WO2010057763A1 - Method and device for using the waste heat of liquid slag - Google Patents

Method and device for using the waste heat of liquid slag Download PDF

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Publication number
WO2010057763A1
WO2010057763A1 PCT/EP2009/064381 EP2009064381W WO2010057763A1 WO 2010057763 A1 WO2010057763 A1 WO 2010057763A1 EP 2009064381 W EP2009064381 W EP 2009064381W WO 2010057763 A1 WO2010057763 A1 WO 2010057763A1
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Prior art keywords
slag
waste heat
liquid slag
liquid
catalyst
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PCT/EP2009/064381
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German (de)
French (fr)
Inventor
Manfred Baldauf
Vladimir Danov
Harald Landes
Thomas Matschullat
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Siemens Aktiengesellschaft
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Publication of WO2010057763A1 publication Critical patent/WO2010057763A1/en

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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B3/00—General features in the manufacture of pig-iron
    • C21B3/04—Recovery of by-products, e.g. slag
    • C21B3/06—Treatment of liquid slag
    • C21B3/08—Cooling slag
    • 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
    • C01B3/382—Multi-step processes
    • 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
    • C01B3/384—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 the catalyst being continuously externally heated
    • 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
    • C01B3/40—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 characterised by the catalyst
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0833—Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2400/00—Treatment of slags originating from iron or steel processes
    • C21B2400/02—Physical or chemical treatment of slags
    • C21B2400/022—Methods of cooling or quenching molten slag
    • C21B2400/026—Methods of cooling or quenching molten slag using air, inert gases or removable conductive bodies
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2400/00—Treatment of slags originating from iron or steel processes
    • C21B2400/05—Apparatus features
    • C21B2400/052—Apparatus features including rotating parts
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2400/00—Treatment of slags originating from iron or steel processes
    • C21B2400/05—Apparatus features
    • C21B2400/052—Apparatus features including rotating parts
    • C21B2400/054—Disc-shaped or conical parts for cooling, dispersing or atomising of molten slag rotating along vertical axis
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2400/00—Treatment of slags originating from iron or steel processes
    • C21B2400/05—Apparatus features
    • C21B2400/066—Receptacle features where the slag is treated
    • C21B2400/068—Receptacle features where the slag is treated with a sealed or controlled environment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2400/00—Treatment of slags originating from iron or steel processes
    • C21B2400/05—Apparatus features
    • C21B2400/066—Receptacle features where the slag is treated
    • C21B2400/076—Fluidised bed for cooling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2400/00—Treatment of slags originating from iron or steel processes
    • C21B2400/08—Treatment of slags originating from iron or steel processes with energy recovery
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C2100/00—Exhaust gas
    • C21C2100/06—Energy from waste gas used in other processes
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/143—Reduction of greenhouse gas [GHG] emissions of methane [CH4]
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency
    • 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

