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WO2006042755A2 - Corps moule servant a produire une masse fondue minerale destinee a etre defibree, pour produire des materiaux isolants a base de fibres minerales - Google Patents

Corps moule servant a produire une masse fondue minerale destinee a etre defibree, pour produire des materiaux isolants a base de fibres minerales Download PDF

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Publication number
WO2006042755A2
WO2006042755A2 PCT/EP2005/011293 EP2005011293W WO2006042755A2 WO 2006042755 A2 WO2006042755 A2 WO 2006042755A2 EP 2005011293 W EP2005011293 W EP 2005011293W WO 2006042755 A2 WO2006042755 A2 WO 2006042755A2
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WO
WIPO (PCT)
Prior art keywords
shaped body
body according
shaped
sheath
mineral
Prior art date
Application number
PCT/EP2005/011293
Other languages
German (de)
English (en)
Other versions
WO2006042755A3 (fr
Inventor
Gerd-Rüdiger Klose
Original Assignee
Deutsche Rockwool Mineralwool Gmbh & Co. Ohg
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 Deutsche Rockwool Mineralwool Gmbh & Co. Ohg filed Critical Deutsche Rockwool Mineralwool Gmbh & Co. Ohg
Publication of WO2006042755A2 publication Critical patent/WO2006042755A2/fr
Publication of WO2006042755A3 publication Critical patent/WO2006042755A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of waste materials, e.g. slags
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/02—Pretreated ingredients
    • C03C1/026—Pelletisation or prereacting of powdered raw materials

Definitions

  • the invention relates to a shaped body for the production of a mineral melt to be fibrillated for the production of insulating materials from mineral fibers, in particular rock wool, consisting of a primary or Sekundippoer ⁇ gielini, such as coke and / or mineral fibers to be melted and to be fibrillated Primary and / or secondary raw materials such as diabase or basalt and limestone and / or dolomite or slags, especially slags from the iron industry, for example blast furnace slags as Korrekturstof ⁇ fe and / or recycled material from Mineralfaserdämmstoffen, especially Weg ⁇ built Mineralmaschinedämmstoffe and / or production-related waste materials in the form of mineral fiber insulating materials, which are comminuted and formed into a shaped block.
  • a primary or Sekundipponic ⁇ gielini such as coke and / or mineral fibers to be melted and to be fibrillated
  • Primary and / or secondary raw materials such as diabase or
  • Insulating materials organically modified silanes, water glass or phosphate binders used.
  • Varieties is their different temperature resistance. ⁇ While so-called stone wool insulation 4102 Part 17 700 0 C melting point to DIN of> virtue of their che ⁇ mix composition melt glass wool insulation already in Tem ⁇ temperatures 1000 0C.
  • Rock wool insulation materials can be produced exclusively from rocks such as diabase or basalt, whereby limestone and / or dolomite can be added as corrective additives. These surcharges can also be completely or partially replaced by blast furnace slag and / or other slags from the iron industry.
  • slag wool Another starting material for the production of insulating materials from mineral fibers is so-called slag wool, which is melted from basic blast furnace hoses with silicate correction additives. These slag wools also meet the criteria according to DIN 4102 Part 17.
  • Insulating materials are therefore also required by circular economy and waste laws to find alternative sources of raw materials.
  • an ⁇ falling waste materials can be used as so-called secondary raw materials in the production of insulation materials made of mineral fibers, in particular in the production of insulating materials from mineral fibers.
  • the raw materials for the production of insulating materials from mineral fibers are melted with preferably high-quality foundry coke as the primary energy source in cupolas.
  • Cupolas are smoothly formed on their inner walls shaft furnaces with constant over its height inside diameters of approx.
  • the raw materials to be melted and fiberized and a primary energy source are introduced into the cupola furnace, wherein usually coke as a primary energy carrier with a proportion of about 12 to about 17% by mass. of the feed material is used.
  • the raw materials have diameters of about 80 mm to about 200 mm. With regard to the sizes and particle size distribution of the raw materials and the coke, a narrow com spectrum is desired in order to keep the flow resistance of the bed low.
  • a supply of air is required, which is blown over approximately 4 to 20, evenly distributed over the circumference of the shaft furnace arranged wind forms with pressures up to about 10 kPa in countercurrent to the cupola.
  • the cupola has upper furnace areas in which a slight negative pressure is generated and maintained.
  • the Gatt istsstrom closes the cupola from the top down and allows a controlled discharge of the exhaust gases, which contain, inter alia, CO gas.
  • the exhaust gases are fed to a downstream cleaning and Nachverbrennungs ⁇ system, so that the energy content of the exhaust gases used in a subsequent combustion chamber and at the same time harmful compounds, for example, by oxidation or destruction in less harmless compounds are converted.
  • the energy required for the subsequent combustion is supplied for example in the form of natural gas.
  • the energy content of the heated exhaust gases is used in each case via heat exchangers both for preheating the exhaust gases in front of the combustion chamber, but essentially for heating the supplied air.
  • the air is usually used in combination with exhaust gas cleaning temperatures of about 600 0 C, heated by additional heating devices to a maximum of about 800 0 C.
  • a hot blast resulting therefrom can additionally be enriched with oxygen.
  • oxygen nozzles are arranged directly distributed in a combustion plane on the circumference of the cupola furnace. These oxygen nozzles can act continuously or impulse-like act on the primary energy sources by regular opening and closing.
  • the oxygen nozzles may be arranged on slidable lances.
  • the primary energy source burns in the area of the bottom of the cupola furnace.
  • Combustion ends in a zone about 0.5 m above the tuyeres.
  • temperatures of> 1500 0 C having zone of the oxygen of the combustion air is used up.
  • an area of low altitude for example ⁇ 1 m, in which a temperature of up to about 1000 ° C. is reached. It is fundamentally advantageous to limit the range of high and very high temperatures above the tuyeres to a low level in order to avoid so-called upper fires.
  • the rocks arranged at a height of up to 1 m above the tuyeres melt and / or release their energy into the area above this zone to the feed material arranged in this area, so that the components of the slipping task are preheated.
