EP3630701A1 - Verfahren zur herstellung von isoliermaterial oder eines isolierenden produkts für die feuerfestindustrie, entsprechende isoliermaterialien und produkte sowie verwendungen - Google Patents

Verfahren zur herstellung von isoliermaterial oder eines isolierenden produkts für die feuerfestindustrie, entsprechende isoliermaterialien und produkte sowie verwendungen

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Publication number
EP3630701A1
EP3630701A1 EP18728150.6A EP18728150A EP3630701A1 EP 3630701 A1 EP3630701 A1 EP 3630701A1 EP 18728150 A EP18728150 A EP 18728150A EP 3630701 A1 EP3630701 A1 EP 3630701A1
Authority
EP
European Patent Office
Prior art keywords
refractory
composite particles
product
group
phosphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP18728150.6A
Other languages
German (de)
English (en)
French (fr)
Inventor
Sandra LEHMANN
Klaus Riemann
Nils Zimmer
Hermann Lieber
Jürgen HÜBERT
Fabio SOLA
Heike MUSHARDT
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.)
Huettenes Albertus Chemische Werke GmbH
Original Assignee
Huettenes Albertus Chemische Werke GmbH
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 Huettenes Albertus Chemische Werke GmbH filed Critical Huettenes Albertus Chemische Werke GmbH
Publication of EP3630701A1 publication Critical patent/EP3630701A1/de
Withdrawn legal-status Critical Current

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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Definitions

  • the present invention relates to a process for producing an insulating product for the refractory industry or an insulating material as an intermediate for producing such a product and a corresponding insulating material or insulating product.
  • the present invention also relates to the use of a matrix encapsulation method in the production of an insulating product for the refractory industry and to a corresponding insulating product and / or an insulating material as an intermediate for producing such a product.
  • the invention is defined in the appended claims and the corresponding passages of the specification.
  • refractory industry includes in the context of the present documents preferably the use of the articles of the invention in the manufacture of or as refractory linings and linings in non-ferrous, iron and steel applications, in the cement and lime industry, in chemistry and Applications of the articles of the invention as described herein in other industries, in particular in the foundry industry, are not subject of the present invention.
  • various materials which also have a low weight, in particular expanded clay, perlite, expanded perlite, vermiculite and fibers such as ceramic fibers or mineral fibers (calcium silicate).
  • Even so-called "spheres" have already been described as constituents of refractory masses, and in the area of refractory applications, the increase in porosity due to the use of expanding particles during firing is also common.
  • hollow spherical corundum empirical formula AI2O3
  • Hollow spherical corundum has a fire resistance up to approx. 2000 ° C.
  • its high bulk density of about 750 to 1000 g / L (depending on the production process) and its comparatively good thermal conductivity are disadvantageous: owing to the high bulk density, it is difficult, e.g. to make lightweight linings of hollow spherical corundum. Due to the high thermal conductivity, the heat and thus energy losses in equipped with hollow spherical corona highly refractory devices are relatively high.
  • the "Paris Agreement” is an agreement of the 195 member countries of the United Nations Framework Convention on Climate Change (UNFCCC) with the goal of successive climate protection
  • the Paris Agreement was adopted at the UN climate Change Conference in Paris in December 2015 and provides for the limitation of man-made global warming to below 2 ° C compared to pre-industrial levels, resulting in the "Climate Change Plan 2050" resulting for Germany November 2016 and sees a decline for the industrial sector until 2030 emissions of greenhouse gases by about 50% compared to 1990 levels.
  • the refractory industry faces the dual challenge of reducing the energy requirements for the production of its own products and of further improving the insulating properties of refractory products in order to save energy when operating high-temperature furnaces.
  • the document DE2037937 describes a method for producing lightweight ceramic shaped bodies.
  • the document DE 2100802 describes a method for the production of refractory bricks for use at high temperatures.
  • Document DE2352188 describes a refractory thermal insulation panel and a method of making the same.
  • the document US5061526 describes a method for producing a porous refractory mass.
  • EP0934785A1 describes a heat-insulating composition containing hollow round balls for use in molds for metal casting.
  • EP0854124A1 describes a refractory ceramic stone.
  • EP216835A1 describes a material composition for producing a refractory material and its use and a refractory shaped body as well as a method for its production.
  • the document DE 10 2015 120 866 A1 (corresponding to WO 2017/093371 A1) specifies a method for the production of refractory composite particles and of feeder elements for the foundry industry, corresponding feeder elements and uses. Nevertheless, in the light of the prior art, there is a need in the refractory industry for particulate refractory or high-refractory materials, which have a low thermal conductivity, high mechanical strength and low weight (ie low bulk density) and homogeneous, regular particle shape for the production insulating products for the refractory industry or as an insulating material as an intermediate for the production of such products.
  • the procedure to be specified should result in an insulating material comprising particles with a grain size of 5 mm or less. Above all, depending on the individual design of the process to be specified, the particles should have a low bulk density, a high thermal resistance, an excellent insulating behavior, i. have a low thermal conductivity and / or a high mechanical strength (grain strength).
  • the process to be specified should comprise or enable the use or the preparation of filler particles which have one or more, preferably all, of the following properties:
  • the process to be specified for the production of an insulating product for the refractory industry or an insulating material as an intermediate for the production of such Product should be flexibly adjustable in the manufacture and use of variable size filler particles;
  • the process should enable the preparation and use of filler particles having a particle size of less than 5 mm (preferably less than 2 mm) in the manufacture of an insulating product for the refractory industry or an insulating material as an intermediate for the manufacture of such a product.
  • the filler particles to be prepared and used should be capable of variable composition.
  • Another aspect of the primary object of the present invention was to provide a process for producing an insulating product for the refractory industry or an insulating material as an intermediate for producing such a product, which has lower energy consumption compared with known such processes.
  • the invention is based inter alia on the finding that by matrix encapsulation (encapsulation) of the starting materials indicated in step (a1) (see point (i) to (iv) in step (a1)) Composite particles can be produced which have the primary properties listed above.
  • the composite particles produced in the process according to the invention have a particle size of less than 5 mm, preferably less than 2 mm, determined by means of screening.
  • the determination by sieving is carried out according to DIN 66165-2 (4.1987) using the method F mentioned there (machine screening with moving single sieve or sieve set in gaseous static fluid).
  • a vibrating sieve machine of the type RETSCH AS 200 control is used; while the amplitude is set to level 2; there is no interval sieving, the sieving time is 1 minute.
  • refractory solids includes solids which, according to DIN 51060: 2000-06, are to be termed “refractory”;
  • refractory solids also includes the solids from the group consisting of alumina, zirconia, titania, graphite, silica, magnesia, calcium oxide, calcium silicate, phyllosilicates (preferably mica), aluminum silicates, magnesium aluminum silicate (preferably cordierite), silicon carbide, boron nitride, mixed oxides containing one or more metal atoms of the aforementioned metal oxides, and mixed silicates containing one or more metal atoms of the aforementioned metal silicates.
  • Refractory solids precursors are materials which, when treating the hardened drops (step (a3)), become “refractory solids” as defined above, e.g. through a heat treatment.
  • a particle or material for example an amount of particles of the same composition
  • a given upper temperature limit eg 1600 ° C or 1700 ° C, preferably 1600 ° C
  • An amount of particles of the same composition is especially considered to be thermally stable if it does not sinter at a certain temperature in the sintering test. To carry out the sintering test, see below "Method for determining the thermal resistance (sintering test)".
  • the feature "producing drops of a suspension from at least the following starting materials” comprises “making drops of a suspension of exclusively the following starting materials” and “producing drops of a suspension of the following starting materials and other starting materials”.
  • a “matrix encapsulation process” as used herein means a process in which droplets of a dispersion are first prepared, the dispersion comprising a solid or liquid substance suspended in a matrix (continuous phase)
  • the process according to the invention comprises in its step (a) a specific matrix encapsulation process with the partial steps defined above.
  • a composite particle prepared by the matrix encapsulation process comprises more than 5, preferably more than 50 discrete microparticles consisting of refractory solid; for preferred refractory solids, see below. Such composite particles are preferred according to the invention.
  • Density-reducing substances are substances whose use in the process according to the invention results in that a reduced bulk density of the composite particles resulting in step (a3) is achieved, in comparison with a non-inventive (comparative process which is carried out in an identical manner but in which Depending on the treatment of a hardened drop, an employed pyrolyzable filler may or may not be pyrolysed, or only if (in step (a3)) a pyrolyzed filler used is pyrolyzed it fulfills the criterion of "density reducing".
  • Light fillers used according to the invention are fillers, each having a bulk density in the range from 10 to 350 g / l, determined according to DIN EN ISO 60 2000-01.
