Method for regenerating molten salt for glass hardening and / or glass strengthening processes - Patents.com

Abstract

A method is presented that allows the use of molten salt for hardening and / or strengthening, in particular multiple glass objects and / or particularly large glass objects, with high quality molten salt even in glass objects made of complex glass materials. The present invention relates to a method for regenerating molten salt for a glass hardening and / or strengthening process, characterized in that at least one first body of regeneration material made of a first regeneration material and at least one second body of regeneration material made of a second regeneration material different from the first regeneration material are brought into contact with the molten salt simultaneously or sequentially.Furthermore, the present invention relates to an apparatus for hardening and / or strengthening glass, comprising a salt bath with molten salt.

Description

[Technical field]

[0001] The present invention relates to a method for regenerating molten salt for the glass hardening and / or strengthening process (glass consolidation process).

[0002] The invention further relates to an apparatus for hardening and / or strengthening glass, comprising a salt bath having a molten salt. [Background technology]

[0003] It is known that certain treatments of glass in molten salts can achieve high compressive stresses by ion exchange in a thin surface layer, which significantly improve the strength properties of the glass. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] German Patent Publication No. 1771232 Summary of the Invention [Problem to be solved by the invention]

[0005] In the treatment in the molten salt, a first type of ion migrates into the glass, while the glass simultaneously releases a second type of ion into the molten salt. Disadvantageously, the effect of the molten salt decreases depending on the frequency of use of the molten salt, especially since the molten salt becomes poor in the first type of ion and rich in the second type of ion in the molten salt. This results in the molten salt having to be replaced frequently.

[0006] It is known to carry out a prestressing process at high temperatures in a molten salt, in particular consisting of potassium nitrate or a mixture with potassium nitrate, in which smaller alkali ions (sodium, lithium) are exchanged for larger alkali ions. However, the exchanged alkali ions remain in the molten salt, which reduces the effectiveness of the molten salt. Furthermore, as a result of the prestressing process, decomposition of the melt into oxides / hydroxides via nitrites takes place, which is disadvantageous.

[0007] The increased deterioration of the effectiveness of the molten salt can at least be delayed by the use of certain regenerative materials.

[0008] For example, from DE 17 71 232 B2, a method is known for exchanging ions between a molten salt and a glass in order to change the properties of the glass, in which ions transferred into the molten salt are absorbed by a regenerating material which is in a separate phase in the molten salt, and at the same time ions required for the ion exchange are released to the molten salt. As regenerating material, a molten salt to which an auxiliary substance is added is used, which is an acceptor for oxygen ions and / or has an acid function and which is able to take up ions transferred from the glass or from the regenerating material into the molten salt, forming a complex and accelerating the redox reaction in the molten salt.

[0009] The object of the present invention is to provide a method for realizing the use of molten salts of high quality even in glass objects made of complex glass materials, in particular for hardening and / or strengthening a large number of glass objects and / or particularly large glass objects.

[0010] It is a further object of the invention to provide an apparatus of the type mentioned at the beginning, which makes it possible to harden and / or strengthen, in particular a large number of glass objects, without the need to replace the molten salt. [Means for solving the problem]

[0011] The first problem is solved by a method characterized in that at least one first recycled material body consisting of a first recycled material and at least one second recycled material body consisting of a second recycled material different from the first recycled material are brought into contact with molten salt simultaneously or sequentially.

[0012] The above-mentioned problem is further solved by an apparatus characterized in that the apparatus has at least one first regenerative material body consisting of a first regenerative material and at least one second regenerative material body consisting of a second regenerative material different from the first regenerative material, which are continuously in contact with the molten salt or can be brought into contact with the molten salt simultaneously or sequentially. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, a mode for carrying out the invention will be described.

[0014] In the present invention, it has been recognized that the depletion of the molten salt in one larger alkali ion, for example potassium, and the enrichment with one smaller alkali metal ion, for example sodium, is not the only cause of the deterioration of the quality of the molten salt with respect to the glass hardening and / or glass strengthening processes of glass objects. Rather, it has been found that several acting factors have a negative influence on the quality of the molten salt, especially when hardening and / or strengthening glass objects made of complexly constructed glass materials. It has been found that, in order to ensure the correct functioning of the ion exchange, especially during the hardening and / or strengthening processes, over a long period of time, several different chemicals must be removed from and / or introduced into the salt bath.

[0015] In the present invention, it has been found that, for example, the molten salt, when hardening and / or strengthening glass objects made of glass materials containing sodium and lithium, leads to a deterioration of the quality of the molten salt due to its enrichment with sodium and, in addition, to a rather greater extent, with its enrichment with lithium.Moreover, in many cases, an increasing basicity of the molten salt occurs with the number of glass hardening and / or glass strengthening processes carried out, which likewise has a detrimental effect on the quality of the molten salt with respect to the glass hardening and / or glass strengthening processes.

[0016] The present invention contemplates the use of at least two regeneration bodies of different regeneration materials, rather than using only one regeneration material, where for example the first regeneration material is configured to absorb and thus remove sodium from the salt bath, and the second regeneration material is configured to absorb and thus remove lithium from the salt bath. Furthermore, for example and advantageously, one of the regeneration materials can be configured to remove or at least reduce the basicity of the molten salt, which can be achieved, for example, by removing OH from the salt bath. - This can be achieved by the relevant regenerating material comprising silicon dioxide to bind to the radicals and thus remove them from the salt bath.

[0017] The present invention has the particular advantage that the use of two (or more than two) different recycling materials makes it possible to counteract the often multiple ageing processes in a targeted and effective manner. A special inventive idea makes it possible, in particular, to bring different recycling material bodies into contact with the molten salt one after the other in time. This has the particular advantage that the different recycling materials cannot at least have a direct adverse effect. However, depending on the application, it is also possible to use different recycling materials simultaneously or at least with a time overlap in the same molten salt, if there is no risk of the different recycling materials having an adverse effect or if the degree of direct or indirect interaction is only slight.

