DE2016766A1 - Artificial stone and method of making the same - Google Patents

Description

2016768

Tatabanyai Szenbanyak / Tatabanya / Hungary KUMSTSTBIH QND YBRFiHREN TO HERSTBLUHG DESSELBEN

The invention beilent eloh on tintn highly hard abrasion-resistant, acid and baeefeeten, furthermore opposite Fluctuations in temperature resists the capable artificial stone and on the process of manufacture.

In the most varied of industrial worlds · especially Ip construction and the chemical industry are in large quantities of all raw materials eruptive rocks in the high

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and civil engineering and used for cladding, etc. There is a disadvantage to processing eruptive rocks in that they can only be machined by sawing and cutting.

The extremely hard, abrasion-resistant, acid and baaenfeaten eruptive rocks retain these beneficial properties physical and chemical properties after melting and casting, or after their recrystallization and are therefore suitable for the production of moldings, pipes and other molds. The known method for processing eruptive rocks is the material to melt at a correspondingly high temperature, pour it into molds and let it crystallize, then to cool off. Basalt species were primarily used for this purpose. The products made in this way are in the Industry known by the trade name "Molten Basalt".

The products made from such types of basalt are used in many fields. In the processing of the eruptive rocks after they were obtained (basalt, diabase, Baaanit, phonolite, etc.) are comminuted to particle sizes of 20-60 mm, and - depending on their chemical composition - melted 1400 ⁰ C - at a temperature between 1200th The melt is then left to stand and poured into molds. According to the molding process, the material is subjected to a heat treatment in a temperature range of 1000-700 ° C - usually in a tunnel oven - and then slowly cooled - generally within 20-22 hours. A common feature of these artificial stones is that their texture is micro-cryptocrietalline, possibly partially glass-like. The latter circumstance has an adverse effect on the otherwise favorable physically and cheaply properties.

Attempts have been made to use the mining dumps which accumulate in large quantities at power plants.

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achlacke, fly ash, ash, etc. carried out. These attempts however, did not produce any significant results. The low price of power plant slag, fly ash, etc. calculated on the weight of this waste material allowed only its use in the manufacture of cement, as an aggregate for concrete, as a filler for prefabricated components or as a Krotze, therefore these substances are either not used at all, or only to a limited extent.

The aim of the present invention is artificial stone from raw materials previously considered waste to manufacture. Artificial stones made from heaps of heaps, from power plant slag or from fly ash can be used as valuable raw materials in the construction industry as well as in the chemical industry.

The inventively produced, highly hard, wear-resistant, acid- and base-resistant, further resistant against Wärmeachwankungen artificial stone is characterized in that it is in the form of mainly 2-20 / do large crystals such Kristallgeniische contains that crystallize between 1200-900 ⁰ C and from 45-60 Gew.fc SiO _2, 15-40 wt.% trivalent (Al, Fe ³⁺⁾ metal oxides containing at least 40 wt j6 ^l Fe _2. O- contain further from 10-20 wt. $ divalent oxides and 1 -5 wt exist. # Alkalioxyden "wherein the magnesium-crystal mixture 55 ~ # 75 wt. # Labradorit-Feldspar consisting of albite ^ Q_4Q-AnortitgQ" _Q, 5-15 wt. monoclinic pyroxenes, 1-10 wt.%, rhombic pyroxene ( Hypersthen), 5-20% by weight oxide, advantageously contains spinel oxides and Fe ₂ O ^ -IiOdIfications.

