DE102020116219B3 - Process for the production of basalt fibers or glass fibers - Google Patents

Abstract

The invention relates to a method for producing basalt fibers or glass fibers, wherein in a first process (P1) pellets (P) and / or frits (F) with a proportion of at least one additive are produced from a basalt material or glass material, in a second process (P2) a granulate (G) of the basalt material or glass material and the pellets (P) and / or frits (F) are melted homogeneously in a remelting process to form a melt, basalt fibers or glass fibers being drawn from the melt, with an additive antimicrobial and / or antiviral and / or fungicidal additive is used, wherein in the first process (P1) a granulate (G) from the basalt material or glass material is brought together with a substrate (K) of the at least one additive and melted to form a first melt (S1) from which the pellets (P) and / or frits (F) are made, whereby in the second process (P2) a quantity of granules (G) from the basalt material or glass material with a quantity of the pellets (P) and / or frits (F) produced in the first process (P1) is fed to the remelting process and melted to a second melt.

Description

The invention relates to a method for producing basalt fibers or glass fibers.

the DE 10 2016 223 453 A1 discloses a use of basalt for reducing fouling and / or as an antibacterial material, a coating for a surface for reducing fouling and / or as an antibacterial material and a method for producing such a coating.

the EP 2 665 687 B1 discloses the use of artificially produced molded bodies produced according to a process for the pretreatment of starting material for the production of a mineral melt for the production of continuous mineral fibers, in particular basalt fibers, the starting material, which is basalt and at least one binding agent, selected from a group comprising water, clay, Bentonite, sulphite liquor, cellulose derivatives, saccharides, sugar, starch, molasses, cement, phosphates, organosilicon substances, in an amount with a lower limit of 1% and an upper limit of 40%, comprising quartz sand and slag, in particular blast furnace slag, ground to particles is, molded bodies are produced from the particles and the molded bodies are tempered at a temperature of approx. 300 ° C +/- 50 ° C.

the EP 0 815 062 B1 discloses a method of making MMV fibers comprising melting in a furnace raw materials to produce a mineral melt and forming fibers from the melt, wherein the raw material charge is a mixture of at least two types of briquettes (a) and (b) having a size of at least 50 mm, each type of briquette having a different chemical analysis, and providing at least 30% by weight of the raw material batch of briquettes (b), and wherein (1) briquette (a ) an initial melting temperature of 1240 ° C or less and briquette (b) has an initial melting temperature of 1200 ° C or more and the initial melting temperature of briquette (b) is at least 20 ° C higher than the initial melting temperature of briquette (a), or (2) the briquettes have an overall chemical analysis which, when provided in the form of a single type of briquette, gives an initial melting temperature (I), and wherein briquettes (b) have an initial melting temperature which is at least 20 ° C higher than the initial melting temperature (I).

The invention is based on the object of specifying a method for producing basalt fibers or glass fibers.

The object is achieved according to the invention by a method having the features of claim 1.

Advantageous refinements of the invention are the subject matter of the subclaims.

Percentages are to be understood in the following as% by mass.

In a method according to the invention for producing basalt fibers or glass fibers, in a first process from a basalt material or glass material, pellets and / or frits with a proportion of at least one antimicrobial and / or antiviral and / or fungicidal additive, for example copper, silver, zinc, lead or Titanium, produced, whereby in a second process granules of the basalt material or glass material and the pellets and / or frits are melted homogeneously in a remelting process (also called indirect melt process) to form a melt, basalt fibers or glass fibers being drawn from the melt. Further additives can be provided in the first process to reduce the tendency to crystallize and thus to improve the temperature resistance.

By means of the method according to the invention, a particularly high homogeneity of the basalt fibers or glass fibers obtained is achieved, which cannot be achieved in the directmelt method because of the greatly different melting temperatures of the basalt material or glass material and the additives. Furthermore, by appropriately selecting the amount of pellets and / or frits, the proportion of which is known in each case, of the additive, even with basalt of varying composition from different deposits or from different locations within a deposit, a constant quality and composition of the basalt fibers obtained can be ensured. In particular, the composition of the respective basalt raw material of a batch is to be analyzed and the amount of the possibly already pre-produced pellets and / or frits to be added must be selected so that the desired material composition of the basalt fibers results.

According to the invention, in the first process a granulate made of the basalt material or glass material is mixed with a substrate of the at least one antimicrobial and / or antiviral and / or fungicidal additive, for example a copper substrate, brought together and melted to a first melt from which the pellets and / or frits are produced.

