EP4630383A1 - Béton comprenant comme constituant des poussières et/ou des cendres issues de cheminées de ferrochrome - Google Patents

Béton comprenant comme constituant des poussières et/ou des cendres issues de cheminées de ferrochrome

Info

Publication number
EP4630383A1
EP4630383A1 EP23901229.7A EP23901229A EP4630383A1 EP 4630383 A1 EP4630383 A1 EP 4630383A1 EP 23901229 A EP23901229 A EP 23901229A EP 4630383 A1 EP4630383 A1 EP 4630383A1
Authority
EP
European Patent Office
Prior art keywords
ferrochrome
concrete
dusts
chimney
ashes
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.)
Pending
Application number
EP23901229.7A
Other languages
German (de)
English (en)
Other versions
EP4630383A4 (fr
Inventor
Gokhan BASMAN
Erdogan KARIP
Seyma YUKSEL SAGMAN
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.)
Eti Krom AS
Original Assignee
Eti Krom AS
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 Eti Krom AS filed Critical Eti Krom AS
Publication of EP4630383A1 publication Critical patent/EP4630383A1/fr
Publication of EP4630383A4 publication Critical patent/EP4630383A4/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/149—Waste materials; Refuse from metallurgical processes other than silica fume or slag

Definitions

  • the invention relates to production method for a product of concrete which comprises dusts and/or ashes obtained from low-cost, high-value-added ferrochrome chimneys as a component.
  • Cement is an important component in concrete.
  • Cement production is an intensive activity that consumes a lot of resources and energy.
  • Cement industries release large amounts of carbon dioxide and other greenhouse gases, which cause global warming.
  • Cement production and consumption should be reduced in order to reduce greenhouse gases, save energy and protect natural resources.
  • High carbon ferrochrome contains 60% to 70% chromium by weight or mass and 4% to 6% carbon by weight or mass.
  • a charge material consisting of a chromite ore, a carbon-containing reductant and a slag forming agent of suitable composition is melted in three-phase submerged arc furnaces containing three carbon electrodes. Almost all ferrochrome is produced in the submerged electric arc furnaces.
  • the alloy requires a chromite ore with a high Cr/Fe ratio (>2). Chromium and iron in chromite ore may form a continuous series of solid solutions under certain heat treatment conditions containing 45-80% chromium.
  • Metallurgical wastes produced as by-products of melting technology are ashes, sludges and slags.
  • a chimney is placed 1 .8-2.4 meters above an edge of the submerged arc furnace ladle. Dust and fumes from the melting process are drawn into the chimney by a large volume of the circulating air.
  • the chimney dust formation also increases with the increase in ferrochrome production.
  • Many research activities are ongoing worldwide to recycle and/or use the waste generated during the ferrochrome production.
  • the research results clearly show that the ferrochrome material found in the chimney dust studied is closely related to the slag-forming materials; therefore, the enrichment techniques can only enrich ferrochrome values to a very limited extent.
  • the slags and ashes formed in the chimneys during the high-carbon ferrochrome production are generally disposed of as a type of waste categorized thereafter.
  • the use of the cast ferrochrome slag in refractory castable materials reduces product cost and is atmosphere-friendly. This material is used in road construction and brick production, and has recently been tried as a base layer material in the cement industry and in pavements due to its excellent technical properties.
  • slags have a wide range of uses such as briquette and brick making, railway ballast, cement industry, concrete aggregate, asphalt aggregate, filler, insulation and glass production. Slags can also be used to improve the abandoned and acid-treated mine sites. In 2011 , global ferrochrome production was around 8.9 million tons.
  • the invention of the patent application no. RU2703036 C1 is related to a method developed to improve the environment by using production waste for the production of a concrete mixture processed with low energy costs and thereby, obtaining high- strength, heat-resistant concrete products.
  • the invention consists of 11.1 -12.2% by weight (w/w)of chamotte chimney dust, 13.8-15.4% of a slag in self-degrading ferrochrome chimneys, and in addition to these components, 40-42.0% of an etching solution of the used aluminum alloys, and 30.4-35.1% of a nickel slag.
  • the materials used for system implementations of the backfill concrete production for use in mines in the present art are known to have disadvantages in terms of preventing environmental pollution, reducing preparation time and cost of the waste recycled raw materials used, failing to achieve the strength provided to the product to which it is applied, and insufficiently preventing the damage to the environment by the waste for reducing the other additives used and the product produced using the waste.
  • the present invention relates to a concrete comprising dusts and/or ashes obtained from low-cost, high value-added ferrochrome chimneys as a component, in order to eliminate the above-mentioned disadvantages and bring new advantages to the relevant technical field.
  • An object of the invention is to reduce the waste of production containing heavy metals and to use high value-added raw materials with increased environmental awareness.
  • An object of the invention is to provide a cement substitute and a binding raw material with higher strength than cement.
  • An object of the invention is to produce a concrete with added value with increased environmental awareness.
  • the subject of the invention relates to a method of producing a product of concrete which comprises dusts and/or ashes obtained from low-cost, high-value-added ferrochrome chimneys as a component and is described only with examples for a better understanding of the subject without any limiting sense.
  • ferrochrome refers to an alloy consisting of chromium and iron, comprising small amounts of elements such as carbon and silicon. In the art, ferrochrome is divided into three groups as “high, medium and low carbon ferrochrome” according to the amount of carbon contained therein.
  • high carbon ferrochrome is the most common alloy comprising 60% to 70% chromium by weight or mass and 4% to 6% carbon by weight or mass.
