WO2025219366A1 - Procédé de production d'un matériau pouzzolanique dans une installation de fabrication de ciment - Google Patents

Procédé de production d'un matériau pouzzolanique dans une installation de fabrication de ciment

Info

Publication number
WO2025219366A1
WO2025219366A1 PCT/EP2025/060326 EP2025060326W WO2025219366A1 WO 2025219366 A1 WO2025219366 A1 WO 2025219366A1 EP 2025060326 W EP2025060326 W EP 2025060326W WO 2025219366 A1 WO2025219366 A1 WO 2025219366A1
Authority
WO
WIPO (PCT)
Prior art keywords
cement
clinker
silico
cooler
mineral material
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
PCT/EP2025/060326
Other languages
English (en)
Inventor
Giovanni David SANTILLAN
Francisco Navarro Gabaldón
Edelio Bermejo
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.)
Holcim Technology Ltd
Original Assignee
Holcim Technology Ltd
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 Holcim Technology Ltd filed Critical Holcim Technology Ltd
Publication of WO2025219366A1 publication Critical patent/WO2025219366A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
    • C04B7/47—Cooling ; Waste heat management
    • C04B7/475—Cooling ; Waste heat management using the waste heat, e.g. of the cooled clinker, in an other way than by simple heat exchange in the cement production line, e.g. for generating steam
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02—Treatment
    • C04B20/04—Heat treatment

