CN102858697B - Glass furnace and glass melting process - Google Patents
Glass furnace and glass melting process Download PDFInfo
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- CN102858697B CN102858697B CN201180021090.7A CN201180021090A CN102858697B CN 102858697 B CN102858697 B CN 102858697B CN 201180021090 A CN201180021090 A CN 201180021090A CN 102858697 B CN102858697 B CN 102858697B
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- burner
- melting chamber
- glass
- venting port
- air
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- 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
- C03B5/2353—Heating the glass by combustion with pure oxygen or oxygen-enriched air, e.g. using oxy-fuel burners or oxygen lances
-
- 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
- C03B5/04—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in tank furnaces
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Glass Melting And Manufacturing (AREA)
Abstract
The invention provides and can suppress CO
2and NO
xoutput increase and fully can regulate the glass furnace of the amount of moisture dissolved in melten glass.A kind of glass furnace, multiple burner 31 ~ 50 is possessed at the sidewall 13,14 of the stream 23 of antetheca 11 to the rear wall 12 from melting chamber 10, wherein, the horal gross heat of combustion amount Qa of multiple burner 31 ~ 50 more than 30% and less than 90% to be produced by oxygen-fired burners.Each configuration one on each sidewall of venting port 24,25 in an opposing fashion in the two side 13,14 of melting chamber 10, with the direction of venting port 24,25 backwards in the region of more than 0.6L, at least one oxygen-fired burners and at least one air-breathing burner are set.Be arranged on more than 5% in the horal gross heat of combustion amount of burner in this region and less than 95% produced by air-breathing burner.
Description
Technical field
The present invention relates to glass furnace and glass melting process that frit is melted.
Background technology
Manufacture the method for glasswork to be generally made up of following operation: frit is melted and obtains the melting process of melten glass, the bubble of removing melten glass and clarification operation that melten glass clarify and the melten glass after clarifying is configured as the forming process of predetermined shape.
In above-mentioned operation, melting process the composition according to glasswork is weighed plurality of raw materials the frit mixed to put in smelting furnace and the operation being heated to the temperature corresponding to the kind of glass and making it melt.
Smelting furnace possesses material pouring inlet on the antetheca of the melting chamber making frit melt, the rear wall of melting chamber possesses conveying end, possessing multiple burner from material pouring inlet to the sidewall of the stream of conveying end, multiple burner jets out flames and heats the glass in melting chamber and make it melt in melting chamber.Burner sprays the flame making the fuel such as Sweet natural gas, heavy oil and gas and vapor permeation burn and be formed.
Generally speaking, as the gas be blended in fuel, can use in air and oxygenous gas any one.When using the air combustion of air, the nitrogen of duty gas about 78 volume % is discharged to outside stove not having burning in contributive situation.When using the oxygen combustion of oxygenous gas, compared with the situation of air combustion, free air delivery is less, therefore, and the high and CO of thermo-efficiency
2output and NO
xoutput is few.
As the gas be blended in fuel, the mixed gas (such as referenced patent document 1) of air and oxygenous gas and vapor permeation also can be used.In this case, the ratio of oxygenous gas shared by mixed gas is higher, then the moisture concentration contained in the gas after burning is higher, and therefore, the amount of moisture dissolved in the melten glass in melting chamber increases.The moisture be dissolved in melten glass forms bubble and floats in clarification operation.Therefore, by optimizing in melten glass the amount of moisture dissolved, can in clarification operation, promote the growth of bubble in melten glass and promote floating of bubble, thus can the few glasswork of manufacturing defect.
But, when using the mixed gas of air and oxygenous gas and vapor permeation as the gas be blended in fuel, compared with the situation of air combustion, NO
xoutput also increases sometimes (such as with reference to non-patent literature 1).Specifically, the oxygen concentration in mixed gas is lower than 93 volume % and more than 25 volume %, compared with the situation of air combustion, NO
xoutput increases.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2000-128549 publication
Non-patent literature
Non-patent literature 1:R & D Kobe Steel skill report, Vol.51, No.2 (2001.9), p.8 ~ 12, " sour plain enrichment empty mood To I Ru is economized the low NOx of エ ネ Le ギ と and is fired the research of Ware に Seki The Ru (about utilizing the energy-conservation of oxygen-rich air and low NO
xthe research of burning) "
Summary of the invention
Invent problem to be solved
Therefore, in the present invention, to suppress CO
2and NO
xthe amount of moisture that dissolves in the melten glass in melting chamber of the increase and regulating of output for the purpose of, the technical scheme arranging air-breathing burner and these two kinds of burners of oxygen-fired burners in smelting furnace is studied.
But, when only arranging air-breathing burner and this two kinds of burners of oxygen-fired burners in smelting furnace, sometimes due to moisture concentration that the impact and being difficult to being arranged on the venting port on the sidewall of melting chamber contains in the gas after fully regulating the burning in melting chamber.As a result, be sometimes difficult to fully regulate the amount of moisture dissolved in the melten glass in melting chamber.
The present invention completes in view of the above problems, its object is to provide to suppress CO
2and NO
xoutput increase and fully can regulate the glass furnace of the amount of moisture dissolved in melten glass.
