text:
|Publication number
|Publication type
|Application number
|Publication date
|Dec 1, 2009
|Filing date
|May 10, 2004
|Priority date
|Jan 9, 1998
|Fee status
|Also published as
|Publication number
|Pierre Jeanvoine, Tanguy Massart, Anne Berthereau
|Original Assignee
|Saint-Gobain Glass France
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (37), Non-Patent Citations (4), Referenced by (15), Classifications (27), Legal Events (1)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a Division of U.S. application Ser. No. 10/195,070 filed on Jul. 15, 2002, now U.S. Pat. No. 6,739,152, which is a Division of U.S. application Ser. No. 09/367,879 filed on Jan. 18, 2000, now U.S. Pat. No. 6,460,376, which is a National Stage of International PCT application No. PCT/FR99/00027, filed Jan. 8, 1999.
1. Field of the Invention
The invention relates to a process for melting and refining vitrifiable materials for the purpose of continuously feeding glass-forming plants with molten glass.
2. Description of the Related Art
More particularly intended are plants for forming flat glass such as float or rolling plants, but also plants for forming glassware of the bottle or flask type, plants for forming glass fibres of the mineral wool type for thermal or acoustic insulation or else textile glass fibres called reinforcing fibres.
A great deal of research has been carried out on these processes, which schematically comprise a first melting step followed by a refining step intended to condition the molten glass thermally and chemically and in eliminating therefrom any batch stone, bubbles or any cause of defects appearing after forming.
In the melting range, it has thus been sought, for example, to speed up the melting process or to improve its energy efficiency. Mention may thus be made of the process consisting in rapidly heating the vitrifiable materials in a homogeneous and controlled manner while carrying out intense mechanical stirring allowing the still-solid vitrifiable materials to be brought into intimate contact with the already-liquid phase. This process is especially detailed in Patents FR-2,423,452, FR-2,281,902, FR-2,340,911 and FR-2,551,746 and generally uses electrical heating means of the submerged-electrode type.
Another type of melting process has been developed, for example of the type of those described in U.S. Pat. No. 3,627,504, U.S. Pat. No. 3,260,587 or U.S. Pat. No. 4,539,034 which consist in using, as heating means, submerged burners, that is to say burners fed with gas and air, these generally being placed so as to be flush with the bottom wall so that the flame develops within the mass of vitrifiable materials during liquefaction.
In either case, although it is possible actually to very significantly reduce the residence time of the vitrifiable materials in the melting chamber and to considerably increase the production efficiency compared with "conventional" melting operations, the molten glass being molten is, on the other hand, in the form of a foam which is difficult to refine—it is especially difficult to guarantee the quality of the final glass, especially optical glass.
Research has also been conducted in the refining field. Thus, it is, for example, known from Patent EP-775,671 and U.S. Pat. No. 4,919,097 to carry out at least part of the refining operation under reduced pressure, thereby making it possible, for example, to obtain glass very low in sulphates and with a high redox. However, such refining causes intense foaming, which may be difficult to control and remove.
The object of the invention is therefore to improve melting and refining processes, aiming especially to use plants which are more compact and/or have greater operating flexibility and/or greater production efficiency, etc., without these industrial advantages being obtained to the detriment of the quality of the glass produced.
The subject of the invention is firstly a process for melting and refining vitrifiable materials, which is characterized by the combination of two characteristics:
on the one hand, all or part of the thermal energy necessary for melting the vitrifiable materials is supplied by the combustion of fossil fuel(s) with at least one oxidizer gas, the fuels/gas or the gaseous products resulting from the combustion being injected below the level of the mass of vitrifiable materials,
on the other hand, the refining of the vitrifiable materials after melting comprises at least one step of subjecting them to subatmospheric pressure.
There has in fact proved to be an extremely advantageous synergy from an industrial standpoint between the use of melting called hereafter "melting by submerged burners" for the sake of simplicity and that of refining at reduced pressure.
However, although the principle of reduced-pressure refining was known in its generality, it remained difficult to use and the user was not sure of obtaining the same acceptable residual level of bubbles/batch stones as with conventional refining. In the invention, very particular refining is used by changing a size parameter, namely instead of feeding the refining zone with "conventional" molten glass to be refined, it is fed here with a glass obtained by melting by submerged burners, that is to say with glass having very special characteristics in the sense that it is foamy throughout, with a relatively low density compared with that of a standard glass. Nothing would suggest that it would be possible to refine an initially relatively foamy glass at reduced pressure.
Surprisingly, this has proved to be possible as it has been discovered that this foamy glass resulting from melting by submerged burners also had the characteristic of containing only an extremely small amount of sulphates, which may or may not have been present initially. The sulphate content is generally less than 600 and even less than 200 or less than 100 ppm, or indeed less than 50 ppm, expressed by weight of SO3 in the glass leaving the melting chamber, this being so without having to control or reduce the amount of sulphate normally contained in the batch materials used, unintentionally, or even by intentionally adding sulphates to the vitrifiable materials. It is this low amount of sulphate which allows effective refining under reduced pressure without any problem. In contrast, a high or simply "standard" sulphate content in the glass to be refined would have caused, during reduced-pressure refining, a very high expansion of the foam by desulphation, which expansion would have been very difficult to control. The fact that there is almost no sulphate in the glass leaving the melting chamber may especially be explained by the partial pressure of water generated by the combustion by burners submerged in the vitrifiable materials.
It should be noted that a desulphated glass gives fewer problems of volatile compounds in the float bath, fewer risks of the formation of tin sulphide and therefore, finally, fewer risks of a tin defect in the sheet of glass.
Another highly advantageous characteristic of the glass leaving the melting chamber according to the invention should also be noted: although it is actually in the form of a kind of foam which remains to be refined, it is possible to control the size of the bubbles which it contains and, especially in certain cases, to remove almost all the smallest bubbles, that is to say those having a diameter of less than 200 μm, by carrying out, on this glass while it is being melted, a kind of "microrefining" prior to the actual refining after the melting, this microrefining facilitating the coalescence of the bubbles and the disappearance of the smaller bubbles in favor of the larger ones and being promoted by the addition into the vitrifiable materials of refining promoters of the coke or sulphate type. Furthermore, this glass leaving the melting chamber generally has a particularly low residual amount of batch stone, thereby also, just like the size of the bubbles, facilitating the refining operation after the melting operation.
The invention therefore makes it possible to have glasses which are very low in sulphate even before the refining operation, therefore glasses which are at least as low, or even deplete, in sulphate after refining, this being so without having to purify/select vitrifiable materials so that they are low in sulphate. On the contrary, it is even possible to add sulphate at the start, something which is completely surprising and advantageous.
One advantageous effect obtained by the combination according to the invention relates to the energy cost of the process; melting by submerged burners makes it possible to avoid using electrical melting of the submerged-electrode type, the cost of which may be very significant depending on the country. Furthermore, and this is the most important point, melting by submerged burners creates convective stirring within the vitrifiable materials during liquefaction, as explained in detail below. This very strong mixing between materials not yet liquefied and those which are already molten is extremely effective and makes it possible to achieve, for vitrifiable materials of the same chemical composition, melting at a lower temperature and/or melting which is much more rapid than with conventional heating means. Refining under reduced pressure also makes it possible to refine the glass at a lower temperature and much more rapidly. This is because lowering the pressure during refining causes an increase in the molar volume of the gases contained in the molten vitrifiable materials, hence an increase in the volume of bubbles that they contain and consequently an increase in their rate of rise to the surface of the bath and to their rate of removal.
By refining at reduced pressure it is possible "to be allowed" to work at lower temperatures than in conventional refining operations, actually within the lower temperatures used in the technique of melting by submerged burners.
The temperatures encountered both in melting and reining according to the invention are therefore completely compatible with and matched to each other, and are everywhere lower than in the usual processes, something which is economically very advantageous, simply in terms of energy cost, but also by the selection of refractory-type materials used in the manufacture of the plants—materials which are less hot corrode more slowly.
The residence times in the melting and refining zones are also very significantly reduced and are compatible, this obviously having a very positive effect on the production efficiency and on the output of the plant in its entirety. At the same time, the invention makes it possible to obtain plants which are very compact—this is because melting by submerged burners, again due to the very strong mixing that it causes, allows the size of the melting chamber to be considerably reduced. Furthermore, refining under reduced pressure has the same consequences on the size of the compartment(s) where this operation is carried out—overall, the plant may therefore be very compact, with clear advantages in terms of construction cost, of operating simplification, of reduction in the wear of the structural materials, etc.
With regard to the melting operation, the oxidizer chosen may, according to the invention, be based on air, on oxygen-enriched air or even substantially based on oxygen. A high oxygen concentration in the oxidizer is in fact advantageous for various reasons: it thus reduces the volume of combustion smoke, this being favorable from the energy standpoint and avoiding any risk of excessive fluidization of the vitrifiable materials which could cause them to splash onto the superstructures or roofs of the melting chamber. Furthermore, "the flames" obtained are shorter and more emissive, allowing more rapid transfer of their energy to the vitrifiable materials and secondarily making it possible to reduce, if desired, the depth of the "bath" of vitrifiable materials being liquefied. We speak here of "flames", but these are not necessarily flames in the usual sense of the term. We may speak, more generally of "combustion regions". Furthermore, any emission of polluting NOx gas is thus reduced to the minimum.