Definitions

  • the invention refers to a method of producing a poz zolanic material in a cement manufacturing plant .
  • the invention refers to a method of producing a composite cement containing cement clinker and a poz zolanic material in a cement manufacturing plant .
  • Supplementary cementitious materials comprise a broad class of siliceous or siliceous and aluminous materials which, in finely divided form and in the presence of water, chemically react with calcium hydroxide at ordinary temperature to form compounds possessing cementitious properties .
  • supplementary cementitious materials include granulated blast- furnace slag, fly ash, natural poz zolans , burnt oil shale , or calcined clay .
  • Cement is a product that in most cases is used in locations relatively close to where it is manufactured . Therefore , in case of composite cements , its production requires the availability of a source of a supplementary cementitious material , this source being either natural or synthetic .
  • kaolinite that has a layered silicate structure , composed of alternating layers of tetrahedral sheets of silica and octahedral sheets of alumina linked with each other by oxygen atoms .
  • kaolinite When kaolinite is heated during a calcination process , dehydroxylation and trans formation of the kaolinite into an amorphous material known as metakaolin are occurring .
  • Various methods have been proposed for producing calcined clay .
  • WO 2022 / 106966 Al discloses a method, which comprises adding raw clay into a clinker cooler to obtain a calcined clay cement . Such a method has several advantages as it enables the production of calcined clay cements without the need of building and operating a dedicated device for the calcination of clays .
  • the method takes advantage of the heat in the clinker that is coming out of the rotary kiln where the clinker is calcined, to then calcine the clay, meaning that clay is calcined without needing an additional source of heat .
  • introducing raw clay into a clinker cooler tends to generate high amounts of dust .
  • This dust can circulate back to the cement kiln, leading to the following concerns : it can contaminate the clinker, thereby af fecting the clinker ' s quality and performance ; it can decrease the proportion of calcined clay present in the final cement products ; it reduces the flame temperature in the kiln due to additional dust in the secondary air ; and it increases the speci fic heat consumption caused by the thermal energy absorption of the silico- aluminous mineral material into the rotary kiln .
  • the calcination process as described lacks precise control . This lack of control can lead to scenarios where the clay is either overburnt or not suf ficiently calcined, which ultimately compromises the reactivity of the resulting cementitious material .
  • the invention provides a method of producing a poz zolanic material in a cement manufacturing plant comprising a cement kiln and a clinker cooler, a head region of the clinker cooler being connected to an outlet end of the cement kiln for cooling cement clinker coming from the cement kiln, the clinker cooler comprising a recuperation zone adj acent the outlet end, in which incoming cooling air is heated by the cement clinker and heated cooling air is fed into the cement kiln via the head region as secondary air and/or used as tertiary air, and a cooling zone remote from the outlet end, in which incoming cooling air is used to cool the cement clinker and exhaust air is released from the clinker cooler through an exhaust duct , the method comprising : providing a silico-aluminous mineral material susceptible of poz zolanic reactivity upon calcination, introducing the silico-aluminous mineral material into the cooling zone of the
  • the invention is based on the idea to introduce the silico-aluminous mineral material into the cooling zone of the clinker cooler, rather than the recuperation zone , which signi ficantly reduces the circulation of dust back to the cement kiln due to the di f ferences in air flow between these two zones .
  • the recuperation zone which is located closer to the outlet end of the cement kiln, the primary obj ective is to heat the incoming cooling air by direct contact with the hot cement clinker . This heated air is then channeled back into the cement kiln as secondary air or used as tertiary air .
  • the cooling zone situated further from the kiln ' s outlet end, employs incoming cooling air primarily to lower the temperature of the cement clinker .
  • the air flow in this zone is designed to cool the clinker and then exit through an exhaust duct , rather than being recirculated back into the kiln .
  • the potential for dust to be picked up by the air flow and transported back to the kiln is minimi zed .
  • the air flow here is not directed towards the kiln but towards the exhaust system, which means any dust generated during the calcination of the silico-aluminous material is more likely to be contained within the cooler and then safely expelled through the exhaust system, where a filter may be arranged to capture the suspended particles in the airflow .
  • the cooling zone of the clinker cooler is usually characteri zed by the so-called zero point of the clinker cooler.
  • the zero point of a cooler is defined as the point in the cooler beyond which no gas flows back to the kiln. It is easily determined by the skilled person by air flow measurements, and is the point where the temperature of the clinker is optimal for the calcination of the silico- aluminous mineral material.
  • An additional effect of the invention is that, by introducing the silico-aluminous mineral material into the cooling zone, in particular at an upstream end region of the cooling zone, where the zero point is located, the silico-aluminous mineral material can be calcined at a temperature of 600-900°C, in order to obtain the pozzolanic material.
  • the clinker At the zero point of a clinker cooler, the clinker is typically at a temperature comprised between 600°C and 900°C.
  • Calcining the silico- aluminous mineral material at a temperature of 600-900°C means that the material is heated to a temperature of 600- 900°C, i.e. to a temperature of at least 600°C and not above 900°C.
  • the desired mineralogical change in the silico-aluminous mineral material can be obtained that is characteristic of the mineralogical composition of the material. This change can develop a pozzolanic activity in the material. If the specific activation temperature range of the silico-aluminous mineral material is surpassed, over-burning takes place and crystallization of the silica phase occurs, resulting in a reduction of the pozzolanic reactivity of the material.
  • the method of the invention preferably comprises an initial step of selecting a silico-aluminous mineral material that activates its pozzolanic activity within a temperature range of 600-900°C, preferably 600-700°C.
  • Said selection process preferably comprises the steps of: a) Chemical XRF analysis of the available silico- aluminous mineral material, b) Activation of the material at different temperatures from 500°C to 900°C in progressive steps of, e.g., 100°C, c) Pozzolanic reactivity analysis of the material at each temperature, d) Selection of the material the pozzolanic reactivity of which matches or surpasses the functional properties of the cement clinker.
  • the step of calcining the silico-aluminous mineral material in the cooling zone of the clinker cooler preferably comprises contacting the silico-aluminous mineral material with the cement clinker that is transported through the cooling zone of the clinker cooler.
  • the invention uses waste energy from the cooling of the clinker to calcine the mineralogical phases of the silico- aluminous mineral material that would otherwise have to be produced in a standalone process with an additional thermal power input to achieve the same temperature conditions as described herein .
  • the silico-aluminous mineral material is introduced into the cooling zone at a vertical distance of 10-20 cm above a bed of cement clinker being conveyed through the clinker cooler . This avoids the suspension of the silico- aluminous mineral material into the air flow .
  • the clinker cooler is designed as a grate cooler .
  • the structure of a grate cooler is essentially a hori zontal , moving grate by means of which cement clinker travels from the kiln ' s outlet end to the cooler ' s discharge end .
  • Cooling air is blown through the grate from beneath, passing through the hot clinker and facilitating heat exchange . This process not only cools the clinker but also heats the cooling air .
  • Cooling air is typically blown into the clinker cooler from below by means of a plurality of cooling fans that are distributed over the length of the cooler, i . e . in the conveying direction of the grate ( s ) . This allows for separate fans for the recuperation zone and for the cooling zone of the clinker cooler .
  • the clinker cooler is designed as a singlechamber cooler and the silico-aluminous mineral material is introduced into the clinker cooler at the zero point of the clinker cooler .
  • the clinker cooler may comprise two or more consecutive cooling chambers and the silico-aluminous mineral material is introduced into a second cooling chamber arranged downstream of a first cooling chamber, wherein the silico- aluminous mineral material is preferably introduced at an upstream end of the second cooling chamber .
  • the at least two cooling chambers allow for a two-stage cooling process , wherein the two stages are typically physically separated, each designed for speci fic cooling and heat recovery tasks within the overall clinker cooling process .
  • the first cooling chamber houses the recuperation zone and the second chamber houses the cooling zone of the clinker cooler .
  • a physical separation of the two stages may be reali zed by, e . g .
  • the physical separation is designed to allow the clinker to transit from the first stage to the second stage , while keeping the flow of cooling air separate .