Definitions

  • the invention relates to a method for utilizing the waste heat of liquid slag, in particular blast furnace or steel mill slag.
  • the invention also relates to an associated apparatus for carrying out the method.
  • blast furnace slag is formed, which is used in cement production.
  • the object of the invention is to provide suitable methods for using the heat content of liquid slag.
  • Reforming cooling allows the thermal energy released during the cooling process to be stored in chemical form and then re-injected elsewhere in the process, thus reducing the fuel consumption of a metallurgical plant and relieving the atmosphere of CO2 serves and that due to the high temperature and the continuous passage of the slag catalyst aging processes are meaningless.
  • FIG. 1 is a process diagram of the heat use of liquid
  • Figure 2 shows an arrangement with a direct contact reformer, in which the slag is cooled on a rotatable plate and Figure 3 is a modification of the arrangement of Figure 2 with an integrated reformer.
  • a container for receiving liquid slag is denoted by 1.
  • the liquid slag is filled from above, granulated in the container 1 and is brought as granules in a reservoir 3.
  • nozzle array 5 with which the liquid slag, which has a temperature of about 1500 0 C, is directed as a liquid jet on the slag stock.
  • the reformate is discharged via a heat exchanger 10 and partially returned to the container 1 via a catalyst 20.
  • FIG. 2 the construction according to FIG. 1 is modified such that a container 100 is provided which has a slag feed 106, wherein the slag is directed by a slag storage container 104 via the feed 106 onto a rotatable plate and sprayed off therefrom. There is a motor drive 105 available. The granulated slag is collected in the container 112.
  • a unit 120 for exhaust gas intake is present.
  • a pre-reformer 121 is provided, from which the synthetic gas on the one hand and the natural gas on the other hand are output via an evaporator 122.
  • a system is constructed substantially in accordance with Figure 2. It is essential here that behind the pre-reformer 121 and the evaporator 122, the gas is added to a gas turbine with a subsequent generator.
  • the advantage of the system according to FIG. 2 consists essentially in a simple structure and in the rapid heat transfer from the slag to the reformate.
  • a disadvantage is the requirement for a catalyst or for catalytic properties of the slag itself. Under certain circumstances, only a partial reduction of the slag results, which could impair the quality of the product. There is also a large volume of gaseous fuel.
  • FIG. 3 The latter negative properties are used in FIG. 3 to the effect that the gas turbine is operated.
  • the operation can be done independently of the slag composition.
  • the slag liquid is fed into a tower via a nozzle field by falling down in parallel threads, these flow threads being characterized by the increasing flow rate and the effect of the surface tension in
  • the tower is flowed through from the ground with a partially pre-reformed steam-natural gas mixture, which enters the tower at about 500 0 C. It is then first heated on the surface of the oncoming, already stared at this point slag droplets and from 700 0 C increasingly ausreformiert, whereby the slag droplets are already solidified further up in the tower.
  • the partial pre-reforming of the steam-natural gas mixture has two purposes: it prevents soot deposition on the surface of the slag particles by cracking higher hydrocarbons because they have already been degraded.
  • the gas produced thereby, in particular hydrogen-containing gas leads to a kinetically effective, reducing atmosphere, which supports the catalytic activity of the Eisenismeengept in the slag.
  • an adiabatic pre-reformer is a tube with pellets of a reforming catalyst, eg. B. nickel (Ni), on porous alumina (Al2O3) is filled and in which a about 700 0 C hot mixture of natural gas and steam flows.
  • Slag particles may serve to heat conducted air or other gas and thus be made usable for other purposes.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Catalysts (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)

Abstract

Particularly for blast furnace slag or steel mill slag, the waste heat released in cooling the slag to 600°C is used to reform a methane-steam mixture, wherein a suitable catalyst is used. The slag itself can be used as a catalyst.

