DE19632697A1 - High early strength slag cement produced using slag wool - Google Patents

High early strength slag cement produced using slag wool

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Publication number
DE19632697A1
DE19632697A1 DE1996132697 DE19632697A DE19632697A1 DE 19632697 A1 DE19632697 A1 DE 19632697A1 DE 1996132697 DE1996132697 DE 1996132697 DE 19632697 A DE19632697 A DE 19632697A DE 19632697 A1 DE19632697 A1 DE 19632697A1
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DE
Germany
Prior art keywords
slag
wool
cement
metallurgical
cottage
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.)
Withdrawn
Application number
DE1996132697
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German (de)
Inventor
Juergen Prof Dr Ing Geiseler
Eberhard Dr Ing Lang
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.)
FORSCHUNGSGEMEINSCHAFT EISENHU
Original Assignee
FORSCHUNGSGEMEINSCHAFT EISENHU
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.)
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Application filed by FORSCHUNGSGEMEINSCHAFT EISENHU filed Critical FORSCHUNGSGEMEINSCHAFT EISENHU
Priority to DE1996132697 priority Critical patent/DE19632697A1/en
Publication of DE19632697A1 publication Critical patent/DE19632697A1/en
Withdrawn legal-status Critical Current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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/38—Fibrous materials; Whiskers
    • C04B14/46—Rock wool ; Ceramic or silicate fibres
    • C04B14/4643—Silicates other than zircon
    • C04B14/4675—Silicates other than zircon from slags
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
    • C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate containing activators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

A novel slag cement consists of 36-80 wt.% slag wool (completely or partially replacing slag sand), balance Portland cement, Portland cement clinker and/or slag sand and optional sulphate sources and additional components. Also claimed are: (i) the use of slag wool of up to max. 50 (preferably less than 5) microns thickness for slag cement manufacture; and (ii) a process for slag cement manufacture using slag wool, in which the SiO2 content of the slag wool is decreased by increasing the CaO, MgO and/or Al2O3 contents.

Description

Die Erfindung betrifft Hüttenzement und ein Verfahren zu seiner Herstellung.The invention relates to metallurgical cement and a method its manufacture.

Die Herstellung von Hüttenzementen (Portlandhütten- und Hochofenzemente) ist in der deutschen Zementnorm DIN 1164-1, Ausgabe 10, 1994, der europäischen Vornorm für Zement ENV 197-1, Ausgabe 12, 1992, genormt.The production of metallurgical cements (Portland metallurgical and Blast Furnace Cements) is in the German cement standard DIN 1164-1, edition 10, 1994, the European pre-standard for cement ENV 197-1, edition 12, 1992, standardized.

Hüttensand, der bei der Granulation oder Pelletierung erzeugt wird, hat üblicherweise eine Kornverteilung im Bereich bis 4 mm. Für die Herstellung von Zementen und anderen mineralischen Bindemitteln muß der Hüttensand fein gemahlen werden. Dies kann sowohl durch die gemeinsame Vermahlung der Bestandteile, z. B. Hüttensand, Portlandzementklinker und Sulfatträger und/oder durch die getrennte Vermahlung der Einzelkomponenten und ihre anschließende Mischung erfolgen. Eine höhere Feinheit der Zementpartikel führt zu einer Erhöhung der Festigkeiten, insbesondere der Frühfestigkeiten. Dabei kommt den Partikeln, etwa kleiner 5 µm, für die Erhöhung der Frühfestigkeiten eine besondere Bedeutung zu, siehe z. B. K. Schweden, "Einfluß der Mahleinheit und der Kornverteilung auf die Eigenschaften von Portland- und Hüttenzementen sowie von hydraulischen Kalken", Dissertation Bergakademie Clausthal 1965, und B. Beke, "Mahlverfahren, Kornaufbau und Festigkeitsverlauf verschiedener Zemente", Zement-Kalk-Gips 13 (1960), Heft 9, S. 419-424. Slag sand used in granulation or pelleting is usually produced with a grain distribution in Range up to 4 mm. For the production of cements and other mineral binders must be found in the slag sand be finely ground. This can be done through both joint grinding of the components, e.g. B. slag sand, Portland cement clinker and sulfate carrier and / or through the separate grinding of the individual components and their subsequent mixing. A greater delicacy of Cement particles leads to an increase in strength, especially the early strengths. Here comes the Particles, approximately smaller than 5 µm, for increasing the Early strengths are of particular importance, see e.g. B. K. Sweden, "Influence of the milling unit and the Grain distribution on the properties of Portland and Metallurgical cements and hydraulic limes ", Dissertation Bergakademie Clausthal 1965, and B. Beke, "Grinding process, grain structure and strength course various cements ", cement-lime-gypsum 13 (1960), Issue 9, pp. 419-424.  