According to the invention, in the second process, a quantity of granulate from the basalt material or glass material with a quantity of the pellets and / or frits produced in the first process is fed to the remelting process and melted to a second melt. In an example not according to the invention, the pellets and / or frits can also be produced with the additive in the desired final concentration, so that mixing with the original granulate is not necessary.

In one embodiment, the granules have a grain size of 2 mm to 5 mm.

In one embodiment, the substrate of the at least one antimicrobial and / or antiviral and / or fungicidal additive is a salt solution or a powder.

In one embodiment, the granulate of the basalt material or glass material and the pellets and / or frits are melted homogeneously in a thin-film melter to form the melt in the remelting process, the melt being fed in a third process to a melting tank from which basalt fibers are drawn in a fourth process.

In a method not according to the invention for the production of basalt fibers or glass fibers, a basalt material or glass material with a proportion of at least one antimicrobial and / or antiviral and / or fungicidal additive is homogenized and melted in a melting tank, basalt fibers or glass fibers being drawn from the melt.

In one embodiment, copper, silver, zinc, titanium, lead and / or a quaternary silane ammonium compound is used as the at least one antimicrobial and / or antiviral and / or fungicidal additive.

In one embodiment, bubbling is carried out in the melting tank, that is to say the introduction of gas bubbles in order to distribute the temperature homogeneously and to promote the homogeneity of the melt.

It is known for the production of glass fibers to add the raw materials as a mixture to a melting tank, where they are homogenized by convection and / or by bubbling (gas bubbles). In the case of basalt material, melting and homogenizing in the melting tank is not possible in the same way, because the dark color means that the thermal radiation cannot penetrate deep enough into the melt and there is therefore a risk of inhomogeneous melt. The homogenization process should therefore be carried out beforehand and the melting should be carried out using a thin-film melter. The bubbling in the melting tank is primarily used for homogeneous temperature distribution, but also promotes the homogeneity of the melt.

The proportions of basalt material or glass material and the at least one antimicrobial and / or antiviral and / or fungicidal additive can be selected so that the additive has a proportion of 0.01% to 10%, in particular 0.1%, in the basalt fibers or glass fibers. to 5%, preferably 0.5% to 2%. In one embodiment of the pelting process, the pellets and / or frits are produced with such a proportion of the at least one antimicrobial and / or antiviral and / or fungicidal additive and / or their quantitative ratio to the granulate is selected when they are fed to the pelting process that the Melt from the remelting process results in a proportion of the antimicrobial and / or antiviral and / or fungicidal additive of 0.01% to 10%, in particular 0.1% to 5%, preferably 0.5% to 2%. For example, the pellets and / or frits can be produced with a copper content of 4%.

For example, seven parts of granulate with one part of pellets and / or frits can be fed to the remelting process.

In one embodiment, the frits are ground and sieved to obtain a defined size.

In one embodiment, the granulate and the pellets and / or frits are first fed to a mixing process and then a resulting mixture is fed to the pelting process. Alternatively, the granulate and the pellets and / or frits are fed separately to the remelting process.

In an alternative embodiment, a size can be applied during the drawing of the basalt fibers or glass fibers, the size being or being provided with at least one antimicrobial and / or antiviral and / or fungicidal additive.

In one embodiment, copper, silver, zinc, titanium, lead and / or a quaternary silane ammonium compound is used as the at least one antimicrobial and / or antiviral and / or fungicidal additive.

Embodiments of the invention are explained in more detail below with reference to drawings.

• 1 einen schematischen Ablaufplan eines Verfahrens zur Herstellung von Basaltfasern,
• 2 einen schematischen Ablaufplan eines Prozesses zur Herstellung von Fritten und/oder Pellets, und
• 3 einen schematischen Ablaufplan eines Prozesses zum Aufschmelzen von Granulat und Pellets und/oder Fritten.

Show in it:

• 1 a schematic flow chart of a process for the production of basalt fibers,
• 2 a schematic flow diagram of a process for the production of frits and / or pellets, and
• 3 a schematic flow chart of a process for melting granules and pellets and / or frits.

Corresponding parts are provided with the same reference symbols in all figures.