For the means of dealing with problems
In order to solve above-mentioned purpose, the invention provides a kind of glass furnace, possess melting chamber that frit is melted and be arranged on from the antetheca of this melting chamber to the multiple burners the sidewall of the stream of rear wall, described multiple burner jets out flames and heats the glass in described melting chamber and make it melt in described melting chamber, in described glass furnace
Described multiple burner uses the oxygen-fired burners spraying the flame making fuel and oxygenous gas and vapor permeation burn and be formed and these the two kinds of burners of air-breathing burner spraying the flame making fuel and air mixed burn and be formed,
Described multiple burner horal gross heat of combustion amount more than 30% and less than 90% to be produced by described oxygen-fired burners,
Each configuration one on each sidewall in an opposing fashion in the two side of described melting chamber of venting port that the gas after the burning in described melting chamber is discharged to the outside, or a sidewall only in the two side of described melting chamber configures one, or be configured in antetheca or the rear wall of described melting chamber
When ultimate range in distance on fore-and-aft direction described in Distance geometry on fore-and-aft direction between described venting port and described antetheca between venting port and described rear wall is set to L, with the direction of described venting port forward and/or direction backwards at a distance of more than 0.6L region in arrange oxygen-fired burners described at least one and at least one described in air-breathing burner
Be arranged on more than 5% in the described burner horal gross heat of combustion amount in this region and less than 95% produced by described air-breathing burner.
Invention effect
According to the present invention, can provide and can suppress NO
xthe increase of output and fully can regulate the glass furnace of the amount of moisture dissolved in melten glass.This glass furnace is effective especially when heating fully melten glass, when making amount of moisture reduce simultaneously.
Accompanying drawing explanation
Fig. 1 is the process picture sheet of the manufacture method of glasswork in embodiments of the present invention.
Fig. 2 is the side-view of the internal structure of glass furnace in the first embodiment.
Fig. 3 is the vertical view of the internal structure of glass furnace in the first embodiment.
Fig. 4 is the side-view of the internal structure of glass furnace in the second embodiment.
Fig. 5 is the vertical view of the internal structure of glass furnace in the second embodiment.
Fig. 6 is the side-view of the internal structure of glass furnace in the 3rd embodiment.
Fig. 7 is the vertical view of the internal structure of glass furnace in the 3rd embodiment.
Fig. 8 is the vertical view of the variation of the internal structure of glass furnace.
Fig. 9 is the vertical view of another variation of the internal structure of glass furnace.
Embodiment
Below, be described for implementing mode of the present invention with reference to accompanying drawing.It should be noted that, in the various figures identical label marked to identical formation and omit the description.
(the first embodiment)
Fig. 1 is the process picture sheet of the manufacture method of glasswork in embodiments of the present invention.Fig. 2 is the side-view of the internal structure of glass furnace in the first embodiment.Fig. 3 is the vertical view of the internal structure of glass furnace in the first embodiment.In Fig. 3, the combustion zone (outer rim of the flame of each burner) of each burner is represented by dotted line.
As shown in Figure 1, the manufacture method of glasswork has: frit is melted and obtains the melting process (S100) of melten glass, the bubble of removing melten glass and clarification operation (S102) that melten glass clarify and the melten glass after clarifying is configured as the forming process (S104) of predetermined shape.
In above-mentioned operation, clarification operation (S102) is supplied in clarifying tank by the melten glass obtained in melting process, the bubble in melten glass is floated and the operation that removes.As the method for floating promoting bubble, such as, have: make decompression in clarifying tank carry out the method etc. of deaeration.
Forming process (S104) be by clarification after melten glass be configured as the operation of the tabular of predetermined thickness of slab.As the method being configured as tabular, such as, there are known float glass process, scorification.
Melting process (S100) composition according to glasswork is weighed plurality of raw materials the frit mixed to put in smelting furnace and the operation being heated to the temperature corresponding to the kind of glass and making it melt.
As shown in Figure 2 and Figure 3, smelting furnace 1 possesses material pouring inlet 21 on the antetheca 11 of the upstream side of the melting chamber 10 making frit melt, the rear wall 12 in the downstream side of melting chamber 10 possesses conveying end 22, possesses multiple burner 31 ~ 50 and a pair venting port 24,25 in the two side 13,14 of the stream 23 from material pouring inlet 21 to conveying end 22.Two side 13,14 extends along the longitudinal direction.
In this smelting furnace 1, the heating such as the radiant heat that the melten glass G2 in the frit G1 dropped into from material pouring inlet 21 and melting chamber 10 is together produced by the flame sprayed by multiple burner 31 ~ 50, thus be slowly melted in melten glass G2.The melten glass G2 obtained like this flows to rear, then, takes out and be supplied to clarifying tank from conveying end 22.
The melting channel 15 of the melten glass that melting chamber 10 makes frit melt by collecting and obtains is formed with the top board 16 of the upper space covered in melting channel 15.Melting channel 15 and top board 16 are made up of refractory bodies such as bricks.
The size of melting chamber 10 is not particularly limited, and such as, the fore-and-aft direction size X1 of melting chamber 10 is 10 ~ 30m, is preferably 10 ~ 25m.In addition, the width size Y1 of melting chamber 10 is 5 ~ 10m.In addition, the short transverse size Z1 of melting chamber 10 is 3 ~ 8m.
