GB2424644A - Method of suppressing foam formation during glass manufacture - Google Patents
Method of suppressing foam formation during glass manufacture Download PDFInfo
- Publication number
- GB2424644A GB2424644A GB0606024A GB0606024A GB2424644A GB 2424644 A GB2424644 A GB 2424644A GB 0606024 A GB0606024 A GB 0606024A GB 0606024 A GB0606024 A GB 0606024A GB 2424644 A GB2424644 A GB 2424644A
- Authority
- GB
- United Kingdom
- Prior art keywords
- metal compound
- molten glass
- furnace
- supplied
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000006260 foam Substances 0.000 title claims abstract description 47
- 239000011521 glass Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 17
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 75
- 239000006060 molten glass Substances 0.000 claims abstract description 64
- 238000002844 melting Methods 0.000 claims abstract description 21
- 238000005507 spraying Methods 0.000 claims abstract description 17
- 239000006105 batch ingredient Substances 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007806 chemical reaction intermediate Substances 0.000 claims abstract description 3
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 239000004615 ingredient Substances 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 239000010937 tungsten Substances 0.000 claims abstract description 3
- 239000000446 fuel Substances 0.000 claims description 11
- 239000003570 air Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 abstract description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000008030 elimination Effects 0.000 description 5
- 238000003379 elimination reaction Methods 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- 238000007670 refining Methods 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000013626 chemical specie Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 229910021343 molybdenum disilicide Inorganic materials 0.000 description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 2
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010061245 Internal injury Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011817 metal compound particle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/235—Heating the glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/225—Refining
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/18—Stirring devices; Homogenisation
- C03B5/193—Stirring devices; Homogenisation using gas, e.g. bubblers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/20—Bridges, shoes, throats, or other devices for withholding dirt, foam, or batch
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Melting And Manufacturing (AREA)
Abstract
A method of manufacturing glass comprising supplying batch ingredients to a glass-melting furnace 10, where said ingredients form molten glass 13, supplying a metal compound to the molten glass, thereby reducing or eliminating a foam layer which is liable to develop on the surface of the molten glass as melting occurs, wherein the metal compound includes a metal chosen from the group containing molybdenum, tungsten and zirconium. The metal compound may be supplied in a solution, a slurry, as a vapour, by spraying into the furnace atmosphere directly above the molten glass (preferably using spraying nozzles), by addition to the batch ingredients or by bubbling into the molten glass. The metal compound may be un-reacted, or part of a reaction intermediate or reaction product as it contacts the molten glass.
Description
Improved Method of Manufacturing Glass The present invention relates to an
improved method of manufacturing glass, especially, but not exclusively, flat glass including float glass.
In conventional methods of manufacturing glass, a mixture of raw materials (known as batch) is typically fed to the upstream end of a glass-melting furnace (known as the melting zone which is usually at a temperature of between 1500 C and 1600 C) where conversion into molten glass begins.
Molten glass typically flows into a mid-section of the furnace (known as the refining zone) where it may be at least partially homogenised and refined, before flowing to the downstream end of the furnace, known as the conditioning zone. There may be a narrower Section or waist between the refining zone and the conditioning zone. Further homogenisation of the molten glass generally occurs in the conditioning zone.
The glass-melting furnace used to melt the batch ingredients utilises some amount of overhead firing to melt the batch. The burners used for the overhead firing are typically one of two types: conventional "air- fuel" burners (which burn natural gas along with air which is usually preheated) and burners that are known in the art as "oxy-fuel" burners. An oxy-fuel burner is a burner that either burns commercially supplied or locally manufactured oxygen (typically of high oxygen purity) along with natural gas, or which burns oxygen-enriched air along with natural gas. The burners are generally located in the side walls of the melting zone of a furnace. Air, or oxygen-enriched air, is generally supplied with some level of pre-heat.
