MX2008005088A - Pellets for se encapsulation - Google Patents
Pellets for se encapsulationInfo
- Publication number
- MX2008005088A MX2008005088A MXMX/A/2008/005088A MX2008005088A MX2008005088A MX 2008005088 A MX2008005088 A MX 2008005088A MX 2008005088 A MX2008005088 A MX 2008005088A MX 2008005088 A MX2008005088 A MX 2008005088A
- Authority
- MX
- Mexico
- Prior art keywords
- selenium
- glass
- pellet
- pellets
- compound
- Prior art date
Links
- 239000008188 pellet Substances 0.000 title claims abstract description 52
- 238000005538 encapsulation Methods 0.000 title abstract description 3
- 239000011669 selenium Substances 0.000 claims abstract description 54
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 51
- 239000011521 glass Substances 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 230000005496 eutectics Effects 0.000 claims abstract description 7
- 239000000470 constituent Substances 0.000 claims abstract description 3
- 229940065287 selenium compound Drugs 0.000 claims description 22
- 150000003343 selenium compounds Chemical class 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 14
- 239000006060 molten glass Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000004571 lime Substances 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004568 cement Substances 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 239000007891 compressed tablet Substances 0.000 claims description 2
- 229910000514 dolomite Inorganic materials 0.000 claims description 2
- 239000010459 dolomite Substances 0.000 claims description 2
- 239000006066 glass batch Substances 0.000 claims description 2
- 238000005816 glass manufacturing process Methods 0.000 claims description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical class O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 claims 1
- 229940091258 selenium supplement Drugs 0.000 description 34
- 239000007787 solid Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005343 cylinder glass Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229940082569 selenite Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 1
- 229960001471 sodium selenite Drugs 0.000 description 1
- 235000015921 sodium selenite Nutrition 0.000 description 1
- 239000011781 sodium selenite Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Abstract
Pellets for Se encapsulation Pellets encapsulating selenium or a compound of selenium comprise one hollow cavity filled with the selenium surrounded by a matrix which is able to form an eutectic with at least one of the constituents of a batch of molten raw materials for the manufacture of glass.
Description
PELLETES FOR SELENIO ENCAPSULATION
BACKGROUND OF THE INVENTION The present invention relates to pellet materials comprising selenium. More precisely, it refers to pellets that encapsulate selenium and / or at least one selenium compound. In particular, the invention relates to pellets that encapsulate selenium that can be incorporated into a batch mixture of components suitable for glass melting manufacturing processes.
SUMMARY OF THE INVENTION According to a first aspect, the invention provides pellets that encapsulate selenium and / or at least one selenium compound as defined in Claim 1. In accordance with a second aspect, the invention provides a process for manufacturing of pellets according to claim 7. According to a third aspect, the pellets according to claim 1 are used as a raw material of selenium to incorporate a molten glass lot according to claim 11. In accordance with a fourth aspect, the invention provides a method to reduce the burning of
selenium in a process for making glass comprising selenium in accordance with claim 12. According to a fifth aspect, the invention provides a bicarbonate lime glass comprising selenium according to claim 13. Dependent claims define additional preferred embodiments of the invention.
DETAILED DESCRIPTION OF THE INVENTION The present invention can provide one or more of the following advantages: • Simple mechanical method of pellet preparation: Simplicity of Selenium incorporation, similar to any other traditional glass component; • No requirements for any special dispensing equipment or dispenser and / or particularly expensive for the incorporation of the Selenium component in a batch of raw materials; • Access to new high Selenium glass formulas. Pellets are small pieces of material of any shape, which are at least 1 cm in their widest dimension. More often, it can be at least 0.5 cm in its widest dimension. Generally, it does not exceed 20 cm for the
wider dimension. Preferably, the pellets are of parallelepiped, cubic or cylindrical shape. The pellets according to the invention are composed of two parts: a hollow cavity filled with a heart of selenium and / or at least one selenium compound and a matrix around the filled roe cavity, which hides and isolates the heart of the environment pellet. The matrix, according to the invention, is a compressed tablet that does not melt below 1300 ° C under normal atmospheric pressure. The matrix must be free of any compound which can increase to a gaseous compound when heated from atmospheric pressure to 2000 ° C. It must also be able to slowly form a eutectic product with at least one of the constituents of a batch of molten raw materials commonly used in a glassmaking process, when immersed in the batch of raw molten glass materials. The eutectic product has a melting temperature of 400 to 1800 ° C under normal pressure. The selenium heart and / or at least one Selenium compound is selected from metallic selenium, organic and inorganic salts, as well as other organic compounds comprising selenium in its molecule. In particular, the selenium compound can be selected from the selenites and the selenates. For example, it can be a
