EP1031623B1 - Process for calaytic cracking of heavy volatile hydrocarbons - Google Patents

Process for calaytic cracking of heavy volatile hydrocarbons Download PDF

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Publication number
EP1031623B1
EP1031623B1 EP00101992A EP00101992A EP1031623B1 EP 1031623 B1 EP1031623 B1 EP 1031623B1 EP 00101992 A EP00101992 A EP 00101992A EP 00101992 A EP00101992 A EP 00101992A EP 1031623 B1 EP1031623 B1 EP 1031623B1
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EP
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Prior art keywords
fluidised bed
particles
raw gas
gas
catalyst
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EP00101992A
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German (de)
French (fr)
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EP1031623A3 (en
EP1031623A2 (en
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Johannes Dr. Albrecht
Claus Gretl
Ernst Bareuther
Peter Sturm
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Envirotherm GmbH
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Envirotherm GmbH
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/482—Gasifiers with stationary fluidised bed
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • C10K1/024—Dust removal by filtration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • C10K1/026—Dust removal by centrifugal forces
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/023—Reducing the tar content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C10J2300/092—Wood, cellulose
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0996—Calcium-containing inorganic materials, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—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

Definitions

  • the invention relates to a process for the catalytic cleavage of in the gasification of carbonaceous masses, in particular biomass and sewage sludge, in a fluidized bed at temperatures of 700 to 1200 ° C, preferably 850 to 950 ° C, and a stoichiometric air factor ⁇ , based on the C. - and H content of the carbonaceous masses, from 0.28 to 0.60 incurred, contained in the crude gas volatile higher, preferably aromatic hydrocarbons of C 6 - to C 22 binding systems.
  • the raw gas must be subjected to gas purification prior to gasification downstream reuse, for example in rotary kilns, boiler plants for energy production, electricity machines, piston engines or the like.
  • gas purification prior to gasification downstream reuse, for example in rotary kilns, boiler plants for energy production, electricity machines, piston engines or the like.
  • the frequently condensing out higher aromatic hydrocarbons hinder gas purification considerably.
  • the D1 refers instead to a process for the production of synthesis gas.
  • the CO and hydrogen synthesis gas is recovered in a gasification process of solid fuels at a pressure of about 5 bar to 150 bar by treatment with oxygen and water vapor at 350 ° C to 700 ° C.
  • the crude gas thus obtained is post-treated in a subsequent reactor at a temperature between 800 ° C and 1400 ° C with the addition of a dust fuel or liquid hydrocarbons and oxygen in the presence of catalysts in a fluidized bed to remove higher hydrocarbons.
  • nickel, cobalt or chromium oxides and / or sulfides are disclosed.
  • the fluidized bed also contains oxides, spinels or silicates of aluminum and / or magnesium.
  • the particles forming the fluidized bed consist of at least one of oxides, hydroxides and carbonates of calcium, aluminum, silicon, nickel, magnesium, titanium, iron, cobalt and molybdenum and are based on the content of hydrocarbons in the raw gas, in stoichiometric Excess used.
  • a considerable reduction in the content of higher aromatic carbons, in particular the C 6 - to C 22 binding systems to contents ⁇ 500 mg / Nm 3 is achieved.
  • an "in-situ" cleavage ie a splitting of the higher aromatic hydrocarbons, is already achieved during the gasification of the carbonaceous masses by the substances forming the fluidized bed.
  • a particular embodiment of the method according to the invention is to be seen in that the fluidized bed leaving raw gas after a dedusting, ie after the deposition of the resulting from the fluidized bed dust particles, is subjected to a catalytic aftertreatment, in which the residual contents of higher hydrocarbons are almost completely split.
  • the fluidized bed leaving and dedusted raw gas is passed through honeycomb catalysts or bulk catalysts.
  • the still existing higher hydrocarbons are split catalytically at the gasification temperatures prevailing there in gas components which are not condensable at ambient temperatures.
  • catalysts can be dispensed with if up to 15% of the particles forming the fluidized bed consist of a conventional cobalt / molybdenum and / or nickel catalyst.
  • the raw gas at the inlet into the catalyst has such a high concentration of flue dust that this results in a cleaning effect.
  • FIG. 1 a flow chart shown in the drawing (FIG. 1) and an exemplary embodiment.
  • FIG. 2 the influence of different substances of the fluidized bed forming particles on the tar reduction in the raw gas is shown as a bar chart.
  • the crude gas formed by the gasification and leaving the reactor in an amount of 800 m 3 / hour still contains 0.329 g / Nm 3 of hydrocarbons which consist of 0.012 g / Nm 3 of naphthalene and 0.285 g / Nm 3 of BTX aromatics ,
  • naphthalene is dominantly present in the volatile higher aromatic hydrocarbons and can be considered as a guide for the cleavage of hydrocarbons, ie, if it is possible to reduce the naphthalene content to ⁇ 50 mg / Nm 3 , it can be assumed that the raw gas in terms of Content of hydrocarbons is so pure that it is easily suitable for further use in boiler systems, gas turbines, gas engines or the like.
  • the Rchgas is directly in the downstream of the fluidized bed reactor (1) recirculation cyclone (2) pre-dedusted from the particles forming the fluidized bed and fed the deposited particles to the fluidized bed reactor (1) via line (11) again.
  • the raw gas is passed through a in the dip tube (9) of the recycle cyclone (2) arranged honeycomb catalyst (10).
  • the honeycomb catalyst (10) via line (8) leaving raw gas is almost ⁇ 0.05 g / Nm 3 free of higher aromatic hydrocarbons and thus can be supplied to the further gas cleaning without the use of special separator stages.
  • the dedusted raw gas is fed to a boiler plant (12) with a heat exchanger and leaves it via line (16).
  • the crude gas is purified in a downstream bag filter (13) and then fed via line (15) for thermal utilization.
  • the fly ash and debris particles of the particles forming the fluidized bed are removed, discharged via line (17), agglomerated and returned to the fluidized-bed reactor.
  • the column diagram shown in Fig. 2 shows the effect of different fluidizing bed forming materials with a grain size of 0.03 to 3 mm on higher hydrocarbons contained in the raw gas.
  • the value of 100% corresponds to a content of hydrocarbons of 3 to 20 g / Nm 3 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Treating Waste Gases (AREA)
  • Treatment Of Sludge (AREA)

