WO2000001640A1 - Materiaux inorganiques expanses - Google Patents

Materiaux inorganiques expanses Download PDF

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Publication number
WO2000001640A1
WO2000001640A1 PCT/GB1999/001950 GB9901950W WO0001640A1 WO 2000001640 A1 WO2000001640 A1 WO 2000001640A1 GB 9901950 W GB9901950 W GB 9901950W WO 0001640 A1 WO0001640 A1 WO 0001640A1
Authority
WO
WIPO (PCT)
Prior art keywords
paste
foamed
carbonate
alkaline earth
earth metal
Prior art date
Application number
PCT/GB1999/001950
Other languages
English (en)
Inventor
Brian Roger Waters
Thomas Richard Jones
Nicholas John Goodwin Wilshaw
Original Assignee
Ecc International Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ecc International Ltd. filed Critical Ecc International Ltd.
Priority to AU45192/99A priority Critical patent/AU4519299A/en
Publication of WO2000001640A1 publication Critical patent/WO2000001640A1/fr

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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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
    • 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
    • C04B28/10—Lime cements or magnesium oxide cements
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00129—Extrudable mixtures

Definitions

  • the present invention relates to foamed inorganic materials .
  • foamed inorganic materials both organic and inorganic are known and have many uses.
  • Foamed inorganic materials made from extruded pellets of foamed kaolin paste which are subsequently dried and calcined are known from GB 2,271,987. Such materials can be expensive to produce owing to the high temperatures required for calcining kaolin.
  • the present invention is concerned with a new method of preparing a foamed inorganic material and with the new product produced thereby.
  • a method of producing a foamed inorganic material which includes the steps of producing in a liquid medium a foamed paste of a particulate material comprising an alkaline earth metal carbonate, extruding the paste and drying the extruded paste, and optionally further heating the extruded paste after drying, to produce a rigid, foamed, porous carbonate-containing material.
  • the extruded foamed paste incorporates a bonding agent, eg in an amount of up to 50 per cent by weight, especially from 1 per cent to 30 per cent by weight, more preferably from 1% to 10% by weight, based on the dry weight of the alkaline earth metal carbonate present.
  • the bonding agent which facilitates bonding of the adhered particles of the particulate material following extrusion, may comprise an inorganic or organic bonding agent or a combination of the two. Suitable bonding agents are described later.
  • the particulate material may include at least 50% by weight, preferably at least 80% by weight, desirably at least 90% by weight, of the alkaline earth metal carbonate.
  • particulate material examples include inorganic particulate materials selected from clays, eg kandite clays, silica, talc, alumina, alumina trihydrate, magnesium hydroxide, titanium dioxide and calcium sulphate, eg in a total amount of not more than 50% by weight, desirably not more than 20% by weight.
  • clays eg kandite clays, silica, talc, alumina, alumina trihydrate, magnesium hydroxide, titanium dioxide and calcium sulphate, eg in a total amount of not more than 50% by weight, desirably not more than 20% by weight.
  • the alkaline earth metal carbonate desirably comprises calcium carbonate, although it may alternatively or in addition comprise magnesium carbonate, barium carbonate, calcium magnesium carbonate or strontium carbonate.
  • the alkaline earth metal carbonate may be obtained from a natural source, eg marble, chalk, limestone or dolomite, or may have been synthesised in one of the ways well known in the carbonates processing field, or may be a mixture of material obtained from natural and synthetic sources. Where the alkaline earth metal carbonate material has been obtained from a natural source, and in some cases where it has been synthesised, the material may have been treated by well known processing techniques.
  • material from natural sources may have been subjected to one or more purification processes, one or more comminution processes, eg medium attrition grinding in an aqueous suspension and one or more particle size separation or fractionation steps, eg using a centrifuge, air classifier or other means well known in the carbonates processing field.
  • one or more purification processes eg medium attrition grinding in an aqueous suspension