With regard to the selection of the fuel, this may or may not be of the gaseous fossil fuel type, such as natural gas, propane, fuel oil or any other hydrocarbon fuel. It may also be hydrogen. The process of melting by submerged burners according to the invention is therefore an advantageous means of using hydrogen, which is, moreover, difficult to use with "overhead", non-submerged, burners, given the low-emissivity character of the flames obtained by H2/O1 combustion.
Combining the use, in melting by submerged burners, of an oxygen oxidizer and of a hydrogen fuel is a good means of ensuring effective heat transfer of the energy from the burners to the molten glass, leading moreover to a completely "clean" process, that is to say without the emission of nitrogen oxides, NOX, or of greenhouse gases of the COx type, other than that which may arise from the decarbonization of the batch materials.
Advantageously, the melting is carried out according to the invention in at least one melting chamber which is equipped with burners which are placed so that their combustion regions or combustion gases develop in the mass of vitrifiable materials during melting. They are thus made to pass through its side walls and/or the bottom wall, and/or to suspend them from the top, fastening them to the roof or to any suitable superstructure. These burners may be such that their gas supply pipes are flush with the wall through which they pass. It may be preferable for these pipes to "enter", at least partly, the mass of vitrifiable materials so as to prevent the flames from being too great near the walls and not to cause premature wear of the refractory materials. It is also possible to choose to inject only the combustion gases, the combustion regions being produced outside the melting chamber proper.
As mentioned above, it has turned out that this method of heating caused intense convective stirring of the vitrifiable materials—convection loops thus form on each side of the combustion regions or "flames" or streams of combustion gases, permanently mixing the molten and not yet molten materials very effectively. This thus results in the highly favorable characteristics of "stirred" melting, without having to make use of mechanical stirring means which are not very reliable and/or subject to rapid wear.
Preferably, the height of the mass of vitrifiable materials in the melting chamber and the height at which the combustion regions or gases resulting from the combustion develop are adjusted so that these combustion regions/gases remain within the mass of the vitrifiable materials—the aim is thus to allow the convective circulation loops to be established in the material during liquefaction.
In general, this type of melting makes it possible to considerably reduce the emission of any type of dust in the melting chamber and of any gas of the NOx type since heat exchange takes place very quickly, thereby avoiding the temperature peaks likely to be conducive to the formation of these gases. It also considerably reduces the emission of gases of the COx type.
Optionally, the melting operation may be preceded by a step of preheating the vitrifiable materials to a temperature which is, however, markedly less than that necessary to liquefy them, for example to at most 900� C. In order to carry out this preheating operation, the thermal energy of the smoke may advantageously be recovered. By thus extracting the heat from the smoke, the specific energy consumption of the plant may be decreased overall.
The vitrifiable materials may comprise batch materials, but also cullet or even scrap intended to be vitrified. They may also comprise combustible elements (organic matter): it is thus possible to recycle, for example, mineral fibres which have been sized with binder (of the type used in thermal or acoustic insulation or of those used in the reinforcement of plastics), window panes laminated with sheets of polymer of the polyvinyl butyral type, such as windscreens, or any type of "composite" material which combines glass with plastics, such as certain bottles. It is thus possible to recycle "glass/metal or metal compound composites" such as window panes functionalized with coatings containing metals, these being difficult hitherto to recycle since this would run the risk of gradually enriching the melting chamber with metals which would build up on the surface of the bottom wall. However, the stirring caused by the melting according to the invention prevents this sedimentation and thus allows, for example, window panes coated with layers of enamel, with layers of metal and/or of various connection elements to be recycled.
The subject of the invention is also the recycling of all these composite elements containing glass because of the melting by submerged burners in a glass furnace. In particular, furnaces with submerged burners may be provided, the essential functional of which is the manufacture of a cullet from these various materials to be recycled, which particular cullet may then serve, possibly combined with standard cullet, as batch materials for conventional glass furnaces.
Advantageously, provision may be made to introduce all or part of the vitrifiable materials into the melting chamber below the level of the mass of vitrifiable materials being melted. Some of these materials may be conventionally introduced from above the mass being liquefied and the rest from below, for example by supply means of the feed-screw type. The materials may thus be introduced directly into the mass being liquefied, at a single point or at various points distributed over the walls of the melting chamber. Such an introduction directly into the mass of materials being liquefied (hereafter referred to as the "melt") is advantageous for more than one reason: firstly, it considerably reduces any risk of batch materials flying off above the melt, and therefore reduces the amount of solid dust emitted by the furnace to the minimum. Thus, it allows better control of the minimum residence time of the materials before they are extracted into the refining zone and allows them to be selectively introduced at the point where the convective stirring is the strongest, depending on the arrangement of the submerged burners. This or these points of introduction into the melt may thus be near the surface or more deeply in the melt, for example at a melt height of between ⅕th and ⅘ths of the total height of the melt above the level of the bottom wall, or else between ⅓ and ⅔ of the height.
It has been seen that the process according to the invention makes it possible to recycle plastics in the form of composite products combined most particularly with glass, these plastics thus serving as part of the fuel. It is also possible, and advantageous, to introduce all or part of the fuel necessary for the melting by submerged burners in the form of a solid fuel (polymer-type organic materials or coal) or even a liquid fuel, this fuel being a partial substitute for at least the liquid (especially fossil) or gaseous fuels feeding the burners. In general, the term "vitrifiable materials" or "batch materials" used in the present text is intended to encompass the materials necessary for obtaining a glassy (or ceramic or glass-ceramic) matrix, but also all the additives (refining additives, etc.), all the optional liquid or solid fuels (plastic of composite or non-composite material, organic matter, coal, etc), and any type of cullet.
The process according to the invention may operate with a high level of cullet.
As mentioned above, the refining according to the invention is therefore carried out on molten vitrifiable materials of the glass type in the foamy state. Typically, this foam has a relative density of approximately 1 to 2 for example (to be compared with a relative density of about 2.4 in the case of non-foamy glass), preferably a sulphate content of at most 100 or even of at most 50 ppm expressed as weight of SO3 and most of the bubbles having a diameter of at least 200 μm. It may thus have a density of between 0.5 and 2 g/cm2, especially 1 to 2 g/cm3.
In order to improve the performance characteristics of the refining operation, various refining promoters are preferably added to the vitrifiable materials, the aim being especially to remove from the glass any bubbles having a diameter of less than 200 μm right from the melting stage, as mentioned above. These may be reducing additives, such as coke (which also allows the redox of the glass to be adjusted). In this case, it is advantageous to select coke powder which has an average particle size of less than 200 μm. They may also be sulphates. Refining under reduced pressure causes the bubbles to grow, the aim being for this growth to occur rapidly and that it is possible to remove and burst the bubbles on the surface of the melt easily. Other refining promoters will be more effective during the stage of the refining proper, after the melting stage. They allow the foam to be "destabilized"; they may, for example, be fluorine of a fluorine or chlorine compound, more generally halides, or else a nitrate of the NaNO3 type; fluorine seems to lower the viscosity of the glass and thus helps to drain the films which form between the bubbles, which draining promotes collapse of the foam. It also lowers the surface tension of the glass.
Another factor influencing the way the bubbles grow during the refining under reduced pressure is the nature of the gases above the molten material. It is possible, of course, simply to choose a partial pressure of air. It is also possible to choose to enrich the atmosphere with an inert gas of the nitrogen type, or even to choose only a partial pressure of an inert gas of the nitrogen type. This is because it has been noticed that choosing a residual pressure of an inert gas of the nitrogen type was favorable to bursting of the bubbles on the surface during the refining operation. In fact, too high a concentration of oxidizing gas of the O2 type seems unfavorably to tend to reduce this bursting.
Advantageously, the subatmospheric pressure at which at least part of the refining is carried out is less than or equal to 0.5 atmospheres (0.5�105 Pa), especially about 0.3 to 0.01 atmospheres (approximately 3�104 to 1�103 Pa).
Advantageously, the process according to the invention makes it possible to carry out the melting and/or refining at temperatures not exceeding 1400� C., especially at 1380� C. or 1350� C.
According to a first variant, the refining according to the invention may be carried out in at least one static compartment (one which does not move during operation) downstream of the melting chamber, at least one zone in the static chamber being at a reduced pressure.
According to a second variant, the refining is always carried out downstream of the melting chamber but in a compartment capable of being rotated so as to ensure centrifugal refining, with at least one zone of the compartment, especially the furthest upstream, at a reduced pressure.
A third variant consists in a combination of the above two, especially by using, for the refining operation, a first compartment which is static with a zone under reduced pressure and then a second compartment which rotates and also comprises a zone under reduced pressure, the pressure preferably being lower than in the static compartment.