Description

Beschreibungdescription
Verfahren und Vorrichtung zur Nutzung der Abwärme flüssiger SchlackeMethod and device for utilizing the waste heat of liquid slag
Die Erfindung bezieht sich auf ein Verfahren zur Nutzung der Abwärme flüssiger Schlacke, insbesondere von Hochofen- oder Stahlwerksschlacke. Daneben bezieht sich die Erfindung auch auf eine zugehörige Vorrichtung zur Durchführung des Verfah- rens .The invention relates to a method for utilizing the waste heat of liquid slag, in particular blast furnace or steel mill slag. In addition, the invention also relates to an associated apparatus for carrying out the method.
Herkömmlicherweise wird Hochofen- oder Stahlwerksschlacke, die bei 1500 bis 16000C flüssig anfällt,Conventionally blast furnace or steel mill slag, which is liquid at 1500 to 1600 0 C,
- entweder in Schlackenbeete gegossen, um sie dort, unter- stützt durch die Verdampfung von aufgespritztem Wasser, langsam abkühlen zu lassen, wobei große, z. B. als Straßenbaumaterial verwendbare Stücke entstehen (Stückschlacke) ;- either poured into slag beds, where they are allowed to cool slowly, supported by the evaporation of sprayed-on water, with large, e.g. B. used as road construction material usable pieces (piece slag);
- oder sie wird durch Verdüsung mit großen Wasser- oder Gas- mengen abgeschreckt, so dass der so genannte Hüttensand gebildet wird, der in der Zementherstellung Anwendung findet.- Or it is quenched by spraying with large amounts of water or gas, so that the so-called blast furnace slag is formed, which is used in cement production.
In beiden Fällen bleibt die hohe Enthalpie der Schlacke ungenutzt .In both cases, the high enthalpy of the slag remains unused.
Bisher wurde die Wärmeenergie aus dem Abkühlvorgang von Schlacken nicht genutzt.So far, the heat energy from the cooling process of slags was not used.
Aufgabe der Erfindung ist es, geeignete Verfahren zur Nutzung des Wärmeinhaltes flüssiger Schlacke anzugeben.The object of the invention is to provide suitable methods for using the heat content of liquid slag.
Die Aufgabe ist erfindungsgemäß durch die Maßnahmen des Patentanspruches 1 gelöst. Eine zugehörige Vorrichtung ist im Patentanspruch 11 angegeben! Weiterbildungen des erfindungs- gemäßen Verfahrens und der zugehörigen Vorrichtung sind Gegenstand der Unteransprüche. Aufgrund des Temperaturniveaus der flüssigen Schlacke (1500 - 1600°C) kann man prinzipiell die bei der Abkühlung bis auf 6000C freigesetzte Abwärme nutzen, um ein Methan-Wasserdampf- Gemisch zu reformieren, d.h. in seinem Heizwert anzuheben. Dieses Gas kann in einer Erdgasfeuerung an anderer Stelle im Prozess einen entsprechenden Teil des Erdgases ersetzen. Die verbleibende fühlbare Wärme in der nun festen Schlackenschüt- tung kann durch Einleiten von Gasen oder Wasser zur Dampferzeugung bis herab auf Umgebungstemperatur genutzt werden. Zwar erfordert die Reformierung einen Katalysator, doch sinken die Anforderungen an diesen mit steigender Temperatur und zudem enthält die Schlacke Eisen, das bei Einstellung einer reduzierenden Atmosphäre als Katalysator wirkt.The object is achieved by the measures of claim 1. An associated device is specified in claim 11! Further developments of the inventive method and the associated device are the subject of the dependent claims. Due to the temperature level of the liquid slag (1500 - 1600 ° C) can be used in principle to the liberated during cooling to 600 0 C waste heat to reform a methane-steam mixture, ie raise in its calorific value. This gas can replace a corresponding part of the natural gas in a natural gas furnace elsewhere in the process. The remaining sensible heat in the now solid slag can be used by introducing gases or water to generate steam down to ambient temperature. Although the reforming requires a catalyst, but the requirements for these decrease with increasing temperature and also contains the slag iron, which acts as a catalyst when adjusting a reducing atmosphere.
Die Reformierungskühlung erlaubt es, die beim Abkühlvorgang freigesetzte Wärmeenergie in chemischer Form zu speichern und an anderer Stelle im Prozess „kalt" wieder einzuspeisen. Damit wird der Brennstoffverbrauch eines Hüttenbetriebes gesenkt und die Atmosphäre von CO2 entlastet. Hervorzuheben ist, dass die Schlacke selbst als Katalysator dient und dass aufgrund der hohen Temperatur und des stetigen Durchlaufs der Schlacke Katalysatoralterungsprozesse bedeutungslos sind.Reforming cooling allows the thermal energy released during the cooling process to be stored in chemical form and then re-injected elsewhere in the process, thus reducing the fuel consumption of a metallurgical plant and relieving the atmosphere of CO2 serves and that due to the high temperature and the continuous passage of the slag catalyst aging processes are meaningless.