As the batch ingredients melt, a layer of foam (i.e. bubbles) forms on the upper surface of the volume of molten glass in the furnace, beginning in the melting zone. If steps are not taken to remove the foam layer during the melting and refining stages of the glass melting process, the bubbles remain in the molten glass and are transferred through to the final glass product. Such a layer of foam occurs with whichever type of burner (described above) is used to melt the batch, however its occurrence is known to be a more acute problem in furnaces that employ oxy-fuel burners.
A further problem with a foam layer on the surface of molten glass is that it effectively acts an insulating shield, reducing the degree of heat transfer from the flames of the overhead burners to the molten glass below (thus reducing the heating efficiency of the burners) and at the same time reflecting heat from the flames of the burners to the surrounding refractory bricks from which the furnace is made, thus reducing the working lifetime of the bricks.
Attempts have been made to reduce the foam layer from the surface of molten glass. For example EP 1 046 618 Al describes a method for melting glass in which at least one metal compound is supplied to the foam layer to diminish or extinguish said foam layer; the metal of the compound being selected from the group consisting of aluminium, titanium, silicon, zinc, magnesium, iron, chromium, cobalt, cerium and calcium. The specific group of metals listed is quite wide-ranging - it includes alkaline earth metals, transition metals and a lanthanide, and would appear to form a substantially comprehensive list of the best performing metals of the periodic table to solve the problem of the foam layer.
Disappointingly however, the metals listed above do not perform as well as may be expected, and a significant layer of foam remains on the surface of molten glass subsequent to its treatment with a metal compound. Furthermore, what appears to be the best performing metal compound according to EP 618, titanium dioxide (to which the majority of the examples are directed), has some serious drawbacks associated with it.
The two alternative precursors for Ti02 (to be formed in the furnace) described in EP 618 are tetrabutyl titanate and titanium tetrachloride. Tetrabutyl titanate is an irritant - inhalation may lead to severe respiratory irritation and absorption through the skin may lead to significant internal injuries. Titanium tetrachloride introduces chloride ions into the furnace, which form hydrogen chloride in the furnace environment. Hydrogen chloride is extremely corrosive and leads to deterioration of the furnace structure.
It is an object of the present invention to provide a method of manufacturing glass using alternative metal compounds to those already known to reduce or eliminate a foam layer on the surface of the molten glass. The alternative metal compounds preferably perform equally effectively, if not better than, the metal compounds already known for the purpose of foam reduction/elimination, and further improve heat transfer between the flames of the burners used in the furnace and the molten glass below.
It is a further object to use metal compounds which, along with their chemical precursors where appropriate, are environmentally safe, do not have a damaging effect on the furnace and do not lead to problems with further processing of the molten glass.
According to the present invention there is provided a method of manufacturing glass comprising: supplying batch ingredients to a glassmelting furnace, where said ingredients form molten glass, and supplying a metal compound to the molten glass, thereby reducing or eliminating a foam layer which is liable to develop on the surface of the molten glass as melting occurs, wherein the metal compound includes a metal chosen from the group containing molybdenum, tungsten and zirconium.
The phrase "reducing or eliminating a foam layer which is liable to develop..." includes both the reduction or elimination of a foam layer that has already formed on the surface of the molten glass, and the reduction or elimination of a foam layer that has not yet formed.
The metal compound supplied to the molten glass preferably contacts the uppermost surface of the foam layer, and in doing so, the reduction or elimination of said foam layer may advantageously occur instantaneously, or substantially instantaneously (in under a couple of seconds). Such a rapid interaction of the metal compound with the foam layer may ensure that the foam layer is controlled as soon as possible in the furnace and reduce the risk of any foam remaining on the surface of the molten glass as it progresses through the furnace.
The degree of foam reduction induced by the metal compound is at least 80 % (that is to say, the amount of foam initially present is reduced by 80 %, or the amount of foam that would have formed on the surface of the molten glass is reduced from 100 % to %), although a reduction of at least 85 % or even 90 % may be achieved. It is furthermore possible that there may be a 100 % reduction (i.e. complete elimination) in the amount of foam present on the surface of the molten glass.
