EP2601318B1 - Aggregate containing coke and titanium and use thereof to repair the lining of metallurgical vessels - Google Patents

Aggregate containing coke and titanium and use thereof to repair the lining of metallurgical vessels Download PDF

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Publication number
EP2601318B1
EP2601318B1 EP11761487.5A EP11761487A EP2601318B1 EP 2601318 B1 EP2601318 B1 EP 2601318B1 EP 11761487 A EP11761487 A EP 11761487A EP 2601318 B1 EP2601318 B1 EP 2601318B1
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EP
European Patent Office
Prior art keywords
titanium
coke
aggregate
anyone
compounds
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.)
Not-in-force
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EP11761487.5A
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German (de)
French (fr)
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EP2601318A1 (en
Inventor
Djamschid Amirzadeh-Asl
Dieter FÜNDERS
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Venator Germany GmbH
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Sachtleben Chemie GmbH
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Priority to EP11761487.5A priority Critical patent/EP2601318B1/en
Priority to PL11761487T priority patent/PL2601318T3/en
Publication of EP2601318A1 publication Critical patent/EP2601318A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C21B5/001—Injecting additional fuel or reducing agents
    • C21B5/003—Injection of pulverulent coal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/16—Making or repairing linings increasing the durability of linings or breaking away linings
    • F27D1/1636—Repairing linings by projecting or spraying refractory materials on the lining
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C21B5/007—Conditions of the cokes or characterised by the cokes used
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B7/00—Blast furnaces
    • C21B7/04—Blast furnaces with special refractories
    • C21B7/06—Linings for furnaces
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/16—Making or repairing linings increasing the durability of linings or breaking away linings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/16—Making or repairing linings increasing the durability of linings or breaking away linings
    • F27D1/1678—Increasing the durability of linings; Means for protecting

Definitions

  • the invention relates to a coke- and titanium-containing additive, to a process for the production thereof and to its use for repairing the lining of metallurgical vessels, and to a process for accelerating the formation of highly refractory titanium compounds by direct reduction in metallurgical processes with its use.
  • the goal is to produce titanium-containing aggregates to form titanium-containing, high-refractory / wear-resistant compounds, such as titanium dioxide.
  • titanium-containing, high-refractory / wear-resistant compounds such as titanium dioxide.
  • TiC, TiN, TiCN, etc. which then precipitate in further steps partially in the endangered by wear processes areas of the respective refractory lining and selbige protect and / or repair.
  • Coal-containing raw materials are usually used for the production of PCl coal, which are ground in a special grinding process fine grained, as well as dried in a mostly parallel drying process at low temperatures.
  • the carbonaceous raw materials in some cases fine-grained titanium carriers are added and then blown into the blast furnace to then form titanium carbides or titanium carbonitrides in the reaction chamber of the blast furnace.
  • a disadvantage of the carbonaceous materials used so far is that these carbonaceous materials usually contain complicated mixtures of hydrocarbons of various kinds and further numerous impurities by ash formers.
  • the desired formation of wear-resistant titanium compounds is reduced, on the other hand, undesirable hindrances of the desired reaction kinetics occur, which hinder or significantly reduce the formation of wear-resistant titanium compounds.
  • the object of the invention is to increase the yield of highly refractory titanium compounds formed in relation to the titanium-containing materials used in the metallurgical vessel.
  • the inventors of the present invention have found that the reaction kinetics in front of the blow molds or in the respective liquid phases such as pig iron and slag can be accelerated by a very significant effect.
  • the object can be achieved by providing the method according to the invention and the additive according to the invention from coke-containing materials and titanium-containing compounds.
  • the invention thus also relates to an aggregate according to the invention of coke-containing material or mixtures of several different coke-containing materials and titanium-containing compounds for introduction into a metallurgical vessel.
  • coked material also includes a carbonaceous material such as coal, coke or mixtures of several different ones Coke-containing materials, understood, containing only a small proportion of less than 25 wt .-%, preferably less than 10 wt .-% volatile at elevated temperatures, in particular organic substances such as hydrocarbons, gases, etc.
  • the carbonaceous material may be subjected to a thermal pretreatment in which the volatiles are expelled and thus no longer interfere with the intimate contact between coke-containing material and titanium-containing compounds in the metallurgical vessel.
  • the material is usually dried in the first phase, if a water content is present.
  • the additive according to the invention may contain up to 60% by weight of water, preferably up to 35% by weight of water. As a rule and depending on the application, partial or drying is then necessary as a thermal pretreatment for such water contents.
  • the aggregate according to the invention of coke-containing material and titanium-containing compounds can thus contain particles of the coke-containing material and of the titanium-containing compounds next to one another as a powder mixture whose particle size is matched to the desired intended use.
  • particle sizes of less than 200 ⁇ m, preferably less than 100 ⁇ m, are used for injection of a powder mixture, while larger particle sizes of up to 200 mm are permissible by other means when introduced into the metallurgical vessel.
  • the grain size can be selected from the blast furnace coke types HK 1 (> 80 mm), HK 2 (> 60 mm), HK 3 (> 40 mm) and HK 4 (> 20 or 25 mm), the smaller sizes being preferred. Therefore, a coarser coke can be further crushed or ground until an advantageous grain size of less than 10mm results.
  • the use of coke breeze with a grain size of up to 10 mm is also an advantage.
  • a carbonaceous material containing no or only small amounts of less than 25 wt .-%, preferably less than 10 wt .-% based on the carbonaceous material, at at the reaction site in the metallurgical vessel given volatile temperatures, in particular organic substances such as hydrocarbons.
  • volatile temperatures in particular organic substances such as hydrocarbons.
  • petroleum coke, coke breeze, activated carbon or spent activated carbon, and charcoal and anthracite preferably with a low volatile content of less than 10% by weight, are mentioned here.
  • the titanium-containing compounds in the desired amount is added to the coking or carbonaceous material which is fed to the coking, so that the coke formation proceeds in the presence of the titanium-containing materials and a lumpy material is formed, the coke and titanium-containing materials "side by side”.
  • This lumpy material can then be brought by sieving, grinding, etc. to the desired grain size. So it is also possible, this lumpy material containing coke and titanium-containing materials "side by side", the metallurgical vessel, as in a blast furnace from above via the filling as an addition to Möller supply.
  • the lumpy material can also be advantageously ground to a particle size that is suitable for injection.
  • the particles of the aggregate according to the invention of coke-containing material and titanium compounds can have a grain size of from 0 to 200, preferably up to 150 mm.
  • the aggregate according to the invention of coke-containing material and titanium-containing compounds advantageously has a fineness of 90%, preferably 100%, less than 100 mm, preferably less than 10 mm, more preferably less than 1 mm and most preferably less than 0.5 mm.
  • the additive according to the invention is characterized by such a finely divided coke-containing and titanium-containing additive, the particles of which 90% have a diameter of at most 100 micrometers. This last embodiment is particularly for the Blowing into a metallurgical vessel, such as a blast furnace, suitable for blow molding.
  • the invention also relates to a coke-containing and titanium-containing aggregate whose particles have at least 95% a diameter of at most 150 microns and a water content of 0.1 to 60%, and a method for producing the aggregate according to procedures described above, thus also a process for producing the aggregate by mixing the carbonaceous fine particulate coke with the finely divided titanium compounds.
  • the invention also provides a coke and titanium-containing aggregate having a particle size of 10 to 150 mm and a water content of 0.1 to 15% by weight.
  • This coke and titanium-containing additive can also be advantageously prepared by mixing the coke-containing material with the titanium-containing compounds and ground together depending on the application and thus to achieve the desired grain size and intimate mixing of the preferably finely divided components.
  • the material used to make the coke as a coke-forming agent such as charcoal, e.g. Hard coal, lignite, pitch, tar and similar carbonaceous materials together with the titanium-containing compounds / material are pyrolyzed by heat exposure to oxygen in a coking stage and, if desired, the resulting lumpy pyrolyzate of coke-containing material and titanium-containing material to the desired, depending on the application Grain size broken or ground.
  • the titanium-containing compounds used with the carbonaceous material can already partially or completely react to TiOC, TiC, TiCN and similar highly refractory compounds.
  • the aggregate of coke-containing material and titanium-containing compounds according to the invention may contain 10 to 98% by weight, preferably 25 to 95% by weight, particularly preferably 35 to 90% by weight, very particularly preferably 45 to 80% by weight of coke-containing material, in particular coke, calculated from the total carbon content and based on preferably dried at 105 ° C material.
  • the aggregate according to the invention of titanium-containing compounds and carbonaceous material in particular in the production via the coking common, preferably contains 10 to 65 wt .-% of titanium-containing material / compounds and an amount of 35 to 90 wt .-% of coke-containing material, preferably one Amount of 20 to 55 wt .-% of titanium-containing material / compounds and an amount of 45 to 80 wt .-% of coke-containing material. All information in the description in% by weight to solids content refers to a dried at 105 ° C material.
  • the titanium-containing materials used to produce the additive according to the invention generally contain 5 to 60, preferably 10 to 60 wt .-% Ti, usually as TiO 2 or in conjunction with other metals as titanates.
  • synthetic titanium dioxide-containing materials those from the production of titanium dioxide, by the sulfate or chloride method, as intermediate or co-products or residuals from the ongoing TiO 2 production can be used become. It is also possible that residues or wastes from the chemical industry or paper industry or from titanium extraction are used as synthetic titanium-containing materials.
  • the typical TiO 2 residues are TiO 2 residues from the TiO 2 production after the sulphate process. It is also advantageous to use titanium-containing catalysts consumed in the context of the invention, for example DENOX catalysts or Claus catalysts.
  • materials such as natural titanium support such.
  • B ilmenite, ilmenite sand, rutile sand and / or titanium-containing slags (eg slag) which are capable of forming refractory titanium carbonitrides under reaction conditions in the blast furnace.
  • the above-mentioned synthetic and natural titanium-containing carriers may be used singly or in mixtures for the production of coke-containing titanium compounds.
  • the additive of coke-containing material and titanium-containing compounds according to the invention may contain other constituents of metal oxides and / or metal hydroxides such as Al 2 O 3 , iron oxides, CaO, MgO, SiO 2 , ZrO 2 , Al (OH) 3 , Ca (OH) 2 , Mg (OH) 2 or mixed oxides thereof and mixtures of several components thereof and further ingredients such as slag formers in an amount of preferably up to 50 wt .-% of the total amount.
  • metal oxides and / or metal hydroxides such as Al 2 O 3 , iron oxides, CaO, MgO, SiO 2 , ZrO 2 , Al (OH) 3 , Ca (OH) 2 , Mg (OH) 2 or mixed oxides thereof and mixtures of several components thereof and further ingredients such as slag formers in an amount of preferably up to 50 wt .-% of the total amount.
  • the aggregate of coke-containing material and titanium-containing compounds according to the invention can also be blown directly into damaged areas in the region of the frame.
  • the additive according to the invention may preferably have a water content of 0.1 to 15 wt .-%.
  • the addition of the inventive / aggregate of coke-containing material and titanium-containing compounds in the course of the preparation of finely divided injection coal (PCI) for the injection into the blast furnace can already be added to the carbonaceous raw materials.
  • the amount of addition of inventive additive from Coke-containing material and titanium-containing compounds may be at from 0.5 to 100% by weight, preferably 0.5 to 80 wt .-%, preferably 1 to 50 wt .-% and most particularly at 2 to 40 wt .-% of the blown Materials lie.
  • the aggregate of coke-containing material and titanium-containing compounds according to the invention can be added to a carbonaceous material such as oil, heavy oil, tar, pitch and / or natural gas and then blown into the metallurgical vessel via the blow molds.
  • a carbonaceous material such as oil, heavy oil, tar, pitch and / or natural gas
  • the coke- and titanium-containing aggregate is characterized by the fact that the time-consuming and costly coking processes occurring only in the blast furnace can be saved and the feedstocks can be used free of volatile constituents and other impurities.
  • the use of the aggregate is thus "energy neutral" since the blast furnace will not be deprived of energy to volatilize volatiles and char to coke and will not use coke supplied to the blast furnace for iron production.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)
  • Coke Industry (AREA)
  • Blast Furnaces (AREA)
  • Carbon And Carbon Compounds (AREA)