  • the rocks and / or slags used as lumpy raw materials must not soften plastically at elevated temperatures, as does the energy carrier, since this increases the flow resistance of the bed and drastically reduces the melting performance. As a consequence, the coupler could become clogged.
  • the constituents of the bed must therefore be dimensionally stable at least up to temperatures of about 1000 ° C.
  • the temperature distribution in the cupola described above is therefore preceded by slow-reacting energy carriers, which burn off only after reaching a certain temperature level.
  • the above-described cupola furnaces are also usually driven down on a weekly basis because of the necessary cleaning of the downstream production units, the remaining contents of the cupola consisting of the melt and more or less melted or combusted constituents of the feed material being replaced by the cupola opened bottom flap can be removed ent.
  • siükatisch On the pig iron melt floats the specific lighter, siükatisch worked ⁇ formed melt into which, among other things, ash components of Primdocer ⁇ gieakis are melted.
  • siükatisch By a between the tuyeres and the bottom of the cupola, disposed designed as a siphon outlet is th the amount of up to about 155o 0 C heated silicate melt kept constant and in a substantially uniform mass flow to the Kupolo ⁇ downstream fiberizing fen passed.
  • cascade fiberizing machines may be used.
  • a nozzle-blow process in which the melt is blown out through nozzles and defibered.
  • Both in the nozzle-blow process and in the use of cascade fiberization machines in addition to the mineral fibers, considerable proportions of non-fibrous particles are produced, which, in agreement with the mineral fibers, are in glass form after cooling.
  • the coarser of these often spherical ones and ste ⁇ geligen particles can be separated from the mass of mineral fibers. Nevertheless, insulating materials produced in this way contain about 25 to 30% by mass of non-fibrous particles ⁇ 125 ⁇ m.
  • the mineral fibers are deposited after their exit from the Zerfaserungsvortechnische on a conveyor as an endless insulation web.
  • This Dämm ⁇ material web is processed in subsequent processing stations, for example, folded and / or compressed. Furthermore, the edges of the insulating material web are trimmed in the longitudinal direction.
  • waste or recycling materials which are processed here to so-called secondary raw materials, for example, blast furnace or steelworks slags and / or slags from coal-fired power plants in the form of so-called melted granules.
  • Other additives may be alumina carriers, such as calcined raw bauxite, or processed slags, dross, and dusts from the aluminum industry.
  • Ais binders are usually used as hydraulically hardening binders, such as Portland cements, in particular finely ground high-strength types of Portland cements, high-hydraulic limes and / or latently hydraulic substances, such as, for example, calcined sewage sludge, ashes from carcass disposal, residues from desulfurization plants of traveling grate boilers Pierverbrennung with appropriate exciters, such as quicklime.
  • Portland cements in particular finely ground high-strength types of Portland cements, high-hydraulic limes and / or latently hydraulic substances, such as, for example, calcined sewage sludge, ashes from carcass disposal, residues from desulfurization plants of traveling grate boilers Pierverbrennung with appropriate exciters, such as quicklime.
  • the moldings may have up to about 45% by mass of insulation waste, but because of their water-repellent properties, in particular the mineral fibers impregnated with mineral oils, they do not form any firm bonds with the binders of the moldings, so that the proportion of binders must be increased in order to obtain storage and transport, in particular pourable Form ⁇ body.
  • the required amount of binders with about 10 to about 20% by mass of Portland cement or equivalent acting binder is limited to an economic level and on the other hand, the moldings obtain a sufficient total, in particular a sufficient edge strength.
  • the moldings are therefore densified to densities of about 1,200 to about 2,000 kg / m 3 , preferably to densities of about 1450 to about 1700 kg / m 3 .
  • the moldings contain organic constituents, in particular in the form of very finely divided organic binders, which are pyrolyzed even at relatively low temperatures, so that their energy content is not directly usable for the actual melting process in the cupola furnace, but in the flue gas cleaning plants or the like coupled heating systems for heating the
  • the porous moldings interspersed with microcracks easily absorb water, so that they should be protected against precipitation and thus also against exposure to low temperatures.
  • the drying of the moldings takes place under atmospheric conditions, although preferably under protective roofs.
  • the heating and evaporation of the proportion of free water in moldings under normal storage conditions in the order of about 7 to 15% by mass and expelling hydrolyzed by cement minerals ge bound crystal water requires appropriate additional amounts of coke or other energy sources, the formation of water vapor can Although it improves the heat transfer in the upper areas of the cupola furnace, it has also wanted side effects on the gas budget.
  • the water vapor loads downstream thermal exhaust air purification systems.
  • the molding of relatively dry masses of the moldings are widely used in the building materials industry.
  • the shape, size and weight of appropriately formed moldings are suitable for cleaning in the existing conveying and storage facilities and, on the other hand, do not adversely affect the flow resistance of the bed in the cupola.
  • the individual weights of the moldings are also similar to the coke particles, so that separations in the bed can be avoided.
  • the shaped bodies should not differ significantly from the coarse-grained homogeneous natural rocks and thus do not plastically soften at elevated temperatures or form melting eutectics at low temperatures. Both, however, may be desirable as local appearance within the moldings.
  • the moldings are the cupola furnace usually together with coarse fractions of the bed and the equivalent sized primary energy source
  • the moldings may be a cube shape with edge lengths of, for example, 80 mm to about 150 mm or in corresponding brick formats, for example, normal format or double format according to DIN 105. Larger moldings generally require longer drying times and thus often too long from an economic point of view.
  • the solid high-temperature coke to be used as the primary energy carrier in particular the foundry coke known by way of example, is scarce and therefore relatively expensive and, moreover, exposed to severe price fluctuations on the world market, especially in the required grain classes.
  • Petroleum coke is used, inter alia, for the cathodic lining and for the anodes of aluminum
  • the release of gaseous constituents, including high levels of vapor, the swelling of the coals at elevated temperatures, and the resulting drop in strength also preclude the direct use of
  • Carbon stones or corresponding masses are refractory building materials, which are first bound with tar pitch. At high temperatures, volatiles are expelled so that broken particles of the refractory building materials or an outbreak, such as coke and graphite particles, can be treated to a great extent.