A pair venting port 24,25 is for being discharged to the outside the gas after the burning in melting chamber 10.A pair venting port 24,25 is configured in an end on the fore-and-aft direction of two side 13,14, and is configured near antetheca 11.
The venting port 24 be configured on left side wall 13 clips stream 23 with the venting port 25 be configured on right side wall 14 and relatively configures.If a pair venting port 24,25 is in staggered configuration in the longitudinal direction, then can clips stream about 23 and asymmetricly be exhausted, therefore, be difficult to the temperature distribution controlling melten glass.
The size of venting port 24,25 is not particularly limited, and such as, the fore-and-aft direction size X2 of venting port 24,25 is about 1m, and the short transverse size Z2 of venting port 24,25 is about 1m.
Multiple burner 31 ~ 50 jets out flames in melting chamber 10, heats and make it melt to the glass in melting chamber 10.Multiple burner 31 ~ 50 can jet out flames continuously, also can jet out flames off and on.When jetting out flames off and on, multiple burner 31 ~ 50 can jet out flames simultaneously, also can jet out flames in the different moment.
Multiple burner 31 ~ 50 is configured on two side 13,14 not interfere the mode of flame each other.Such as, the multiple burners 31 ~ 40 be configured on left side wall 13 clip stream 23 with the multiple burners 41 ~ 50 be configured on right side wall 14 and relatively configure.That is, multiple burner 31 ~ 50 clips stream 23 and configures symmetrically.It should be noted that, it is interconnected that multiple burner 31 ~ 50 also can clip stream 23.
The multiple burners 31 ~ 40 be configured on left side wall 13 along stream 23 in the longitudinal direction with arrangement such as the spacing do not waited, also can arrange with equal spacing.For the multiple burners 41 ~ 50 be configured on right side wall 14 too.
Multiple burner 31 ~ 50 sprays the flame making fuel and gas and vapor permeation burn and be formed.As the fuel that burner 31 ~ 50 uses, use the liquid fuels such as the such as geseous fuel such as Sweet natural gas and gas, heavy oil.When using liquid fuel, use after liquid fuel spray is nebulized.Identical fuel can be used in multiple burner 31 ~ 50, also can use different fuel.
Generally speaking, as the gas be blended in fuel, use in air and oxygenous gas any one.When using the air combustion of air, the nitrogen accounting for air about 78 volume % is discharged to outside stove not having burning in contributive situation.When using the oxygen combustion of oxygenous gas, compared with the situation of air combustion, free air delivery is less, therefore, and the high and CO of thermo-efficiency
2output and NO
xoutput is few.
As the gas be blended in fuel, the mixed gas of air and oxygenous gas and vapor permeation also can be used.In this case, the ratio of oxygenous gas shared by mixed gas is higher, then the moisture concentration contained in the gas after burning is higher, and therefore, the amount of moisture dissolved in the melten glass in melting chamber increases.The moisture be dissolved in melten glass forms bubble and floats in clarification operation.Therefore, by optimizing in melten glass the amount of moisture dissolved, can in clarification operation, promote the growth of bubble in melten glass and promote floating of bubble, thus can the few glasswork of manufacturing defect.
But, when using the mixed gas of air and oxygenous gas and vapor permeation as the gas be blended in fuel, compared with the situation of air combustion, NO
xoutput also increases sometimes.Specifically, the oxygen concentration in mixed gas is lower than 93 volume % and more than 25 volume %, compared with the situation of air combustion, NO
xoutput increases.
On the other hand, in present embodiment, burner 31 ~ 50 uses the air-breathing burner spraying the flame making fuel and air mixed burn and be formed and the oxygen-fired burners spraying the flame making fuel and oxygenous gas and vapor permeation burn and be formed.At this, oxygenous gas refers to that oxygen concentration is the gas of 93 more than volume %.Like this, by using air-breathing burner and oxygen-fired burners, NO can be suppressed
xthe increase of output.
In addition, in present embodiment, more than 30% (preferably more than 35%) of the horal gross heat of combustion amount Qa of multiple burner 31 ~ 50 and less than 90% (preferably less than 87%) are produced by oxygen-fired burners.Or, always add more than 60% (preferably more than 68%) of heat Qb for the glass in heat fused room 10 horal and less than 97% (preferably less than 95%) is produced by oxygen-fired burners.
At this, the gas after always adding for the glass in heat fused room 10 horal the burning that heat Qb refers in multiple burner 31 ~ 50 horal gross heat of combustion amount Qa and melting chamber 10 takes the difference (Qa-Qc) of horal total exhaust gas heat Qc of the outside of melting chamber 10 out of via venting port 24,25.This horal total exhaust gas heat Qc calculates based on the temperature etc. of horal free air delivery, Exhaust Gas.