Description

Die Erfindung betrifft einen koks- und titanhaltigen Zuschlagstoff, Verfahren zu dessen Herstellung und dessen Verwendung zur Reparatur der Auskleidung von metallurgischen Gefäßen sowie ein Verfahren zur Beschleunigung der Bildung von hochfeuerfesten Titanverbindungen durch Direktreduktion bei metallurgischen Prozessen unter dessen Verwendung.The invention relates to a coke- and titanium-containing additive, to a process for the production thereof and to its use for repairing the lining of metallurgical vessels, and to a process for accelerating the formation of highly refractory titanium compounds by direct reduction in metallurgical processes with its use.

Die Verwendung titanhaltiger Zuschlagstoffe zur Reparatur der Auskleidung von metallurgischen Gefäßen wie z.B. Hochöfen ist seit langem bekannt.The use of titanium-containing aggregates to repair the lining of metallurgical vessels, e.g. Blast furnaces has been known for a long time.

In den meisten Bereichen ist das Ziel, titanhaltige Zuschlagstoffe unter Bildung von titanhaltigen, hochfeuerfesten/verschleißfesten Verbindungen wie z.B. TiC, TiN, TiCN usw. umzusetzen, welche dann in weiteren Schritten teilweise sich in den durch Verschleißprozesse gefährdeten Bereichen der jeweiligen feuerfesten Auskleidung niederschlagen und selbige schützen und/oder reparieren sollen.In most areas, the goal is to produce titanium-containing aggregates to form titanium-containing, high-refractory / wear-resistant compounds, such as titanium dioxide. TiC, TiN, TiCN, etc., which then precipitate in further steps partially in the endangered by wear processes areas of the respective refractory lining and selbige protect and / or repair.

Es gehört zum Stand der Technik, titanhaltige Materialien in Mischungen mit kohlenstoffhaltigen Materialien in metallurgischen Gefäßen einzusetzen. DE 19830102 offenbart ein solches Material.It is well known in the art to use titanium-containing materials in blends with carbonaceous materials in metallurgical vessels. DE 19830102 discloses such a material.