  • Teer-bound basic dolomite, magnesia or bound chromium-magnesia stones and ramming masses contain the formed graphite in pores after the volatiles have fumed.
  • Industrial pellets of conditioned natural biomass consist of wood and / or mixtures with other renewable raw materials, such as trays, vegetable residues. These biomasses are pressed, for example, as pellets with briquettes or other shaped bodies, with particle sizes of up to about 30 mm.
  • Posidonia schist is known, which is named after the mussel Posidonia Bronni considered to be the leading fossil.
  • Posidonia schists of the Lias formation in southern Germany can contain about 10% by weight, in some horizons up to 20% by weight of organic material, which in turn is 80-90% in the form of so-called kerogens.
  • Kerogens are high molecular weight, simultaneously high-polymer hydrocarbons
  • the calorific value of the slate is given with a average content of organic substance of 11.2 mass% with about 3900 kJ / m 3 .
  • the calorific values of hard coal are approx. 29,300 kJ / kg, of brown coal approx. 8,000 kJ / kg.
  • the finely ground burnout is latently hydraulic to hydraulic and, after joint grinding with Portland cement clinker, produces a reddish-brown colored cement whose strength level is, however, lower than that of normal Portland cements.
  • Finely milled slate is burnt together with limestone, quartz sand and clay in the rotary kiln to cement clinker, which naturally here the sulfide content in the slate for the product are not detrimental.
  • the finely ground burnt out gestei ⁇ ne were used as strengthening additives in the production of structural panels or aerated concrete.
  • Refractory building materials are gebun ⁇ with water glasses or phosphate binders. Carbon-containing refractory building materials in the form of shaped bodies or staple masses are bound with coal tar, the volatile constituents being driven off either at a place of use by a heating process or by careful heating.
  • briquettes are suitable as additional fuel of mineral material in the production of slag wool and coke and / or coal particles and a hydraulic binder, wherein the briquettes at least 8% of the dry weight Contain binder and contained in the briquettes fine coke and / or
  • Carbon particles have a particle size of more than 2 mm and further as further ren constituents fine oxide-containing, mineral particles having a particle size less than 2 mm.
  • binder Portland cement is provided in an amount of 8 to 35% of the dry weight of the briquette.
  • the oxide-containing mineral Particles are selected from the materials sand, slag, stone dust, fly ash, lime stone dust, dolomite dust, silicon dioxide, slag wool sawdust or any other waste materials obtained in the slag wool.
  • DE 195 25 022 A1 discloses a heatable, solid shaped article and method for its production, the main components of which are coke particles and cement.
  • the coke particles are formed by coke breeze.
  • the previously known shaped bodies are only conditionally suitable for replacing the primary energy carriers or the raw material, since their strength leads to an insufficiently abrasion-resistant or dimensionally stable shaped body due to the materials or mass fractions used.
  • the invention is therefore based on the object of providing a generic molded article which does not have the disadvantages of the molded articles known from the prior art and which has a shape which is particularly advantageous for the melt process in a melting unit and which is simpler and more economical Way can be produced.
  • the shaped block is of circular, elliptical or regular circular arc shape in cross section, at least in a large body axis.
  • the shaped block is polygonal in cross section at least in a large body axis, wherein the shaped block has surfaces which converge towards one another at obtuse angles.
  • Form stone is designed as a cube with an edge length of more than 200 mm, in particular up to 300 mm, preferably between 200 and 250 mm.
  • the abovementioned alternative solutions to the problem form shaped bodies which permit an ordered arrangement in a melting unit, for example a cupola furnace, the design of the shaped bodies enabling good gas diffusion through a heap formed from them.
  • the shaped bodies according to the invention can be produced in an economical production process, it being possible in particular to use conventional presses.
  • the shaped bodies according to the invention have the advantage that they can be used as energy carriers and / or as raw material carriers, depending on their material.
  • the shaped body can have a shaped block which is coated with a layer of a binder, in particular a thin layer of a cement paste.
  • This layer behaves on the impact of the molding substantially tough elastic and tends only in the immediate deformation area to flake off.
  • both the steam and the coagulating organic constituents can escape without unfolding explosive effects.
  • the layer of cement paste on the shaped brick also prevents or prevents the oxidation of the primary energy source by the carbon dioxide CO 2 formed during the reduction of the iron oxides.
  • the thin layer of cement paste can be reinforced by additions of ground [mineral fibers together with the comminuted non-fibrous particles, which are optionally contained therein. Their proportion is limited with respect to the binder to a maximum of 20% by mass, but preferably ⁇ 8% by mass.
  • the shaped brick can subsequently be immersed in a suitable binder-containing slurry or sprayed onto this slurry.
  • the binder is preferably arranged in a thin layer fully or partially on the molded block.
  • the binder consists of waterglass, phosphate binder, phosphate cement as a mixture of metal oxides with phosphoric acid and / or organically modified silanes.
  • the binder is provided as a coating in a carbon-containing fraction of high-temperature coke, petroleum coke, pitch coke and / or graphite.
  • the coated molded block is inserted into the sheathing in order to further improve the strength of the shaped body.
  • This alternative has proven to be particularly advantageous if the molded block has a volume that is smaller than the volume of the envelope, so that relative movements of the molded block to the jacket would lead to abrasion of the molded block.
  • the shaped block may have a carbon-containing fraction having at least two particle size classes, of which a particle size class at least 50% by mass, which has a particle size ⁇ 25 mm and thus fills interspaces, which are arranged between the particles of grain size class ⁇ 25 mm.
  • the packing density of> 1,250 kg / m 3 of Be ⁇ interpretation since this packing density is achieved by a pressing process in which, in conjunction with the particle size distribution can produce a molded body, the by its abrasion and shape stability for the mentioned purpose is particularly suitable.
  • This molded block is coated with a sheath or inserted into a sheath, as will be described in detail hereinafter.
  • fine-grained fractions When breaking up freshly produced coke, about 50% by weight of fine-grained fractions are formed, but these can not be used as fine-grained constituents for the operation of a cupola furnace.