1 shows a schematic flow chart of a method for producing basalt fibers. In a first process PI, the embodiment of the invention in more detail in 2 is shown, pellets and / or frits with a proportion of at least one antimicrobial and / or antiviral and / or fungicidal additive, for example a relatively high copper proportion of, for example, 4%, are produced from a basalt material. A basalt material with a natural proportion of the antimicrobial and / or antiviral and / or fungicidal additive can be selected as the base material. The antimicrobial and / or antiviral and / or fungicidal additive is added to a basalt material in an appropriate amount. Additives can be provided in the first process to reduce the tendency to crystallize and thus to improve the temperature resistance.

A pellet is a small body made of compacted material that can have different geometric shapes. The compression can take place in different ways. Frits are an intermediate product (semi-finished product) in the field of mineral processing (glass, ceramics). Granulate / powder mixtures are melted on the surface in order to be able to control downstream processes better or to achieve specific functions. Pellets are not heated, but pressed. Basalt and the respective antimicrobial and / or antiviral and / or fungicidal additive can have different melting temperatures. The first trial P1 ensures that the basalt and the antimicrobial and / or antiviral and / or fungicidal additive melt evenly and are homogeneous even at different melting temperatures.

In a second process P2 granules of the basalt material and the pellets and / or frits are melted homogeneously to form a melt in a remelting process, for example in a thin-film melter.

In a third process P3 the melt can be fed to a melting tank, where bubbling can take place, i.e. the introduction of gas bubbles in order to distribute the temperature homogeneously and to promote the homogeneity of the melt.

In a fourth process P4 Basalt fibers are drawn from the melt. This can be done using methods known from glass fiber production. Due to the antimicrobial and / or antiviral and / or fungicidal additive, the basalt fibers have antimicrobial properties.

2 shows a schematic flow chart of the first process P1 for the production of frits and / or pellets according to the present invention. This is a granulate G from the basalt material, for example with a grain size of 2 mm to 5 mm, with a substrate K of the at least one antimicrobial and / or antiviral and / or fungicidal additive, for example a copper substrate K , for example in the form of a salt solution or a powder, brought together and form a first melt S1 melted. From this first melt S1 become pellets P. with a defined shape and size and / or frits F. made with an undefined shape and size. The frits can also be ground and sieved to obtain a defined size.

3 shows a schematic flow chart of the second process P2 for melting granules G and pellets P. and / or fries F. . This gets a lot of granules G from the basalt material, for example with a grain size of 2 mm to 5 mm, with an amount of the in the first process P1 produced pellets P. and / or fries F. a remelt process D. , for example a thin film smelter D. , fed and melted to a second melt. For example, seven parts are made of granules G with a part of pellets P. and / or fries F. the remelt process D. supplied, so that a second melt results with a proportion of the antimicrobial and / or antiviral and / or fungicidal additive of 0.5%. The granules G and the pellets P. and / or fries F. initially a mixing process M. are fed. A supply then takes place Z1 of the mixture to the pelting process D. . Alternatively, you can use the granules G and the pellets P. and / or fries F. the remelt process D. with separate feed Z2 fed and mixed there if necessary.

The additives in the end product are, for example, a maximum of 5%, copper for example 1%, zinc for example 5%. It is important that frits (with additive) and granules are in such a ratio that the ingredients can still mix. For example, up to 100 parts of granules can be used G with a part of pellets P. and / or fries F. , especially one to eight parts of granules G with a part of pellets P. and / or fries F. , preferably two to four parts of granules G with a part of pellets P. and / or fries F. can be used.

With an increasing proportion of the antimicrobial and / or antiviral and / or fungicidal additive, for example copper, silver, zinc or titanium, better antimicrobial and / or antiviral and / or fungicidal effects are achieved. The antimicrobial and / or antiviral and / or fungicidal additive can also have a positive or negative effect on the drawability of the fibers. For example, the proportion of the antimicrobial and / or antiviral and / or fungicidal additive, for example copper, in the second melt can be 0.01% to 10%, in particular 0.1% to 5%, preferably 0.5% to 2%.

If you tried to manufacture the basalt fibers in a single process, the heat from gas burners would not penetrate deep enough into the (basalt) mixture / melt to melt everything. A thin-film melter can therefore be used in the method described here. The mixture "flows" in a thin layer down a slight slope and is heated by several flat burners, so that it flows in liquid form into the melting tank at the end.

