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WO2001098220A1 - Briquette, procede de fabrication et d utilisation - Google Patents

Briquette, procede de fabrication et d utilisation Download PDF

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Publication number
WO2001098220A1
WO2001098220A1 PCT/FI2001/000579 FI0100579W WO0198220A1 WO 2001098220 A1 WO2001098220 A1 WO 2001098220A1 FI 0100579 W FI0100579 W FI 0100579W WO 0198220 A1 WO0198220 A1 WO 0198220A1
Authority
WO
WIPO (PCT)
Prior art keywords
binder
dispersion
molar ratio
briquette
silica
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/FI2001/000579
Other languages
English (en)
Inventor
Michael Perander
Jean Le Bell
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.)
Paroc Group Oy AB
Original Assignee
Paroc Group Oy AB
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 Paroc Group Oy AB filed Critical Paroc Group Oy AB
Priority to AU2001270648A priority Critical patent/AU2001270648A1/en
Publication of WO2001098220A1 publication Critical patent/WO2001098220A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/02—Pretreated ingredients
    • C03C1/026—Pelletisation or prereacting of powdered raw materials

Definitions

  • the present invention relates to a briquette containing particulate mineral material and a binder therefor.
  • the invention also relates to a method for the manufacture of the briquette, as well as to its use, for example for mineral wool production.
  • Mineral wool is manufactured by melting mineral raw material in a melting furnace, either in a traditional cupola furnace, in a gas cupola furnace or an electrical furnace.
  • heat energy is introduced in the mineral raw material in different ways: in a traditional cupola furnace the mineral raw material is charged together with the fuel, usually coke, in a gas cupola furnace heat is introduced by burning gas or some other fluid fuel, and in an electrical furnace electrodes are used which extend into the furnace.
  • the present invention is aimed at providing a further improvement in the manufacture of briquettes containing particulate mineral material.
  • the term briquette is to be interpreted as meaning various kinds of agglomerates, i. a. also pellets and granules.
  • the briquettes according to the invention are especially suitable for mineral wool production, although also other briquette uses are conceivable, such as any use where the excellent binding properties of the binder can be taken advantage of. Such a use can be, for example, in iron ore briquettes for iron manufacture.
  • an object of the present invention is a briquette containing a particulate mineral material and a binder for the mineral material.
  • the binder comprises an amorphous silicate based gel binder having a content of silicium and aluminium, calculated as their respective oxides, that is of silica and alumina, wherein the molar ratio between silica and alumina (SiO 2 /Al 2 O 3 ) is in the range of 2 - 12, that is 2: 1 - 12: 1.
  • the said range is 2.5 - 8, in particular 3.5 - 6.
  • the present invention is also directed to a method for the manufacture of briquettes containing a particulate mineral material and a binder, the method comprising the steps of
  • a binder which comprises a colloidal silicate dispersion containing silica and alumina in a molar ratio in the range of 2 - 12.
  • the invention is also directed to a method for the manufacture of mineral wool, whereby mineral raw material in the form of briquettes containing a particular mineral material and a binder, is added to a melting furnace, the formed melt is withdrawn and fiberized.
  • the method is characterized in that the binder in the briquette comprises an amorphous silicate based gel binder containing silica and alumina in a molar ratio in the range of 2 - 12.
  • the briquettes according to invention show improved properties due to the increased alumina content in the binder. Such properties manifest themselves i.a. as improved strength and stability.
  • the silicate based binder to be used in the briquettes according to the invention can be characterized as being an amorphous porous silica based gel, i. e. an aerogel, which is obtainable by dissolving a particulate silicate mineral material containing silica and alumina in a molar ratio of 2 - 12 in an aqueous solution to form a solution containing nucleated re-precipitated particles of the material, which solution is stabilized to form a colloidal dispersion and coagulating the dispersion to form a gel which, when dry, forms the desired amorphous gel.
  • an amorphous porous silica based gel i. e. an aerogel
  • the binder has excellent binding, strengthening and fire resistant properties and is also acceptable from a use or labour hygiene point of view.