selenite of an alkali metal, similar to sodium selenite (Na2Se03). The matrix can comprise any organic and inorganic compound, possibly mixed, capable of efficiently encapsulating the heart of selenium and / or selenium compound. Efficiency is intended to mean being able to cover for a time of not less than 5 or 15 minutes the presence of selenium and its component parts of batches of hot molten glass, such as Si02, CaO, Na20, K20, A1203 and the like. According to the invention, the matrix can comprise at least one of the following compounds: Si02, Na20, K20, Li20, B203, CaO, MgO, BaO, ZnO, A1203, Fe203, Se, Ti02, CoO, MnO, Cr203, Ce02, Zr02, NiO, Sn02, Cu20, V205 and S03. These compounds can be present as such in the matrix, or mixed or combined with others to form special components similar to sand, cement of any kind, dolomite and the like. Two or more of these can also be mixed together. According to one embodiment of the invention, the matrix is generally capable of forming a eutectic with one or more molten CaO, MgO, Na20, Si02 or A1203 present in a glass batch of raw material. As mentioned above, a second aspect of the invention is to provide a process
for the manufacture of pellets according to claim 7. In the process: • part of the total amount of matrix material is dry mixed "the mixture is poured into a mold having an open cavity • a rod having a section slightly smaller transversal one of the cavity opening, then inserted into the cavity and allows to be placed in the matrix material mixture • the rod is then pressed with the help of a press to solidify the matrix material in a lower half pellet • the rod is removed and the selenium and / or selenium compound is deposited in the upper central area of the medium pellet • a second and last part of the amount of the mixed matrix material is poured over the selenium and / or selenium compound • the rod is placed back into place in the mold cavity and compressed • the finished pellet is removed from the mold. One embodiment of the process according to the invention consists of using two different rods, first one with a smooth section end to compress
the first lower middle pellet and a second, one with a small hole located in the center of its exposed section end to maintain the selenium and / or selenium compound in the pellet core during the processing operation. In accordance with another interesting embodiment, a small portion of a binding agent can be added to the selenium and / or selenium compound before being compressed into the matrix. This has the advantage of maintaining the selenium and / or selenium compound within the finished pellets at a distance from the outer surfaces. The binding agent can be selected from any sticky, preferably organic, composition to allow its escape in the form of water vapor and C02 from the batch mixture by the action of heat. Water by itself in small amounts can also be used as a binding agent. Generally, the binding agent may be present in amounts as low as 0.05% by weight of selenium and / or selenium compound and does not exceed a small percentage of the weight. It is most often kept below 10% of the weight. The invention also relates to the use of the pellets according to the invention to incorporate a batch of molten glass to reduce the selenium burning in the exhaust gas. It also refers to a method for
reducing the selenium burning in a process for manufacturing glass comprising selenium by incorporating at least part of the raw selenium material into the pellets compatible with the invention. A final aspect of the invention is to provide a glass comprising selenium, which has been manufactured by the method detailed above. In a preferred embodiment, the glass is a glass of bicarbonate lime. In another preferred embodiment, bicarbonate lime glass comprising Selenium is a supernatant glass obtained by floating a molten glass ribbon on the upper surface of a molten tin metal bath. The glass can also be, alternatively, any other type of glass that includes, without limitations: drain glass, extracted glass and blown cylinder glass. Preferably, the supernatant glass of bicarbonate lime is a smooth glass. The invention will now be illustrated below by examples which are intended to better describe the invention, without in any way attempting to limit its scope.
Example IR: (not in accordance with the invention) A first reference examples melted (Example
IR) has involved a batch of raw materials that do not include pellets in everything. The following solid components have been mixed in powder form in the indicated amount:
Table 1
To these components 4% of the total weight of the batch of water in liquid form is added to facilitate the mixing of the different solid components. After dry mixing of batch solids, they are poured into a ZAC crucible (zirconia-alumina), the latter is inserted for 2 hours in a laboratory furnace filled with a reductive gaseous atmosphere consisting of a mixture of 95% nitrogen and 5% hydrogen, which is It has preheated to 1400 ° C. The molten batch, which becomes a molten glass, then melts into a cold plate and the resulting solid glass breaks into small pieces. The pieces are then inserted again into a crucible and placed in
the oven at 1400 ° C. The temperature is then increased to 1450 ° C at a rate of about 5 ° C / min. The molten glass is then melted, broken and inserted back into the oven at 1450 ° C. The total duration of the suspension at the temperature is approximately 2 hours. The temperature is then increased to 1500 ° C with the same ratio of 5 ° C / min. The molten glass is then maintained at the temperature by refining it for about an hour, then by a return at 1450 ° C for thermal conditioning for about 1.5 hours. At the end of the thermal conditioning period, the molten glass has been melted in small 4 cm x 4 cm steel molds, which are placed in an annealing furnace at 600 ° C for 2.5 hours. The electrical heating of the annealing furnace is then interrupted and the temperature is allowed to fall to room temperature overnight. On the following day, the glass samples are removed from the molds and their faces are mechanically polished. Its chemical composition is then analyzed by X-ray fluorescence technique and its remaining selenium yield computed by comparison with the initial amount added to the batch mixture. Selenium's performance computation gives a
result of 14%
Example 2R: (not according to the invention) In a second reference example (2R: mixed pellet), the composition "A" described in patent EP 0618 177 Al has been used to compress a pellet that has been inserted into the half of the solids of raw materials in the same crucible as in the IR example. The batch of raw materials and the pellet are of the following composition:
Table 2:
The same process of melting, refining and hardening the glass has been carried out as in the
IR example. The Selenium performance measurement has been 12% for this example.