[0018] A particularly advantageous feature is a method for hardening and / or strengthening a glass object, in which the glass object is brought into contact with a molten salt, and the molten salt is regenerated by continuously or, in particular at regular time intervals, simultaneously or successively bringing into contact at least one first body of regenerating material made of a first regenerating material and at least one second body of regenerating material made of a second regenerating material different from the first regenerating material. A third body of regenerating material, in particular made of a third regenerating material different from the first and second regenerating materials (and possibly further bodies of regenerating material), can also be used to regenerate the molten salt by being brought into contact simultaneously or successively.

[0019] Particularly advantageously, a plurality of first regenerative material bodies, for example in the form of spheres, granules, frits, fibres or platelets, made of the first regenerative material, and / or a plurality of second regenerative material bodies, made of the second regenerative material in the form of spheres, granules, frits, fibres or platelets, can be brought into contact with the molten salt simultaneously or successively. In this way, advantageously, a large surface compared to the volume and therefore a large contact surface for the molten salt can be achieved, whereby a high efficiency can be achieved for a given regenerative material use.

[0020] The first and / or second recycled material bodies in the form of irregularly corrugated plates and / or plates with irregular surfaces are particularly advantageous, since they do not allow surface adhesion to one another, which would disadvantageously reduce the total usable surface of the recycled material bodies. As a result, very generally advantageously, the first recycled material bodies can have a similar basic shape, but the individual recycled material bodies are different, provided that surface adhesion to one another (such as flat plates) is avoided. The same applies analogously to the second recycled material body.

[0021] The first recycled material bodies can advantageously have the same or at least similar shape and / or size as each other. Alternatively or additionally, the second recycled material bodies can have the same or at least similar shape and / or size as each other. The shape and / or size of the first recycled material body can be the same as the shape and / or size of the second recycled material body. However, it is advantageous if the at least one first recycled material body differs from the at least one second recycled material body in terms of shape and / or size. This has the great advantage that mix-ups are avoided and, if different recycled material bodies are used simultaneously, they can be separated from each other by a sieving process if necessary.

[0022] The at least one first body of recycled material can advantageously be configured as a sphere, or as a plate, or as a (preferably irregular) corrugated plate, or as a frit, or as a fiber. Alternatively or additionally, the at least one second body of recycled material can also be configured as a sphere, or as a plate, or as a (preferably irregular) corrugated plate, or as a plate with an irregular surface, or as a frit.

[0023] Preferably, a plurality of first and / or second regenerative material bodies are used, which are advantageously brought into contact with the molten salt, for example, in the form of granules. Particularly advantageously, the granules can have a particle size in the range of 0.1 mm to 10 mm, in particular in the range of 0.1 mm to 3 mm, or in the range of 0.1 mm to 0.8 mm, or in the range of 0.3 mm to 0.8 mm. Such a particle size provides the advantage, on the one hand, that the granules can be held in a container with relatively large openings, whereas the granules at the same time provide a large contact surface for the molten salt.

[0024] Alternatively, the first and / or second bodies of recycling material can be used in the form of glass frit or sintered material. Such an embodiment also offers the advantage that the recycling bodies can be held in a (preferably respective) container with relatively large openings, whereas at the same time there is a large contact surface for the molten salt. The glass frit can have a thickness (dimension) in the range of 0.1 mm to 10 mm, in particular in the range of 0.1 mm to 3 mm, or in the range of 0.1 mm to 0.8 mm, or in the range of 0.3 mm to 0.8 mm.

[0025] Alternatively, and with the same advantages, the first and / or second recycled material bodies can be configured as plates (preferably irregularly corrugated) or as pieces of plates (preferably irregularly and / or irregularly corrugated), which plates or pieces can be brought into contact with the molten salt. The plates or plate pieces can advantageously have a thickness in the range of 0.1 mm to 10 mm, in particular in the range of 0.1 mm to 3 mm, or in the range of 0.1 mm to 0.8 mm, or in the range of 0.3 mm to 0.8 mm. The production of the plates or plate pieces can, for example, include rolling out the recycled material. In this case, the rollers are preferably smooth in glatt in order to give the plates or plate pieces a structure that makes it impossible for them to adhere to each other surface-wise.

[0026] Alternatively, and with the same advantages, the first and / or second recycled material body can be brought into contact with the molten salt in the form of fibres, in particular glass fibres, or in the form of at least one fleece made from fibres, in particular glass fibres, or in the form of fibre wool, in particular glass wool, which fibres can advantageously have a thickness in the range from 0.1 mm to 3 mm, in particular in the range from 0.1 mm to 0.8 mm, or in the range from 0.3 mm to 0.8 mm.

[0027] In a particularly advantageous embodiment, at least one of the recycling materials is glass or contains glass. This has the advantage that the recycling material bodies can be easily brought into contact with the molten salt as a solid, for example in the form of spheres or glass fibers, or as a fleece or glass frit or sintered material. For example, it is possible to introduce the recycling material bodies into a salt bath and remove them from the salt bath again simply and without complexity. Instead, these recycling material bodies can be simply arranged in a flow path through which a portion of the molten salt is introduced continuously or at intervals spaced apart in time.

[0028] If the recycled material concerns glass, there is advantageously a further possibility of complete recycling, in particular the recycled material body can be used after its use as raw material for other applications or as raw material for producing glass objects.

[0029] Particularly advantageously, at least one of the recycled materials can be a glass, particularly from a porous glass system with a tendency to phase separation, or can comprise a glass, particularly from a porous glass system with a tendency to phase separation. In particular, at least one of the recycled materials can be a glass, particularly from a porous glass, rich in silicon dioxide, or can comprise a glass, particularly from a porous glass, rich in silicon dioxide.