  • Light-weight fillers preferred for use in the process according to the invention are: Spheres, preferably fly ash, such as eg Spheres "Fillite 106" of the company Omya GmbH, or Glass such as the glass with the name “GHL 450” from LÜH Georg H. Lüh GmbH, the product with the name “JJ Glass Bubbles” from Jebsen & Jessen GmbH & Co. KG, the product named “Q-cel®300” from Potters Industries or the products "K1", "K15” or “K20” from 3M.
  • “Pyrolysable fillers” are fillers that are partially or fully, preferably completely, pyrolyzed when the hardened drops are treated in step (a3), eg, when heated
  • a pyrolyzable filler can simultaneously be a light filler having a bulk density in the range of 10 to be 350 g / L.
  • Composite particles which are produced in step (a) of the process according to the invention, due to the use of density reducing substances in step (ii) have a particularly low, but individually adjusted according to the needs of the individual case bulk density and especially when using pyrolyzable fillers a high, but individually adjusted in accordance with the needs of the individual case porosity, so that the resulting individually manufactured composite particles have a high insulating effect with low bulk density.
  • blowing agents can be used as additional further density-reducing substances in step (a1), point (ii) of the process according to the invention.
  • blowing agents are substances which, when treating the hardened drops in step (a3), eg during heating, puffing or release expanding gases and thereby create voids in the composite particles.
  • Colloidal silica used as the starting material in step (a1), item (iii) of the process of the invention is preferably a dispersion comprising an aqueous (ie: water-containing) continuous phase and a dispersed phase comprising nanoparticulate silica, preferably with an average particle size (determined by electron microscopic measurement) in the range of 5 to 30 nm, preferably in the range of 7 to 25 nm.
  • the specific surface area of the particulate silicon dioxide is preferably in the range of 100 to 300 m 2 / g, particularly preferably in the range of 200 to 300 m 2 / g, determined by the "BET method" (see S. Brunauer, PH Emmet, E. Teller: J.
  • the content of the dispersion of silica is preferably in a range of 10 to 50% by weight, more preferably in a range of 15 to 40% by weight, most preferably in a range of 18 to 35% by weight %, based on the total weight of the dispersion.
  • the "colloidal silica” is an anionic colloidal silica, More preferably, the colloidal silica is a surface-modified, anionic, colloidal silica.
  • “Dispersion” here is the entirety of the colloidal silica continuous phase (s) and dispersed phase (or phases) understood.
  • Preferred colloidal silicon dioxides for use in the process according to the invention described above are the product “Ludox® TMA” from WR Grace & Co., the product “Lithosol® 1530" from Zschimmer & Schwarz GmbH & Co. KG, the product “Levasil® 200E / 20%”, the product “Levasil® 200B / 30%” (both from HCStarck) and the product "Köstrosol® 0820BS” from Chemiewerk Bad Köstritz GmbH.
  • the colloidally dispersed silica particles used in step (a1) are present as nanoparticulate silicon dioxide, provided that the temperature for the thermal treatment in step (a3) (or another thermal treatment applied to the composite particles such as sintering) is not chosen so high that the nanoparticles merge or sinter completely together with loss of particle shape.
  • Evidence for the presence of nanoparticulate silica may be obtained by scanning electron microscopy (“SEM”) or transmission electron microscopy (“TEM").
  • the composite particles or insulating materials produced according to the abovementioned process according to the invention which comprise colloidal silica as constituent (iii), are distinguished by particularly high grain strength combined with low bulk density, refractory properties and high insulation effect. They are therefore particularly suitable for the production of insulating products for the refractory industry, where it depends on high mechanical stability. Without guarantee of correctness, it is assumed that the particularly good grain strength of the composite particles or insulating materials produced by the abovementioned process according to the invention results from a - u.U.
  • step (a3) synergistic - interaction of two or all three of the factors (j-1) thermal treatment in step (a3) in the preferred temperature range (see below), (j-2) curing the preferred solidifiable liquid (see below) in step (a2 ) and (j-3) the action of the colloidal silica in step (a1) as a binder.
  • step (a3) for a desired high grain strength of composite particles for use in the To achieve refractory industry can therefore be advantageously reduced by the process according to the invention over other similar processes.
  • step (a1) droplets are produced by means of one or more nozzles, preferably vibration nozzles, and / or in step ( a2) the solidification of the solidifiable liquid is induced by cooling, drying or chemical reaction.
  • step (a2) droplets are produced by means of one or more nozzles, preferably vibration nozzles, and / or in step ( a2) the solidification of the solidifiable liquid is induced by cooling, drying or chemical reaction.
  • the use of one or more nozzles, preferably vibration nozzles, is preferred in step (a1) in order to produce the composite particles in a time-efficient manner and with as uniform as possible a grain size.
  • step (a1) is a chemical-solidifiable liquid and in step (a2) the solidification of the solidifiable Liquid is induced by chemical reaction.
  • the solidification of the solidifiable liquid by chemical reaction has the advantage that this process is usually irreversible and also fast enough, so that when dripping and thus solidifying the solidifiable liquid, the solidifiable liquid usually retains the shape of the drop.
  • Solidification by physical methods, such as cooling or drying are in some cases reversible and can be reversed in these cases, for example, by the supply of heat or moisture (at least partially).
  • Particular preference is given to a process according to the invention as described above (in particular a process which is referred to above or below as preferred), wherein the solidifiable liquid is a liquid which can be solidified by cation exchange reaction, preferably a by reaction with calcium ions and / or barium ions and / or manganese. Ions, preferably by reaction with calcium ions, solidifiable liquid.
  • Cation exchange reactions have the advantage in practice that they are regularly completed in a relatively short period of time.
  • step (a2) preference is given to carrying out a cation exchange reaction in which the solidifiable liquid contains monovalent cations and is brought into contact with calcium ions so as to solidify the solidifiable liquid; Instead of calcium ions but also barium ions or manganese ions can be used. Monovalent cations contained in the solidifiable liquid are exchanged for calcium ions in the preferred procedure to solidify the solidifiable liquid. Calcium ions have a good balance between charge and ion mobility. In general, the following applies: The charge of the cation which is to be exchanged with the monovalent cation present in the solidifiable liquid should be as high as possible so that sparingly soluble compounds are formed during cation exchange. However, the cation should also have the highest possible ion mobility, so that the desired chemical reaction proceeds as quickly as possible. The ion mobility of cations decreases with increasing cation charge.
  • the solidifiable liquid is a liquid solidifiable by reaction with calcium ions, which comprises one or more binders selected from the group consisting of Alginate, polyvinyl alcohol (PVA), chitosan and sulfoxyethyl cellulose, and / or (preferably "and") an aqueous solution, wherein the solidifiable liquid is preferably an aqueous alginate solution, wherein the solidifiable liquid is particularly preferably an aqueous sodium alginate solution.
  • binders selected from the group consisting of Alginate, polyvinyl alcohol (PVA), chitosan and sulfoxyethyl cellulose, and / or (preferably "and") an aqueous solution
  • the solidifiable liquid is preferably an aqueous alginate solution
  • the solidifiable liquid is particularly preferably an aqueous sodium alginate solution.
  • Alginate solutions in particular sodium alginate solutions, preferably in the form of an aqueous solution, are particularly suitable for use as a liquid which can be solidified by reaction with calcium ions in a method according to the invention, since they comprise friendly, degradable and in particular not poisonous.
  • alginate solutions can be solidified reproducibly and standardized.
  • step (a) Preference is given to a process according to the invention as described above (in particular a process which is referred to as preferred above), wherein the or at least one of the light fillers used in step (a) as a density-reducing substance of component (ii), preferably with a particle size smaller as 0.8 mm, particularly preferably smaller than 0.5 mm, very particularly preferably smaller than 0.3 mm, determined by sieving (for determination method see above), selected from the group consisting of: inorganic hollow spheres, organic hollow spheres, particles of porous and / or foamed material, preferably of glass, rice husk ash, core-shell particles and calcined diatomaceous earth and / or wherein the or at least one of the pyrolyzable fillers used as component (ii) in step (a) is selected from the group consisting out:
  • Plastic beads preferably plastic beads "Expancel® 091 DE 80 d30" from Akzo Nobel or plastic beads "SPHERE ONE
  • Styrofoam beads preferably styrofoam beads "F655-N" from BASF, particularly preferred is a method according to the invention as described above (in particular a method which is referred to above or below as being preferred), wherein the total amount of light fillers used in the range up to 30% by weight is particularly preferably in the range from 1 to 10% by weight, particularly preferably in the range from 2 to 5% by weight, based on the total mass of in step (a1) prepared suspension, and / or the total amount of the pyrolyzable fillers used in the range to 30 wt .-%, more preferably in the range of 1 to 20 wt .-%, particularly preferably in the range of 2 to 10 wt .-%, based on the total mass of the suspension prepared in step (a1).
