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WO2009098727A2 - Procédé de production de chaux hydraulique naturelle - Google Patents

Procédé de production de chaux hydraulique naturelle Download PDF

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Publication number
WO2009098727A2
WO2009098727A2 PCT/IT2009/000034 IT2009000034W WO2009098727A2 WO 2009098727 A2 WO2009098727 A2 WO 2009098727A2 IT 2009000034 W IT2009000034 W IT 2009000034W WO 2009098727 A2 WO2009098727 A2 WO 2009098727A2
Authority
WO
WIPO (PCT)
Prior art keywords
raw materials
lime
natural
intermediate product
cooking
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/IT2009/000034
Other languages
English (en)
Other versions
WO2009098727A3 (fr
Inventor
Arrigo Piovan
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.)
VILLAGA CALCE SpA
Original Assignee
VILLAGA CALCE SpA
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 VILLAGA CALCE SpA filed Critical VILLAGA CALCE SpA
Publication of WO2009098727A2 publication Critical patent/WO2009098727A2/fr
Publication of WO2009098727A3 publication Critical patent/WO2009098727A3/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
    • C04B7/34—Hydraulic lime cements; Roman cements ; natural cements

Definitions

  • the present invention relates generally to a process for production of natural hydraulic lime. More in particular, the invention concerns a production process, suitable to give marls, marly limestones and their mixtures the shape and compactness suit for undergoing a cooking process in traditional layers furnaces for producing hydraulic lime, or equicurrent or countercurrent vertical furnaces .
  • the lime is a material used mainly in construction building sector, but also in other uses, known since the ancient times: the Romans and the Phoenicians had learned to use lime as a material for buildings construction, mixed with sand to form mortar.
  • Vitruvius in his work "De architectura” , describes its production starting from white stones, cooked in special ovens, to give rise to strongly hygroscopic caustic lime (calcium oxide, CaO) .
  • the caustic lime was then turned off (calcium hydroxide, Ca(OH) 2 ), throwing it in special tanks filled with water. Initially, the lime was used in the form of air lime, i.e. lime able to harden only when in contact with air.
  • the caustic lime was mixed with pieces of cooked clay (crockery, bricks, etc.) or with pozzuolana, a sand rich in silica, so as to alter the characteristics of strength and water resistance, in order to allow its hardening also in environments outside the contact with air, typically under water: air mortars and lime-based hydraulic limes were thus born.
  • the raw material for the production of lime is limestone, a sedimentary rock rich in calcium carbonate (CaCO 3 ) extracted from apposite quarries. Such a material, coarsely crushed, is introduced into special ovens or furnaces, where it is gradually heated up to 800-1000 0 C so as to exit from the bottom of the furnace .
  • Lime is also used as bleach and whitener, as disinfectant for environments, as correction of acid soils in agriculture and as desiccant and absorber of carbon dioxide in chemistry.
  • the caustic lime is preserved in perfectly airtight containers because of its high hygroscopicity .
  • the final lime, or slaked lime is obtained through a turning off reaction of the material, resulting in a violent release of heat and the weathering of the stone due to the expansive effect of the transformation from oxide to calcium hydroxide.
  • the slaked lime is used as construction material (joined to sand) , as raw material for plasters (mixed with cement) , in leathers tanning, in petrochemical industry to produce additives for lubricants, for producing calcium stearate, for neutralizing and absorbing pollutants, for treating water used in food industry, for correcting acidity of soils, for preparing salts of calcium and magnesium in pharmaceutical industry, as medicament in odontologist and as a fungicide in agriculture.
  • the lime is not only a basic element in building, but its applications have extended to many fields such as, for example, steel industry, refineries, agriculture and ecology industry, just to mention some of the main sectors .
  • the hydraulic lime in particular, is, as the name suggests, a hydraulic binder and is therefore prepared to resist to water action,- it can be natural or artificial .
  • artificial hydraulic lime is obtained starting from air lime, as said able to harden when in contact with air, and mixing it with potentially hydraulic materials, such as pozzuolana or blast furnace slag (loppa) .
  • Natural hydraulic lime is produced from impure calcareous sedimentary rocks, known as marl, typically composed by a predominantly clayish fraction and a carbonate fraction, generally given by calcium carbonate (calcite) or magnesium carbonate (dolomite) .
  • the marl comes from muddy sediments, of predominantly marine origin, produced in absence of current, in which the clayish component lays down for slow settling of particles of clay.
  • the raw material of natural hydraulic lime limestone and clay up to 20% is crushed and cooked at a temperature of about 1100 0 C.
  • Decomposition of limestone (CaCO 3 ) in lime (CaO) and carbon dioxide (CO 2 ) , as well as clay decomposition, is achieved at around 900 0 C, while the products of clay decomposition bind with lime (CaO) , giving rise to aluminates and silicates, at around 1000-1100 0 C.
  • the residual caustic lime undergoes the same turning off reaction which occurs for air lime in order to produce slaked lime or calcium hydroxide (Ca(OH) 2 ) .
