CN1827540B

CN1827540B - Method and device for melting and refining materials capable of being vitrified

Info

Publication number: CN1827540B
Application number: CN2005101286793A
Authority: CN
Inventors: P·让沃伊尼; T·马萨尔特; A·贝尔特雷奥
Original assignee: Saint Gobain Glass France SAS
Current assignee: Saint Gobain Glass France SAS; Compagnie de Saint Gobain SA
Priority date: 1998-01-09
Filing date: 1999-01-08
Publication date: 2013-05-22
Anticipated expiration: 2019-01-08
Also published as: CN1827540A; FR2773555B3; FR2773555A1

Abstract

All or part of the thermal energy required for melting the materials is supplied by the combustion of fossil fuel(s) with at least one combustive gas. The fuel/gas or the gaseous products derived from combustion are injected beneath the mass of vitrifiable materials. Refining of melted materials incorporates at least one step of pressurization at sub-atmospheric pressure. An Independent claim is included for apparatus used to implement the method of melting and refining vitrifiable materials.

Description

But the method and apparatus of vitrification substance melting and clarification

The application be that January 8, application number in 1999 are 99800024.8 the applying date, denomination of invention divides an application for the application for a patent for invention of " but vitrification substance melting and refining method and apparatus ".

Technical field

But the present invention relates to a kind of method of vitrification substance melting and clarification, in order to continuously melten glass is supplied with device for shaping glass.

Relate more specifically to the formed from plate glass device, as float shaping equipment or formed from plate glass equipment, but also relate to the double glazing molding device of bottle, flask type, heat insulation or the glass fibre molding device of mineral wool class of sound insulation or the molding device of so-called reinforced fabric glass yarn.

Technical background

These methods many research work have been carried out, these methods comprise first fusing step briefly, it is then clarification steps, its clarification steps is to adopt thermal means and chemical process to regulate melten glass, also is to remove not fusant, the bubble in melten glass and eliminates any causes of defects that occurs after moulding.

Aspect fusing, therefore for example studied and accelerated its fusing, or improved the efficient of its energy.So can enumerate a kind of method, but the method with evenly with control ground rapid heating vitrification substance, carry out simultaneously strong mechanically mixing, but but can make or the vitrification substance of solid fully contacts with the vitrification substance that is liquid phase.This method was described in patent FR-2 423 452, FR-2 281 902, FR-2340 911, FR-2 551 746 particularly, and this method is generally used the electrical heating device of immersion electrode type.

Also once developed an other class melting method, class methods of for example describing in US-3 627 504, US-3 260 587 or US-4 539 034, these methods are used the immersion nozzle, namely usually with the mode equal with furnace bottom configure with the nozzle of gas and air feed as heating installation, but in order to even scatter in vitrification substance inside at the liquefaction process Flame.

Under any circumstance, compare with " common " fusing, but reduce the residence time of vitrification substance in melting chamber although can effectively reach very significantly, greatly boost productivity, but then, molten glass is the spumescence that is difficult to clarify, and is difficult to especially guarantee the quality of final glass, particularly opticglass.

Also did some research work aspect clarification.Therefore, for example known by patent EP-775 671 and patent US-4 919 697, at least under reduced pressure carry out part clarification operation, so for example can access the glass of the very poor high oxidation reduction of vitriol.But this clarification can produce strong foam, and this foam may be difficult to Control and elimination.

Summary of the invention

Therefore, the objective of the invention is to improve fusing and defecation method, relate to particularly the equipment usage comparison compactness and/or that operation is more flexible and/or production efficiency is higher, and these industrial advantage can not be damaged again the quality of the glass of producing.

But the present invention is the method that purpose is fusing and the clarification of vitrification substance at first, it is characterized in that following two features are combined:

On the one hand, but being burnt with at least a combustion-supporting gas by one or more fossil class A fuel As, vitrification substance needed all or part of heat energy of when fusing provides, but with described fuel/air or come the gaseous product of auto-combustion to spray into below the vitrification substance material liquid surface.

On the other hand, but the clarification of vitrification substance after fusing comprises at least one step makes it be placed in step under subatmospheric.

Confirmed to be referred to as below for simplicity " adopting the immersion nozzle " fusing and to have an extremely favourable synergy industrial with adopting decompression between clarifying using.

But, because this combination also can be used far away, also can expect just to reach take medium glass quality as cost all these above-mentioned advantages, it has not been this situation.Although this is known because of decompression clarification principle, its principle is unworkable, and be not sure reach with adopt that common clarification technique reaches same allow the fusant retained percentage of bubble/not.Yet, in the present invention, by varying sized parameter, use this clarification very especially, Here it is replaces supplying with toward the clarifying area " common " melten glass to be clarified, and in fact supplies with here and adopts the resulting glass of immersion nozzle fusing, namely has the very glass of special characteristic on frothy this connotation always, and compare with the density of normal glass, its density is quite low.Much less, might under reduced pressure clarify the more glass of initial foam.

Yet astoundingly, confirm that this is possible, because find that the feature that this frothy glass from adopting the fusing of immersion nozzle also has is only to contain minute quantity at the vitriol that begins to contain or do not contain.In fact, from the glass out of molten glass chamber, with SO ₃The sulphate content that weight represents is generally lower than 600ppm, even lower than 200ppm or below 100ppm, lower than 50ppm, needn't control or be reduced in the vitriol percentage that usually contains in the raw material of use what is more, but namely add vitriol even wittingly in vitrification substance unintentionally.This protosulfate percentage just can under reduced pressure be clarified and no problem effectively.On the contrary, high-content vitriol or " standard " content vitriol simply in treating fining glass when the decompression clarification, adopt the desulfating processing can cause that very strong foam expands, and this expansion is difficult to control.This glass of discharging from melting chamber does not almost have the fact of vitriol, but can make explanations with the dividing potential drop of the water that is produced by the jet combustion that is immersed in vitrification substance.It is worthy of note, the volatile compound problem occurs seldom through glass that desulfating is processed in the float glass process molten bath, generate the dangerous low of tin sulfide, therefore at last on sheet glass the danger of tin defects also very low.In the situation that reductibility glass, this has just reduced the amount (removing even fully) of sulfide, particularly reduced the amount that to bring not too desirable residual yellow/amber iron sulphide, or reduced the nickelous sulfide wrap, when the thermal treatment of quenching type, this wrap may cause glass fragmentation faced.

it is also worth noting that, according to the present invention, the favourable characteristics of another one from melting chamber glass out: although still in fact be a kind of form of foam at the glass of clarifying, but can control the bubble size that it contains, particularly can almost remove all minimum bubbles in some cases, be diameter less than the bubble of 200 microns, before fusing is really clarified afterwards, on glassly carry out a kind of " little-clarification " at it when glass melting, little-clarification is conducive to the coalescent and smaller bubble of bubble and disappears, be conducive to larger bubble, but and the clarification aid that adds coke or vitriol type in vitrification substance be conducive to this little-clarification.In addition, the ratio of this general residual not fusant from melting chamber glass out is low especially, is also here so, is exactly bubble size simply, the clarification operation after being conducive to melt.