  • the binder can be manufactured from inexpensive and easily available raw materials, or by-products from industrial processes, in a simple manner, allowing for the tailor-making of or designing the composition of the binder to suit the desired purpose.
  • An important advantage is that the binder for use according to the invention presents no ecological load on the environment, but contains only such components that are already inherently present in nature.
  • the binder used has, in contrast to traditional water glass, which has been used i.a. for the binding of briquettes for example for mineral wool production, a low alkali content, that is, it has a low content of alkali oxides, in particular sodium and potassium oxides.
  • the dispersion contains also earth alkali metal oxides, such as calcium and/or magnesium oxides. Such an embodiment gives i.a. improved water resistance properties to the briquette due to the fact that the aqueous solubility of earth alkali metals is inferior to that of, for example, the alkali metals.
  • the binder contains silica and alkali oxide in a molar ratio, that is the ratio of the silica moles to the sum of the alkali oxide moles, that is essentially the sum of the sodium oxide and/or potassium oxide moles, which is in the range of 10 - 350, preferably 15 - 150.
  • the desired molar ratio can be obtained by properly selecting the starting mineral raw material to be used for making the binder dispersion.
  • the binder contains calcium and/or magnesium oxide and/or iron oxide, wherein the molar ratio between silica and the sum of calcium oxide, magnesium oxide and iron oxide is in the range of 0.5 - 2, preferably 0.6 - 1.5.
  • the iron oxide is calculated in the form of FeO
  • the binder to be used in the briquette according to the invention is obtainable by dissolving a particulate mineral material containing silica and alumina in a molar ratio of 2 to 12 in an aqueous solution, to form a solution containing nucleated re- precipitated particles of the material, stabilizing the so obtained solution to form a colloidal dispersion, i.e. a silicate containing sol, having a desired particle size, and op- tionally adjusting the dry matter content of the dispersion, and/or optionally coagulating the dispersion to form a gel.
  • the primary particle size of the dispersion in the form of a sol is 1 to 1000 nm, preferably 10 to 100 nm.
  • the dry matter content of the dispersion used to form the binder can vary, depending on the intended application, but for most purposes a dry matter content, above 1 % by weight, such as ranging between 5 and 60 % by weight is suitable.
  • the dry matter content of the dispersion can be adjusted by removing water, for example by evaporation, or adding water in a suitable manner.
  • the dispersion can easily be converted to a gel, for example using physico-chemical means, such as removing the electrostatic repulsion between the sol particles by changing pH or by adding an electrolyte, or a surfactant. Gel formation can also be carried out by drying the dispersion.
  • the colloidal binder dispersion can be used as such, whereby the binder can be converted to a gel, typically immediately before applying the same to the mineral materials to be bound, or is converted to a gel when in the end product, that is, in the briquette.
  • the particulate mineral material used as a starting material for making the binder is a material having a glassy amorphous structure.
  • a glassy structure has better dissolution properties than a crystalline structure and is formed when mineral raw materials are molten and formed into fibres at high temperature.
  • a suitable raw material is thus a mineral wool material or mineral fibre product, for example a waste or by-product from mineral fibre production, such as spinning waste, unused fibres or products, as well as post-consumer mineral fibre products.
  • Naturally a material is chosen which has an optimal or desired composition for the preparation of the binder.
  • a mineral material suitable for use as a starting material contains SiO 2 in an amount of 35 - 45 % by weight and Al 2 O 3 in an amount of 8 - 25 % by weight.
  • a low alkali particulate mineral material contains, calculated as % by weight, SiO 2 35 - 45
  • R 2 O 0.2 - 3 wherein R means Na or K.
  • such a material can contain, calculated as % by weight,
  • a further suitable mineral material is a material having the following composition, calculated as % by weight
  • such a material can contain, calculated as % by weight, CaO 30 - 40
  • This composition is a typical composition for example for a slag wool product.
  • an advantageous starting material for making the dispersion can be a product or by-product obtained from the manufacture of slag wool.
  • earth alkali metal oxides has the further advantage of providing materials suitable for water resistant binders. Such inclusion is of special importance for example when used in briquettes, such as raw material briquettes for mineral wool production, or in ore briquettes.