Es ist ferner Stand der Technik, durch die Blasformen der Hochöfen Kohle (pulverized coal injection - im Folgenden PCl genannt) Öl/Erdgas und/oder Teer, Pech, als Energieträger und Reduktionsmittel für den Verhüttungsprozess einzublasen. Außerdem wird Koks als Brennstoff und als Reduktionsmittel bei der Eisenproduktion z. B. in Hochöfen eingesetzt. Die Herstellung von Koks erfolgt durch Pyrolyse der Fettkohle. Bei der Verhüttung wird Koks mit einer Körnung zwischen 20 bis 150 mm verarbeitet.It is also state of the art, by the blow molding of blast furnaces coal (pulverized coal injection - hereinafter called PCl) to inject oil / natural gas and / or tar, pitch, as an energy source and reducing agent for the smelting process. In addition, coke is used as fuel and as a reducing agent in iron production z. B. used in blast furnaces. The production of coke is carried out by pyrolysis of the coal. In smelting, coke with a grain size between 20 to 150 mm is processed.

Für die Herstellung der PCl-Kohle werden dabei in der Regel kohlehaltige Rohstoffe eingesetzt, welche in einem speziellen Mahlprozess feinkörnig gemahlen werden, als auch in einem meist parallel geschalteten Trocknungsprozess bei niedrigen Temperaturen getrocknet werden.Coal-containing raw materials are usually used for the production of PCl coal, which are ground in a special grinding process fine grained, as well as dried in a mostly parallel drying process at low temperatures.

So werden den kohlehaltigen Rohstoffen in einigen Fällen feinkörnige Titanträger zugemischt und anschließend in den Hochofen eingeblasen, um dann in dem Reaktionsraum des Hochofens Titancarbide bzw. Titancarbonitride zu bilden. Im Bereich der Hochofentechnologie kommt es dabei darauf an, möglichst schnell im Bereich des Gasraumes um die Blasformen herum und in den jeweiligen Flüssigphasen wie Roheisen und Schlacke die gewünschten verschleißfesten Titancarbide zu erzeugen und diese verschleißfesten Titancarbide dann im zweiten Schritt auf den jeweils zu reparierenden/zu schützenden feuerfesten Ausmauerungen mit möglichst hoher Ausbeute abzulagern.Thus, the carbonaceous raw materials in some cases fine-grained titanium carriers are added and then blown into the blast furnace to then form titanium carbides or titanium carbonitrides in the reaction chamber of the blast furnace. In the field of blast furnace technology, it is important to produce the desired wear-resistant titanium carbides as quickly as possible in the region of the gas space around the blow molds and in the respective liquid phases, such as pig iron and slag, and then, in the second step, to process these wear-resistant titanium carbides deposit protective refractory linings with the highest possible yield.

Ein Nachteil der bisher eingesetzten kohlenhaltigen Materialien ist, dass diese kohlenhaltigen Materialien in der Regel komplizierte Gemische von Kohlenwasserstoffen diverser Art und weitere zahlreiche Verunreinigungen durch Aschebildner enthalten. Dadurch wird einerseits die gewünschte Bildung von verschleißfesten Titanverbindungen reduziert, andererseits kommt es zu unerwünschten Behinderungen der gewünschten Reaktionskinetik, welche die Bildung von verschleißfesten Titanverbindungen behindert, bzw. deutlich reduziert. Dadurch wird die Menge von verschleißfesten Titanverbindungen (z.B. TiCN) reduziert, und die Folge ist, dass der Hauptteil des eingesetzten Titans dem System durch die Verschlackung ungenutzt entzogen wird.A disadvantage of the carbonaceous materials used so far is that these carbonaceous materials usually contain complicated mixtures of hydrocarbons of various kinds and further numerous impurities by ash formers. As a result, on the one hand, the desired formation of wear-resistant titanium compounds is reduced, on the other hand, undesirable hindrances of the desired reaction kinetics occur, which hinder or significantly reduce the formation of wear-resistant titanium compounds. This reduces the amount of wear-resistant titanium compounds (e.g., TiCN), and the result is that most of the titanium used is depleted of the system by the slag.

Aufgabe der Erfindung ist, die Ausbeute an gebildeten hochfeuerfesten Titanverbindungen im Verhältnis zu den eingesetzten titanhaltigen Materialien zur Anwendung im metallurgischen Gefäß zu steigern.The object of the invention is to increase the yield of highly refractory titanium compounds formed in relation to the titanium-containing materials used in the metallurgical vessel.

In diesem Zusammenhang haben die Erfinder der vorliegenden Erfindung herausgefunden, dass die Reaktionskinetik vor den Blasformen bzw. im Bereich jeweiligen Flüssigphasen wie Roheisen und Schlacke durch einen sehr bedeutsamen Effekt beschleunigt werden kann.In this connection, the inventors of the present invention have found that the reaction kinetics in front of the blow molds or in the respective liquid phases such as pig iron and slag can be accelerated by a very significant effect.

Gemäß den Untersuchungen der Erfinder treffen beim Einblasen von PCI-Gemischen zusammen mit Titanverbindungen mit hoher Geschwindigkeit die jeweiligen Teilchen statistisch nur selten aufeinander. Wenn die Teilchen dann irgendwann aufeinandertreffen, werden die Titanverbindungen von den vergasten bzw. freigesetzten Kohlenwasserstoffen der Injektionskohle wieder zurückgestoßen, so dass zu diesem Zeitpunkt trotz eines Teilchenkontaktes keine Titancarbide gebildet werden. Erst bei einem weiteren Aufeinandertreffen im zweiten, dritten usw. Anlauf, wenn die flüchtigen Kohlenwasserstoffe ihren abweisenden Einfluss nicht mehr ausüben können, da der Großteil von ihnen vergast ist, ist die Reaktion von "quasi reinem" Kohlenstoff und den jeweiligen Titanverbindungen zu Titankarbiden möglich.According to the investigations of the inventors, when injecting PCI mixtures together with titanium compounds at high speed statistically only rarely on each other. If the particles then meet at some point, the titanium compounds are again repelled by the gasified hydrocarbons of the injection coal, so that no titanium carbides are formed at this time despite a particle contact. It is only at a further meeting in the second, third, etc. start-up, when the volatile hydrocarbons can no longer exert their repellent effect, since most of them are gasified, the reaction of "quasi-pure" carbon and the respective titanium compounds to titanium carbides is possible.

Die Aufgabe kann mit der Bereitstellung des erfindungsgemäßen Verfahrens und des erfindungsgemäßen Zuschlagstoffes aus kokshaltigen Materialien und titanhaltigen Verbindungen gelöst werden.The object can be achieved by providing the method according to the invention and the additive according to the invention from coke-containing materials and titanium-containing compounds.

Mit dem erfindungsgemäßen Verfahren ist es so möglich, insbesondere die Menge der pro Zeiteinheit gebildeten hochfeuerfesten Titanverbindungen zu erhöhen und gleichzeitig das metallurgische Ausbringen der dem System zugeführten Titanverbindungen zu verbessern.With the method according to the invention it is thus possible, in particular to increase the amount of high-refractory titanium compounds formed per unit time and at the same time to improve the metallurgical application of the titanium compounds fed to the system.

Die Erfindung betrifft somit auch einen erfindungsgemäßen Zuschlagstoff aus kokshaltigem Material oder Mischungen mehrerer unterschiedlicher kokshaltiger Materialien und titanhaltigen Verbindungen für die Einbringung in ein metallurgisches Gefäß.The invention thus also relates to an aggregate according to the invention of coke-containing material or mixtures of several different coke-containing materials and titanium-containing compounds for introduction into a metallurgical vessel.