[0030] In a particular embodiment, at least one of the recycled materials is or comprises VYCOR® glass. VYCOR glass is produced in a process at relatively low temperatures. Whereas normally, the production of quartz glass requires a temperature of 2000° C., the VYCOR process allows production at temperatures of 1000° C. to 1300° C. The VYCOR process includes, in particular, the process steps of melting the base glass (ternary composition, for example: M2O-B2O3-SiO2), forming the base glass, heat treatment (time- and temperature-dependent), etching the surface of the formed body (hydrofluoric acid, caustic soda solution, mechanical), cleaning processes (alcohol, water, dilute soda solution), extraction processes (acids, inorganic salt solutions, from 90° C. to 100° C.), washing processes, drying processes, and / or sintering processes (from 1000° C. to 1300° C.). In the sintering process, the porous glass is often sintered to a transparent and almost pure silica glass under a volumetric shrinkage of 30%. Advantageously, it is also possible to add aluminum oxide to the VYCOR glass melt, which is favorable for controlling the phase separation and leaching processes (demineralization processes).

[0031] Alternatively or additionally, at least one of the regenerating materials can advantageously contain amorphous silicic acid. The regenerating mass made of such regenerating materials has the special advantage that they act against the basicity of the molten salt. In this case, the porous glass has the special advantage of a large contact surface with the molten salt, thereby providing a large efficiency.

[0032] In a particularly advantageous embodiment, one of the recycling materials is configured to absorb calcium from the molten salt. It has been found that chemical and physical processes in glass hardening and / or glass strengthening processes are often hindered by calcium, which often originates from the glass object to be hardened and / or strengthened. For this reason, it is advantageous to remove calcium from the molten salt or to reduce the calcium content. Particularly advantageously, at least one of the recycling materials contains calcium, for example in the form of calcium oxide, but can be configured not to release calcium into the molten salt.

[0033] In a particularly advantageous embodiment, one of the recycling materials is configured to absorb lithium from the molten salt. It has been found that the chemical and physical processes in the glass hardening and / or glass strengthening processes can often be hindered by lithium, which often originates from the glass object to be hardened and / or strengthened. For this reason, it is advantageous to remove lithium from the molten salt or to reduce the lithium content. Particularly advantageously, at least one of the recycling materials contains lithium, but can be configured not to release lithium into the molten salt.

[0034] In a particularly advantageous embodiment, the first regenerating material is configured to absorb calcium from the molten salt, whereas the second regenerating material is configured to absorb lithium from the molten salt. In this case, it has been found to be particularly advantageous to bring the molten salt into contact with at least one first regenerating material body and at least one second regenerating material body successively, so that the regenerating materials do not directly interact with each other. However, the simultaneous use of at least one first regenerating material body and at least one second regenerating material body is not fundamentally excluded.

[0035] In a particularly advantageous embodiment, one of the recycled materials is a potassium-containing silicate glass, in particular a potassium aluminosilicate glass. This recycled material has the particularly advantageous feature that three very essential ageing phenomena of the molten salt can be avoided or at least significantly delayed. In particular, the increase in the concentration of extraneous alkali ions is avoided or at least significantly delayed. Furthermore, the increase in the pH value of the molten salt due to salt decomposition is avoided or at least significantly delayed. Furthermore, particulate contamination is avoided, in particular because the particulate contamination of the molten salt is bound as soon as it comes into contact with the recycled material in the molten salt. Furthermore, the recycled material does not adversely affect devices for hardening and / or strengthening glass objects. Such recycled material does not cause corrosive reactions, in particular with the glass objects to be hardened and / or strengthened or with the molten salt. In particular, since the recycled material relates to glass, it is advantageously possible to completely recycle it. In particular, the recycled material can be used in a particularly simple manner after its use according to the invention as a raw material for other applications or as a raw material for producing glass objects. For example, after its use according to the invention, this recycled material can be cleaned of any salts still adhering thereto and used as raw material for the production of siliceous bulk glass.

[0036] In an advantageous embodiment, at least one of the regenerator materials is melted from a raw material mixture which additionally comprises at least one further oxide other than potassium oxide, in particular at least one further oxide from the group of aluminum oxide, boron oxide, sulfur oxide, calcium oxide. Particularly advantageously, at least one of the regenerator materials can be melted from a raw material mixture which additionally comprises several oxides other than potassium oxide, in particular several oxides from the group of aluminum oxide, boron oxide, sulfur oxide, calcium oxide, in the same or different proportions.

[0037] Particularly advantageous and effective are regenerator materials of the above-mentioned type, which are melted from a raw material mixture having a proportion of silicon oxide in the range of 40 to 75 weight percent, in particular in the range of 50 to 65 weight percent, or 57.5 weight percent.

[0038] Alternatively or additionally, at least one of the regenerator materials can advantageously be melted from a raw material mixture having a proportion of potassium oxide in the range from 20 to 40 percent by weight, in particular in the range from 25 to 35 percent by weight, or 32.5 percent by weight.

[0039] Alternatively or additionally, at least one of the recycling materials can advantageously be melted from a raw material mixture having a proportion of aluminum oxide in the range from 1 to 10 percent by weight, in particular in the range from 2 to 6 percent by weight, or alternatively 2.5 percent by weight or 5 percent by weight.

[0040] Furthermore, alternatively or additionally, at least one of the regenerator materials can advantageously be melted from a raw material mixture having a calcium oxide proportion in the range from 0 to 15 weight percent, in particular in the range from 6 to 10 weight percent, or 8 weight percent.

[0041] Further alternatively or additionally, at least one of the regenerator materials can advantageously be melted from a raw material mixture having a proportion of boron oxide in the range from 0 to 10 weight percent.

[0042] One embodiment in which at least one of the regenerator materials comprises at least one alkaline earth metal is particularly advantageous.

[0043] For example, at least one of the regenerator materials can be melted from a raw material mixture including 2.5 weight percent aluminum oxide, 32 weight percent potassium oxide, 8 weight percent calcium oxide, and 57.5 weight percent silicon oxide. It has been found that with such regenerator material introduced into the contaminated molten salt bath in a weight percentage of 5 percent, a reduction in the initial sodium content of 60% or more can be achieved within 24 hours.