  • the starting material used for forming the binder dispersion is in the form of a mineral wool material, especially obtained as a side or waste product from mineral wool production, as indicated above.
  • a material can then be chosen which has the optimal or desired composition for the preparation of the dispersions according to the invention.
  • waste materials are formed in large quantities, typically in amounts up to 20-30 % by weight of the starting raw material, in the form of spinning waste, shots and unused fibres of rejected fibrous products (pre-consumer products).
  • One applicable source for the material are also different constructions which are taken down and in which mineral wool material has been used, for instance, as heat insulation (post- consumer products).
  • Such a waste material is already in finely divided, typically fibrous form and can thus be used as such, or alternatively it can also be divided to an even finer form to provide a product with a large surface area, such as 0.4 m 2 /g or larger, such as up to 25 m 2 /g, and thus has good dissolution properties in the aqueous solution.
  • Fibres obtained from mineral wool production typically have a diameter of 0.5 to 20, usually 2 to 15 ⁇ m, such as 3 to 5 ⁇ m as measured with OM or SEM using a suitable method (e.g.
  • the aqueous solution is an acidic solution, such as an aqueous solution made acidic by adding an inorganic or organic acid, such as HC1, HNO 3 , H 2 SO 4 , H 3 PO 4 , formic, acetic, propionic acid or any other suitable mineral or organic acid.
  • the pH of the solution is adjusted suitably.
  • a low pH value results in a rapid dissolution of the mineral material to form a gel, the gelling time being dependent on the pH, a lower pH resulting in a more rapid gelling than a higher pH.
  • Good dissolution for a wide range of mineral materials is obtained at a pH of 0 to 6.
  • the strength of the acid can be, depending on the acid, from 0.1 to 10 M, such as 0.5 to 5 M.
  • the aqueous solution can also be an alkaline solution, such as an alkali metal or earth alkali metal hydroxy, carbonate or hydrocarbonate solution, especially a sodium, potassium or lithium hydroxide solution, or an ammonium hydroxide solution.
  • an alkaline solution such as an alkali metal or earth alkali metal hydroxy, carbonate or hydrocarbonate solution, especially a sodium, potassium or lithium hydroxide solution, or an ammonium hydroxide solution.
  • Such a solution is preferably 0.1 to 2 molar with respect to the alkaline agent, or has a pH of 10 to 14, in order to easily dissolve also such mineral raw materials which are poorly soluble in neutral solutions.
  • the dispersion tends to be stable and an increase in particle size can be seen.
  • an increase in particle size is obtained, the increase being less pronounced if the solution in addition contains salts.
  • salts such as inorganic salts, e.g. sodium chloride
  • the particles tend to aggregate to form gels, which precipitate.
  • the same gel formation will also take place by providing an acid pH to the solution, whereby a pH of appr. 2 to below 7 is suitable for gel formation.
  • the dispersion state can be maintained, or the dispersion can be made to gel.
  • the gel can be dispersed and stabilized by using high-shear mixing and raising the pH, and then again be brought to gelling by readjusting (lowering) the pH, or by the addition of an electrolyte.
  • Alumina containing particulate mineral materials are generally relatively poorly soluble in neutral solutions, but exhibit improved dissolution in acidic and alkaline media, thus providing aqueous dispersions containing dissolved silica and dissolved alumina in the desired ratio.
  • organic acids are preferred to inorganic acids. This is due to the fact that inorganic acids can form insoluble salt precipitations, for example with calcium and magnesium included in the starting material. Also some of the inorganic acids are highly corrosive and thus not preferred for obvious reason.
  • the dissolution of the raw material is preferably carried out at an increased temperature, such as at a temperature of 80 to 100°C, preferably while simultaneously stirring, in order to facilitate the dissolution process.
  • Dissolution takes place within a period from 1-2 hours up to 20 hours depending on the dissolving medium used and the solids content of the solution.
  • an amount of starting mineral material is dissolved in the solution to provide a metal oxide containing solution which advantageously contains over 1 % by weight, preferably 5 to 60 % by weight of dry matter, which is a suitable concentration for the subsequent use as the binder.
  • the material nucleates to form a dispersion with the desired particle size.