• - antimikrobielle Faser in Tapeten,
• - antimikrobielle Faser in Putz/Farbe,
• - temperaturbeständige Faser im Objektbereich,
• - alkalibeständige Faser in mineralischen Faserverbunden (Textilbeton),
• - technische Textilien mit verbesserter Verarbeitbarkeit.

The fibers produced in this way are antimicrobial and / or antiviral and / or fungicidal, and optionally alkali-resistant, high-temperature-resistant, high-strength and have improved loopability. Alkali resistance can be achieved by using zirconium oxide as an additive. High temperature resistance can be achieved by adding certain additives, for example lithium borate, in particular 1% to 5%. This can go hand in hand with a reduction in the tendency to crystallize. The fibers can be used to protect against fouling, for paper and fleece, for example wallpaper and filters, and as an aggregate for paints and plasters. In particular, the fibers can be used as:

• - antimicrobial fiber in wallpaper,
• - antimicrobial fiber in plaster / paint,
• - temperature-resistant fiber in the object area,
• - alkali-resistant fibers in mineral fiber composites (textile concrete),
• - technical textiles with improved processability.

In an example not according to the invention, a direct melt process is used to produce glass fibers or basalt fibers.

The directmelt process can be carried out for all types of glass fibers as well as for basalt fibers.

If necessary, the raw materials are processed and stored before the melting process, for example in silos.

In addition to the usual raw materials (such as quartz sand, borax, potash, soda, feldspar, etc. for glass fibers and basalt rock for basalt fibers), raw materials are also provided for antimicrobial effectiveness (in particular compounds such as salts with the elements copper, silver, zinc, titanium or Lead).

The raw materials are fed to a process room with a defined mixing ratio. The raw materials fed in are homogenized there, preferably in a suitable process room. The homogenization can be carried out continuously or discontinuously.

The homogenized raw materials are then fed to a melting tank and melted there. Both electrical heating and heating by means of fuels, for example fossil or renewable fuels, or a combination of these possibilities can be used.

A refining of the melt and further homogenization can be supported by a bubbling and / or a so-called wall. The melt is then fed to one or more bushings (nozzle troughs) through so-called feeder channels. By pulling it out of the bushings' nozzles, glass fibers or basalt fibers are created.

Immediately after it has been withdrawn from the nozzles, a size can be applied to the fibers, which can be permeable to the antimicrobially active components in the fibers. An example of this is a size based on chitosan. Silane sizes with the lowest possible polymer content are also suitable.

In a further example, not according to the invention, an indirect melt process (also called remelt process) is used to produce glass fibers or basalt fibers.

If necessary, the raw materials are processed and stored before the melting process, for example in silos.

In addition to the usual raw materials (such as quartz sand, borax, potash, soda, feldspar, etc. for glass fibers and basalt rock for basalt fibers), raw materials are also provided for antimicrobial effectiveness (in particular compounds such as salts with the elements copper, silver, zinc, titanium or Lead).

The raw materials are fed to a process room with a defined mixing ratio. The raw materials fed in are homogenized there, preferably in a suitable process room.

The homogenized raw materials are then fed to a melting tank and melted there. Both electrical heating and heating by means of fuels, for example fossil or renewable fuels, or a combination of these possibilities can be used.

A refining of the melt and further homogenization can be supported by a bubbling and / or a so-called wall.

The melt is then fed through so-called feeder channels to one or more outlet nozzles, from which the melt emerges and is fed to a pelletizing machine. Pellets are formed on the pelletizing machine. The pellets are then cooled on a cooling section and, if necessary, stored in a storage container.

The pellets are fed to a melting tank.

By pulling it out of the bushings' nozzles, glass fibers or basalt fibers are created.

Immediately after it has been withdrawn from the nozzles, a size can be applied to the fibers, which can be permeable to the antimicrobially active components in the fibers. An example of this is a size based on chitosan. Silane sizes with the lowest possible polymer content are also suitable.

The following is an example of a possible glass composition including around 1% CuO, in this case alkali-resistant glass for use in a basic environment (e.g. fiber reinforcement for concrete, etc.): Element or oxide Glass pellets AR glass with doping content [%] Measurement uncertainty fluorine 0.78 ± 0.05 Na ₂ O 13.90 ± 0.05 MgO 0.14 ± 0.02 Al ₂ O ₃ 0.61 ± 0.05 SiO ₂ 57.9 ± 0.2 P ₂ O ₅ 0.12 ± 0.02 SO ₃ 0.045 ± 0.03 K ₂ O 1.57 ± 0.01 CaO 6.22 ± 0.09 TiO ₂ 0.414 ± 0.002 MnO 0.007 ± 0.002 Cr ₂ O ₃ 0.004 ± 0.002 Fe ₂ O ₃ 0.165 ± 0.002 ZrO ₂ 17.05 ± 0.05 BaO 0.03 ± 0.01 CuO 0.98 ± 0.05 total 99.94

The chemical analysis can be carried out using XRF in accordance with DIN 51001, for example.