Abstract

Process for catalytically splitting carbonaceous material during gasification at 700-1200 (preferably 850-950) degrees C comprises using a fluidized bed made up of particles selected from oxides, hydroxides and carbonates of calcium, aluminum, silicon, nickel, titanium, iron, cobalt, and molybdenum in a stoichiometric excess.

Description

Die Erfindung betrifft ein Verfahren zur katalytischen Spaltung von bei der Vergasung von kohlenstoffhaltigen Massen, insbesondere Biomassen und Klärschlamm, in einer Wirbelschicht bei Temperaturen von 700 bis 1200°C, vorzugsweise 850 bis 950°C, und einem stöchiometrischen Luftfaktor λ, bezogen auf den C- und H-Gehalt der kohlenstoffhaltigen Massen, von 0,28 bis 0,60 anfallenden, im Rohgas enthaltenen flüchtigen höheren, vorzugsweise aromatischen Kohlenwasserstoffen der C6- bis C22-Bindungssysteme.The invention relates to a process for the catalytic cleavage of in the gasification of carbonaceous masses, in particular biomass and sewage sludge, in a fluidized bed at temperatures of 700 to 1200 ° C, preferably 850 to 950 ° C, and a stoichiometric air factor λ, based on the C. - and H content of the carbonaceous masses, from 0.28 to 0.60 incurred, contained in the crude gas volatile higher, preferably aromatic hydrocarbons of C 6 - to C 22 binding systems.