Therefore, the present invention even just can obtain the low-down glass of vitriol before clarification operation, even at clarification vitriol very low glass also afterwards, but does not need like this for making its glass there is no too many vitriol purifying/selection vitrification substance.On the contrary, even can add vitriol when beginning, this is fully wonderful, is also favourable.

Adopt the resulting advantageous effects of combining method of the present invention to relate to the cost of energy of the method: adopt the fusing of immersion nozzle can remove the electrofusion of using the immersion electrode type from, its electrofusion cost may be very high in some country.In addition, the most important just will explain as following, mix but adopt the immersion nozzle to be melted in to produce convection current in vitrification substance in liquefaction.This is extremely effective in mixing of also not being listed as very by force between material and the material that has liquefied of liquefaction, compare with the common type of heating of employing, but use the vitrification substance of identical chemical constitution, can just can reach fusing at lower temperature and/or with faster speed.The decompression clarification can also be at lower temperature, faster ground fining glass.This is because the pressure when reducing clarification, but the molar volume of gas that can cause containing in the vitrification substance of fusing increase, the bubble volume that contains of this material also increases thus, therefore increases toward the weld pool surface lift velocity, and increases it and get rid of speed.

When clarification decompression can allow people to operate at lower temperature than common clarification the time, in fact operates at the lower temperature that adopts immersion nozzle smelting technology to use.

According to the present invention, the temperature of encountering when fusing and clarification is compatible fully, all be fit to each other, these temperature are low than in usual method all, only according to cost of energy, also by being chosen in the material of the high temperature material class of using when making these equipment, i.e. thermal etching is material slowly, and this is very significant economically.

Also greatly shorten and compatible in melting range and the residence time in the clarifying area, this is to production efficiency, have significantly very favourable influence to the throughput of its whole equipment.Simultaneously, the present invention can access very compact equipment: this is because adopt the fusing of immersion nozzle, then because fusing causes very strong mixing, therefore can greatly reduce the size of melting chamber.The size in one or more cabins that the clarification of reducing pressure in addition operates also has same result: in a word, therefore this equipment can be very compact, and according to cost, predigested running, the wearing and tearing of reduction structured material etc., its benefit is obvious.

About melting operation, the ignition dope of selection can be the ignition dope take air, oxygen-rich air as main component according to the present invention, perhaps the ignition dope take oxygen as main component even basically.In fact be all favourable at this ignition dope middle and high concentration oxygen because of following a variety of causes: it reduces the volume of combustion product gases, from energy viewpoint, this is favourable, but also can avoid occurring the danger of the excessive fluidisation of vitrification substance, and this excessive fluidisation may cause with its surge to superstructure, melting chamber top.In addition, " flame " that obtains is shorter, more easily emit, but this just can transfer to vitrification substance rapidly with its energy comparison, if desired, but also can reduce by way of parenthesis the degree of depth in vitrification substance in liquefaction " molten bath ".Here spoken of " flame ", but these flames flame on this term ordinary meaning not necessarily.As speaking of hereinafter, can be " combustion zone " more in general.In addition, any can be with the dusty gas NO that emits _xDrop to minimum.

About the selection of fuel, this can be the fuel of the fossil oil type of gas or non-pneumatic, as Sweet natural gas, propane, oil fuel or any other hydrocarbon containing fuels.Hydrogen also.Adopting the method for immersion nozzle fusing of the present invention is a kind of favorable method that uses hydrogen, in addition, and owing to adopting H ₂With O ₂The resulting flame that burns has the characteristics of low emission, uses overhead non-immersion " air " nozzle very difficult.

When adopting the fusing of immersion nozzle, oxygen and aiding combustion agent and hydrogen fuel are combined use that to be a kind of assurance transfer to good method in molten glass with the effective heat energy of nozzle, also cause a kind of method of " cleaning " fully, namely except the product that may come from the raw material decarburization, neither emit oxynitride NO _x, do not emit greenhouse gases CO yet _x

Advantageously, melt at least one melting chamber according to the present invention, its melting chamber configuration nozzle, but its combustion zone or combustion gases of being configured to them scatter in the vitrification substance material in melting process.So can allow them pass its sidewall, bottom and/or allow above they are suspended on, they are fixed on furnace roof or any suitable superstructure.These nozzles can be like this, and the wall that their gas feed pipe and they are passed through flushes.Preferably but these pipelines enter in the vitrification substance material at least in part, in order to avoid flame to be too near to wall, and avoid causing that high temperature material weares and teares too early.Can also select just to inject combustion gases, namely produce capable combustion zone outside melting chamber.

As mentioned above, but confirmed that this type of heating can cause the vitrification substance intense mixing because of convection action: both form convection cell so burning is " flame " or combustion gas flowing, melted or also unfused material mixing enduringly very effectively.So obtain very favorable " stirring " fusing feature, needn't use mechanical stirring equipment not too insecure and/or the energy Fast Wearing.

Preferably, but regulate the height of vitrification substance material in melting chamber, and burning or the height that comes the gas of auto-combustion to scatter, but so that these burning/gases still stay in described vitrification substance material: its objective is still to keep these convection circulation rings in liquefaction.

Usually, this class fusing can reduce dust and the NO of any type in melting chamber greatly _xClass gas because rate of heat exchange is very fast, has therefore avoided may being conducive to generate the thermal spike of these gases.Also greatly reduce and emit CO _xClass gas.