The method according to the invention for producing a highly hard, abrasion-resistant acid and baaefest, compared to Artificial stone resistant to thermal fluctuations is characterized by the fact that freshly accumulating slag and / or fly ash and / or the material of the mountain heaps of coal mining, which has a melting temperature below 1500 C own, melted and the composition of the melt

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is adjusted by adding additives in such a way that these 45-60% by weight of 31O ₂ , 15-40% by weight of trivalent (Al, Fe metal oxides, namely at least 40% by weight of Fe ^ Oj and 10-20% by weight . divalent and contains 1-5 # alkali oxides, which will turn off Schmel ze gelaasen in a temperature range of 1500-1350 ° C, preferably bi3 escape the dissolved Gaae and in a temperature range of 1350 to 1200 ⁰ C in the form gegO38en and in a temperature range 1200-900 between ⁰ C, crystallized 0.5-4 hours such that it / jiigchen in the form of Kristallge mainly 55 ~ "75 percent".% Labradorit-Feld3pat consisting aua albite ^ ₀ _ ₄₀ -AnortitcQ_r, Q 5-15% by weight of raonoclinic pyroxene, 1-10% by weight of magnesium-containing rhombic pyroxene (hyperathene), 5 ~ 25% by weight of oxides, preferably spinel oxides and FeoO-i-iiodifications, with the crystallizing heat treatment under Maintaining a constant or gradually decreasing temperature gradient is listed and the ausk crystallized melt is cooled at a rate of 80-20 ° C / h.

The raw material Y / ird used to manufacture the artificial stone is supplied with heat from outside and / or is recycled the heat generated by the combustion of the combustible part of the raw material is melted. the Hard coal is expediently burned in a Zyklonkesael. In order to adjust the composition of the artificial stone accordingly, the necessary aggregates of the coal are used added, or after charging the combustion chamber a. The melt material that forms from the slag then becomes auo directly fed into the furnace for the production of artificial stone.

The necessary additives are preferably added in finely comminuted form. The aggregates can be rocks, minerals and in certain cases also inorganic compounds in oxide form.

Becomes a raw material with a high content of aluminum oxide

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used, fluorine- and carbonate-containing substances are used as additives, e.g. fluorite (cryolite), as well as K-, MgT Na- or Ca carbonate, also ankerite, siderite, red mud from the production of clay, or carbonate manganese ore. AIa aggregates proven 3% on the eruptive rocks or sediments Wehrllt, phonolite, granite, lpl | th, tuff, also dolomite, limestone, marl, Sandstone. In addition, carbonate and oxide-based manganese ores can also be used.

The KriatalliBations-Temperaturgradlent is set so that the melting material is kept in a temperature range of 1200 - 900 ⁰ C at a constant lowering temperature or a gradually lowering temperature. is in order to let the parts of the crystal mixture, which auakristailiaieren at a given temperature, carry out this process in practice.

The physical, mechanical and chemical properties of the manufactured artificial stone can be between wide limits can be varied. The melt can be easily poured and shaped and so stone slabs and other appropriate shapes can be poured. There is no need therefore the previously necessary cutting up of the stone blocks. Have the stone slabs made by casting a smooth surface that can be polished, so you do not need to make a suggestion. E ^ net even without polishing calibrate the artificial stone for cladding purposes. Sin advantage 1st, that as raw material mainly worthless or inferior Substances are used. Bs means a large economic part of the goal · that such the building sites on which the Slag fly ash and tailings accumulated and released

When working out the invention, one proceeded on the one hand from the knowledge that in thermal power plants slag, fly ash and ash from old coal combustion, but also the mountains of the mine dumps have a chemical

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ache composition that in some respects the chemical Composition of certain ultra-basic-basic eruptive rocks. The other finding was that with appropriate adjustment of the chemical composition and the viscosity of the melt and the appropriate choice of the crystallization conditions Kunststel ie can be produced in terms of their characteristics are similar to the volcanic peoples.

The method for producing the artificial stone according to the invention is explained in more detail below:

At the beginning the appropriately chosen raw materials and aggregates, if not in a molten state, melted. Does the raw material not contain any more combustible material, the melting takes place with the help of external heat supply. According to an expedient embodiment the raw material and the aggregates utilizing the inherent heat that is released when the combustible Burning substances of the raw material, melted.

The melting process can depend on the temperature and the physical state of the mixture, which after the combustion of the combustible ones present in the hard coal Substances left behind with the help of various technological Methods are carried out.