According to one way of carrying out the process according to the invention, provision is made to treat the flux of molten vitrifiable materials, between the melting phase, by at least one flow-dividing means. This means, for example an element drilled with holes via which the flow of molten glass is forced to pass, makes it possible to divide this flow into a large number of small-diameter streams. The size of the holes is advantageously chosen so as to be close to the size of the bubbles which it is desired to remove. Thus, if the flow-dividing means is placed just downstream of the atmospheric-pressure zone of the refining compartment, the reduced pressure will act very rapidly on the streams generated by the flow-dividing means and allow rapid refining, even with very large glass throughputs. The feeding of the refining compartment with glass to be refined may thus become similar to that obtained by a die emerging in a reduced-pressure chamber.
(In the context of the invention, the terms "upstream" and "downstream" refer to the direction of flow of the glass through the plant from the point where the vitrifiable materials are fed into the melting chamber to the point where the refined glass is extracted).
The melting/refining process according to the invention allows glasses of highly varied compositions and properties to be manufactured. Moreover, it makes it possible, because of its low inertia, to switch from one composition to another with very short transition times.
It thus allows relatively reduced glasses, especially those having a redox of greater than or equal to 0.3, to be manufactured. (The redox is defined as the ratio of the ferrous iron FeO content, as a percentage by weight, to the total iron content by weight of the composition expressed in the form of Fe2O3).
It also allows glasses having a high SiO2 content, for example at least 72 or even at least 750 by weight, to be manufactured, these glasses generally being difficult to melt but advantageous, especially in terms of batch material cost, because they have a low density and are very compatible with plastics. It also makes it possible to manufacture quite special glasses, having a high alkaline-earth oxide content, for example containing at least 18% by weight of CaO, which glasses are, however, quite corrosive using the conventional melting processes at a higher temperature than in the invention, as well as glasses having a low sodium oxide content of at most 11% by weight for example, or having a very low sulphate content, for example of at most 100 ppm. Glasses containing iron, with a high redox but a low sulphate content also allow glasses to be obtained which have a residual blue color which is particularly attractive and sought after in the field of flat glass for motor vehicles and for buildings, for example. Highly selective solar-protection glasses may thus be obtained on which may be deposited solar-protection layers in order to enhance the thermal performance characteristics thereof, for example layers of the TiN type, these being described especially in Patents EP-638,527 and EP-511,901.
The subject of the invention is also a melting and refining apparatus which is especially suitable for implementing the process described above and which comprises:
at least one melting chamber equipped with burners which are fed with fossil fuel(s) of the (natural) gas type and with oxidizer(s) of the air or oxygen type, the burners being placed so as to inject these gases or the gases resulting from the combustion below the level of the mass of vitrifiable materials introduced into the melting chamber,
at least one refining compartment downstream of the melting chamber and comprising at least one zone which can be subjected to subatmospheric pressure.
Advantageously, as mentioned previously, the melting chamber may be equipped with at least one means of introducing vitrifiable materials below the level of the melt, especially at least two of them, preferably in the form of an opening (or openings in the associated wall(s), with a supply means of the feed-screw type. The risks of dust flying off are thus minimized, while at the same time also optionally allowing the introduction, above the melt, of the vitrifiable materials, such as silica, on which a preheating operation may be carried out without the risk of them setting solid.
Independently of the refining operation too, the invention also depends on design improvements with regard to the walls of the melting chamber which are intended to be in contact with the melt. Several variants are possible. In certain cases, known oxide-based refractory materials may be used, such as alumina, zirconia, chromium oxide and so-called AZS refractories. It is generally preferred to combine them with a cooling system involving the circulation of a fluid of the water type (water jacket). The water jacket may be placed on the outside, the refractories then being in direct contact with the glass, or on the inside. The water jacket then has the function of creating a cooler stream of glass near the refractories, these being particularly stressed in this context as the melt generated by the submerged burners causes strong convective currents against the walls.
Another variant consists in using, in the melt zone, not refractories but only the abovementioned water jacket.
Another variant consists in using refractory materials (optionally combined with a cooling system of the water-jacket type) and in lining them with a lining made of a highly refractory metal such as molybdenum (or an Mo alloy). This lining may advantageously be held at some distance (for example from 1 to a few millimeters) from the walls of the refractories and may present the melt with a continuous contact surface (solid plate or plates made of Mo) or a discontinuous contact surface (Mo plate or plates drilled with holes). This lining has the purpose of mechanically preventing direct convection of the glass onto the refractories by generating a "still" layer of glass along the refractories, or even by preventing any contact of the glass with the latter.
In the melting chamber, all or some of the submerged burners are preferably designed so that they can inject, into the melt, a fluid which does not participate in the combustion by substituting (temporarily) for the oxidizer and/or the fuel. This fluid may be an inert gas of the N2 type or a coolant of the liquid-water type which immediately vaporizes in the melt. The fact of thus temporarily stopping the combustion, while continuing to inject a fluid at the burner, generally has two objectives: either it is desired to stop the operation of the burner and more generally, for example, of the melting chamber in its entirety, the injection of inert gas of the N2 type allowing the chamber to be made safe in the region of the burners, or it is desired to change the burner for another while the other burners are operating and while it is therefore still in the presence of a glass melt. In this case, as explained in detail below, spraying water suitably via the burner allows the glass above the burner to be temporarily frozen, creating a kind of "bell", which allows a time long enough to carry out the change without glazing the burner.
As mentioned above, the apparatus according to the invention may be provided with a flow-dividing means between the melting chamber and the refining compartment, especially just at the inlet of the refining compartment or in its furthest upstream part. This may be an element drilled with holes of suitable size.
Moreover, it should be noted that using such a flow-dividing means may also be envisaged independently of the melting means adopted: such a dividing means allows more rapid refining, with large glass throughputs, whatever the manner in which the glass is melted, for example by conventional means of the overhead (non-submerged) burner type and/or by electric melting using submerged electrodes.
Likewise, it may be advantageous to use it even if the refining operation is carried out at atmospheric pressure.
However, it is particularly advantageous to employ it in a context of melting by submerged burners which tends to generate a foam having a very high bubble content and/or in a context of refining under reduced pressure, as it considerably increases its effectiveness, which is already particularly high.
According to a first variant mentioned above, the refining compartment is static and in a vertical orientation (i.e., its height is significantly greater than its floor dimensions). This compartment comprises, according to a first embodiment, an approximately vertical internal partition which defines, in combination with the internal walls of the compartment, at least two channels. These consist, in succession, of a first channel which forces the molten vitrifiable materials to follow an ascending path and then a second channel which forces the vitrifiable materials to follow a descending path, the first channel being preferably the one which is subjected to subatmospheric pressure. A kind of siphon for the glass to be refined is thus created. This compartment is advantageously equipped with means for adjusting/regulating the head loss of the molten vitrifiable materials at the inlet of the refining compartment. Likewise, the height of the refining compartment may be adjusted depending on various criteria, especially depending on the level of underpressure chosen in the reduced-pressure zone.
According to a second embodiment, the static refining compartment used in the context of the invention is in a vertical orientation and comprises means for introducing the molten vitrifiable materials to be refined in the upper part and means for removing the refined materials in the lower part, the materials everywhere following a mainly vertical descending path in the compartment. Its design may, for example, be derived from the teachings from Patents EP-231,518, EP-253,188, EP-257,238 and EP-297,405.
According to a second variant, the refining compartment comprises at least one device capable of being rotated in order to ensure centrifugal refining, the internal walls of the device substantially defining the shape of a hollow vertical cylinder, at least in its central part. Advantageously, the device comprises a so-called upper zone at subatmospheric pressure and a so-called lower zone left at ambient pressure, these being separated from each other by one or more mechanical means of the type consisting of a metal plate drilled with one or more holes.
According to a preferred design, the device is fed at the upper part with molten vitrifiable materials by a static supply means of the flow-channel type. These supply means may comprise at least one compartment at reduced pressure in order to allow the device to be fed and/or to allow a first refining operation to be carried out.
Sealing means have to be provided in order to join the end of this supply means to the device, the sealing means being of the "dynamic seal" type or rotating seal, as explained in detail below. The device is advantageously provided with means for trapping solid particles having a density greater than that of the glass, these means especially being located in its lower zone and being in the form of notches/grooves made in its internal walls. Preferably, the speed of rotation of the device is selected to be between 100 and 1500 revolutions per minute.
The apparatus may also be provided with mechanical means which are stationary or which follow its rotation, and are capable of shearing the foam and of driving it downwards into the lower zone of the device from which the refined glass is drawn off.