  • ferrochrome chimney dust refers to a waste material obtained in large amounts from the gas cleaning facility of the ferrochrome industry. Said waste material is released into nature without preventing pollution, being controlled, or taking remedial measures, thus occupying acres of valuable land.
  • a "submerged electric arc furnace” is essentially defined as a furnace used for the production of ferro alloys, where the furnace electrodes are buried deep within the furnace load, and a reduction reaction takes place near the tip of the electrodes to facilitate the furnace process.
  • a “backfill concrete” is a self-compacting cementitious slurry consisting of a filler instead of a compacted ground filler, or a fine aggregate used as a filler, or a mixture of a filler, water and a cementitious material.
  • cement is essentially meant as a hydraulic binding material obtained by grinding a mixture of natural limestones and clay after heating at high temperatures.
  • the present inventors suggest to reduce the use of cement in the relevant technical field and instead to use ferrochrome chimney dust, which is a recycling product providing high strength and heat resistance, and to use the same in obtaining backfill concrete as a raw material. Accordingly, the invention prevents environmental pollution and material waste as a result of a reduction in the amount of waste by adding added value to the waste material and a reduction in use of cement by the use of alternative materials.
  • another advantage of reducing cement production with ferrochrome chimney dust in the production of backfill concrete used in the mines is that the desired value in the uniaxial compressive strength results was 12 MPa in the experiments conducted without using chimney dust, while an increase in the uniaxial compressive strength of the backfill concrete used in the mines is detected when the chimney dust released from the submerged electric arc furnaces is used, resulting in an increase in the strength value of the backfill concrete.
  • the cement intermediate products are formed during the cement production.
  • Portland cement is formed by grinding clinkers with certain amounts of gypsum.
  • the compounds 3CaO.SiO 2 , 2CaO.SiO 2 , 3CaO.AI 2 O3 and 4CaO.AI 2 O3.Fe2O3 are included as the main phases in the cement and clinkers.
  • the dusts and/or ashes obtained from the ferrochrome chimneys are preferably high carbon ferrochrome chimney dusts and ashes resulting from the submerged arc furnaces.
  • the ferrochrome chimney dusts in the concrete of the invention should be between 200 pm to 400 pm.
  • the limestones and clays used during the cement production are expected to be within the specified ranges of grain size. This is because the coarse grained components may cause problems in obtaining concrete. Additionally, it may cause problems in the formation of the desired phases and bond structures. Therefore, the ferrochrome dusts to be used for the cement obtained are important to have the specified grain sizes.
  • said ferrochrome chimney dusts are expected to preferably have a grain size of 300 pm. Accordingly, in this invention, no sizing process or any pre-treatment is performed on the chimney dust released from the submerged electric arc furnaces during the production of each high carbon ferrochrome, and it is used directly. In this aspect, the invention provides an advantage in terms of production time and cost.
  • ferrochrome chimney dusts are included in the concrete as a raw material in the range of 0.01% to 20% by weight. It is observed that the mechanical strength values of the cement obtained at values above the specified value ranges decrease. It has been determined that the targeted cement form and mechanical strength values are not met at values below the specified value ranges.
  • dusts and/or ashes obtained from the ferrochrome chimneys are mixed with other components in the specified weight ratios and subjected to the processes to obtain concrete.
  • Said resulting concrete premix is preferred to be obtained at ambient temperatures between 1 to 55 °C. Additionally, the setting time is expected to be between 3 to 24 hours.
  • the resulting concrete is then placed into the molds for use and allowed to shape.
  • a premix is prepared for the concrete of the invention using the other components and methods previously known in the art.
  • This premix preferably contains dusts and/or ashes obtained from the ferrochrome chimneys in the range of 0.01% to 20%.
  • Mixing is carried out for a period of 1 to 60 minutes, depending on the amount of the components.
  • the resulting mixture is poured into the clay molds.
  • the process temperature is between 1 to 55 °C.
  • the setting time is between 3 to 24 hours depending on the characterization of the components.
  • the concretes set are removed from their molds and placed in curing pools.
  • the concrete comprising dusts and/or ashes obtained from the ferrochrome chimneys as a component in the weight ratios specified in the invention complies with TS 500, TS EN 206-1 and TS EN 450-1 standards by the tests performed.
  • the Cr (VI) amount of the concrete obtained was determined to be in compliance with the Regulations on Water Pollution.
  • the concrete comprising dusts and/or ashes obtained from the ferrochrome chimneys as a component in the weight ratios specified in the invention has been determined to comply with TS 2513 (average hardness is appropriate), TS EN 1097-6 (water absorption and grain density is found to be appropriate), TS 9582 EN 933-3 (flatness index is found to be appropriate), TS 3530 EN 933-1 (fineness values are found to be appropriate), TS EN 1367-01 (mass loss after freezing and thawing is found to be appropriate), TS EN 1744 (acid-soluble sulfate ratio is found to be appropriate) standards.
  • the concrete of the invention comprising dusts and/or ashes obtained from the ferrochrome chimneys as a component in the specified weight ratios has been determined to have a compressive strength between 23.79 to 37.83 MPa in the tests in accordance with TS EN 206-1 standards.
  • Cr (VI) analyzes were observed to be in the range of 0.008-0.027 mg/L, which is much lower than the desired values (0.5 mg/L) according to the Regulations on Water Pollution.
  • the invention reduces the amount of cement in the total mortar by using chimney dust along with cement in the backfill concrete mortar used in the mines, provides added value and high strength to the backfill concrete currently obtained and reduces the concrete production cost.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Civil Engineering (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