  • the fine-grained fraction of the coke or another solid carbon-containing primary energy carrier for example refractory outbreak substances or anodic linings of smelting furnaces or electrode material with coarser carbonaceous particles, which form a scaffold for receiving the fine-grained fraction, it is possible to to create a free-flowing and abrasion-resistant molded body, which in particular special as a primary energy source for the production of mineral wool melts is operational.
  • Portland cements including Portlandölschieferzemente, Tonerdeschmelzze ⁇ elements and latent hydraulic substances with appropriate exciters as Binde ⁇ medium for Hochtemperaturkoks- or graphite fractions can be used.
  • the selection of the binders also depends on the desired development of strength of the shaped bodies, with the alumina cements developing very quickly sufficiently high strengths, which under certain circumstances may justify their substantially higher price.
  • Coke and graphite particles with grain sizes ⁇ 50 mm, preferably ⁇ 25 mm are intensively mixed with the hydraulic binders.
  • the particle size distribution of the carbon-containing fraction is selected such that the coarser constituents form a scaffold, while the finer particles only fill the intermediate spaces to such an extent that a sufficient packing density and thus a load-bearing molded body result, but at the same time has a certain permeability , It is advantageous in this case to use a carbon-containing fraction having a broad particle size range different grain size classes and to mix these in corresponding gradations and different proportions in order to press the corresponding shaped bodies from them.
  • the mixing process can be carried out in two stages, first by the carbonaceous
  • Particles with Portland cement optionally with the addition of redispersible Netz ⁇ medium and / or adhesion-promoting and strength-increasing redispersible plastics are mixed before then mixing water is added in the next mixing stage.
  • the cement content is about 12 to about 30 mass%, preferably ⁇ 25 mass%.
  • the carbonaceous fraction is then pressed into shaped bricks.
  • the gross densities of these conglomerates are more than about 1250 kg / m 3 .
  • the carbonaceous fraction may be fine-grained and consist of coke, graphite and / or carbonaceous compounds, in particular refractory outbreaks or anodic linings of smelting furnaces and / or preferably consumed electrode material.
  • the binder is thermally stable and preferably consists of Portland cement, Portlandölschieferzement, Tonerdeschmelzzement and / or la ⁇ tenthydraulischen substances with stimulators, especially free lime-containing substances, such as hydrated lime or cement.
  • the carbon-containing fraction and / or the binder are redispersible wetting agents, for example surface-active substances and / or adhesion-promoting and / or strength-increasing redispersible agents
  • Plastics such as acrylate, styrene acrylate and / or copolymers.
  • the carbon-containing fraction is preferably bonded with 12 to 30% by mass, in particular with 15 to 25% by mass of binder, so that the outstanding
  • the support com consists of a mineral melt to be shredded for the production of insulating materials from mineral fibers, in particular rock wool, suitable rock and / or secondary raw materials. This embodiment ensures as far as possible residue-free melting, wherein constituents of the primary energy carrier pass into the melt and contribute to the formation of the mineral fibers.
  • carbon coke is suitable insofar as its content can be limited to ⁇ 30% by weight of the foundry coke or graphite or a mixture of both, and the support structure made of solid dense high-temperature coke or graphite, optionally supplemented by supporting grain from rocks or comparable secondary substances.
  • the cube-shaped moldings can have edge lengths of up to approximately 300 mm. Edge lengths of approximately 200 to 250 mm have proven to be advantageous, since the shaped bodies are still dimensionally stable with such edge lengths and do not disintegrate in the cupola furnace even under the influence of temperature.
  • the carbon-containing fraction with the binder and the optionally present supporting grain and / or the optionally present envelope is arranged as a filling in a load-bearing and / or temperaturbe ⁇ permanent sheath.
  • the carbonaceous fraction bound in this way with hydraulic binders can thus be treated with raw material-containing, i. the desired melt-forming masses together form a shaped body.
  • raw material-containing i. the desired melt-forming masses
  • special shapes of the molded articles from the primary energy source and the raw material can advantageously affect the melting process. Such shapes will be described below.
  • the shaped bodies can also be made of natural rocks and / or other secondary raw materials, if appropriate with fractions of primary energy sources and suitable binders.
  • the filling is arranged in briquetted form or as a bed in the sheathing.
  • the Ummante ⁇ ment at least in some areas an air permeability for the controlled Ent ⁇ gassing of the filling, in order to avoid too high a pressure in the sheath. Such a pressure could lead to damage or destruction of the casing, so that a controlled release of energy or a controlled melting of the raw material is not possible.
  • the casing consists of a rock fraction, in particular of minerals for the production of a mineral melt for the production of insulating materials from mineral fibers, preferably rock wool, suitable rock and / or secondary raw materials, which are bound with hydraulic binders.
  • This embodiment provides a shaped body which serves both as a primary energy carrier and as a raw material carrier.
  • sheath als ⁇ an outer circumferential surface, on which a, in particular fine-grained rocks and / or mineral fibers having coating layer of hydraulic binders is arranged.
  • the casing has according to a further feature an opening which can be closed with a lid.
  • an opening which can be closed with a lid.
  • Such a trained sheath has a high abrasion resistance and is particularly suitable for the pouring of a cupola furnace.
  • the hydraulically hardening binders are partially substituted by hydraulically setting or latently hydraulic secondary raw materials or by latently hydraulic pozzolans, tufts with stimulators, in particular free lime-containing substances, for example carbohydrate or cement.
  • a geometry of the casing has proved to be advantageous in which the casing has a length and / or a diameter whose ratio to one another is 1: 1, preferably 1.2: 1 to 2.5: 1.
  • the casing and / or the molded block has a center of gravity which is arranged eccentrically on the longitudinal axis of the shaped body.
  • the complete and firm enclosure of the filling in the casing is achieved by the fact that the lid, which is preferably formed from a material which corresponds to the material of the casing, is pressed into the casing after it has been filled with the filling.
  • a development of this embodiment provides that the casing has a recess which serves to receive the lid.
  • the lid has at least one predetermined breaking point at which the lid breaks at a certain pressure. Furthermore, for targeted control of the melting process is the advantageous feature that the sheath has at least two chambers for receiving under ⁇ different fillings.