These means are especially in the form of pierced deflectors, or fins placed in the upper zone of the device.
This type of centrifugal refining, with passage into a reduced-pressure zone, is particularly effective. This is because the reduced pressure will allow the greatest possible increase in the bubbles before the centrifugal refining proper: the bubbles are removed more rapidly in the device the larger their diameter. The reduced pressure will also make it possible to further decrease the residual sulphate content of the glass produced. It should be noted that a desulphated glass (this remark also applies to the first variant in which the refining is carried out statically) gives fewer problems of volatile compounds in the float bath, a reduced risk of the formation of tin sulphide and therefore finally a reduced risk of a tin defect in the sheet of glass. This also guarantees the absence of sulphides in the case of reduces glasses, especially iron sulphides which give not very desirable yellow/orange residual colors or inclusions of nickel sulphide which may cause the glass to break during heat treatment of the quenching type.
The centrifugal refining comprising a reduced-pressure phase is particularly indicated in the case of the refining of relatively foamy glass.
The invention will be explained in detail below with the aid of two non-limiting-embodiments illustrated by the following figures:
These figures are not necessarily to scale and for the sake of clarity have been extremely simplified.
The apparatuses described below are designed to melt and refine glasses of highly varied composition, here glasses intended to feed a float plant for producing flat glass. But this application is not limiting.
Furthermore, of course, all the standard glasses of the silica-soda-lime type and various types of special glasses are particularly advantageous to manufacture using the apparatuses according to the invention, especially those deemed hitherto to be difficult to melt:
glasses having a low Na2O content and a relatively high alkaline-earth oxide, especially CaO, content, this being advantageous from an economic standpoint in terms of the cost of batch materials, but also glasses which are quite corrosive at conventional melting temperatures and which are relatively hard to melt using standard processes. These may be the glass compositions described, for example, in Patent: FR 97/08261 of 1 Jul. 1997, such as (in % by weight):
SiO2 72-74.3% Al2O3 0-1.6% Na2O 11.1-13.3% K2O 0-1.5% CaO 7.5-10% MgO 3.5-4.5% Fe2O3 0.1-1%
or else of compositions of the type (expressed in percentages by weight):
66-72, especially 68-70%
0-6, especially 3-6%
4-9, especially 5-6%
0-2, especially 0-1%
Another example illustrating this family of compositions is as follows:
This glass has a lower annealing temperature, also called the strain-point temperature, of 590� C. (at which temperature the glass has a viscosity of 1014.5 poise). It also has a liquidus temperature of 1225� C., a temperature Tηlog2 of 1431� C. and a temperature Tηlog3.5 of 1140� C. (Tηlog(2) and Tηlog3.5 correspond to the temperatures that the glass has when it reaches a viscosity, in poise, of log 2 and log 3.5, respectively);
glasses having a high silica content, these also being advantageous from the economic standpoint, and having a relatively low density, the compositional ranges of which, again expressed in percentages by weight, are as follows:
SiO2 72 to 80% CaO + MgO + BaO 0.3 to 14% Na2O 11 to 17% alkaline oxides 11 to 18.5% Al2O3 0.2 to 2% B2O3 0 to 2% Fe2O3 0 to 3% SO3 optionally traces coke 0-600 ppm
and optionally coloring oxides, for example the oxide of Ni, Cr, Co, etc. (These glasses have the feature of being particularly viscous).
An example illustrating this family of compositions is as follows:
It has a relative density of approximately 2.46 (compared with relative densities of 2.52 for the standard silica-soda-lime glass of the "Planilux" type sold by Saint-Gobain Vitrage).
It was also seen above that the process according to the invention could be used to obtain reduced glasses, the high redox, the iron content and the very low sulphate content which allow glasses with a residual blue color to be obtained.
Using the process according to the invention, it is also possible to manufacture glasses having a zero or almost zero content of alkali metal oxides of the Na2O type, especially for the purpose of applications for fire-resistance glazing or for substrates used for the electronics industry. For such compositions, reference may be made especially to Patents EP-526,272 and EP-576,362.
Other glasses, especially those having a low MgO content, of the type described in Patents EP-688,741 and WO 96/00194 may also be manufactured using the process of the invention.
A first method of implementation is therefore shown in
In fact, several injection points may be provided in the walls (front walls or side wails) which may or may not be at this same height, especially in the upper half or in the lower half of this height B, for example between ⅓ and ⅔ of this height. In fact, this injection directly into the melt makes it possible to greatly reduce the amount of material flying off above the melt (emission of solid dust particles). Furthermore, depending on its configuration, it makes it possible to direct the materials at the point where the convective stirring is strongest and/or to take account of this in order for these materials to remain for at least the minimum period of time in the chamber 2 before passing into the refining zone.
The bottom wall 4 of the chamber is equipped with rows of burners 5 which pass through it and penetrate into the melting chamber over a small height. The burners 5 are preferably provided with cooling means, not shown, of the water-jacket type. The burners 5 in operation develop combustion regions in zones 6, creating, near them, convective streams within the vitrifiable material being liquefied. This convective stirring creates a foam which will transfer the thermal energy throughout the melt 7. The melting preferably takes place at about 1350� C., for example in the case of a standard glass of the family of silica-soda-lime glasses.
The walls of the chamber 2 which are in contact with the melt 7 here are made of refractory materials cooled, on the outside, by a cooling system of the water-jacket type (not shown). A variant consists in that this cooling system, with metal walls, lies against the refractories but on the inside and is therefore in contact with the melt. These two variants make it possible to slow down the wear of the refractories by superficially cooling the class near the walls of the refractories.
The operation of the burners 5 has been adapted to submerged melting in the manner shown very diagrammatically in
In normal operation (operation [a]), the pipe 51 is fed with a combustible gas of the natural-gas type (or another combustible gas or fuel oil) and the pipes 52 are fed with oxidizer, in this case oxygen for example, the CH4/O2 interaction creating a combustion region in the melt.
In safety operation (operation [b]), that is to say when it is desired to stop the combustion at the burner without the risk of it being completely glazed, nitrogen is injected via the pipe 51 and/or via the pipes 52.
In operation intended to allow the burner to be exchanged for another (operation [c]), water is injected via the pipe 51, which water instantly vaporizes in the burner or right after leaving the burner, the vapor creating a kind of roof of cooled glass above the burner; any operation of the burner is then stopped and there is then enough time to carry out the exchange before the "roof" collapses. The injected water is at least partially collected in the burner by the pipes 52 (the roles of the pipes 51 and 52 in this operating mode may also be reversed). Any other coolant being thus able to freeze the glass may also be substituted.
The burner and its various operating modes described above form one subject of the invention, independently of the overall melting and refining operation involved in the glass plant.
The molten foamy glass resulting from the melting by submerged burners is then drawn off at the bottom part by a channel 8 provided with means for adjusting the head loss of the plunger type (not shown). The head loss of the foamy glass entering the static refining compartment 9 is thus controlled. This compartment has side walls 10, a bottom wall 11 at the same level as the bottom wall of the melting chamber, and an upper wall 12 defining an approximately parallelepidal internal volume. Also provided is a partition 13 fixed to the bottom wall 11, but leaving a passage at the top. This assembly also defines a channel 14 which forces the glass to follow an ascending path and then a channel 15 forcing the glass to follow a descending path. At the highest part 16, a glass level H is formed.
The refined glass is then drawn off via a channel 17 which feeds a compartment 18 supplying the glass to the float-type forming plant (not shown).
In the refining compartment, the region of the channel 14 is put under reduced pressure, for example 0.3 atmospheres. The foamy glass coming from the channel 8 will then rise in this channel, any residual batch stone being gradually "digested" and the bubbles growing in size as they rise up in the channel. However, the degree of expansion of the foam remains very moderate because the foam coming from the melting chamber 3 has a very low residual sulphate content. In zone 16, the bubbles burst at the surface H, the foam rapidly disappears and the fully refined glass goes back down along the channel 15. If necessary, provision may be made in this region 16 for there to be auxiliary heating means, of the conventional burner or electrical-resistance element type, these being attached to the wall 12, and optionally mechanical means (not shown) of the dam type, which are intended to facilitate the bursting of the bubbles.
In order to give an order of magnitude, the height h of the refining compartment may be of the order of a few meters, for example 3 meters, the case of the chosen reduced pressure of 0.3 atm.
This sheet 40 is drilled with holes, firstly in its horizontal zone lining the bottom wall 4, so as to be able to be penetrated by the burners 5, as well as in all its other walls, with a homogeneous partition in the holes: this piercing therefore does not prevent contact between the refractories and the molten glass, however it mechanically breaks the convection movements of the glass near the refractories and thus reduces their rate of wear. The holes 41 in the walls of the lining 40, apart from those lining the bottom wall, are preferably cylindrical and of varying dimensions, those in the wall on the bottom wall side comprise holes 42 whose size is sufficient to allow the burners 5 to pass through them. The lining 40 must also be widely pierced (at 43) in its wall lining at the downstream transverse wall of the chamber so that the glass can be removed via the channel 20 a. The same applies to the zone 1′ for introducing the batch materials: there is necessarily complementarity between the holes made in the walls made of refractories and in the lining made of molybdenum.
This Mo lining is in itself an invention, which is particularly appropriate in combination with a chamber for melting by submerged burners, independently of the way in which any subsequent refining may be carried out. (The same applies to the cooling, on the external side or the glass side, of the refractories, illustrated in the previous figure).
The other difference with