Die DE-OS 42 04 727 beschreibt einen hochfesten Hochofenschlackenbeton, der feingemahlene granulierte Hochofenschlacke (Hüttensand) mit einer spezifischen Oberfläche von ca. 12.000 cm²/g und einen Hauptanteil im Korngrößenbereich von < 2 µm und < 5 µm enthält. Die Herstellung dieses feingemahlenen Hüttensandes erfolgt in einer Strahlmühle und anschließender Klassierung in einem Alpine-Sichter.DE-OS 42 04 727 describes a high-strength Blast furnace slag concrete, the finely ground granulated Blast furnace slag (slag sand) with a specific Surface of approx. 12,000 cm² / g and a major part in Grain size range of <2 microns and <5 microns contains. The This finely ground slag sand is produced in a jet mill and subsequent classification in one Alpine classifier.

Die umfangreichen Untersuchungen zum Einsatz von Silikastaub haben darüberhinaus gezeigt, daß durch die Zugabe von feinsten reaktiven Partikeln zum Zement oder bei der Betonherstellung nicht nur die Frühfestigkeiten, sondern auch die Dauerhaftigkeit der mit diesen Zementen und Betonen hergestellten Bauwerke und Bauteile wesentlich erhöht wird, siehe Th. Telford, "Condensed Silica Fume in Concrete", State of art report, Thomas Telford Ltd, London (1988).The extensive studies on the use of Silica dust have also shown that through the Adding the finest reactive particles to the cement or in the production of concrete not only the early strengths, but also the durability of using these cements and concreting manufactured structures and components is significantly increased, see Th. Telford, "Condensed Silica Fume in Concrete ", State of Art Report, Thomas Telford Ltd, London (1988).

Der spezifische Arbeitsaufwand in kWh/t Mahlgut steigt exponentiell mit der Feinheit an. Die Verringerung des Lageparameters x′ von 25 µm auf 5 µm für eine Portlandzementklinker hat eine Erhöhung des spezifischen Arbeitsaufwands von etwa 25 kWh/t auf etwa 80 kWh/h zur Folge, siehe B. Schiller, "Mahlbarkeit der Hauptbestandteile des Zements und ihr Einfluß auf den Energieaufwand beim Mahlen und die Zementeigenschaften", Schriftenreihe der Zementindustrie, Heft 54 (1992), Beton-Verlag GmbH, Düsseldorf. Für Hüttensand liegt der Mahlaufwand in ähnlicher Größenordnung tendenziell darüber. The specific workload in kWh / t of regrind increases exponentially with the fineness. The reduction of Position parameters x 'from 25 µm to 5 µm for one Portland cement clinker has an increase in specific Workload from about 25 kWh / t to about 80 kWh / h Consequence, see B. Schiller, "Grindability of the Main components of the cement and their influence on the Energy expenditure during grinding and the cement properties ", Series of the cement industry, volume 54 (1992), Beton-Verlag GmbH, Dusseldorf. For slag sand it lies Grinding effort tends to be of a similar magnitude about that.  

Überraschend zeigte sich nun, daß Hüttenwolle auch zur Herstellung von Hüttenzementen geeignet ist. Hüttenwolle ist ein der Mineral- und Glaswolle ähnliches feinfaseriges Produkt, das mittels verschiedener Verfahren aus flüssiger Hochofenschlacke hergestellt wird. Die wesentlichsten Verfahren sind von F. Klein in "Hochofenschlacke", Verlag Stahleisen mbH, Düsseldorf, 2. Auflage (1963), S. 300-314, beschrieben worden. Hüttenwolle hat im allgemeinen eine Faserlänge von wenigen Zentimetern. Die Länge hängt sehr stark von dem Herstellungsverfahren und der chemischen Zusammensetzung der Hochofenschlacke ab. Hüttenwolle wird ebenso wie Mineral- und Glaswolle zu verschiedensten Produkten der Wärme-, Kälte- und Schallisolierung weiterverarbeitet.Surprisingly, it has now been found that cottage wool is also used for Production of metallurgical cements is suitable. Cottage wool is similar to mineral and glass wool fine-fiber product, which by means of different Process made from liquid blast furnace slag becomes. The most important procedures are by F. Klein in "Blast furnace slag", Verlag Stahleisen mbH, Düsseldorf, 2nd edition (1963), pp. 300-314. Cottage wool generally has a fiber length of a few centimeters. The length depends very much on that Manufacturing process and chemical composition the blast furnace slag. Cottage wool is made as well Mineral and glass wool for various products from Processed heat, cold and sound insulation.

