EP2917163A1 - Method for producing a hydraulic binding agent - Google Patents

Method for producing a hydraulic binding agent

Info

Publication number
EP2917163A1
EP2917163A1 EP13786669.5A EP13786669A EP2917163A1 EP 2917163 A1 EP2917163 A1 EP 2917163A1 EP 13786669 A EP13786669 A EP 13786669A EP 2917163 A1 EP2917163 A1 EP 2917163A1
Authority
EP
European Patent Office
Prior art keywords
silicate
mill
component
containing component
coating
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
EP13786669.5A
Other languages
German (de)
French (fr)
Inventor
Oliver Maier
Viktor Marchuk
Michael Wilczek
Dirk Schefer
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 Industrial Solutions AG
Original Assignee
ThyssenKrupp Industrial Solutions AG
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 ThyssenKrupp Industrial Solutions AG filed Critical ThyssenKrupp Industrial Solutions AG
Publication of EP2917163A1 publication Critical patent/EP2917163A1/en
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
    • 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
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/06—Quartz; Sand
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • 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
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/14—Minerals of vulcanic origin
    • C04B14/18—Perlite
    • 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
    • C04B18/08—Flue dust, i.e. fly ash
    • 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
    • C04B18/146—Silica fume
    • 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
    • C04B20/026—Comminuting, e.g. by grinding or breaking; Defibrillating fibres other than asbestos
    • 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
    • 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
    • C04B20/10—Coating or impregnating
    • C04B20/1055—Coating or impregnating with inorganic materials
    • 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
    • C04B20/10—Coating or impregnating
    • C04B20/1055—Coating or impregnating with inorganic materials
    • C04B20/1077—Cements, e.g. waterglass
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/06—Oxides, Hydroxides
    • C04B22/062—Oxides, Hydroxides of the alkali or alkaline-earth metals
    • C04B22/064—Oxides, Hydroxides of the alkali or alkaline-earth metals of the alkaline-earth metals
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
    • C04B2103/0088—Compounds chosen for their latent hydraulic characteristics, e.g. pozzuolanes
    • 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

Definitions

  • the invention relates to a method for producing a hydraulic binder and to a method for producing a binder mixture by processing a silicate-containing component with calcium silicate hydrate and / or belite-containing components.
  • EP 2 243 754 A1 describes a process for the preparation of a hydraulic binder which is based on a calcium silicate compound and has properties similar to those of conventional Portland cement, but in the production of which significantly less CO 2 is liberated.
  • a calcium and silicon-containing starting material is first hydrothermally treated at temperatures of 120-250 ° C, whereby a calcium silicate hydrate-containing intermediate product is formed.
  • the intermediate is reaction-milled alone at a temperature of 100-150 ° C alone or together with another silicate-containing material, whereby under reaction and dehydration at least partially a belitumbles binder is formed, which is highly reactive and a comparable with Portland cement binder low reaction heat and high Medfestmaschine corresponds.
  • the present invention is an object of the invention to provide a method for producing a hydraulic binder, a method for producing a binder mixture and the use of a plant for the two production processes, wherein the proportion of calcium silicate hydrate and / or belitumblen component in Binders can be reduced. According to the invention, this object is achieved by the features of claims 1, 8, 9 and 13.
  • the inventive method for producing a hydraulic binder by processing a silicate-containing component with calcium silicate hydrate and / or belit ambiencen components is characterized by the combination of the following two steps:
  • the silicate-containing component is comminuted in at least one comminution device to particle sizes of ⁇ 100 ⁇ , wherein for surface activation at least partially Si-O-Si bonds and / or hydrogen bonds in the structure of the surface layer of the silicate-containing component are broken, and
  • the silicate-containing component activated in the first step is brought into contact as a silicate-containing carrier with calcium silicate hydrate and / or belite-containing components in a coating device, wherein the calcium silicate hydrate and / or belite-containing components are at least Enrich 50% of the surface of the silicate-containing carrier with a reaction coating.
  • a silicate-containing component eg quartz sand, slag or fly ash
  • a silicate-containing component eg quartz sand, slag or fly ash
  • the basic structure of the silicates is characterized by Si0 4 tetrahedra, whose center consists of a silicon atom and whose four corners each consist of one oxygen atom. Essentially all silicates are built up by linkages of these Si0 4 pyramids.
  • roller mill in particular a pendulum roller mill, and / or a roller mill, but preferably high energy mills such as a jet mill, an impact mill, a ball mill, in particular an agitator ball mill, a vibration mill and / or a magnetic mill and a circuit u nd / or combination of these types of mill in question.
  • high energy mills such as a jet mill, an impact mill, a ball mill, in particular an agitator ball mill, a vibration mill and / or a magnetic mill and a circuit u nd / or combination of these types of mill in question.
  • the thus activated silicate-containing component is then coated as a silicate-containing carrier in a second treatment unit with a calcium silicate hydrate and / or belit ambiencen substance.
  • This coating may also be in at least one mill, for example in a ball mill, in particular an agitator ball mill, a vibration mill, a jet mill and / or impact mill, but preferably in a roller mill, in particular a pendulum roller mill, and / or roller mill, and an interconnection and / or combination of these types of mill.
  • a magnetic coating according to US Pat. No. 6,037,019 and use of a magnetic mill is also conceivable.
  • relatively soft grinding media for example plastic-coated cast iron or magnetic bodies, are used in the coating. The aim of this coating or sheathing is to largely avoid further comminution of the particles and to achieve a coating of the coarser silicate-containing carriers with the calcium silicate hydrate and / or belite-containing components.
  • the at least one comminution device in the first method step is operated together with a separator which separates a coarser silicate-containing component from a finer silicate-containing component, so that at least the coarser silicate-containing component is again fed to the at least one comminution device. It can also be provided that a part of the finer silicate-containing component is discharged from the process and possibly used elsewhere or further processed.
  • the coating device can intensify the contact between the silicate-containing carriers and the calcium-silicate-hydrate and / or belit ambiencen component loose auxiliary body can be used in the coating device.
  • another substance preferably a fines such as microsilica, may be added up to 20% in at least one of the two process steps.
  • the calcium silicate hydrate and / or belite-containing component is expediently dewatered before the second process step in at least one separate treatment device and / or activated at elevated temperature of preferably greater than 100 ° C.
  • the coating step is expediently likewise carried out at temperatures of at least 100 ° C.