By setting the contribution rate of oxygen-fired burners to gross heat of combustion amount Qa in the above described manner, can suppress by the reduction of the thermo-efficiency using air-breathing burner to cause, CO
2the increase of output, NO
xthe increase of output.In addition, due to the reduction of thermo-efficiency can be suppressed, therefore, the temperature in melting chamber 10 is easily made to remain on comparatively high temps.Therefore, except being suitable for manufacturing except soda-lime glass goods, be also particularly suitable for manufacturing dystectic glasswork.As this dystectic glasswork, such as liquid crystal display glass substrate (so-called alkali-free glass substrate) can be enumerated.The fusing point of non-alkali glass is higher than the fusing point of common soda lime glass more than 100 DEG C.
But, when only arranging air-breathing burner and this two kinds of burners of oxygen-fired burners in smelting furnace, sometimes due to moisture concentration that the impact and being difficult to being arranged on the venting port 24,25 on the sidewall 13,14 of melting chamber 10 contains in the gas after fully regulating the burning in melting chamber 10.As a result, be sometimes difficult to fully regulate the amount of moisture dissolved in the melten glass in melting chamber 10.
When the amount of moisture dissolved in melten glass is very few, in clarification operation, fully cannot promote floating of the bubble in melten glass.On the other hand, when the amount of moisture dissolved in melten glass is too much, in clarification operation, in melten glass, remain bubble sometimes.In addition, generally known, when the amount of moisture dissolved in melten glass is too much, in clarification operation etc., when the inner-wall surface of the stream of melten glass is covered by platinum, bubble can be produced on the interface of melten glass and platinum.
In addition, there is the tendency towards venting port 24,25 movement in the gas after melting chamber 10 combustion.
Therefore, in present embodiment, with the direction of venting port 24,25 backwards in the region of more than 0.6L (preferred more than 0.7L), be provided with at least one air-breathing burner and at least one oxygen-fired burners.At this, L represents the ultimate range (being L2 in the example shown in Fig. 2, Fig. 3) in the distance L2 on the distance L1 on the fore-and-aft direction between venting port 24,25 and antetheca 11 and the fore-and-aft direction between venting port 24,25 and rear wall 12.
Like this, due to the direction of venting port 24,25 backwards in the region of more than 0.6L, at least one air-breathing burner and at least one oxygen-fired burners are set, therefore, it is possible to fully guarantee the region of the gas and vapor permeation after the burning of the G&O after air combustion.Therefore, it is possible to fully guarantee the region that can regulate the moisture concentration contained in the gas after burning, thus the amount of moisture dissolved in the melten glass in melting chamber 10 can be made to change in wider scope.As a result, can fully regulate the amount of moisture dissolved in the melten glass in melting chamber 10, can the growth of bubble in melten glass be promoted and promote floating of bubble in clarification operation, thus can the few glasswork of manufacturing defect.
It should be noted that, self-evident, the amount of moisture dissolved in melten glass in melting chamber 10 suitably can regulate according to the change of the composition of glasswork, kind, also suitably can regulate according to the change etc. of the change of the deterioration of furnace wall, frit batch, fuel batch.
The adjustment of the amount of moisture dissolved in the melten glass in melting chamber 10 is carried out with the horal heat output ratio of oxygen-fired burners by regulating air-breathing burner.The object of this adjustment is mainly arranged on the burner 37 ~ 40,47 ~ 50 with venting port 24,25 on direction backwards in the region of more than 0.6L.Air-breathing burner is higher relative to the heat output ratio of oxygen-fired burners, then the moisture concentration contained in the gas after the burning in melting chamber 10 is lower, and therefore, the amount of moisture dissolved in the melten glass in melting chamber 10 is fewer.
At this, be arranged on the horal heat output Qd of burner 37 ~ 40,47 ~ 50 with a pair venting port 24,25 on direction backwards in the region of more than 0.6L more than 5% and less than 95% (preferably more than 10% and less than 90%, more preferably more than 15% and less than 90%) produced by air-breathing burner.
Lower than 5% time, the moisture concentration contained in the gas after the burning in melting chamber 10 is too high, thus makes the amount of moisture that dissolves in the melten glass in melting chamber 10 too much.On the other hand, during more than 95%, the moisture concentration contained in the gas after the burning in melting chamber 10 is too low, thus makes the amount of moisture that dissolves in the melten glass in melting chamber 10 very few.
Consider that the amount of moisture in the amount of moisture and manufactured glass dissolved in melten glass is equal, thus utilize the value of the β-OH in manufactured glass (unit :/mm) to represent.The value of β-OH is larger, represents that the amount of moisture in glass is more.The value B of β-OH calculates by measuring the thickness of slab C of glass and transmissivity T and this measurement result being substituted into following formula.It should be noted that, the mensuration of the transmissivity of glass uses common Fourier transformation infrared spectrometer (FT-IR).
B=(1/C)log
10(T1/T2)
T1: the transmissivity (unit: %) of the glass under reference wave number 4000/cm, T2: the minimum transmittance (unit: %) of the glass near hydroxyl group absorption wave number 3570/cm
Such as, when non-alkali glass, β-OH is preferably 0.25 ~ 0.52/mm, is more preferably 0.3 ~ 0.5/mm, more preferably 0.35 ~ 0.48/mm.
In addition, preferably at least one oxygen-fired burners (such as burner 39) is set between two air-breathing burners (such as burner 38,40).