A first solution consists in adopting a "dynamic" seal. The foamy glass leaving the hollow piece 23 will, due to the centrifugal force, tend to "rise" in the zone 26 and to leave spontaneously via the space left clear level with the junction 25—it is thus the glass itself which, being continuously ejected, provides the sealing function. The flow rate of the ejected glass may be limited or regulated by modulating the space between the moving assembly 21 and the fixed assembly 20.
Another solution consists in placing a so-called rotating seal of suitable composition in the junction 25. This may be a liquid-ring rotating seal, using a liquid having a very low vapor pressure, of the silicone-oil type, the operating principle of which is the same as that of liquid (ring vacuum pumps—the under pressure, in opposition to the partial vacuum existing inside the centrifuger.
The glass then flows via the holes in the plate 24 into the zone 23 provided with a venting line 27. This plate, at the very least for those parts completely submerged in the glass, may advantageously be made of molybdenum. The outer lining of the internal walls of the body of the centrifuger may consist of electrocast refractory pieces 32 comprising heat insulator 31 incorporated so that the later is not crushed by the centrifugal force. Also provided is a notch or groove 28 going around the internal (or discontinuous) wall of the part 30, which allows all the solid particles of density greater than that of the glass, of the refractory-inclusion type, to be trapped. This is because the upward flow of the glass in the centrifuger takes place in the following manner: the plate 24 divides the centrifuger into two parts and allows centrifusion of the glass as a thin layer reducing the height of the device with respect to that which would be necessary without it and without a reduced pressure being applied. One of the conditions for the glass to flow correctly upwards is that the pressure of the glass corresponding to the distance between the tops of the two parabolas be greater than the sum of the head losses and of the difference between the reduced pressure in the part 22 and the ambient pressure in the part 23, which is achievable. The glass flowing through the plate 24 will therefore be pressed against the internal walls of the part 30 in the form of a thin layer, the solid particles denser than the glass then being thrown against the walls and trapped in the grooves 28 from which they can no longer emerge. On the other hand, the bubbles grow and burst under the centripetal action towards the inside of the body of the centrifuger. Finally, in the lowest part of the part 30, the refined glass is drawn off via a channel the top of which has the approximate shape of a funnel 29. Under the standard operating condition, it is not necessary to provide glass-reheating means, the speed of rotation may be about 700 revolutions per minute and the height h of the centrifuger is, for example, 1 to 3 meters.
The use of such a flow divider also has an advantage in the case in which the refining is carried out in a static refiner, as shown in
In either case (static or centrifugal refiner), it is clear that the size of the melting/refining apparatuses currently available may be spectacularly reduced. It may furthermore be noted that it is advantageous for the partial vacuum, both in the case of the static refiner and the centrifugal refiner, to be a nitrogen vacuum, which facilitates the bursting of the bubbles and is less damaging for the metal pieces such as the piece 24 of the centrifugal refiner. It has also been advantageous to add to the vitrifiable materials refining promoters, the function of which has been described above, especially coke having a small particle size, sulphate, nitrate or fluorine.
Moreover, it should be noted that molybdenum optionally used in the melting chamber and/or in the refining compartment may consist of platinum.
It is important to emphasize that, although the combination of melting by submerged burners with a refining step using reduced pressurization is extremely advantageous, the invention also relates to these two aspects taken separately. Thus, it may be advantageous to use the method of melting by submerged burners with a standard refining step and, reciprocally, to use refining stet, with reduced pressurization following a melting step using conventional heating means, while still remaining within the scope of the invention, even if the synergy emphasized above is then no longer obtained.
It should also be noted that it may be advantageous to use the method of melting by submerged burners without any longer having to make any use of refining in the usual sense of the term. This may be the case in the field of fiberizing, in which it may be envisaged to feed the internal centrifugal fiberizing machines directly with foamy glass obtained using melting by submerged burners, the centrifuging necessarily carried out by this fiberizing technique achieving, de facto, the refining of the glass. It is also possible to envisage direct flotation of the foamy glass coming from the melting operation, for the purpose of manufacturing foam glass used as insulation, for example in the building industry.
It is also possible to apply this method of melting for recycling glass/metal or glass/plastic composite products, as mentioned above, either for producing usable glass or to produce cullet for feeding a conventional glass-making furnace (depending, in particular, on the proportion of these composite products with respect to the rest of the more conventional vitrifiable materials).
|Cited Patent
|Filing date
|Publication date
|Dec 24, 1969
|Sep 21, 1971
|Glass Container Ind Res
|Process fo melting glass
|Apr 2, 1971
|Aug 28, 1973
|Owens Illinois Inc
|Method for refining molten glass
|Sep 28, 1972
|Jun 25, 1974
|Owens Illinois Inc
|Method for rapidly melting and refining glass
|Oct 29, 1974
|Feb 17, 1976
|Owens-Illinois, Inc.
|Method for removing gaseous inclusions from molten glass
|Nov 29, 1974
|Apr 20, 1976
|Owens-Illinois, Inc.
|Method for rapidly melting and refining glass
|Jan 20, 1975
|Nov 16, 1976
|Owens-Illinois, Inc.
|Apparatus for refining glass
|Apr 16, 1975
|Aug 9, 1977
|Lothar Jung
|Method for the conversion of crystalline silica raw materials into amorphous silica
|Mar 9, 1977
|Mar 28, 1978
|Ppg Industries, Inc.
|Apparatus and method for cooling a glass ribbon forming chamber
|Apr 17, 1981
|Oct 12, 1982
|Owens-Illinois, Inc.
|Method and apparatus for preheating pulverous materials prior to their introduction into a melting furnace
|Jul 19, 1984
|Sep 3, 1985
|Ppg Industries, Inc.
|Melting of glass with staged submerged combustion
|Aug 12, 1986
|Nov 3, 1987
|Ppg Industries, Inc.
|Vacuum refining of glassy materials with controlled foaming
|Aug 7, 1986
|Apr 19, 1988
|Ppg Industries, Inc.
|Melting and vacuum refining of glass or the like and composition of sheet
|Apr 3, 1987
|Oct 25, 1988
|Ppg Industries, Inc.
|Method for rapid induction heating of molten glass or the like
|Jun 29, 1987
|Oct 25, 1988
|Ppg Industries, Inc.
|Vacuum refining of glass or the like with enhanced foaming
|Jan 25, 1988
|Mar 14, 1989
|Owens-Corning Fiberglas Corporation
|Refractory metal substrate and coatings therefor
|Jan 3, 1989
|Apr 24, 1990
|Ppg Industries, Inc.
|Vacuum refining of glassy materials with selected water content
|Dec 20, 1991
|Sep 21, 1993
|Youichi Yabuki
|Apparatus for cutting molten glass for forming glass products
|Jan 19, 1993
|May 31, 1994
|Asahi Glass Company Ltd.
|Vacuum degassing method and its apparatus
|Mar 10, 1995
|Sep 3, 1996
|Masson; Guy
|Device for sampling and pumping liquids contained in a chemical reaction vessel, drum or storage tank
|Nov 20, 1996
|Dec 15, 1998
|Asahi Glass Company Ltd.
|Refining method for molten glass and an apparatus for refining molten glass
|Oct 1, 1998
|Sep 19, 2000
|Asahi Glass Company Ltd.
|Vacuum degassing apparatus for molten glass
|Feb 12, 1999
|Mar 20, 2001
|Asahi Glass Company Ltd.
|Vacuum degassing apparatus for molten glass and method to rise vacuum degassing apparatus temperature
|Sep 15, 1999
|Sep 25, 2001
|Asahi Glass Company Ltd.
|Vacuum gas releasing system
|Jun 1, 1999
|Oct 30, 2001
|Asahi Glass Company Ltd.
|Vacuum degassing apparatus for molten glass
|Jun 8, 1999
|Nov 20, 2001
|Asahi Glass Company Ltd.
|Vacuum degassing method for molten glass
|Jun 7, 1999
|Jan 1, 2002
|Asahi Glass Company Ltd.
|Vacuum degassing apparatus for molten glass and method for building it
|May 14, 1999
|Jun 11, 2002
|Schott Glas
|Process for physical refinement of a liquid especially a glass melt, and apparatus for performing said process
|Dec 29, 1999
|Jun 18, 2002
|Asahi Glass Company Ltd.
|Vacuum degassing apparatus for molten glass
|May 17, 2001
|Nov 8, 2001
|Asahi Glass Company Ltd.
|Vacuum degassing apparatus for molten glass
|Jan 22, 1999
|Nov 7, 2002
|Pierre Jeanvoine
|Method and device for melting and refining materials capable of being vitrified
|May 31, 1996
|Feb 9, 1999
|Asahi Glass Company Ltd.
|Vacuum degassing method and its apparatus
|Dec 24, 1986
|Aug 12, 1987
|Ppg Industries, Inc.
|Melting and refining of glass or the like with vacuum refining
|Title not available
|Title not available
|Title not available
|Title not available
|Title not available
|An Experimental Furnace with Gas Combustion in the Melt and Thin-Layer Fining, Babich and Pankova, Avtosteklo Plant Institute of Gas, Academy of Sciences of the Ukrainian SSR; State Scientific Research Institute of Glass, Sep. 1974, pp. 623-625.
|An Experimental Furnace with Gas Combustion in the Melt and Thin-Layer Fining, Babich and Pankova, Avtosteklo Plant Institute of Gas, Academy of Sciences of the Ukrainian SSR; State Scientific Research Institute of Glass, Sep. 1974. pp. 623-625.
|Japanese Patent Document 59-111943 (English Abstract).
|Zaitsev, et al.. "Cooling by evaporation of oven walls for glass melting" Kharkov, published by "Osnova" from Kharkow University, 1993, pp. 13, 14 (Russian Text).
|Citing Patent
|Filing date
|Publication date
|Dec 4, 2012
|Zhaolin Wang
|Powder formation by atmospheric spray-freeze drying
|Mar 20, 2008
|Jun 11, 2013
|Pilkington Group Limited
|Glass composition
|Oct 7, 2011
|Apr 29, 2014
|Johns Manville
|Submerged combustion glass manufacturing systems and methods
|Oct 7, 2011
|Nov 4, 2014
|Johns Manville
|Burner apparatus, submerged combustion melters including the burner, and methods of use
|Oct 7, 2011
|Mar 10, 2015
|Johns Manville
|Methods of using a submerged combustion melter to produce glass products
|Oct 3, 2012
|Mar 10, 2015
|Johns Manville
|Apparatus, systems and methods for reducing foaming downstream of a submerged combustion melter producing molten glass
|Oct 3, 2012
|Mar 31, 2015
|Johns Manville
|Methods and systems for controlling bubble size and bubble decay rate in foamed glass produced by a submerged combustion melter
|Oct 7, 2011
|Apr 7, 2015
|Johns Manville
|Systems and methods for making foamed glass using submerged combustion
|Oct 7, 2011
|May 5, 2015
|Johns Manville
|Systems and methods for glass manufacturing
|Oct 3, 2012
|Aug 4, 2015
|Johns Manville
|Methods and systems for destabilizing foam in equipment downstream of a submerged combustion melter
|Mar 1, 2013
|Feb 2, 2016
|Owens-Brockway Glass Container Inc.
|Process and apparatus for refining molten glass
|Jul 27, 2005
|Oct 23, 2008
|Saint-Gobain Isover
|Method and Device for Treating Fibrous Wastes for Recycling
|Mar 20, 2008
|Feb 18, 2010
|Pilkington Group Limited
|Glass composition
|Jun 9, 2009
|Mar 31, 2011
|Pilkington Group Limited
|Glass plate for a solar unit, and glass composition
|Sep 20, 2011
|Mar 28, 2012
|Johns Manville
|Methods and apparatus for recycling glass products using submerged combustion
|U.S. Classification
|65/157, 65/134.7, 65/134.2, 65/134.3, 65/347, 65/134.9, 65/346
|International Classification
|Cooperative Classification
|European Classification


