• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    The present invention adds a treatment solution (2) containing fluoride to the cleaning solution (1) discharged from the cleaning tank (11), and reacts with the fluorosilicate in the cleaning solution to precipitate a precipitate (4) containing fluorinated silicate. , Remove it. The cleaning liquid regenerated by the regeneration device 10 is again conveyed to the cleaning tank 11 and used as the cleaning liquid of the cathode ray tube panel 20.
    公开号:KR20010031464A
    申请号:KR1020007004498
    申请日:1999-08-23
    公开日:2001-04-16
    发明作者:후지와라겐지；야토히사노리；고토마사오；사사다쥬이치；야마우치마사노리；다테누마가츠요시；아라이오사무；다구치다쿠지
    申请人:모리 가즈히로；마츠시다 덴시 고교 가부시키가이샤；다테누마 가츠요시；가부시키가이샤 가켄；
    IPC主号:
    专利说明:

    METHOD AND UNIT FOR REGENERATION OF SOLUTION FOR CLEANING GLASS, METHOD AND UNIT FOR CLEANING SILICATE GLASS, AND CATHODE-RAY TUBE}
    Since hydrofluoric acid has the property of dissolving silicic acid, it is used for the etching process of the glass surface in the manufacturing process of decorative glass. Moreover, it is used also for washing a glass using the property which corrodes a glass surface. For example, the glass panel for cathode ray tubes used for various displays etc., if an adherent remains on the inner surface of a panel, adversely affects the phosphor layer formed on it, and the performance of a cathode ray tube falls. Therefore, in the process of manufacturing a glass product which requires a very clean surface like a panel for cathode ray tubes, the washing | cleaning process using hydrofluoric acid becomes an essential process.
    In the washing | cleaning process of a cathode ray tube panel, the glass cleaning solution containing hydrofluoric acid is used for washing of the panel which is repeated while circulating by the circulation apparatus connected with the panel washing tank. However, if the cleaning solution is repeatedly used in this manner, as the number of cleaning increases, deposits or glass components on the glass surface elute in the cleaning solution, and the cleaning ability of the cleaning solution is reduced. Moreover, impurities, such as the eluted glass component, adhere to the panel for cathode ray tubes, and may be a cause of panel failure. In view of such circumstances, the cleaning liquid is periodically replaced in the cleaning process of the cathode ray tube panel. The used cleaning liquid containing impurities is treated as industrial waste.
    By supplementing the lowering of the washing ability by replenishing hydrofluoric acid, it is possible to lengthen the replacement cycle of the washing liquid to some extent. However, replenishing hydrofluoric acid alone is not a solution for reducing industrial waste. In addition, it is impossible to prevent impurities in the panel by removing impurities in the cleaning liquid.
    Particularly problematic as impurities in the cleaning solution are silicic acid fluoride (hexafluoric acid; H 2 SiF 6 ) generated by the reaction of silicic acid (SiO 2 ) and hydrogen fluoride (HF) in the glass. The fluorosilicate is combined with various cations contained in the cleaning liquid to form a gel fluoride silicate. Since this low-flow gel material is transparent, it is hard to observe visually when the glass surface is wet when it adheres to the glass surface, and it is easy to cause a glass product defect.
    For example, as described in Japanese Unexamined Patent Publication No. 46-15768, it is possible to remove impurities in hydrofluoric acid using electrolysis. However, electrolysis is not suitable as a method of efficiently removing impurities from the glass cleaning solution discharged in a large amount. Moreover, although it is excellent as a method of removing a trace amount of cations from hydrofluoric acid, it is not effective as a method of removing silicic acid fluoride.
    The cleaning process of the cathode ray tube panel is applied not only to a newly molded panel but also to the reuse of a cathode ray tube panel in which a black matrix layer or a phosphor layer is formed. By washing with a cleaning liquid containing hydrofluoric acid, the black matrix layer and the like are etched and removed together with the glass of the panel surface layer. However, these layers contain substances that are difficult to dissolve in hydrofluoric acid (for example, carbon in the black matrix layer). For this reason, in the cleaning process for reusing the cathode ray tube panel, a large amount of fine insoluble matter is likely to occur in the cleaning liquid. If this impurity is left unattended, the surface of the panel is damaged, and therefore, there is a need to remove insoluble matter floating in the solution. As a method of removing an insoluble matter, the method of sedimenting in a sedimentation tank and the method of filtering by a filter can be considered.
    However, the method of settling in the settling tank is effective if the particles are large impurities, but are not suitable for the fine insoluble matter suspended in the glass cleaning solution. In addition, in the method of filtering by a filter, if the filter's ability is high, the filter is clogged quickly. If the filter's ability is low, the insoluble matter cannot be removed.
    As mentioned above, the method of efficiently regenerating the glass cleaning solution containing hydrofluoric acid is not known conventionally. Reduction of industrial waste is already a social task, and it has become a task to continue corporate activities with the enactment of the International Standard for Environment (ISO14001). Even in such a situation, in order to restore the cleaning ability of the glass cleaning solution, a phenomenon in which no effective method has been found other than the replacement of the glass cleaning solution has been a serious problem in the manufacture of glass products.