  • the coating device provided for the coating can have guide elements and / or stirring elements and / or loose auxiliary bodies.
  • the material coming from the coating device can optionally be supplied to a separating device 9. This separates the predominantly completely coated substances 1 'from the incompletely coated substances 1 ", which would lead to a return to the coating device or to the discharge of the finished product
  • the finished product could serve as a binder or as an additive for a binder mixture
  • the finished product could be mixed with substances 11, such as fly ash, clinker flour, various types of slag, Portland cement, limestone powder or various mixtures of these substances
  • the substances should have corresponding subtleties, so that the final product can serve as a binder mixture.
  • a further variant could likewise be that the substances listed above, in particular also limestone as inert filler, are fed together with the silicate-containing carriers to the comminuting device (process step 1) and comminuted or ground together. This has the advantage of saving an additional and costly comminution process.
  • Fig. 1 is a block diagram of a plant for producing a hydraulic
  • Binder and / or a binder mixture and Fig. 2 is an X-ray diffractogram of calcium silicate hydrate-containing
  • the plant shown in FIG. 1 for producing a hydraulic binder 1 and / or a binder mixture 12 has a comminution device 2 for comminuting silicate-containing carriers 3 and / or further substances 11 'to particle sizes of ⁇ 100 ⁇ m, and a subsequently arranged coating device 4 with a first feeder 4a for the silicate-containing carrier 3 a comminuted in the comminuting device 2 and a second feed 4b for a calcium silicate-hydrate and / or belite-containing component 5.
  • the comminution device 2 is operated together with a classifier 6 which separates coarser carriers 3b from finer carriers, at least the coarser carriers 3b being fed again to the comminution device 2, while the finer carriers as activated silicate-containing carrier 3a together with the calcium silicate carrier. Hydrate and / or belit ambiencen component 5 of the coating device 4 are supplied.
  • the crushing device 2 and the coating device 4 may each be operated by a (agitator) ball mill, a vibration mill, a magnetic mill, a (shuttle) roller mill, a roller mill, an impact mill or a jet mill or the like. An interconnection and / or combination of these types of mill is conceivable.
  • auxiliary bodies are used both in the comminution device 2 and in the coating device 4, relatively soft auxiliary bodies are used in the coating device 4.
  • auxiliary bodies are used both in the comminution device 2 and in the coating device 4
  • relatively soft auxiliary bodies are used in the coating device 4.
  • further comminution of the silicate-containing carriers is largely avoided and intimate contact with the calcium-silicate-hydrate and / or belit ambiencen component allows to achieve a coating of the surface of the silicate-containing carrier of at least 50%, preferably at least 80%.
  • the coating device 4 can also be fed with a further substance 7, preferably a fine substance, such as microsilica, up to 20%.
  • the coating in the coating device 4 is advantageously carried out at a temperature of at least 100 C.
  • the calcium silicate hydrate and / or belitance component 5 can be dehydrated before being fed into the coating device 4 in at least one separate treatment device 8 and / or activated at elevated temperature of preferably 100 ° C and / or subjected to a heat pressure treatment.
  • the product can be used as a binder.
  • the coater may be followed by a mixing or screening device. In this then hydraulic and / or latent hydraulic substances, such as clinker, fly ash, steel mill and / or blast furnace slag, OPC or mixtures of these substances are mixed, so that a binder mixture with low C0 2 emissions.
  • inert fillers especially limestone flour, is possible.
  • quartz sand is activated as a silicate-containing carrier by grinding and then reaction-coated with aC 2 SH as a calcium silicate hydrate component.
  • aC 2 SH as a calcium silicate hydrate component.
  • other substances such as, for example, slag and / or fly ash can be added to the grinding process together with quartz sand and activated.
  • Quartz sand was used with a particle size fraction of 90 ⁇ to 250 ⁇ .
  • the silicate-containing carrier activated after treatment in a disk-vibrating mill had, according to analysis with a laser diffraction spectrometer, an average particle size of about 6 ⁇ m.
  • aC 2 SH with a mean particle size of less than 20 ⁇ m was reaction-coated together with the activated quartz in a mass ratio of 2: 1 in a disk vibration mill. From the Analysis with the laser diffraction spectrometer, a mean particle size of about 5 ⁇ was determined for the resulting hydraulic binder.
  • Table 1 shows the results of the quantitative X-ray diffraction analyzes.
  • the calcium silicate hydrate component contained 81% aC 2 SH, some portlandite and calcite, further CSH phases (kilchoanite, foshagite) and a calcium aluminate phase (katoite, 9%).
  • the hydraulic binder obtained after the reaction coating was determined to be 60% amorphous, 7% crystalline aC 2 SH and 33% quartz.
  • the X-ray diffractogram of FIG. 2 shows for the calcium silicate hydrate component signals of the aC 2 SH, which is present as a main component. After reaction coating with activated quartz in the disk vibratory mill, the reflections of the aC 2 SH decrease markedly, while at the same time the background signal rises sharply due to the formation of amorphous phases.

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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)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Paints Or Removers (AREA)
  • Glanulating (AREA)

Abstract

The method according to the invention for producing a hydraulic binding agent by processing a silicate-containing component with components containing calcium silicate hydrate and/or larnite is characterized by the combination of the following two method steps: in the first method step, the silicate-containing component is comminuted in at least one comminution device to particle sizes of <100 µm, wherein Si-O-Si bonds and/or hydrogen bridges in the structure of the surface layer of the silicate-containing component are broken, at least in part, for surface activation; and in the second method step, the silicate-containing component activated in the first step is brought into contact as the silicate-containing carrier material with components containing calcium silicate hydrate and/or larnite in a coating device, wherein the components containing calcium silicate hydrate and/or larnite are enriched on at least 50% of the surface of the silicate-containing carrier material.

Description

Verfahren zur Herstellung eines hydraulischen Bindemittels  Process for the preparation of a hydraulic binder
Die Erfindung betrifft ein Verfahren zur Herstellung eines hydraulischen Bindemittels sowie ein Verfahren zur Herstellung einer Bindemittelmischung durch Verarbeitung einer silikathaltigen Komponente mit Calcium-Silikat-Hydrat- und/oder belithaltigen Komponenten. The invention relates to a method for producing a hydraulic binder and to a method for producing a binder mixture by processing a silicate-containing component with calcium silicate hydrate and / or belite-containing components.