  • the chambers by a
  • Wall of ground mineral fibers and / or from the material of the shell matching cement-bonded molding compounds are separated.
  • the chambers are subdivided transversely to the longitudinal axis of the sheathing. Furthermore, the invention can be further developed was ⁇ that the sheath is divided by extending parallel to the longitudinal axis webs into individual chambers.
  • the casing has in the region of a wall a perforated disk or at least one opening through which volatile constituents can escape.
  • the filling and / or the casing are rotationally symmetrical.
  • the filling and / or the Ummante ⁇ ment have a cylindrical or prism-shaped cross section and preferably a curved to hemispherical end face and a face opposite the end face arranged contact patch. Both the storage and the orientation of the moldings in the cupola furnace can thereby be influenced in a particularly advantageous manner.
  • silicate glasses instead of hydraulically setting substances, also silicate glasses, phosphate binders, phosphate cements as mixtures of metal oxides with phosphoric acid and organically modified silanes as binders preferably in conjunction with high-temperature coke; petroleum coke; Pitch coke or graphite are used, which have solid surfaces.
  • the reinforced surface layer of the described, usable as filling shaped blocks forms the transition to the load-bearing and temperature-resistant sheath, the sheathing and the filling are to be understood in the sense of small reactors.
  • these small reactors may contain, in particular, primary energy carriers which, on heating, release volatile substances and thereby inflate. Such reactions are to be considered in the design of the sheathing body and the respective degree of filling.
  • the released volatiles may be due to the intensification of
  • Energy transfer to the raw material particles substantially intensify the melting process or replace part of the primary energy carriers in the furnace bed.
  • the energy-containing volatiles are withdrawn in the upper part of the Ku ⁇ polofen and burned in a downstream combustor.
  • the energy content ultimately serves to preheat the combustion air.
  • Various primary energy carriers can be introduced into this casing as shaped blocks, in bonded, for example in briquetted form, or as a fine-grained packing.
  • shaped blocks in bonded, for example in briquetted form, or as a fine-grained packing.
  • inorganic and organic binders naturally fine coal is suitable for briquetting or coal tar pitch.
  • polysaccharides, Me ⁇ can be used or the like.
  • Figure 2 shows a second embodiment of a shaped body in a sectional side view shown
  • Figure 3 shows a third embodiment of a shaped body in a sectional side view shown
  • Figure 4 shows a fourth embodiment of a shaped body in a sectional plan view shown
  • Figure 5 shows a fifth embodiment of a shaped body in side view
  • FIG. 6 shows the shaped body according to FIG. 5 in plan view
  • FIG. 7 shows a sixth embodiment of a shaped body in a side view
  • FIG. 8 shows the shaped body according to FIG. 7 in plan view
  • Figure 9 shows a seventh embodiment of a shaped body in a sectional side view
  • Figure 10 shows an eighth embodiment of a shaped body in a sectional side view
  • Figure 11 shows a ninth embodiment of a shaped body in a sectional side view
  • FIG. 12 shows the shaped body according to FIG. 11 in plan view
  • FIG. 13 shows a tenth embodiment of a shaped body in a sectional side view
  • FIG. 14 shows the shaped body according to FIG. 13 in plan view
  • Figure 15 shows an eleventh embodiment of a shaped body in plan view
  • Figure 16 shows a twelfth embodiment of a shaped body in plan view
  • FIG. 17 shows the shaped body according to FIG. 16 in a sectional view, shown in section, along the section line VXII - XVII in FIG. 16;
  • FIG. 18 shows the shaped body according to FIG. 16 in a sectional view cut along the section line VXIII-XVIII in FIG. 16;
  • FIG. 19 shows a thirteenth embodiment of a shaped body in a top view
  • FIG. 20 shows the shaped body according to FIG. 19 in a sectional view cut along the section line XX-XX in FIG. 19 and FIG
  • Figure 21 is a fourteenth embodiment of a shaped body in marnit ⁇ th illustrated side view.
  • FIG. 1 shows a shaped body 1 which can be used as a primary energy source for the production of a mineral melt to be fiberized for the production of insulation materials from mineral fibers, in particular from rock wool.
  • the molded body 1 can be used as a primary energy source for the production of a mineral melt to be fiberized for the production of insulation materials from mineral fibers, in particular from rock wool.
  • the carbon-containing fraction consists of a molded block V of a bound with a binder fine-grained and carbon-containing fraction.
  • the carbon-containing fraction has a maximum particle size of 50 mm, wherein at least half of the carbon-containing fraction has a particle size ⁇ 25 mm.
  • the coarser constituents of the carbon-containing fraction form a supporting framework (not shown), while the finer constituents having a particle size of ⁇ 25 mm fill the intermediate spaces in the supporting framework.
  • the carbonaceous fraction and the binder have a packing density of 1,250 kg / m 3 .
  • the molded body 1 is round in cross-section and has at its one end 2 a conical section 3rd
  • FIG. 1 further shows a casing 4, which has a receiving space 5 into which the molded block is completely inserted, so that inner wall surfaces 6 of the receiving space 5 abut on the outer wall 7 of the molded piece V as completely as possible.
  • the casing 4 is cylindrical and has a peripheral wall
  • the bottom 9 has an increased thickness relative to the wall 8 and moreover has a conical depression 10, which is formed corresponding to the ko ⁇ nischen section 3 of the molded block.
  • a lid 11 is arranged, which the receiving space 5 above the
  • Formstones 1 ' closes.
  • the molded block 1 'thus represents a filling 12.
  • the Ummanteiung 4 consists of rock fractions and / or Sekundärrohstof ⁇ fen, which in the production of mineral fiber insulation in the course of the manufacturing process as, for example, sections, faulty products or derglei ⁇ chen incurred. Furthermore, such secondary raw materials may also be available in the course of recycling demolished mineral fiber insulating materials.
  • the casing 4 has a high mechanical and thermal stability at the same time high air permeability.
  • the rock fractions and / or secondary raw materials are bound together by hydraulic binders.