It is also conceivable that but employing vitrifying material preheater step melts, but when its temperature liquefies than it, necessary temperature is much lower, for example at the most 900 ℃.In order to carry out this preheating, the heat energy of recovered flue gas advantageously.Heat energy is taken out in employing from cigarette, can reduce generally the consumption of equipment particular energy.

But the vitrifying material can comprise raw material, but also comprises cullet, or even is used for vitrified waste material.They can also comprise combustible ingredient (organism): therefore, inorganic fibre (this class inorganic fibre that uses when heat insulation or sound insulation that for example can recirculation scribbles tackiness agent, or the inorganic fibre that uses when reinforced plastics), with the laminated windowpanes of polyvinylbutyral base polymer plate, as windshield glass, or the matrix material of any type, this material is combined with each other glass and plastics, for example some bottle.All right recirculation " matrix materials of glass-metal or some metals ", as the window glass that works with the coating that contains metal, these are difficult to recirculation so far, because this can appear at melting chamber enriched in metals gradually, are accumulated in the danger on bottom faces.But adopt the mixing carried out of fusing can avoid this deposition according to the present invention, therefore can recirculation for example scribble the window glass of enamel paint layer, metal level and/or different connect elements.

A further object of the invention is that all these contain the composite component of glass by adopt immersion nozzle fusing recirculation in glass furnace.Immersion nozzle stove can be set particularly, and its basic function is to make sheet glass by these different recycle substance, and then, specific sheet glass and normal glass sheet merge or do not merge with the normal glass sheet, can be as the raw material of common glass furnace.

Advantageously, but but can consider in melting process to add all or part of vitrification substance toward melting chamber under vitrification substance material water plane.Can add these materials of part in common mode on liquefaction layer material, rest part for example can adopt the worm feeder apparatus to be added to below liquefaction layer material.Therefore can be in fusing locular wall a single point or the material in different distributed points directly joins liquefaction with these materials.A kind of like this method that directly joins (following use " molten-glass pool " expression) in the material that is in liquefaction process is because following a plurality of reasons are favourable: at first, can greatly reduce any danger that raw material flies up this directly adding above molten-glass pool, the pressed powder percentage of therefore discharging from stove can be down to minimum.Secondly, can control preferably short residence time(SRT) this directly adding before described material is delivered to the clarifying area, according to immersion nozzle layout, can mix the strongest place in convection current and optionally add them.Therefore this or these molten-glass pool adds a little can be near its surface, or can be in molten-glass pool darker place, and for example the height in molten-glass pool is from 1/5 to 4/5 of base plane meter molten-glass pool total height, or 1/3 to 2/3 place of the described degree of depth.

Once saw, method of the present invention can recirculation with the plastics of the composite prod shape of being combined with glass, therefore these plastics can be used as part of fuel.Also can will adopt the necessary all or part of fuel of immersion nozzle fusing with solid fuel shape (polymer class organic substance, charcoal) or even liquid fuel is introduced, be still favourable, this fuel replaces at least part of liquid or the geseous fuel (specifically fossil oil) of supplying-nozzle.Usually, the term " but vitrification substance " that uses in this article or " raw material " comprise the necessary material of acquisition glass basis (or pottery or glass-ceramic), but also comprise any additive (clarification additive etc.), all possible liquid or solid fuel (plastics of compound or non-matrix material, organic substance, charcoal etc.) and the sheet glass of any type.

The inventive method can be carried out with high sheet glass ratio.

As previously described, but therefore clarification of the present invention is that vitrification substance with the fusing shape of the category of glass of show bubble carries out.Typically, this foam density for example is about 1-2, and namely volume mass is the 1-2 gram per centimeter ³(being 2.4 to compare with non-foam glass density), preferably sulphate content is with SO ₃Weighing scale is 600ppm at the most, 100ppm even at the most, at least 200 microns of most of bubble diameters.Therefore, the volume mass of this foam can be the 0.5-2 gram per centimeter ³, 1-2 gram per centimeter preferably ³

In order to improve Clarification Performance, but preferably add various clarification aids in vitrification substance, its purpose is mainly to remove the diameter that occurs since the fusion stage less than the bubble of 200 microns, as previously mentioned from glass.This may relate to the reductibility additive, as coke (also allowing to regulate the glass redox-potential).In this case, advantageously select mean particle size less than the coke powder of 200 microns.Also may relate to vitriol.The decompression clarification can cause air bubble growth, its objective is to make this bubble Fast Growth, and at an easy rate from molten-glass pool surface discharge, and it is broken.Other clarification aid exactly the clarification stage after the fusion stage, be quite effective.They especially can make foam " unstable ": for example relate to fluorine or fluorochemicals or chlorine-containing compound, more generally also relate to halogenide or NaNO ₃Class nitrate; As if fluorine (halogen) reduce glass viscosity.Therefore, fluorine may be conducive to remove the film that generates between bubble, and namely this film of removing is conducive to break foam.Fluorine also reduces glass surface tension.

During impact decompression clarification, other factors of air bubble growth mode are the gas properties on melted material.Certainly can select simply the air dividing potential drop.Can also select to be rich in the atmosphere of nitrogen class rare gas element, even only select the dividing potential drop of nitrogen class rare gas element.This is that when being conducive to clarify because of the residual pressure of selecting nitrogen class rare gas element, open bubble breaks.In fact, the unusual O of high density just ₂The oxidizing gas of type this breaking of seemingly adversely slowing down.

Advantageously, subatmospheric is less than or equal to 0.5 normal atmosphere (0.5 * 10 when proceeding to the small part clarification ⁵Handkerchief), about 0.3-0.01 normal atmosphere (approximately 3 * 10 preferably ⁴-0.1 * 10 ⁵Handkerchief).

Advantageously, method of the present invention can be no more than 1400 ℃ in temperature, preferably at the most 1380 ℃ or 1350 ℃ melt and/or clarify.

According to the first scheme, the present invention's clarification can be carried out at least one static cabin in melting chamber downstream, and at least one zone in its static cabin is placed under decompression.

According to first scheme, clarification but is carried out in the cabin that can be rotated always in the melting chamber downstream, in order to guarantee to adopt centrifugal the clarification, also has at least one zone in the described cabin of especially upstream to be placed under decompression.

