EP2601318B1 - Fondant contenant du coke et du titane et son utilisation pour la réparation du revêtement de récipients métallurgiques - Google Patents

Fondant contenant du coke et du titane et son utilisation pour la réparation du revêtement de récipients métallurgiques 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
Application number
EP11761487.5A
Other languages
German (de)
English (en)
Other versions
EP2601318A1 (fr
Inventor
Djamschid Amirzadeh-Asl
Dieter FÜNDERS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Venator Germany GmbH
Original Assignee
Sachtleben Chemie GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sachtleben Chemie GmbH filed Critical Sachtleben Chemie GmbH
Priority to PL11761487T priority Critical patent/PL2601318T3/pl
Priority to EP11761487.5A priority patent/EP2601318B1/fr
Publication of EP2601318A1 publication Critical patent/EP2601318A1/fr
Application granted granted Critical
Publication of EP2601318B1 publication Critical patent/EP2601318B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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

Claims (15)

  1. Agrégat contenant du coke et du titane destiné à être introduit dans des récipients métallurgiques pour augmenter la durabilité et réparer le garnissage réfractaire, avec une teneur en composés contenant du titane et une teneur de 10 à 98 % en poids en matière contenant du coke, par rapport à la quantité totale d'agrégat, qui ne contient pas ou seulement de faibles quantités inférieures à 25 % en poids, par rapport à la matière contenant du coke, de substances volatiles aux températures rencontrées au lieu de réaction, l'agrégat étant obtenu par cokéfaction commune de matière carbonée et de composés contenant du titane.
  2. Agrégat contenant du coke et du titane selon la revendication 1, lequel agrégat est obtenu par cokéfaction commune de matière carbonée et de composés contenant du titane ainsi que d'au moins un parmi des oxydes métalliques et des hydroxydes métalliques, sélectionnés dans le groupe comprenant Al2O3, des oxydes de fer, CaO, MgO, SiO2, ZrO2, des oxydes mixtes ainsi que des mélanges de ceux-ci dans une quantité pouvant aller jusqu'à 50 % en poids, par rapport à la quantité totale d'agrégat.
  3. Agrégat selon la revendication 1 ou 2, dans lequel on utilise comme matière carbonée un agent cokéfiant qui est sélectionné parmi des composés carbonés pyrolysables.
  4. Agrégat selon l'une des revendications 1 à 3, avec une teneur en matière contenant du coke de moins de 10 % en poids, par rapport à la matière contenant du coke, de substances volatiles aux températures rencontrées au lieu de réaction.
  5. Agrégat selon l'une des revendications 1 à 4, avec 25 à 95, de préférence 35 à 85, particulièrement de préférence 45 à 80 % en poids de matière contenant du coke, par rapport à la quantité totale d'agrégat.
  6. Agrégat selon l'une des revendications 1 à 5, avec une teneur de 10 à 65 % en poids en composés contenant du titane et avec une teneur de 35 à 90 % en poids en matière contenant du coke, par rapport à la quantité totale d'agrégat.
  7. Agrégat selon l'une des revendications précédentes, avec une taille de particules à 90 %, de préférence à 100 %, inférieure à 100 mm, de préférence inférieure à 10 mm, particulièrement de préférence inférieure à 1 mm et tout particulièrement de préférence inférieure à 0,5 mm.
  8. Agrégat selon l'une des revendications précédentes, avec une taille de particules à 90 %, de préférence à 100 %, inférieure à 200 µm, de préférence inférieure à 100 µm.
  9. Procédé de fabrication d'un agrégat contenant du coke et du titane selon l'une des revendications 1 à 8, caractérisé en ce que des composés contenant du titane sont mélangés avec une matière carbonée comme agent cokéfiant et le mélange ainsi obtenu est soumis à un traitement thermique sous la forme d'une pyrolyse dans un four à coke ou un four à lit fluidisé.
  10. Procédé selon la revendication 9, caractérisé en ce que les composés contenant du titane sont mélangé avec du charbon et le mélange ainsi obtenu est soumis à une cokéfaction en l'absence d'oxygène dans un four à coke ou un four à lit fluidisé.
  11. Procédé selon la revendication 9 ou 10, dans lequel, après la cokéfaction, le mélange est soumis à une étape de fragmentation telle que broyage ou criblage.
  12. Procédé de fabrication d'un agrégat contenant du coke et du titane selon la revendication 1, dans lequel des composés contenant du titane sont mélangés avec du coke et/ou coke de pétrole, le mélange obtenu étant de préférence séché, et, si nécessaire, le mélangé séché étant ensuite broyé dans un broyeur.
  13. Procédé pour accélérer la formation de carbures de titane hautement réfractaires par réduction directe dans des processus métallurgiques, caractérisé en ce que l'on introduit un agrégat contenant du coke et du titane selon l'une des revendications 1 à 8, de préférence à grains fins, de préférence par insufflation, dans un récipient métallurgique.
  14. Procédé selon la revendication 13, caractérisé en ce que l'on ajoute l'agrégat contenant du coke et du titane selon l'une des revendications 1 à 8 à du charbon PCI pour l'insufflation dans le haut-fourneau et que l'on insuffle ensuite ce mélange par les moules de soufflage, l'addition d'agrégat contenant du coke et du titane au charbon PCI représentant de préférence 0,5 à 80, particulièrement de préférence 1 à 50 et tout particulièrement de préférence 2 à 40 % en poids de la quantité totale de mélangé insufflé.
  15. Utilisation d'un agrégat contenant du coke et du titane selon l'une des revendications 1 à 8 destiné à être introduit dans des récipients métallurgiques pour augmenter la durabilité et réparer le garnissage réfractaire.
EP11761487.5A 2010-08-03 2011-07-22 Fondant contenant du coke et du titane et son utilisation pour la réparation du revêtement de récipients métallurgiques Not-in-force EP2601318B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL11761487T PL2601318T3 (pl) 2010-08-03 2011-07-22 Wypełniacz zawierający koks i tytan i jego zastosowanie do naprawy wyłożenia zbiorników metalurgicznych
EP11761487.5A EP2601318B1 (fr) 2010-08-03 2011-07-22 Fondant contenant du coke et du titane et son utilisation pour la réparation du revêtement de récipients métallurgiques