[0044] For example, at least one of the regenerating materials can be melted from a raw material mixture containing 5% by weight aluminum oxide, 32.5% by weight potassium oxide, 8% by weight calcium oxide, and 54.5% by weight silicon oxide. It has been found that such regenerating materials can be used particularly well in the form of a fleece in separate channels through which the molten salt to be regenerated flows continuously or at intervals spaced apart in time (intermittent).

[0045] Particularly advantageously, quite generally, the first regenerative material can be configured to absorb a first ionic component, e.g., sodium ions, from the molten salt, and the second regenerative material can be configured to absorb a second ionic component different from the first ionic component, e.g., lithium ions, from the molten salt.

[0046] The at least one first and / or the at least one second regenerative material body can, for example, be introduced directly into a salt bath containing molten salt or placed in a flow path through which the molten salt flows continuously or at timed intervals. There are no fundamental limitations regarding the manner of bringing into contact.

[0047] Alternatively and particularly advantageously, the at least one first regenerative material body can be placed in a container, in particular a basket or sieve, and brought into contact with the molten salt, the container having at least one opening through which the molten salt of the molten salt can flow without the first regenerative material body leaking out of the container. Alternatively or additionally, the at least one second regenerative material body can be placed in a container, in particular a basket or sieve, and brought into contact with the molten salt, the container having at least one opening through which the molten salt of the molten salt can flow without the second regenerative material body leaking out of the container. Such an embodiment facilitates handling when brought into contact with the molten salt and also allows the use of a large number of small regenerative material bodies, for example in the form of granules or in the form of a large number of small plates, thereby providing a large surface as a contact surface for the molten salt.

[0048] If the at least one first and at least one second regenerative material body are to be brought into contact with the molten salt simultaneously, they can be arranged in a common vessel, but preferably the at least one first and at least one second regenerative material body are each arranged in their own vessels, which are handled separately and, in particular, brought into contact with the molten salt sequentially or with a time lag.

[0049] The container can advantageously be configured, for example, as a cage, as a basket or as a sieve. Preferably, the container is made of special steel (stainless steel). In this way, chemical reactions with the molten salt or with the regenerating material or with the glass object to be hardened and / or strengthened are avoided.

[0050] It is particularly advantageous if the regeneration material bodies are moved in the molten salt, in particular continuously or at intervals spaced apart in time, in order to constantly bring another portion of the molten salt into contact with the regeneration material bodies. Alternatively or additionally, it is also possible that a portion of the molten salt is respectively removed continuously or at intervals spaced apart in time from the salt bath in which the glass hardening and / or glass strengthening process is carried out and brought into contact, in particular into flow contact, with at least one of the regeneration material bodies, with the respective removed portion of the molten salt subsequently being introduced back into the salt bath.

[0051] In an advantageous embodiment, a portion of the molten salt is guided continuously or at time-spaced intervals through a channel (Kanal) in which at least one first regenerative material body and / or at least one second regenerative material body are present.

[0052] The molten salt may in particular contain potassium and / or potassium nitrate or may consist (except for impurities or contaminants) of potassium nitrate or a mixture with potassium nitrate.

[0053] As already mentioned, a method for hardening and / or strengthening a glass body is particularly advantageous, in which the glass body is brought into contact with a molten salt, the molten salt being regenerated continuously or, in particular, at regular time intervals using the method according to the invention. In this way, it can be advantageously achieved that the quality of the molten salt remains maintained for a number of glass hardening and / or glass strengthening processes and is free of fluctuations or subject to only minor fluctuations.

[0054] In this case, it is advantageously considered that at least one first recycling material body and glass object are brought into contact with the molten salt so that they are in contact with the molten salt simultaneously or at least with a time overlap. Alternatively or additionally, it is considered that at least one second recycling material body and glass object are brought into contact with the molten salt so that they are in contact with the molten salt simultaneously or at least with a time overlap. In this way, fluctuations in the quality of the molten salt are avoided or at least kept at a low level.

[0055] The device according to the invention for hardening and / or strengthening glass objects comprises a first vessel containing at least one first body of regenerative material and capable or incorporated in the molten salt, the first vessel having at least one opening through which the molten salt of the molten salt can flow. Alternatively or additionally, the device comprises a second vessel containing at least one second body of regenerative material and capable or incorporated in the molten salt, the second vessel having at least one opening through which the molten salt of the molten salt can flow.

[0056] If the recycling material body arranged in the container no longer provides sufficient recycling capacity, it is sensible to replace the container with another (preferably the same) container with at least one fresh recycling material body. In this case, it is advantageous to provide a plurality of first containers that are configured identically (at least to each other) and / or a plurality of second containers that are configured identically (at least to each other). In particular, the first container and / or the second container can be configured as an exchangeable cartridge.

[0057] The device may have a first receiver for receiving a first vessel having at least one first body of regenerative material. Alternatively or additionally, the device may have a second receiver for receiving a second vessel having at least one second body of regenerative material. The first receiver and / or the second receiver may be part of a flow path through which the molten salt flows.

[0058] The first container and the second container can advantageously be configured differently, in particular with regard to shape and / or size. Such a configuration has the particular advantage that mix-ups when exchanging the containers are avoided. This can be supported in particular by the receivers being configured (e.g. due to their shape and / or size) in such a way that the first container cannot be inserted into the second receiver and / or the second container does not need to be inserted into the first receiver.

[0059] Very generally, it is considered advantageous that the regeneration material body is brought into contact with the molten salt continuously or at intervals spaced apart in time. This can be done, for example, by introducing the regeneration material body into a vessel (bath) in which the molten salt to be regenerated is provided. The regeneration material body is particularly effective if the regeneration material body and the molten salt are moved relative to one another so that always another part of the molten salt is in contact with the regeneration material body. The device according to the invention can advantageously have in this respect a movement device for moving at least one of the regeneration material bodies in and / or into the molten salt continuously or at intervals spaced apart in time.