  • one or more particle size separation or fractionation steps eg using a centrifuge, air classifier or other means well known in the carbonates processing field.
  • the particulate material employed in the method according to the present invention may have a particle size distribution such that at least 90% by weight of the particles have an equivalent spherical diameter less than lO ⁇ m.
  • Such a material may carry an associated chemical, eg dispersant, employed to process the material to its required particle size and other properties.
  • an associated chemical eg dispersant
  • the method according to the first aspect of the present invention may beneficially be employed to produce a rigid, foamed material suitable for use in a variety of applications as described later. Because such foamed material is produced partially or wholly from a particulate alkaline earth metal carbonate, it may be produced cheaply but may have a combination of properties which make it a versatile product. Calcium carbonate is cheaper, for example, than kaolin which is known in the prior art for the production of foamed, extruded, calcined inorganic material.
  • the mineral and/or synthetic particulate material comprising alkaline earth metal carbonate employed to produce the required paste of foamed material in the method according to the first aspect will generally be employed initially as particulate material incorporated in a suitable liquid medium in which a suitable suspension or dispersion can be formed from the particulate material.
  • suitable liquid media are known in relation to the formation of suspensions from the various classes of known material incorporating alkaline earth metal carbonates and other particulate materials.
  • a suitable liquid medium comprises water or a dilute aqueous solution.
  • the aqueous suspension contains at least 50% by weight, desirably at least 60% by weight, of the particulate material.
  • the particulate material may carry a dispersant and this may initially assist dispersion in the aqueous suspension to improve the fluidity of the suspension.
  • the dispersant or dispersing agent may comprise one of the polyelectrolytes known for dispersion of particulate alkaline earth metal carbonates, eg polycarboxylates such as acrylate-containing homopolymers and copolymers and salts thereof.
  • the dispersing agent may be present in an amount of up to 1% by weight based on the dry weight of alkaline earth metal carbonate present.
  • the foamed paste to be extruded may be produced by adding to and mixing with the aqueous suspension of the particulate material a liquid foam.
  • a foam may be produced directly in the water of the aqueous suspension of the particulate material.
  • a liquid foam may be made from a liquid medium by a process involving incorporating a gas in the liquid.
  • the liquid may contain a surface active agent or surfactant to facilitate formation of a stable foam or froth. Amphoteric agents are preferred.
  • the gas employed may for example be air incorporated by agitating the liquid medium to form a froth.
  • the gas may be added to the liquid medium before or after the particulate material (and other optional additives) is added thereto.
  • an aqueous foam containing a surface active agent is formed separately prior to addition to a suspension of the particulate material.
  • the aqueous foam may be added to the aqueous suspension containing the particulate material, eg in the form of a paste or slurry.
  • the addition may conveniently be carried out in a mixer or compounder, conveniently which feeds into or is part of an extrusion machine from which a foamed paste material may be extruded.
  • the machine may be a screw extruder, eg a co-rotating twin screw extruder.
  • the machine may extrude foamed material into a plurality of individual elongate portions, eg strings, noodles or ribbons.
  • a plurality of such portions may be formed at the same time by extrusion through a nozzle having multiple extrusion apertures.
  • the portions may be divided in a known way, eg by a cutting means or by allowing extrudate to fall onto a moving belt which by the action of carrying away the material causes lengths or portions to break from the extruding material.
  • portions, prills, pellets and the like, herein generally referred to as ⁇ granules' may be formed by division of the elongate portions.
  • Such granules may be collected and optionally sized, eg by use of one or more screen meshes so that only granules of a certain selected size range, eg in the range 0.5mm to 10mm are retained as required product. Unselected material may be comminuted and recycled for re-use in the formation of the aqueous suspension of the particulate material.