If you burn the coal in a kesael, where the Slag is melted, the slag enters the tepid}> the invention as a raw material is already in the melted State from the boiler. In this case, no further supply of heat is necessary for the melting process. Dependent • \ The additives are of their corrosive properties added to the coal either before charging the combustion chamber a of the boiler or immediately in the combustion chamber, or when the slag from the boiler let out. It is suggested the aggregates that are not corrosive to the coal in the combustion chamber to. because these catfish have their even distribution

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is guaranteed. This brings the aggregates into the armchair, homogenized with coal dust.

The additives are in a different form just tellirelae the coal In the firebox added. Ϊ3 lat advantageous the k-orroalven aggregate— to mix in the melt when it leaves the boiler.

If an armchair is used to burn the coal at which slag »fly ash, or yacht leaks at a lower temperature, must 'dlesea material be molten with the help of an external "supply of heat, while the additives are either the raw material or the Schmelze DelgegeDen will

It often happens that the slag used as raw material leaves the Xeasel at a relatively high temperature but in a solid state. DIEA iat the case 2,2, Ibein furnace Xettenroat, "in which the slag outlet at a temperature of ⁰ C .800-1000. Dieae Schlack" is dea utilizing melted anweaenden Wärmeinhalta in the slag, by passing through more l * rmezufuhr in the hearth heated beateht "Sine similar situation, irenn Aela Höhst off Plugaaehe is used by a temperature of about 100 ^0C. the convenient Yerfahrena variant s is then melt dea raw material mögllchat little heat energy benbtlgt. Ils Hohatoff or ZuaclilagBtoff can also - The mountains of the mine dumps are partially or completely used.The material is heated by the supply of heat from the outside in such a way that the "burning of the combustible coal contenta of the mine dumps contributes to the thermal energy necessary for melting. Burning can be promoted in this ialle by blowing in air.

The ingredients play an important role because they all enable the melting temperature, the ViaCoBlity lower the melt and the crystallization temperature. To reduce the YlBkoaltÄt the melt is the? luor and carbonate content of the melt is important because

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due to the viscosity of the same still in that temperature range can be adjusted accordingly where the solidification of the melt is disadvantageous. la needless to say au explain that depending on the original composition of the raw material in practice the composition and the amount of aggregate can be varied within wide limits. If e.g. the aluminum content of the raw material is relatively high, the Krlstalliaationsproß - In the absence of aggregates ■ unfavorably from or else such crystals precipitate that the properties of the artificial stone, e.g. its hardness, or adversely affect its acid resistance, or an unfavorable texture is formed. In such cases it is the addition of substances containing Oa and Ra is important, as this ensures the elimination of the neutral plagioclase is »whereby the formation of the mullite can be eliminated« The missing amount of SiOp can be eliminated by adding the Easily meltable rhyolite tuffs can be advantageously increased. By adding phonolite, the alkali content, by adding limestone the Ca content, with the help of dolomite the Ga-Mg content can be regulated or increased.

Optionally, the mixture is brought to melting in a furnace, and at a temperature of ⁰ C I5OO-I35O leave behind. The primary purpose of this shutdown area is to remove the gaseous products present in the melt . remove, ie to "clean" the melt. The low viscosity melt is now formed. The casting can be done according to the usual methods of metallurgy, eg casting, rolling and drawing. After shaping, the material is preferably crystallized in a tunnel furnace, the temperature gradient having to be maintained. The crystallized product is then gradually cooled.

The composition of the artificial stone according to the invention can from the chemical composition of the raw material

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and aas of the type of treatment are calculated in advance. the crystalline composition of this artificial stone agrees with the calculated values match well. The texture of the artificial stone is the texture of eruptive rocks more identical chemical Composition very similar.