[0060] Alternatively, as already mentioned, it is also contemplated that at least one of the regenerating bodies is arranged in a separate flow path through which the molten salt to be regenerated flows continuously or at time-distant intervals. The device according to the invention can advantageously comprise a pump for pumping the molten salt through the flow path. Preferably, the flow path is actively heated to avoid a temperature drop of the molten salt in the flow path and thus a solidification of the molten salt in the flow path.

[0061] The subject matter of the invention is illustrated in an exemplary and schematic manner in the drawings, which are to be described below with reference to the drawings, in which similar or similarly acting elements are to a large extent provided with the same reference signs even in different embodiments. [Brief description of the drawings]

[0062] [Figure 1] 1 shows a first embodiment of an apparatus according to the invention for hardening and / or strengthening glass objects in different situations during the execution of an embodiment of the method according to the invention; FIG. [Diagram 2] 1 shows a first embodiment of an apparatus according to the invention for hardening and / or strengthening glass objects in different situations during the execution of an embodiment of the method according to the invention; FIG. [Diagram 3] 1 shows a first embodiment of an apparatus according to the invention for hardening and / or strengthening glass objects in different situations during the execution of an embodiment of the method according to the invention; FIG. [Figure 4] 1 shows a first embodiment of an apparatus according to the invention for hardening and / or strengthening glass objects in different situations during the execution of an embodiment of the method according to the invention; FIG. [Diagram 5] 2 shows a second embodiment of the device according to the invention for hardening and / or strengthening glass objects in one situation during the execution of an embodiment of the method according to the invention; FIG. [Figure 6] 2 shows a second embodiment of the device according to the invention for hardening and / or strengthening glass objects in one situation during the execution of an embodiment of the method according to the invention; FIG. [Figure 7] 2 shows a second embodiment of the device according to the invention for hardening and / or strengthening glass objects in one situation during the execution of an embodiment of the method according to the invention; FIG. [Figure 8] 2 shows a second embodiment of the device according to the invention for hardening and / or strengthening glass objects in one situation during the execution of an embodiment of the method according to the invention; FIG. [Figure 9] 2 shows a second embodiment of the device according to the invention for hardening and / or strengthening glass objects in one situation during the execution of an embodiment of the method according to the invention; FIG. [Figure 10] 2 shows a second embodiment of the device according to the invention for hardening and / or strengthening glass objects in one situation during the execution of an embodiment of the method according to the invention; FIG. [Figure 11]FIG. 3 shows a third embodiment of the device according to the invention for hardening and / or strengthening glass objects. [Figure 12] FIG. 4 shows a fourth embodiment of the device according to the invention for hardening and / or strengthening glass objects. EXAMPLES

[0063] Figures 1 to 4 show a first embodiment of an apparatus 1 according to the invention for hardening and / or strengthening (consolidating) a glass object 2 (here depicted merely as an example a wine glass) in different situations during the execution of an embodiment of a method according to the invention.

[0064] The apparatus 1 comprises a bath body 3 with a molten salt 4 into which a support 5 with at least one glass object 2 to be hardened and / or strengthened can be immersed using a downward movement, after which the support 5 can be removed again from the molten salt 4 using an upward movement.

[0065] The device 1 comprises a first container 6 in which a number of first regenerative material bodies 7 are arranged. The first container 6 has a number of openings through which the molten salt 4 can flow but through which the first regenerative material bodies 7 do not leak out. The first container 6 can in particular be configured as a basket with a closable lid or as a closed sieve with a closable lid.

[0066] The device 1 further comprises a second container 8 in which a plurality of second regenerative material bodies 9 are arranged. The second container 8 has a plurality of openings through which the molten salt 4 can flow but through which the second regenerative material bodies 9 do not leak out. The second container 8 can in particular be configured as a basket with a closable lid or as a closed sieve with a closable lid.

[0067] The first recycled material body 7 consists of a first recycled material, whereas the second recycled material body 9 consists of a second recycled material which is different from the first recycled material.

[0068] A guide device 10 having a number of guide rails 11 is arranged in the basin body 3. The guide device 10 guides the support body 5 and the first container 6 and the second container 8 during the downward and upward movements.

[0069] 1 shows the situation before the downward movement of the support 5 is performed. In this situation the first container 6 and the second container 8 are in a first functional position 12. The first container 6 and the second container 8 are held in the first functional position 12 by a guide device 10 in the horizontal direction and by means of a spring device 13 in the vertical direction. The spring device 13 is supported on the one hand by the bottom of the basin body 3 and on the other hand by the bottom of the first container 6 and the bottom of the second container 8.

[0070] Figure 2 shows the situation during the downward movement. The support 5 is moved, for example by means of a robot (not shown) or a transport device (not shown), onto the guiding device 10 and then vertically downwards, so that the support 5 is in effective contact with the guiding device 10 and is guided by the guide rail 11 during the further vertical movement. With its downward movement, the support 5 presses the first container 6 and the second container 8 downwards from the first functional position 12 against the force of the spring device 13 until the first container 6 and the second container 8 reach the second functional position 14. This is illustrated in Figure 3.

[0071] In the upward movement (not shown), in which the support 5 is again removed from the molten salt 4 together with the glass object 2 to be hardened and / or strengthened, the first container 6 and the second container 8 are again pushed upwards from the second position 14 by the spring device 13 until they reach the first position 12 again. This is shown in FIG. 4. The support 5 can then be lowered again with a new one (with the glass object 2) or a new next support 5 can be lowered. With each downward movement and each upward movement, a part of the molten salt 4 flows through the openings of the first container 6 and the openings of the second container 8, respectively, and thus comes into contact with the first regenerative material body 7 and the second regenerative material body 9. The molten salt 4 is also thereby stirred, so that a homogeneous distribution of all the contents in the tank body 3 is achieved.

[0072] 5 to 10 show a second embodiment of an apparatus 1 according to the invention for hardening and / or strengthening a glass body 2 in different situations during the execution of an embodiment of the method according to the invention.