text:
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subset: commoncrawl


text:
Fun107's Exclusive Birthday Bash Featuring Timeflies
Fun 107 is celebrating our 25th birthday all year long, and this time we're taking it to Fall River!
Fun 107 is celebrating our 25th birthday all year long, and this time we're taking it to Fall River!
Earlier today on the FUN Morning Show I talked about my brother Joe and how today is his birthday.
Happy Birthday to Nicole and Vicki of course! Wait...who are Nicole & Vicki? We have no idea.
If you give a boy a Barbie, he'll want a G. I. Joe to go with it... right?
February 26, 2014 marks a very important day in history. It has been dubbed 'National Larry Day!' Today, I celebrate my 36th birthday and I hope all of the listeners will join me.
This will never get old for me. I love seeing kids and teenagers get reunited with their parents who serve in the military. It's such a heartwarming moment filled with joy and happiness, especially when they're taken by surprise.
This story made me tear up this morning on the FUN Morning Show. A 10 year old Michigan boy who told his mother he didn't want a birthday party because he didn't have any friends, now has plenty! The boys mom set up a Facebook page for him called "Happy Birthday Colin". Colin was diagnosed about a year ago with a sensory processing disorder, similar to Autism.
Its flashback time! I was having a discussion in the office about old records, and out of no where, I sang out a line from this very famous Happy Birthday song...
Acid-tongued reality singing show judge Simon Cowell is celebrating his 54th birthday today (Oct. 7). Former 'X Factor' contestants helped him celebrate by toilet papering his Beverly Hills abode.
Happy 21st birthday today (Sept. 16) to Nick Jonas! The youngest Jonas Brother marked the milestone in Las Vegas with family and friends, including girlfriend Olivia Culpo and big brothers Joe and Kevin.


text: Woman Who Lost Her iPhone Recreates Selfies of Man Who Has It NowNeetzan Zimmerman12/30/13 6:40pmFiled to: SelfieRevengeInstant KarmaCloudiPhone16510EditInvite manuallyPromoteDismissUndismissHideShare to KinjaToggle Conversation toolsGo to permalink Danielle Bruckman doesn't know what happened to her iPhone. All she knows is that it disappeared last New Year's Eve and that the guy who has it now has a pretty fanstatic mustache. She knows he has a pretty fantastic mustache because the guy who has her phone now never turned off the cloud sync, so all of his selfies show up in her photo stream. Advertisement Once Danielle realized what was going on, she realized there was really only one thing she could do: Recreate his selfies herself. An thus My Cloud Pal was born. Sponsored Calling it "one woman's journey, through another man's selfies," Danielle's Tumblr project has become a kinda-creepy way for her to connect with a man she doesn't actually know, but also kinda does. "He somehow grew on me and I actually enjoy getting his updates and see it as a window to peer into his daily life," she told BuzzFeed. "In a way, it's a selfie diary of sorts and now I can paint a more full picture of this man's life." Danielle is now asking other people to send her photos of their Cloud Pals. "Who knows," she says, "I may just re-enact them too." [screengrabs via My Cloud Pal] Advertisement Reply165 repliesLeave a reply


text:
Two different bills on two separate subjects
Says property insurance rates are going up because Rick Scott signed a bill preventing the state from regulating insurance.
— PolitiFact Florida
on Friday, October 24th, 2014
Jobs claim derailed in 2011
Says high-speed rail would have created 60,000 jobs.
— PolitiFact Florida
on Tuesday, October 21st, 2014
Not in cahoots, but GOP sure likes to remind Crist about his Ponzi pal
Says Rick Scott has "teamed up with a felon convicted of running a Ponzi scheme to smear Charlie Crist."
— PolitiFact Florida
on Tuesday, September 2nd, 2014
Reich has something else in mind
"I've also offered a plan that can help (fix Social Security) that's supported by Robert Reich, secretary of labor previously, in a previous administration."
— PolitiFact Florida
on Monday, October 18th, 2010
Cherry-picking to the max
"The average cost for health insurance in Florida went from about $600 a month for an individual to about $150 a month."
— PolitiFact Florida
on Monday, March 29th, 2010
Overall, Floridians would have paid less taxes
Rubio's tax swap proposal "would have been a massive tax increase."
— PolitiFact Florida
on Sunday, March 28th, 2010
Based on bad projections
"We worked together to enact ... the largest tax cut in Florida history."
— PolitiFact Florida
on Tuesday, March 2nd, 2010
Declining home values wrecked his estimate -- and another tax cut is bigger
"I signed the largest single tax cut in the history of Florida, a $25 billion tax cut over five years, directed at property tax cuts."
— PolitiFact National
on Tuesday, November 10th, 2009
It's an apples to oranges comparison
"Usually it's about $900 a month to get health coverage. (Florida's program has) reduced that, on average, to about $150 a month."
— PolitiFact Florida
on Friday, October 23rd, 2009
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text:
GameOn is bringing together cosplayers' communities, hardcore fans of eSports, inspiring speakers and game developers from all around . Thus indicating a solid establishment of gaming industry and gaming community in the region.
GameOn expo is going to be the best place to experience gameplay of latest games from Blizzard, Ubisoft, NCsoft, Activision, Game Insight, Wargaming, Beatshapers, Tag of joy, Sneaky Box, A-steroids and many more products of industry leaders and startups. Check-out latest VR products and solutions together with Nordic/Baltic VR community.
Meet game developers from all around the world check out trending indie games, try out brand new VR devices such Oculus rift. Visit EXPO town at GameOn!
ESports part of the show is going to take place in the mainstage amfitheatre area of Siemens Arena. Here you will witness spectacular CS:GO final of the Baltics and finally find out what team is the best in our region. Later on the day Final match of League of Legends World Championship will start streaming directly from Mercedes arena in Berlin!
Popularity of electronic sport is skyroketing not only in Baltics, but all around the globe. Celebrities from the Baltic region are also a part of Gameon. Do not miss exciting celebrity CS:GO Show-off game as a joyfull and surpirsing part of GameOn.
Every age has its storytelling form, and video gaming is a huge part of our culture. You can ignore or embrace video games and imbue them with the best artistic quality. People are enthralled with video games in the same way as other people love the cinema or theatre. GameOn – is a manifestation of gaming culture!


text:
I'm pretty new to programming, specifically Ruby and I've been bumping my head working with regular expressions.
What I have is a string such as the following:
s = 'Your Product Costs $10.00'
What I'm trying to do is write an expression, so my match data is only equal to the price, for example I've been able to do the following.
r = /[$]\d....\Z/
and therefore
match = r.match s
=> #<MatchData "$10.00">
My problem is, what if the product price is $100.00 dollars. Well I don't have enough wild cards and my match is nil.
It there away with regular expressions, to say "wild cards until the end of a string?" or "wild cards until [characters]" Or will I have to find the length of a string, find the location of my $ character, and count it out based off each input?


text:
AirPort Base Station Agent
AirPort background helper process.
Required OS: not specified
, extreme
, express
, base
, station
We provide RSS Feeds for most of our views. You can read more about it
in the about section.
please give us feedback |
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Created by Arne & Marcus.
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text:
Carmichael Lynch: The Holiday Stocking
Advertising Agency: Carmichael Lynch, USA
Executive Creative Director: Dave Damman
Copywriter: Tim Bildsten
Art Director: Phil Jones
Director of Integrated Production: Joe Grundhoefer
Content Producer: Tara Mulholland
Business Manager: Vicki Oachs
Project Manager: Melanie Callahan
Director of Marketing: Char Roseblade
Communications and Marketing Manager: Maria Hileman
Director: Jason Ho
Editor: Brad Baker
Edit House: CLIP
Published:December 2011
9 comments
Nike DieselDec 19, 2011 - 18:13
Kinda interesting idea, but not convincing in any way, shape or fashion. Jokes are funny but the actors messed it up. Including the narrator.


text:
It convince you with this down side trading volume???
Who is selling??? Day traders!!!
CEO tells who that ALH is in danger???
French government!!!
For what???
Ask/Force French government support him!!!
What is ALU real value right now???
Check the book value first; Many analysts believe ALU should be traded at rang $4.5-$5.5.
Do you know the Bell Lab???
How many Nobel price winners work/come from this lab, do a google search!!! With Bell Lab ALU has over 35,000 patents!!!
Invest your money into ALU for long term, believe me that ALU will be traded above $15!!!
Sentiment: Strong Buy


text:
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When a girl gets play when she least expects it.
"I wasn't even to go out, but it was a night of serendickity! I made out with that cutie pie all night long."
por AP Style 22 de Junho de 2009
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I have tried three times to listen to this book, and have not been able to make it beyond about an hour or so.
I was very excited by the prem..Show More »
I only wish that Sam Elliott could have voiced the wizard. Teri did a fantastic job and at times I wish I could have added sound effects or slowed he..Show More »
Oh My!!! Wow.