When being configured adjacent to each other by two air-breathing burners, as mentioned above when carrying out air combustion, thermal efficiency ratio oxygen combustion is low, and therefore, easily local produces low-temperature region.
It should be noted that, in present embodiment, have employed the formation of each configuration one on each sidewall of venting port 24,25 in an opposing fashion in the two side 13,14 of stream 23, but also can be a formation sidewall only in the two side of stream configuring a venting port.
In addition, in present embodiment, venting port 24,25 is configured in an end on the fore-and-aft direction of sidewall 13,14, and is configured near antetheca 11, but the position of venting port does not limit.Such as, venting port can be configured near rear wall.In addition, venting port also can be arranged on the centre of the one end on the fore-and-aft direction of sidewall and the central authorities on fore-and-aft direction.
(the second embodiment)
Second embodiment relates to glass furnace of the present invention.Specifically, glass furnace of the present invention has the formation that a pair venting port is configured in the central authorities on the fore-and-aft direction of sidewall.That is, glass furnace of the present invention has the formation that a pair venting port is configured in the central authorities between antetheca and rear wall.
Fig. 4 is the side-view of the internal structure of glass furnace in the second embodiment.Fig. 5 is the vertical view of the internal structure of glass furnace in the second embodiment.In Fig. 5, the outer rim of the flame of each burner dotted line is represented.It should be noted that, in Fig. 4, Fig. 5, identical label is marked to the formation identical with Fig. 2, Fig. 3 and omits the description.
As shown in Figure 4, Figure 5, smelting furnace 1A possesses material pouring inlet 21 on the antetheca 11 of melting chamber 10, the rear wall 12 of melting chamber 10 possesses conveying end 22, possesses multiple burner 31A ~ 50A and a pair venting port 24A, 25A at the sidewall 13,14 of the stream 23 from material pouring inlet 21 to conveying end 22.
A pair venting port 24A, 25A are configured in the central authorities on the fore-and-aft direction of two side 13,14, and are configured in the central authorities between antetheca 11 and rear wall 12.The venting port 24A be configured on left side wall 13 clips stream 23 with the venting port 25A be configured on right side wall 14 and relatively configures.
In present embodiment, same with the first embodiment, burner 31A ~ 50A uses air-breathing burner and oxygen-fired burners.Therefore, same with the first embodiment, can NO be suppressed
xthe increase of output.
In addition, in present embodiment, same with the first embodiment, more than 30% (preferably more than 35%) of the horal gross heat of combustion amount Qa of multiple burner 31A ~ 50A and less than 90% (preferably less than 87%) are produced by oxygen-fired burners.Or, always add more than 60% (preferably more than 68%) of heat Qb for the glass in heat fused room 10 horal and less than 97% (preferably less than 95%) is produced by oxygen-fired burners.
Therefore, same with the first embodiment, can suppress by the reduction of the thermo-efficiency using air-breathing burner to cause, CO
2the increase of output, NO
xthe increase of output.In addition, due to the reduction of thermo-efficiency can be suppressed, therefore, the temperature in melting chamber 10 is easily made to remain on comparatively high temps.
In addition, in present embodiment, same with the first embodiment, with direction backwards of venting port 24A, 25A in the region of more than 0.6L (preferred more than 0.7L), be provided with at least one air-breathing burner and at least one oxygen-fired burners.At this, L represents the ultimate range (in the example as shown in fig. 5, L3=L4) in the distance L4 on the distance L3 on the fore-and-aft direction between venting port 24A, 25A and antetheca 11 and the fore-and-aft direction between venting port 24A, 25A and rear wall 12.Therefore, same with the first embodiment, fully can guarantee the region that can regulate the moisture concentration contained in the gas after burning, thus the amount of moisture dissolved in the melten glass in melting chamber 10 can be made to change in wider scope.As a result, can fully regulate the amount of moisture dissolved in the melten glass in melting chamber 10, can the growth of bubble in melten glass be promoted and promote floating of bubble in clarification operation, thus can the few glasswork of manufacturing defect.
The adjustment of the amount of moisture dissolved in the melten glass in melting chamber 10 is carried out with the horal heat output ratio of oxygen-fired burners by regulating air-breathing burner.The object of this adjustment is mainly arranged on burner 39A ~ 40A, 49A ~ 50A with venting port 24A, 25A on direction backwards in the region of more than 0.6L.Air-breathing burner is higher relative to the heat output ratio of oxygen-fired burners, then the moisture concentration contained in the gas after the burning in melting chamber 10 is lower, and therefore, the amount of moisture dissolved in the melten glass in melting chamber 10 is fewer.
At this, to be arranged on venting port 24A, 25A the horal heat output Qd of burner 39A ~ 40A, 49A ~ 50A on direction backwards in the region of more than 0.6L more than 5% and less than 95% (preferably more than 10% and less than 90%, more preferably more than 15% and less than 90%) produced by air-breathing burner.
Lower than 5% time, the moisture concentration contained in the gas after the burning in melting chamber 10 is too high, thus makes the amount of moisture that dissolves in the melten glass in melting chamber 10 too much.On the other hand, during more than 95%, the moisture concentration contained in the gas after the burning in melting chamber 10 is too low, thus makes the amount of moisture that dissolves in the melten glass in melting chamber 10 very few.