  • the moving belt employed itself may comprise a wire mesh providing a screen.
  • the selected granules may be further treated by drying in a heated atmosphere, eg at a temperature not greater than 100°C, eg in the range 30°C to 80°C, and may thereafter be treated by baking or calcining as described hereinafter.
  • a foamed inorganic product produced by the method according to the first aspect of the present invention, the foamed inorganic product comprising granules which have been produced by dividing, drying and heating the extruded paste of particulate material comprising alkaline earth metal carbonate.
  • the foamed inorganic product according to the second aspect of the invention may have the following properties:
  • the bonding agent preferably employed to bind the carbonate-containing inorganic material may include an inorganic or organic binder.
  • a binder may comprise less than 20% by weight, eg less than 10% by weight, based on the dry weight of the inorganic particulate material employed to produce the foamed paste.
  • the binder may be treated with a co- reactant, eg during compounding prior to extrusion and/or during drying or heating following extrusion.
  • a co-reactant may serve to enhance the effect of the bonding agent eg by strengthening, stiffening or cross-linking the same.
  • the bonding agent may comprise a reagent which is convertible into an inorganic insoluble precipitate in the said foamed paste during mixing to provide formation of the foamed paste in a mixer or compounder, eg which feeds into or is part of an extruder machine.
  • a reagent which is convertible into an inorganic insoluble precipitate in the said foamed paste during mixing to provide formation of the foamed paste in a mixer or compounder, eg which feeds into or is part of an extruder machine.
  • an alkaline earth metal oxide or hydroxide may be added to an aqueous suspension of the particulate material including alkaline earth metal carbonate to be formed into the foamed paste.
  • Carbon dioxide may be added to the aqueous suspension to convert the alkaline earth metal hydroxide (obtained from added oxide or hydroxide) into a precipitated alkaline earth metal carbonate, eg precipitated calcium carbonate.
  • Such a carbonate can serve to bind together the particulate material already present in the aqueous suspension, including alkaline earth metal particles already included therein.
  • suitable inorganic bonding agents include silicates, eg calcium or sodium silicate, phosphate, eg calcium phosphate.
  • Suitable organic bonding agents may for example be selected from polymers or copolymers of vinyl acetate, natural or synthetic latices, for example of natural rubber, of natural rubber substituted with functional groups, synthetic rubber, styrene-butadiene copolymers and acrylic acid containing polymers or copolymers.
  • the oxide or hydroxide may alternatively or in addition serve as a flocculating agent to form an extrudable aqueous paste of the inorganic particulate material.
  • the method according to the first aspect of the present invention may include the following steps:
  • step (b) introducing into a compounder or mixer containing the dispersed aqueous suspension produced in step (a) a stable aqueous foam which has been separately prepared by adding a suitable surfactant to an aqueous medium;
  • step (e) drying the elongate portions of extruded foamed paste formed in step (d) .
  • the paste produced in step (a) and the stable aqueous foam produced separately and introduced in step (b) may be introduced into the compounder or mixer at the same time, continuously via separate inlets to the compounder or mixer.
  • the elongate portions formed in step (d) may be divided or broken into granules before, during or after step (e) .
  • the aqueous suspension is preferably flocculated by adding thereto from 0.5% to 5.0% by weight, based on the dry weight of alkaline earth metal carbonate present, of an alkaline earth metal oxide or hydroxide. More preferably, the amount of the alkaline earth metal oxide or hydroxide added is that which is sufficient to supply a quantity of the oxide or equivalent thereof in the range of from 1% to 3% by weight, based on the dry weight of the alkaline earth metal carbonate present.
  • the alkaline earth metal oxide is most advantageously calcium oxide or hydroxide.
  • the flocculating agent required is conveniently added in the form of the hydroxide of the appropriate alkaline earth metal, especially calcium hydroxide.
  • the hydroxide is supplied in the form of a separately prepared aqueous suspension containing from 5% to 40% by dry weight of the hydroxide which is added to the aqueous suspension of particulate material.