The metal compound may be typically supplied to the molten glass in a continuous manner. In doing so, the amount of foam should not develop or redevelop to the extent initially observed, prior to the metal compound being supplied to the molten glass. Alternatively, the metal compound may be supplied to the molten glass in intervals, which may be regular intervals or irregular intervals. If the metal compound is supplied in intervals rather than continuously, the length of an interval between metal compound supply is preferably less than two minutes, further preferably less than one minute and most preferably less than 30 seconds, so as to avoid formation or re-formation of a foam layer. The period of time over which the metal compound is supplied, between intervals of nonsupply, is preferably at least one minute, further preferably two minutes and most preferably three minutes.
Preferably, the metal compound supplied to the molten glass is a mixture of two or more of the metal compounds identified. This may be beneficial, for example if one compound acts to reduce surface tension whilst a second compound acts the increase surface tension.
Different metal compounds may be supplied to the molten glass at different stages along the length of the furnace - one metal compound may be supplied in the melting zone, whilst a different metal compound may be supplied further downstream, for example in the refining zone.
Preferably, the metal compound is supplied to the furnace in a solution. The solution may be aqueous or non-aqueous. Non-aqueous solvents that are suitable for making such a solution include butanol, isopropyl alcohol and ethanol. Alternatively, the metal compound may be supplied to the furnace in a slurry (a liquid-solids mixture), as a vapour, or as a powder. Most preferable is to supply the metal compound as a vapour because it is relatively easy to distribute a vapour over a large surface area.
Typically, the metal compound is supplied to the molten glass (and hence to the foam layer) solely in the melting zone of the furnace.
The metal compound is preferably supplied to the furnace by spraying into the furnace atmosphere directly above the molten glass. One or more spraying nozzles may be employed for this purpose. By spraying directly into the furnace atmosphere, the metal compound may be uniformly distributed over substantially the entire surface area of the molten glass affected by the presence of a foam layer. Typically the one or more spraying nozzles are located at regular intervals along each of the side walls of the furnace, although they can additionally or alternatively be located in the ceiling of the furnace structure. The spraying nozzles usually rely on air or nitrogen to provide the backing pressure to enable the metal compound to be sprayed into the furnace atmosphere, but other gases can be used. The pressures used typically range from 35 to 550 kPa. The air or nitrogen effectively atomises the metal compound to create a substantially uniform gaseous mixture of air or nitrogen molecules and particles of the metal compound.
At the upstream end of the furnace, in the melting zone, the one or more spraying nozzles are each preferably located adjacent to a burner used to melt the batch ingredients (however the one or more spraying nozzles may be located additionally or alternatively downstream of the fired area of the furnace via suitable access points in the furnace superstructure). Location of one or more spraying nozzles in the melting zone means that the metal compound may effectively inhibit the formation of a foam layer in the first instance or drastically reduce the volume of foam present (i.e. by at least 80 %). Location or one or more spraying nozzles adjacent to a burner is beneficial because it is in the region of the burners that formation of the foam layer on the surface of the molten glass occurs.
Further preferably each of said spraying nozzles is located below its corresponding burner such that each is positioned between its burner and the volume of molten glass in the furnace. In such a position, the sprayed metal compound may have maximum effect because it reduces or eliminates the foam layer on the surface of the molten glass in the region where maximum heat transfer from the burner to the molten glass may occur.
In a typical oxy-fuel furnace there may be a total of twelve burners in the melting zone of the furnace - six along each side wall, which are preferably in a staggered configuration. There may also be, therefore, a total of twelve spraying nozzles in the melting zone of the furnace.
The metal compound may alternatively be sprayed into the furnace atmosphere via the combustion air, oxygen or fuel supplies. The nozzles that supply the combustion gases to the furnace for combustion also supply the metal compound, preferably as a vapour, to the furnace atmosphere. Once in the furnace atmosphere, the metal compound may undergo an oxidation reaction to form a metal oxide; this then being the species that contacts the foam layer. Using the air, oxygen or fuel supplies to introduce the metal compound into the furnace atmosphere is advantageous because the distribution of the metal compound may tend more towards being uniform over the entire area of molten glass affected by the foam layer.