    The present invention relates to a method for regenerating and cleaning a glass cleaning solution containing hydrofluoric acid, a method for cleaning silicate glass (silicate glass), and a cleaning device. In particular, the present invention relates to a method and apparatus for providing a glass surface for which high cleanliness is required, such as for example a panel for a cathode ray tube, and also relates to a cathode ray tube having the panel.
    BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing the configuration of an embodiment of a washing apparatus of the present invention;
    2 is a diagram showing the configuration of another embodiment of the washing apparatus of the present invention;
    3 is a graph showing the relationship between the molar ratio of the added KF to Si in the glass cleaning solution and the weight reduction rate of the glass piece immersed in the solution;
    4 is a graph showing the relationship between the molar ratio of added KF to Si in a glass cleaning solution, and the Si concentration and Si removal rate in the solution;
    Fig. 5 shows the change in the cation concentration in the hydrofluoric acid washing liquid in the continuous test;
    6 is a view showing a change in the weight loss rate of the glass piece in the continuous test
    7 is a view showing a change in the weight loss rate of glass pieces when KF is not added in a continuous test;
    8 is a diagram comparing the relationship between the precipitation of insoluble matter and time in a glass cleaning solution in which fine insoluble matter is dispersed, with or without KF; and
    Fig. 9 is a partial sectional view of one embodiment of a cathode ray tube including a panel cleaned by the present invention.
    <Start of invention>
    SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide an efficient regeneration method and regeneration apparatus for a glass cleaning solution containing hydrofluoric acid which is used in the cleaning or processing of silicate glass and discharged in a large amount. An object of the present invention is to provide an efficient regeneration method and a regeneration device for a glass cleaning solution containing suspended insoluble matter and silicate fluoride.
    Moreover, an object of this invention is to provide the washing | cleaning method and washing | cleaning apparatus of the silicate glass using the recycled washing | cleaning solution.
    Moreover, an object of this invention is to provide the cathode ray tube using the panel wash | cleaned using the recycled washing | cleaning solution.
    In order to achieve the above object, the method for regenerating the glass cleaning solution of the present invention comprises adding fluoride to the glass cleaning solution containing hydrofluoric acid after cleaning the surface of the silicate glass, thereby fluorine in the glass cleaning solution. The silicic acid is reacted with the fluoride to precipitate fluorinated silicate, and the fluorinated silicate is removed from the glass cleaning solution.
    According to such a regeneration method, a large amount of glass cleaning solutions can be efficiently regenerated. In particular, according to the above method, hydrogen fluoride is generated in the precipitation reaction of the fluorosilicate, and the hydrogen fluoride contributes to the recovery of the cleaning ability of the glass cleaning solution. According to the said regeneration method, since the solution for glass cleaning can be recycled by the method which can be applied industrially, it becomes possible to prolong the exchange cycle of the solution for glass cleaning.
    In the above regeneration method, the fluoride is lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, magnesium fluoride, strontium fluoride, barium fluoride, cobalt fluoride, manganese fluoride, fluoride It is preferred to include at least one compound selected from copper and ammonium fluoride. This is because by using these fluorides, silicic acid fluoride can be effectively removed.
    In the regeneration method, hydrofluoric acid is preferably added to the glass cleaning solution after removing the fluorosilicate. In the regeneration method, fluoride is preferably added together with hydrofluoric acid. The hydrogen fluoride produced by the regeneration method does not recover all of the hydrogen fluoride consumed for the production of silicic acid fluoride. However, according to the said preferable example, the washing | cleaning ability of the glass cleaning solution fully recovers, and the replacement | exchange period of the glass cleaning solution can be prolonged further.
    In the regeneration method, it is preferable that the amount of fluoride added by measuring the concentration of Si in the glass cleaning solution after cleaning the surface of the silicate glass is more than the amount required when the entire Si is changed to fluorosilicate. Do. The amount of fluoride to be added is more preferably 1 to 2 times the amount required for the entire Si to be changed to fluorinated silicate. According to this preferred example, since an amount of fluoride is added in accordance with the Si concentration, it is possible to prevent excess fluoride from becoming an impurity and cause new problems or insufficient removal of fluorinated silicic acid.
    In addition, in order to achieve the above object, the method for cleaning the silicate glass of the present invention is characterized in that the surface of the silicate glass is cleaned by using the glass cleaning solution recycled by the regeneration method.
    In addition, another washing rice method of the silicate glass of the present invention is a cleaning step for regenerating the glass cleaning solution regenerated by the above regeneration method, and cleaning for cleaning the surface of the silicate glass using the glass cleaning solution obtained in this regeneration step The process is carried out in parallel, and the glass cleaning solution used in this cleaning step is regenerated in the regeneration step to be used while regenerating the glass cleaning solution.
    According to these washing methods, it is possible to reduce the quantity of industrial waste containing hydrofluoric acid more conventionally, and also to reduce the defect of glassware resulting from adhesion of fluorosilicate.
    In the said washing | cleaning method, it is preferable that a silicate glass is a panel for cathode ray tubes. This is because the cathode ray tube panel requires a particularly clean surface and is cleaned using a glass cleaning solution containing a large amount of hydrofluoric acid.
