatur-Wärmeträger (40) zunächst eine vom Rauchgas des Gasbrenners (34) und/oder der Koksfeuerung (4) beheizt Vorwärmkammer (41 ) und danach eine davon durch eine Feststoffschleuse abgetrennte Reaktionskammer (42) durchläuft, die vom zu reformierenden Pyrolysegas durchströmt wird. 7. The method according to claim 2 and / or 3, characterized in that the reforming process takes place in a moving bed reactor, the circulating high-temperature heat transfer medium (40) first one of the flue gas of the gas burner (34) and / or the coke firing (4) heated preheating chamber ( 41) and thereafter one of them through a solids sluice separated reaction chamber (42) passes through which is traversed by the pyrolysis gas to be reformed.
8. Verfahren nach den Ansprüchen 2 und/oder 3, dadurch gekennzeichnet, dass der dem Pyrolysereaktor (2) vorgeschaltete Vorwärmer (1 ) in zwei Vorwärmkammern (1a und 1b) unterteilt ist, die aufeinanderfolgend vom Wärmeträger (8) durchlaufen werden und von denen die eine vom durchgeleiteten Produktgas und die andere vom durchgeleiteten Rauchgas aus dem Reformierungsreaktor beheizt wird. 8. The method according to claims 2 and / or 3, characterized in that the pyrolysis reactor (2) upstream preheater (1) is divided into two preheating chambers (1a and 1b), which are sequentially passed through by the heat carrier (8) and of which one is heated by the product gas passed through and the other by the passed flue gas from the reforming reactor.
9. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass die Vorwärmkammer (41 ) des Wanderbettreaktors in zwei Vorwärmkammern (41a und 41 b) unterteilt ist, die aufeinanderfolgend vom Hochtemperatur-Wärmeträger (40) durchlaufen werden und von denen die eine vom durchlaufenden Produktgas und die andere vom Rauchgas des Gasbrenners (34) und/oder der Koksfeuerung (4) beheizt wird. 9. The method according to claim 7, characterized in that the preheating chamber (41) of the moving bed reactor is subdivided into two preheating chambers (41a and 41b), which are successively passed through by the high-temperature heat carrier (40) and of which one of the continuous product gas and the other of the flue gas of the gas burner (34) and / or the coke (4) is heated.
10. Verfahren nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass mit dem Abgas aus dem Vorwärmer ( ) Dampf für die Reformierung erzeugt wird. 10. The method according to one or more of claims 1 to 9, characterized in that with the exhaust gas from the preheater () steam is generated for the reforming.
EP10805202.8A 2010-12-20 2010-12-20 Process for the pyrolysis of organic feedstock Withdrawn EP2655552A1 (en)

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