Weitere Einzelheiten und Vorteile der Erfindung ergeben sich aus der nachfolgenden Figurenbeschreibung von Ausführungsbeispielen in Verbindung mit den Patentansprüchen.Further details and advantages of the invention will become apparent from the following description of exemplary embodiments in conjunction with the claims.
Es zeigenShow it
Figur 1 ein Prozessschema der Wärmenutzung von flüssigerFigure 1 is a process diagram of the heat use of liquid
Schlacke durch Dampfreformierung von Naturgas, Figur 2 eine Anordnung mit einem Direktkontakt-Reformer, bei dem die Schlacke auf einem rotierbaren Teller gekühlt wird und Figur 3 eine Abänderung der Anordnung gemäß Figur 2 mit einem integrierten Reformer. In Figur 1 ist ein Behälter zur Aufnahme von flüssiger Schlacke mit 1 bezeichnet. Die flüssige Schlacke wird von oben eingefüllt, granuliert im Behälter 1 und wird als Granulat in einen Vorratsbehälter 3 gebracht.Slag by steam reforming of natural gas, Figure 2 shows an arrangement with a direct contact reformer, in which the slag is cooled on a rotatable plate and Figure 3 is a modification of the arrangement of Figure 2 with an integrated reformer. In FIG. 1, a container for receiving liquid slag is denoted by 1. The liquid slag is filled from above, granulated in the container 1 and is brought as granules in a reservoir 3.
Es ist ein Düsenarray 5 vorhanden, mit dem die flüssige Schlacke, die eine Temperatur von etwa 15000C hat, als Flüssigkeitsstrahl auf den Schlackenvorrat gelenkt wird.There is a nozzle array 5, with which the liquid slag, which has a temperature of about 1500 0 C, is directed as a liquid jet on the slag stock.
Mit 8 ist ein Abgang für das Reformat bezeichnet. Das Refor- mat wird über einen Wärmetauscher 10 ausgetragen und teilweise über einen Katalysator 20 in den Behälter 1 zurückgeführt.With 8 is designated a departure for the Reformat. The reformate is discharged via a heat exchanger 10 and partially returned to the container 1 via a catalyst 20.
In der Figur 2 ist der Aufbau nach Figur 1 derart abgewan- delt, dass ein Behälter 100 vorgesehen ist, der eine Schlackenzuführung 106 hat, wobei die Schlacke von einem Schlackenvorratsbehälter 104 über die Zuführung 106 auf einen drehbaren Teller gelenkt wird und von dort absprüht. Es ist dazu ein Motorantrieb 105 vorhanden. Die granulierte Schlacke wird im Behälter 112 aufgefangen.In FIG. 2, the construction according to FIG. 1 is modified such that a container 100 is provided which has a slag feed 106, wherein the slag is directed by a slag storage container 104 via the feed 106 onto a rotatable plate and sprayed off therefrom. There is a motor drive 105 available. The granulated slag is collected in the container 112.
Weiterhin ist eine Einheit 120 zur Abgasaufnahme vorhanden.Furthermore, a unit 120 for exhaust gas intake is present.
Entsprechend Figur 1 ist ein Vorreformer 121 vorhanden, von dem über einen Verdampfer 122 das synthetische Gas einerseits und das Naturgas andererseits ausgegeben wird.According to FIG. 1, a pre-reformer 121 is provided, from which the synthetic gas on the one hand and the natural gas on the other hand are output via an evaporator 122.
In Figur 3 ist eine Anlage im Wesentlichen entsprechend Figur 2 aufgebaut. Wesentlich ist hier, dass hinter dem Vorreformer 121 und dem Verdampfer 122 das Gas auf eine Gasturbine mit anschließendem Generator gegeben wird. Der Vorteil der Anlage gemäß Figur 2 besteht im Wesentlichen in einem einfachen Aufbau und in dem schnellen Wärmetransfer von der Schlacke zum Reformat. Nachteilig ist allerdings die Forderung nach einem Katalysator bzw. nach katalytischen Ei- genschaften der Schlacke selbst. Unter Umständen ergibt sich nur eine teilweise Reduktion der Schlacke, wodurch die Qualität des Produktes leiden könnte. Außerdem liegt ein großes Volumen an gasförmigem Brennstoff vor.In Figure 3, a system is constructed substantially in accordance with Figure 2. It is essential here that behind the pre-reformer 121 and the evaporator 122, the gas is added to a gas turbine with a subsequent generator. The advantage of the system according to FIG. 2 consists essentially in a simple structure and in the rapid heat transfer from the slag to the reformate. However, a disadvantage is the requirement for a catalyst or for catalytic properties of the slag itself. Under certain circumstances, only a partial reduction of the slag results, which could impair the quality of the product. There is also a large volume of gaseous fuel.