  • the air permeability of the sheath 4 enables a controlled release of the molded block 1 ', which is located within the receiving space 5 and represents the filling 12, which serves as an energy source in a melting process in a cupola (not shown).
  • the controlled degassing of the molded block 1 'takes place via the wall 8, the cover 11 and the bottom 9 under the influence of temperature expanding molded block 1 'the shell 4 is subjected to increased gas pressure, so that it comes to a damage of the casing 4.
  • a regulated gas pressure within the casing 4 for example the expansion pressure of coal, low-temperature coke or other energy sources, on the other hand, serves to support the casing 4.
  • the strength of the casing 4 can therefore be reduced to form the casing 4 so permeable to air, that a delayed energy release of the molded block 1 'is possible.
  • Cover 11 have a thin layer of a hydraulic not shown Bin ⁇ deffens.
  • This hydraulic binder can be reinforced by fine-grained rock fractions or secondary raw materials, namely in particular waste fibers. Such a layer can be applied by dipping or spraying the sheathing 4.
  • the casing 4 is pressed as a body open on one side. Subsequently, the molded block V is inserted into the body of the casing 4 and the Ummante ⁇ ment 4 closed by the lid 11.
  • the cover 11 has circumferentially a projection 13 which engages in a korrespondie ⁇ ing recess 14 formed in the inner wall surface 6 of Ummante ⁇ ment 4.
  • the recess 14 may be formed, for example, as an undercut, which is introduced in the region of an upper edge of the casing 4 with a friction screw press.
  • the casing 4 may also consist of haufwerkporigem mortar or concrete, with aggregates of rocks, slags and mineral fiber waste and hydraulically hardening binder, such as Portland cements can be provided.
  • the hydraulically hardening binders can be at least partially substituted by hydraulically setting or latent-hydraulic secondary raw materials, respectively latent-hydraulic pozzolans or tufts with corresponding exciters, if a sufficiently long storage time for hardening is granted.
  • the wall thickness 8 of the lid 11 corresponds to the material thickness of the wall 8.
  • the wall thickness is adapted to the required strength of the shaped block 1 'and the casing 4, wherein In particular, the transport and storage of the combination of molded block 1 'and sheathing 4 and on the stresses during the furnace journey rub ⁇ view is to take.
  • the design of the bottom 9 with the conical recess 10 in combination with the conical section 3 of the molded block 1 'and the high packing density means that the combination of coating 4 and shaped block V is not closer, particularly in the bed
  • the cupola arranged in the desired manner aligns the cupola so that the combination of shaped brick V and casing 4 is arranged substantially in the orientation shown in FIG. 1 in the bed.
  • the combination of molded block 1 'and sheath 4 shown in FIG. 1 has a ratio of length to diameter of 1: 1. By changing this ratio up to 2.5: 1, the above-described effects with respect to alignment in the cupola furnace can be further improved.
  • the above-described molded block 1 ' which may consist of a primary energy source, for example coke or another carbon-containing fraction, is preformed and pressed. But it is also possible to fill the primary energy source or another carbon-containing fraction in several stages as a loose bed up to a certain height in the casing 4 and to press there. Of course, it is alternatively also possible to pour the primary energy carrier or the carbon-containing fraction completely into the casing 4 and then to compress it before the lid 11 is formed in both cases by a mortar / concrete mixture a composition corresponding to the casing 4 is finally filled in and pressed with the primary energy carrier or the carbon-containing fraction and the casing 4. The lid 11 may alternatively have a deviating from the casing 4 composition. Due to the procedure described above, all components are compressed to the density which is possible and desired by the type of substances and their particle size distribution.
  • the recess 14 at the upper edge of the Ummanteiung 4 is particularly advantageous if the lid 11 is formed of a lower compared to the wall 8 and bottom 9 permeable molding compound or a pourable and finally strongly dwindling mass.
  • the positive connection zwi ⁇ tween the lid 11 and the Ummanteiung 4 prevents the lid 11 is separated at the different stresses during storage, transport and loading of the cupola of the Ummanteiung 4, the lid 11 can also in such a way be dimensioned that it tears under thermal loads, namely at too high an internal pressure, but does not fall out of its anchorage in the Ummanteiung 4.
  • the lid 11 may have a predetermined breaking point, not shown. The cover 11 thus prevents the falling out of the molded block 1 'or a comparable bed of material from the Ummanteiung. 4
  • coal, coke, graphite, activated carbon or soot can also wood waste, bark, waste wood, chips and dusts from wood and paper processing, chipboard chips and shreds, Textil ⁇ snippets, peanut shells, cotton stalks in briquetted form as a molded block 1 'or filling 12 are used.
  • a second embodiment of a shaped body 1 is shown with a form-stone V, which is formed in two parts and has portions, wherein a release layer 15 is disposed between the sections of the shaped block 1 1 which extends transversely to the longitudinal axis of the sheath 4 and adjoins the inner wall surface 6 of the casing 4.
  • the two sections of the Form ⁇ stone 1 ', which are separated by the separation layer 15 from each other, may be identical or different. This applies in particular with regard to the composition of the primary energy carrier or of an alternative fraction containing carbonyl.
  • a deviating lid 11 can be seen, which is essentially T-shaped in cross section, so that the lid rests on an end face 16 of the wall 8 of the casing 4, while one with the inside diameter the sheathing 4 matching section 17 sealingly engages in the receiving space 5 of the casing 4.
  • a positive connection according to FIG. 1 can also be provided, in which case a corresponding projection 13 and a corresponding recess 14 are integrated into the inner wall surface 6 and the lid 11, respectively ,
  • the shaped block 1 'can consist of a pelletized, briquetted or otherwise compressed energy carrier and can be stretched by broken kerogens containing the slate and / or ground insulation waste and thus be braked in its reactivity.
  • a similar effect is achieved by the Trenn ⁇ layer 15, which divides the molded block V into two sections.
  • the separating layer 15 thus leads to a combination of a shaped block 1 'and a sheath 4, in which the sheath 4 has a multi-chamber structure.
  • FIG. 4 has a polygonal cross-section casing 4 whose receiving space 5 is subdivided into four chambers by right-angled partition walls 18, each receiving part of a shaped block Y.