Bei der Herstellung von Zementklinker wird kalkhaltiges Rohmehl zunächst vorgewärmt, dann kalziniert und schließlich fertiggebrannt. Bei der Kalzination des Kalksteins werden enorme Mengen an C02 freigesetzt. Man ist daher bemüht, die C02-Emissionen zu reduzieren. In the production of cement clinker, lime-containing raw meal is first preheated, then calcined and finally finished. The calcination of the limestone releases enormous amounts of C0 2 . Efforts are therefore being made to reduce C0 2 emissions.
In der EP 2 243 754 AI wird ein Verfahren zur Herstellung eines hydraulischen Bindemittels beschrieben, welches auf einer Calcium- Silikat- Verbindung basiert und ähnliche Eigenschaften aufweist, wie herkömmlicher Portland-Zement, aber bei dessen Herstellung deutlich weniger C02 freigesetzt wird. Dort wird zunächst ein calcium- und siliziumhaltiges Ausgangsmaterial bei Temperaturen von 120-250 °C hydrothermal behandelt, wodurch ein Calcium-Silikat-Hydrat-haltiges Zwischenprodukt entsteht. Anschließend wird das Zwischenprodukt bei einer Temperatur von 100-150 °C alleine oder gemeinsam mit einem anderen silikathaltigen Material in einer Mühle reaktionsvermahlen, wodurch unter Reaktion und Entwässerung zumindest teilweise ein belithaltiges Bindemittel entsteht, das hochreaktiv ist und einem mit Portland-Zement vergleichbaren Bindemittel mit niedriger Reaktionswärme und hoher Füllfestigkeit entspricht. EP 2 243 754 A1 describes a process for the preparation of a hydraulic binder which is based on a calcium silicate compound and has properties similar to those of conventional Portland cement, but in the production of which significantly less CO 2 is liberated. There, a calcium and silicon-containing starting material is first hydrothermally treated at temperatures of 120-250 ° C, whereby a calcium silicate hydrate-containing intermediate product is formed. Subsequently, the intermediate is reaction-milled alone at a temperature of 100-150 ° C alone or together with another silicate-containing material, whereby under reaction and dehydration at least partially a belithaltiges binder is formed, which is highly reactive and a comparable with Portland cement binder low reaction heat and high Füllfestigkeit corresponds.
Der vorliegenden Erfindung liegt nun die Aufgabe zugrunde, ein Verfahren zur Herstellung eines hydraulischen Bindemittels, ein Verfahren zur Herstellung einer Bindemittelmischung sowie die Verwendung einer Anlage für die beiden Herstellungsverfahren anzugeben, wobei der Anteil der Calcium-Silikat-Hydrat- und/oder belithaltigen Komponente im Bindemittel verringert werden kann. Erfindungsgemäß wird diese Aufgabe durch die Merkmale der Ansprüche 1, 8, 9 und 13 gelöst. The present invention is an object of the invention to provide a method for producing a hydraulic binder, a method for producing a binder mixture and the use of a plant for the two production processes, wherein the proportion of calcium silicate hydrate and / or belithaltigen component in Binders can be reduced. According to the invention, this object is achieved by the features of claims 1, 8, 9 and 13.
Das erfindungsgemäße Verfahren zur Herstellung eines hydraulischen Bindemittels durch Verarbeitung einer silikathaltigen Komponente mit Calcium-Silikat-Hydrat- und/oder belithaltigen Komponenten ist durch die Kombination der folgenden beiden Verfahrensschritte gekennzeichnet: The inventive method for producing a hydraulic binder by processing a silicate-containing component with calcium silicate hydrate and / or belithaltigen components is characterized by the combination of the following two steps:
• Im ersten Verfahrensschritt wird die silikathaltige Komponente in wenigstens einer Zerkleinerungseinrichtung auf Partikelgrößen von < 100 μιη zerkleinert, wobei zur Oberflächenaktivierung wenigstens teilweise Si-O-Si-Bindungen und/oder Wasserstoffbrücken in der Struktur der Oberflächenschicht der silikathaltigen Komponente aufgebrochen werden, und In the first process step, the silicate-containing component is comminuted in at least one comminution device to particle sizes of <100 μιη, wherein for surface activation at least partially Si-O-Si bonds and / or hydrogen bonds in the structure of the surface layer of the silicate-containing component are broken, and
• Im zweitem Verfahrensschritt wird die im ersten Schritt aktivierte silikathaltige Komponente als silikathaltiger Trägerstoff mit Calcium-Silikat- Hydrat- und/oder belithaltigen Komponenten in einer Beschichtungseinrichtung in Kontakt gebracht, wobei sich die Calcium- Silikat-Hydrat- und/oder belithaltigen Komponenten auf wenigstens 50 % der Oberfläche des silikathaltigen Trägerstoffs durch eine Reaktionsbeschichtung anreichern. In the second process step, the silicate-containing component activated in the first step is brought into contact as a silicate-containing carrier with calcium silicate hydrate and / or belite-containing components in a coating device, wherein the calcium silicate hydrate and / or belite-containing components are at least Enrich 50% of the surface of the silicate-containing carrier with a reaction coating.
Die in der EP 2 243 754 AI beschriebene Reaktionsmahlung wird bei der vorliegenden Erfindung also in zwei voneinander getrennte Verfahrensschritte aufgelöst. So wird im ersten Verfahrensschritt eine silikathaltige Komponente (z.B. Quarzsand, Schlacke oder Flugasche) auf Partikelgrößen kleiner 100 μιη zerkleinert. Bei dieser Zerkleinerung wird die kristalline oder auch amorphe Struktur der silikathaltigen Komponente aufgebrochen, wodurch zusätzliche, aktivierte Oberflächen entstehen. Die grundlegende Struktur der Silikate zeichnet sich durch Si04-Tetraeder aus, deren Zentrum aus einem Silizium- Atom und deren vier Ecken aus je einem Sauerstoffatom bestehen. Im Wesentlichen sind alle Silikate durch Verknüpfungen dieser Si04-Pyramiden aufgebaut. An den Sauerstoffatomen der Ecken des Tetraeders knüpfen bei Stoffen mit einem hohen Silikatanteil hauptsächlich Siliziumatome an. Diese Si-O-Si-Bindungen haben einen großen kovalenten Anteil, woraus u.a. die große Härte von Quarz resultiert. Neben Siliziumatomen können an diesen Stellen aber auch beliebige andere Atome anknüpfen. The reaction milling described in EP 2 243 754 A1 is therefore dissolved in the present invention into two separate process steps. Thus, in the first process step, a silicate-containing component (eg quartz sand, slag or fly ash) is comminuted to particle sizes smaller than 100 μm. In this comminution, the crystalline or even amorphous structure of the silicate-containing component is broken, resulting in additional, activated surfaces. The basic structure of the silicates is characterized by Si0 4 tetrahedra, whose center consists of a silicon atom and whose four corners each consist of one oxygen atom. Essentially all silicates are built up by linkages of these Si0 4 pyramids. At the oxygen atoms of the corners of the tetrahedron knot at fabrics with a high silicate content mainly silicon atoms. These Si-O-Si bonds have a large covalent part, which, among other things, results in the high hardness of quartz. In addition to silicon atoms but can also attach any other atoms at these sites.