Letztere Negativeigenschaften werden bei Figur 3 dahingehend genutzt, dass die Gasturbine betrieben wird. Dabei kann der Betrieb unabhängig von der Schlackenzusammensetzung erfolgen. Dadurch, dass kein Einfluss der Schlacke selbst auf die Anlage beobachtet wird, kann die übliche Reformertechnologie ver- wendet werden.The latter negative properties are used in FIG. 3 to the effect that the gas turbine is operated. The operation can be done independently of the slag composition. The fact that no influence of the slag itself on the system is observed, the usual reformer technology can be used.
Die Schlackenflüssigkeit wird über ein Düsenfeld in einen Turm eingespeist, indem sie in parallelen Fäden nach unten fällt, wobei diese Strömungsfäden durch die zunehmende FaIl- geschwindigkeit und die Wirkung der Oberflächenspannung inThe slag liquid is fed into a tower via a nozzle field by falling down in parallel threads, these flow threads being characterized by the increasing flow rate and the effect of the surface tension in
Tropfen aufreißen. Der Turm wird vom Boden her mit einem partiell vorreformierten Dampf-Erdgas-Gemisch durchströmt, das mit ca. 5000C in den Turm einritt. Es wird dann an der Oberfläche der entgegenkommenden, an dieser Stelle bereits er- starrten Schlackentröpfchen zunächst erwärmt und ab 7000C zunehmend ausreformiert, wodurch die Schlackentröpfchen weiter oben im Turm schon erstarrt sind.Tear up the drops. The tower is flowed through from the ground with a partially pre-reformed steam-natural gas mixture, which enters the tower at about 500 0 C. It is then first heated on the surface of the oncoming, already stared at this point slag droplets and from 700 0 C increasingly ausreformiert, whereby the slag droplets are already solidified further up in the tower.
Die partielle Vorreformierung des Dampf-Erdgas-Gemisches hat zweierlei Aufgaben: sie verhindert die Rußabscheidung auf der Oberfläche der Schlackepartikel durch Cracken höherer Kohlenwasserstoffe, weil diese schon abgebaut wurden. Außerdem führt das dadurch erzeugte, insbesondere Wasserstoff enthaltende Gas zu einer auch kinetisch wirksamen, reduzierenden Atmosphäre, die die katalytische Aktivität der Eisenbeimengungen in der Schlacke unterstützt. Es erfolgt also eine adiabatische Vorreformierung. Als adiabatischer Vorreformer dient ein Rohr, das mit Pellets eines Reformerkatalysators, z. B. Nickel (Ni) , auf porösem Aluminiumoxid (AI2O3) gefüllt ist und in das ein ca. 7000C heißes Ge- misch aus Erdgas und Dampf einströmt. Durch den Vorreformie- rungsprozess hat sich dieses Gas bis zum Ausgang soweit abgekühlt hat, bspw. auf ca. 5500C, dass dieser Prozess zum Stillstand kommt. Die Wärme für diesen Vorreformierungspro- zess wird dadurch bereitgestellt, indem das aus dem Fallturm bei ca. 10000C abgezogene Reformat über einen WärmetauscherThe partial pre-reforming of the steam-natural gas mixture has two purposes: it prevents soot deposition on the surface of the slag particles by cracking higher hydrocarbons because they have already been degraded. In addition, the gas produced thereby, in particular hydrogen-containing gas leads to a kinetically effective, reducing atmosphere, which supports the catalytic activity of the Eisenbeimengungen in the slag. So there is an adiabatic pre-reforming. As an adiabatic pre-reformer is a tube with pellets of a reforming catalyst, eg. B. nickel (Ni), on porous alumina (Al2O3) is filled and in which a about 700 0 C hot mixture of natural gas and steam flows. By Vorreformie- insurance process, this gas has got to the exit cooled down, for example. To about 550 0 C, that this process comes to a standstill. The heat for this Vorreformierungspro- process is provided by the withdrawn from the tower at about 1000 0 C reformate via a heat exchanger
Wasserdampf von 9000C erzeugt. Dieser Dampf wird vor dem adiabatischen Vorreformer mit kaltem Erdgas gemischt, wobei vorzugsweise ein Dampf-zu-Methan- bzw. S/C(= S_team to (Carbon) - Verhältnis von 2 eingestellt wird. Die am trichterförmigen Boden des Fallturms sich ansammelnden Schlackepartikel werden z. B. über eine diskontinuierlich entleerte Schleusenkammer abgezogen, deren (Rest-) Volumen für die Wechselvorgänge mit Dampf gefüllt wird.Water vapor produced by 900 0 C. This steam is mixed with cold natural gas prior to the adiabatic pre-reformer, preferably setting a steam to methane (S / T) ratio of 2. The slag particles accumulating at the funnel-shaped bottom of the drop tower become For example, it is drawn off via a discontinuously emptied lock chamber, the (residual) volume of which is filled with steam for the change processes.
Die fühlbare Wärme in der Schüttung der ausgeschleustenThe sensible heat in the bulk of the discharged
Schlackepartikel kann zur Erhitzung durchgeleiteter Luft oder eines anderen Gases dienen und damit für andere Zwecke nutzbar gemacht werden. Slag particles may serve to heat conducted air or other gas and thus be made usable for other purposes.

