WO2024200066A1 - Optimisation de la teneur en sulfate du ciment - Google Patents

Optimisation de la teneur en sulfate du ciment Download PDF

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Publication number
WO2024200066A1
WO2024200066A1 PCT/EP2024/057137 EP2024057137W WO2024200066A1 WO 2024200066 A1 WO2024200066 A1 WO 2024200066A1 EP 2024057137 W EP2024057137 W EP 2024057137W WO 2024200066 A1 WO2024200066 A1 WO 2024200066A1
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WO
WIPO (PCT)
Prior art keywords
sample
sulfate carrier
case
mixing
cement
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.)
Ceased
Application number
PCT/EP2024/057137
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German (de)
English (en)
Inventor
Michael Enders
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.)
ThyssenKrupp AG
Thyssenkrupp Polysius GmbH
Original Assignee
ThyssenKrupp AG
Thyssenkrupp Polysius 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
Priority claimed from LU103093A external-priority patent/LU103093B1/de
Priority claimed from DE102023107837.2A external-priority patent/DE102023107837A1/de
Application filed by ThyssenKrupp AG, Thyssenkrupp Polysius GmbH filed Critical ThyssenKrupp AG
Priority to EP24712241.9A priority Critical patent/EP4689623A1/fr
Priority to CN202480021875.1A priority patent/CN120898129A/zh
Publication of WO2024200066A1 publication Critical patent/WO2024200066A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C04B7/02—Portland cement
    • C04B7/04—Portland cement using raw materials containing gypsum, i.e. processes of the Mueller-Kuehne type
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
    • G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/38—Concrete; Lime; Mortar; Gypsum; Bricks; Ceramics; Glass
    • G01N33/383—Concrete or cement