Durch eine mechanische Beanspruchung der silikathaltigen Komponente kommt es zur Bildung zusätzlicher Oberflächen mit zahlreichen freien Valenzen an den Silicium- und Sauerstoffatomen auf den Oberflächen. Diese freien Valenzen (ungesättigte Bindungen, engl, „dangling bonds") führen zu energiereichen Oberflächenstrukturen, was wiederum zu einer hohen Reaktivität an den Oberflächen führt. Dadurch werden Folgereaktionen wie die Beschichtung der silikathaltigen Komponente mit der Calcium-Silikat-Hydrat- und/oder belithaltigen Komponente unter Bildung neuer Bindungen begünstigt. Konkurrenzreaktionen wären z.B. Rekombinationen mit freien Wassermolekülen. Sowohl Mahlung (Verfahrensschritt 1) als auch Reaktionsbeschichtung (Verfahrensschritt 2) sollten daher zweckmäßig bei erhöhten Temperaturen von mind. > 100 °C erfolgen. Als Zerkleinerungseinrichtungen für den Verfahrensschritt 1 kommen eine Rollenmühle, insbesondere eine Pendel-Rollenmühle, und/oder eine Walzenmühle, bevorzugt aber Hochenergiemühlen wie eine Strahlmühle, eine Prallmühle, eine Kugelmühle, insbesondere eine Rührwerks-Kugelmühle, eine Vibrationsmühle und/oder eine Magnetmühle sowie eine Verschaltung und/oder Kombination dieser Mühlentypen in Frage. Mechanical stress on the silicate-containing component results in the formation of additional surfaces with numerous free valencies on the silicon and oxygen atoms on the surfaces. These free valences (unsaturated bonds, dangling bonds) lead to high-energy surface structures, which in turn leads to a high reactivity at the surfaces, leading to subsequent reactions such as the coating of the silicate-containing component with the calcium silicate hydrate and / or Competing reactions would be, for example, recombinations with free water molecules Both milling (process step 1) and reaction coating (process step 2) should therefore be carried out expediently at elevated temperatures of at least> 100 ° C. As comminution devices for process step 1 come a roller mill, in particular a pendulum roller mill, and / or a roller mill, but preferably high energy mills such as a jet mill, an impact mill, a ball mill, in particular an agitator ball mill, a vibration mill and / or a magnetic mill and a circuit u nd / or combination of these types of mill in question.
Die so aktivierte silikathaltige Komponente wird anschließend als silikathaltiger Trägerstoff in einer zweiten Behandlungseinheit mit einem Calcium-Silikat-Hydrat- und/oder belithaltigen Stoff beschichtet. Diese Beschichtung kann ebenfalls in wenigstens einer Mühle, beispielsweise in einer Kugelmühle, insbesondere einer Rührwerks-Kugelmühle, einer Vibrationsmühle, einer Strahlmühle und/oder Prallmühle, bevorzugt aber in einer Rollenmühle, insbesondere einer Pendel- Rollenmühle, und/oder Walzenmühle, sowie einer Verschaltung und/oder Kombination dieser Mühlentypen erfolgen. Auch eine magnetische Beschichtung gemäß der US 6,037,019 und Verwendung einer Magnetmühle ist denkbar. Im Gegensatz zum ersten Verfahrensschritt werden bei der Beschichtung relativ weiche Mahlkörper, beispielsweise kunststoffummantelte Guss- oder Magnetkörper, eingesetzt. Ziel dieser Beschichtung bzw. Ummantelung ist, eine weitere Zerkleinerung der Partikel weitgehend zu vermeiden und eine Beschichtung der gröberen silikathaltigen Trägerstoffe mit dem Calcium-Silikat-Hydrat- und/oder belithaltigen Komponenten zu erreichen. The thus activated silicate-containing component is then coated as a silicate-containing carrier in a second treatment unit with a calcium silicate hydrate and / or belithaltigen substance. This coating may also be in at least one mill, for example in a ball mill, in particular an agitator ball mill, a vibration mill, a jet mill and / or impact mill, but preferably in a roller mill, in particular a pendulum roller mill, and / or roller mill, and an interconnection and / or combination of these types of mill. A magnetic coating according to US Pat. No. 6,037,019 and use of a magnetic mill is also conceivable. in the In contrast to the first method step, relatively soft grinding media, for example plastic-coated cast iron or magnetic bodies, are used in the coating. The aim of this coating or sheathing is to largely avoid further comminution of the particles and to achieve a coating of the coarser silicate-containing carriers with the calcium silicate hydrate and / or belite-containing components.
Bei der Reaktionsmahlung gemäß der EP 2 243 754 AI, bei der beide Komponenten gemeinsam vermählen werden, findet zwar auch eine Umhüllung statt, die jedoch immer wieder aufgebrochen wird, sodass auch die Partikel immer weiter zerkleinert werden. Dieser Nachteil kann durch die Trennung des Zerkleinerungsschrittes des silikathaltigen Trägerstoffs von der Beschichtung mit der Calcium-Silikat-Hydrat- und/oder belithaltigen Komponente vermieden werden, wodurch auch der Anteil der Calcium-Silikat-Hydrat- und/oder belithaltigen Komponente reduziert werden kann. In the case of the reaction milling according to EP 2 243 754 A1, in which both components are ground together, an encapsulation also takes place, which however is broken up again and again, so that also the particles are comminuted more and more. This disadvantage can be avoided by the separation of the comminution step of the silicate-containing carrier from the coating with the calcium silicate hydrate and / or belithaltigen component, whereby the proportion of calcium silicate hydrate and / or belithaltigen component can be reduced.