  • the subsequent stabilization of the dispersion is brought about by creating in the solution electrostatic repulsion between the particles.
  • the electrostatic repulsion between the particles can be effected for example by providing suitable ions in the solution, or by changing the pH of the solution. If necessary, additional water can be added or removed, e.g. by evaporation, if necessary, for example for adjusting the viscosity of the solution obtained.
  • Stabilization may also be achieved by using suitable surfactants and/or polymers, especially non-ionic ones.
  • Non-ionic surfactants and polymers can be preferred in some cases as they are not very sensitive to an environment which contains high concentra- tions of electrolytes and other chemicals, especially when the ionic strength is high.
  • suitable polymers are polyethylene oxide and polyethylene glycol.
  • suitable surfactants are nonylphenols, Tween and Span. In a typical situation, such surfactants and polymers are used in an amount of 0.5 to 2.5 % by weight, calculated from the total solids of the solution.
  • the particle size of the dispersion can be adjusted by adjusting the pH.
  • the dispersions so obtained can be made to gel either directly after formation, or only immediately prior to application, for example prior to application of the dispersion as a binder onto the mineral raw material.
  • the dispersion can also be made to gel when heating or evaporating water when the final product is shaped.
  • the composition of the particulate mineral material to be used as raw material for making the briquettes naturally varies depending on the intended use of the briquettes.
  • the particulate mineral material is chosen according to the desired chemical composition of the fibres to be produced. Suitable materials include any of the stone and other mineral materials nor- mally used for this purpose, such as quartz sand, olivine sand, glass, basalt stone, slags, waste material from mineral wool production, lime stone, dolomite, wollastonite, etc.
  • the briquettes are made by simply mixing the mineral material with the binder dispersion, and if necessary, adding water to form a mixture of suitable stiffness.
  • This mixture or mass can be formed into briquettes by compression or compression vibration into briquettes, using per se known techniques, and hardened in connection with the manufacturing process, or later.
  • the hardening process can be accelerated for example by heating. It is also possible to control the hardening time of the briquettes by appropriate selection of pH for the binder solution, thus making it possible for example to manufacture briquettes by extrusion moulding for example.
  • surplus or waste material from mineral wool production are re-used for the manufacture of raw material briquettes for mineral wool production, forming both the mineral raw material as well as the starting material for the binder.
  • the inclusion of such briquettes in the raw material charge does not require any adjustment of the raw material charge.
  • the charge can be formed exclusively of briquettes, or the briquettes according to the invention can form a suitable portion of the charge, for use together with further suitable raw materials, which are chosen depending on the composition desired in the final product.
  • the amount of dispersion to be used as binder can easily be determined by a person skilled in the art. As an example it can be mentioned that when used as a binder in briquettes for mineral wool production, the amount of binder generally is appr. 1 - 15 % by weight, calculated as dry substance, of the dry weight of the product, but it is naturally possible to use higher and lower amounts depending on the desired product and the reactivity of the binder. When used as a binder in metal ore briquettes, a typical amount would be appr. 1 to 15, such as 1 to 5 % by weight of the total weight of the batch.
  • Briquettes for mineral wool manufacture can be produced in the following way.
  • nucleation and stabilization of the solution can be effected by raising the pH close to neutral by adding a suitable alkaline agent, such as sodium hydroxide. Water is evaporated to give a solids content e.g. of 5 % for the dispersion.
  • An amount of the dispersion so obtained is mixed with the dry components forming the raw material for the briquette, whereby a typical composition for the raw material can be glass waste, basalt and sand, in a ratio of 25: 15:60.
  • the dispersion is added in an amount so that the dry matter of the binder corresponds to 10 % by weight of the total batch. If necessary, additional water can be added to give a stiff mixture.
  • the mass is then formed by compressing or compression vibration into briquettes of a suitable size, a typical volume being appr. 0.5 to 1.0 dm 3 .