Das bei der Vergasung kohlenstoffhaltiger Massen, wie Bioabfällen, Müll, Klärschlamm, Kohlen und dergleichen in einer Wirbelschicht unter Sauerstoffmangel bei Temperaturen von 700 bis 1200°C entstehende Rohgas enthält bis zu 20 g/Nm3 höhere, vorzugsweise aromatische Kohlenwasserstoffe der C6-bis C22-Bindungssysteme.The in the gasification of carbonaceous masses such as biowaste, garbage, sewage sludge, coal and the like in a fluidized bed under oxygen deficiency Temperatures of 700 to 1200 ° C resulting crude gas contains up to 20 g / Nm 3 higher, preferably aromatic hydrocarbons of C 6 to C 22 binding systems.

Das Rohgas muß in der Regel vor der der Vergasung nachgeschalteten Weiterverwertung, beispielsweise in Drehrohröfen, Kesselanlagen für Energieerzeugung, Strommaschinen, Kolbenmaschinen oder dergleichen einer Gasreinigung unterworfen werden. Die dabei häufig auskondensierenden höheren aromatischen Kohlenwasserstoffe behindern die Gasreinigung erheblich.As a rule, the raw gas must be subjected to gas purification prior to gasification downstream reuse, for example in rotary kilns, boiler plants for energy production, electricity machines, piston engines or the like. The frequently condensing out higher aromatic hydrocarbons hinder gas purification considerably.

Üblicherweise wird der Teergehalt des Rohgases durch Waschen erniedrigt. Die dabei eintretende Bildung von Aerosolen erschwert die Teerentfernung. Diesem Nachteil versucht mittels einem aus der EP-B 0 310 584 bekannten Verfahren zur Reinigung von aus einem kohlenstoffhaltigen Material durch Vergasung hergestellten Rohgas abzuhelfen. Bei diesem Verfahren wird das in einer ersten Stufe erzeugten Rohgas in einer zweiten, aus einer zirkulierenden Wirbelschicht gebildeten Stufe in Gegenwart von Magnesium-Calciumcarbonat enthaltendem Material einer katalytischen Behandlung unterworfen. Dabei wird der Teergehalt im Rohgas auf weniger als 500 mm/Nm3 gesenkt. Ein solch niedriger Teergehalt erlaubt in aller Regel die Reinigung des Rohgases mittels Schlauchfiltern, da die niedrigen Teergehalte an den noch vorhandenen kohlenstoffreichen Flugstaubpartikeln absorbiert sind, so daß die Partikel rieselfähig bleiben und die Schlauchfilter nicht verkleben.Usually, the tar content of the raw gas is lowered by washing. The occurring formation of aerosols complicates the tar removal. This disadvantage tries by means of one of the EP-B 0 310 584 known methods for the purification of raw material gas produced from a carbonaceous material by gasification. In this process, the raw gas produced in a first stage is subjected to a catalytic treatment in a second stage formed by a circulating fluidized bed in the presence of magnesium-calcium carbonate-containing material. The tar content in the raw gas is reduced to less than 500 mm / Nm 3 . As a rule, such a low tar content allows the purification of the raw gas by means of bag filters, since the low tar contents are absorbed by the remaining carbon-rich dust particles, so that the particles remain free-flowing and do not stick to the bag filters.