    In particular, when at least one selected from the black matrix layer, the phosphor layer, and the metal back layer includes a panel present on the surface before the cathode ray tube panel is cleaned, the effect of the cleaning method becomes remarkable. In each layer, an insoluble matter is generated in the glass cleaning solution. By applying the cleaning method, such an insoluble matter can be removed together with the fluorinated silicate.
    In order to achieve the above object, the apparatus for regenerating the glass cleaning solution of the present invention includes a treatment tank for adding a fluoride to a glass cleaning solution containing hydrofluoric acid after cleaning the surface of the silicate glass, and the glass cleaning solution. And fluorinated silicate recovery means for removing the precipitated fluorosilicate from the glass cleaning solution by reacting the fluorosilicate with the fluoride.
    According to such a regeneration apparatus, a large amount of glass cleaning solutions can be efficiently regenerated. Insoluble matter suspended in the glass cleaning solution can also be removed together with the fluorosilicate. In addition, according to the above apparatus, hydrogen fluoride is generated in the precipitation reaction of silicate fluoride, and the hydrogen fluoride contributes to the recovery of the cleaning ability of the glass cleaning solution. Thus, according to the said regeneration apparatus, since the solution for glass cleaning can be recycled by the method which can be applied industrially, it becomes possible to prolong the exchange cycle of the solution for glass cleaning.
    In the said regeneration apparatus, it is preferable to further provide the precipitation tank which takes in the solution for glass cleaning from the bottom part of a processing tank.
    In the regeneration apparatus, the fluorinated silicate recovery means is not particularly limited as long as it is a device having a solid liquid separation function capable of separating solid and liquid, and may be a filtration apparatus such as a filter. It is preferable to include the discharge coke provided in the bottom part. This is because efficient separation is possible and suitable for continuous operation of the playback apparatus.
    In the regeneration apparatus, it is preferable to further include an adjusting tank for replenishing hydrofluoric acid in the glass cleaning solution from which the fluorinated silicate is removed. According to this preferred example, the replacement cycle of the glass cleaning solution can be further extended. In addition, although it does not specifically limit, it is preferable that the said adjustment tank is arrange | positioned so that the solution for glass washing | cleaning may be received from the liquid level vicinity of the said precipitation tank (processing tank when not using a precipitation tank).
    In order to achieve the above object, the apparatus for cleaning silicate glass of the present invention includes a regeneration device and a cleaning tank supplied with a solution for cleaning glass from the regeneration device, and for cleaning the surface of the silicate glass by the glass cleaning solution. It is characterized by including.
    Further, another cleaning apparatus for the silicate glass of the present invention includes the regeneration apparatus and a cleaning tank supplied with the glass cleaning solution from the regeneration apparatus, and for cleaning the surface of the silicate glass by the glass cleaning solution. And regenerating the glass cleaning solution by regenerating the glass cleaning solution used in the cleaning tank in the regeneration apparatus.
    According to these regeneration apparatuses, it becomes possible to reduce the quantity of industrial waste containing hydrofluoric acid more conventionally, and also to reduce the defect of glassware resulting from adhesion of fluorosilicate.
    Moreover, according to this invention, the cathode ray tube containing the cathode ray tube panel wash | cleaned by the said washing | cleaning method is provided.
    EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described with reference to drawings.
    In the cleaning apparatus of the silicate glass shown in FIG. 1, the circulation path | route of the glass cleaning solution is comprised by the regeneration apparatus 10 and the glass cleaning tank 11 of the glass cleaning solution.
    The regeneration device 10 includes a treatment tank 13, a settling tank 14, and an adjustment tank 15, and the treatment tank 13 and the adjustment tank 15 respectively have a treatment liquid tank 12 and a hydrofluoric acid tank 16. ) Is connected via a pipe provided with pumps 22 and 26.
    The processing tank 13 receives the glass cleaning liquid 1 discharged from the cleaning tank 11 and the processing liquid 2 injected by the pump 22 from the processing liquid tank 12, and these liquids are mixed. . The treatment liquid tank 12 stores a solution containing fluoride, which will be described later. In addition, you may provide the processing tank 13 with the stirring apparatus which is equipped in the adjustment tank mentioned later.
    The settling tank 14 is arrange | positioned below the processing tank 13. The washing liquid 3 in which the treatment liquid 2 is mixed is discharged from the bottom of the treatment tank 13 to the settling tank 14. The precipitate 4 precipitated from the cleaning liquid 3 by incorporating the treatment liquid 2 contains an insoluble matter contained in the cleaning liquid 3. This precipitate 4 is settled in the liquid and accumulates at the bottom of the settling tank 14. A discharge coke (drain coke) 34 is provided at the bottom of the settling tank 14, and the precipitate 14 is discharged out of the apparatus through the discharge coke 34. On the other hand, the washing liquid after the precipitate 4 is removed flows upward through the filter 24 to the partition separated by the inner wall in the settling tank and flows out to the adjusting tank 15. Traces of suspended matter remaining in solution without being removed from the outlet coke out of the apparatus are filtered by the filter 24.
    In the case where the precipitate can be sufficiently precipitated in the treatment tank 13, the discharge coke may be installed at the bottom of the treatment tank 13 without providing the precipitation tank 14, and the precipitate may be discharged from the discharge coke. Does not matter.