Definitions

  • the invention relates to a method for optimizing the sulfate content in cement.
  • the content of tricalcium aluminate, or C3A for short is particularly relevant for the stiffening and setting behavior. This can lead to too rapid setting during use (spoon binder).
  • a sulfate carrier typically calcium sulfate
  • cement mixtures with different sulfate contents are therefore produced today, mixed to form a mortar by adding water and sand, and then tested for compressive strength, for example, at the time periods usually specified in the standards (e.g. ASTM, EN 196).
  • ASTM Standard
  • EN 196 the time periods usually specified in the standards
  • a cement production process is known from WO 2020 / 091 821 A1.
  • the object of the invention is to provide a method for interactively controlling the sufficient addition of sulfate carriers during cement production. This object is achieved by the method with the features specified in claim 1.
  • the method according to the invention is used to produce a cement mixture, for example the mixing of clinker with a sulfate carrier, ideally with other components such as artificial pozzolans.
  • a cement mixture for example the mixing of clinker with a sulfate carrier, ideally with other components such as artificial pozzolans.
  • the method according to the invention has the following steps: a) providing at least one first reactant and one sulfate carrier, b) mixing the at least one first reactant and the sulfate carrier to form the cement mixture according to a predetermined mixing ratio, c) taking a sample of the cement mixture from step b), d) mixing the sample with water to form a paste and recording the heat generated by the ongoing reaction, e) analyzing the recorded heat generated in the time window from 7 minutes to 60 minutes after mixing the sample with the water and distinguishing between case I and case II, wherein in case I the heat generated is constantly falling in the time window and wherein in case II the heat is at least temporarily increasing, f) adjusting the mixing ratio of the cement mixture, wherein in case I the mixing ratio is adjusted to reduce the amount of sulfate carrier added and wherein in case II the mixing ratio is adjusted to increase the amount of sulfate carrier added.
  • Steps a) and b) are carried out as is known and customary in the art.
  • a mixing ratio is usually specified as the starting value, which guarantees reliable setting behavior even with a high C3A content.
  • a mixing ratio of 10% by weight of sulfate carrier can be used as the starting value.
  • the original starting value is less relevant.
  • reactants are provided in step a).
  • the first reactant is usually clinker, the other reactants are selected from the list including fly ash, granulated blast furnace slag, slag, activated clay, artificial and natural pozzolans, waste cement or limestone. These are then mixed in different compositions in step b), for example and in particular in accordance with EN 197-1.
  • Sampling in step c) is preferably carried out continuously or periodically. For example, a sample is taken from the product stream every 30 minutes. For example, the sample can also be transported to a laboratory by pneumatic tube, as is often the case.
  • step d) or optionally after step c) and before step d), additional sand and other aggregates can be added to a mortar or concrete. This allows the setting behavior to be simulated as it occurs during use.
  • step d water is then added and mixed. This is preferably done quickly to enable the measurement to begin as early as possible.
  • the heat generated by the reaction can be recorded in various ways. For example, it can be done isothermally, for example using differential scanning calorimetry (DSC), or adiabatically, for example using differential thermal analysis (DTA).
  • DSC differential scanning calorimetry
  • DTA differential thermal analysis
  • the measurement is preferably carried out in a calorimeter, into which the (usually paste-like) mixture of water and the sample is introduced and the temperature is recorded under thermal insulation.
  • the exact recording method is less important here, since in step e) absolute values, concrete energies or the like are evaluated.
  • step e) the heat generated by the reaction recorded in step d) is then analyzed. This analysis is limited to whether a peak for the uncontrolled hydration of the C3A can be recognized. If there is sufficient or too much sulfate carrier, an initial peak is initially obtained, with a first peak with a maximum at about 2 to 5 minutes, which in particular represents the first reaction of the burnt lime (CaO) to slaked lime (Ca(OH)2) and the C3A with already available sulfate carrier to ettringite. After the maximum, the heat then drops steadily (strictly monotonically decreasing curve).
  • step e) the analysis can be dramatically simplified and accelerated, since only two simple cases need to be distinguished from one another in an event that occurs very early within one hour after the start of hydration.
  • the heat generated is constantly falling in the time window. This means that there is sufficient sulfate carrier, and there is no uncontrolled hydration of the C3A.
  • case II the heat increases at least temporarily, so there is a second exothermic reaction that can be attributed to uncontrolled hydration of the C3A after the sulfate carrier has been completely consumed. If case II with a second increase in the heat generated is observed during the measurement of a sample, the amount of sulfate carrier must be increased so that the second exothermic reaction no longer occurs in the range between 10 and 30 minutes.
  • the adjustment in step f) is preferably carried out as a percentage based on the sulfate carrier content.
  • the adjustment in step f) is initially carried out with a first step size.
  • a second step size is used to adjust the mixing ratio.
  • the second step size is half as large as the first step size. If case II is determined, the step size can be further adjusted, for example halved each time (for example up to a predetermined technically reasonable minimum step size, which is typically selected depending on the accuracy of the system). This makes it possible to approach the optimal mixing ratio as quickly as possible and at the same time as well as reliably.
  • the analysis in step e) is limited to the time window of 5 min to 40 min. Since the process approaches the limit at which uncontrolled C3A hydration occurs as the sulfate carrier content decreases, the maximum is initially in the range of longer times, from the initial peak of hydration. In this very low-interference range, the second maximum can be reliably and extremely easily detected.
  • the analysis in step e) is limited to the time window of 10 min to 40 min. Since the process approaches the limit at which uncontrolled C3A hydration occurs as the sulfate carrier content decreases, the maximum is initially in the range of longer times, from the initial peak of hydration. In this very low-interference range, the second maximum can be reliably and extremely easily detected.
  • the analysis in step e) is limited to the time window of 20 min to 40 min. Since the process approaches the limit at which uncontrolled C3A hydration occurs as the sulfate carrier content decreases, the maximum is initially in the range of longer times, from the initial peak of hydration. In this very low-interference range, the second maximum can be reliably and extremely easily detected.
  • the analysis in step e) is limited to determining the slope exclusively at two points in time, for example 20 minutes and 40 minutes.
  • the ratio of the two slopes alone makes it extremely easy to detect an incipient underdosing of the sulfate carrier (case II).
  • the heat generated in step d) is recorded in the form of the temperature of the sample. Since the evaluation is comparatively robust, the measurement does not have to be carried out isothermally or adiabatically, as is the case with DTA or DSC, for example. It is therefore sufficient to measure the temperature of the sample in a thermally somewhat insulated measuring area in which the sample is located.
  • the sample is ground between step c) and step d). It has been found that the observed effect is stronger the finer the material is, as this also increases the surface area. The sample is therefore ground for 2 to 5 minutes using a vibrating disc mill, for example. This makes it quicker and easier to detect an underdosage of the sulfate carrier.
  • the mixing ratio is changed abruptly from time to time so that a safe overdose of the sulfate carrier occurs, for example to a mixing ratio of 10% by weight of sulfate carrier. This ensures that the sulfate carrier content does not accidentally drop too much. Subsequently, according to the method according to the invention, a reduction is carried out again to the necessary minimum, from which a heat increase in the range of 10 to 30 minutes can be observed.
  • Fig. 1 Flowchart The method is illustrated by way of example in Fig. 1.
  • the cement is mixed from clinker (burnt from limestone, clay, sand and iron ore) and artificial pozzolan (activated clay).
  • the clinker comes from a clinker store 10, the artificial pozzolan from a pozzolan store 12.
  • a sulfate carrier from a sulfate carrier store 11 is metered in according to a mixing ratio, the addition being regulated by a control unit 30 on the basis of a mixing ratio.
  • the reactant streams are mixed and ground together in the mill 13.
  • a sample is taken from the product stream leaving the mill 13 in the sampling device 14, for example every 30 minutes, while the remaining product stream is fed to a cement store 15.
  • the sample from sampling 14 is ground in a laboratory mill 20 for 4 minutes, mixed with water from water supply 21 and quickly introduced into a calorimeter 22 where the temperature of the sample is recorded. This temperature is recorded by or transmitted to the control unit 30 and the increase in temperature is determined from the increase between 20 minutes and 40 minutes after the water was added to the sample. If this is constantly falling (case I), the mixing ratio in the control unit 30 is adjusted such that the proportion of sulfate carrier is reduced. This is continued until a renewed increase in temperature between 20 minutes and 40 minutes after the water was added to the sample (case II) indicates that the amount of sulfate carrier is too low. The control unit 30 therefore adjusts the mixing ratio accordingly to increase the amount of sulfate carrier again.
  • a setting unit 31 which, for example, sets the mixing ratio to a sulfate carrier content of 10 wt.% during start-up and cyclically, for example once a week, and thus ensures that there is always sufficient sulfate carrier available.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Investigating Or Analyzing Materials Using Thermal Means (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