  • the total amount of the density-reducing substances used is preferably in the range from 1 to 20% by weight, particularly preferably in the range from 2 to 10% by weight, based on the total mass of the suspension prepared in step (a1).
  • component (ii) may be used singly or in combination with each other.
  • component (ii) may be used singly or in combination with each other.
  • the light fillers and pyrolyzable fillers used above as components (ii) can each be used individually or in combination with one another.
  • blowing agents which may optionally be used in addition to the inventively provided density-reducing substances as additional further density-reducing substances in the method according to the invention are preferably selected from the group consisting of:
  • Carbonates, bicarbonates and oxalates preferably with cations selected from the group consisting of alkali metals and alkaline earth metals, preferably calcium carbonates, hydrogen carbonates and oxalates,
  • coconut shell meal preferably coconut shell meal with the name "Coconit 300" from the company Mahlwerk Neubauer-Friedrich Geffers GmbH, Walnut shell meal, preferably walnut shell meal with the name “walnut shell meal 200m” from Ziegler Minerals,
  • Grape seed flour preferably grape seed flour with the name "grape seed flour M100" from A + S BioTec,
  • Olive-seed flour preferably olive-seed flour with the names "OM2000” or “OM3000” from JELU-Werk,
  • Wheat flour preferably wheat flour with the name "Flour 405" from Hummel,
  • Corn flour preferably corn flour with the name “maize flour” MK100 "from the company Hummel,
  • Wood flour preferably wood flour with the name "wood flour Ligno-Tech 120mesh TR” from the company Brandenburg Holzmühle, and
  • Rice husk ash preferably rice husk ash with a high content of carbon, e.g. a rice husk ash with the name "Nermat AF ( ⁇ 80 ⁇ )" from the company Refractech,
  • blowing agents which may optionally be used as further additional component (ii) may be used individually or in combination with one another, preferably in a total amount of up to 30% by weight, more preferably in the range of 1 to 20% by weight, particularly preferably in the range of 3 to 10 wt .-%, based on the total mass of the suspension prepared in step (a1).
  • the above-mentioned density reducing substances (such as light fillers or pyrolyzable fillers, also blowing agents) for the production of composite particles having a particularly low bulk density are widely available in the market.
  • Your commitment In the method according to the invention enables the reproducible production of lightweight, well insulating products for the refractory industry or insulating materials as intermediates for the production of such products.
  • Oxides, nitrides and carbides each comprising one or more elements selected from the group consisting of Si, Al, Zr, Ti, Mg and Ca, and
  • Alumina e.g., CAS No. 21645-51-2
  • Zirconium oxide e.g., CAS number 1314-23-4
  • Titanium dioxide e.g., CAS number 13463-67-7
  • silica e.g., quartz with the CAS number: 14808-60-7 or glassy S1O2 with the CAS numbers: 60676-86-0
  • Magnesium oxide (e.g., CAS number: 1309-48-4),
  • Calcium oxide (e.g., CAS number 1305-78-8),
  • Calcium silicate (e.g., CAS number: 1344-95-2),
  • - phyllosilicates preferably mica, - aluminum silicates
  • Magnesium aluminum silicate preferably cordierite
  • Silicon carbide, and boron nitride and / or the or at least one of the refractory solids precursors used in step (a1) as the refractory substance of component (i) is selected from the group consisting of aluminum hydroxide (eg CAS number: 1344-28- 1 ),
  • Magnesium hydroxide (e.g., CAS number: 1309-42-8),
  • Phyllosilicates preferably kaolinite, montmorillonite and lllite
  • Clays preferably kaolin and bentonite
  • Phosphates such as tricalcium phosphate (e.g., CAS number: 7758-87-4) and
  • Carbonates such as calcium carbonate and magnesium carbonate e.g., CAS numbers:
  • a method according to the invention as described above (in particular a method which is referred to above or below as preferred), wherein the total amount of the refractory substances used in step (a1) in the range of 1 to 70 wt .-%, particularly preferably in the range from 5 to 50 wt .-%, most preferably in the range of 10 to 30 wt .-%, based on the total mass of the suspension prepared in step (a1).
  • All of the abovementioned species can also be used in mixture with one another, for example carbonates / phosphates in the form of bone ash.
  • refractory solids may be used singly or in combination.
  • the above precursors may be used singly or in combination. Only refractory solids or exclusively precursors can be used, or both in combination.
  • Preferred sheet silicates for use as refractory solids are the following: - "Pyrax® RG-140" from C.H. Erblslöh
  • the above preferred layered silicates may be used singly or in combination.
  • Alumina e.g., CAS No. 21645-51-2
  • Zirconium oxide eg CAS number 1314-23-4
  • Titanium dioxide eg CAS number 13463-67-7
  • Silica eg quartz with the CAS number: 14808-60-7 or glassy SiO 2 with the CAS numbers: 60676-86-0
  • a particulate solid as distinct from colloidal silica, according to step (a1), point (iii ) of the method according to the invention
  • - magnesium oxide eg CAS number: 1309-48-4
  • Calcium oxide (e.g., CAS number 1305-78-8).
  • the above oxides may be used singly or in combination.
  • Preferred aluminum oxides are the aluminum oxide "Nabalox® N0315” from the company Nalbaltec AG, the aluminum oxide “Alodur® EK S1” from Schwarzacher Schleifsch, the aluminum oxide “Alumina DF2” from MAL Magyar Aluminum and the aluminum oxide "Edel Corund white EK filter dust "from the company Wester Minerals.
  • a preferred combination of metal oxides is a mixture of aluminum oxide and zirconium oxide, such as "Alodur® ZKSF" from Treibacher Schleifsch, the preferred silicon oxides being the silicon oxide “Sillimat GS ( ⁇ 80 ⁇ m)” from Refractie, the silicon oxide " Calcined rice husks “from Ziegler Minerals, the silica” Aerosil 200 “Fa.Evonik, the silica” Si02 “RW filler Q1 plus” of the company. RW silicon GmbH and the silica "Millisil-flour W8" from Quarzwerke ,
  • a preferred calcium silicate is the calcium silicate "China Wollastonite TMM S.G.” Fa. Possehl Erzchyr.
  • Preferred aluminum silicates for use as refractory solids or precursors are magnesium aluminum silicates and the following aluminum silicates:
  • Magnesium aluminum silicates and / or the aforementioned preferred aluminum silicates may be used singly or in combination.
  • Preferred magnesium aluminum silicates for use as refractory solids are cordierites, preferably "cordierite C 65" from Ceske Lupkove Zävody SA, “cordierite B” from Alroko GmbH & Co KG and “cordierite 0-1 mm” or “cordierite DIN 70 “of the company Spitzer commodity trading mbH. These preferred magnesium aluminum silicates may be used singly or in combination.
  • the above-mentioned compounds or mixtures may be used in combination with each other as refractory solids in the present invention.
  • the person skilled in the art can, for example, set the desired thermal stability of the composite particles and the bulk density dependent thereon only to a certain extent by the type and amount of the refractory solids.
  • a preferred mixture for use as refractory solids precursors is bone ash, e.g. "CALTAN Knochenasche” from Neue Leimfabrik Tangermünde GmbH
  • Especially preferred kaolins for use as precursors for refractory solids are:
  • Particularly preferred bentonites for use as precursors for refractory solids are:
  • the above particularly preferred bentonites may be used singly or in combination.
  • the refractory substances in step (a1) are preferably present as non-aggregated and non-agglomerated particles, wherein preferably the ratio of the maximum grain size (as defined above) of the particles of the refractory substances to the maximum grain size of the composite produced in the process according to the invention. particle is in the range of 0.01 to 0.2. In this way, many particles of the refractory substances can be arranged in a single composite particle.
  • Fireproof substances used in step (a1) are preferably particles, preferably particles of refractory solids, preferably refractory solids having a particle size of less than 0.1 mm, determined by sieving in accordance with DIN 66165-2 (4.1987) using method D mentioned there (Machine screening with resting single wire in gaseous moving fluid, with air jet sieve).
  • a process according to the invention as described above (in particular a process which is referred to as preferred above or below) is preferred, wherein the treatment according to step (a3) is carried out such that the bulk density of the resulting composite particles is lower than the bulk density of the cured Drops in the dried state (this is particularly easy to achieve when using density-reducing substances, preferably pyrolyzable fillers, if the treatment is carried out so that it leads to pyrolysis of the pyrolyzable fillers) and / or the said composite particles have a bulk density ⁇ 750 g / L , preferably ⁇ 500 g / L, more preferably ⁇ 350 g / L.
  • a targeted treatment of the hardened droplets in step (a3) results in many If advantageous or required reduction in bulk density is achievable (for example, by pyrolyzing components or reacting with the release of expanding gases).