  • the silico-aluminous mineral material is introduced into the cooling zone by means of an air-tight dosing system .
  • the airtight dosing system ensures that the exact required amount of silico-aluminous mineral material is introduced into the cooling zone , thereby eliminating the risk of atmospheric contamination and preventing the escape of fine particulate matter into the surrounding environment .
  • the silico-aluminous mineral material is introduced into the cooling zone at a dosing rate of 5-20 wt . -% , preferably 10-20 wt . -% , of the cement clinker .
  • a dosing rate of 5-20 wt . -% preferably 10-20 wt . -%
  • This ensures an optimal ratio of cement clinker to poz zolanic material in the final product , and achieves a balance that maximi zes the reactivity of the poz zolanic material without compromising the performance of the final product .
  • the silico-aluminous mineral material is charged onto a bed of cement clinker in the clinker cooler in a continuous manner, preferably by means of a rotary valve or a feeding screw .
  • Rotary valves or feeding screws have the advantage of providing a more continuous supply of material on the hot clinker bed .
  • a feeding device that makes use of a double-inlet valve is not preferred as it delivers materials in a non-continuous manner, resulting in varying thicknesses of silico-aluminous mineral material on the hot clinker, which then does not allow for a homogeneous calcination of the material .
  • the material is discharged onto the hot clinker bed in the clinker cooler by means that do not include a double-inlet valve .
  • a first temperature of the cement clinker is measured upstream of the cooling zone and a second temperature of the cement clinker is measured at a discharge end of the clinker cooler and a feeding rate of the silico- aluminous mineral material introduced into the clinker cooler is controlled as a function of said first and second temperature so that the silico-aluminous mineral material is heated to a temperature of at least 600 ° C and not above 900 ° C .
  • the first temperature is measured at the inlet of the clinker cooler .
  • the method improves the ef ficiency of the heat exchange process , optimi zing the use of residual thermal energy from the clinker for the calcination of the mineral material .
  • the raw clay material is used as said silico- aluminous mineral material.
  • the raw clay material may preferably comprise at least 40 wt.-% raw clay. This substantial proportion of raw clay ensures that the final calcined material retains a high content of aluminosilicates, which are essential for the pozzolanic reaction in cementitious applications.
  • the raw clay material may contain various clay minerals, such as kaolinite, smectite, illite, sepiolite, attapulgite, and vermiculite .
  • GBFS granulated blast furnace slag
  • BOF basic oxygen furnace
  • EAF electric arc furnace
  • ACBF air-cooled blast furnace slag
  • mining sludges bottom ash
  • incineration ash incineration ash
  • refractory residues foundry sand
  • waste glass oil shale, or mixture thereof
  • natural pozzolan as defined in EN 197-1 published in September 2011, or mixtures of natural pozzolan and raw clay, can be used as the silico-aluminous mineral material.
  • the suitable particle size for the silico-aluminous mineral material in the calcination process may be selected according to the circumstance of the individual process. A finer particle size is generally preferred as it provides a larger surface area for the heat and chemical reactions to occur, facilitating a more uniform and complete calcination.
  • the particle si ze should not be excessively fine as it can lead to operational challenges like dusting or handling di f ficulties .
  • the optimal particle si ze is typically determined through a balance between maximi zing reactivity and practical considerations related to processing and handling in the speci fic calcination system being used .
  • the particle si ze of the silico-aluminous mineral material when being subj ected to the calcination step is in the range of 50 micrometers to 1000 micrometers .
  • the silico-aluminous mineral material comprises a water content of 5-25 wt . -% of the total weight of the silico-aluminous mineral material .
  • the silico- aluminous mineral material has a humidity above 25 wt . -%
  • waste heat from the cement process can be used to reduce the amount of water in the material before the material is being introduced into the clinker cooler .
  • the water should preferably be above 5 wt . -% of the amount of the silico- aluminous mineral material to ensure that the occurrence of dust during the process of adding the material onto the hot clinker bed is minimi zed .
  • Calcining the silico-aluminous mineral material in the clinker cooler of a cement manufacturing plant advantageously results in that the poz zolanic material is obtained in combination with the cement clinker . Therefore , a preferred embodiment of the invention provides that a combined material comprising the cement clinker and the poz zolanic material is discharged from a discharge end of the clinker cooler .
  • the combined material results in environmental benefits due to the poz zolanic material ' s ability to substitute a portion of the cement clinker, ef fectively reducing the carbon footprint of the cement .
  • the combined material may later be ground, with a source of calcium sul fates and other optional mineral components to form a composite Portland cement .
  • Calcium sul fate serves as a setting time regulator for the hydrated cement in a concentration of 1- 10 wt . -% . Since clinker sets quickly, the addition of calcium sul fate lengthens the setting time of the cement in proportion to its increase in the composite cement .
  • calcium carbonate may be added as an additional component to the composite cement in an amount of 1-30 wt . -% of the total weight of the composite cement .
  • the present invention provides a method of producing a composite cement containing cement clinker and a poz zolanic material in a cement manufacturing plant comprising a cement kiln and a clinker cooler, a head region of the clinker cooler being connected to an outlet end of the cement kiln for cooling cement clinker coming from the cement kiln, the method comprising : calcining cement clinker in the cement kiln, discharging cement clinker from the cement kiln into the clinker cooler and cooling the cement clinker in the clinker cooler producing a poz zolanic material by a method according to the first aspect of the invention, wherein the poz zolanic material is contacted with the cement clinker present in the clinker cooler, discharging a combined material comprising the cement clinker and the poz zolanic material from the clinker cooler, grinding the mixture in a cement mill together with a source of calcium sul fates in order
  • the composite cement further comprises calcium carbonate , preferably in an amount of 1-30 wt . -% of the total weight of the composite cement .
  • the composite cement further comprises a supplementary cementitious material , such as a natural poz zolan, fly ash, granulated blast furnace slag and/or a silica-aluminous natural or arti ficial mineral having poz zolanic activity .
  • a supplementary cementitious material such as a natural poz zolan, fly ash, granulated blast furnace slag and/or a silica-aluminous natural or arti ficial mineral having poz zolanic activity .
  • Fig . 1 shows the outlet end of a cement kiln 1 , such as a rotary kiln, for calcining cement clinker .
  • Cement clinker is discharged from the cement kiln 1 into the clinker cooler 2 , as illustrated by arrow 3 and forms a clinker bed 4 that is conveyed through the clinker cooler 2 by means of moving grates 6 to a discharge end 5 , from where the clinker falls onto a conveyor 7 for being further transported to a storage facility .
  • a burner for providing thermal energy to the cement kiln 1 is denoted by reference numeral 8 , to which fuel 9 and primary air 10 are fed .
  • ambient air is blown into the clinker cooler 2 by means of a plurality of fans 11 that are distributed over the length of the clinker cooler 2 . Cooling air is blown through the grates 6 from beneath and passes through the clinker bed 4 , thereby cooling the cement clinker and increasing the temperature of the cooling air .
  • the clinker cooler comprises a recuperation zone 12 adj acent the outlet end of the cement kiln 1 , in which incoming cooling air is heated by the cement clinker and heated cooling air is fed into the cement kiln 1 via the head region 20 as secondary air 14 and/or used as tertiary air 15 , and a cooling zone 13 remote from the outlet end, in which incoming cooling air is used to cool the cement clinker and exhaust air 17 is released from the clinker cooler 2 through an exhaust duct 16 .
  • the zero point 18 of the clinker cooler 2 is located at the beginning of the cooling zone 13 . As illustrated by arrows pointing upwards , the flow of cooling air in the recuperation zone 12 is directed to the head region 20 of the cooler, and the flow of cooling air in the cooling zone 13 is directed to the exhaust duct 16 .
  • a silico-aluminous mineral material susceptible of poz zolanic reactivity upon calcination such a raw clay material is introduced into the cooling zone 13 of the clinker cooler 2 , as illustrated by the arrow 18 , in order to calcine the silico-aluminous mineral material at a temperature of 600- 900 ° C .
  • the introduction point of the silico-aluminous mineral material 19 is located approximately 10-20 cm above the clinker bed 4 . In this way, the silico-aluminous mineral material 19 gets into contact with the clinker bed 4 and is heated to a temperature of 600- 900 ° C in order to get calcined .
  • the calcined material is entrained by the moving clinker bed 4 and conveyed to the discharge end 5 . Therefore , as a result of the method described, a combined product containing cement clinker and a calcined poz zolanic material is obtained .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