Wird Hüttenwolle nun erfindungsgemäß mit Portlandzement und/oder Portlandzementklinker und/oder Hüttensand und ggf. Sulfatträger gemeinsam vermahlen, so erhält man einen Hüttenzement, der im Vergleich zu einem aus herkömmlichem Hüttensand, der eine der Hüttenwolle entsprechende chemische Zusammensetzung aufweist, und Portlandzementklinker hergestellten Hüttenzement vergleichbare Eigenschaften aufweist. Aufgrund der mit geringem Mahlaufwand erreichbaren hohen Feinheit der Hüttenwolle sind die Frühfestigkeiten der mit Hüttenwolle hergestellten Zemente im allgemeinen günstiger. According to the invention, cottage wool is now made with Portland cement and / or Portland cement clinker and / or slag sand and if necessary, sulfate carriers are ground together to obtain a cottage cement that compared to one conventional slag sand, which is one of the slag wool has the appropriate chemical composition, and Portland cement clinker produced metallurgical cement has comparable properties. Because of the low grinding effort achievable high fineness of Cottage wool is the early strength of those with cottage wool manufactured cements generally cheaper.  

Es ist auch möglich, Hüttenwolle, Portlandzement und/oder Portlandzementklinker und ggf. Sulfatträger getrennt zu vermahlen und anschließend zu mischen. Schließlich kann die getrennt gemahlene Hüttenwolle auch als Betonzusatzstoff verwendet werden. Hüttenwolle kann mit Hüttensand oder allein zu dem Hüttenzement zugesetzt werden.It is also possible to use cottage wool, Portland cement and / or Portland cement clinker and, if necessary, sulfate carriers are added separately grind and then mix. Finally, can the separately ground cottage wool also as Concrete additive can be used. Cottage wool can with Slag sand or added alone to the cement will.

Die Vorteile, die sich aus der Anwendung des erfindungsgemäßen Verfahrens ergeben, lassen sich wie folgt zusammenfassen:The benefits of using the method according to the invention can be how summarize as follows:

  • - Herstellung eines feinstkörnigen Haupt- oder Nebenbestandteils für die Zementherstellung oder eines feinstkörnigen Betonzusatzstoffs mit sehr geringem Mahlaufwand,- Making a fine grain main or Auxiliary ingredient for cement production or a very fine-grained concrete additive with very low grinding effort,
  • - hohe Reaktivität der gemahlenen Hüttenwolle aufgrund ihrer hohen Feinheit und damit mindestens gleiche, im allgemeinen verbesserte Festigkeitsentwicklung und erhöhte Dauerhaftigkeit der damit hergestellten Zemente und Betone.- high reactivity of the ground cottage wool due to their high delicacy and thus at least the same, in general improved strength development and increased durability of the manufactured with it Cements and concretes.

Claims (5)

1. Hüttenzement, bestehend aus Hüttenwolle als ganzem oder teilweisem Ersatz von Hüttensand in einer Menge von 36 bis 80 Masse-%, Rest im wesentlichen Portlandzement und/oder Portlandzementklinker und/oder Hüttensand sowie ggf. Sulfatträger und Nebenbestandteile.1. Metallurgical cement, consisting of metallurgical wool as Complete or partial replacement of slag sand in one Amount from 36 to 80% by mass, the rest essentially Portland cement and / or Portland cement clinker and / or Slag sand as well as possibly sulfate carriers and secondary components. 2. Verwendung von Hüttenwolle mit einer Faserstärke bis max. 50 µm, vorzugsweise < 5 µm, zur Herstellung von Hüttenzementen.2. Use of cottage wool with a fiber strength up to max. 50 microns, preferably <5 microns, for the production of Metallurgical cements. 3. Verfahren zur Herstellung von Hüttenzementen unter Verwendung von Hüttenwolle, dadurch gekennzeichnet, daß der SiO₂-Gehalt der Hüttenwolle durch Erhöhung der Gehalte an CaO, MgO und/oder Al₂O₂ verringert wird.3. Process for the production of metallurgical cements using cottage wool, characterized in that the SiO₂ content of the cottage wool by increasing the content CaO, MgO and / or Al₂O₂ is reduced. 4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß der CaO-, MgO-, Al₂O₃-Gehalt der Hochofeneinsatzstoffe zur Verringerung des SiO₂-Gehalts gesteigert wird.4. The method according to claim 3, characterized in that the CaO, MgO, Al₂O₃ content of the blast furnace feedstock for Reduction of the SiO₂ content is increased. 5. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß der flüssigen Hochofenschlacke zur Verringerung ihres SiO₂-Gehalts Zusätze an Ca, MgO, und/oder Al₂O₂ beigegeben werden.5. The method according to claim 3, characterized in that the liquid blast furnace slag to reduce their SiO₂ content additions of Ca, MgO, and / or Al₂O₂ added will.
DE1996132697 1996-08-14 1996-08-14 High early strength slag cement produced using slag wool Withdrawn DE19632697A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE800287C (en) * 1949-04-09 1950-10-25 Eisenwerke Gelsenkirchen Akt G Process for the production of slag wool
DE2247616A1 (en) * 1972-09-19 1974-04-04 Tac Construction Materials Ltd CEMENTAL MATERIALS

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE800287C (en) * 1949-04-09 1950-10-25 Eisenwerke Gelsenkirchen Akt G Process for the production of slag wool
DE2247616A1 (en) * 1972-09-19 1974-04-04 Tac Construction Materials Ltd CEMENTAL MATERIALS

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