Further alternatively, the metal compound may be supplied to the furnace by addition to the batch ingredients. As the batch ingredients are fed to the melting zone of the furnace and begin to melt, the metal compound dissolves in the forming molten glass.
By supplying the metal compound in this way, its effects are felt from the moment the batch ingredients begin to melt and so it is more likely that the foam layer may be prevented from forming at all on the surface of the molten glass.
Still further alternatively, the metal compound may be supplied to the molten glass in the furnace in the form of a vapour by bubbling it into the molten glass via gas supply ports. The gas supply ports (such as "bubblers", which are known in the glass industry) are usually submerged in the molten glass. The gas supply ports may be located in the floor of the furnace or along the side walls. It may be useful to supply the metal compound to the foam layer in this manner because it can be delivered directly to the locations in the molten glass where foam formation occurs.
The metal compound itself may be inorganic. Examples of inorganic compounds include molybdenum trioxide (MoO3), molybdenum pentachloride (MoCl5), molybdenum disilicide (MoSi2), ammonium heptamolybdate ((NH4) 6Mo7O24.xH2O), tungsten trioxide (W03), tungsten chloride (WCI6), ammonium metatungstate ((NH4)6H2W1 2040'xH2O), zirconium dioxide (Zr02) and zirconium tetrachioride (ZrCL1). Use of an ammonium counter-ion is especially beneficial because the ion readily and completely volatilises without having a deleterious effect on the furnace superstructure.
Alternatively, the metal compound may be organic. Examples of organic compounds include zirconium propoxide (Zr(C3H70)4), zirconium t-butoxide (Zr(C4H90)4) and zirconium n-butoxide (Zr(C4H9O)4).
The metal compound, as it supplied to the furnace, may be the chemical species which contacts the foam layer, i.e. once supplied to the furnace, the metal compound does not undergo any reaction, but remains in its original, un-reacted state. However, it is possible that the metal compound may undergo a chemical reaction once supplied into the furnace atmosphere and thus the particular chemical species which contacts the foam layer may be a reaction intermediate or reaction product (of the chemical reaction between the metal compound and other chemical species in the furnace atmosphere).
For a better understanding, the present invention will now be more particularly described by way of non-limiting example with reference to, and as shown in, the accompanying Figure which is a schematic plan view of the interior of the upstream end of a glass-melting furnace.
Glass-melting furnace 10 shown in the Figure comprises two side walls 11, upstream end wall 12 and a downstream end wall (not shown), all of which constrain and contain molten glass 13 in furnace 10. Upstream end wall 12 is provided with a batch- feeding port 14, through which batch ingredients 15 are fed into the furnace and into contact with molten glass 13 already present in furnace 10. Batch ingredients 15 dissolve and melt away into molten glass 13, thereby producing yet more molten glass. To aid the melting process, a series of twelve burners 16 are located in side walls 11 of furnace 10; there being six burners 16 located in each side wall 11. The burners 16 may be air-fuel burners, oxy-fuel burners or a combination of both. Heat is transferred from the flames (not shown) of each of burners 16 to batch ingredients 15 and molten glass 13 below.
Furnace 10 is further provided with a series of gas inlets 17 in the floor structure thereof The metal compound of choice, according to the invention, is bubbled into molten glass 13 via gas inlets 17 such that the metal compound is able to effectively reduce or eliminate foam layer 18 which is liable to form on the upper surface of molten glass 13 as batch ingredients 15 melt and gases are released therefrom into the surrounding molten glass.
The effectiveness of the metal compounds of the present invention is demonstrated in the following examples. The percentage reduction in the total foam volume after a metal compound has been supplied to the furnace is measured with respect to the total foam volume when there has been no addition to the molten glass. The examples were conducted in a laboratorysized electric furnace which had its internal "furnace" atmosphere controlled to simulate the steam content of the internal atmosphere of a typical full-sized oxy-fuel furnace. For each of the examples, there is clearly a massive reduction in the total observed foam volume in the period subsequent to addition of the particular metal compound.