Procédé de production d'un matériau pouzzolanique dans une installation de fabrication de ciment comprenant un four à ciment (1) et un refroidisseur à clinker (2), une région de tête (20) du refroidisseur à clinker (2) étant reliée à une extrémité de sortie du four à ciment (1) pour refroidir le clinker de ciment provenant du four à ciment, le refroidisseur à clinker (2) comprenant une zone de récupération (12) adjacente à l'extrémité de sortie, dans laquelle de l'air de refroidissement entrant est chauffé par le clinker de ciment (4) et de l'air de refroidissement chauffé est introduit dans le four à ciment (1) par l'intermédiaire de la région de tête (20) en tant qu'air secondaire et/ou utilisé en tant qu'air tertiaire, et une zone de refroidissement (13) à distance de l'extrémité de sortie, dans laquelle de l'air de refroidissement entrant est utilisé pour refroidir le clinker de ciment (4) et de l'air d'échappement est libéré du refroidisseur à clinker (2) à travers un conduit d'échappement (16), le procédé consistant à : - fournir un matériau minéral silico-alumineux susceptible de réactivité pouzzolanique lors de la calcination, - introduire le matériau minéral silico-alumineux dans la zone de refroidissement (13) du refroidisseur à clinker (2) et calciner le matériau minéral silico-alumineux dans la zone de refroidissement (13) à une température comprise entre 600 et 900°C, afin d'obtenir ledit matériau pouzzolanique.
PCT/EP2025/060326 2024-04-15 2025-04-15 Procédé de production d'un matériau pouzzolanique dans une installation de fabrication de ciment Pending WO2025219366A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP24020117.8 2024-04-15
EP24020117 2024-04-15