    The adjusting tank 15 communicates with the settling tank at the upper portion so as to have a common liquid level with the settling tank 14. Thus, the supernatant liquid of the washing | cleaning liquid from which the sediment isolate | separated in the sedimentation tank 14 is made to flow into the adjustment tank 15 in this way. In addition, a hydrofluoric acid tank 16 is connected to the adjustment tank 15, and a predetermined amount of hydrofluoric acid 6 is injected by the pump 26 from the hydrofluoric acid tank 16. In addition, in the adjustment tank 15, the stirrer 25 for mixing the washing | cleaning liquid 5 to which hydrofluoric acid 6 was added, and the exhaust port 35 for local exhaust are arrange | positioned.
    The adjustment tank 15 is equipped with the monitoring system 30 near the drain port arrange | positioned at the bottom. The monitoring system 30 is an HF monitor for measuring the concentration of hydrofluoric acid in the cleaning liquid, and is also provided with a controller for controlling the liquid amount of hydrofluoric acid. This controller transmits an operation signal to the pump 26 in accordance with the concentration of hydrofluoric acid, the state of the washing liquid, and the like, and controls the amount of the hydrofluoric acid 6 added. In this way, the regeneration device 10 includes an adjustment mechanism capable of controlling the concentration of hydrofluoric acid in the cleaning liquid within a predetermined range.
    The drain port of the adjustment tank of hydrofluoric acid is connected to the washing tank 11 through the piping which has the circulation pump 27, and the recycled glass washing liquid is conveyed from the adjustment tank 15 to the washing tank 11. As shown in FIG.
    The cleaning tank 11 shown in FIG. 1 is a cleaning tank of the cathode ray tube panel. In this washing tank, the regenerated washing liquid is discharged upward from the nozzle 21, and washes the inner surface of the cathode ray tube panel 20 which is supported substantially horizontally. The cleaning liquid is again supplied to the treatment tank 13 in a state containing a deposit present on the panel surface and a glass component eluted with the deposit. The cathode ray tube panel is carried in to the washing tank 11 continuously by a conveying apparatus (not shown), and is further carried out from the washing tank after washing. Moreover, the exhaust port 31 is arrange | positioned like the adjustment tank 15 in the washing tank 11. The cathode ray tube panel is cleaned while performing local exhaust from the exhaust port 31.
    As described above, in the cleaning apparatus, the cleaning liquid is reciprocated between the cleaning tank and the regeneration apparatus by a liquid circulation system composed of a pump or the like to clean and regenerate the cathode ray tube panel, and the circulation for cleaning the panel is repeated.
    The other cleaning apparatus of the silicate glass shown in FIG. 2 is the same as the apparatus shown in FIG. 1 except that the Si monitoring system 36 is installed in the treatment tank 13.
    In the apparatus shown in FIG. 2, the Si concentration in the glass cleaning liquid 3 is measured by the Si monitoring system 36. This system is also equipped with an addition amount control means (controller) for adjusting the amount of the processing liquid to be added. The controller calculates the required amount of processing liquid according to the amount of Si obtained by the measurement, and adjusts the amount of processing liquid 2 to be injected by sending an operation signal to the pump 22 according to this value. Thus, when the Si monitoring system 36 is provided in the processing tank 13, the amount of processing liquid 2 can be injected, monitoring the amount of Si in the glass cleaning liquid 3, and also feeding back.
    In this way, since the treatment liquid 2 can be added while confirming the effect, the Si monitoring system 36 is preferably installed in the treatment tank 13.
    In addition, as a major insoluble substance for hydrofluoric acid contained in the deposit on the surface of the cathode ray tube panel, for example, the phosphor contained in the carbon and phosphor layers included in the black matrix layer in the case of cleaning to regenerate the cathode ray tube panel Aluminum contained in a particle | grain, a metal back layer, etc. are mentioned.
    Moreover, what is necessary is just to determine the density | concentration of the preferable hydrofluoric acid in a glass cleaning liquid according to the washing | cleaning method and the glass used for washing | cleaning, For example, about 3-20 weight% is preferable.
    Hereinafter, one Embodiment of the glass cleaning method and the regeneration method of a glass cleaning liquid is demonstrated.
    The glass to be cleaned is silicate glass (silicate glass) containing silica (SiO 2 ) as the glass skeleton component. The composition of the silicate glass is not particularly limited, and various compositions can be used, for example, a general-purpose plate glass composition that can be produced by a float method, a glass composition of a panel for a cathode ray tube. Table 1 shows an example of the glass composition for the cathode ray tube. This glass composition has a point, which contains not less than 5% by weight of K 2 O, more than 10% by weight of BaO as one of the features.
    Table 1
    Composition example of panel glass for cathode ray tube
    The glass component is not eluted at a ratio that accurately reflects a content ratio as exemplified in Table 1, but the alkali component is often eluted above the content ratio. In any case, however, SiO 2 , which accounts for more than half of the glass component, is present in the cleaning liquid as a major elution component. SiO 2 is eluted in the cleaning liquid as a as shown in the following reaction formula (1), by reaction with hydrogen fluoride fluorinated silicate (hexa fluoride silicate).