The physical properties of the artificial stone according to the invention are as follows:
specific weight
Raumgeificht

Weight of water absorption (weight *) Suifatic crystallization 'acid resistance

Compressive strength after heat treatment Compressive strength (air dry) Compressive strength (saturated with water )

Druekfeatigkeiti (after 25-mallgeia freezing) p

Flexural strength 260-300 kp / cm ²

2,998 3
g / cm 0.1864 kp / cm. 2.85-2.864 g / cm ³ . 0.0321 * ο
kp / cm 0.2125 * p
¹ CpZ cm 3,900 4,500-6,200 5,400

calculated modulus of elasticity 9, PZ thermal Ausdehnungakoeffizient 12 »1 χ 10 'mm / C ⁰ W ^ä rmeleitungsfaktor. ^Ί , 1? kcal / h / ° C

The physical and chemical properties of the Artificial stone can be varied between wide limits. The melt can be easily shaped, it can be used » Stone slabs are poured, which are suitable for immediate utilization. The castability means an extraordinary advantage over the rocks, which initially Mined and then shaped and polished den must * The glass battens manufactured according to the invention have a smooth, polishable surface that does not have to be pre-sanded.

The procedure is explained in more detail in the following examples explainedi

example 1

For fly ash, containing: 49tO wt. * SlO ₂ , 17.5 O ₃ , 19.3 wt. * Fe ₂ O ₃ , 2.2 wt. * KgO, 7 * 7 wt. * CaO,

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2.0 wt. * Ha ₂ O and 2.7 wt. <J & SO ₃ , 3 wt.% Bauxite is added. The mixture is melted at 1300 ⁰ C and leave at I35O-I36O C gelaasen. After cast molding is crystallized for 3 hours at 1150 ⁰ C, then lä0t at a rate of 80-60 ° C / h to cool. The crystal grain size of the completely crystalline artificial stone is predominantly between 5 ~ 20 μm.

Example 2

BIe fly ash »according to the example!» is 5 wt. '% <bauxite and 5 wt.% tonigee ntangankarbonatiaches Sedim-jpt admixed. The mixture is melted at 1320 ⁰ C tasi 13 50 ° ü correct left and after pouring Fa for 3 hours at ⁰ C II50 crystallized. The crystalline Maane is cooled at a rate of Ί00-50 ° C / Ii. The predominant grain size of the crystals in artificial stone UeI.iact 2-20 to.

Example 3

Zui · fly ash, after Beiapiel l _r will J? üew ,; ' Tortig.-Mangankarbonatiaches Gea te Ln added. The mixture is heated at 1250-1300 ° c gericViiaolsen, at 1320-1350 ⁰ G aha share gelaasen kriatalltsiert and for 3 hours at 1150-1120 ° C, cooled achließlich 18 hours.

The forehead & e grain size of the crystals in the Kunafe— stone is between 2-15 / um.

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To fly ash, containing 55 _{% by weight of SiO., 30.3% by weight of Al 2} O ₃ , 7.2% by weight of Fe ₂ O ₃ , 2.1% by weight of MgO, 3.1% by weight. X * OaO, 1 »0 G <9W. ^ Na ₂ O and 0, ß Gew. # SO ₃ , becomes 10 Gew. I & Ι, ίπιοηί t-calcium carbonate» 3 Cew.'Jß · Sodium carbonate and 2 Gew. ^ tonir ^ catigankarbonatiecheo sediment beiötaln cht . The L is .ntach bet melted 1400 ⁰ C, stop at 1440 ⁰ O * allowed to crystallized after yormguO for 1 hour at 1200 ° C and from ⁰ C 12OQ bia 1000 ⁰ G with a Geachwindlgkölfc of 100 ° C / h, below 1000 ⁰ C, however, cooled at a rate of BO-50 ° e / h. The artificial stone produced has a microcrystalline 'texture'

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Claims (7)