[0073] The apparatus 1 comprises a bath body 3 with a molten salt 4 into which a support 5 with at least one glass object 2 to be hardened and / or strengthened can be immersed using a downward movement, after which the support 5 can be removed again from the molten salt 4 using an upward movement.

[0074] The device 1 comprises a first container 6 in which a number of first regenerative material bodies 7 are arranged. The first container 6 has a number of openings through which the molten salt 4 can flow but through which the first regenerative material bodies 7 do not leak out. The first container 6 can in particular be configured as a basket with a closable lid or as a closed sieve with a closable lid.

[0075] The device 1 further comprises a second container 8 in which a plurality of second regenerative material bodies 9 are arranged. The second container 8 has a plurality of openings through which the molten salt 4 can flow but through which the second regenerative material bodies 9 do not leak out. The second container 8 can in particular be configured as a basket with a closable lid or as a closed sieve with a closable lid.

[0076] The first recycled material body 7 consists of a first recycled material, whereas the second recycled material body 9 consists of a second recycled material which is different from the first recycled material.

[0077] A guide device 10 having a number of guide rails 11 is arranged in the basin 3. The guide device 10 guides the support body 5 and the first and second containers 6 and 8 during the downward and upward movements. In this embodiment, the guide device 10 is designed in such a way that the first and second containers 6 and 8 remain fixed in their respective current vertical positions unless the first and second containers 6 and 8 are actively pulled upwards or actively pushed downwards by means of the support body 5.

[0078] 5 shows the situation before the execution of the downward movement of the support 5. In this situation the first container 6 and the second container 8 are in the first functional position 12. The first container 6 and the second container 8 are held in the first functional position 12 by the guiding device 10 in the horizontal and vertical directions.

[0079] The first container 6 and the second container 8 have connecting elements 15 and the support 5 has counter-connecting elements 16, by means of which the first container 6 and the second container 8 can again be removably fastened to the support 5. It is particularly advantageously provided for the locking connection by means of the connecting elements 15 and the counter-connecting elements 16 to be established, in particular automatically or in an externally controlled manner, when the support 5 is placed on the first container 6 and the second container 8. Alternatively or additionally it is also advantageously provided for the locking connection to be released automatically or in an externally controlled manner when the first container 6 and the second container 8 reach the first functional position 12 or the maintenance position 17 after the upward movement, as will be explained in more detail in the following paragraphs.

[0080] The support 5 is moved, for example by means of a robot (not shown) or a transport device (not shown), onto the guiding device 10 and then vertically downwards, so that the support 5 is in effective contact with the guiding device 10 and is guided by the guide rails 11 during the further vertical movement. With its downward movement, the support 5 pushes the first container 6 and the second container 8 downwards from the first functional position 12 until the first container 6 and the second container 8 reach the second functional position 14. This is illustrated in Figure 6, which shows the situation after the downward movement has been performed.

[0081] 7 shows the situation during the upward movement, during which the support 5 is again removed from the molten salt 4 together with the glass object 2 to be hardened and / or strengthened. In the process, the support 5 simultaneously pulls the first container 6 and the second container 8 connected by means of the connecting element 15 and the counter-connecting element 16 upwards until the first and second containers 6, 8 reach the first functional position 12.

[0082] Subsequently, the effective connection of the connecting element 15 and the counter-connecting element 16 is released and the support 5 can be removed. The support 5 can then be lowered again with a new one (with glass object 2) or a new next support 5 can be lowered. With each lowering movement and each rising movement, a part of the molten salt 4 flows through the openings of the first container 6 and the openings of the second container 8, respectively, and thus comes into contact with the first regenerative material body 7 and the second regenerative material body 9. The molten salt 4 is also thereby stirred, so that a homogeneous distribution of all the contents in the tank body 3 is achieved.

[0083] The regenerator material 9 must be replaced, for example after a preset or predefinable number of hardening and / or strengthening processes. In order to be able to carry out the replacement, the first container 6 and the second container 8 are transferred to a maintenance position 17 outside the molten salt 4. For this purpose, the connection of the first container 6 and the second container 8 to the support 5 is not released after the upward movement, so that the support 5 can lift the first container 6 and the second container 8 beyond the first functional position 12 from the molten salt 4 to the maintenance position 17. This is illustrated in FIG. 9. Subsequently, the effective connection of the connecting element 15 and the counter-connecting element 16 is released and the support 5 can be removed.

[0084] The used first regenerative material body 7 and / or the used second regenerative material body 9 can be removed from the first container 6 and the second container 8 in the maintenance position 17 and a new first regenerative material body 7 and / or a new second regenerative material body 9 can be filled. Alternatively, it is also possible to replace the first container 6 with a first container 6 already filled with a fresh first regenerative material body 7 and / or to replace the second container 8 with a second container 8 already filled with a fresh second regenerative material body 9. For this purpose, it is advantageously provided that the respective container 6, 8 is removed from the maintenance position 17 and the container 6, 8 filled with a new regenerative material body 7, 9 is brought to the maintenance position 17.

[0085] Subsequently, the first vessel 6 and the second vessel 8 can be connected again to the support 5 and transferred into the molten salt 4 .

[0086] Figure 11 shows a third embodiment of an apparatus 1 according to the invention for hardening and / or strengthening a glass object 2 (not shown in Figure 11), the apparatus 1 having a bath body 3 with a molten salt 4. The molten salt 4 comprises for example potassium nitrate or consists for example of potassium nitrate.

[0087] The apparatus 1 comprises a movement device 18. The movement device 18 comprises a first robotic arm 19 which supports a first container 6 in which a plurality of first recyclable material objects 7 are arranged. The movement device 18 further comprises a second robotic arm 20 which supports a second container 8 in which a plurality of second recyclable material objects 9 are arranged. Alternatively, it is also possible for a single robotic arm to handle the first container 6 and the second container 8 simultaneously or in succession.