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102010038831 2010-08-03
EP11151418A EP2415880A1 (fr) 2010-08-03 2011-01-19 Matière de charge contenant du coke et du titane et son utilisation pour la réparation du revêtement de récipients métallurgiques
PCT/DE2011/075173 WO2012022343A1 (fr) 2010-08-03 2011-07-22 Fondant contenant du coke et du titane et son utilisation pour la réparation du revêtement de récipients métallurgiques
EP11761487.5A EP2601318B1 (fr) 2010-08-03 2011-07-22 Fondant contenant du coke et du titane et son utilisation pour la réparation du revêtement de récipients métallurgiques

Publications (2)

Publication Number Publication Date
EP2601318A1 EP2601318A1 (fr) 2013-06-12
EP2601318B1 true EP2601318B1 (fr) 2014-07-09

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Family Applications (2)

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EP11151418A Withdrawn EP2415880A1 (fr) 2010-08-03 2011-01-19 Matière de charge contenant du coke et du titane et son utilisation pour la réparation du revêtement de récipients métallurgiques
EP11761487.5A Not-in-force EP2601318B1 (fr) 2010-08-03 2011-07-22 Fondant contenant du coke et du titane et son utilisation pour la réparation du revêtement de récipients métallurgiques

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EP11151418A Withdrawn EP2415880A1 (fr) 2010-08-03 2011-01-19 Matière de charge contenant du coke et du titane et son utilisation pour la réparation du revêtement de récipients métallurgiques

Country Status (9)

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

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Publication number Priority date Publication date Assignee Title
US20150344363A1 (en) * 2013-01-07 2015-12-03 Sachtleben Chemie Gmbh Titanium-Containing Aggregate, Method for its Manufacture, and Use Thereof

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Also Published As

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