The third scheme is above-mentioned two schemes is combined, and first static cabin is used in clarification particularly, and the decompression of being placed in lower zone is arranged, second rotatable cabin then, and this cabin also comprises the zone that is placed under decompression, preferably its pressure ratio static state cabin is lower.

According to a kind of embodiment, method of the present invention considers to adopt at least one injection stream dispenser device to process between fusing section and settling section, but or the vitrification substance of the fusing shape when settling section begins stream.This equipment, for example a kind of element of boring, adopt this facility constraints molten glass stream to pass through, and this molten glass stream can be divided into the little molten glass stream of a large amount of diameters.Selecting hole diameter advantageously is so that its diameter approaches the size that will remove bubble.Because of than, if just in time at the atmospheric regional downstream configuration in clarification cabin injection stream dispenser device, to adopting the silk that the injection stream dispenser device produces to apply soon depressurization, and can High-speed clarification, it be also like this even adopting high glass flow rate.Therefore, lead to some similar fashion that wortle was reached in pressure reduction vessel to treat that fining glass feed clarification cabin can become with employing.

(term " upstream " and " downstream " but mean delivering to melting chamber from vitrification substance until the direction of glass flow taking out the equipment of fining glass) within the scope of the present invention.

The method of the present invention's fusing/clarification can be produced the glass with various different compositions and character.Because its inertia is low, can also change into another kind of the composition from a kind of composition in addition, its transformation time is very short.

Therefore, can produce the glass of suitable reductibility, the oxidation-reduction quality of this glass is particularly greater than or equal to 0.3.(oxidation-reduction quality be defined as the iron weight percentage of ferrous FeO with Fe ₂O ₃The ratio of total iron weight content in this composition that form represents).

Can also produce high SiO ₂The glass of content, for example at least 72% (weight), even at least 75% (weight), these glass are difficult to fusing usually, but very favourable, especially all the more so according to raw materials cost, because their density is very low, and the consistency of they and plastics is very good.Can also produce the quite special glass with high alkaline earth metal oxide content, for example contain at least 18% (weight) CaO, yet this class glass is at the temperature higher than the present invention, adopt common melting method that very strong corrodibility is arranged, also sodium oxide content can be produced low, the glass of 11% (weight) sodium oxide at the most for example, or have very protosulfate content, for example glass of 100ppm at the most.Contain iron, high oxidation reductibility but the glass of protosulfate content also allows to produce the glass with residual blueness, this glass is for example attractive especially in automobile and building slab glass art, and is also deeply popular to people.Therefore can obtain the very strong sun-shielding glass of selectivity, on glassly be coated with sun-proof layer at it, in order to strengthen its thermal characteristics, the sun-proof layer of TiN type for example, the sun-proof layer of describing in patent EP-638 527 and EP-511 901 particularly.

A further object of the invention is fusing and clarifying plant, especially is fit to implement the device of aforesaid method, and this device comprises:

At least one melting chamber, its chamber is configured to one or more fossil oils of gas (natural) and the nozzle of air or oxygen class ignition dope feed, described nozzle arrangement becomes but these gases or the gas that comes from burning is joined below the liquid level of the vitrification substance material of introducing melting chamber

At least one clarification cabin in the melting chamber downstream, this cabin comprises that at least one can be placed in the zone under subatmospheric.

Advantageously, as previously mentioned, add the parts of vitrification substance, particularly at least two parts but melting chamber can configure at least one under the molten-glass pool liquid level, and preferably with wall that scroll bar class feeding device is connected on be poroid.Therefore reduce the danger that powder flies upward, but the vitrification substance as silicon-dioxide and so on can also have been introduced on molten-glass pool simultaneously, has adopted this molten bath can carry out warm-up operation and the danger that do not have to lump.

Except clarification operation, the invention still further relates to the improvement of the wall of relevant melting chamber for contacting with molten-glass pool.Kinds of schemes is all possible.In some cases, can just use with the known high temperature material of oxide compound as main component, as aluminum oxide, zirconium dioxide, chromated oxide, as described in AZS high temperature material (take aluminum oxide, zirconium dioxide and silicon-dioxide as main component).Usually, more preferably these high temperature materials and the cooling system that adopts the recirculated water class I liquid I are combined (" water jacket " or adopt the water tank cooling in France).Can design water tank is installed in the outside, at this moment high temperature material directly contacts with glass, or at the installed inside water tank.Water tank function at this moment is to produce colder glass flows near the high temperature material place, and this is ben in this article, because the glass melt that adopts the immersion nozzle to produce causes strong flow liquid is flowed to wall.

Another kind of scheme is not use high temperature material in molten-glass pool, but only uses water tank above-mentioned.

Another kind of scheme is to use high temperature material, (can coordinate with water tank class cooling system), allows these high temperature material linings with the refractory metal filler, as molybdenum (or Mo alloy).This filler and high temperature material wall can maintain a certain distance (for example 1 millimeter to several millimeters), provide Continuous Contact surface (one or more Mo is dull and stereotyped) or discontinuous surface in contact at molten-glass pool, (one or more boring Mo plate).The purpose of this filler is because producing one deck " static state " glass coating along high temperature material, even contacting with any of these fillers because having eliminated glass, so mechanically avoided the direct convection current of glass towards high temperature material.

At melting chamber, preferably design all or part of immersion nozzle, so that they can not participate in burning with a kind of, replace the fluid of (temporarily) ignition dope and/or fuel to add in molten-glass pool.This liquid can be N ₂Class rare gas element or the liquid water class cooling fluid that evaporates at once in molten-glass pool.Therefore interim cease combustion, and continuation toward the fact of nozzle filling liquid, usually has two purposes simultaneously: perhaps wish to stop the nozzle operation, more generally for example stop at the melting chamber operation in its system, injection N ₂The class rare gas element can make this chamber very safe at the nozzle place, perhaps wish to change nozzle, and other nozzle is in operation, and therefore always under the molten glass liquation exists.In this case, as will be described in detail below, by nozzle suitably injection water the glass on nozzle is solidified, produce simultaneously a kind of " bell ", leaving like this for some time is enough to carry out this replacing and can polish nozzle.