[0088] The first vessel 6 and the second vessel 8 have a plurality of openings through which the molten salt 4 can flow. The first body of recycled material 7 consists of a first recycled material, whereas the second body of recycled material 9 consists of a second recycled material different from the first recycled material.

[0089] The openings of the first container 6 are dimensioned such that a first body of recycled material 7 cannot pass through them. The openings of the second container 8 are dimensioned such that a second body of recycled material 9 cannot pass through them.

[0090] Using the movement device 18, the first container 6 is lowered (immersed) into the molten salt 4. The movement device 18 can further move the first container 6 in the molten salt 4, which enhances the action of the first regenerative material body 7. The movement device 18 can also lower (immerse) the second container 8 into the molten salt 4. The movement device 18 can also move the second container 8 in the molten salt 4, which enhances the action of the second regenerative material body 9. The movement device 18 can be controlled so that the first container 6 and the second container 8 are brought into contact with the molten salt 4 at a time interval. However, it is also possible that the first container 6 and the second container 8 are brought into contact with the molten salt 4 simultaneously or with a time overlap.

[0091] Figure 12 shows a fourth embodiment of an apparatus 1 according to the invention for hardening and / or strengthening a glass object 2 (not shown in Figure 12), the apparatus 1 having a bath body 3 with a molten salt 4. The molten salt 4 for example comprises potassium nitrate or consists of potassium nitrate (apart from contaminants).

[0092] The tank body 3 is connected at two points to a flow path 21, in which a pump 22 is provided. By means of the pump 22, a part of the molten salt 4 is respectively taken from the tank body 3 and, after passing through the flow path 21, is supplied again to the tank body 3. The flow path 21 is actively heated by means of a heating wire 23 in order to avoid a temperature drop of the molten salt 4 in the flow path 21 and thus a solidification of the molten salt 4 in the flow path 21.

[0093] A first receiver 24 is provided in the flow path 21 for receiving a first container 6 having at least one first recycled material body 7. A second receiver 25 is also provided in the flow path 21 for receiving a second container 8 having at least one second recycled material body 9.

[0094] The device 1 further has a plurality of further first containers 6 containing a first recycled material body 7, as well as a plurality of further second containers 8 containing a second recycled material body 9, which can be taken into the respective receptacles 24, 25 when the first recycled material body 7 to the second recycled material body 9 in the respective first receptacle 24 to the second receptacle 25 has been used. [Explanation of symbols]

[0095] 1 device 2 Glass objects 3 Tank body 4 Molten Salt 5 Support 6 First Container 7. The first recycled material 8 Second Container 9. Second recycled material body 10 Guidance device 11 Guide rail 12 First functional position 13 Spring device 14 Second Functional Position 15 Connected Elements 16 Opposite connecting elements 17 Maintenance Position 18 Exercise equipment 19 First Robot Arm 20 Second Robot Arm 21 Flow Path 22 Pump 23 Heating wire 24 First Receptor 25 Second Receptor

Claims

1. A method for regenerating a molten salt for a glass hardening process and / or a glass strengthening process, comprising: bringing at least one first regeneration material body (7) made of a first regeneration material and at least one second regeneration material body (9) made of a second regeneration material different from the first regeneration material into contact with the molten salt (4) simultaneously or sequentially; A method characterized by the above.

2. A plurality of first regeneration material bodies (7) made of the first regeneration material and a plurality of second regeneration material bodies (9) made of the second regeneration material are brought into contact with the molten salt (4) simultaneously or sequentially; The method according to claim 1, characterized by the above.

3. a. The first regeneration material bodies (7) have the same or at least similar shapes and / or sizes to each other, and / or b. The second regeneration material bodies (9) have the same or at least similar shapes and / or sizes to each other; The method according to claim 2, characterized by the above.

4. The at least one first regeneration material body (7) is different from the at least one second regeneration material body (9) in terms of shape and / or size; The method according to claim 1, characterized by the above.

5. The at least one first regeneration material body (7) is configured as a sphere, or a plate, or a corrugated plate, or a corrugated plate with an irregular surface, or a frit, or a fiber, and / or The at least one second regeneration material body (9) is configured as a sphere, or a plate, or a corrugated plate, or a frit, or a fiber; The method according to claim 1, characterized by the above.

6. At least one of the regeneration materials is glass or contains glass; The method according to claim 1, characterized by the above.

7. At least one of the regeneration materials is a glass or a porous glass made of a glass system having a phase separation tendency, or contains a glass or a porous glass made of a glass system having a phase separation tendency; The method according to claim 6, characterized by the above.

8. At least one of the regeneration materials is a silicon dioxide-rich glass or a porous silicon dioxide-rich glass, or contains a silicon dioxide-rich glass or a porous silicon dioxide-rich glass; The method according to claim 6, characterized by the above.

9. At least one of the recycled materials is, or contains, Vycor glass, The method according to claim 6, characterized in that.

10. At least one of the recycled materials contains amorphous silicic acid, The method according to claim 1, characterized in that.

11. One of the recycled materials is configured to absorb calcium from the molten salt (4), The method according to claim 1, characterized in that.

12. One of the recycled materials contains calcium but is configured not to release calcium into the molten salt (4), The method according to claim 1, characterized in that.

13. At least one of the recycled materials is configured to absorb lithium from the molten salt (4), The method according to claim 1, characterized in that.

14. One of the recycled materials contains lithium but is configured not to release lithium into the molten salt (4), The method according to claim 1, characterized in that.

15. One of the recycled materials is potassium-containing silicate glass or potassium-aluminosilicate glass, The method according to claim 1, characterized in that.

16. One of the recycled materials is melted from a raw material mixture containing at least one additional oxide other than potassium oxide, or at least one additional oxide from the group of aluminum oxide, boron oxide, sulfur oxide, calcium oxide, The method according to claim 1, characterized in that.