PATENT CLAIMS Characterized in that it contains highly hard, abrasion-resistant, acid- and base-resistant Kunatateln geke η η ζ e ic h η et in the form of mainly 2-20 to large crystals, such crystal mixtures which crystallize between 1200-900 ⁰ C and from 45 -60 wt. # SiO ₉ , 15-40 wt. S trivalent {Al, Fe-) metalloids containing at least 40 wt.% Fe ₂ Oy, further from 10-20 wt. # Divalent oxides and 1-5 wt.% Alkali oxides exist, whereby the Krietallgemlsch 55-7.5 Gew. ^ Labradorit - Feldspar consisting of AIbIt ^ ₀ . _Q -. -AnortltgQ ^ Q, 5 ~ 15 Gew.gt monoclinic pyroxenes, 1-10 wt% magneaiumhältigen rhombic pyroxene (Hyper Athens), 5 ~ 25 Gew.g6 oxide, advantageously spinel oxides and Fe ₂ O ₃ modifications . 2. A method for the production of a highly hard, abrasion-resistant acid and base-resistant artificial stone, thereby k β η η ζ ei ch η et that freshly accumulating slag and / or fly ash and / or the material of the heaps of coal mining that have a melting temperature below 1500 ⁰ C, melted and the composition of the melt is adjusted by adding additives in such a way that these 45-60 wt .% SiO ₉ , 15-4O wt. S trivalent (Al, Fe) metal oxides, namely at least 40 wt. * Fe ₂ O ^ ^ and 10-20 wt. divalent and contains 1-5 # alkali oxides, the melt is in a temperature range of ⁰ C I5OO-I35O correct left, preferably up the dissolved gases to escape and in a temperature range of 1350-1200 ⁰ C. cast into shape, and crystallized in a temperature range between ⁰ C 1200-900 0.5-4 hours such that it, in the form of aua consisting mainly Kriatallgemischen 55 ~ 75 wt.% Labradorit-FeldBpar hbit ^ Q ^ _Q-60 lnortIt _n _Qt 5-15 Wt. * Monoclinic pyroxenes, 1-10 wt.% Magneaiumhältigen rhombic pyroxene (ltyperethen), 5-25 Gern Λ oxides vorzugeweiee spinel oxides and Fe ₂ OJ-containing modifications, wherein the krlstalllBierende W * rmebe- 009845/1280 BAD ORIGINAU action is carried out while maintaining a constant or gradually decreasing temperature gradient and the crystallized melt at a speed is cooled from 80-20 ° 0 / h. 3. The method according to claim 2, characterized in that the raw material with the help of external Heat supply and / or using their own heat combustible Mafcerlalteile is melted. 4. The method according to claims 2 and 3, characterized »that the coal is burned in a Zyklonkea'eel and the necessary additives before or after the coal has been charged into the furnace, the slag melt obtained is then fed directly to the artificial stone production. 5 · Method according to one of claims 2-4 »thereby marked * that as aggregates, preferably in finely divided form, rocks, minerals or inorganic compounds in oxide form are added to the raw material. 6. The method according to any one of claims 2-5 »thereby characterized · that to reduce the melting temperature, the viscosity and the crystallization water temperature »in the case of the use of an aluminum oxide saturated raw material F-, Cl- and carbonate-containing substances, like cryolite, fluorite, sodium chloride, Ca-, Mg-, Na- or K carbonate, also ankerite, siderite, limestone, dolomite, Carbonate manganese ore or red mud from the production of clay can be added. 7. The method according to any one of claims 2-6, characterized in that eruptive as an additive Rocks or sediments, namely Wehrlite, Phonolite, Granite, Aplith, tuff, dolomite, limestone, marl, sandstone or carbonate or oxidic manganese ores are used. 8. Method according to one of claims 2-7, characterized in that the crystallization 009845/1280 ORIGINAL BATHROOM '■■ - 13 - Temperature gradient so set-is "that the melt inside the Temperaturbereichea of 1200-900 ⁰ C to a certain temperature, at several itself sinking constant temperatures or at a plurality of stepwise decreasing temperatures is maintained until those Kristallasooziationen the mixture which crystallize at a certain temperature" almost completely eliminated. 009845/1280