    SiO 2 + 6 HF → H 2 SiF 6 + 2 H 2 O (1)
    The glass cleaning liquid 1 containing a silicic acid fluoride and a fine insoluble matter flows out into the processing tank 13, and is mixed with the processing liquid 2 in this processing tank. The treatment liquid 2 is supplied as an aqueous solution containing fluoride or hydrofluoric acid containing fluoride. Here, as the fluoride, inorganic fluorides, particularly hydrofluoric acid salts, are preferable.
    When fluoride is added to the washing solution 1, a hydrogen fluoride separation reaction occurs. That is, the fluoride reacts with the silicic acid fluoride generated from the silica in the glass to produce silicate fluoride and hydrogen fluoride. For example, the separation of hydrogen fluoride when potassium fluoride is used as the fluoride can be represented by the following reaction formula (2).
    H 2 SiF 6 + 2KF → K 2 SiF 6 ↓ + 2HF (2)
    In the washing liquid 3 to which the treating liquid 2 is added, a reaction for producing fluorinated silicate as exemplified by the above reaction scheme proceeds. The precipitated fluorosilicate is dispersed in the washing liquid 3 and settled in the treatment tank 13 while surrounding the floating insoluble matter and discharged into the settling tank 14 connected to the bottom of the treatment tank. Insoluble matter and fluorinated silicate discharged to the settling tank 14 are sedimented again in the settling tank 14 to form a precipitate 4 and are deposited at the bottom of the tank. This precipitate 4 is discharged from the discharge coke 34 disposed at the bottom of the settling tank.
    When only the fluorosilicate is precipitated, the precipitate 4 turns white. However, when an impurity precipitates with a fluorosilicate, the precipitate 4 may color. For example, in the case where black carbon particles are present as impurities, the precipitate 4 is colored by mixing white of fluorosilicate and black of carbon. In this case, although the washing | cleaning liquid before precipitation of a fluorosilicate is colored black because of carbon particle | grains, the supernatant liquid of the washing | cleaning liquid after isolate | separating from the precipitate 4 becomes substantially colorless and transparent. This washing | cleaning liquid transfers the compartment in a sedimentation tank upward while filtering by the filter 24, and flows out from the liquid level vicinity of the sedimentation tank 14 to the adjustment tank 15. As shown in FIG.
    Hydrogen fluoride is partially regenerated, as shown in the reaction (2) above. However, referring to Scheme (1) together with this, as is apparent, not all hydrogen fluoride consumed by reacting with SiO 2 is regenerated. Therefore, hydrofluoric acid is replenished in the adjustment tank 15 to the cleaning liquid 5 in which impurities other than the floating fluoride silicate and the floating component contained in the cleaning liquid 3 are removed. The addition of hydrofluoric acid is done by measuring the concentration in the cleaning liquid by the monitoring system 30. The preferable concentration of hydrofluoric acid adjusted in this way is as having illustrated above.
    The monitoring system 30 may simultaneously measure the concentration of remaining fluorosilicate. In this case, it is preferable to fine-tune the amount of fluoride supplied to the processing tank 13 again according to the measured concentration of silicic acid fluoride.
    In this way, the glass cleaning liquid in which the impurity in the cleaning liquid 3 is reduced and the concentration of hydrofluoric acid is adjusted is supplied to the cleaning tank 11 again by the circulation pump 27, and again the cathode ray tube panel 20 Used for cleaning.
    Hereinafter, the fluoride to add is examined. The fluoride is not particularly limited as long as it reacts with silicic acid fluoride to generate silicate fluoride and hydrogen fluoride, as shown in Scheme (2). Specifically, lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), fluoride, rubidium (RbF), cesium fluoride (CsF), magnesium fluoride (MgF 2), fluoride, strontium (SrF 2), barium fluoride (BaF 2), fluoride, cobalt (CoF 2 ), manganese fluoride (MnF 2 ), copper fluoride (CuF 2 ) and at least one compound selected from ammonium fluoride (NH 4 F) are suitable.
    In order to remove fluoride silicate efficiently, the fluoride preferably has a small solubility in water of the corresponding fluorosilicate. On the other hand, it is preferable that the fluoride itself has some degree of solubility in water. It is because it is easy to mix with a washing | cleaning liquid. From this point of view, NaF, KF, RbF and CsF are more preferable as the fluoride. The solubility of these alkali metals (R) in fluoride (RF) in water and the solubility in water of fluorinated silicates (R 2 SiF 6 ) corresponding to these fluorides are shown in Table 2. In addition, all solubility is the value at the time of making water temperature 25 degreeC.
    <Table 2>
    In order to precipitate all the silicic acid fluorides in the glass cleaning liquid according to the reaction formula (2), it is theoretically necessary to add the same equivalent (same chemical equivalent) of fluoride as the silicic acid fluoride present in the glass cleaning liquid. Therefore, in order to confirm the amount of fluoride actually required, various amounts of fluoride (KF) were added to the cleaning solution after cleaning the cathode ray tube panel, and the cleaning ability of the glass cleaning solution was examined.