It should be noted that, in present embodiment, have employed the formation of each configuration one on venting port 24A, 25A each sidewall in an opposing fashion in the two side 13,14 of stream 23, but also can be a formation sidewall only in the two side of stream configuring a venting port.
In addition, in present embodiment, have employed with direction backwards of venting port 24A, 25A on the formation of at least one air-breathing burner and at least one oxygen-fired burners is set in the region of more than 0.6L (preferred more than 0.7L), but the present invention is not limited thereto.Such as, can for direction forward of venting port 24A, 25A on the formation of at least one air-breathing burner and at least one oxygen-fired burners is set in the region of more than 0.6L (preferred more than 0.7L), also two kinds of formations can be combined.
(the 3rd embodiment)
3rd embodiment relates to glass furnace of the present invention.Specifically, glass furnace of the present invention has the formation that multiple burner clips flow arrangement toothing.
Fig. 6 is the side-view of the internal structure of glass furnace in the 3rd embodiment.Fig. 7 is the vertical view of the internal structure of glass furnace in the 3rd embodiment.In Fig. 7, the outer rim of the flame of each burner dotted line is represented.It should be noted that, in Fig. 6, Fig. 7, identical label is marked to the formation identical with Fig. 2, Fig. 3 and omits the description.
As shown in Figure 6, Figure 7, smelting furnace 1B possesses material pouring inlet 21B on the antetheca 11B of melting chamber 10B, the rear wall 12B of melting chamber 10B possesses conveying end 22B, possesses multiple burner 31B ~ 33B, 41B ~ 42B and a pair venting port 24B, 25B at sidewall 13B, the 14B of the stream 23B from material pouring inlet 21B to conveying end 22B.
The size of melting chamber 10B is not particularly limited, and such as, the fore-and-aft direction size X3 of melting chamber 10B is 2 ~ 5m, and the width size Y3 of melting chamber 10B is 1 ~ 3m, and the short transverse size Z3 of melting chamber 10B is 1 ~ 3m.
A pair venting port 24B, 25B are configured in an end on the fore-and-aft direction of two side 13B, 14B, and are configured near antetheca 11B.The venting port 24B be configured on left side wall 13B clips stream 23B with the venting port 25B be configured on right side wall 14B and relatively configures.
The size of venting port 24B, 25B is not particularly limited, and such as, the fore-and-aft direction size X4 of venting port 24B, 25B is about 0.3m, and the short transverse size Z4 of venting port 24B, 25B is about 0.2m.
Multiple burner 31B ~ 33B, 41B ~ 42B clip stream 23B and are configured to zig-zag.The multiple burner 31B ~ 33B be configured on left side wall 13B are arranged in front rear upwards along stream 23B.Similarly, the multiple burner 41B ~ 42B be configured on right side wall 14B are arranged in front rear upwards along stream 23B.
In present embodiment, same with the first embodiment, burner 31B ~ 33B, 41B ~ 42B use air-breathing burner and oxygen-fired burners.Therefore, same with the first embodiment, can CO be suppressed
2and NO
xthe increase of output.
In addition, in present embodiment, same with the first embodiment, more than 30% (preferably more than 35%) of the horal gross heat of combustion amount Qa of multiple burner 31B ~ 33B, 41B ~ 42B and less than 90% (preferably less than 87%) are produced by oxygen-fired burners.Or, always add more than 60% (preferably more than 68%) of heat Qb for the glass in the 10B of heat fused room horal and less than 97% (preferably less than 95%) is produced by oxygen-fired burners.
Therefore, same with the first embodiment, can suppress by the reduction of the thermo-efficiency using air-breathing burner to cause, CO
2the increase of output, NO
xthe increase of output.In addition, due to the reduction of thermo-efficiency can be suppressed, therefore, the temperature in melting chamber 10B is easily made to remain on comparatively high temps.Therefore, be suitable for manufacturing dystectic glasswork.
In addition, in present embodiment, same with the first embodiment, with direction backwards of venting port 24B, 25B in the region of more than 0.6L (preferred more than 0.7L), be provided with at least one air-breathing burner and at least one oxygen-fired burners.At this, L represents the ultimate range (being L6 in the example shown in Fig. 7) in the distance L6 on the distance L5 on the fore-and-aft direction between venting port 24B, 25B and antetheca 11B and the fore-and-aft direction between venting port 24B, 25B and rear wall 12B.Therefore, same with the first embodiment, fully can guarantee the region that can regulate the moisture concentration contained in the gas after burning, thus the amount of moisture dissolved in the melten glass in melting chamber 10B can be made to change in wider scope.As a result, can fully regulate the amount of moisture dissolved in the melten glass in melting chamber 10B, can the growth of bubble in melten glass be promoted and promote floating of bubble in clarification operation, thus can the few glasswork of manufacturing defect.
The adjustment of the amount of moisture dissolved in the melten glass in melting chamber 10B is carried out with the horal heat output ratio of oxygen-fired burners by regulating air-breathing burner.The object of this adjustment is mainly arranged on burner 33B, 42B with venting port 24B, 25B on direction backwards in the region of more than 0.6L.Air-breathing burner is higher relative to the heat output ratio of oxygen-fired burners, then the moisture concentration contained in the gas after the burning in melting chamber 10B is lower, and therefore, the amount of moisture dissolved in the melten glass in melting chamber 10B is fewer.