  • the surfactant included in the stable aqueous foam is preferably an amphoteric surfactant.
  • the amount of the surfactant used may be generally in the range of from 0.1% to 1.0% by weight, based on the combined dry weight of the alkaline earth metal carbonate and other optional particulate material including any alkaline earth metal oxide or hydroxide.
  • the surfactant is an amphoteric surfactant which is an amidoamine based amphoteric glycinate.
  • step (d) the foamed paste is preferably extruded through a plurality of apertures of diameter in the range of from 1mm to 5mm.
  • step (d) the elongate portions of extruded foamed paste are preferably dried at a temperature not exceeding 100°C, eg a temperature of from 40°C to 80°C, eg for a time of from 2 hours to 16 hours depending on the temperature.
  • the elongate portions or the granules produced therefrom may be subsequently heated in a further step (f) to a temperature in the range of from 200°C to
  • a suitable pozzolanic material comprises a metakandite which has been prepared by calcining a kandite clay mineral at a temperature in the range of from 450°C to 1300°C, desirably from 600°C to 900°C, for a time such that the loss on ignition of a sample of the calcined clay at 1000°C for 2 hours is not more than 1% by weight.
  • the metakandite comprises metakaolin.
  • the foamed inorganic product according to the second aspect of the present invention is a stiff, strong, lightweight, porous, high surface area material which may be tipped, poured or filled into containers or cavities or inner volumes bonded by outer walls or structures. It may also be bonded to a variety of other materials, eg ceramics, wood, metals, plastics, rubbers and fibre reinforced composites, using various adhesives and glues known to be suitable for bonding the different types of material together.
  • the foamed inorganic product like other foamed inorganic products produced in the prior art, eg from calcined pellets of foamed kaolin produced in the manner described in GB-A- 2271987, may be employed in a variety of applications which make use of one or more of these properties.
  • liquid absorbing media eg for pet litter, where porosity, strength, low bulk density are desirable
  • An aqueous suspension was prepared containing 74% by weight of a finely ground natural calcium carbonate having a particle size distribution such that 88% by weight consisted of particles having an equivalent spherical diameter smaller than 2 ⁇ m and 63% by weight consisted of particles having an equivalent spherical diameter smaller than l ⁇ m.
  • the suspension contained 0.4% by weight, based on the dry weight of calcium carbonate, of a sodium polyacrylate dispersing agent already present with the calcium carbonate from previous processing.
  • To this suspension was added sufficient of a 20% by weight aqueous suspension of calcium hydroxide to provide 2% by weight equivalent of CaO based on the dry weight of calcium carbonate.
  • the calcium hydroxide suspension was mixed by hand until the calcium carbonate was fully flocculated, and a homogeneous thick paste was formed.
  • the surfactant foam consisted of 28g of a 2% by weight aqueous solution of the surfactant.
  • the surfactant was an amphoteric surfactant, viz a sodium carboxymethyl cocopolypropylamine - amphoteric glycinate sold under the trade name "AMPHOLAK 7 CX" .
  • the foamed paste produced in the mixer was extruded in the form of strings having a diameter of 3mm and a stable moist solid foam with small bubbles having sizes in the range of from lO ⁇ m to lOO ⁇ m was formed which was divided into granules, dried at a temperature of less than 100°C and heated at a temperature of about 600 °C following drying to form rigid, foamed, porous granules of the resulting calcium carbonate-containing composition.
  • Example 2 The procedure employed in Example 1 was repeated except that in this case the surfactant employed was a caprylonphocarboxyglycinate - an amphoteric glycinate sold under the trade name AMPHOLAK XCO/30.
  • the surfactant employed was a caprylonphocarboxyglycinate - an amphoteric glycinate sold under the trade name AMPHOLAK XCO/30.
  • Example 2 The procedure employed in Example 1 was repeated except that in this case the surfactant employed was an amphoteric polycarboxylated surfactant which is sold under the trade name AMPHIONIC XL.
  • a stable foamed solid with uniform small bubbles was again formed following mixing and extrusion in the form of strings and was suitable for granulating, drying and heating.