As mentioned above, can be between the melting chamber of apparatus of the present invention and clarification cabin, just in time be equipped with at least one injection stream dispenser device in clarification cabin import or in its upstream portion particularly.May be out the element in appropriate size hole.

In addition, it is worthy of note, it is also conceivable that a kind of like this injection stream dispenser device except the fusing mode that adopts: a kind of like this injection stream dispenser device allows to clarify quickly with high glass flow rate, no matter how reach the mode of glass melting, for example adopt the electrofusion of common equipment and/or the employing immersion electrode of air nozzle type (not submergence).

Similarly, even under atmospheric pressure clarify, it may be also favourable using this equipment.

Yet, particularly advantageous in the situation that adopt the fusing of immersion nozzle to use this equipment, described fusing has the very trend of the foam of height ratio bubble that produces, and/or in the situation that this equipment of decompression clarification use is also particularly advantageous, because greatly increased already extra high clarifying efficiency.

According to the first scheme above-mentioned, the clarification cabin is static and is in vertical configuration (being that its size on ground of aspect ratio is much bigger).According to first embodiment, this clarification cabin comprises a basic vertical internal partition, and this dividing plate coordinates with the inwall in its cabin has determined at least two passages.But one after the other relate to the mobile pipeline of vitrification substance rising that article one makes the fusing shape, but then second makes the pipeline that described vitrification substance descends and moves, article one pipeline preferably is under subatmospheric.So produce a kind of syphonic effect for the treatment of fining glass.But the equipment of the vitrification substance pressure-losses of fusing shape is advantageously adjusted/is regulated in this cabin in the configuration of clarification cabin ingress.Similarly, according to different standards, especially according in the selected step-down level of reduced pressure zone, consider to regulate the height in clarification cabin.

According to the second embodiment, the static state of using is within the scope of the present invention clarified the cabin and is in vertical configuration, but and be included in the equipment that part adds the vitrification substance of fusing shape to be clarified, but with the device for transferring of the vitrification substance of having clarified in lower part, but described vitrification substance roughly moves in described cabin vertically downward.Its principle for example can be known with EP-297 405 specification sheetss by patent EP-231518, EP-253188, EP-257 238.

According to first scheme, clarify the cabin and comprise at least one the equipment that can rotate, to guarantee adopting centrifuging to clarify, the inwall of described equipment part at least therebetween consists of vertical hollow cylindrical basically.Advantageously, this equipment comprises that the zone of described top subatmospheric and described bottom still are in atmospheric zone, and separate by the mechanical part of one or more boring metal sheet classes each other in these zones.

According to preferred design, but this device is supplied with fusing shape vitrification substance by the static supply part of flow duct type at an upper portion thereof.These supply parts can comprise that at least one is placed in the cabin under decompression, in order to can give this equipment feed and/or clarify for the first time operation.

Should be equipped with and guarantee the sealing member that is connected between this root feeding pipeline end and this device, i.e. the sealing member of the sealing member of " active joint " type or the type that is rotatably connected, this will will be described in detail below.This installs advantageously that packing density higher than the equipment of catching solia particle of glass, namely is positioned at this device lower region particularly, and is the equipment of groove/ditch shape in their inwall.Preferably, this device speed of rotation is selected in 100-1500 rev/min.

This device can also configure solid mechanical equipment or follow the equipment of its rotation, and these equipment can be sheared foam, and foam is taken to discharge the device lower region of fining glass from high to low.

This equipment is specifically that the perforate water conservancy diversion is tabular, wing, and they are arranged on the upper area of described device.

This employing is effective especially by the centrifugal clarification method of reduced pressure zone.In fact, this decompression is adopting centrifuging can guarantee the growth of bubble maximum possible before clarifying fully: these bubbles are removed in than the large device of their diameter fasterly.This decompression can also reduce the content of the residual sulphur hydrochlorate in glass of producing more.It is worthy of note, the glass of desulfating (this formulation also is suitable for adopting the first string of the static clarification) problem that occurs volatile compound in the float glass process molten bath reduces, the danger that generates tin sulfide reduces, therefore last on sheet glass tin defects danger also still less.This also guarantees in the situation that reductibility glass does not have sulfide, iron sulphide particularly, this sulfide can provide not too the residual yellow of wishing/amber, or the nickelous sulfide wrap, and these wraps just may cause glass breakage when quenching type thermal treatment.

In the situation that the glass clarifying of suitable foam is arranged, mention especially the centrifugal clarification that comprises the decompression section.

Description of drawings

Two kinds of embodiments by following description of drawings will illustrate in greater detail the present invention:

◇ Fig. 1: the fusing of the static clarifying plant of use/clarification devices illustrated,

◇ Fig. 2: the fusing of use centrifugal clarification device/clarification devices illustrated,

◇ Fig. 3: the clarifying equipment enlarged view of accompanying drawing 2 shown type devices,

◇ Fig. 4: the divider enlarged view that uses in accompanying drawing 2 devices,

◇ Fig. 5: the immersion nozzle throat area view that is disposed at melting chamber in accompanying drawing 1 and 2 devices.

These accompanying drawings are not essential proportional, and for the purpose of clearer, these accompanying drawings are extremely simplified.

Embodiment

The device that the following describes is suitable for melting and the glass of clarifying various different compositions, and the glass here is used for supplying with the float glass equipment of producing sheet glass.But this application is not restrictive.