Die D1 betrifft statt dessen ein Verfahren zur Herstellung von Synthesegas. Das aus CO und Wasserstoff bestehende Synthesegas wird in einem Vergasungsprozeß von Festbrennstoffen bei einem Druck von ungefähr 5 bar bis 150 bar durch Behandlung mit Sauerstoff und Wasserdampf bei 350°C bis 700°C gewonnen. Das so gewonnene Rohgas wird in einem nachfolgenden Reaktor bei einer Temperatur zwischen 800°C und 1.400°C unter Zugabe eines Staubbrennstoffes oder von flüssigen Kohlenwasserstoffen und Sauerstoff in der Anwesenheit von Katalysatoren in einer Wirbelschicht nachbehandelt, um höhere Kohlenwasserstoffe zu entfernen. Als für die Wirbelschicht geeignete Katalysatoren werden Nickel, Cobalt oder Chromoxide und/oder Sulfide offenbart. Die Wirbelschicht enthält darüber hinaus Oxide, Spinelle oder Silikate des Aluminiums und/oder Magnesiums.The D1 refers instead to a process for the production of synthesis gas. The CO and hydrogen synthesis gas is recovered in a gasification process of solid fuels at a pressure of about 5 bar to 150 bar by treatment with oxygen and water vapor at 350 ° C to 700 ° C. The crude gas thus obtained is post-treated in a subsequent reactor at a temperature between 800 ° C and 1400 ° C with the addition of a dust fuel or liquid hydrocarbons and oxygen in the presence of catalysts in a fluidized bed to remove higher hydrocarbons. As suitable for the fluidized bed catalysts nickel, cobalt or chromium oxides and / or sulfides are disclosed. The fluidized bed also contains oxides, spinels or silicates of aluminum and / or magnesium.

Die Lösung diese Aufgabe ergibt sich aus dem Verfahren mit den Merkmalen des Patentanspruches 1.The solution to this problem arises from the method with the features of claim 1.

Die Merkmale der Ansprüche 2 bis 7 stellen Ausgestaltungen der Merkmale des Anspruchs 1 dar.The features of claims 2 to 7 represent embodiments of the features of claim 1.

Es ist die Aufgabe der vorliegenden Erfindung, ein verbessertes Verfahren zur weitgehenden Entfernung der in den durch die Vergasung von kohlenstoffhaltigen Massen in einer Wirbelschicht erzeugten Rohgas enthaltenen höheren, vorzugsweise aromatischen Kohlenwaserstoffen der C6- bis C22-Bindungssysteme bereitzustellen.It is the object of the present invention to provide an improved method for substantially removing the higher, preferably aromatic hydrocarbons of the C 6 to C 22 binding systems contained in the raw gas produced by the gasification of carbonaceous masses in a fluidized bed.

Die das Wirbelbett bildenden Partikel bestehen aus wenigstens einem der Stoffe, ausgewählt aus Oxiden, Hydroxiden und Carbonaten des Calciums, Aluminiums, Siliciums, Nickels, Magnesiums, Titans, Eisens, Cobalts und Molybdäns und sind bezogen auf den Gehalt an Kohlenwasserstoffen im Rohgas, in stöchiometrischem Überschuß eingesetzt. Durch diese Maßnahme wird eine beachtliche Senkung des Gehalts an höheren aromatischen Kohlenstoffen, insbesondere der C6- bis C22-Bindungssysteme auf Gehalte < 500 mg/Nm3 erreicht. Durch die das Wirbelbett bildenden Stoffe wird während der Vergasung der kohlenstoffhaltigen Massen eine "in-situ"-Spaltung, d. h. eine Spaltung der höheren aromatischen Kohlenwasserstoffe bereits während der Vergasung der kohlenstoffhaltigen Massen erreicht.The particles forming the fluidized bed consist of at least one of oxides, hydroxides and carbonates of calcium, aluminum, silicon, nickel, magnesium, titanium, iron, cobalt and molybdenum and are based on the content of hydrocarbons in the raw gas, in stoichiometric Excess used. By this measure, a considerable reduction in the content of higher aromatic carbons, in particular the C 6 - to C 22 binding systems to contents <500 mg / Nm 3 is achieved. During the gasification of the carbonaceous masses, an "in-situ" cleavage, ie a splitting of the higher aromatic hydrocarbons, is already achieved during the gasification of the carbonaceous masses by the substances forming the fluidized bed.