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

Abstract

L'invention concerne un procédé permettant de produire un matériau inorganique expansé, consistant à produire dans un milieu liquide, une pâte expansée d'un matériau particulaire contenant un carbonate alcalin de métal terreux, à extruder ladite pâte, à la sécher, et éventuellement à la chauffer après le séchage, de façon à produire un matériau rigide, expansé, poreux contenant un carbonate.
PCT/GB1999/001950 1998-07-01 1999-06-30 Materiaux inorganiques expanses WO2000001640A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU45192/99A AU4519299A (en) 1998-07-01 1999-06-30 Foamed inorganic materials

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9814231.8 1998-07-01
GBGB9814231.8A GB9814231D0 (en) 1998-07-01 1998-07-01 Foamed inorganic materials

Publications (1)

Publication Number Publication Date
WO2000001640A1 true WO2000001640A1 (fr) 2000-01-13

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ID=10834744

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PCT/GB1999/001950 WO2000001640A1 (fr) 1998-07-01 1999-06-30 Materiaux inorganiques expanses

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AU (1) AU4519299A (fr)
GB (1) GB9814231D0 (fr)
WO (1) WO2000001640A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2940163A1 (fr) * 2008-12-19 2010-06-25 Maussa Filali Procede de fabrication de bloc de materiau imitant la pierre naturelle
WO2010094084A1 (fr) * 2009-02-23 2010-08-26 Refire Glass Research Pty Limited Processus et procédé de fabrication d'un produit à base de silice
WO2013007957A1 (fr) * 2011-07-13 2013-01-17 Saint-Gobain Isover Materiaux d'isolation thermique hautes performances

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1934534A (en) * 1932-02-13 1933-11-07 Carbonated Lime Processes Ltd Process of making synthetic building blocks from lime
GB531733A (en) * 1939-07-31 1941-01-09 F E Berry Jr & Co Inc Improvements in or relating to the manufacture of cellular products
US2428555A (en) * 1943-03-27 1947-10-07 Johns Manville Manufacture of magnesia insulation
JPS5044218A (fr) * 1973-08-23 1975-04-21
JPS598661A (ja) * 1982-07-08 1984-01-17 アイン・エンジニアリング株式会社 無機質発泡板の成形方法
JPS6119329A (ja) * 1984-07-06 1986-01-28 Kanegafuchi Chem Ind Co Ltd 連続押出発泡体およびその製法
EP0288071A2 (fr) * 1987-04-24 1988-10-26 Arturo Broggini Pierres artificielles et leur procédé de fabrication

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1934534A (en) * 1932-02-13 1933-11-07 Carbonated Lime Processes Ltd Process of making synthetic building blocks from lime
GB531733A (en) * 1939-07-31 1941-01-09 F E Berry Jr & Co Inc Improvements in or relating to the manufacture of cellular products
US2428555A (en) * 1943-03-27 1947-10-07 Johns Manville Manufacture of magnesia insulation
JPS5044218A (fr) * 1973-08-23 1975-04-21
JPS598661A (ja) * 1982-07-08 1984-01-17 アイン・エンジニアリング株式会社 無機質発泡板の成形方法
JPS6119329A (ja) * 1984-07-06 1986-01-28 Kanegafuchi Chem Ind Co Ltd 連続押出発泡体およびその製法
EP0288071A2 (fr) * 1987-04-24 1988-10-26 Arturo Broggini Pierres artificielles et leur procédé de fabrication

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 84, no. 12, 22 March 1976, Columbus, Ohio, US; abstract no. 78848m, Y. KATAYAMA page 325; XP000063240 *
DATABASE WPI Week 8408, Derwent World Patents Index; AN 84-046672, XP002116066 *
DATABASE WPI Week 8610, Derwent World Patents Index; AN 86-066451, XP002116065 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2940163A1 (fr) * 2008-12-19 2010-06-25 Maussa Filali Procede de fabrication de bloc de materiau imitant la pierre naturelle
WO2010076404A1 (fr) * 2008-12-19 2010-07-08 Maussa Filali Procédé de fabrication de bloc de matériau imitant la pierre naturelle et le bloc de matériau obtenu par sa mise en oeuvre
US8663516B2 (en) 2008-12-19 2014-03-04 Maussa Filali Process for manufacturing a block of material that imitates natural stone and the block of material obtained by the implementation thereof
WO2010094084A1 (fr) * 2009-02-23 2010-08-26 Refire Glass Research Pty Limited Processus et procédé de fabrication d'un produit à base de silice
WO2013007957A1 (fr) * 2011-07-13 2013-01-17 Saint-Gobain Isover Materiaux d'isolation thermique hautes performances
FR2977889A1 (fr) * 2011-07-13 2013-01-18 Saint Gobain Isover Materiaux d'isolation thermique hautes performances
JP2014527500A (ja) * 2011-07-13 2014-10-16 サン−ゴバン イゾベ 高性能断熱材
US9506244B2 (en) 2011-07-13 2016-11-29 Saint-Gobain Isover High-performance heat-insulating materials

Also Published As

Publication number Publication date
GB9814231D0 (en) 1998-09-02
AU4519299A (en) 2000-01-24

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