17. a. One of the recycled materials is melted from a raw material mixture containing a plurality of oxides other than potassium oxide, or a plurality of oxides from the group of aluminum oxide, boron oxide, sulfur oxide, calcium oxide, or b. One of the recycled materials is melted from a raw material mixture containing a plurality of oxides other than potassium oxide, or a plurality of oxides from the group of aluminum oxide, boron oxide, sulfur oxide, calcium oxide in different proportions, The method according to claim 1, characterized in that.

18. One of the recycled materials is melted from a raw material mixture having a proportion of silicon oxide in the range from 40% by mass to 75% by mass, or in the range from 50% by mass to 65% by mass, or at 57.5% by mass, The method according to claim 1, characterized in that.

19. One of the recycled materials is melted from a raw material mixture having a potassium oxide ratio in the range of 20 mass percent to 40 mass percent, or in the range of 25 mass percent to 35 mass percent, or 32.5 mass percent. The method according to claim 1, characterized in that.

20. One of the recycled materials is melted from a raw material mixture having an aluminum oxide ratio in the range of 1 mass percent to 10 mass percent, or in the range of 2 mass percent to 6 mass percent, or 2.5 mass percent or 5 mass percent. The method according to claim 1, characterized in that.

21. One of the recycled materials is melted from a raw material mixture having a calcium oxide ratio in the range of 0 mass percent to 15 mass percent, or in the range of 6 mass percent to 10 mass percent, or 8 mass percent. The method according to claim 1, characterized in that.

22. One of the recycled materials is melted from a raw material mixture having a boron oxide ratio in the range of 0 mass percent to 10 mass percent. The method according to claim 1, characterized in that.

23. One of the recycled materials contains at least one alkaline earth metal. The method according to claim 1, characterized in that.

24. The first recycled material is configured to absorb a first ionic component from the molten salt (4), and the second recycled material is configured to absorb a second ionic component different from the first ionic component from the molten salt (4). The method according to claim 1, characterized in that.

25. a. The at least one first recycled material body (7) is disposed in a first container (6) to be in contact with the molten salt (4), and the first container (6) has at least one opening through which the molten salt of the molten salt (4) can flow without the at least one first recycled material body (7) leaking out of the first container (6), and / or b. The at least one second regeneration material body (9) is disposed in a second container (8) and brought into contact with the molten salt (4), and the second container (8) has at least one opening through which the molten salt of the molten salt (4) can flow without the at least one second regeneration material body (9) leaking out of the second container (8). The method according to claim 1, characterized in that.

26. The first container (6) and / or the second container (8) is made of special steel. The method according to claim 25, characterized in that.

27. The at least one first regeneration material body (7) and / or the at least one second regeneration material body (9) is moved in the molten salt (4) or in the molten salt (4) at continuous or time-spaced intervals. The method according to claim 1, characterized in that.

28. A part of the molten salt (4) is guided through a flow path (21) where the at least one first regeneration material body (7) and / or the at least one second regeneration material body (9) is present at continuous or time-spaced intervals. The method according to claim 1, characterized in that.

29. The molten salt (4) contains potassium and / or potassium nitrate. The method according to claim 1, characterized in that.

30. At least one other regeneration material body made of a regeneration material different from the first regeneration material and the second regeneration material is used to regenerate the molten salt (4) by being brought into contact simultaneously or sequentially. The method according to claim 1, characterized in that.

31. A method for hardening and / or strengthening a glass object, in which the glass object is brought into contact with a molten salt, and the molten salt (4) is regenerated continuously, or at time intervals, or at regular time intervals, using the method according to any one of claims 1 to 30. A method characterized in that.

32. a. The at least one first regeneration material body (7) and the glass object (2) are brought into contact with the molten salt (4) such that they are in contact with the molten salt (4) simultaneously or at least temporally overlapping, and / or b. The at least one second recycled material body (9) and the glass object (2) are brought into contact with the molten salt (4) such that they are in contact with the molten salt (4) simultaneously or at least temporally overlapping. A method according to claim 31, characterized in that.

33. An apparatus for hardening and / or strengthening glass, comprising a salt bath having a molten salt, wherein the apparatus (1) has at least one first recycled material body (7) made of a first recycled material and at least one second recycled material body (9) made of a second recycled material different from the first recycled material, and these can be continuously in contact with the molten salt (4) or brought into contact with the molten salt (4) simultaneously or sequentially. An apparatus characterized by that.

34. The apparatus (1) includes the at least one first recycled material body (7) and has a first container (6) that can be or has been incorporated into the molten salt (4), and the first container (6) has at least one opening through which the molten salt of the molten salt (4) can flow, and / or The apparatus (1) includes the at least one second recycled material body (9) and has a second container (8) that can be or has been incorporated into the molten salt (4), and the second container (8) has at least one opening through which the molten salt of the molten salt (4) can flow. An apparatus according to claim 33, characterized in that.

35. The first container (6) is configured as a cage, a basket, or a sieve, and / or The second container (8) is configured as a cage, a basket, or a sieve. An apparatus according to claim 34, characterized in that.

36. The first container (6) and / or the second container (8) is made of special steel. An apparatus according to claim 34, characterized in that.

37. The first container (6) and the second container (8) are configured differently with respect to shape and / or size. An apparatus according to claim 34, characterized in that.

38. The first container (6) and / or the second container (8) is configured as an exchangeable cartridge. An apparatus according to claim 34, characterized in that.

39. The device (1) has a moving device (18) for moving and / or displacing the regeneration material bodies (7, 9) continuously or at time-intervals spaced apart in the molten salt (4). The device according to claim 33, characterized in that.

40. The device (1) has a flow path (21) in which the first regeneration material body (7) and / or the second regeneration material body (9) is / are located, and a part of the molten salt (4) can flow through the flow path (21) continuously or at time-intervals spaced apart. The device according to claim 33, characterized in that.

41. The device (1) has a pump (22) for pumping the molten salt (4) through the flow path (21). The device according to claim 40, characterized in that.

42. The device (1) has at least one other regeneration material body made of at least one other regeneration material different from the first and the second regeneration materials. The device according to claim 33, characterized in that.

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