  • the dimensional stability or thermal stability of the resulting from the cured droplets composite particle is surprisingly not adversely affected.
  • a method according to the invention as described above is preferred, wherein the composite particles resulting in step (a3) at least partially have a particle size in the range of less than 5.0 mm, preferably less than 2.0 mm, determined by sieving.
  • Composite particles with a grain size of less than 2.0 mm form the fine grain in an insulating refractory material and are therefore particularly suitable for processing an insulating material for the refractory industry or a corresponding insulating product; their preparation in step (a) of the process according to the invention and their use in step (b) (see below) is preferred.
  • component (ii) comprises one or more pyrolyzable fillers as density-reducing substance or substances and the treatment according to step (a3 ) is carried out so that the or more pyrolyzable fillers pyrolyiseren and thereby form cavities in the resulting composite particles.
  • step (a3) is a partial aspect of the present invention when using pyrolyzable fillers, since this reduces the bulk density of the resulting composite particles and increases the insulating effect.
  • the amount and particle size of the pyrolyzable fillers are relevant parameters for the bulk density and the porosity of the resulting composite particles.
  • component (i) comprises one or more precursors for refractory solids as refractory substances and the treatment according to step (a3) comprises a thermal Treatment in which the precursors are converted into a refractory solid (this can usually be detected by XRD measurement), preferably wherein the or at least one of the refractory solids precursors is a clay or clay-bearing rock and the treatment according to step (a3) comprises thermal treatment at a temperature in the range 900 to 980 ° C such that the clay is converted to a refractory solid
  • the clay preferably contains kaolinite and / or lllite (this can usually be detected by XRD measurement).
  • step (a3) in the range of 900 to 980 ° C composite particles containing as component (iii) colloidal silica, are obtained with very high mechanical strength (grain strength). It has also been found that the formation of the mechanical strength of the composite particles by the thermal treatment in step (a3) of the inventive method at a temperature in the range of 900 to 980 ° C is time-dependent, in the sense that a longer thermal treatment in the specified Temperature range results in a higher mechanical strength.
  • the porosity of the composite particles by the thermal treatment in step (a3) of the process according to the invention at a temperature in the range of 900 to 980 ° C is time-dependent, in the sense that a longer thermal treatment in the specified temperature range has a lower porosity result.
  • the possibility of producing composite particles even at relatively low temperatures in the range from 900 to 980 ° C., which are outstandingly suitable for insulating products for the refractory industry or for insulating materials as intermediates for producing such insulating products, is a further particular advantage of the process according to the invention.
  • Previously known methods for producing similar insulating products or intermediates for the refractory industry usually work with significantly higher temperatures, with a concomitant higher energy consumption.
  • step (a3) of the process according to the invention composite particles with desired values for grain strength and surface porosity can therefore be produced.
  • a clay or clay-containing rock for use as a precursor are, for example, kaolin and bentonite. It is a particular achievement of the present application to have recognized that certain precursor materials (kaolins, for example "Chinafill 100” or “kaolin TEC” from Amberg Kaolinwerke and “Käreueronmehl” from Käreuer Ton- and Schamottewerke Mannheim & Co. KG, "Satintone W" of the company BASF AG) in a thermal treatment in step (a3) already at relatively low temperatures in a different phase of particular thermal stability and thus to an even better thermal resistance of contribute composite particles in the process according to the invention contribute.
  • the hardened drop is preferably heated to a temperature in the range from 900 to 980 ° C., so that, for example, kaolinite passes over intermediate phases into the refractory solid mullite, which is a very high has thermal resistance.
  • precursors of refractory solids particularly the use of preferred precursors of refractory solids as described above, as well as the immediate use of refractory solids, contributes to increased thermal stability of the composite particles made in accordance with the present invention.
  • a method as described above in particular a method which is referred to above or below as preferred, wherein preferably a temperature of 1000 ° C is not exceeded during thermal treatment.
  • a thermal treatment at 980 ° C or less contributes to a reduction in reactor complexity and has a significantly lower energy requirement.
  • the thermal stability of the composite particles produced according to the invention is particularly surprising when compared with the thermal resistance of the standard hollow spherical corundum material.
  • a melt of alumina is produced, which is subsequently blown.
  • temperatures in the range of about 2000 ° C are regularly necessary according to the melting temperature of Al2O3.
  • the production of ceramic or glassy hollow microspheres takes place, for example, according to EP1832560 in temperature ranges from 1000 to 2000.degree.
  • Composite particles prepared according to the invention using suitable precursors have increased thermal stability even after treatment at lower temperatures (sintering / tempering, see above).
  • step (a3) the hardened drops are washed and preferably the resulting washed drops are dried.
  • step (a3) the hardened drops are washed and preferably the resulting washed drops are dried.
  • further treatment steps are then carried out, preferably treatment steps, as described above or below as being preferred.
  • a thermal treatment of the washed and optionally dried drops at a temperature below 1000 ° C is performed.
  • the composite particles produced in step (a) are preferably free-flowing. Preference is given to a process as described above (in particular a process which is referred to above or below as preferred), wherein in step (a3) the hardened droplets are treated so that solid particles result as an intermediate, and subsequently the surface of these solid particles is sealed, preferably by means of an organic coating agent or a silicon-containing binding agent, so that the said composite particles result. In individual cases, the use of another inorganic coating agent is advantageous.
  • a particularly preferred organic coating agent is egg white, which is preferably applied in the form of an aqueous solution.
  • An aqueous egg white solution is preferably prepared by mixing a protein powder with water.
  • Corresponding egg whisker solutions are e.g. made with:
  • Protein powder standard (product number 150061) from NOVENTUM Foods
  • Protein powder High Whip (product number 150062) from the company NOVENTUM Foods
  • Protein powder High Gel (product number 150063) from NOVENTUM Foods.
  • Non-organic coating agents are silicon-containing binders, preferably alkoxysilanes ("silanes”) and / or alkoxysiloxane (“siloxane”) mixtures, in particular the product SILRES® BS 3003 from Wacker Silicones.
  • Non-organic coating agents such as the preferred alkoxysilanes and alkoxysiloxane mixtures have the advantage of being water repellent and heat resistant.
  • the said composite particles in some cases have a high porosity, it is particularly advantageous to seal them with one of the preferred coating compositions.
  • the preferred coating agents as described above are readily available on the market, non-toxic and easily processable.
  • Egg white is particularly preferred as an organic coating agent because it seals the surface of the composite particles in an excellent manner and thus advantageously reduces their ability to absorb binders.
  • step (b) mixing the composite particles prepared in step (a) with a binder comprising a binder component selected from the group consisting of
  • Boron compounds preferably boron oxide, Magnesium sulfate or solution of magnesium sulfate,
  • Aluminum sulfate preferably
  • step (b) mixing the composite particles prepared in step (a) with a binder comprising a binder component selected from the group consisting of
  • Boron compounds preferably boron oxide
  • step (b) Sols of alumina, and optionally in step (b) or a further step after step (a) mixing with one or more further substances to produce a curable refractory composition, and optionally curing the curable refractory composition and / or (c) preparing the insulating product for the refractory industry or the insulating material as an intermediate for producing such a product using the composite particles of step (a), wherein step (c) is preferably carried out after step (a) and / or after step (b) and / or preferably wherein the insulating product for the refractory industry or the insulating material is selected from the group consisting of shaped and unshaped refractory and high-refractory products, preferably non-basic refractory materials, as an intermediate product for producing such a product, and is more preferably selected from Group consisting of
  • Eingussmassen preferably perforated bricks and dishwasher, and
  • a "silica sol” referred to above has the standard meaning in the art of an aqueous (i.e., water-containing) solution of approximately spherical, colloidally solubilized polysilicic acid molecules with a content in the range from 30% by weight to 60% by weight (based on the total mass of the aqueous solution) of silicon dioxide Depending on the particle size of the particles, silica sol is milky-cloudy to colorless-clear, the average particle diameter is 5-150 nm.
  • the preparation is carried out by treating an aqueous alkali silicate solution ("water glass").
  • step (a) can be mixed with a binder or with a mixture of a plurality of binders.
  • a binder may comprise one or more of the foregoing binder components, such as a mixture of several such binder components.
  • step (a3) Also preferred is a method as described above (in particular a method which is referred to above or below as being preferred), wherein the composite particles resulting in step (a3) are characterized by
  • (C) a grain strength> 1, 5 N / mm 2 , preferably> 2.0 N / mm 2 , more preferably> 3.0 N / mm 2 determined according to DIN EN 13055-1: 2008-08, Appendix A (method 1, 2 * 30 sec shake with amplitude 0.5) at a grain size (for determination method see below) in the range of 0.25-0, 5mm, and or
  • the "thermal conductivity value” (see inter alia the above item “(B)") is determined in accordance with the standard DIN EN 12667: 2001-05, "Thermal properties of building and construction products; Determining the forward resistance according to the method with the disk device and the heat flow meter device; Products with high and medium thermal resistance ".