Es wurde überraschenderweise gefunden, dass durch Einblasen eines solchen Zuschlagstoffes aus kokshaltigem Material und titanhaltigen Materialien/Verbindungen die Umsetzung der Reaktionspartner zur Bildung von hochfeuerfesten Titancarbonitriden in einer unmittelbaren Reaktion (Direktreduktion) deutlich verbessert wird und die Ausbeute von Titancarbonitriden dadurch stark erhöht wird.It has surprisingly been found that by blowing in such an additive of coke-containing material and titanium-containing materials / compounds, the reaction of the reactants to form highly refractory titanium carbonitrides in a direct reaction (direct reduction) is significantly improved and the yield of titanium carbonitrides is thereby greatly increased.

Unter kokshaltigem Material wird erfindungsgemäß auch ein kohlenstoffhaltiges Material wie Kohle, Koks oder Mischungen mehrerer unterschiedlicher kokshaltiger Materialien, verstanden, das nur einen geringen Anteil von weniger als 25 Gew.-% bevorzugt weniger als 10 Gew.-% an bei den erhöhten Temperaturen flüchtigen, insbesondere organischen Substanzen wie Kohlenwasserstoffen, Gasen etc. enthält. Um dies zu erreichen, kann das kohlenstoffhaltige Material einer thermischen Vorbehandlung unterzogen werden, bei der die flüchtigen Substanzen ausgetrieben werden und so bei der Verwendung den innigen Kontakt zwischen kokshaltigem Material und titanhaltigen Verbindungen im metallurgischen Gefäß nicht mehr beeinträchtigen. Bei einer solchen thermischen Vorbehandlung wird in der Regel in der ersten Phase das Material getrocknet, falls ein Wassergehalt vorhanden ist. Der erfindungsgemäße Zuschlagstoff kann bis zu 60 Gew.-% Wasser, bevorzugt bis zu 35 Gew.-% Wasser enthalten. In der Regel und je nach Anwendung ist bei solchen Wassergehalten dann eine Teil- bzw. Trocknung als thermische Vorbehandlung notwendig.According to the invention, coked material also includes a carbonaceous material such as coal, coke or mixtures of several different ones Coke-containing materials, understood, containing only a small proportion of less than 25 wt .-%, preferably less than 10 wt .-% volatile at elevated temperatures, in particular organic substances such as hydrocarbons, gases, etc. To accomplish this, the carbonaceous material may be subjected to a thermal pretreatment in which the volatiles are expelled and thus no longer interfere with the intimate contact between coke-containing material and titanium-containing compounds in the metallurgical vessel. In such a thermal pretreatment, the material is usually dried in the first phase, if a water content is present. The additive according to the invention may contain up to 60% by weight of water, preferably up to 35% by weight of water. As a rule and depending on the application, partial or drying is then necessary as a thermal pretreatment for such water contents.

Der erfindungsgemäße Zuschlagstoff aus kokshaltigem Material und titanhaltigen Verbindungen kann somit Teilchen des kokshaltigen Materials und der titanhaltigen Verbindungen nebeneinander als Pulvermischung enthalten, deren Korngröße auf den angestrebten Verwendungszweck abgestimmt ist. So werden für die Einblasung einer Pulvermischung Korngrößen von weniger als 200mµ bevorzugt weniger als 100µm eingesetzt, während bei einer Einbringung in das metallurgische Gefäß auf anderem Wege auch größere Korngrößen von bis zu 200mm zulässig sind.The aggregate according to the invention of coke-containing material and titanium-containing compounds can thus contain particles of the coke-containing material and of the titanium-containing compounds next to one another as a powder mixture whose particle size is matched to the desired intended use. For example, particle sizes of less than 200 μm, preferably less than 100 μm, are used for injection of a powder mixture, while larger particle sizes of up to 200 mm are permissible by other means when introduced into the metallurgical vessel.

Wenn beispielsweise Koks als kohlenstoffhaltiges Material in einer solchen Mischung eingesetzt werden soll, kann die Korngröße aus den Hochofenkokssorten HK 1 (> 80 mm), HK 2 (> 60 mm), HK 3 (> 40 mm) sowie HK 4 (> 20 bzw. 25 mm) ausgewählt werden, wobei die kleineren Größen bevorzugt sind. Daher kann auch ein gröberer Koks weiter gebrochen oder gemahlen werden, bis sich eine vorteilhafte Körnung von unter 10mm ergibt. Auch die Verwendung von Koksgrus mit einer Körnung von bis zu 10 mm bietet sich vorteilhaft an.If, for example, coke is to be used as the carbonaceous material in such a mixture, the grain size can be selected from the blast furnace coke types HK 1 (> 80 mm), HK 2 (> 60 mm), HK 3 (> 40 mm) and HK 4 (> 20 or 25 mm), the smaller sizes being preferred. Therefore, a coarser coke can be further crushed or ground until an advantageous grain size of less than 10mm results. The use of coke breeze with a grain size of up to 10 mm is also an advantage.

Anstelle oder zusammen mit Koks kann erfindungsgemäß ein kohlenstoffhaltiges Material verwendet werden, das keine oder nur geringe Mengen von weniger als 25 Gew.-%, bevorzugt weniger als 10 Gew.-% bezogen auf das kohlenstoffhaltige Material, an bei den am Reaktionsort im metallurgischen Gefäß gegebenen Temperaturen flüchtigen, insbesondere organischen Substanzen wie Kohlenwasserstoffen enthält. Beispielhaft ist hier Petrolkoks, Koksgruß, Aktivkohle oder verbrauchte Aktivkohle sowie Magerkohle und Anthrazit vorzugsweise mit einem geringen flüchtigen Anteil von weniger als 10 Gew.-% genannt.Instead of or together with coke can be used according to the invention, a carbonaceous material containing no or only small amounts of less than 25 wt .-%, preferably less than 10 wt .-% based on the carbonaceous material, at at the reaction site in the metallurgical vessel given volatile temperatures, in particular organic substances such as hydrocarbons. By way of example, petroleum coke, coke breeze, activated carbon or spent activated carbon, and charcoal and anthracite, preferably with a low volatile content of less than 10% by weight, are mentioned here.

Von besonderem Vorteil ist es, der Kohle oder dem kohlenstoffhaltigen Material, das der Verkokung zugeführt wird, bei der Verkokung die titanhaltigen Verbindungen in der gewünschten Menge zuzugeben, so dass die Koksbildung in Gegenwart der titanhaltigen Materialien abläuft und ein stückiges Material gebildet wird, das Koks und titanhaltige Materialien "nebeneinander" enthält. Dieses stückige Material kann dann durch Sieben, Mahlen etc. auf die gewünschte Körnung gebracht werden. So ist es auch möglich, dieses stückige Material, das Koks und titanhaltige Materialien "nebeneinander" enthält, dem metallurgischen Gefäß, wie bei einem Hochofen von oben über die Befüllung als Zusatz zum Möller, zuzuführen. Das stückige Material lässt sich aber auch vorteilhaft zu einer Korngröße vermahlen, die für die Einblasung geeignet ist.It is particularly advantageous to add the titanium-containing compounds in the desired amount to the coking or carbonaceous material which is fed to the coking, so that the coke formation proceeds in the presence of the titanium-containing materials and a lumpy material is formed, the coke and titanium-containing materials "side by side". This lumpy material can then be brought by sieving, grinding, etc. to the desired grain size. So it is also possible, this lumpy material containing coke and titanium-containing materials "side by side", the metallurgical vessel, as in a blast furnace from above via the filling as an addition to Möller supply. However, the lumpy material can also be advantageously ground to a particle size that is suitable for injection.