Eine besondere Ausbildung des erfindungsgemäßen Verfahrens ist darin zu sehen, daß das die Wirbelschicht verlassende Rohgas nach einer Vorentstaubung, d. h. nach dem Abscheiden der aus dem Wirbelbett stammenden Flugstaubpartikel, einer katalytischen Nachbehandlung unterworfen wird, bei der die Restgehalte an höheren Kohlenwasserstoffen nahezu vollständig gespalten werden.A particular embodiment of the method according to the invention is to be seen in that the fluidized bed leaving raw gas after a dedusting, ie after the deposition of the resulting from the fluidized bed dust particles, is subjected to a catalytic aftertreatment, in which the residual contents of higher hydrocarbons are almost completely split.

Zweckmäßigerweise wird das die Wirbelschicht verlassende und vorentstaubte Rohgas über Wabenkatalysatoren oder Schüttgutkatalysatoren geleitet. Dabei werden die noch vorhandenen höheren Kohlenwasserstoffe bei den dort vorherrschenden Vergasungstemperaturen katalytisch in bei Umgebungstemperaturen nicht kondensierbare Gaskomponenten gespalten. Auf derartige Katalysatoren kann jedoch verzichtet werden, wenn bis zu 15 % der die Wirbelschicht bildenden Partikel aus einem üblichen Cobalt/Molybdän- und/oder Nickel-Katalysator bestehen.Advantageously, the fluidized bed leaving and dedusted raw gas is passed through honeycomb catalysts or bulk catalysts. The still existing higher hydrocarbons are split catalytically at the gasification temperatures prevailing there in gas components which are not condensable at ambient temperatures. However, such catalysts can be dispensed with if up to 15% of the particles forming the fluidized bed consist of a conventional cobalt / molybdenum and / or nickel catalyst.

Eventuell vorhandener oder sich am Katalysator bildender Ruß wird durch gezielte Sauerstoff- und/oder Dampfzugabe vor dem Katalysator vermieden. Darüber hinaus besitzt das Rohgas am Eintritt in den Katalysator eine so hohe Flugstaubkonzentration, daß dadurch ein Reinigungseffekt eintritt.Possibly existing or forming on the catalyst carbon black is avoided by targeted oxygen and / or steam addition before the catalyst. In addition, the raw gas at the inlet into the catalyst has such a high concentration of flue dust that this results in a cleaning effect.

Die Erfindung ist nachstehend anhand eines in der Zeichnung (Fig. 1) dargestellten Fließbilds und eines Ausführungsbeispiels näher erläutert. In Fig. 2 ist der Einfluß unterschiedlicher Stoffe der das Wirbelbett bildenden Partikel auf die Teerreduktion im Rohgas als Säulendiagramm wiedergegeben.The invention is explained in more detail below with reference to a flow chart shown in the drawing (FIG. 1) and an exemplary embodiment. In Fig. 2, the influence of different substances of the fluidized bed forming particles on the tar reduction in the raw gas is shown as a bar chart.

Die Anlage zur Durchführung des erfindungsgemäßen Verfahrens besteht aus einer zirkulierenden Wirbelschichteinrichtung mit vertikalem Reaktor (1), dem über Leitung (3) ein Gemisch aus 100 kg Aluminiumoxid und 600 kg Rohbauxit mit einer mittleren Korngröße d50 von 1,5 mm zur Ausbildung des Wirbelbetts zugeführt wird. Über Leitung (4) wird dem Reaktor (1) 300 kg Holz aufgegeben, das bei einer Temperatur von 910°C und einem stöchiometrischen Luftfaktor von λ = 0,39 und einer Gasgeschwindigkeit von 3,0 m/sec vergast wird. Die Luft wird über Leitung (5) in den Reaktor (1) eingeleitet. Die Rückstände aus der Vergasung werden aus dem Reaktor (1) über Leitung (7) entfernt. Das durch die Vergasung gebildete, aus dem Reaktor in einer Menge von 800 m3/Stunde austretende Rohgas enthält noch 0,329 g/Nm3 Kohlenwasserstoffe, die zu 0,012 g/Nm3 aus Naphthalin und zu 0,285 g/Nm3 aus BTX-Aromaten bestehen.The plant for carrying out the process according to the invention consists of a circulating fluidized bed device with a vertical reactor (1), via line (3) a mixture of 100 kg of alumina and 600 kg Rohbauxit with a mean particle size d 50 of 1.5 mm to form the fluidized bed is supplied. Via line (4) the reactor (1) 300 kg of wood is given, which is gasified at a temperature of 910 ° C and a stoichiometric air factor of λ = 0.39 and a gas velocity of 3.0 m / sec. The air is introduced via line (5) in the reactor (1). The residues from the gasification are removed from the reactor (1) via line (7). The crude gas formed by the gasification and leaving the reactor in an amount of 800 m 3 / hour still contains 0.329 g / Nm 3 of hydrocarbons which consist of 0.012 g / Nm 3 of naphthalene and 0.285 g / Nm 3 of BTX aromatics ,