Claims

Patentansprüche claims
1. Verfahren zur Nutzung der Abwärme flüssiger Schlacke, insbesondere von Hochofen- oder Stahlwerksschlacke, mit folgenden Verfahrensschritten:1. A method for utilizing the waste heat of liquid slag, in particular blast furnace or steel mill slag, with the following process steps:
- die bei der Abkühlung der Schlacke bis auf 6000C freigesetzte Abwärme wird genutzt, um ein Methan-Wasserdampf- Gemisch zu reformieren,the waste heat released by the cooling of the slag up to 600 ° C. is used to reform a methane-steam mixture,
- wobei ein geeigneter Katalysator verwendet wird.- Using a suitable catalyst is used.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als Katalysator die Schlacke selbst verwendet wird2. The method according to claim 1, characterized in that the slag itself is used as the catalyst
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der verbleibende Wärmeinhalt in der festen Schlackenschüttung durch Einleiten von Gasen oder Wasser zur Dampferzeugung oder zu Heizzwecken bis herab auf Umgebungstemperatur genutzt wird.3. The method according to claim 1, characterized in that the remaining heat content is used in the solid slag fill by introducing gases or water for steam generation or for heating purposes down to ambient temperature.
4. Vorrichtung zur Durchführung des Verfahrens nach Anspruch 1 oder einem der Ansprüche 2 bis 3, mit einer Anlage zur Ver- düsung von flüssiger Schlacke, dadurch gekennzeichnet, dass die Schlackenverdüsungsanlage einen abgeschlossenen Behälter bildet, in den die Schlacke eingebracht wird.4. A device for carrying out the method according to claim 1 or one of claims 2 to 3, with a plant for the dosing of liquid slag, characterized in that the Schlackenverdüsungsanlage forms a sealed container into which the slag is introduced.
5. Vorrichtung nach Anspruch 4, dadurch gekennzeichnet, dass die flüssige Schlacke über einen Verteiler granuliert wird.5. Apparatus according to claim 4, characterized in that the liquid slag is granulated via a distributor.
6. Vorrichtung nach Anspruch 4, dadurch gekennzeichnet, dass die flüssige Schlacke auf einen Drehteller fällt und von dort zur Granulation absprüht.6. Apparatus according to claim 4, characterized in that the liquid slag falls on a turntable and sprayed from there to granulation.
7. Vorrichtung nach einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, dass ein Behälter zur Aufnahme des Schlacken- granulates vorhanden ist. 7. Device according to one of claims 4 to 6, characterized in that a container for receiving the slag granules is present.
8. Vorrichtung nach einem der Ansprüche 4 bis 7, dadurch gekennzeichnet, dass eine Einheit zur Abgasreinigung vorhanden ist .8. Device according to one of claims 4 to 7, characterized in that a unit for exhaust gas purification is present.
9. Vorrichtung nach einem der Ansprüche 4 bis 8, dadurch gekennzeichnet, dass Wärmetauscher vorhanden sind.9. Device according to one of claims 4 to 8, characterized in that heat exchangers are present.
10. Vorrichtung nach Anspruch 4, dadurch gekennzeichnet, dass mit der Abwärme eine Gasturbine (125) betrieben wird. 10. The device according to claim 4, characterized in that with the waste heat, a gas turbine (125) is operated.
PCT/EP2009/064381 2008-11-21 2009-10-30 Method and device for using the waste heat of liquid slag WO2010057763A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011036180A1 (en) * 2009-09-24 2011-03-31 Siemens Aktiengesellschaft Method and device for using waste heat released in granulating a liquid slag
CN102721029A (en) * 2011-03-29 2012-10-10 鞍钢股份有限公司 Method and apparatus for recovering and utilizing sensible heat from liquid blast furnace slag
CN106989608A (en) * 2017-04-18 2017-07-28 南京工业大学 A kind of metallurgical liquid slag residual neat recovering system of hot blast dynamical type granulation and method
CN113816337A (en) * 2021-10-25 2021-12-21 上海驰春节能科技有限公司 Device and method for preparing hydrogen by reforming natural gas steam based on sensible heat of liquid metallurgical slag