  • a purpose of the invention is to provide a process for production of natural hydraulic lime, which allows to give marls, marly limestones and mixtures thereof, the shape and compactness suitable to undergo a process of cooking in traditional type layers furnaces for producing hydraulic lime or in vertical kilns.
  • Another purpose of the present invention is to provide a process for production of natural hydraulic lime which allows to use materials which, otherwise, would be used in less valuable applications, recovering sub- screens of other productions, with consequent effective savings of natural resources.
  • Further purpose of the invention is to develop a process for production of natural hydraulic lime which uses marls mixtures and marly limestones of various types, in order to reproduce the chemical composition and the physical performance of the limes used in the ancient times and whose bodies are one and for all exhausted, with obvious utility in various application fields, especially in architectural restoration.
  • the process according to the present invention does not aim to change the chemical composition of the material, but only the physical shape, in order to optimize the cooking thereof .
  • an artificially produced marl suitable to be cooked in ordinary lime kilns for producing natural hydraulic lime, is obtained.
  • any chemical nature and petrography rocks such as limestones, limestone marls, marly limestones, clayish marls, marly clays, pozzuolana effect artificial materials; quarry or river sands ; - clays and limes; products of working of previous materials, such as coarse crushed aggregates, washing limes, crushing powders, etc., provided they're not identified as waste, can be used as raw materials.
  • Sub- screens of chemical and/or iron and steel industries, products of petrochemical origin, waste of industrial origin, coming from processes of casting, working, smokes damp, burning, etc., are, however, excluded from the raw materials used in the production process according to the present invention.
  • the process provides that starting from the selected raw materials, the composition of mixtures of a series of components is carried out, making their weight dosage in order to obtain compounds with a hydraulic index substantially included between 0,2 and 0,55.
  • the hydraulic index also known as hydraulicity modulus, allows to know in which ratio the different percentages of components are and is calculated as the ratio between the content of "acid" oxides (CaO and MgO) and "alkaline” oxides (Fe 2 O 3 , Al 2 O 3 , SiO 2 ) , expressed as a percentage.
  • the mixture may, for example, reproduce a particular kind of no longer available marl in order to replicate a type of lime necessary, for example, for a restoration operation.
  • the mixture used a body of material which cannot used as it is owing to particular lying conditions or physical state, for example, because too crushed, altered by weather agents or collapsed or other.
  • the mixture serves to produce a natural hydraulic lime with certain physical- mechanical properties .
  • the process of production of natural hydraulic lime comprises drying in a rotating drum the raw materials used, prior to their mixing. After the mixing of raw materials or simultaneously with it, the reduction of raw materials into powders, with a fineness of 90 microns, occurs in a spheres mill.
  • the mixture of fine powders is, then, transformed, using a rotating drum or granulator, into granules of raw flour, having sizes equal to about 25-30 mm, which are subsequently dried, if necessary, on a conveyor belt made of net.
  • a rotating drum or granulator it is also possible to opt for the formation of briquettes, by using a rollers compacting press.
  • the powder mixture is transformed into product pieces (granules or briquettes) of marl, having mass and sizes so that they can be cooked in normal lime kilns.
  • the stage of calcination follows, i.e. the cooking of marl granules or briquettes in a layers vertical static furnace, with blowing of combustion air from the bottom, or in a double-vat equicurrent static regenerative furnace, or in a countercurrent static vertical furnace, using coal, petrolcoke, gas, combustible oil or wood sawings as fuel.
  • any type of furnace is used, the maximum cooking temperature is kept at values included between 900 0 C and 1100 0 C, lower than the sintering temperature .
  • a crushing phase of the product by means of a hammers mill which disaggregate the granules or briquettes, and the turning off of the intermediate product (caustic natural hydraulic lime) , by means of a single-stage or multistage hydrating device, adding a predefined and controlled amount of water, so as to, however, turning off the magnesium and/or calcium oxide formed during cooking, are then carried out.
  • the seasoning of the intermediate product then occurs, consisting in the seasoning of the slaked natural hydraulic lime, into a proper environment with adjusted and controlled humidity, for a time which allows to reach the volume stability, e.g. about 1 month .
  • the following operation provides the grinding of the intermediate product in a spheres mill having a closed path with separator, or in a track or rollers mill, so as to obtain powders with finenesses corresponding with standard EN 459-1:2002, for example not superior to 90 microns.
  • the storage of the finished product (natural hydraulic lime) in special silos is carried out.
  • the finished product is to all intents and purposes a natural hydraulic lime (NHL or "Natural Hydraulic Lime”), according to the definitions provided in the current Italian and European standards, and, depending on its characteristics, will be classified as NHL2, NHL3.5 or NHL5 and provided with CE marking, in accordance with the relative legislation of relevance.
  • NEL Natural Hydraulic Lime