  • the "bulk density” (see inter alia the above item “(D)) is determined according to DIN EN ISO 60 2000-1.
  • the "particle size” of the composite particles (see inter alia the above item “(E)) is determined by screening according to DIN 66165-2 (4.1987) using the method F mentioned therein (machine screening with moving single sieve or sieve set in US Pat gaseous static fluid). A vibrating sieve machine of the type RETSCH AS 200 control is used; while the amplitude is set to level 2; there is no interval sieving, the sieving time is 1 minute.
  • the "water absorbency" (see, inter alia, the above item “(F)) is determined according to the method of Enslin.
  • the method is known to the person skilled in the art. It uses the so-called “Enslin apparatus", in which a glass suction chute is connected to a graduated pipette via a tube, and the pipette is mounted exactly horizontally so that it is level with the glass frit. 5 mL / g corresponds to a water absorption of 1.5 ml of water per 1 g of composite particles and is evaluated in accordance with DIN 18132: 2012-04.
  • the invention also relates to the use of a matrix encapsulation method, preferably using a nozzle, particularly preferably using a vibrating nozzle, for producing composite particles having a bulk density ⁇ 750 g / L, preferably ⁇ 500 g / L, particularly preferably ⁇ 350 g / L in the manufacture of an insulating product for the refractory industry which comprises a plurality of composite particles bound together by a phase acting as a binder.
  • This aspect of the invention is based on the surprising finding that the use of such prepared composite particles having a bulk density of ⁇ 750 g / L, preferably ⁇ 500 g / L, particularly preferably ⁇ 350 g / L, very light, well insulating materials with preferably high thermal resistance results.
  • the explanations given for the method according to the invention apply correspondingly.
  • feeder elements for the foundry industry are not considered by the skilled person as products for the refractory industry.
  • Feeder elements for the foundry industry are not the subject of the present invention and are not considered as products for the refractory industry.
  • the term "feeder element” encompasses feeder shells, feeder inserts, and feeder caps as well as heating pads.
  • Typical products for the refractory industry, for the production of the composite particles produced by the process according to the invention or an insulating material comprising these are suitable - especially because of their high grain strength and low bulk density - are shaped and unshaped refractory and / or high refractory - preferably refractory - Products, in particular all non-basic refractory materials.
  • Preferred examples of such shaped or unshaped refractory and / or high refractory products for the refractory industry are selected from the group consisting of:
  • Casting compounds preferably perforated stones and dishwashers and oven deliveries.
  • the present invention also relates to an insulating product for the refractory industry or an insulating material as an intermediate for producing such a product containing a number of refractory composite particles, said composite particles
  • nanoparticulate silicon dioxide which acts as a binder or binder component for the said particles of the refractory substances
  • the silicon dioxide particles are in the form of nanoparticulate silicon dioxide provided that the sintering temperature in step (a3) of the process according to the invention is not selected so high that the silica nanoparticles sinter together completely with loss of the particle shape
  • the detection of the presence of nanoparticulate silicon dioxide can be carried out by scanning electron microscopy ( "REM") or transmission electron microscopy (“TEM").
  • an insulating product for the refractory industry or an insulating material as an intermediate for the production of such a product wherein the composite particles contained in the product or intermediate are characterized by (C) a grain strength> 1, 5 N / mm 2 , preferably> 2.0 N / mm 2 , more preferably> 3.0 N / mm 2 determined according to EN 13055-1, Appendix A, method 1, with a grain size in the range of 0.25-0, 5mm, and / or (D) a bulk density ⁇ 750g / L, preferably ⁇ 500g / L, more preferably ⁇ 350g / L, and / or
  • an insulating product according to the invention for the refractory industry or an insulating material as an intermediate for producing such a product comprising the curing product of a binder component selected from the group out:
  • Alumina cements calcium aluminate cements
  • an insulating product according to the present invention for the refractory industry or an insulating material as an intermediate for producing such a product (particularly, an insulating product or an insulating material referred to above or below as being preferable) additionally comprising one or more substances selected from the group consisting of:
  • the invention also relates to a (second method according to the invention) for producing an insulating product for the refractory industry or an insulating material as an intermediate for producing such a product, comprising the following steps:
  • step (b) mixing the composite particles prepared in step (a3) with a binder comprising a binder component selected from the group consisting of
  • Boron compounds preferably boron oxide
  • step (a1) drops are produced by means of one or more nozzles, preferably vibration nozzles, and / or solidification of the solidifiable liquid by cooling, drying or in step (a2) chemical reaction is induced.
  • step (a2) also preferred is a second process according to the invention as described above (in particular such a process, referred to above or below as preferred) wherein the solidifiable liquid used in step (a1) is a chemical solidifiable liquid and in step (a2) the solidification the solidifiable liquid is induced by chemical reaction.
  • step (a1) is a liquid which can be solidified by cation exchange reaction, preferably one by reaction with calcium ions and / or or barium ions and / or manganese ions, preferably by reaction with calcium ions, solidifiable liquid.
  • a second process according to the invention comprising as an additional step, (c) producing the insulating product for the refractory industry or the insulating material as an intermediate for producing such Product using the composite particles of step (a) and / or the curable refractory composition or of the cured refractory composition of step (b), wherein preferably step (c) is carried out after step (a) and / or after step (b), and or preferably wherein the insulating product for the refractory industry or the insulating material is selected as an intermediate for the production of such a product from the group consisting of shaped and unshaped refractory and high-fire-resistant Er-certificates, and is more preferably selected from the group consisting of:
  • Insulating compounds comprising bulk materials, casting compounds, ramming compounds, sprayed materials and vibrating compounds,
  • Ceiling tiles and ceiling elements for suspended ceilings preferably for moveable ceiling constructions and vault constructions in furnace and plant construction,
  • the solidifiable liquid is a liquid which can be solidified by reaction with calcium ions and comprises one or more binders from the group consisting of alginate, polyvinyl alcohol (PVA), chitosan and sulfoxyethyl cellulose, and / or an aqueous solution, wherein the solidifiable liquid is preferably an aqueous alginate solution.
  • PVA polyvinyl alcohol
  • step (a) a density reducing substance of component (ii) used light fillers, preferably with a particle size of less than 0.8 mm, more preferably less than 0.5 mm, most preferably less than 0.3 mm, determined by sieving, selected from the group consisting of: inorganic hollow spheres, organic hollow spheres, particles of porous and / or foamed material, rice husk ash, core-shell particles and calcined diatomaceous earth and / or wherein the or at least one of the pyrolyzable fillers used in step (a) as component (ii) is selected from the group consisting of:
  • a second process according to the invention as described above is also preferred, wherein the or at least one of the refractory solids used in step (a1) as the refractory substance of component (i) is selected is selected from the group consisting of: oxides, nitrides and carbides, each comprising one or more
  • Mixed oxides Mixed carbides and mixed nitrides, each comprising one or more elements selected from the group consisting of Si, Al, Zr, Ti, Mg and Ca, preferably the or at least one selected in step (a1) as refractory substance of component (i) refractory solids is from the group consisting of:
  • Phyllosilicates preferably mica, aluminum silicates,
  • Magnesium aluminum silicate preferably cordierite, silicon carbide, and
  • Boron nitride and / or the or at least one of the precursors for refractory solids used in step (a1) as the refractory substance of component (i) is selected from the group consisting of
  • Phyllosilicates preferably kaolinite, montmorillonite and lllite
  • Clays preferably kaolin and bentonite
  • step (a3) is carried out so that the bulk density of the resulting composite particles is lower than that Bulk density of the cured droplets in the dried state and / or the said composite particles have a bulk density ⁇ 750 g / L, preferably ⁇ 500 g / L, more preferably ⁇ 350 g / L.
  • step (a3) and / or the composite particles used in step (b) at least partially Grain size of less than 5.0 mm, preferably less than 2.0 mm, determined by sieving.
  • Component (i) comprises as refractory substances one or more precursors for refractory solids and the treatment according to step (a3) comprises a thermal treatment in which the precursors are converted into a refractory solid, preferably the or at least one of the precursors for refractory solids Clay is and the treating according to step (a3) comprises a thermal treatment at a temperature in the range of 900 to 980 ° C, so that the clay is converted into a refractory solid, the clay preferably contains kaolinite and / or lllit.
  • step (a3) the hardened droplets are treated so that solid particles result as an intermediate and subsequently the surface of these solid particles is sealed, preferably by means of an organic coating agent, so that the said composite particles result.