Example 3-5 (according to the invention) The same procedure as that used in example 2R has been carried out with modified pellets of three different natures. Approximately half of the batch materials are carefully pressed and have to present a hollow cavity in the middle of the compressed mixture. The last cavity was subsequently filled with 0.059 g of Na2Se03 (encapsulated selenium pellets) and covered with the remaining half of the batch materials. The complete pellet comprising the selenium compound at its center has therefore been pressed.
Table 3:
Selenium yields have been computed and indicated in the bottom of the table. It can be observed that encapsulating selenium compounds within the pellets can increase the yield up to 100% compared to the references.
Claims (15)
1. The pellets of at least 0.5 cm in their largest dimension encapsulating selenium and / or at least one Selenium compound, characterized in that the pellets are made of: a) a hollow cavity, located within the body of each pellet and filled with a pellet. selenium heart and / or at least one selenium compound; b) a matrix around the filled roe cavity, which covers and isolates the heart of the pellet from the environment, the matrix is a compressed tablet that does not melt below 1300 ° C under normal pressure, free of any compound which can increase to a gaseous compound when heated from atmospheric temperature to 2000 ° C and which is capable of slowly forming a eutectic product with at least one of the constituents of a batch of molten raw materials commonly used in a glass manufacturing process , when it dips into the batch of raw materials of molten glass, the eutectic product has a melting temperature of 400 to 1800 ° C under normal pressure.
2. Pellets according to claim 1, characterized in that the selenium core and / or at least one selenium compound is selected from selenium metal and organic and inorganic salts, as well as other compounds comprising selenium in their molecules.
3. Pellets according to claim 2, characterized in that the selenium compound is selected from selenites and selenates.
Pellets according to one of claims 1 to 3, characterized in that the matrix comprises at least one of the following compounds SiO2, NaO2, K20, Li20, B203, CaO, MgO, BaO, ZnO, A1203, Fe203, Se, Ti02, CoO, MnO, Cr203, Ce02, Zr02, NiO, Sn02, Cu20, V205 and S03.
Pellets according to claim 4, characterized in that the matrix comprises at least sand, cement, dolomite or any combination of two or more of these compounds.
Pellets according to any of claims 1 to 5, characterized in that the matrix is capable of forming a eutectic with one or more of CaO, MgO and Si02 fused present in a glass batch of raw material.
Process for manufacturing pellets according to any of claims 1 to 6, characterized in that: • part of the total amount of the matrix material is dry mixed • the mixture is poured into a mold having an open cavity • a rod having a slightly smaller cross section one of the cavity opening, then inserted into the cavity and allows to be placed in the matrix material mixture • the rod is then pressed with the help of a press to solidify the material matrix in a lower half pellet • the rod is removed and the selenium and / or selenium compound is deposited in the upper central area of the medium pellet • a second and last part of the amount of the mixed matrix material is poured over the selenium and / or selenium compound • the rod is placed back into place in the molded cavity and compressed • the finished pellet is removed from l mold
8. Process for the manufacture of pellets according to claim 7, characterized in that two different rods are used, first one with a smooth section end to process the lower middle pellet and a second with a small hole located in the center of its final section in view to maintain the selenium and / or selenium compound in the heart of the pellet during the processing operation.
Process for manufacturing pellets according to claim 7 or 8, characterized in that a small proportion of a binding agent is added to the selenium or selenium compound.
10. Pellet manufacturing process according to claim 9, characterized in that the binding agent is selected from at least one sticky organic composition and water.
11. Use of the pellets according to one of claims 1 to 10 to incorporate a batch of molten glass to reduce the selenium burning in the exhaust gas.
12. A method for reducing selenium burning in a process for manufacturing glass, characterized in that it comprises selenium incorporating at least part of the raw selenium material within the pellets according to one of claims 1 to 10.
13. A glass of carbonated lime, characterized in that it comprises selenium, which has manufactured by the method according to claim 12. 1.
Glass of carbonated lime comprising selenium according to claim 13, characterized in that it is a supernatant glass obtained by floating a ribbon of molten glass on the upper surface of a bath of molten tin metal.
15. A smooth glass comprising selenium, characterized in that it is the supernatant glass according to claim 14.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP05109699.8 | 2005-10-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MX2008005088A true MX2008005088A (en) | 2008-09-26 |
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