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My dash back lighting all the lights on my heat and fan pannel in the middle and map light on my mirror do not work this problem was there when I got the car, there in an after market sterio that was in the car when I got it. PLEASE HELP!
Monday, November 19th, 2012 AT 3:57 AM


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Activists criticize whaling plan
Say government's 'scientific' explanation is excuse for commercial whaling
ucanews.com reporter, Seoul
July 6, 2012
Local and international environmental groups yesterday criticized the government's decision earlier this week to resume whaling to protect the country's fishing grounds. A Korean delegation attending the annual meeting of the International Whaling Commission in Panama on Wednesday said they would submit a plan to resume whaling for scientific research purposes. A statement on the same day by the Ministry of Food, Agriculture, Forestry and Fisheries stated that the plan also aimed to protect the country's fishing grounds, which it said were threatened by an increase in the whale population. But Greenpeace Korea dismissed the plan as a transparent effort to resume commercial whaling. "There is no scientific evidence that the increasing number of whales causes damage to the annual catch of fish. We see that [the government] aims to restart commercial whaling," the group said in a statement yesterday. Commercial whaling in Korea ended in 1986 after Korea became a signatory to the International Convention for the Regulation of Whaling, which banned whaling except for scientific purposes and subsistence whaling for indigenous peoples. Since that time, the whale population in Korean waters has reached 86,000, according to the Ministry of Food, Agriculture, Forestry and Fisheries, and poses a significant threat to the commercial fishing industry. The Korean Federation for Environmental Movement of Ulsan – formerly the hub of commercial whaling in Korea – said any decision on whaling should be made on the basis of what's best for the environment. "The Fisheries Ministry should hand over conrol [of the issue] to the Environment Ministry," which would act principally to protect the whale population, the group said in a statement yesterday. Related reports Lawmaker issues predator fish warning
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Police accuse her of trying to convert Hindu children in orphanage she runs with husband


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Skip to comments.TWA Flight 800 - Someone Has Finally Talked!
Posted on 01/31/2002 5:49:54 PM PST by VectoRama
click here to read article
The case of TWA 800 and the case of the recent plane crash in Flushing are entirely different. There is overwhelming evidence that TWA 800 was brought down by a missile. The evidence in last fall's disaster is unclear so far, and the witness testimony is conflicting and uncertain, to my mind at least.
Once the government covers something up, for whatever reason, it usually stays covered up, even under a new administration. But we can always hope. Clinton is such a scum. He has hundreds of crimes to answer for.
Hmmm....how many aircraft have been shot down with torpedoes? For that matter, how many have been shot down with Tomahawks and Harpoons?
I'd like to hear what the submariners here think of the Navy fellow's terminology, and whether that's what they call being outside on the hull or on the sail.
Yes but the Submariner was Monica and she went down on Bill no up on a plane.
Ross Perot has yet to admitt that great sucking sound was Monica in the oval office.
There would be no reason for there to be THREE surfaced submarines in an "exercise" for example.
This all stinks on ice. WND give DEBKA a run for its money most days for pure unadulterated crap.
It's also pretty rare to step on the deck of a sub when it's out at sea. Unless you're doing something like launching/recovering a boat or the like. It would be useful to know what he was supposedly doing. Or did he mean he was up on the sail and the story just got the terminology wrong? Something else to contemplate.
I heard that years ago, they were talking about a mast mounted Stinger system for the Seawolf. I'd be interested in seeing any sources you have on this submarine mounted SAM system, especially range.
"Anonymous"? Reed knows who the guy is, and is withholding the name due to the person fearing retaliation. Reed is not the type to make this up.
Stingers and maybe a little gismo launched out or the "tubes" the kinda floats on the surface bobbing nose up when the anti sub plane or whatever flies over....well surprise....just guessing don't know for sure.
I agree that the Navy should be able to track the guy down with just this information and so he'd be better off coming out of the closet. But if by that you suggest that the story is questionable. Consider that the actions of two people are involved, Irvine and a source. The actions of Irvine in reporting what someone told him are not the same as the actions or fears of the person he spoke to. The source did not think "I'll report my story but keep my identity secret." If he did, that would be strange... but that is not the case here. The source also became spooked after their first discourse.
It will be interesting to see what if anything develops from this.
Opps. That was suppose to be a Clinton secret.
The tin foilers still don't believe it. They wrap that foil too tight around their heads they can't see, I guess.
I'm not a fan of the friendly fire scenario. That would involve a wide ranging coverup. What's really weird is the night of the crash some kind of practice "missile" was photographed over the area. This photograph was included in one of the issues of Paris Match.
This should properly be termed a "drone", perhaps towed by another aircraft.
Why the article at this time?
In my opinion, this submariner, if he does exist, has an axe to grind with the Navy. After his first interview with Irvine, he probably realized he was in over his head with his "sea story" and hence his reticence when Irvine tried to get his story on tape.
The story is a story still though.
Clinton covered things up and lied more or less instinctively, so it could easily have been terrorists who were responsible, and he didn't want that to get out because he might have to do something about it.
As for losing his pension, a number of retiring generals were threatened with just that penalty by clinton. There are ways of doing it. Anyone who has been in the service knows that the mysterious military bureaucracy can do anything it wants, and no one ever knows who was responsible.
Well thats just because YOU ARE STILL WORKING for THEM!! You must be part of the COVERUP! {/sarcasm}
Hey, dont you know that on FR we already have amateur aviation and military experts whose knowledge dwarfs yours? What, you worked on a sub? Heck, these guys read an article in popular mechanics about them!
Oh, so true! I had to give up on tinfoil.
A collander works better. Cooler too.It's holes are too small for radio reception, but big enough for ventilation. I attach a bungee cord to the legs as a chin strap. Stays on when I hang my head out the car window.
You all should try it!
So I guess James Kallstrom also had an axe to grind with the Navy when he told Irvine that the Navy was conducting classified maneuvers under the crash..... Surely you can come up with a better cover story than that.
There are two reasons for a coverup. One reason is to keep the trust of the people. When you perpetrate this kind of cover-up, it's to make sure that the citizens have faith in your military, and or leaders. We can look to a few examples like the JFK and MLK assassinations. Another cover up would be Waco. Yet another cover up would be Gary Condit. These are examples of keeping the faith types of coverups.
Then there's the other reason, The reason that you can't explain what happened, because if the truth got out it would bring down governments world wide. These coverups are the kind you see on TV. The UFO things, and the conspiracy type coverups. Things that make the X-files look like non-fiction. If it was a UFO that brought down TWA 800, there would be many questions asked of our government. The first would be, how come we didn't know about it. The next questions would be even more intrusive. How long have aliens been visiting us? Have you made a deal with them for technology. Are abductions happening, and how come you let it happen? Why are our cows being mutilated in goofy ways? How come you're grabbing up so much land, are you making room for them to live in our country too?
The main question I would ask, if it were a UFO accident, is what kind of retribution or apology can we exact upon them?
This is why if you cover it up, just to keep the faith, you're better off, than if it's to hide something more sinister.
I've now removed my tin foil hat.
OK, some problems with your idea:
First, the range of the missile is going to be extremely limited--if by nothing other than the limits on SENSORS passing through the air/water interface. The only thing you're going to be able to rely on that doesn't involve coming to periscope/mast depth and sticking up the BPS-15 radar set will be passive sonar, listening to the noise of the aircraft on the ocean surface. That signal fades out very quickly as the target gains altitude.
Second, a SUBSAM doesn't NEED to reach up to 13,000 feet to bag an ASW aircraft; most ASW ops are flown at much lower altitude.
Third, the missile can easily generate what is known as a "flaming datum." In other words, if the plane manages to get off a warning that it's under missile attack, that area of ocean is going to suddenly have a LOT of ASW aircraft overhead, and any other ASW assets (ships and subs) will start closing in. A submarine's greatest weapon is its stealth. Once it loses that, it's in BIG trouble, as it has very few weapons available to it.
I don't have any specific information. I just remember reading about the development of such a missile about 5 years ago.
I firmly believe it was a terrorist missile or bomb. Stephanopoulos did not call it an accident. He called it a bombing
Disclaimer: Opinions posted on Free Republic are those of the individual posters and do not necessarily represent the opinion of Free Republic or its management. All materials posted herein are protected by copyright law and the exemption for fair use of copyrighted works.