Weitere Ausgestaltungen der Erfindung sind Gegenstand der Unteransprüche. Further embodiments of the invention are the subject of the dependent claims.
Gemäß einer bevorzugten Ausgestaltung der Erfindung wird die wenigstens eine Zerkleinerungseinrichtung im ersten Verfahrensschritt zusammen mit einem Sichter betrieben, der eine gröbere silikathaltige Komponente von einer feineren silikathaltige Komponente trennt, sodass zumindest die gröbere silikathaltige Komponente erneut der wenigstens einen Zerkleinerungseinrichtung zugeführt wird. Dabei kann auch vorgesehen werden, dass ein Teil der feineren silikathaltige Komponente aus dem Prozess ausgeschleust und ggf. anderweitig verwendet oder weiter verarbeitet wird. According to a preferred embodiment of the invention, the at least one comminution device in the first method step is operated together with a separator which separates a coarser silicate-containing component from a finer silicate-containing component, so that at least the coarser silicate-containing component is again fed to the at least one comminution device. It can also be provided that a part of the finer silicate-containing component is discharged from the process and possibly used elsewhere or further processed.
Zur Intensivierung des Kontakts zwischen den silikathaltigen Trägerstoffen und der Calcium-Silikat-Hydrat- und/oder belithaltigen Komponente können lose Hilfskörper in der Beschichtungseinrichtung eingesetzt werden. Außerdem kann ein weiterer Stoff, vorzugsweise ein Feinstoff, wie Mikrosilica, bis zu 20 % bei wenigstens einem der beiden Verfahrensschritte zugegeben werden. Die Calcium-Silikat-Hydrat- und/oder belithaltige Komponente wird zweckmäßigerweise vor dem zweiten Verfahrensschritt in wenigstens einer separaten Behandlungseinrichtung entwässert und/oder bei erhöhter Temperatur von vorzugsweise größer 100 °C aktiviert. Der Beschichtungsschritt erfolgt zweckmäßigerweise ebenfalls bei Temperaturen von mindestens 100 °C. To intensify the contact between the silicate-containing carriers and the calcium-silicate-hydrate and / or belithaltigen component loose auxiliary body can be used in the coating device. In addition, another substance, preferably a fines such as microsilica, may be added up to 20% in at least one of the two process steps. The calcium silicate hydrate and / or belite-containing component is expediently dewatered before the second process step in at least one separate treatment device and / or activated at elevated temperature of preferably greater than 100 ° C. The coating step is expediently likewise carried out at temperatures of at least 100 ° C.
Die für die Beschichtung vorgesehene Beschichtungseinrichtung kann zur Begünstigung der Beschichtung Leitelemente und/oder Rührelemente und/oder lose Hilfskörper aufweisen. Das aus der Beschichtungseinrichtung kommende Material kann optional einer Trenneinrichtung 9 zugeführt werden. Diese trennt die überwiegend vollständig beschichteten Stoffe 1 ' von den unvollständig beschichteten Stoffen 1 ", was eine Rückführung zur Beschichtungseinrichtung oder zur Ausschleusung des Fertigproduktes zur Folge hätte. Das Fertigprodukt könnte als Bindemittel oder als Zusatz für eine Bindemittelmischung dienen. In einem optional nachgeschalteten Mischer oder Sichter 10 könnte das Fertigprodukt mit Stoffen 11 , wie beispielsweise Flugasche, Klinkermehl, verschiedene Schlackearten, Portlandzement, Kalksteinmehl oder auch verschiedene Mischungen dieser Stoffe, gemischt werden. Für einen solchen Mischvorgang müssten die Stoffe entsprechend Feinheiten aufweisen, damit das Endprodukt als Bindemittelmischung dienen kann. For the purpose of promoting the coating, the coating device provided for the coating can have guide elements and / or stirring elements and / or loose auxiliary bodies. The material coming from the coating device can optionally be supplied to a separating device 9. This separates the predominantly completely coated substances 1 'from the incompletely coated substances 1 ", which would lead to a return to the coating device or to the discharge of the finished product The finished product could serve as a binder or as an additive for a binder mixture In an optional downstream mixer or Classifier 10, the finished product could be mixed with substances 11, such as fly ash, clinker flour, various types of slag, Portland cement, limestone powder or various mixtures of these substances For such a mixing process, the substances should have corresponding subtleties, so that the final product can serve as a binder mixture.
Eine weitere Variante könnte ebenfalls sein, dass die oben aufgeführten Stoffe, insbesondere auch Kalkstein als inerter Füllstoff, gemeinsam mit den silikathaltigen Trägerstoffen der Zerkleinerungseinrichtung (Verfahrensschritt 1) zugeführt und gemeinsam zerkleinert bzw. vermählen werden. Dieses hat den Vorteil, dass man einen zusätzlichen und kostenintensiven Zerkleinerungsprozess einspart. A further variant could likewise be that the substances listed above, in particular also limestone as inert filler, are fed together with the silicate-containing carriers to the comminuting device (process step 1) and comminuted or ground together. This has the advantage of saving an additional and costly comminution process.
Weitere Ausgestaltungen der Erfindung werden im Folgenden anhand der Beschreibung und der Zeichnung näher erläutert. Further embodiments of the invention are explained in more detail below with reference to the description and the drawing.
In der Zeichnung zeigen In the drawing show
Fig. 1 eine Blockschaltbild einer Anlage zur Herstellung eines hydraulischen Fig. 1 is a block diagram of a plant for producing a hydraulic
Bindemittels und/oder einer Bindemittelmischung und Fig. 2 ein Röntgendiffraktogramm der Calcium-Silikat-Hydrat-haltigen Binder and / or a binder mixture and Fig. 2 is an X-ray diffractogram of calcium silicate hydrate-containing
Komponente und des erhaltenen hydraulischen Bindemittels.  Component and the resulting hydraulic binder.