  • step (b) mixing the composite particles produced in step (a) with a binder comprising a binder deffenkomponente selected from the group consisting of
  • Boron compounds preferably boron oxide
  • the second process according to the invention is also preferably as described above (in particular such a process, which is referred to as preferred above or below), wherein in step (a1) as a further starting material for producing drops of a suspension and as a dispersed phase (iii) in addition to components (i) and (ii), colloidal silica, preferably anionic colloidal silica, is used.
  • a second method according to the invention as described above is also preferred, wherein the composite particles resulting in step (a3) are characterized by
  • (C) a grain strength> 1, 5 N / mm 2 , preferably> 2.0 N / mm 2 , more preferably> 3.0 N / mm 2 determined according to DIN EN 13055-1: 2008-08, Appendix A (method 1, 2 * 30 sec shake with amplitude 0.5), with a grain size (for determination method see above) in the range of 0.25-0, 5mm, and / or
  • the invention also relates to a second insulating product for the refractory industry or a second insulating material as an intermediate for producing such a product, containing a number of refractory composite particles, said composite particles - particles of one or more refractory substances and preferably nanoparticulate, for said particles of the refractory substances
  • Binder or binder component functioning silica and the curing product of a binder component selected from the group consisting of:
  • the product or the intermediate product can be produced by a second process according to the invention (in particular such a process, which is referred to as preferred above) and / or wherein the composite particles contained in the product or intermediate are characterized by
  • Products for the refractory industry, for the production of which the composite particles produced by the second process according to the invention or an insulating material comprising them are suitable - in particular because of their high refractoriness and at the same time low bulk density - comprise shaped and unshaped refractory and / or high-refractory products, preferably highly refractory products, especially all non-basic ones Refractories.
  • Preferred shaped or unshaped refractory and / or high-refractory products for the refractory industry, for the production of which the composite particles produced by the second process according to the invention or an insulating material comprising them are suitable are selected from the group consisting of: - lightweight refractory bricks,
  • Insulating bricks lightweight bricks
  • Insulating compounds including bulk materials, casting compounds, ramming compounds, sprayable compounds and vibrating compounds, - ceiling tiles and ceiling elements for suspended ceilings, in particular for movable ceiling constructions and vault structures in furnace and plant construction,
  • a second insulating product for the refractory industry or second insulating material is preferred as an intermediate for producing such a (second inventive) product, wherein the composite particles contained in the second product or second intermediate product are characterized by
  • (C) a grain strength> 1, 5 N / mm 2 , preferably> 2.0 N / mm 2 , more preferably> 3.0 N / mm 2 determined according to DIN EN 13055-1: 2008-08, Appendix A (method 1, 2 * 30 sec shake with amplitude 0.5) at a grain size (for determination method see above) in the range of 0.25-0, 5mm, and / or
  • Enslin ⁇ 4.5, preferably ⁇ 3.5, more preferably ⁇ 2.0 mL / g (for determination method, see above).
  • a second insulating product for the refractory industry or second insulating material as an intermediate for producing such (in particular, such an insulating product or insulating material as referred to above or below as being preferable) additionally comprising one or more substances selected from the group consisting of:
  • Chamotte lightweight chamotte, corundum, hollow spherical corundum, sintered corundum, fused corundum, sintered mullite, enamel mullite, alumina, andalusite, kyanite, sillimanite, cordierite, clays, wollastonite, zircon mullite, zircon corundum, fly ash and vermiculite spheres.
  • FIG. 1 In FIG. 1, the residue in the crucible after the sintering test at 1600 ° C. of the composite particle B36 is shown.
  • FIG. 3 shows a picture of the contents of the crucible after the sintering test at 1600 ° C. of the composite particles KHP 108 not according to the invention.
  • FIG. 4 shows a micrograph of the composite particles B36 after the sintering test at 1600 ° C.
  • the composite particles have not yet formed sintering necks after the sintering test.
  • FIG. 5 shows a micrograph of the non-inventive composite particles W250-6 after the sintering test at 1600 ° C.
  • FIG. 6 In FIG. 6, the residue in the crucible after the sintering test at 1700 ° C. of the composite particle B36 is shown.
  • FIG. 8 In FIG. 8, the crucible residue after the sintering test at 1700 ° C. of the composite particle hollow spherical corundum "NPP" not according to the invention is shown.
  • FIG. 9 shows a micrograph of the composite particles B36 after the sintering test at 1700.degree.
  • the composite particles have not yet formed sintering necks after the sintering test.
  • 10 shows a micrograph of the composite particles hollow spherical corundum "hargreaves" not according to the invention after the sintering test at 1700 ° C.
  • FIG. 10 shows a micrograph of the composite particles hollow spherical corundum "hargreaves" not according to the invention after the sintering test at 1700 ° C.
  • Fig. 1 1 is an enlarged micrograph of Fig. 10 of the composite particles according to the invention hollow spherical corundum "NPP" after the sintering test at 1700 ° C shown.
  • the particles have melted superficially during the sintering test, as a result of which all composite particles not according to the invention have solidified on solidification to form a coherent "pot cake”.
  • FIG. 13 In FIG. 13, an enlarged scanning electron micrograph of the composite particles labeled "B36" (see examples below) is shown.
  • FIG. 14 shows a greatly enlarged scanning electron micrograph of the composite particles "B36".
  • Fig. 15 shows the temperature within each of the insulating materials of Examples 4a (second intermediate products according to the invention, produced according to the second method of the invention, lower temperature / time curve (gray)) and 4b (comparative example, upper temperature / time Curve (black)), or the crucible made of the respective second insulating materials, as a function of the time after the casting process.
  • FIG. 16 In FIG. 16, the residue in the crucible after the sintering test at 1600 ° C. of the composite particles C6 produced according to the invention is shown.
  • FIG. 17 shows a microscopic image of the composite particles C6 produced according to the invention after the sintering test at 1600 ° C.
  • the composite particles produced according to the invention have formed only a few sintering necks after the sintering test.
  • FIG. 18 shows the crucible residue after the sintering test at 1700 ° C. of the composite particle "C6" produced according to the invention.
  • FIG. 19 shows a micrograph of the composite particles C6 produced according to the invention after the sintering test at 1700.degree.
  • Grain size determination The particle sizes of composite particles were determined by sieving in accordance with DIN 66165-2 (4.1987) using method F mentioned therein (machine sieving with moving single sieve or sieve set in gaseous static fluid). A vibrating sieve machine of the type RETSCH AS 200 control was used; while the amplitude was set to level 2; there was no interval sieving, the sieving time was 1 minute.
  • step (a) The determination of the particle sizes of light fillers used in step (a) as a density-reducing substance of component (ii) was also carried out according to DIN 66165-2 (4.1987) using the method F mentioned therein (machine screening with moving single sieve or sieve set in gaseous static fluid).
  • a vibration sieving machine of the type RETSCH AS 200 control was also used; while the amplitude was set to level 2; there was no interval sieving, the sieving time was 1 minute.
  • the determination of the particle sizes of refractory solids with a particle size of less than 0.1 mm was carried out by screening according to DIN 66165-2 (4.1987) using the method mentioned there D (machine screening with resting single wire in gaseous agitated fluid, with air jet sieve).
  • the bulk density was determined according to DIN EN ISO 60 2000-1.
  • the morphology of the samples was carried out with the aid of a SEM from Jeol JSM 6510.
  • the chemical composition was carried out by means of an EDX analysis using an EDX from Oxford INCA.
  • a light microscope VisiScope ZTL 350 with Visicam 3.0 camera was used to determine the morphology.
  • the sintering test was carried out in the present invention for determining the thermal stability of various raw materials on the basis of the VDG leaflet P26 "Testing of mold bases.”
  • An amount of particles of the same composition to be tested was subjected to a defined thermal treatment (for example 1600 ° C. or 1700 ° C.) ° C for half an hour each) in a Carbolite HTF 1800 oven with a temperature controller type E 3216 and then evaluated by means of a defined mechanical load by screening Firstly, a sieving of the amount of particles to be tested was carried out with a sieve of mesh size 0 , 5 mm, see Table 2 below, or 0.71 mm, see Table 3 below, to ensure the reproducibility and comparability of the different experiments.
  • Annealing of the samples with defined furnace travel (oven Fa. Carbolite HTF 1800 with temperature controller type E3216): from 25 ° C to 200 ° C at 1 K / min, then to the final temperature (1600 ° C for half an hour, see Table 2 below, or 1700 ° C for half an hour, see Table 3 below) at 3K / min and then cool to room temperature at 3K / min. Thereafter, the cooled particles were photographed with alumina crucible (see Fig. 3 (Particles melted), Figs. 6 and 7) or without alumina crucible (see Figs.
  • the alumina crucible in which the examined particles were tempered, clamped in a sieve stack and by a defined sieving with a control sieve on a Retsch AS 200 for 1 minute at an amplitude of 2 without interval sieving, ie Permanent sieving mechanically stressed.