La présente invention concerne un béton comprenant comme constituant des poussières et/ou des cendres issues de poussières de cheminées de ferrochrome, qui sont un produit de recyclage qui permet de réduire l'utilisation de ciment dans le domaine technique concerné et de donner à en contrepartie une résistance mécanique et une résistance à la chaleur élevées.
EP23901229.7A 2022-12-08 2023-10-26 Béton comprenant comme constituant des poussières et/ou des cendres issues de cheminées de ferrochrome Pending EP4630383A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2022/018844A TR2022018844A2 (tr) 2022-12-08 2022-12-08 Ferrokrom bacalarindan elde edi̇len tozlari ve/veya külleri̇ bi̇leşen olarak i̇çeren bi̇r beton
PCT/TR2023/051205 WO2024123281A1 (fr) 2022-12-08 2023-10-26 Béton comprenant comme constituant des poussières et/ou des cendres issues de cheminées de ferrochrome

Publications (2)

Publication Number Publication Date
EP4630383A1 true EP4630383A1 (fr) 2025-10-15
EP4630383A4 EP4630383A4 (fr) 2026-05-06

Family

ID=91379937

Family Applications (1)

Application Number Title Priority Date Filing Date
EP23901229.7A Pending EP4630383A4 (fr) 2022-12-08 2023-10-26 Béton comprenant comme constituant des poussières et/ou des cendres issues de cheminées de ferrochrome

Country Status (3)

Country Link
EP (1) EP4630383A4 (fr)
TR (1) TR2022018844A2 (fr)
WO (1) WO2024123281A1 (fr)

Also Published As

Publication number Publication date
TR2022018844A2 (tr) 2023-01-23
EP4630383A4 (fr) 2026-05-06
WO2024123281A1 (fr) 2024-06-13

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