Die in Fig. 1 dargestellte Anlage zur Herstellung eines hydraulischen Bindemittels 1 und/oder einer Bindemittelmischung 12 weist eine Zerkleinerungseinrichtung 2 zur Zerkleinerung von silikathaltigen Trägerstoffen 3 und/oder weiteren Stoffen 11 ' auf Partikelgrößen von < 100 μιη auf, sowie eine nachfolgend angeordnete Beschichtungseinrichtung 4 mit einer ersten Zuführung 4a für den in der Zerkleinerungseinrichtung 2 zerkleinerten silikathaltigen Trägerstoff 3 a und einer zweiten Zuführung 4b für eine Calcium- Silikat-Hydrat- und/oder belithaltige Komponente 5. The plant shown in FIG. 1 for producing a hydraulic binder 1 and / or a binder mixture 12 has a comminution device 2 for comminuting silicate-containing carriers 3 and / or further substances 11 'to particle sizes of <100 μm, and a subsequently arranged coating device 4 with a first feeder 4a for the silicate-containing carrier 3 a comminuted in the comminuting device 2 and a second feed 4b for a calcium silicate-hydrate and / or belite-containing component 5.
Die Zerkleinerungseinrichtung 2 wird zusammen mit einem Sichter 6 betrieben, der gröbere Trägerstoffe 3b von feineren Trägerstoffen trennt, wobei zumindest die gröberen Trägerstoffe 3b erneut der Zerkleinerungseinrichtung 2 zugeführt werden, während die feineren Trägerstoffe als aktivierter silikathaltiger Trägerstoff 3 a zusammen mit der Calcium- Silikat-Hydrat- und/oder belithaltigen Komponente 5 der Beschichtungseinrichtung 4 zugeführt werden. Die Zerkleinerungseinrichtung 2 und die Beschichtungseinrichtung 4 können jeweils durch eine (Rührwerks-)Kugelmühle, eine Vibrationsmühle, eine Magnetmühle, eine (Pendel-)Rollenmühle, eine Walzenmühle, eine Prallmühle oder eine Strahlmühle oder dergleichen betrieben werden. Auch eine Verschaltung und/oder Kombination dieser Mühlentypen ist denkbar. Werden sowohl in der Zerkleinerungseinrichtung 2 als auch in der Beschichtungseinrichtung 4 Hilfskörper eingesetzt, kommen in der Beschichtungseinrichtung 4 relativ weiche Hilfskörper zum Einsatz. Dadurch wird eine weitere Zerkleinerung der silikathaltigen Trägerstoffe weitgehend vermieden und dafür ein inniger Kontakt mit der Calcium-Silikat-Hydrat- und/oder belithaltigen Komponente ermöglicht, um eine Beschichtung der Oberfläche des silikathaltigen Trägerstoffs von wenigstens 50 %, vorzugsweise wenigstens 80 % zu erreichen. Über eine dritte Zuführung 4c kann der Beschichtungseinrichtung 4 auch ein weiterer Stoff 7, vorzugsweise ein Feinstoff, wie Mikrosilica, bis zu 20 % zugegeben werden. Die Beschichtung in der Beschichtungseinrichtung 4 erfolgt vorteilhafter Weise bei einer Temperatur von mindestens 100 C. The comminution device 2 is operated together with a classifier 6 which separates coarser carriers 3b from finer carriers, at least the coarser carriers 3b being fed again to the comminution device 2, while the finer carriers as activated silicate-containing carrier 3a together with the calcium silicate carrier. Hydrate and / or belithaltigen component 5 of the coating device 4 are supplied. The crushing device 2 and the coating device 4 may each be operated by a (agitator) ball mill, a vibration mill, a magnetic mill, a (shuttle) roller mill, a roller mill, an impact mill or a jet mill or the like. An interconnection and / or combination of these types of mill is conceivable. If auxiliary bodies are used both in the comminution device 2 and in the coating device 4, relatively soft auxiliary bodies are used in the coating device 4. As a result, further comminution of the silicate-containing carriers is largely avoided and intimate contact with the calcium-silicate-hydrate and / or belithaltigen component allows to achieve a coating of the surface of the silicate-containing carrier of at least 50%, preferably at least 80%. Via a third feed 4c, the coating device 4 can also be fed with a further substance 7, preferably a fine substance, such as microsilica, up to 20%. The coating in the coating device 4 is advantageously carried out at a temperature of at least 100 C.
Die Calcium-Silikat-Hydrat- und/oder belithaltige Komponente 5 kann vor der Zuführung in die Beschichtungseinrichtung 4 in wenigstens einer separaten Behandlungseinrichtung 8 entwässert und/oder bei erhöhter Temperatur von vorzugsweise 100 °C aktiviert und/oder einer Wärmedruckbehandlung ausgesetzt werden. Nach dem Beschichtungsprozess kann das Produkt als Bindemittel genutzt werden. Um die C02-Emmissionen bei üblich hergestellten Zementen, wie beispielsweise OPC oder Hochofenzemente, weiter zu senken, kann der Beschichtungseinrichtung eine Misch- oder Sichteinrichtung nachgeschaltet sein. In dieser werden dann hydraulische und/oder latent hydraulische Stoffe, wie beispielsweise Klinker, Flugasche, Stahlwerks- und/oder Hochofenschlacke, OPC oder Mischungen von diesen Stoffen gemischt, sodass eine Bindemittelmischung mit niedrigen C02-Emissionen entsteht. Auch die Zumischung inerter Füllstoffe, insbesondere Kalksteinmehl, ist möglich. The calcium silicate hydrate and / or belithaltige component 5 can be dehydrated before being fed into the coating device 4 in at least one separate treatment device 8 and / or activated at elevated temperature of preferably 100 ° C and / or subjected to a heat pressure treatment. After the coating process, the product can be used as a binder. In order to further reduce the CO 2 emissions in custom-made cements, such as OPC or blast furnace cements, the coater may be followed by a mixing or screening device. In this then hydraulic and / or latent hydraulic substances, such as clinker, fly ash, steel mill and / or blast furnace slag, OPC or mixtures of these substances are mixed, so that a binder mixture with low C0 2 emissions. The addition of inert fillers, especially limestone flour, is possible.
Anhand der folgenden Beschreibung wird das Verfahren zur Herstellung eines hydraulischen Bindemittels und/oder einer Bindemittelmischung näher beschrieben, wobei im ersten Verfahrensschritt Quarzsand als silikathaltiger Trägerstoff durch Mahlung aktiviert und anschließend mit a-C2SH als Calcium-Silikat-Hydrat- Komponente reaktionsbeschichtet wird. Ebenfalls zum ersten Verfahrensschritt können andere Stoffe wie beispielweise Schlacke und/oder Flugasche gemeinsam mit Quarzsand dem Mahlprozess zugegeben und aktiviert werden. The method for producing a hydraulic binder and / or a binder mixture will be described in more detail with reference to the following description. In the first method step, quartz sand is activated as a silicate-containing carrier by grinding and then reaction-coated with aC 2 SH as a calcium silicate hydrate component. Likewise for the first method step, other substances such as, for example, slag and / or fly ash can be added to the grinding process together with quartz sand and activated.