The following is an example of a possible basalt composition including about 1% CuO: oxide Salary [%] SiO ₂ 52 Al ₂ O ₃ 16 Fe ₂ O ₃ 9.3 TiO ₂ 1.3 CaO 9.4 MgO 6.8 K ₂ O 0.6 Na ₂ O 3.1 BaO 0.1 MnO ₂ 0.2 P ₂ O ₅ 0.2 CuO 1.0

Additives can also be added to the manufacture of glass wool or microfibers.

Microfibers made of glass are used for insulation materials, filters, battery separators, etc. These microfibers have a diameter of 0.1 to 10 µm, depending on the process and application.

Well-known manufacturing processes for microfibers include the rotary process, the cascade process and the flame attenuation process.

In the rotary process, the liquid melt is poured in the form of a melt stream onto a rapidly rotating disk. The glass fibers, which are thrown away radially by the centrifugal force, are further frayed by an external burner or a stream of hot air. An example of such an arrangement is in US 8 250 884 B2 to see. With the rotary process, good fiber quality is achieved with high productivity.

In the Cascade process, the liquid melt is poured in the form of a melt stream onto rapidly rotating rollers and blown into glass fibers by a strong air stream. An example of such an arrangement is in U.S. 5,356,450 A to see. With the Cascade process, a low fiber quality is achieved with very high productivity.

In the flame attenuation process, fibers are pulled out of a bushing by rollers, for example, and then shredded using a burner. With this process, very good fiber quality with very small diameters and low productivity is possible.

List of reference symbols

D.

Remelt process, thin film smelter

F.

Fries

G

granules

K

Copper substrate, substrate

M.

Mixing process

P.

Pellets

P1

first trial

P2

second process

P3

third process

P4

fourth process

S1

first melt

Z1

supply

Z2

supply

Claims (6)

Method for the production of basalt fibers or glass fibers, wherein in a first process (P1) from a basalt material or glass material pellets (P) and / or frits (F) with a proportion of at least one additive are produced, in a second process (P2) a Granulate (G) of the basalt material or glass material and the pellets (P) and / or frits (F) are melted homogeneously in a remelting process to form a melt, basalt fibers or glass fibers being drawn from the melt, with an antimicrobial and / or antiviral and / or fungicidal additive is used, wherein in the first process (P1) a granulate (G) from the basalt material or glass material is combined with a substrate (K) of the at least one additive and melted to a first melt (S1), from which the pellets (P) and / or frits (F) are produced, wherein in the second process (P2) an amount of granules (G) from the basalt material or glass material with an amount of de r pellets (P) and / or frits (F) produced in the first process (P1) are fed to the remelting process and melted to a second melt. Procedure according to Claim 1 , whereby in the remelting process the granulate (G) of the basalt material or glass material and the pellets (P) and / or frits (F) are melted homogeneously in a thin-film melter (D) to form the melt, with the melt in a third process (P3) a Melting tank is supplied, from which basalt fibers or glass fibers are drawn in a fourth process (P4). Method according to one of the Claims 1 or 2 , wherein the at least one antimicrobial and / or antiviral and / or fungicidal additive is a salt solution or a powder. Method according to one of the Claims 1 until 3 , wherein copper, silver, zinc, lead, titanium or a quaternary silane ammonium compound is used as the at least one antimicrobial and / or antiviral and / or fungicidal additive. Method according to one of the preceding claims, wherein the proportions of basalt material or glass material and the at least one additive are selected so that the additive has a proportion of 0.01% by mass to 10% by mass, in particular 0, in the basalt fibers or glass fibers. 1% by mass to 5% by mass, preferably 0.5% by mass to 2% by mass, results. Method for producing basalt fibers or glass fibers according to one of the preceding claims, wherein a size is applied during the drawing of the basalt fibers or glass fibers, the size being or being provided with at least one antimicrobial and / or antiviral and / or fungicidal additive.

Images