  • the individual parts of the molded block 1 ' can again be formed identically or differently, in particular, different compositions of the individual parts of the molded block 1' can be provided.
  • FIG. 3 shows a further embodiment of a molded block 1 'arranged in a casing 4, wherein it can be seen that, in contrast to the embodiment according to FIG. 1, the bottom 9 is designed as a perforated plate with degassing openings 19 and a form fit into an opening of the casing 4 is used.
  • the bottom 9 in the region of its edge on a umlau ⁇ fenden projection 20 which engages in a corresponding recess 21 of the wall 8.
  • the projection 20 and the recess 21 are formed in a semi-circular cross-section to facilitate the insertion of the bottom 9 in the casing 4.
  • a further degassing opening 19 is arranged in the lid 11, the design of which is otherwise associated with the
  • the degassing opening 19 in the lid 11 is arranged centrally. It can be seen that the degassing openings 19, which are arranged centrally in the cover 11 and in the bottom 9, are conical and constrict towards the shaped block V. In contrast, the degassing openings arranged eccentrically in the bottom 9 are cylindrical. A defined degassing of the molded block 1 'is possible via the degassing openings 19 in order to regulate the gas pressure within the casing 4.
  • Shape design of these individual melt-containing moldings 1 and the energy-carrying shaped stones 1 ' may be different in shape, size, weight and Festig ⁇ speed, with a vote on each other is possible.
  • shape of the cupola, the distribution of the moldings 1 in the oven, the transport of the moldings 1 to the oven and the feed plays an essential
  • the moldings 1 are mechanically loaded in this case and should in particular be made resistant to abrasion and breakage.
  • FIGS. 5 and 6 show a shaped block 1 'in a side view (FIG. 5) and in a plan view (FIG. 6).
  • the molded block 1 ' is designed in the shape of a double-pyramidal truncated shape and consists of a primary energy source.
  • the shaped block 1 ' has a cuboid central region 22 with a square base surface.
  • Truncated pyramid-shaped elements 23 are arranged on both sides of the middle region 22, wherein a truncated pyramid-shaped element 23 can consist of a primary energy carrier and the further truncated pyramidal element 23 of a melt-forming substance.
  • the truncated pyramidal elements 23 have square end surfaces 24th
  • the molded block 1 'can also ei ⁇ NEN middle region in the form of a circular disk, wherein the elements 23 can then be frusto-conical.
  • the molded block 1 ' accordinging to FIGS. 5 and 6 represents a simple geometric shape with which hybrid forms can be realized by bonding bonded energy carriers with melt-forming substances.
  • FIGS. 7 and 8 show further embodiments of a rotationally symmetrical shaped block 1 '.
  • the elements 23 are formed with concave surfaces.
  • the elements 23 have a round or polygonal cross-section, but extend in each case as far as an end face 24.
  • the edge regions of the molded block 1 ' are formed with increased edge strength.
  • the shaped block Y can additionally have an opening 25 running parallel to the longitudinal axis, which serves to degas the shaped block Y or flow through the shaped block 1 '.
  • the concave surfaces of the elements 23 serve to improve the degassing and flow through a arranged in a cupola not shown bed of moldings 1, as by the concave surfaces dense concerns neighboring mold blocks Y is not possible.
  • Central portion 26 has, which is designed as einschaliger Rotationshyperboloid.
  • a circular disc portion 27 is arranged an ⁇ , wherein the material thickness of the disc portions 27 may be identical or un ⁇ different formed, for example, an orientation of the molded block 1 'in the introduction of the molded block Y as a bed in the Kupol ⁇ cause to be able to.
  • FIG. 11 shows a further embodiment of a molded block 1 ', which may have a round or polygonal cross-section.
  • the 11 has two disk sections 27 and a middle section 26, wherein the diameter or the width of the central part 26 telabschn ⁇ tts 26 is smaller than the diameter or the width of Scheiben ⁇ sections 27.
  • the disc sections 27 have at its the central portion 26 facing the end of an inclined surface 28, wherein the central portion 26 is aligned centrally with the disc portions 27.
  • An opening 25 is provided transversely to the longitudinal axis of the middle section 26 which in turn serves to improve the flowability of a bed formed from such shaped stones 1 'in a cupola furnace.
  • FIG. 12 shows a shaped block 1 'with a polygonal or circular cross section, which consists of a plurality of discs 29, 30 and 31, wherein the discs 29, 30 and 31 are arranged concentrically with one another and have different diameters or widths, so that a staircase structure of the molded block Y results.
  • the disks 29 to 31 have a circumferential edge bead, which increases the edge strength of the disks 29 to 31.
  • Edge bead is also the position of such a shaped block Y stabilized within ei ⁇ ner furnace bed.
  • the shaped brick 1 'can in turn have an opening 25 for improving the flowability of the shaped block 1' or a bed formed from a plurality of shaped blocks 1 'in a cupola furnace.
  • Such openings 25 also serve to improve the heat transfer, since the shaped brick 1 'is also heated from the inside through the openings.
  • moisture can escape from the shaped brick 1 'via the opening 25.
  • FIGS. 13 and 14 show a further embodiment of a molded block Y, wherein FIG. 14 shows a top view and FIG. 13 shows a side view of the molded block 1 'according to FIG.
  • the molded block 1 'according to FIGS. 13 and 14 has a substantially elliptical cross section and consists of a body which is homogeneous in terms of its density or of a body with a partially different mass.
  • the shaped brick 1 ' In its central area, the shaped brick 1 'has an opening 25 for the purposes already described above.
  • the shaped blocks 1 ' In addition to the elliptical Embodiment of the molded block 1 1 are also other shapes to Ro ⁇ tion ellipsoids possible.
  • the advantage of such shaped blocks 1 'with an elliptical cross-section is that such shaped blocks V can be arranged in a stable flat position in the cupola furnace. Therefore, the openings 25 in such shaped blocks 1 'are also aligned at right angles to the longitudinal extent of the shaped stones 1'.
  • FIG. 15 shows another simple embodiment of a molded block 1 ', which is particularly suitable for the use in question here.