Somit können die Teilchen des erfindungsgemäßen Zuschlagstoffes aus kokshaltigem Material und Titanverbindungen (koks- und titanhaltiger Zuschlagstoff) eine Körnung von 0 bis 200, bevorzugt bis 150 mm haben. Der erfindungsgemäße Zuschlagstoff aus kokshaltigem Material und titanhaltigen Verbindungen weist vorteilhaft eine Feinheit von 90%, bevorzugt 100 %, kleiner als 100 mm, bevorzugt kleiner als 10 mm, besonders bevorzugt kleiner 1 mm und ganz besonders bevorzugt von kleiner als 0,5 mm auf. In einer anderen vorteilhaften Ausführungsform ist der erfindungsgemäße Zuschlagstoff charakterisiert durch einen solchen feinteiligen koks- und titanhaltigen Zuschlagstoff, dessen Teilchen zu 90 % einen Durchmesser von höchstens 100 Mikrometer aufweisen. Diese letzte Ausführungsform ist insbesondere für die Einblasung in ein metallurgischen Gefäß, wie einen Hochofen, über Blasformen geeignet.Thus, the particles of the aggregate according to the invention of coke-containing material and titanium compounds (coke-containing and titanium-containing aggregate) can have a grain size of from 0 to 200, preferably up to 150 mm. The aggregate according to the invention of coke-containing material and titanium-containing compounds advantageously has a fineness of 90%, preferably 100%, less than 100 mm, preferably less than 10 mm, more preferably less than 1 mm and most preferably less than 0.5 mm. In another advantageous embodiment, the additive according to the invention is characterized by such a finely divided coke-containing and titanium-containing additive, the particles of which 90% have a diameter of at most 100 micrometers. This last embodiment is particularly for the Blowing into a metallurgical vessel, such as a blast furnace, suitable for blow molding.

Gegenstand der Erfindung ist auch ein koks- und titanhaltiger Zuschlagstoff, dessen Teilchen zu mindestens 95 % einen Durchmesser von höchstens 150 µm und einen Wassergehalt von 0,1 bis 60 % aufweisen, sowie ein Verfahren zur Herstellung des Zuschlagstoffes gemäß oben beschriebenen Verfahrensweisen, somit auch ein Verfahren zur Herstellung des Zuschlagstoffes durch Vermischen des kohlenstoffhaltigen feinteiligen Kokses mit den feinteiligen Titanverbindungen.The invention also relates to a coke-containing and titanium-containing aggregate whose particles have at least 95% a diameter of at most 150 microns and a water content of 0.1 to 60%, and a method for producing the aggregate according to procedures described above, thus also a process for producing the aggregate by mixing the carbonaceous fine particulate coke with the finely divided titanium compounds.

Gegenstand der Erfindung ist auch ein koks- und titanhaltiger Zuschlagstoff mit einer Körnung von 10 bis 150 mm und einem Wassergehalt von 0,1 bis 15 Gew%.The invention also provides a coke and titanium-containing aggregate having a particle size of 10 to 150 mm and a water content of 0.1 to 15% by weight.

Dieser koks- und titanhaltige Zuschlagstoff kann auch dadurch vorteilhaft hergestellt werden, das kokshaltige Material mit den titanhaltigen Verbindungen zu vermengen und je nach Anwendungsgebiet gemeinsam zu vermahlen und so die gewünschte Körnung und innige Vermischung der bevorzugt feinteiligen Komponenten zu erzielen.This coke and titanium-containing additive can also be advantageously prepared by mixing the coke-containing material with the titanium-containing compounds and ground together depending on the application and thus to achieve the desired grain size and intimate mixing of the preferably finely divided components.

Wie oben beschrieben, kann das zur Herstellung des Kokses als Koksbildner eingesetzte Material wie Fettkohle, z.B. Steinkohle, Braunkohle, Pech, Teer und ähnliche kohlenstoffhaltigen Materialien gemeinsam mit den titanhaltigen Verbindungen/Material durch Wärmeeinwirkung unter Sauerstoffabschluss in einer Verkokungsstufe pyrolysiert werden und, falls gewünscht, das erhaltene, oft stückige Pyrolysat aus kokshaltigem Material und titanhaltigem Material je nach Anwendungsgebiet auf die gewünschte Korngröße gebrochen bzw. vermahlen werden.As described above, the material used to make the coke as a coke-forming agent, such as charcoal, e.g. Hard coal, lignite, pitch, tar and similar carbonaceous materials together with the titanium-containing compounds / material are pyrolyzed by heat exposure to oxygen in a coking stage and, if desired, the resulting lumpy pyrolyzate of coke-containing material and titanium-containing material to the desired, depending on the application Grain size broken or ground.

Auf diese Weise ist durch eine thermische Vorbehandlung wie eine Verkokung zuverlässig gewährleistet, dass während der Verkokung die flüchtigen Bestandteile, die einen innigen Kontakt zwischen kokshaltigem Material und titanhaltigem Material Im Hochofen beeinträchtigen, ausgetrieben werden und so der innige Kontakt zwischen kokshaltigem Material und titanhaltigem Material gewährleistet ist.. Bei dieser Verfahrensweise können die eingesetzten titanhaltigen Verbindungen mit dem kohlehaltigen Material schon teilweise oder vollständig zu TiOC, TiC, TiCN und ähnlichen hochfeuerfesten Verbindungen reagieren. So kann das Gemisch, bzw. die teilweise stofflich miteinander verbundenen Materialien (kokshaltiges Material und titanhaltiges Material), das auch als erfindungsgemäßer koks- und titanhaltigen Zuschlagstoff verstanden wird, am Reaktionsort im metallurgischen Gefäß unmittelbar und ohne störende "Verdampfungsreaktionen" der flüchtigen Bestandteile zu den Titancarbonitriden reagieren.In this way, it is reliably ensured by a thermal pretreatment such as coking that during the coking the volatile constituents, which impair intimate contact between coke-containing material and titanium-containing material in the blast furnace, are expelled and so forth the intimate contact between coke-containing material and titanium-containing material is ensured. In this procedure, the titanium-containing compounds used with the carbonaceous material can already partially or completely react to TiOC, TiC, TiCN and similar highly refractory compounds. Thus, the mixture, or the partially materially interconnected materials (coke-containing material and titanium-containing material), which is also understood as inventive coke and titanium-containing additive, at the reaction site in the metallurgical vessel immediately and without disturbing "evaporation reactions" of the volatile components to the Titancarbonitriden react.