At this, to be arranged on venting port 24B, 25B the horal heat output Qd of burner 33B, 42B on direction backwards in the region of more than 0.6L more than 5% and less than 95% (preferably more than 10% and less than 90%, more preferably more than 15% and less than 90%) produced by air-breathing burner.
Lower than 5% time, the moisture concentration contained in the gas after the burning in melting chamber 10B is too high, thus makes the amount of moisture that dissolves in the melten glass in melting chamber 10B too much.On the other hand, during more than 95%, the moisture concentration contained in the gas after the burning in melting chamber 10B is too low, thus makes the amount of moisture that dissolves in the melten glass in melting chamber 10B very few.
Above, the of the present invention first to the 3rd embodiment is illustrated, but the present invention is not by the restriction of above-mentioned embodiment, can carry out various distortion and displacement without departing from the present invention to above-mentioned embodiment.
Such as, can glass furnace 1C as shown in Figure 8 such, two side 13C, 14C of melting chamber 10C arrange the necking part 19 melting chamber 10C being divided into two rooms 17,18.In this case, the room 18 of rear side is the room of the temperature for regulating melten glass, and the sidewall of the room 18 of rear side does not arrange burner.
In addition, can glass furnace 1D as shown in Figure 9 such, two side 13D, 14D of melting chamber 10D arrange material pouring inlet 21D, and venting port 24D are set on antetheca 11D.It should be noted that, venting port 24D can be arranged on antetheca 11D and/or rear wall 12D.
In addition, as the method heated melten glass, the method for directly melten glass being carried out to electrified regulation can be combinationally used on the basis of the method for the flame radiation heat utilizing said burner to spray.
In addition, the gas be blended in the present invention in the fuel of air-breathing burner is preferably air, but, as long as be the degree not making NOx output increase as mentioned above, specifically, as long as make the oxygen be blended in the gas in fuel be 25 below volume %, then also can mix oxygenous gas in addition to air.
In addition, on the sidewall of melting chamber, being preferably provided with the observation window (not shown) for confirming glass melting situation, in order to improve stopping property during upper and lower switch, the sash of observation window being preferably set in the mode tilted slightly.
Embodiment
Below, by embodiment, the present invention will be described particularly, but the present invention is not limited to following embodiment.
(example 1 ~ 10)
In example 1 ~ 10 (table 1,2), by calculating the β-OH (unit :/mm) obtained in the glass using the glass furnace manufacture shown in Fig. 2, Fig. 3.β-OH is the index of the amount of moisture represented in glass, and β-OH is larger, represents that the amount of moisture in glass is more.Example 2,4 ~ 6,10 is embodiment, and example 1,3,7 ~ 9 is comparative example.
At this, the method for calculation of β-OH are briefly described.First, the fuel burnt based on each burner and the composition etc. of gas, calculate the moisture concentration etc. contained in the gas after burning.Then, the gas after burning is taken into account to the flowing of venting port, calculates the distribution of the moisture concentration in the atmosphere in melting chamber.Then, based on the distribution of moisture concentration and the mean flow rate of melten glass, calculate the amount of moisture be finally diffused in melten glass, and be converted into the β-OH contained in the glass after manufacture.
In each example 1 ~ 10, the fore-and-aft direction size X1 of melting chamber 10 is set as 25m, the width size Y1 of melting chamber 10 is set as 10m, the short transverse size Z1 of melting chamber 10 is set as 8m.In addition, be 300m by the volume settings of the melten glass in melting chamber 10
3, the volume settings being put into frit in melting chamber 10 (that is, each hour take out from melting chamber 10 melten glass) each hour is 1.25m
3.In addition, the fore-and-aft direction size X2 of venting port 24,25 is set as 1m, the short transverse size Z2 of venting port 24,25 is set as 1m.In addition, for left side wall 13, distance L1 on fore-and-aft direction between antetheca 11 and venting port 24 is set as 2m, distance from venting port 24 to the fore-and-aft direction of each burner 31 ~ 40 is set as 2m × N (N is the natural number of 1 ~ 10) respectively, the distance on the fore-and-aft direction between venting port 24 and burner 40 is set as 20m.For right side wall 14, set the configuration of venting port 25 and multiple burner 41 ~ 50 similarly.
Then, in each example 1,2,4,5,7 ~ 10, respective for multiple burner 31 ~ 50 horal heat output is set as identical.On the other hand, in example 3, by multiple oxygen-fired burners separately horal heat output be set as identical, by multiple air-breathing burner separately horal heat output be set as identical, further, the horal heat output of each air-breathing burner is set smaller than the horal heat output of each oxygen-fired burners.In addition, in example 6, by multiple oxygen-fired burners separately horal heat output be set as identical, by multiple air-breathing burner separately horal heat output be set as identical, further, the horal heat output of each air-breathing burner is set greater than the horal heat output of each oxygen-fired burners.It should be noted that, the burner 31 ~ 50 of example 1,9 only uses oxygen-fired burners, and the burner 31 ~ 50 of example 2 ~ 8,10 uses oxygen-fired burners and air-breathing burner.