    First, the cathode ray tube panel which has a composition of the range shown in Table 1 was arrange | positioned in the same washing tank as shown in FIG. 1, and the cathode ray tube panel which was sequentially conveyed to the washing tank was circulated, circulating a glass washing liquid. At this time, hydrofluoric acid was added to the washing liquid so that the concentration was constant while monitoring the concentration of hydrofluoric acid without adding KF in the circulation step. After a lapse of a predetermined time, a part of the washing liquid was collected, and the Si concentration in the washing liquid was quantified by ICP emission spectroscopy. And KF was added to the washing | cleaning liquid so that the molar ratio with respect to Si concentration might become a predetermined ratio. Subsequently, a glass piece having a thickness of 1 mm and a diameter of 15 mm having the same composition as that of the cathode ray tube panel was immersed in 30 ml of the respective cleaning liquids, and left to stand for 10 minutes while stirring with a stirrer at room temperature, and the weight of the glass pieces before and after immersion was measured. did. The weight reduction rate of each glass piece is shown in FIG.
    As shown in Fig. 3, as the molar ratio of KF to Si increased, the weight reduction rate of the glass pieces increased. As a result, as shown in the reaction formula (2), it was confirmed that the chemical reaction for generating HF proceeded by the addition of KF. On the other hand, when the molar ratio of KF to Si exceeds 2 (in other words, the equivalent of KF exceeds the equivalent of silicic acid fluoride in the cleaning liquid), the weight loss rate of the glass only slightly increased even if KF was added. This tendency is also consistent with the results expected from Scheme 2 above.
    Excessive addition of KF is undesirable because excess potassium ions are produced. Therefore, the fluoride to be added is preferably in an amount corresponding to 1 to 2 times (especially 1 to 1.5 times) the equivalent of silicic acid fluoride present in the glass cleaning liquid, in consideration of the generation of HF according to the above reaction formula (2). Do.
    Next, the Si concentration change and Si removal rate change in the glass cleaning liquid by KF addition are shown in FIG.
    As shown in Fig. 4, when the molar ratio of KF to Si is 2 (equivalent point of KF to Si), approximately 70% of Si in the glass cleaning liquid is 90% of Si in the glass cleaning liquid when the molar ratio is 3. Abnormalities were removed.
    From the results shown in Fig. 4, considering the removal of Si in the glass cleaning liquid, the molar ratio of KF to Si is 2 to 4 (1 to 2 times when expressed in equivalents to fluorinated silicic acid of fluoride), more preferably 2 -3.5, especially 2.5-3.5 are preferable. However, even when excess KF is present, KF with a molar ratio of about 2 to 4.5 may be added in consideration of the reaction rate of the actual device or the like.
    From the results of Figs. 3 and 4, in the following test, the addition amount of KF was made into molar ratio 3 with respect to Si.
    In order to confirm the result of KF addition and the behavior of the various cations eluted from glass when regenerating a repeating glass cleaning liquid, the following examination was performed.
    First, the glass piece was dissolved in hydrofluoric acid, and the washing | cleaning liquid which prepared 2500 ppm of Si concentrations and 11 weight% of hydrofluoric acid was prepared. A glass piece having a thickness of 1 mm and a diameter of 15 mm having the same composition as in Table 1 was immersed in 30 ml of the cleaning solution, and the temperature of the cleaning solution was maintained at 34 ° C. and left for 10 minutes while stirring with a stirrer. The weight reduction amount of the glass piece at this time and the cation concentration in the washing | cleaning liquid were measured. The cation concentration was measured by ICP emission spectroscopy.
    Subsequently, KF corresponding to molar ratio 3 was added with respect to Si in washing | cleaning liquid, and the hydrofluoric acid concentration was adjusted to 11 weight%. A glass piece having a thickness of 1 mm and a diameter of 15 mm having the same composition as in Table 1 was immersed in 30 ml of the cleaning liquid, the concentration of the cleaning liquid was maintained at 34 ° C, and left to stir for 10 minutes with stirring with a stirrer. The weight reduction of the glass piece at this time and the cation concentration in the washing | cleaning liquid were measured.
    The above was made into the test of 1 cycle, the glass piece of the same quantity as 1st cycle was melt | dissolved again with respect to the said washing | cleaning liquid after completion | finish of 1 cycle, and the test similar to the above was repeated 4 cycles in total. 5 shows the concentration change of various cations in the cleaning liquid, and FIG. 6 shows the weight reduction rate of the glass pieces. In addition, although the concentration change was measured simultaneously with respect to the cation which is not shown in FIG. 5, the density | concentration with respect to other cations was about Ba or less.
    As shown in Fig. 5, it was confirmed that by adding KF, 90% or more of Si can be continuously removed. In addition, Si and K do not substantially accumulate. In addition, as shown in FIG. 6, it was confirmed that the weight reduction amount of the glass was also substantially constant, and the cleaning ability of the cleaning liquid was also substantially maintained. On the other hand, when the same test was performed without adding KF at all, as shown in Fig. 7, the cleaning ability of the glass was monotonously lowered.
    Next, the result of having measured the temporal change of the precipitation amount of the insoluble matter in a glass washing liquid is demonstrated.
    Similarly to the above, first, the cathode ray tube panel having the composition shown in Table 1 is disposed as the glass to be cleaned in the same washing tank as shown in FIG. 1, and the cathode ray tube panel which is sequentially conveyed to the washing tank while circulating the glass cleaning liquid is washed. did. At this time, hydrofluoric acid was added to the washing liquid so that the concentration was constant while monitoring the hydrofluoric acid concentration without adding KF in the circulation step.