Das Naphthalin ist in den flüchtigen höheren aromatischen Kohlenwasserstoffen dominierend vorhanden und kann als Leitgröße für die Spaltung der Kohlenwasserstoffe angesehen werden, d. h., wenn es gelingt, den Naphthalingehalt auf < 50 mg/Nm3 zu senken, ist davon auszugehen, daß das Rohgas hinsichtlich des Gehalts an Kohlenwasserstoffen so rein ist, daß es für die Weiterverwertung in Kesselanlagen, Gasturbinen, Gasmotoren oder dergleichen problemlos geeignet ist.The naphthalene is dominantly present in the volatile higher aromatic hydrocarbons and can be considered as a guide for the cleavage of hydrocarbons, ie, if it is possible to reduce the naphthalene content to <50 mg / Nm 3 , it can be assumed that the raw gas in terms of Content of hydrocarbons is so pure that it is easily suitable for further use in boiler systems, gas turbines, gas engines or the like.

Das Rchgas wird unmittelbar in dem dem Wirbelschichtreaktor (1) nachgeschalteten Rückführzyklon (2) von den das Wirbelbett bildenden Partikeln vorentstaubt und die abgeschiedenen Partikel dem Wirbelschichtreaktor (1) über Leitung (11) wieder zugeführt. Für den Fall, daß nahezu vollkommene Freiheit von flüchtigen höheren aromatischen Kohlenwasserstoffen im Rohgas verlangt wird, wird das Rohgas über einen im Tauchrohr (9) des Rückführzyklons (2) angeordneten Wabenkatalysator (10) geleitet. Das den Wabenkatalysator (10) über Leitung (8) verlassende Rohgas ist nahezu mit < 0,05 g/Nm3 frei von höheren aromatischen Kohlenwasserstoffen und kann somit der weiteren Gasreinigung ohne Einsatz besonderer Abscheiderstufen zugeführt werden. Das entstaubte Rohgas wird einer Kesselanlage (12) mit Wärmeaustauscher aufgegeben und verläßt diese über Leitung (16). Das Rohgas wird in einem nachgeschalteten Schlauchfilter (13) gereinigt und dann über Leitung (15) einer thermischen Verwertung zugeführt. Aus dem aus dem Rückführzyklon (2) austretenden Rohgas werden die noch darin enthaltenen Flugasche- und Abriebteilchen der das Wirbelbett bildenden Partikel entfernt, über Leitung (17) ausgetragen, agglomeriert und in den Wirbelschichtreaktor zurückgeleitet.The Rchgas is directly in the downstream of the fluidized bed reactor (1) recirculation cyclone (2) pre-dedusted from the particles forming the fluidized bed and fed the deposited particles to the fluidized bed reactor (1) via line (11) again. In the event that almost complete freedom from volatile higher aromatic hydrocarbons in the raw gas is required, the raw gas is passed through a in the dip tube (9) of the recycle cyclone (2) arranged honeycomb catalyst (10). The honeycomb catalyst (10) via line (8) leaving raw gas is almost <0.05 g / Nm 3 free of higher aromatic hydrocarbons and thus can be supplied to the further gas cleaning without the use of special separator stages. The dedusted raw gas is fed to a boiler plant (12) with a heat exchanger and leaves it via line (16). The crude gas is purified in a downstream bag filter (13) and then fed via line (15) for thermal utilization. From the raw gas emerging from the recycle cyclone (2), the fly ash and debris particles of the particles forming the fluidized bed are removed, discharged via line (17), agglomerated and returned to the fluidized-bed reactor.