Verwendet wurde Quarzsand mit einer Korngrößenfraktion von 90 μιη bis 250 μιη. Der nach Behandlung in einer Scheibenschwingmühle aktivierte silikathaltige Trägerstoff wies gemäß Analyse mit einem Laserbeugungsspektrometer eine mittlere Korngröße von ca. 6μιη auf. Im zweiten Verfahrensschritt wurde a-C2SH mit einer mittleren Korngröße von kleiner 20 μιη zusammen mit dem aktivierten Quarz im Massenverhältnis 2: 1 in einer Scheibenschwingmühle reaktionsbeschichtet. Aus der Analyse mit dem Laserbeugungsspektrometer wurde für das resultierende hydraulische Bindemittel eine mittlere Korngröße von ca. 5 μιη ermittelt. Quartz sand was used with a particle size fraction of 90 μιη to 250 μιη. The silicate-containing carrier activated after treatment in a disk-vibrating mill had, according to analysis with a laser diffraction spectrometer, an average particle size of about 6 μm. In the second process step, aC 2 SH with a mean particle size of less than 20 μm was reaction-coated together with the activated quartz in a mass ratio of 2: 1 in a disk vibration mill. From the Analysis with the laser diffraction spectrometer, a mean particle size of about 5 μιη was determined for the resulting hydraulic binder.
Tabelle 1 zeigt die Ergebnisse der quantitativen Röntgenbeugungsanalysen. Die Calcium-Silikat-Hydrat-Komponente enthielt neben 81 % a-C2SH, etwas Portlandit und Calcit noch weitere CSH-Phasen (Kilchoanit, Foshagit) sowie eine Calcium- Aluminat-Phase (Katoit, 9 %). Das nach der Reaktionsbeschichtung erhaltene hydraulische Bindemittel wurde bestimmt zu 60 % amorphem Anteil, 7 % kristallinem a-C2SH und 33 % Quarz. Table 1 shows the results of the quantitative X-ray diffraction analyzes. The calcium silicate hydrate component contained 81% aC 2 SH, some portlandite and calcite, further CSH phases (kilchoanite, foshagite) and a calcium aluminate phase (katoite, 9%). The hydraulic binder obtained after the reaction coating was determined to be 60% amorphous, 7% crystalline aC 2 SH and 33% quartz.
Tabelle 1 : Quantitative Röntgenbeugungsanalyse (Rietveld-Bestim Table 1: Quantitative X-ray diffraction analysis (Rietveld-Bestim
Das Röntgendiffraktogramm der Fig. 2 zeigt für die Calcium-Silikat-Hydrat- Komponente Signale des a-C2SH, welches als Hauptbestandteil vorliegt. Nach der Reaktionsbeschichtung mit aktiviertem Quarz in der Scheibenschwingmühle nehmen die Reflexe des a-C2SH deutlich ab, während das Untergrundsignal gleichzeitig aufgrund der Bildung amorpher Phasen stark ansteigt. The X-ray diffractogram of FIG. 2 shows for the calcium silicate hydrate component signals of the aC 2 SH, which is present as a main component. After reaction coating with activated quartz in the disk vibratory mill, the reflections of the aC 2 SH decrease markedly, while at the same time the background signal rises sharply due to the formation of amorphous phases.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung eines hydraulischen Bindemittels (1) durch Verarbeitung einer silikathaltigen Komponente (3) mit Calcium-Silikat-Hydrat- und/oder belithaltigen Komponenten (5), gekennzeichnet durch die Kombination der folgenden beiden Verfahrensschritte: 1. A process for producing a hydraulic binder (1) by processing a silicate-containing component (3) with calcium silicate hydrate and / or belite-containing components (5), characterized by the combination of the following two process steps:
• Im ersten Verfahrensschritt wird die silikathaltige Komponente (3) in wenigstens einer Zerkleinerungseinrichtung (2) auf Partikelgrößen von < 100 μιη zerkleinert, wobei zur Oberflächenaktivierung wenigstens teilweise Si-O-Si-Bindungen und/oder Wasserstoffbrücken in der Struktur der Oberflächenschicht der silikathaltigen Komponente aufgebrochen werden, und In the first process step, the silicate-containing component (3) is comminuted in at least one comminuting device (2) to particle sizes of <100 μιη, wherein for surface activation at least partially Si-O-Si bonds and / or hydrogen bonds in the structure of the surface layer of the silicate-containing component be broken up, and
• Im zweitem Verfahrensschritt wird die im ersten Schritt aktivierte, silikathaltige Komponente als silikathaltiger Trägerstoff (3a) mit Calcium- Silikat-Hydrat- und/oder belithaltigen Komponenten (5) in einer Beschichtungseinrichtung in Kontakt gebracht, wobei sich die Calcium- Silikat-Hydrat- und/oder belithaltigen Komponenten (5) auf wenigstens 50 % der Oberfläche des silikathaltigen Trägerstoffs (3 a) durch eine Reaktionsbeschichtung anreichern. In the second process step, the silicate-containing component activated in the first step as a silicate-containing carrier (3a) is brought into contact with calcium silicate-hydrate and / or belite-containing components (5) in a coating device, whereby the calcium silicate hydrate and / or containing belithaltigen components (5) on at least 50% of the surface of the silicate-containing carrier (3 a) by a reaction coating.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die wenigstens eine Zerkleinerungseinrichtung (2) im ersten Verfahrensschritt zusammen mit einem Sichter (6) betrieben wird, der eine gröbere silikathaltige Komponente (3b) von einer feineren silikathaltigen Komponente (3 a) trennt und zumindest die gröbere silikathaltige Komponente (3b) erneut der wenigstens einen Zerkleinerungseinrichtung (2) zugeführt wird. 2. The method according to claim 1, characterized in that the at least one comminution device (2) in the first method step is operated together with a separator (6) which separates a coarser silicate-containing component (3b) from a finer silicate component (3 a) and at least the coarser silicate-containing component (3b) is again supplied to the at least one comminuting device (2).
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass ein Teil der feineren silikathaltigen Komponente (3 a) aus dem Prozess ausgeschleust wird. 3. The method according to claim 1, characterized in that a part of the finer silicate-containing component (3a) is discharged from the process.