  • the molded block Y according to FIG. 15 has the known form of a domestic fire brigade and is therefore easy to stack and transport. As a result of its shape, a number of shaped blocks 1 'form a highly permeable bed in a cupola furnace.
  • a further embodiment of a shaped block 1 ' is shown in FIGS. 16 to 18. This molded block Y is particularly suitable for insertion into the cupola and can be used both as hybrid moldings, as well as monolithic
  • Shaped brick 1 ' i. primary melt forming or be designed as an energy source.
  • the molded block 1 ' has six surfaces 32, in which gas guide channels 33 are formed.
  • the gas guide channels 33 are open to the surfaces 32 and connect in each case oppositely disposed and parallel aligned surfaces 32nd
  • the large surfaces 32 each have four gas guide channels 33, of which two are aligned in parallel.
  • In the formed as narrow sides surfaces 32 each have two gas guide channels 33 are formed.
  • bores 34 are arranged which, for example, have an oval, round or cloverleaf-shaped cross section.
  • the holes 34 connect opposing surfaces 32 to each other.
  • the molded block 1 'according to FIGS. 16 to 18 can have a height between 50 and 500 mm and side lengths between 150 and 500 mm.
  • the shaped block 1 'according to FIGS. 16 to 18 preferably has a square base surface.
  • the covering is additionally illustrated as a coating 35, which adheres to the surfaces 32, for example, of a binder, such as in particular a cement paste.
  • the binder may have mahamed insulation fibers to increase the abrasion resistance of the molded body 1. According to FIG. 16, this coating 35 is only in the region of one
  • the coating 35 thus likewise serves to displace the center of gravity of the shaped body 1, so that the shaped body 1 is aligned in a specific arrangement during the impact of a cupola furnace.
  • FIGS. 19 and 20 show a further embodiment of a molded block 1 'which, in the region of its two large surfaces 36, has grooves 37 that are substantially U-shaped in cross-section. These grooves 37 in turn serve to guide air and gas during the melting process within the cupola.
  • the molded block Y is cuboid in FIGS. 19 and 20.
  • FIG. 21 shows an element 39 which has a shaped body 1 in a casing 4, wherein the casing 4 forms a central element 38 with the molded brick 1 'arranged therein, to which smaller elements 40 pass
  • the smaller elements 40 correspond in their construction to the central element 38 and therefore also have a shaped block Y in a casing 4.
  • the casing 4 is in each case composed of a melt-forming mass, while the shaped brick Y represents an energy carrier. With a plurality of elements 39 according to FIG. 21, a very permeable furnace filling can be produced.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Processing Of Solid Wastes (AREA)
  • Inorganic Fibers (AREA)

Abstract

L'invention concerne un corps moulé servant à générer une masse fondue minérale destinée à être défibrée, pour produire des matériaux isolants à base de fibres minérales, en particulier à base de laine de roche. Le corps moulé selon l'invention comprend un support d'énergie primaire ou secondaire, par exemple du coke et/ou des matières premières primaires et/ou secondaires destinées à être fondues et défibrées pour former des fibres minérales, par exemple de la diabase ou du basalte, ainsi que de la roche calcaire et/ou de la dolomite ou du laitier, issu en particulier de l'industrie du fer, par exemple du laitier de haut fourneau en tant que matériaux de correction, ou des matières de recyclage comprenant des matériaux isolants à base de fibres minérales, en particulier des matériaux isolants à base de fibres minérales qui sont désintégrés et/ou des déchets de production se présentant sous la forme de matériaux isolants à base de fibres minérales qui sont broyés et façonnés de manière à former une brique moulée. L'objectif de cette invention est de créer un corps moulé présentant une forme qui est avantageuse pour le processus de fusion dans une unité de fusion, et qui peut être produite de manière simple et peu onéreuse. A cet effet, la section transversale de la brique moulée est configurée de manière circulaire, elliptique ou présente la forme d'un arc de cercle régulier, au moins dans un grand axe du corps, ou la section transversale de la brique moulée est configurée de manière polygonale, au moins dans un grand axe du corps. Selon l'invention, la brique moulée comporte des surfaces qui se rencontrent au niveau d'angles obtus, ou la brique moulée est conçue à la manière d'un cube dont les arêtes présentent une longueur supérieure à 200 mm, qui peut notamment atteindre 300 mm, et qui est de préférence comprise entre 200 et 250 mm.
PCT/EP2005/011293 2004-10-20 2005-10-20 Corps moule servant a produire une masse fondue minerale destinee a etre defibree, pour produire des materiaux isolants a base de fibres minerales WO2006042755A2 (fr)

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DE102004051007 2004-10-20
DE102004051007.5 2004-10-20
DE102004062781.9 2004-12-21
DE102004062781 2004-12-21
DE200510040268 DE102005040268A1 (de) 2004-10-20 2005-08-24 Formkörper für die Erzeugung einer zu zerfasernden mineralischen Schmelze zur Herstellung von Dämmstoffen aus Mineralfasern
DE102005040268.2 2005-08-24

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EP2918555A4 (fr) * 2012-11-12 2016-09-28 Valorización Y Logística Ambiental S L L Briquette utilisée pour la production de laine de roche et procédé d'obtention de ladite briquette
CN111333339A (zh) * 2020-04-21 2020-06-26 河北地质大学 玄武岩纤维制备方法以及玄武岩纤维

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2918555A4 (fr) * 2012-11-12 2016-09-28 Valorización Y Logística Ambiental S L L Briquette utilisée pour la production de laine de roche et procédé d'obtention de ladite briquette
EP2918555B1 (fr) 2012-11-12 2021-05-05 Valorización y Logística Ambiental, S.L.L. Briquette utilisée pour la production de laine de roche et procédé d'obtention de ladite briquette
CN111333339A (zh) * 2020-04-21 2020-06-26 河北地质大学 玄武岩纤维制备方法以及玄武岩纤维
CN111333339B (zh) * 2020-04-21 2022-09-16 河北地质大学 玄武岩纤维制备方法以及玄武岩纤维

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