Any silicon-the normal glass of Sodium/Calcium type and dissimilar special glass, it is particularly advantageous adopting device production of the present invention, especially those also think the glass that is difficult to melt so far:

Has low Na ₂The glass of O content and relative high alkaline earth metal oxide (specifically CaO) content is favourable according to raw materials cost from economic aspect, and corrosion-resistant very strong to common temperature of fusion, and adopts the usual method fusing also harder.This for example may relate to the glass of describing and form in the FR97/08261 of application on July 1st, 1997, as (in % (weight)):

SiO ₂ 72-74.3％

Al ₂O ₃ 0-1.6％

Na ₂O 11.1-13.3％

K ₂O 0-1.5％

CaO 7.5-10％

MgO 3.5-4.5％

Fe ₂O ₃ 0.1-1％

Or the composition of following type (in weight percent):

SiO ₂66-72%, preferably 68-70%

Al ₂O ₃ 0-2％

Fe ₂O ₃ 0-1％

CaO 15-22％

MgO 0-6%, preferably 3-6%

Na ₂O 4-9%, preferably 5-6%

K ₂O 0-2%, preferably 0-1%

SO ₃Trace

The other example that this group composition is described is as follows:

SiO ₂ 69％

Al ₂O ₃ 1％

Fe ₂O ₃ 0.1％

CaO 18.9％

MgO 5％

Na ₂O 5.6％

K ₂O 0.3％

SO ₃Trace

This glass has 590 ℃ of low annealing temperatures, and its temperature also is referred to as " strain point ", and (viscosity of glass at this temperature is 10 ^14.5Pool).Its liquefaction temperature is that to be 1431 ℃ be 1140 ℃ [T (log2) and T (log3.5) reach to moor the log2 of expression or the temperature of log3.5 viscosity separately corresponding to this glass] with temperature T (log3.5) for 1225 ℃, temperature T (log2).

Glass with high silicon dioxide content is also favourable from economic aspect, has relatively low density, and its compositing range always represents with weight percentage, and these glass are:

SiO ₂ 72-78％

CaO+MgO+BaO 0.3-14％

Na ₂O 11-17％

Basic oxide 11-18.5%

Al ₂O ₃ 0.2-2％

B ₂O ₃ 0-2％

Fe ₂O ₃ 0-3％

SO ₃Can trace

Coke 0-600ppm

With the colored oxides such as Ni, Cr, Co may be arranged

(characteristics of these glass are special thickness).

The example that this class composition is described is as follows:

SiO ₂ 76.4％

Fe ₂O ₃ 0.1％

Al ₂O ₃ 0.1％

CaO 7.6％

MgO 5％

Na ₂O 10％

K ₂O 0.3％

The density of this glass is 2.46 (comparing with the density 2.52 of " Planilux " class standard Si-Na-Ca glass of being sold by Saint-Gobain Vitrage) approximately.

Can also be seen by top, adopt method of the present invention can access reductibility glass, the content of high oxidation reductibility, iron and low-down sulphate content might obtain the glass of residual blueness.

Adopt method of the present invention, can also produce and do not contain or contain hardly Na ₂The glass of O class alkalimetal oxide particularly can also be produced fire-proof glass window or the glass of the body material that uses from application point electronic industry.Some compositions were reported in patent EP-526 272 and EP-576 362 like this.

The glass of other that adopt method of the present invention to produce to describe in EP-688 741 and WO96/00194, the glass of especially low MgO content.

Therefore, drawn the first embodiment in accompanying drawing 1: pipeline 1 can add in melting chamber 2 by top 3 the vitrifiable material of a part simultaneously and discharge the flue gas of burning.But with these vitrification substances of these smoke pre-heatings, therefore reclaimed their heat energy.The raw material that can so be added to molten bath 7 mainly comprises and is suitable for preheating and non-caking silicon-dioxide.Remaining raw material is positioned at point 1 below the liquid level of molten-glass pool 7 ' add at least one, adopts particularly the scroll bar charging opening to add.Here only represent a point, be configured in or rather the higher position of molten-glass pool total height B, this height about 2/3 height location place on this chamber antetheca.

In fact, can be upper on its equal height or on different height at wall (antetheca or sidewall), particularly or at an upper portion thereof, perhaps lower than half of this height B, for example in a plurality of adding a little of 1/3 to 2/3 place design of this height.In fact, this ratio (emitting pressed powder) that directly adds raw material greatly to reduce to fly up below molten-glass pool toward molten-glass pool.In addition, according to this structure, can deliver to material convection current mix the strongest and/or will consider this this point this adding, so that these materials stopped the shortest at least for some time in chamber 2 before leading to the clarifying area.

The ends 4 many rows of the configuration nozzle 5 of chamber, these nozzles pass and pass into melting chamber than low height.These nozzles 5 are preferably installed the cooling apparatus of the water tank type of not expressing.These nozzles 5 burn in zone 6 when work, but in the vitrification substance in liquefaction, produce the convection current logistics at its end.This convection current mixes can produce the foam that transfers heat energy to whole molten bath 7.The normal glass of Si-Na-Ca glass class for example, fusing are preferably approximately carrying out under 1350 ℃.

The wall of the chamber 2 that contacts with molten bath 7 is here high temperature material, and its outside adopts the cooling system (not shown) of water tank type cooling.A kind of scheme is this cooling system being attached on high temperature material on metallic walls, but in the inboard, therefore contacts with molten glass.These two schemes all delay the wearing and tearing of high temperature material near the glass of high temperature material wall with surface cool.

Nozzle 5 operations are suitable for summarizing the immersion fusing of the mode that represents in accompanying drawing 5.Accompanying drawing 5a represents nozzle 5 vertical sections, and accompanying drawing 5b represents along the cross section of AA ' face in accompanying drawing 5a.The cooling system 50 of nozzle and water tank type and central duct 51 configure many pipelines 52 around pipe core 51 also together with one heart, and all these cylindrical cross-section pipelines all lead to nozzle-end 53.

When normal operation (operation [a]), pipeline 51 is provided with the fuel (or other geseous fuel or oil fuel) of Sweet natural gas class, and pipeline 52 is provided with ignition dope, is for example oxygen here.CH in molten-glass pool ₄/ O ₂Interact and burn.

When safe operation (operation [b]), when namely not having scouring dangerous fully when wishing to stop jet combustion, add nitrogen by pipeline 51 and/or pipeline 52.

When making the operation of a nozzle and another one nozzle exchange (operation [c]), by pipeline 51 injected waters, even in jet exit or constantly evaporation nozzle from jet exit, this steam produces a cooled glass convex outlet to its water on nozzle; At this moment stop any nozzle operation, and had time enough to change before " convex outlet " do not collapse.The water that injects is recovered in nozzle (in this operation scheme, can also put upside down the effect of pipeline 51 and 52) at least in part by pipeline 52.Can also be fit to so solidify with any other cooling liqs replacement water of glass.

Except whole fusings of relating in glass device and clarification operation, above-described nozzle is theme of the present invention from different operation scheme.