    At this time, as a panel for cathode ray tubes, the panel in which the black matrix layer, the phosphor layer, and the metal back layer were formed was used.
    After a lapse of a predetermined time, a part of the washing liquid was taken out and placed in a beaker, and the temporal change in the amount of the precipitate was measured. The results are shown in FIG. In addition, the volume ratio of the deposit of FIG. 8 is the value obtained by reading the volume ratio of the deposit with respect to a washing | cleaning liquid according to the scale of a beaker.
    In Fig. 8, the curve (a) shows the result when it was left as it is without adding KF to the collected washing liquid. The precipitate in this case is composed of insoluble matters such as carbon and phosphor particles. Curve (b) shows the result of leaving KF added to the collected washing liquid. The precipitate in this case consists of a fluorosilicate and the insolubles. Curve (c) shows the result of filtering the collected washing liquid to remove insoluble matters in the washing liquid, and then leaving KF added to the washing liquid. In this case, the precipitate consists of silicic acid fluoride.
    By comparing the curves a to c, it can be confirmed that the precipitation of the fluorinated silicate promotes the precipitation of impurities suspended in the solution. In fact, even when the solution is observed, when it is still standing and the impurities are settled (curve (a)), the suspension of carbon particles or the like is observed even after 10 minutes has elapsed, whereas when KF is added (curve (b)), the same time After elapsed, impurities were hardly observed.
    Further, in the curves (b) and (c), after 4 minutes of the settling time, the volume ratio of the precipitate decreases because the precipitate gradually condenses.
    In this way, it was confirmed that precipitation of the insoluble matter dispersed in the washing liquid was accelerated by precipitation of the fluorinated silicate.
    An embodiment of the cathode ray tube panel using the glass panel 52 cleaned by the method and apparatus described above in FIG. 9 is shown. The cathode ray tube valve 51 is composed of a panel 52, a funnel 53, and a neck 54. The phosphor layer 55 is formed on the inner surface of the panel 52 cleaned by the above method. The cathode ray tube of the present invention is manufactured by a manufacturing method well known among those skilled in the art, except that the inner surface of the panel is cleaned by the above method.
    In addition, this invention is not limited to embodiment described above.
    As described in detail above, according to the regeneration method and apparatus of the present invention, a large amount of cation washing solution can be efficiently regenerated. Moreover, according to the washing | cleaning method and apparatus of this invention, industrial waste can be reduced by prolonging the replacement | exchange period of the glass cleaning solution containing hydrofluoric acid. As described above, the present invention enables the reduction of industrial wastes containing hydrofluoric acid, which has been difficult in the past, and at the same time reduces the cleaning failure of glass, and has great utility in the technical field of glass product production.
    权利要求:
    Claims (18)
    [1" claim-type="Currently amended] By adding fluoride to the glass cleaning solution containing hydrofluoric acid after cleaning the surface of the silicate glass, the fluoride silicate reacts with the fluoride to precipitate the fluorinated silicate. Removing the glass cleaning solution from the glass cleaning solution.
    [2" claim-type="Currently amended] The method of claim 1, wherein the fluoride is lithium fluoride, sodium fluoride, potassium fluoride, sodium fluoride, cesium fluoride, magnesium fluoride, strontium fluoride, barium fluoride, cobalt fluoride, manganese fluoride, fluoride A method for regenerating a glass cleaning solution comprising at least one compound selected from copper and ammonium fluoride.
    [3" claim-type="Currently amended] The method for regenerating a glass cleaning solution according to claim 1, wherein hydrofluoric acid is supplemented with the glass cleaning solution after removing the fluorosilicate.
    [4" claim-type="Currently amended] The method of regenerating a glass cleaning solution according to claim 1, wherein fluoride is added together with hydrofluoric acid.
    [5" claim-type="Currently amended] The method for regenerating a glass cleaning solution according to claim 1, wherein an insoluble matter in the glass cleaning solution resulting from the deposit present on the surface of the silicate glass is removed together with the fluorosilicate before the cleaning.
    [6" claim-type="Currently amended] The concentration of Si in the glass cleaning solution after cleaning the surface of the silicate glass is measured, and the amount of fluoride added is equal to or greater than the amount required when the entire Si is changed to fluorinated silicate. Regeneration method of a glass cleaning solution, characterized in that.
    [7" claim-type="Currently amended] 7. The method for regenerating a glass cleaning solution according to claim 6, wherein fluoride is added in an amount of 1 to 2 times the amount required to change the entire Si into fluorinated silicate.
    [8" claim-type="Currently amended] By adding fluoride to the glass cleaning solution containing hydrofluoric acid after cleaning the surface of the silicate glass, the fluoride silicate reacts with the fluoride to precipitate the fluorinated silicate. The surface of a silicate glass is wash | cleaned using the said glass cleaning solution which removed and regenerated from the said glass cleaning solution, The cleaning method of the silicate glass characterized by the above-mentioned.