  • the mesh size of the control sieve was adjusted to the maximum expected grain size of the particles tested (either 0.5 mm, see Table 2 below, or 0.71 mm, see Table 3 below).
  • the ratio of screen residue to screen penetration is used as the evaluation criterion (see VDG leaflet P26 "Testing of molding materials", October 1999.) With a sieve residue / sieve factor factor greater than 1, the sample is considered to be sintered and therefore not thermally stable.
  • Sample-specific parameters such as the particle size of the respective sample were taken into account in the evaluation.
  • the grain strength of the samples was determined according to DIN EN 13055-1: 2008-08, Appendix A (Method 1, shaking for 2 * 30 sec with amplitude 0.5), with a grain size in the range of 0.25 to 0.5 mm
  • Example 1 The grain strength of the samples was determined according to DIN EN 13055-1: 2008-08, Appendix A (Method 1, shaking for 2 * 30 sec with amplitude 0.5), with a grain size in the range of 0.25 to 0.5 mm
  • Example 1 Example 1 :
  • composite particles (C6) having a particle size of less than 5 mm are described below
  • composite particles (B36, B361) were produced, with a particle size of less than 5 mm, likewise as described below: Unless stated otherwise, the composite particles B36 and B361 analogous to the preparation of the composite particles C6.
  • the dispersant Sokalan® FTCP 5 from BASF was diluted with water to prepare a corresponding dispersing solution; the mass ratio Sokalan® FTCP 5 to water was 1: 2.
  • the prepared 1% sodium alginate aqueous solution and the prepared dispersing solution were then mixed in a mixing ratio shown in Table 1 to give a solidifiable liquid (solidifying liquid for use as a continuous phase in the sense of the component (iv) according to the step (a1) of the first method according to the invention or in the sense of component (iv) according to step (a1) of the second method according to the invention.
  • Borosilicate balls were then added with stirring in the creamy suspension in an amount according to Table 1 below as an example of a light filler (component (ii) according to step (a1)) and subsequently an amount of water according to Table 1. This resulted in a dilute suspension.
  • the diluted suspension was filled into plastic syringes and clamped in a LA-30 syringe pump.
  • the feed was 12 to 15 ml / min.
  • the diluted suspension in the syringes was then forced through a vibrating nozzle so that the diluted suspension dripped out of the vibrating nozzle in even drops.
  • the droplets dropping out of the vibrating nozzle fell into a 2% aqueous calcium chloride solution (CaCb, product name "Calcium Chloride 2-hydrate powder for analysis ACS" from Applicchem, CAS No. 10035-04-8, 2 wt.
  • CaCb 2% aqueous calcium chloride solution
  • the size of the hardened drops was dependent on the composition of the diluted suspension, the flow rate of the pump and the vibration frequency of the nozzle.
  • the hardened drops were skimmed off and washed in water. Subsequently, the washed and hardened drops were dried in a drying oven at 180 ° C for 40 min. After drying, there were free-flowing hardened drops whose bulk density "immediately before treatment in the muffle furnace" is shown in Table 1. Subsequently, the free-flowing hardened drops were heated in a preheated muffle for 30 minutes at 950 ° C.
  • Composite particles which are excellent insulating materials for the refractory industry, preferably insulating materials as intermediates for the production of insulating products for the refractory industry
  • the measured bulk densities of the composite particles produced according to the invention are below 400 g / L
  • the bulk density of resulting composite particles produced in accordance with the invention may optionally be further reduced Table 1
  • the composite particles "C6" produced by the process according to the invention have a surprisingly high grain strength.
  • composite particles "B36" prepared in accordance with the first Herste II process according to the invention and composite particles “B36” produced according to the second inventive production process (step (a) were compared with composite particles "KHP 108" (core Shell particles of the company Chemex) and particles not prepared according to the invention "W 205- 6 "(product” White Spheres W250-6 “from Omega Minerals).
  • the particles produced according to the invention and not produced according to the invention had a particle size in the range from 0.25 to 0.5 mm.
  • the sintering temperature was 1600 ° C.
  • the control sieve for the determination of the sieve residue and the sieve passage had a mesh width of 0.5 mm.
  • the ratio of screen residue to screen penetration in the composite particles "B36” and “C6” after sintering is less than 1, while this ratio in the case of the composite particles not prepared according to the invention after sintering is over 1.
  • the thermal stability of the composite particles "B36” and “C6" at 1600 ° C is better than that of the composite particles not according to the invention.
  • the particle sizes of the composite particles were always within the specified range of 0.18 to 0.71 mm.
  • the sintering temperature was 1700 ° C.
  • the control sieve for determining the sieve residue and the sieve passage had a mesh size of 0.71 mm.
  • the results of the sintering test at 1700 ° C are shown in Table 3:
  • Table 3 Results of the sintering test at 1700 ° C (presintering of the samples, 30 ° C 900 ° C in the preheated oven, then sintering temperature of 1700 ° C for 30 minutes).
  • the composite particles B36 (see Table 1), after being annealed at 900 ° C for 30 minutes in a preheated oven, were surface sealed as follows.
  • the surface sealing was carried out with an aqueous egg white solution containing 6% by weight protein powder High Gel (product number 150063) from NOVENTUM Foods, based on the total weight of the resulting aqueous solution.
  • the composite particles B36 were mixed with the prepared egg white solution in a weight ratio of composite particles to egg white solution of 2: 1 and stirred in the resulting mixture until the egg white solution was completely absorbed. Subsequently, the composite particles treated with the egg white solution were dried in a drying oven at 110 ° C. for 40 minutes. The resulting composite particles are referred to as B36 egg white.
  • Example 4 Comparison of the insulating effect of insulating materials
  • ISOSAT® 150 is a commercially available refractory material with a content of about 57% by weight of Al2O3 and T1O2 and a content of about 2% by weight Fe2O3.
  • thermocouples type K
  • both crucibles were cast off with iron (gray cast iron) at a temperature of 1500 ° C, and the resulting temperature rise in the insulating material was measured and recorded.
  • the data was recorded by means of a digital thermometer PCE-T 390 (PCE Deutschland GmbH). The result of the temperature measurement is shown graphically in FIG. 15:
  • Fig. 15 shows the temperature within the insulating materials of Examples 4a (concerning a second insulating material according to the invention, lower temperature / time curve (gray)) and 4b (comparative example, upper temperature / time curve (black)), respectively.
  • the (first) invention (first inventive methods and products) is summarized in the following aspects 1 to 18: 1.
  • step (a1) the production of drops by means of one or more nozzles, preferably vibrating nozzles takes place
  • step (a2) the solidification of the solidifiable liquid is induced by cooling, drying or chemical reaction.
  • step (a1) is a liquid solidifiable by chemical reaction and in step (a2) the solidification of the solidifiable liquid is induced by chemical reaction.
  • the solidifiable liquid is a cation exchange reaction solidifiable liquid, preferably a liquid solidifiable by reaction with calcium ions and / or barium ions and / or manganese ions, preferably by reaction with calcium ions.
  • the one or more binders selected from the group consisting of alginate, PVA, chitosan and sulfoxyethyl cellulose,
  • the solidifiable liquid is preferably an aqueous alginate solution.
  • the or at least one of the in step (a) as a density reducing substance of component (ii) used light fillers preferably having a particle size smaller than 0.8 mm, more preferably smaller than 0.5 mm, most preferably smaller than 0.3 mm , determined by sieving, is selected from the group consisting of: inorganic hollow spheres, organic hollow spheres, particles of porous and / or foamed material, rice husk ash, core-shell particles and calcined diatomaceous earth and / or wherein or at least one of in step ( a) used as component (ii) pyrolyzable fillers is selected from the group consisting of:
  • the or at least one of the refractory solids used in step (a1) as the refractory substance of component (i) is selected from the group consisting of: Oxides, nitrides and carbides, each comprising one or more elements selected from the group consisting of Si, Al, Zr, Ti, Mg and Ca, and
  • Mixed oxides Mixed carbides and mixed nitrides, each comprising one or more elements selected from the group consisting of Si, Al, Zr, Ti, Mg and
  • refractory solids used in step (a1) as the refractory substance of component (i) is selected from the group consisting of:
  • Magnesium aluminum silicate preferably cordierite
  • Boron nitride and / or the or at least one of the precursors for refractory solids used in step (a1) as the refractory substance of component (i) is selected from the group consisting of
  • Phyllosilicates preferably kaolinite, montmorillonite and lllite
  • Clays preferably kaolin and bentonite
  • step (a3) wherein the treatment according to step (a3) is carried out such that the bulk density of the resulting composite particles is less than the bulk density of the cured droplets in the dried state and / or said composite particles have a bulk density ⁇ 750 g / Have L, preferably ⁇ 500 g / L, more preferably ⁇ 350 g / L.