From the frothy melten glass that adopts the fusing of immersion nozzle, then to discharge from the bottom by pipeline 8, it disposes the loss of pressure head setting device of the awl type of not drawing.Controlled the frothy glass loss of material that enters static clarification cabin 9.This cabin has comprised sidewall 10, has been in the base plate 11 of same level bottom melting chamber, and limits the upper wall 12 of substantially parallel internal volume.Also designed a kind of being fixed on base plate 11 but still the baffle plate that can pass through on top.Passage 14 that glass is moved up has also been determined in this combination, and then passage 15 moves down glass.Formed glass planar H at highest point 16.

Then fining glass supplies with cabin 18 through pipeline 17, more this glass is delivered to the shaped device of the float glass class of not drawing.

In the clarification cabin, allow passage 14 zones be placed under decompression, for example 0.3 normal atmosphere.At this moment frothy glass from passage 8 rise in this passage, may little by little melt by unfused residue, and the size of these bubbles rises in this passage with them and increases.But the foam turgidity is still very appropriate, because very low from residual sulphur phosphate content in the foam of melting chamber 3.In zone 16, bubble breaks at surperficial H, and foam disappears fast, and all at this moment fining glass descends along passage 15 again.If necessary, can design in this zone 16 the attached heater block of common bleed types or resistance type, and these parts are arranged on wall 12, and mechanical part (not drawing) also can be arranged, these parts are Flapper type, so that bubble easily breaks.

In order to provide the order of magnitude, be 0.3 normal atmosphere for the decompression of selecting, can design the height h that clarifies the cabin is several meters orders of magnitude, for example 3 meters.

Accompanying drawing 2 and 3 has represented the second embodiment.Melting chamber 2 identical with accompanying drawing 1 expression on design overall.Unique difference is the protected mode of chamber 2 high temperature material walls.Here, the refractory metal lining that submergence is made of thin molybdenum wall 40 in molten-glass pool 7, the shape of its lining applying melting chamber, and keep at a distance of several millimeters by suitable positioning element and high temperature material wall, and/or by being arranged in the high temperature material wall on molten-glass pool or hanging over molten-glass pool by top-hung.

This plate 40 is drilled with the hole, at first be drilled with the hole in being the zone of level with base plate 4, so that nozzle 5 can pass through, also be drilled with the hole in every other wall, these holes evenly distribute: therefore this boring can not stop high temperature material/molten glass contact, but the convection current of mechanically ending the glass of close high temperature material is moved, and therefore reduces their wearing and tearing.Except the hole of bottom doubled, the hole 41 of lining 40 walls was all preferably cylindrical, and size is different, should be porose at least on the wall on base plate 42, and its size is enough to allow nozzle 5 to pass through.Also should beat macropore (43) on the lining at transverse wall place, the downstream of lining 40, in order that glass can be discharged from pipeline 20a.For the zone 1 that adds raw material ' same so: between the perforate of high temperature material wall and molybdenum-liner, complementarity need be arranged.

This Mo lining itself is a kind of particularly suitable invention when coordinating with employing immersion nozzle melting chamber, and is irrelevant with the mode of the clarification that may carry out later on.(to illustrate in earlier drawings in the outside or the high temperature material of glass side cooling same so).

Another one and accompanying drawing 1 difference are the mode that glass is discharged from melting chamber.In the situation that accompanying drawing 2, glass is discharged by guiding pipeline 20 in slightly higher place, and its pipeline is divided into first horizontal component 20 (a), and second vertical component 20 (b) and the 3rd horizontal component 20 (c) lead in centrifuge apparatus 21.For glass being raise in this pipeline and therefore supplying with whizzer, conduit region 20 (b) is under the appropriateness decompression, for example be under 0.5 normal atmosphere.Another kind of scheme is that as known in glass art, for example by the immersion passage, molten glass is from melting chamber top discharge.

Accompanying drawing 3 shows that mainly from the horizontal zone 20 (c) of the guiding tube 20 of the foam molten glass of melting chamber 2 discharges, this pipe is supplied with glass to whizzer 21.Whizzer has the upper-part 22 between parts 23 and metal sheet 24, with the lower component 30 that is positioned at below metal sheet.Parts 23 are empty, and this is a porose right cylinder, can regulate flow, loss of pressure head that glass enters whizzer 21.Glass also enters upper-part 22, is for example partial vacuum or the normal atmosphere of 0.1 bar here.This has proposed to be at pipeline 20 stationary parts and whizzer 21 problem of joint 25 between the part of rotation.

First solution is to adopt active joint.Frothy glass trend " risings " zone 26 of discharging from hollow object 23 under centrifugal action, and discharging voluntarily by the freeboard that leaves in joint: so glass itself just, because injecting continuously, glass guaranteed stopping property.Can consider to adjust the space between whole moving member 21 and whole mounting block 20, to limit, to regulate the glass flow rate that is injected.

Another kind of solution is that the described swivel joint with suitable composition is installed in joint 25.May relate to the swivel joint with liquid ring particularly, the liquid that uses is the very liquid of low-steam pressure that has of silicone oil, therefore its principle of work is identical with the vacuum pump with liquid ring: by rotation, liquid ring is carried out centrifugal, and be in the pressure opposite with negative pressure in whizzer.

Then, glass enters zone 23 through the orifice flow of plate 24, and gas exhaust duct 27 is installed in its zone.Advantageously, this piece plate can be molybdenum plate, and the part that is immersed at least in glass is molybdenum plate entirely.Outer lining in centrifugal body inwall can consist of by containing high temperature resistant 32 of the electric smelting that adds heat insulator, so that its isolator is not crushed by centrifugal force.Also have groove, groove 28 consists of a circle at part 30 inwalls (or interruption), and it can catch density greater than glass, any solia particle high temperature material wrap type.This is because glass flows from lower toward eminence in whizzer in the following manner: plate 24 is divided into two portions with whizzer, allow glass to carry out centrifugal with thin layer, therefore compare with the height that there is no centrifugal device with there is no application of reduced pressure, the height of this device has reduced.Glass reasonably one of them condition from lower toward eminence circulation is, corresponding to the glass pressure of distance between two para-curve summits higher than the pressure reduction of the decompression of loss of pressure head and part 22 and the normal pressure of part 23 with, this is accessible.Therefore the glass that flows through plate 24 be close to the inwall of part 30 with lamelliform, at this moment density project on wall greater than the solia particle of glass, is captured in groove 28, and they can not be more out.On the other hand, bubble is grown up, and due to the centripetal force effect, bubble is to centrifugal body implosion.At last, the fining glass in the lowermost portion of part 30 is approximate funnel shaped pipeline 29 decants by its top and goes out.Under the operation standard condition, do not need to provide the glass preliminary heating device, speed of rotation can be that approximately per minute 700 turns, the height h of whizzer is for example 1-3 rice.