Der erfindungsgemäße Zuschlagstoff aus kokshaltigem Material und titanhaltigen Verbindungen kann 10 bis 98 Gew.-%, bevorzugt 25 bis 95 Gew.-%, besonders bevorzugt 35 bis 90 Gew.-%, ganz besonders bevorzugt 45 bis 80 Gew.-% kokshaltiges Material, insbesondere Koks, berechnet aus dem Gesamtkohlenstoffgehalt und bezogen auf bei vorzugsweise 105°C getrocknetes Material, enthalten.The aggregate of coke-containing material and titanium-containing compounds according to the invention may contain 10 to 98% by weight, preferably 25 to 95% by weight, particularly preferably 35 to 90% by weight, very particularly preferably 45 to 80% by weight of coke-containing material, in particular coke, calculated from the total carbon content and based on preferably dried at 105 ° C material.

Der erfindungsgemäße Zuschlagstoff aus titanhaltigen Verbindungen und kohlenstoffhaltigem Material, insbesondere bei der Herstellung über die gemeinsame Verkokung, enthält bevorzugt 10 bis 65 Gew.-% an titanhaltigem Material/Verbindungen und eine Menge von 35 bis 90 Gew.-% an kokshaltigem Material, bevorzugt eine Menge von 20 bis 55 Gew.-%, an titanhaltigem Material/ Verbindungen und eine Menge von 45 bis 80 Gew.-% an kokshaltigem Material. Alle Angaben der Beschreibung in Gew.-% zu Feststoffgehalten beziehen sich auf ein bei 105°C getrocknetes Material.The aggregate according to the invention of titanium-containing compounds and carbonaceous material, in particular in the production via the coking common, preferably contains 10 to 65 wt .-% of titanium-containing material / compounds and an amount of 35 to 90 wt .-% of coke-containing material, preferably one Amount of 20 to 55 wt .-% of titanium-containing material / compounds and an amount of 45 to 80 wt .-% of coke-containing material. All information in the description in% by weight to solids content refers to a dried at 105 ° C material.

Die zur Herstellung des erfindungsgemäßen Zuschlagstoffes verwendeten titanhaltigen Materialien enthalten in der Regel 5 bis 60, bevorzugt 10 bis 60 Gew.-% Ti, zumeist als TiO2 oder in Verbindung mit anderen Metallen als Titanate. Als synthetische titandioxidhaltige Materialien können solche aus der Produktion von Titandioxid, nach dem Sulfat- oder Chloridverfahren, als Zwischen- oder Kuppelprodukte oder Reststoffe aus der laufenden TiO2-Produktion verwendet werden. Es ist ebenfalls möglich, dass als synthetische titanhaltigen Materialien Rückstände oder Abfälle aus Chemischen Industrie oder Papierindustrie bzw. aus Titangewinnung verwendet werden. Die typischen TiO2-Rückstände sind TiO2-Rückstände aus der TiO2-Produktion nach dem Sulfatverfahren. Ebenfalls können vorteilhaft im Rahmen der Erfindung verbrauchte titanhaltige Katalysatoren z.B. DENOX-Katalysatoren oder Claus-Katalysatoren Verwendung finden. Ferner können dazu Materialien wie natürliche Titanträger wie z. B Ilmenit, Ilmenitsand, Rutilsand und/oder titanhaltige Schlacken ( z. B.Sorelschlacke), die dazu in der Lage sind, unter den Bedingungen am Reaktionsort im Hochofen feuerfeste Titancarbonitride zu bilden, verwendet werden. Die oben genannten synthetischen und natürlichen titanhaltigen Träger können einzeln oder in Mischungen zur Herstellung von kokshaltigen Titanverbindungen verwendet werden.The titanium-containing materials used to produce the additive according to the invention generally contain 5 to 60, preferably 10 to 60 wt .-% Ti, usually as TiO 2 or in conjunction with other metals as titanates. As synthetic titanium dioxide-containing materials, those from the production of titanium dioxide, by the sulfate or chloride method, as intermediate or co-products or residuals from the ongoing TiO 2 production can be used become. It is also possible that residues or wastes from the chemical industry or paper industry or from titanium extraction are used as synthetic titanium-containing materials. The typical TiO 2 residues are TiO 2 residues from the TiO 2 production after the sulphate process. It is also advantageous to use titanium-containing catalysts consumed in the context of the invention, for example DENOX catalysts or Claus catalysts. Furthermore, materials such as natural titanium support such. B ilmenite, ilmenite sand, rutile sand and / or titanium-containing slags (eg slag) which are capable of forming refractory titanium carbonitrides under reaction conditions in the blast furnace. The above-mentioned synthetic and natural titanium-containing carriers may be used singly or in mixtures for the production of coke-containing titanium compounds.

Der erfindungsgemäße Zuschlagstoff aus kokshaltigem Material und titanhaltigen Verbindungen kann neben Kohlenstoff und TiO2 (berechnet aus Gesamt-Titan) noch andere Bestandteile aus Metalloxiden und/oder Metallhydroxiden wie z.B. Al2O3, Eisenoxide, CaO, MgO, SiO2, ZrO2, Al(OH)3, Ca(OH)2, Mg(OH)2 oder Mischoxide davon sowie Gemische von mehreren Komponenten davon sowie weiterhin Bestandteile wie Schlackebildner in einer Menge von vorzugsweise bis zu 50 Gew.-% der Gesamtmenge enthalten.In addition to carbon and TiO 2 (calculated from total titanium), the additive of coke-containing material and titanium-containing compounds according to the invention may contain other constituents of metal oxides and / or metal hydroxides such as Al 2 O 3 , iron oxides, CaO, MgO, SiO 2 , ZrO 2 , Al (OH) 3 , Ca (OH) 2 , Mg (OH) 2 or mixed oxides thereof and mixtures of several components thereof and further ingredients such as slag formers in an amount of preferably up to 50 wt .-% of the total amount.

Je nach Anwendung kann der erfindungsgemäße Zuschlagstoff aus kokshaltigem Material und titanhaltigen Verbindungen auch im Bereich des Gestells unmittelbar an schadhaften Stellen eingeblasen werden. In diesem Falle können der erfindungsgemäße Zuschlagstoff bevorzugt einen Wassergehalt von 0,1 bis 15 Gew.-% aufweisen.Depending on the application, the aggregate of coke-containing material and titanium-containing compounds according to the invention can also be blown directly into damaged areas in the region of the frame. In this case, the additive according to the invention may preferably have a water content of 0.1 to 15 wt .-%.

Alternativ kann die Zugabe de erfindungsgemäßen /Zuschlagstoffes aus kokshaltigem Material und titanhaltigen Verbindungen im Laufe der Aufbereitung der feinteiligen Injektionskohle (PCI) für die Einblasung in den Hochofen erfolgen. Dabei kann der erfindungsgemäße Zuschlagstoff aus kokshaltigem Material und titanhaltigen Verbindungen bereits den kohlenstoffhaltigen Rohstoffen zugegeben werden. Die Zugabemenge an erfindungsgemäßem Zuschlagstoff aus kokshaltigem Material und titanhaltigen Verbindungen kann bei 0,5 bis 100 Gew.- %, bevorzugt 0,5 bis 80 Gew.-%, vorzugsweise bei 1 bis 50 Gew.-% und ganz besonders bei 2 bis 40 Gew.-% des eingeblasenen Materials liegen.Alternatively, the addition of the inventive / aggregate of coke-containing material and titanium-containing compounds in the course of the preparation of finely divided injection coal (PCI) for the injection into the blast furnace. In this case, the additive according to the invention of coke-containing material and titanium-containing compounds can already be added to the carbonaceous raw materials. The amount of addition of inventive additive from Coke-containing material and titanium-containing compounds may be at from 0.5 to 100% by weight, preferably 0.5 to 80 wt .-%, preferably 1 to 50 wt .-% and most particularly at 2 to 40 wt .-% of the blown Materials lie.