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015044403A1 (en) * 2013-09-30 2015-04-02 Siemens Aktiengesellschaft Use of waste heat
CN109402309B (en) * 2018-11-13 2020-08-11 辽宁方盛环保科技有限公司 Method for recovering waste heat of steam released from slag stewing
US11401163B2 (en) * 2020-10-19 2022-08-02 Xenophon Verykios Catalytic materials for pyrolysis of methane and production of hydrogen and solid carbon with substantially zero atmospheric carbon emissions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000030989A1 (en) * 1998-11-25 2000-06-02 Holderbank Financiere Glarus Ag Method for crushing and granulating slag
EP1234890A1 (en) * 2001-02-27 2002-08-28 Tribovent Verfahrensentwicklung GmbH Device for atomising melts
CN2923723Y (en) * 2006-07-20 2007-07-18 重庆大学 Liquid furnace-sludge heat recovering apparatus

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000030989A1 (en) * 1998-11-25 2000-06-02 Holderbank Financiere Glarus Ag Method for crushing and granulating slag
EP1234890A1 (en) * 2001-02-27 2002-08-28 Tribovent Verfahrensentwicklung GmbH Device for atomising melts
CN2923723Y (en) * 2006-07-20 2007-07-18 重庆大学 Liquid furnace-sludge heat recovering apparatus

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MIZUOCHI T ET AL: "Granulation of molten slag for heat recovery", 37TH INTERSOCIETY ENERGY CONVERSION ENGINEERING CONFERENCE. (IECEC). WASHINGTON, DC, JULY 29 - 31, 2002; [IECEC. PROCEEDINGS OF THE INTERSOCIETY ENERGY CONVERSION ENGINEERING CONFERENCE], NEW YORK : IEEE, US, 29 July 2002 (2002-07-29), pages 641 - 646, XP010767114, ISBN: 978-0-7803-7296-2 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011036180A1 (en) * 2009-09-24 2011-03-31 Siemens Aktiengesellschaft Method and device for using waste heat released in granulating a liquid slag
CN102721029A (en) * 2011-03-29 2012-10-10 鞍钢股份有限公司 Method and apparatus for recovering and utilizing sensible heat from liquid blast furnace slag
CN106989608A (en) * 2017-04-18 2017-07-28 南京工业大学 A kind of metallurgical liquid slag residual neat recovering system of hot blast dynamical type granulation and method
CN106989608B (en) * 2017-04-18 2023-04-28 南京工业大学 Hot air power type granulating metallurgical liquid slag waste heat recovery system and method
CN113816337A (en) * 2021-10-25 2021-12-21 上海驰春节能科技有限公司 Device and method for preparing hydrogen by reforming natural gas steam based on sensible heat of liquid metallurgical slag
CN113816337B (en) * 2021-10-25 2023-01-31 上海驰春节能科技有限公司 Device and method for preparing hydrogen by reforming natural gas steam based on sensible heat of liquid metallurgical slag

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