Das in Fig. 2 dargestellte Säulendiagramm zeigt die Wirkung unterschiedlicher das Wirbelbett bildenden Stoffe mit einer Körnung von 0,03 bis 3 mm auf im Rohgas enthaltene höhere Kohlenwasserstoffe. Der Wert von 100 % entspricht dabei einem Gehalt an Kohlenwasserstoffen von 3 bis 20 g/Nm3.The column diagram shown in Fig. 2 shows the effect of different fluidizing bed forming materials with a grain size of 0.03 to 3 mm on higher hydrocarbons contained in the raw gas. The value of 100% corresponds to a content of hydrocarbons of 3 to 20 g / Nm 3 .

Claims (10)

  1. Method for the catalytic cracking of volatile, higher, preferably aromatic hydrocarbons of the C6 to C22 bond system which are contained in raw gas and occur in the gasification of carbon-containing masses, in particular biomasses and sewage sludge, in a fluidised bed at temperatures from 700 to 1200°C, preferably 850 to 950°C, and a stoichiometric air factor λ, related to the C and H content of the carbon-containing masses, from 0.28 to 0.60, characterised in that the catalytic cracking takes place during the gasification and the particles which form the fluidised bed consist of at least one of the substances selected from oxides, hydroxides and carbonates of calcium, aluminium, silicon, nickel, magnesium, titanium, iron, cobalt and molybdenum and are used in a stoichiometric excess, related to the content of hydrocarbons in the raw gas, wherein up to 15% of the particles which form the fluidised bed consist of a conventional cobalt-molybdenum catalyst and/or a nickel catalyst with an average grain size d50 of 0.5 to 3.0 mm.
  2. Method according to Claim 1, characterised in that the particles which form the fluidised bed consist of at least one of the substances selected from sand, dolomite, zeolite, alumina, laterite and nickel-containing materials.
  3. Method according to either of Claims 1 and 2, characterised in that the average grain size d50 of the particles which form the fluidised bed is 0.03 to 3.0 mm.
  4. Method according to any one of Claims 1 to 3, characterised in that the gas speed is 1.0 to 7.0 m/sec.
  5. Method according to any one of Claims 1 to 4, characterised in that the gas dwell time is 2.0 to 15.0 sec.
  6. Method according to any one of Claims 1 to 5, characterised in that the raw gas is pre-dedusted in a recycling cyclone which is disposed downstream of the fluidised bed reactor, wherein the fly-ash and abrasion particles contained therein of the particles which form the fluidised bed are separated and returned to the fluidised bed.
  7. Method according to Claim 6, characterised in that the fly-ash and abrasion particles are agglomerated following separation.
  8. Method according to any one of Claims 1 to 5, characterised in that the subsequently pre-dedusted raw gas leaving the fluidised bed is subjected to a catalytic aftertreatment.
  9. Method according to Claim 8, characterised in that the raw gas flows via a honeycomb catalyst.
  10. Method according to Claim 8, characterised in that the raw gas flows via a particulate catalyst.
EP00101992A 1999-02-24 2000-02-02 Process for calaytic cracking of heavy volatile hydrocarbons Expired - Lifetime EP1031623B1 (en)

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DE19907901C2 (en) 2001-11-29
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ATE364672T1 (en) 2007-07-15
DE19907901A1 (en) 2000-09-07
EP1031623A2 (en) 2000-08-30

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