Ex. Metal Compound Supplied to Molten Glass % Reduction in Total No. Observed Foam Volume on Surface of Molten Glass 1. Zirconium (IV) propoxide solution 82 2. 0.25 M ZrCL1 in paraffin suspension 80 3. MoO3 powder in N2 flow 92 4. MoO3 powder in paraffin suspension 92 5. 1.0 M MoO3 in paraffin suspension 95 6. 0.5 M MoO3 in paraffin suspension 94 7. 0.1 M MoO3 in dilute HC1 93 8. 0.25 M solution of ammonium heptamolybdate 95 9. 0.5 M W03 in paraffin suspension 95
Claims (17)
- Claims: 1. A method of manufacturing glass comprising supplying batchingredients to a glass-melting furnace, where said ingredients form molten glass, and supplying a metal compound to the molten glass, thereby reducing or eliminating a foam layer which is liable to develop on the surface of the molten glass as melting occurs, wherein the metal compound includes a metal chosen from the group containing molybdenum, tungsten and zirconium.
- 2. A method according to claim I wherein the metal compound is a mixture of two or more of the metal compounds identified.
- 3. A method according to claim I or claim 2 wherein different metal compounds may be supplied to the molten glass at different stages along the length of the furnace.
- 4. A method according to any preceding claim wherein the metal compound is supplied in a solution.
- 5. A method according to any of claims 1 to 3 wherein the metal compound is supplied in a slurry.
- 6. A method according to any of claims 1 to 3 wherein the metal compound is supplied as a vapour.
- 7. A method according to any preceding claim wherein the metal compound is supplied to the furnace by spraying into the furnace atmosphere directly above the molten glass.
- 8. A method according to claim 7 wherein one or more spraying nozzles are employed for said spraying.
- 9. A method according to claim 8 wherein the one or more spraying nozzles are each located adjacent to a burner used to melt the batch ingredients.
- 10. A method according to any of claims I to 7 wherein the metal compound is sprayed into the furnace atmosphere via the combustion air, oxygen or fuel supplies.
- 11. A method according to any of claims 1 to 6 wherein the metal compound is supplied to the furnace by addition to the batch ingredients.
- 12. A method according to any of claims 1 to 3 or 6 wherein the metal compound is bubbled into the molten glass via gas supply ports.
- 13. A method according to any preceding claim wherein the metal compound is inorganic.
- 14. A method according to any of claims 1 to 12 wherein the metal compound is organic.
- 15. A method according to any preceding claim wherein the metal compound is un- reacted when it contacts the molten glass.
- 16. A method according to any of claims I to 14 wherein the metal compound undergoes a chemical reaction once supplied into the furnace, and a reaction intermediate or reaction product of this reaction contacts the molten glass.
- 17. A method of manufacturing glass substantially as hereinbefore described with reference to, and as illustrated in, the accompanying Figure.
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US66636405P | 2005-03-30 | 2005-03-30 |
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WO2012125665A1 (en) * | 2011-03-17 | 2012-09-20 | Ppg Industries Ohio, Inc. | Method of, and apparatus for, using a glass fluxing agent to reduce foam during melting of glass batch |
CN104692616A (en) * | 2015-02-14 | 2015-06-10 | 无锡顺鼎阿泰克科技有限公司 | Bubble removal technology for glass total-oxygen kiln |
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EP2903941A4 (en) * | 2012-10-03 | 2016-06-08 | Johns Manville | Methods and systems for destabilizing foam in equipment downstream of a submerged combustion melter |
US9492831B2 (en) | 2010-06-17 | 2016-11-15 | Johns Manville | Methods and systems for destabilizing foam in equipment downstream of a submerged combustion melter |
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EP1046618A1 (en) * | 1999-04-21 | 2000-10-25 | Asahi Glass Co., Ltd. | Method for melting glass |
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US10196294B2 (en) | 2016-09-07 | 2019-02-05 | Johns Manville | Submerged combustion melters, wall structures or panels of same, and methods of using same |
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