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My daughter's car, a Toyota Camry, 1996 with 129,000 has been leaking brake fluid. My husband checked and it appears to be coming from the rear. We cannot keep brake fluid in it - what could be the part that needs replacing? Is there a rear brake line, someone said a rear wheel cylinder?
Wednesday, April 18th, 2007 AT 5:20 PM


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103 Resort Reviews
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http://www.snowbird.com (801) 933-2222
It seems as if Utah doesn't have any resorts that aren't world-reknowned. Snowbird is another terrific resort, nestled in the beautiful canyons of the Wasatch Range, mere minutes from the hustle and bustle of Salt Lake City. True to its reputation, Snowbird boasts some of the greatest skiing you'll ever take part in.
Snowbird contrasts differently from its neighboring (and linked) resort, Alta, because Snowbird has something for everyone: terrific grooming, a terrain park, and steep and expert terrain. Snowbird has an inviting atmosphere—relaxed and friendly, as well. It's the big, warm fuzzy in Little Cottonwood Canyon. If you need a family ski resort, this is the place.
During the week, Snowbird is your own place. Although the parking lot may appear to be crammed, you'll barely spend too much time in the lift or tram lines. If the tram line is busy, however, you can jump on the much-needed Peruvian Express chair (which replaces an old, antiquated, always-busy two-seater) and get into some great all-around terrain. Treat yourself to a trip through the revolutionary Peruvian Tunnel, even if you don't want access to the other side (Mineral Basin is a lot of expert terrain, but there is a cat track to get beginners or the intimidated down safely), just to say you've been through the only ski tunnel in North America.
Last year, I was treated to a pounding snow storm that filled up Snowbird with 10" of fresh snow while I was there. This year contrasted quite differently: a lot of hazards were exposed due to the low snow fall, and what snow did cover areas with many rocks and stumps (mineral basin, Baldy), had hard, icy snow. Groomers were iced over as well, while only the runs that were exposed to the sun immediately in the morning were soft. We spent most of our time in Mineral Basin, skiing corned snow that was soft and ran through some technical runs that got your legs and heart working. Later, we chased the sun into the Peruvian Gulch area and just under the Baldy traverse for some more great snow (comparatively) and technical runs.
One problem with Snowbird is the price…spendy! Granted, you get tons of terrain for your price, but the tickets some of the highest priced in the Cottonwood canyons. Additionally, bring a sack lunch when you go, because food is expensive (especially mid-mountain, where a slice of pizza runs you $9).
Snowbird is also a very cautious resort, which someone of my skill really appreciates. While I can handle most of what is thrown at me terrain-wise, I can't anticipate terrain as well as most people, so I usually have a friend who skis ahead of me and scouts a line first. Compared to many other resorts, Snowbird recognizes how easily someone can access terrain that may be beyond their skill, and marks them appropriately (ropes and hazards of the tram and in the receding area help you navigate anything sketchy). However, once you get closer to the base area, the runs become muddled and trail markings get poorer (Chip's Run, Chip's Bypass Run, Lower Chip's Run…enough with the Chip's!). Myself and two other friends scouted a path down on the trail map to just go as fast as we could (we were timing ourselves), and we all ended up in a hardened mogul field because we missed the trail markings.
To get the very best bang for your buck, jump immediately on the tram. No matter what your skiing ability is, there's a way for you to get down safely, but you have to experience the thrill of the tram going up, and relish the view from the top of Snowbird. On a clear day (like yesterday), you can see all the way down into Salt Lake City. It's really quite incredible.
Advanced and Expert skiers will highly enjoy Snowbird. Snowbird doesn't have as much expert terrain as neighboring Alta, but that's not to say that the expert terrain that they do have isn't challenging. A hike up Baldy will ensure that non-believers in the challenge of the terrain are silenced. And if you want fast and steep, check the Cirque—a breath-taking snowfield visible from the terrain. Skiers look like dots among the massive face. Go scary fast here without fear of any hazards.
Snowbird is truly a great resort, and I'm glad to have skied it both on gnarly days with no snow, and days where it was pounding snow. On a good snow day, Snowbird literally doubles in size, making everything within the ropes ski-able. No matter what your needs, Snowbird has it: if you want a terrific, expansive family resort, or if you want challenging, easy-to-access terrain. Just don't get any pizza…
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CHICAGO – Governor Bruce Rauner issued the following statement on a Cook County judge's decision regarding the redistricting referendum on the November ballot:
"Today's ruling is a harsh reminder that the political system in Illinois is in need of major reforms. I hope the decision to deny voters the chance to consider the Independent Map redistricting referendum is appealed and reversed.
CARBONDALE - Governor Bruce Rauner today signed House Bill 6083 and House Bill 4715, the bills known as Molly's Law. These bills strengthen Illinois' Freedom of Information Act and extend the period of time in which a victim's family can file a wrongful death lawsuit where the act is intentional and violent in nature.
Executive Order 2016-08 offers reforms to address disparity among minority, women and persons with disabilities owned businesses that utilize state contracts
Governor Bruce Rauner


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Tags » 5S
One of the methods of determining an organisations approach to its business is to evaluate its workplace organisation capability & visual management standards.
5S engages people through the use of 'Standards' and 'Discipline'. 237 more words
One Year to Clean
Welcome to my quest for an eternally clean house! Sounds wonderful, doesn't it? An eternally clean house. It's a dream for me. I am currently 29 weeks pregnant with my first child. 234 more words
An audience will consider the messenger before considering the message. They want evidence that the speaker is sincere, honest, interested, confident, and in control. 244 more words
S1486 Colorful Chameleon Case Cover For IPHONE 5 5S
No matter from appearance or material, it is worth you have. Color is rich, the quality pass, be short of one cannot, such as function groove with mobile phone match exactly.
Click to see
Handling Q&A in Presentation Session
With the speech completed, it is time to take questions. This should be a five-step process:
- Listen to the entire question.
- Repeat the entire question. 116 more words
S1622 Doctor Who Tardis Case Cover For IPHONE 5 5S
The design of novel is easy to full access to all buttons and it is easy to clean and keep. This case can protect your phone from scratches, dust and it is a anti-skid, shock-resistant case. 7 more words


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2000 ford expedition triton v8 motor, the heat would not switch to a/ c so we put in 2 different actuators and neither one of them fixed the problem, we have no broken wires no shorts and no blown fuses. Help! What else can it be?
Friday, July 15th, 2011 AT 3:50 AM


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Review: Standzfree iPad floor stand serves niche audiences well
For watching videos and reading in bed—either in an upright or a prone position—or just for keeping your iPad off the dinner table or away from your exercise bike or musical instrument, the Standzfree Tubular Stand for iPad is a fine concept that's nicely executed.
QuarkXPress 10 is around the corner
Quark is getting ready to release version 10 of its pioneering desktop publishing program. Meantime, the company is offering a deal on the year-old version 9.
Review: Playful Widge stand and case makes your iPad more inviting
X-Doria's Widge is a cheerful, child-friendly iPad stand and case that's light, easy to carry, and secure.
Flickr's new interface emphasizes social media, but will anger long-time users
Flickr's new upgrade showcases big, bold images, but many do not like the change.
Review: ChillTab 2 is a sturdy, single-angle tablet stand
The ChillTab 2 tablet stand is made of high-quality materials, and it has a reliable and sturdy feel, but it's limited to a single angle.
Review: iPhome 2 case and stand keeps your iPad safe and sound
Designed for the rough and tumble of classroom use, the iPhome 2 is also handy for keeping adult-owned and -operated tablets safe and secure around the house.
Cloud cover: What Creative Cloud means to you
What's the big objection to Creative Cloud and what should you do about it?
Hands-on: New photo features in Google+ challenge Facebook and Twitter
Google steps up to the plate with increasingly competitive photographic features for its Google+ service.
Creative Cloud and iPhoto improvements
We begin this two-part podcast with Jackie Dove speaking with Adobe's Scott Morris about Creative Cloud and its license. Chris Breen then speaks to Jeff Carlson about addressing iPhoto annoyances.
Review: The FlipStands is a versatile, portable tablet stand
The FlipStands portable tablet stand is compact and versatile.
National Park apps aid your trek from sea to shining sea
Visiting the national parks this summer? If you're carrying your smartphone in your pocket, you'll have all the guidance you'll need to get around rough terrain with apps from the Apple App Store and Google Play.
Hands on with Oggl, the Instagram for serious photographers
Leave aside the photo dump. Hipstamatic has launched Oggl for the iPhone to encourage extreme sharing with insightful curation.
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Easy Venison Steaks
Total Time
Prep 5 mins
Cook 10 mins
Whenever I don't have alot of time to make supper, this is so easy and quick. You can mix all the ingredients on wax paper and when finished just throw it away. My man loves venison this way.
Ingredients Nutrition
- 3 tablespoons flour
- 2 teaspoons Mrs. Dash seasoning mix (original)
- 1 teaspoon garlic salt
- 1 teaspoon onion salt
- 2 lbs venison steak
- 2 tablespoons butter
- Mix together dry ingredients.
- Coat venison steaks with flour mixture.
- Melt butter over medium heat.
- Saute steaks in butter for 10 minutes or until done.
Most Helpful
I cook and eat a lot of venison and have many delicious recipes. This one definitely rates high! very simple and quick. I used back straps cut one inch thick. I used powders instead of salts for the garlic and onion and added a small amount of regular salt. I had no Mrs. Dash and used a pinch of Crazy Mixed Up Salt. My oil was 2 parts butter to1 part bacon grease. Cast iron skillet, 7 minutes per side. my wife loved it! PERFECT! Made pan gravy with the drippings with more flour and milk. TOO GOOD!!!!
So, i tried this recipe, and was very impressed. I did change up the ingredients a little bit to get other flavors. I tried using granulated garlic, onion powder, i experimented with some cajun seasoning, and some SPICY Mrs Dash. Either way, was mighty tasty. I didnt cook nearly as long per side, as i dont like well done meat. I sliced my loins into about 1-1.5" chunks, coated with the flour mixture, and tried it in straight butter, oil, and oil/butter. Over a medium - medium high heat, i cooked about 4 minutes a side, so to keep the medium rare center; lets just say, my daughter, whom is 5 liked it, and i couldnt get enough. Definately try this recipe.
My significant other and I work different shifts so I like to make good easy meals. I have to say this is one of the best, and simplest ways to make venison I have found yet. Even my three year old loved it. Two thumbs up