Alternativ kann der erfindungsgemäße Zuschlagstoff aus kokshaltigem Material und titanhaltigen Verbindungen einem kohlenstoffhaltigem Material wie Öl, Schweröl, Teer, Pech und oder Erdgas hinzugeführt werden und anschließend über die Blasformen in das metallurgische Gefäß eingeblasen werden.Alternatively, the aggregate of coke-containing material and titanium-containing compounds according to the invention can be added to a carbonaceous material such as oil, heavy oil, tar, pitch and / or natural gas and then blown into the metallurgical vessel via the blow molds.

In entsprechender Weise kann eine gemeinsame Einblasung des erfindungsgemäßen Zuschlagsstoffes aus kokshaltigem Material und titanhaltigen Verbindungen mit Einblasstoffen wie Kunststoffen, in einer Menge bis zu 50 Gew.- % bezogen auf die Gesamtmenge an eingeblasenem Stoff über die Blasformen in das metallurgische Gefäß erfolgen.In a similar manner, a common blowing of the aggregate according to the invention from coke-containing material and titanium-containing compounds with Einblasstoffen such as plastics, in an amount up to 50% by weight based on the total amount of injected material on the blow molds in the metallurgical vessel.

Der koks- und titanhaltige Zuschlagstoff zeichnet sich dadurch aus, dass die zeitraubenden und kostspieligen erst im Hochofen ablaufenden Verkokungsprozesse eingespart werden können und die Einsatzstoffe frei von flüchtigen Bestandteilen und sonstigen Verunreinigungen eingesetzt werden können. Die Verwendung des Zuschlagstoffes ist somit "energieneutral", da dem Hochofen keine Energie zur Verdampfung flüchtiger Bestandteile und zur Verkokung der Kohle entzogen werden sowie kein dem Hochofen zur Eisenerzeugung zugeführter Koks dafür verwendet wird.The coke- and titanium-containing aggregate is characterized by the fact that the time-consuming and costly coking processes occurring only in the blast furnace can be saved and the feedstocks can be used free of volatile constituents and other impurities. The use of the aggregate is thus "energy neutral" since the blast furnace will not be deprived of energy to volatilize volatiles and char to coke and will not use coke supplied to the blast furnace for iron production.

Wenn man die feinkörnigen Koksteilchen (ohne flüchtige Inhaltsstoffe) mit den hochreaktiven Titanteilchen zusammenbringt, erfolgt die Bildung von Titankarbiden deutlich schneller als bei der Einblasung von üblicherweise verwendeten pulverisierten Kohleteilchen. Durch die Einbringung des koks- und titanhaltigen Zuschlagstoffe in einen Ofen erfolgt aufgrund der örtlichen Nähe der beiden Reaktionspartner in situ die Bildung von hochverschleißfesten Titanverbindungen, ohne dass die Reaktion im Wesentlichen durch flüchtige Bestandteile behindert wird. Hierdurch werden pro Zeiteinheit deutlich mehr hochfeuerfeste Titanverbindungen gebildet, welche sich dann anschließend an den zu schützenden feuerfesten Ausmauerungen ablagert.When the fine-grained coke particles (without volatile ingredients) are combined with the highly reactive titanium particles, the formation of titanium carbides is much faster than with the blowing-in of pulverized coal particles usually used. Due to the local proximity of the two reactants in situ, the incorporation of the coke- and titanium-containing additives into a furnace results in the formation of highly wear-resistant titanium compounds, without the reaction being hindered substantially by volatile constituents. As a result, significantly more per unit time formed high-refractory titanium compounds, which then deposited then to be protected refractory linings.

Beim Einbringen von kokshaltigem Titanträger für die Bildung und Ablagerung von verschleißfesten Titanverbindungen wird somit eine Direktreduktion ausgelöst. Durch diesen Effekt der Direktreduktion werden geringere Mengen an Einsatzmengen an titanhaltigen Einsatzstoffen benötigt als bei Verwendung der titanhaltigen Träger gemäß dem Stand der Technik. Somit wird der Einsatz teuren titanhaltigen Träger reduziert und die Wirtschaftlichkeit des Prozesses erhöht.When introducing coke-containing titanium support for the formation and deposition of wear-resistant titanium compounds thus a direct reduction is triggered. By this effect of the direct reduction smaller amounts of amounts of titanium-containing starting materials are required than when using the titanium-containing carrier according to the prior art. Thus, the use of expensive titanium-containing carrier is reduced and increases the efficiency of the process.

Die geringeren Einsatzmengen und der höhere Umsetzungsgrad zu Ti(C,N)-Verbindungen führt dann zu verbesserter Schlackenqualität durch niedrigere TiO2-Gehalte und somit zur erleichterten Verwertung des Hüttensandes.The lower amounts used and the higher degree of conversion to Ti (C, N) compounds then leads to improved slag quality due to lower TiO 2 contents and thus to the easier utilization of the granulated blastfurnace slag.

Claims (15)

  1. Aggregate containing coke and titanium for introduction into metallurgical vessels for increasing the durability and for repairing the refractory lining, with a content of titanium-containing compounds and with a content of 10 up to 98 wt.-% of coke-containing material, based on the total amount of aggregate, which contains no or only small amounts of less than 25 wt.-%, based on the coke containing material of substances being volatile at the temperatures present at the reaction site, whereby the aggregate is obtained by the combined coking of carbonaceous material and titanium-containing compounds.
  2. Aggregate containing coke- and titanium according to claim 1, obtainable by the combined coking of carbonaceous material and titanium containing compounds as well as of at least one of metal oxides and metal hydroxides selected from Al2O3, iron oxides, CaO, MgO, SiO2, ZrO2, mixed oxides as well as mixtures thereof in an amount of up to 50 wt.-%, based on the total amount of aggregate.
  3. Aggregate according to claim 1 or 2, wherein a coke producer, which is selected from pyrolyzable carbonaceous compounds, is used as carbonaceous material.
  4. Aggregate according to anyone of claims 1 to 3, with a content of coke-containing material with less than 10 wt.-%, based on the coke-containing material, of substances being volatile at the temperatures present at the reaction site.
  5. Aggregate according to anyone of claims 1 to 4, with 25 to 95, preferably 35 to 85, more preferred 45 to 80 wt.-% of coke containing material, based on the total amount of aggregate.
  6. Aggregate according to anyone of claims 1 to 5, with a content of 10 to 65 wt.-% titanium containing compounds and a content of 35 to 90 wt.-% coke containing material, based on the total amount of aggregate.
  7. Aggregate according to anyone of preceding claims, with a particle size of 90%, preferably 100 %, smaller than 100 mm, preferably smaller than 10 mm more preferred smaller than 1 mm and especially preferred smaller than 0.5 mm.
  8. Aggregate according to anyone of preceding claims, with a particle size of 90 %, preferably 100% of less than 200 µm, preferably less than 100 µm.
  9. Process for producing a coke- and titanium-containing aggregate according to anyone of the claims 1 to 8, characterized in that titanium-containing compounds are mixed with a carbonaceous material as coke producer and the thus resulting mixture is subjected to a thermal treatment, especially a pyrolysis, in a coke oven or fluidized bed furnace.
  10. Process according to claim 9, characterized in that the titanium-containing compounds are mixed with coal and that the resulting mixture is then subjected to a coking under exclusion of oxygen in a coke oven or fluidized bed furnace.
  11. Process according to claim 9 or 10, wherein, after the coking, the mixture is subjected to a comminution step such as milling or sieving.
  12. Process for the production of a coke- and titanium-containing aggregate according to claim 1, wherein the titanium-containing compounds are mixed with coke and/or petroleum coke, where the resulting mixture is preferably dried, and if required, the dried mixture is then ground in a mill.
  13. A process for the acceleration of the formation of highly refractory titanium carbides through direct reduction in metallurgical processes, characterized in that a preferably fine-grained coke- and titanium-containing aggregate according to anyone of the claims 1 to 8 is introduced, preferably through blowing-in, into a metallurgical vessel..
  14. Process according to claim 13, characterized in that PCI-coals are added to the coke- and titanium-containing aggregate according to anyone of the claims 1 to 8 for the blowing-into the blast furnace and said mixture is then blown in through the blow mouldings, wherein the addition to the coke- and titanium-containing aggregate of the PCI-coals preferably lies at 0.5 to 80, more preferably at 1 to 50, and especially preferred at 2 to 40 wt.-% of the total amount of the blown-in mixture.
  15. Use of a coke- and titanium-containing aggregate according to anyone of the claims 1 to 8, for the introduction into the metallurgic vessels in order to increase the durability and to repair the refractory lining.
EP11761487.5A 2010-08-03 2011-07-22 Aggregate containing coke and titanium and use thereof to repair the lining of metallurgical vessels Not-in-force EP2601318B1 (en)