L'invention concerne un procédé de production d'un mélange de ciment, ledit procédé comprenant les étapes suivantes : a) la fourniture d'au moins un réactif et d'un transporteur de sulfate ; b) le mélange du ou des premiers réactifs et du transporteur de sulfate selon un rapport de mélange donné afin de former le mélange de ciment ; c) le prélèvement d'un échantillon du mélange de ciment de l'étape b) ; d) le mélange de l'échantillon avec de l'eau et la détection la chaleur générée par la réaction en cours ; e) l'analyse de la chaleur générée détectée dans un laps de temps compris entre 10 et 60 minutes après mélange de l'échantillon avec l'eau et la différenciation entre un événement I et un événement II, dans l'événement I, la chaleur générée diminuant constamment pendant le laps de temps de l'événement I et augmentant au moins temporairement pendant l'événement II ; et f) l'adaptation du rapport de mélange. Dans le cas de l'événement I, le rapport de mélange est adapté pour réduire la quantité fournie de transporteur de sulfate, et dans le cas de l'événement II, le rapport de mélange est adapté afin d'augmenter la quantité fournie de transporteur de sulfate.
PCT/EP2024/057137 2023-03-28 2024-03-18 Optimisation de la teneur en sulfate du ciment Ceased WO2024200066A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP24712241.9A EP4689623A1 (fr) 2023-03-28 2024-03-18 Optimisation de la teneur en sulfate du ciment
CN202480021875.1A CN120898129A (zh) 2023-03-28 2024-03-18 水泥中硫酸盐含量的优化

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
LULU103093 2023-03-28
LU103093A LU103093B1 (de) 2023-03-28 2023-03-28 Optimierter Sulfatgehalt in Zement
DE102023107837.2A DE102023107837A1 (de) 2023-03-28 2023-03-28 Optimierter Sulfatgehalt in Zement
DE102023107837.2 2023-03-28

Publications (1)

Publication Number Publication Date
WO2024200066A1 true WO2024200066A1 (fr) 2024-10-03

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Family Applications (1)

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PCT/EP2024/057137 Ceased WO2024200066A1 (fr) 2023-03-28 2024-03-18 Optimisation de la teneur en sulfate du ciment

Country Status (3)

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EP (1) EP4689623A1 (fr)
CN (1) CN120898129A (fr)
WO (1) WO2024200066A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104965532A (zh) 2015-06-25 2015-10-07 济南大学 一种水泥生料配料控制系统及方法
DE102014018489A1 (de) * 2014-12-16 2016-06-16 Thyssenkrupp Ag Vorrichtung sowie ein Verfahren zur Herstellung und Analyse einer Mehrzahl von Probewerkstoffen
WO2020091821A1 (fr) 2018-11-02 2020-05-07 Gcp Applied Technologies, Inc Production de ciment
CN111551698A (zh) 2020-05-22 2020-08-18 绵阳钢猫科技有限公司 一种水泥生产质量在线检测方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014018489A1 (de) * 2014-12-16 2016-06-16 Thyssenkrupp Ag Vorrichtung sowie ein Verfahren zur Herstellung und Analyse einer Mehrzahl von Probewerkstoffen
CN104965532A (zh) 2015-06-25 2015-10-07 济南大学 一种水泥生料配料控制系统及方法
WO2020091821A1 (fr) 2018-11-02 2020-05-07 Gcp Applied Technologies, Inc Production de ciment
CN111551698A (zh) 2020-05-22 2020-08-18 绵阳钢猫科技有限公司 一种水泥生产质量在线检测方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LI PEI ET AL: "Effect of Gypsum on Hydration and Hardening Properties of Alite Modified Calcium Sulfoaluminate Cement", MATERIALS, vol. 12, no. 19, 25 October 2019 (2019-10-25), CH, pages 3131, XP093087433, ISSN: 1996-1944, DOI: 10.3390/ma12193131 *

Also Published As

Publication number Publication date
CN120898129A (zh) 2025-11-04
EP4689623A1 (fr) 2026-02-11

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