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne une briquette, en particulier dans la production de laine minérale, contenant un matériau minéral particulaire et un liant. Le liant comprend un gel liant à base de silicate amorphe contenant du silice et de l'alumine en rapport molaire compris entre 2 et 12. L'invention concerne également un procédé de fabrication de briquettes, ainsi qu'un procédé de production de laine minerale, grâce aux briquettes susmentionnées comme matière première.
PCT/FI2001/000579 2000-06-20 2001-06-19 Briquette, procede de fabrication et d utilisation Ceased WO2001098220A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001270648A AU2001270648A1 (en) 2000-06-20 2001-06-19 Briquette, method for its manufacture and its use

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20001459 2000-06-20
FI20001459A FI110607B (fi) 2000-06-20 2000-06-20 Menetelmä briketin ja mineraalivillan valmistamiseksi

Publications (1)

Publication Number Publication Date
WO2001098220A1 true WO2001098220A1 (fr) 2001-12-27

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2001/000579 Ceased WO2001098220A1 (fr) 2000-06-20 2001-06-19 Briquette, procede de fabrication et d utilisation

Country Status (3)

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AU (1) AU2001270648A1 (fr)
FI (1) FI110607B (fr)
WO (1) WO2001098220A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012083335A1 (fr) * 2010-12-22 2012-06-28 Asamer Basaltic Fibers Gmbh Prétraitement de matériau brut pour la fabrication de fibres de basalte

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4720295A (en) * 1986-10-20 1988-01-19 Boris Bronshtein Controlled process for making a chemically homogeneous melt for producing mineral wool insulation
WO1992004289A1 (fr) * 1990-08-29 1992-03-19 Paroc Oy Ab Briquette de matiere premiere pour la production de laine de scorie et procede de fabrication et d'utilisation de la briquette
WO1995034516A1 (fr) * 1994-06-15 1995-12-21 Rockwool International A/S Production de fibres minerales
WO1996028395A1 (fr) * 1995-03-14 1996-09-19 Rockwool International A/S Procede de fabrication de fibres minerales
WO1999028252A1 (fr) * 1997-12-02 1999-06-10 Rockwool International A/S Briquettes pour la production de fibres minerales et leur utilisation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4720295A (en) * 1986-10-20 1988-01-19 Boris Bronshtein Controlled process for making a chemically homogeneous melt for producing mineral wool insulation
WO1992004289A1 (fr) * 1990-08-29 1992-03-19 Paroc Oy Ab Briquette de matiere premiere pour la production de laine de scorie et procede de fabrication et d'utilisation de la briquette
WO1995034516A1 (fr) * 1994-06-15 1995-12-21 Rockwool International A/S Production de fibres minerales
WO1996028395A1 (fr) * 1995-03-14 1996-09-19 Rockwool International A/S Procede de fabrication de fibres minerales
WO1999028252A1 (fr) * 1997-12-02 1999-06-10 Rockwool International A/S Briquettes pour la production de fibres minerales et leur utilisation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012083335A1 (fr) * 2010-12-22 2012-06-28 Asamer Basaltic Fibers Gmbh Prétraitement de matériau brut pour la fabrication de fibres de basalte
CN103502160A (zh) * 2010-12-22 2014-01-08 阿萨默玄武岩纤维有限公司 用于制备玄武岩纤维的初始材料的预处理

Also Published As

Publication number Publication date
FI20001459L (fi) 2001-12-21
FI20001459A0 (fi) 2000-06-20
FI110607B (fi) 2003-02-28
AU2001270648A1 (en) 2002-01-02

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