Accompanying drawing 4 has represented with reference to the accompanying drawings 2 and 3 possible clarification schemes very simply, this scheme mainly illustrates under barometric point guiding tube 20c and the connecting zone 40 between centrifugal body 21 under reduced pressure: from then on accompanying drawing can be seen piston 41, and it is suitable for regulating loss of pressure head and treats that fining glass enters the flow of whizzer 21.In the pipeline 20c taphole 42 of whizzer, a regular boring of insertion, the molybdenum dividing plate 43 of cylindrical hole preferably, its effect is the reinforced spinning nozzle of whizzer, import glassine stream is divided into many filaments of glass that very roughly represent with label 44 on its accompanying drawing, for example approximately 1 millimeter to several millimeters of its diameter.Therefore the effect of this dividing plate 43 is glassine fluidic distributors, the bubble ratio that contains in each filament 44 in the cross section the much wide bubble that contains in glass jet remove faster.By administering reduced pressure, these filaments 44 being merged to make these bubbles in glass break as quick as thought.The filament 44 of removing bubble is droplet-like in whizzer 21 bottoms, and due to the effect of centrifugal force, they are flocked on its inwall.

The situation of using a kind of like this Jet flow distribution device to clarify in static settler as shown in Figure 1 also has a benefit.

Under any circumstance (static state or centrifugal clarification), people can see, in fact spendable fusing/clarifying equipment size can reduce greatly.It is also worth noting that, partial vacuum advantageously, in the situation that static putting-down machine and in the situation that centrifugal clarifier is a kind of nitrogen vacuum, this is conducive to bubble and breaks and can not damage metalwork as centrifugal clarifier parts 24 and so on.But it is also favourable adding the clarification aid with top description effect toward vitrification substance, specifically the coke of small grain size, vitriol, nitrate, fluorine or chlorine.

It is also worth noting that, the spendable molybdenum of melting chamber and/or clarification cabin can be made of platinum.

Importantly emphasizing, is extremely favourable even will adopt the fusing of immersion nozzle to combine with the clarification of using decompression, but these two aspects that the present invention also can consider respectively.Therefore may advantageously use and adopt the fusing of immersion nozzle and standard clarification steps, vice versa, adopts the decompression clarification steps, then adopts common heating installation fusing, this is still within the scope of the invention, even at this moment no longer reach the synergy of emphasizing previously.

It is also worth noting that, adopt the mode of immersion nozzle fusing, and the clarification that does not re-use common explicans can be also favourable.May be exactly this situation aspect fibrosis, at this moment people may wish that the frothy glass that directly will adopt the fusing of immersion nozzle to obtain is centrifuged into fibre machine, the centrifugal glass clarifying that in fact reaches that adopts this technology to carry out in supplying with.Also may wish directly to process the frothy glass from fusing, in order to produce the multicellular glass that uses as lagging material in building field for example.

This fusing mode can also be applied to glass/metal as above or the recirculation of glass/plastic composite prod uses, perhaps produce spendable glass, perhaps produce as the sheet glass of glass furnace raw material usually (but particularly according to these composite prods and all the other ratio of vitrification substance more generally).

Claims

1. but device that is used for the vitrification substance of clarification fusing under subatmospheric and centrifugal force, this device comprises the equipment for guaranteeing to adopt centrifugal clarification to be rotated, wherein said equipment comprises upper area and lower region, glass described in described upper area subatmospheric and centrifugal under clarify, and glass described in described lower region normal pressure and centrifugal under clarify, wherein said equipment is that but the static feeder apparatus with partial vacuum is supplied with the vitrification substance of fusing to it from top, between the equipment of described static feeder apparatus and described active joint or swivel joint type, sealing element is arranged.

2. device according to claim 1, the inwall of wherein said the equipment heart therein partly consist of the perpendicular cylinder form of hollow.

3. device according to claim 1 and 2, wherein said upper area and lower region are separated from each other with the one or more mechanical means with the metal sheet class that is drilled with one or more holes.

4. device according to claim 1 and 2, the one or more solia particle catching apparatus of wherein said equipment configuration.

5. device according to claim 4, wherein said solia particle catching apparatus is positioned at the lower region of this equipment, and is ditch or groove shape in inwall.

6. device according to claim 1 and 2, the speed of rotation of wherein said equipment is 100-1500 rev/min.

7. device according to claim 1 and 2, wherein said equipment are equipped with fixing or with the mechanical means of its rotation, but these equipment can be sheared vitrification substance.

But 8. the method for the vitrification substance that in the described device of any one, clarification is melted in claim 1-7, wherein

But the vitrification substance of the fusing of clarifying is supplied with the static feeder apparatus of partial vacuum from the top of described equipment, and then

In the equipment that can be rotated of described device, but the vitrification substance of fusing clarify under subatmospheric and centrifugal force, described equipment is in rotation.

9. method according to claim 8, but wherein said vitrification substance contains clarification aid.

10. method according to claim 9, wherein said clarification aid is reductibility additive, vitriol, the additive take fluorine or chlorine as main component or the NaNO that is selected from coke ₃

11. method according to claim 8, wherein said subatmospheric is less than or equal to 0.5 normal atmosphere.

12. method according to claim 11, wherein said subatmospheric are 0.3-0.01 normal atmosphere.

13. the described method of any one according to claim 8-12, wherein said clarification is being carried out under 1400 ℃ at the most.

14. method according to claim 13, wherein said clarification is being carried out under 1350 ℃ at the most.

15. the described method of any one according to claim 8-12, but wherein vitrification substance show bubble and fusing that be glass is clarified.

16. method according to claim 15, but the density of the vitrification substance of the fusing of wherein said spumescence category of glass is the 0.5-2 gram per centimeter ³