4. Verfahren nach wenigstens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass zur Intensivierung des Kontakts zwischen den silikathaltigen Trägerstoffen (3a) und der Calcium- Silikat-Hydrat- und/oder belithaltigen Komponente (5) lose Hilfskörper in der Beschichtungseinrichtung eingesetzt werden. 4. The method according to at least one of the preceding claims, characterized in that to intensify the contact between the silicate-containing carriers (3a) and the calcium silicate hydrate and / or belithaltigen component (5) loose auxiliary body are used in the coating device.
5. Verfahren nach wenigstens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass ein weiterer Stoff (7), vorzugsweise ein Feinstoff, wie Mikrosilica, bis zu 20 % bei wenigstens einem der beiden Verfahrensschritte zugegeben wird. 5. The method according to at least one of the preceding claims, characterized in that a further substance (7), preferably a fines, such as microsilica, is added up to 20% in at least one of the two process steps.
6. Verfahren nach wenigstens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass die Calcium-Silikat-Hydrat- und/oder belithaltige Komponente (5) vor dem zweiten Verfahrensschritt in wenigstens einer separaten Behandlungseinrichtung (8) entwässert und/oder bei erhöhter Temperatur aktiviert wird. 6. The method according to at least one of the preceding claims, characterized in that the calcium silicate hydrate and / or belithaltige component (5) before the second process step in at least one separate treatment device (8) dehydrated and / or activated at elevated temperature ,
7. Verfahren nach wenigstens einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass der erste und/oder der zweite Verfahrensschritt bei einer Temperatur von mindestens 100 °C stattfinden. 7. The method according to at least one of the preceding claims, characterized in that the first and / or the second process step take place at a temperature of at least 100 ° C.
8. Verfahren zur Herstellung einer Bindemittelmischung (12), wobei das nach dem Anspruch 1 hergestellte hydraulische Bindemittel nach dem zweiten Verfahrensschritt einem Misch-/Sichtaggregat (10) aufgegeben wird und mit hydraulischen und/oder latent hydraulischen Stoffen und/oder einem inertem Füllstoff vermischt wird. 8. A process for the preparation of a binder mixture (12), wherein the hydraulic binder produced according to claim 1 after the second process step a mixing / classifying unit (10) is abandoned and mixed with hydraulic and / or latent hydraulic substances and / or an inert filler becomes.
9. Verwendung einer Anlage mit: 9. Using an installation with:
• wenigstens einer Zerkleinerungseinrichtung (2) zur Zerkleinerung einer silikathaltigen Komponente (3) auf Partikelgrößen von < 100 μΐϊΐ υηά • at least one comminution device (2) for comminuting a silicate-containing component (3) to particle sizes of <100 μΐϊΐ υηά
• wenigstens einer nachfolgend angeordneten Beschichtungseinrichtung (4) mit einer ersten Zuführung (4a) für die in der Zerkleinerungseinrichtung (2) zerkleinerte silikathaltige Komponente (3') und einer zweiten Zuführung für eine Calcium-Silikat-Hydrat- und/oder belithaltige Komponente (5) zur Herstellung eines hydraulischen Bindemittels (1) gemäß einem der Ansprüche 1 bis 7. At least one subsequently arranged coating device (4) with a first feed (4a) for the in the comminuting device (2) Comminuted silicate-containing component (3 ') and a second feed for a calcium silicate hydrate and / or belithaltige component (5) for producing a hydraulic binder (1) according to one of claims 1 to 7.
10. Verwendung der Anlage nach Anspruch 9, wobei die wenigstens eine Zerkleinerungseinrichtung (2) eine Rollenmühle und/oder eine Walzenmühle, bevorzugt aber eine Hochenergiemühle wie eine Strahlmühle, eine Prallmühle, eine Kugelmühle, eine Vibrationsmühle und/oder eine Magnetmühle und/oder eine Verschaltung und/oder Kombination dieser Mühlentypen ist. 10. The use of the plant according to claim 9, wherein the at least one comminuting device (2) is a roller mill and / or a roller mill, but preferably a high-energy mill such as a jet mill, an impact mill, a ball mill, a vibration mill and / or a magnetic mill and / or a Interconnection and / or combination of these types of mill is.
11. Verwendung der Anlage nach Anspruch 9, wobei die wenigstens eine Beschichtungseinrichtung durch wenigstens eine Mühle gebildet wird. 11. Use of the plant according to claim 9, wherein the at least one coating device is formed by at least one mill.
12. Verwendung der Anlage nach Anspruch 9, wobei die wenigstens eine Beschichtungseinrichtung (4) eine Kugelmühle, eine Vibrationsmühle, eine Strahlmühle und/oder eine Prallmühle, bevorzugt aber eine Rollenmühle, eine Walzenmühle und/oder eine Magnetmühle und/oder eine Verschaltung und/oder Kombination dieser Beschichtungseinrichtungen ist. 12. Use of the system according to claim 9, wherein the at least one coating device (4) comprises a ball mill, a vibration mill, a jet mill and / or an impact mill, but preferably a roller mill, a roller mill and / or a magnetic mill and / or an interconnection and / or or combination of these coating devices.
13. Verwendung der Anlage nach Anspruch 9, wobei die Beschichtungseinrichtung (4) zur Begünstigung der Beschichtung Leitelemente und/oder Rührelemente und/oder lose Hilfskörper aufweist. 13. Use of the system according to claim 9, wherein the coating device (4) for promoting the coating has guide elements and / or stirring elements and / or loose auxiliary body.
14. Verwendung der Anlage nach Anspruch 9 zur Herstellung einer Bindemittelmischung (12) nach Anspruch 8, wobei der Beschichtungseinrichtung wenigstens ein Aggregat zum Mischen und/oder Sichten (10) nachgeschaltet ist. 14. Use of the system according to claim 9 for the preparation of a binder mixture (12) according to claim 8, wherein the coating device at least one unit for mixing and / or sifting (10) is connected downstream.
EP13786669.5A 2012-11-09 2013-11-06 Method for producing a hydraulic binding agent Ceased EP2917163A1 (en)

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DE201210110743 DE102012110743A1 (en) 2012-11-09 2012-11-09 Process for the preparation of a hydraulic binder
PCT/EP2013/073159 WO2014072337A1 (en) 2012-11-09 2013-11-06 Method for producing a hydraulic binding agent

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