  • step (a3) and / or the composite particles used in step (b) at least partially have a particle size of less than 5.0 mm, preferably less than 2.0 mm , determined by sieving.
  • component (i) comprises one or more precursors for refractory solids as firing substances and the treatment according to step (a3) comprises a thermal treatment in which the precursors are converted to a refractory solid become, wherein preferably or at least one of the refractory solids precursors is a clay and the treating according to step (a3) comprises thermal treatment at a temperature in the range 900 to 980 ° C so that the clay is converted to a refractory solid, the clay preferably contains kaolinite and / or lllite.
  • step (a3) the hardened drops are treated, so that solid particles result as an intermediate, and then the surface of these solid particles is sealed, preferably by means of an organic Coating agent or a silicon-containing binder, so that said composite particles result.
  • step (b) mixing the composite particles prepared in step (a) with a binder comprising a binder component selected from the group consisting of
  • Boron compounds preferably boron oxide
  • Aluminum sulfate preferably (b) mixing the composite particles produced in step (a) with a binder comprising a binder component selected from the group consisting of - alumina cements,
  • Boron compounds preferably boron oxide
  • step (b) Sols of alumina, and optionally in step (b) or a further step after step (a) mixing with one or more further substances to produce a curable refractory composition, and optionally curing the curable refractory composition.
  • step (a3) are characterized by (A) thermal resistance at a temperature of 1600 ° C or higher, determined according to the sintering test, and / or
  • a matrix encapsulation method preferably using a nozzle, particularly preferably using a vibrating nozzle, for producing composite particles having a bulk density ⁇ 750 g / L, preferably ⁇ 500 g / L, particularly preferably ⁇ 350 g / L, in which Production of an insulating product for the refractory industry, which comprises a plurality of composite particles bound together by a phase acting as a binder.
  • An insulating product for the refractory industry or insulating material as an intermediate product for the production of such a product according to aspect 15, wherein the composite particles contained in the product or intermediate product are characterized by
  • (C) a grain strength> 1, 5 N / mm 2 , preferably> 2.0 N / mm 2 , more preferably> 3.0 N / mm 2 determined according to EN 13055-1, Appendix A, method 1, with a grain size in the range of 0.25-0, 5mm, and / or
  • Boron compounds preferably boron oxide
  • An insulating product for the refractory industry or insulating material as an intermediate for producing such a product additionally comprising one or more substances selected from the group consisting of:
  • Chamotte lightweight chamotte, corundum, hollow spherical corundum, sintered corundum, fused corundum, sintered mullite, enamel mullite, alumina, andalusite, kyanite, sillimanite, cordierite, clays, wollastonite, zircon mullite, zircon corundum, fly ash spheres and vermiculite.
  • A1 Process for the production of an insulating product for the refractory industry or of an insulating material as an intermediate for the production of such a product, comprising the following steps: (a) Producing composite particles having a particle size of less than 5 mm, determined by sieving, in a Matnx encapsulation process, comprising the following steps:
  • step (b) mixing the composite particles prepared in step (a3) with a binder comprising a binder component selected from the group consisting of
  • Boron compounds preferably boron oxide
  • step (b) optionally in step (b) or a further step after step (a) mixing with one or more further substances to produce a curable refractory composition, and optionally curing the curable refractory composition.
  • step (a1) the production of drops by means of one or more nozzles, preferably vibrating nozzles takes place
  • step (a2) the solidification of the solidifiable liquid is induced by cooling, drying or chemical reaction.
  • step (a1) is a chemical-solidifiable liquid and in step (a2) the solidification of the solidifiable liquid is induced by chemical reaction.
  • the solidifiable liquid is a cation exchange reaction solidifiable liquid, preferably a liquid solidifiable by reaction with calcium ions and / or barium ions and / or manganese ions, preferably by reaction with calcium ions.
  • the solidifiable liquid is a liquid solidifiable by reaction with calcium ions
  • the one or more binders selected from the group consisting of alginate, PVA, chitosan and sulfoxyethyl cellulose,
  • solidifiable liquid is preferably an aqueous alginate solution.
  • the or at least one of the in step (a) as a density reducing substance of component (ii) used light fillers preferably having a particle size smaller than 0.8 mm, more preferably smaller than 0.5 mm, most preferably smaller than 0.3 mm , determined by sieving, is selected from the group consisting of: inorganic hollow spheres, organic hollow spheres, particles of porous and / or foamed material, rice husk ash, core-shell particles and calcined diatomaceous earth and / or wherein or at least one of in step ( a) used as component (ii) pyrolyzable fillers is selected from the group consisting of:
  • the or at least one of the refractory solids used in step (a1) as the refractory substance of component (i) is selected from the group consisting of:
  • Oxides, nitrides and carbides each comprising one or more elements selected from the group consisting of Si, Al, Zr, Ti, Mg and Ca, Mixed oxides.
  • refractory solids used in step (a1) as the refractory substance of component (i) is selected from the group consisting of:
  • Magnesium aluminum silicate preferably cordierite
  • Boron nitride and / or the or at least one of the precursors for refractory solids used in step (a1) as the refractory substance of component (i) is selected from the group consisting of Aluminum hydroxide, magnesium hydroxide,
  • Phyllosilicates preferably kaolinite, montmorillonite and lllite, clays, preferably kaolin and bentonite, phosphates and
  • step (a3) wherein the treatment according to step (a3) is carried out so that the bulk density of the resulting composite particles is less than the bulk density of the cured droplets in the dried state and / or said composite particles have a bulk density ⁇ 750 g / L , preferably ⁇ 500 g / L, more preferably ⁇ 350 g / L.
  • step (a3) and / or the composite particles used in step (b) at least partially have a particle size of less than 5.0 mm, preferably of less than 2.0 mm by sieving.
  • component (i) comprises one or more refractory solids precursors as fire test substances and the treating according to step (a3) comprises a thermal treatment in which the precursors are converted to a refractory solid, wherein preferably or at least one of the refractory solids precursors is a clay and the treating according to step (a3) comprises thermal treatment at a temperature in the range 900 to 980 ° C so that the clay is converted to a refractory solid, the clay preferably contains kaolinite and / or lllite.
  • step (a3) the hardened droplets are treated so that solid particles result as an intermediate, and subsequently the surface of these solid particles is sealed, preferably by means of an organic Coating agent or a silicon-containing binder, so that said composite particles result.
  • step (b) mixing the composite particles produced in step (a) with a binder comprising a binder component selected from the group consisting of
  • Boron compounds preferably boron oxide
  • step (a1) as a further starting material for producing drops of a suspension and as a dispersed phase
  • colloidal silica preferably anionic colloidal silica, is used in addition to ingredients (i) and (ii).
  • A14. Method according to one of the preceding aspects, wherein the composite particles resulting in step (a3) are characterized by
  • (C) a grain strength> 1, 5 N / mm 2 , preferably> 2.0 N / mm 2 , more preferably> 3.0 N / mm 2 determined according to EN 13055-1, Appendix A, method 1, with a grain size in the range of 0.25-0, 5mm, and / or
  • Boron compounds preferably boron oxide
  • the product or the intermediate product can be produced by a method according to one of the aspects A1 to A1 1 and / or wherein the composite particles contained in the product or intermediate are characterized by
  • An insulating product for the refractory industry or insulating material as an intermediate for producing such a product additionally comprising one or more substances selected from the group consisting of:
  • Chamotte lightweight chamotte, corundum, hollow spherical corundum, sintered corundum, fused corundum, sintered mullite, enamel mullite, alumina, andalusite, kyanite, sillimanite, cordierite, clays, wollastonite, zircon mullite, zircon corundum, fly ash and vermiculite spheres.

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  • Chemical & Material Sciences (AREA)
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  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Insulating Materials (AREA)
  • Insulating Bodies (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)
EP18728150.6A 2017-05-30 2018-05-30 Verfahren zur herstellung von isoliermaterial oder eines isolierenden produkts für die feuerfestindustrie, entsprechende isoliermaterialien und produkte sowie verwendungen Withdrawn EP3630701A1 (de)

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DE102017111849.7A DE102017111849A1 (de) 2017-05-30 2017-05-30 Verfahren zur Herstellung von Isoliermaterial oder eines isolierenden Produkts für die Feuerfestindustrie, entsprechende Isoliermaterialien und Produkte sowie Verwendungen
PCT/EP2018/064201 WO2018220022A1 (de) 2017-05-30 2018-05-30 Verfahren zur herstellung von isoliermaterial oder eines isolierenden produkts für die feuerfestindustrie, entsprechende isoliermaterialien und produkte sowie verwendungen

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MX2019014337A (es) 2020-08-03
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