    [9" claim-type="Currently amended] By adding fluoride to the glass cleaning solution containing hydrofluoric acid after cleaning the surface of the silicate glass, the fluoride silicate reacts with the fluoride to precipitate the fluorinated silicate. Removing from the glass cleaning solution to regenerate the glass cleaning solution, and performing a cleaning step of cleaning the surface of the silicate glass using the glass cleaning solution obtained in the regeneration step. A method for cleaning silicate glass, wherein the glass cleaning solution used in the step is regenerated in the regeneration step, thereby regenerating the glass cleaning solution.
    [10" claim-type="Currently amended] The method for cleaning a silicate glass according to claim 8 or 9, wherein the silicate glass is a panel for a cathode ray tube.
    [11" claim-type="Currently amended] The method for cleaning a silicate glass according to claim 10, wherein the cathode ray tube panel includes a panel in which at least one selected from a black matrix layer, a phosphor layer, and a metal back layer exists on the surface before cleaning.
    [12" claim-type="Currently amended] The glass cleaning process is performed by adding a fluoride to a glass cleaning solution containing hydrofluoric acid after cleaning the surface of the silicate glass, and a fluorinated silicate formed by reacting the fluoride silicate and the fluoride in the glass cleaning solution. And a fluorinated silicate recovery means for removing from the solution.
    [13" claim-type="Currently amended] The apparatus for regenerating a glass cleaning solution according to claim 12, further comprising a precipitation tank that receives the glass cleaning solution from the bottom of the treatment tank.
    [14" claim-type="Currently amended] The regeneration apparatus of the glass cleaning solution according to claim 13, wherein the fluorinated silicate recovery means includes a discharge coke provided at the bottom of at least one tank selected from a treatment tank and a precipitation tank.
    [15" claim-type="Currently amended] The glass cleaning solution regeneration device according to claim 12, further comprising an adjusting tank for replenishing hydrofluoric acid in the glass cleaning solution after removing the fluorinated silicate.
    [16" claim-type="Currently amended] The glass cleaning process is performed by adding a fluoride to a glass cleaning solution containing hydrofluoric acid after cleaning the surface of the silicate glass, and a fluorinated silicate formed by reacting the fluoride silicate and the fluoride in the glass cleaning solution. A regeneration device for a glass cleaning solution comprising a fluorinated silicate recovery means for removing from a solution;
    A glass cleaning solution is supplied from the regeneration apparatus, and the cleaning apparatus includes a cleaning tank for cleaning the surface of the silicate glass by the glass cleaning solution.
    [17" claim-type="Currently amended] The glass cleaning process is performed by adding a fluoride to a glass cleaning solution containing hydrofluoric acid after cleaning the surface of the silicate glass, and a fluorinated silicate formed by reacting the fluoride silicate and the fluoride in the glass cleaning solution. A regeneration device for a glass cleaning solution comprising a fluorinated silicate recovery means for removing from a solution;
    A glass cleaning solution is supplied from the regeneration device, and includes a cleaning tank for cleaning the surface of the silicate glass by the glass cleaning solution.
    The glass cleaning solution used in the cleaning tank is regenerated by the regeneration apparatus, and the glass cleaning solution is used while regenerating the glass cleaning solution.
    [18" claim-type="Currently amended] By adding fluoride to the glass cleaning solution containing hydrofluoric acid after cleaning the surface of the silicate glass, the fluoride silicate reacts with the fluoride to precipitate the fluorinated silicate. And a cathode ray tube panel made of silicate glass whose surface has been cleaned using the glass cleaning solution, which has been removed from the glass cleaning solution and regenerated.
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    同族专利:
    公开号 | 公开日
    CN1287543A|2001-03-14|
    WO2000012443A1|2000-03-09|
    CN1121992C|2003-09-24|
    EP1029833A1|2000-08-23|
    US6521575B1|2003-02-18|
    EP1029833A4|2003-08-20|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-08-26|Priority to JP98-239713
    1998-08-26|Priority to JP23971398A
    1999-02-19|Priority to JP04158299A
    1999-02-19|Priority to JP99-41582
    1999-02-19|Priority to JP04158399A
    1999-02-19|Priority to JP99-41583
    1999-08-23|Application filed by 모리 가즈히로, 마츠시다 덴시 고교 가부시키가이샤, 다테누마 가츠요시, 가부시키가이샤 가켄
    1999-08-23|Priority to PCT/JP1999/004546
    2001-04-16|Publication of KR20010031464A
    2002-11-23|Application granted
    2002-11-23|Publication of KR100361800B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP98-239713|1998-08-26|
    JP23971398A|JP3623663B2|1998-08-26|1998-08-26|Method and apparatus for regenerating glass cleaning solution, and method and apparatus for cleaning silicate glass|
    JP04158399A|JP3677164B2|1999-02-19|1999-02-19|Method and apparatus for regenerating glass cleaning solution, and method and apparatus for cleaning silicate glass|
    JP99-41583|1999-02-19|
    JP04158299A|JP3677163B2|1999-02-19|1999-02-19|Method and apparatus for regenerating glass cleaning solution, and method and apparatus for cleaning silicate glass|
    JP99-41582|1999-02-19|
    PCT/JP1999/004546|WO2000012443A1|1998-08-26|1999-08-23|Method and unit for regeneration of solution for cleaning glass, method and unit for cleaning silicate glass, and cathode-ray tube|
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