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Seasonings (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

La présente invention concerne un procédé de production de chaux hydraulique naturelle comprenant au moins les opérations suivantes: sélection de matières brutes d'origine naturelle, mélange des matières brutes en des proportions appropriées, par un dosage pondéral donnant des composés dont l'indice hydraulique est sensiblement compris entre 0,2 et 0,55, réduction en grains fins des matières brutes mélangées, transformation des grains fins des matières brutes mélangées en des morceaux de produit de poids et de dimensions permettant une cuisson dans un four à chaux, cuisson des morceaux de produit à une température prédéfinie de façon à obtenir un produit intermédiaire (chaux éteinte), extinction du produit intermédiaire, stabilisation du produit intermédiaire pendant une période de temps prédéterminée dans une atmosphère à humidité contrôlée, et broyage du produit intermédiaire de façon à obtenir la chaux hydraulique naturelle.
PCT/IT2009/000034 2008-02-06 2009-02-05 Procédé de production de chaux hydraulique naturelle Ceased WO2009098727A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITVI20080030 ITVI20080030A1 (it) 2008-02-06 2008-02-06 Procedimento per la produzione di calce idraulica naturale.
ITVI2008A000030 2008-02-06

Publications (2)

Publication Number Publication Date
WO2009098727A2 true WO2009098727A2 (fr) 2009-08-13
WO2009098727A3 WO2009098727A3 (fr) 2009-09-24

Family

ID=40292100

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IT2009/000034 Ceased WO2009098727A2 (fr) 2008-02-06 2009-02-05 Procédé de production de chaux hydraulique naturelle

Country Status (2)

Country Link
IT (1) ITVI20080030A1 (fr)
WO (1) WO2009098727A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103466968A (zh) * 2013-08-23 2013-12-25 西安建筑科技大学 一种利用铅锌尾矿制备天然水硬性石灰的方法
US20200331806A1 (en) * 2017-12-27 2020-10-22 Yildiz Teknik Universitesi Production method of ready injection material comprising nano hydraulic lime
WO2025145008A1 (fr) * 2023-12-28 2025-07-03 Supernatural Holdings, Pbc Système et procédé pour matériau de construction composite absorbant le carbone

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO127185B (fr) * 1971-10-08 1973-05-21 Elkem Spigerverket As
DE2625067C3 (de) * 1976-06-04 1980-01-10 Anneliese Zementwerke Ag, 4722 Ennigerloh Verfullmasse auf Zementbasis mit hohen Wasser-Bindemittelwerten
RU2074133C1 (ru) * 1992-07-16 1997-02-27 Новосибирский аграрный университет Сырьевая смесь для получения гидравлического вяжущего
DE19743742C2 (de) * 1997-10-02 2001-08-23 Sicowa Verfahrenstech Verfahren zum Herstellen von Branntkalk
JP4336793B2 (ja) * 2003-05-30 2009-09-30 吉澤石灰工業株式会社 水硬性材料の製造方法および水硬性建築材料

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103466968A (zh) * 2013-08-23 2013-12-25 西安建筑科技大学 一种利用铅锌尾矿制备天然水硬性石灰的方法
US20200331806A1 (en) * 2017-12-27 2020-10-22 Yildiz Teknik Universitesi Production method of ready injection material comprising nano hydraulic lime
US11691918B2 (en) * 2017-12-27 2023-07-04 Yildiz Teknik Universitesi Production method of ready injection material comprising nano hydraulic lime
WO2025145008A1 (fr) * 2023-12-28 2025-07-03 Supernatural Holdings, Pbc Système et procédé pour matériau de construction composite absorbant le carbone

Also Published As

Publication number Publication date
WO2009098727A3 (fr) 2009-09-24
ITVI20080030A1 (it) 2009-08-07

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