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EP11761487.5A EP2601318B1 (en) 2010-08-03 2011-07-22 Aggregate containing coke and titanium and use thereof to repair the lining of metallurgical vessels
PL11761487T PL2601318T3 (en) 2010-08-03 2011-07-22 Aggregate containing coke and titanium and use thereof to repair the lining of metallurgical vessels

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Application Number Priority Date Filing Date Title
DE102010038831 2010-08-03
EP11151418A EP2415880A1 (en) 2010-08-03 2011-01-19 Additive containing coke and titanium and use of same to repair the cladding of metallurgical containers
EP11761487.5A EP2601318B1 (en) 2010-08-03 2011-07-22 Aggregate containing coke and titanium and use thereof to repair the lining of metallurgical vessels
PCT/DE2011/075173 WO2012022343A1 (en) 2010-08-03 2011-07-22 Aggregate containing coke and titanium and use thereof to repair the lining of metallurgical vessels

Publications (2)

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EP2601318A1 EP2601318A1 (en) 2013-06-12
EP2601318B1 true EP2601318B1 (en) 2014-07-09

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EP11151418A Withdrawn EP2415880A1 (en) 2010-08-03 2011-01-19 Additive containing coke and titanium and use of same to repair the cladding of metallurgical containers
EP11761487.5A Not-in-force EP2601318B1 (en) 2010-08-03 2011-07-22 Aggregate containing coke and titanium and use thereof to repair the lining of metallurgical vessels

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EP11151418A Withdrawn EP2415880A1 (en) 2010-08-03 2011-01-19 Additive containing coke and titanium and use of same to repair the cladding of metallurgical containers

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US (1) US20130168889A1 (en)
EP (2) EP2415880A1 (en)
JP (1) JP5893023B2 (en)
KR (1) KR101524237B1 (en)
BR (1) BR112013002593A2 (en)
DE (1) DE102011079627A1 (en)
ES (1) ES2504980T3 (en)
PL (1) PL2601318T3 (en)
WO (1) WO2012022343A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2634831C2 (en) * 2013-01-07 2017-11-03 Захтлебен Хеми Гмбх Titan containing filler, method for its manufacturing and its application

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US2805120A (en) * 1954-04-29 1957-09-03 Columbia Southern Chem Corp Chlorination process
GB898602A (en) * 1957-05-01 1962-06-14 British Aluminium Co Ltd Improvements in or relating to electrolytic cells for the production of metals
DE1904195A1 (en) * 1969-01-29 1970-08-06 Bergwerksverband Gmbh Use of coke pellets as a carbonizing agent for iron and steel baths
US3786133A (en) * 1970-09-11 1974-01-15 Quebec Iron & Titanium Corp Titanium carbide preparation
JPS50120406A (en) * 1974-03-09 1975-09-20
GB1485332A (en) * 1975-04-19 1977-09-08 Chviruk V Graphitic packing material for amalgam decomposers
US4187117A (en) * 1976-04-12 1980-02-05 Quebec Iron And Titanium Corporation - Fer Et Titane Du Quebec, Inc. Titanium slag-coke granules suitable for fluid bed chlorination
FR2423546B1 (en) * 1978-01-21 1986-02-07 Sumitomo Electric Industries HARD SINTERED METALS AND THEIR MANUFACTURING METHOD
JPS60228611A (en) * 1984-04-26 1985-11-13 Nippon Kokan Kk <Nkk> Method for operating blast furnace
DE4419816C1 (en) * 1994-06-07 1995-06-29 Metallgesellschaft Ag Titanium-contg. additive used in refractory linings and as a slagging agent
GB9526516D0 (en) * 1995-12-23 1996-02-28 Surface Transforms Ltd Metal containing refrectory products
DE19830102C1 (en) * 1998-07-06 1999-07-29 Metallgesellschaft Ag Chloride process titanium dioxide production waste fines are used to increase refractory lining durability
DE19935251A1 (en) * 1999-07-27 2001-02-08 Metallgesellschaft Ag Application of TiO¶2¶-containing particulate materials for refractory products
KR100726312B1 (en) * 2000-03-30 2007-06-08 신닛뽄세이테쯔 카부시키카이샤 Carbonaceous Refractory and Method for Preparing the Same
MY138532A (en) * 2000-08-31 2009-06-30 Foseco Int Refractory articles
DE10343687A1 (en) * 2003-09-20 2005-04-21 Sachtleben Chemie Gmbh Process for improving the durability of carbon or graphite electrodes by using products containing TiO 2 O 2
RU2280657C1 (en) * 2004-12-20 2006-07-27 Алтайский государственный университет Conductive polymeric material and method for production thereof
DE102005051953B3 (en) * 2005-10-29 2007-06-06 Tu Bergakademie Freiberg Process for the preparation of refractory moldings or masses
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DE102008056809A1 (en) * 2008-11-11 2010-05-27 Kronos International, Inc. Titanium-containing aggregate and process for its preparation from chloride-containing residues of titanium dioxide production

Also Published As

Publication number Publication date
WO2012022343A1 (en) 2012-02-23
ES2504980T3 (en) 2014-10-09
KR20130098992A (en) 2013-09-05
US20130168889A1 (en) 2013-07-04
EP2415880A1 (en) 2012-02-08
KR101524237B1 (en) 2015-05-29
PL2601318T3 (en) 2014-12-31
JP2013539001A (en) 2013-10-17
BR112013002593A2 (en) 2016-06-07
EP2601318A1 (en) 2013-06-12
DE102011079627A1 (en) 2012-02-09
JP5893023B2 (en) 2016-03-23

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