Publications (1)

Publication Number Publication Date
WO2025219366A1 true WO2025219366A1 (fr) 2025-10-23

Family

ID=90731520

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2025/060326 Pending WO2025219366A1 (fr) 2024-04-15 2025-04-15 Procédé de production d'un matériau pouzzolanique dans une installation de fabrication de ciment

Country Status (2)

Country Link
MX (1) MX2024012427A (fr)
WO (1) WO2025219366A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2234523C (fr) * 1997-04-10 2004-12-21 Lafarge Canada Inc. Methode pour l'obtention d'un clinker de ciment renfermant des cendres volantes
CA2923644A1 (fr) * 2015-03-17 2016-09-17 Secil-Companhia Geral De Cal E Cimento, S.A. Methode de production de machefer a faible teneur en carbone
WO2022106966A1 (fr) 2020-11-18 2022-05-27 Secil-Companhia Geral De Cal E Cimento, S.A. Ciment à faible teneur en carbone et son procédé de production
EP4194417A1 (fr) * 2023-03-07 2023-06-14 HeidelbergCement Georgia Ltd. Procédé de fabrication de ciment composite

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2234523C (fr) * 1997-04-10 2004-12-21 Lafarge Canada Inc. Methode pour l'obtention d'un clinker de ciment renfermant des cendres volantes
CA2923644A1 (fr) * 2015-03-17 2016-09-17 Secil-Companhia Geral De Cal E Cimento, S.A. Methode de production de machefer a faible teneur en carbone
WO2022106966A1 (fr) 2020-11-18 2022-05-27 Secil-Companhia Geral De Cal E Cimento, S.A. Ciment à faible teneur en carbone et son procédé de production
EP4194417A1 (fr) * 2023-03-07 2023-06-14 HeidelbergCement Georgia Ltd. Procédé de fabrication de ciment composite

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