In table 1,2, CO
2the unit Nm of output
3represent the volume (table 3, table 4 are too) under standard state (0 DEG C, 1 normal atmosphere).In table 1,2, by illustrating the numbering (No.) of air-breathing burner and eliminating the numbering (table 3, table 4 are too) of oxygen-fired burners.
[table 1]
[table 2]
From table 1,2, for the example 1 ~ 8 that fuel is Sweet natural gas, in example 2,4 ~ 6, with the direction of venting port 24,25 backwards in the region of more than 0.6L, be provided with at least one air-breathing burner and at least one oxygen-fired burners, compared with the situation of example 1, the β-OH in glass reduces more than 10%.In addition, for the example 9,10 that fuel is heavy oil, in example 10, with the direction of venting port 24,25 backwards in the region of more than 0.6L, be provided with at least one air-breathing burner and at least one oxygen-fired burners, compared with the situation of example 9, the β-OH in glass reduces more than 10%.When β-OH reduces by more than 10%, by changing air-breathing burner heat output ratio horal with oxygen-fired burners, can fully regulate β-OH.Therefore, in example 2,4 ~ 6,10, by regulating the horal heat output ratio of air-breathing burner and oxygen-fired burners, can fully regulate the amount of moisture dissolved in the melten glass in melting chamber 10.
On the other hand, in example 7,8, with the direction of venting port 24,25 backwards in the region of more than 0.6L, air-breathing burner is not set, therefore, β-OH does not reduce by more than 10% relative to example 1.Therefore distinguish, even if regulate the horal heat output ratio of air-breathing burner and oxygen-fired burners, be also difficult to fully regulate the amount of moisture dissolved in the melten glass in melting chamber 10.
In addition, in example 3, in the same manner as example 2 with the direction of venting port 24,25 backwards in the region of more than 0.6L, be provided with at least one air-breathing burner and at least one oxygen-fired burners, but with example 2 unlike, horal 99% of the heat Qb that always adds for the glass of heat fused indoor is produced by oxygen-fired burners.Therefore, in example 3, the β-OH in glass does not reduce by more than 10% relative to example 1.Therefore distinguish, in example 3, be difficult to fully reduce the amount of moisture dissolved in the melten glass in melting chamber 10.
(example 11 ~ 12)
In example 11 ~ 12 (table 3), obtained the β-OH (unit :/mm) in the glass using the glass furnace shown in Fig. 4, Fig. 5 to manufacture by above-mentioned calculating.Example 12 is embodiment, and example 11 is comparative example.
In each example 11 ~ 12, except venting port 24A, 25A being arranged on the central authorities on the fore-and-aft direction of sidewall 13,14, the distance etc. in the size of melting chamber, the size of venting port, fore-and-aft direction between venting port with each burner sets in the same manner as example 1 ~ 10.In each example 11 ~ 12, by multiple burner 31A ~ 50A separately horal heat output be set as identical.It should be noted that, the burner 31A ~ 50A of example 11 only uses oxygen-fired burners, and the burner 31A ~ 50A of example 12 uses oxygen-fired burners and air-breathing burner.
[table 3]
As shown in Table 3, in example 12, with direction backwards of venting port 24A, 25A in the region of more than 0.6L, be provided with at least one air-breathing burner and at least one oxygen-fired burners, compared with the situation of example 11, the β-OH in glass reduces more than 10%.Therefore distinguishing, in example 12, by regulating the horal heat output ratio of air-breathing burner and oxygen-fired burners, can fully regulate the amount of moisture dissolved in the melten glass in melting chamber 10.
(example 13 ~ 14)
In example 13 ~ 14 (table 4), obtained the β-OH (unit :/mm) in the glass using the glass furnace shown in Fig. 6, Fig. 7 to manufacture by above-mentioned calculating.Example 14 is embodiment, and example 13 is comparative example.
In each example 13 ~ 14, the fore-and-aft direction size X3 of melting chamber 10B is set as 3m, the width size Y3 of melting chamber 10B is set as 2m, the short transverse size Z3 of melting chamber 10B is set as 2m.In addition, be 4.5m by the volume settings of the melten glass in melting chamber 10B
3, the volume settings being put into frit in melting chamber 10B (that is, each hour take out from melting chamber 10B melten glass) each hour is 0.04m
3.In addition, the fore-and-aft direction size X4 of venting port 24B, 25B is set as 0.3m, the short transverse size Z4 of venting port 24B, 25B is set as 0.3m.In addition, for left side wall 13B, distance L5 on fore-and-aft direction between antetheca 11B and venting port 24B is set as 0.2m, distance on fore-and-aft direction between venting port 24B and burner 31B is set as 0.3m, distance on fore-and-aft direction between venting port 24B and burner 32B is set as 1.0m, the distance on the fore-and-aft direction between venting port 24B and burner 33B is set as 2.0m.On the other hand, for right side wall 14B, distance L5 on fore-and-aft direction between antetheca 11B and venting port 25B is set as 0.2m, distance on fore-and-aft direction between venting port 25B and burner 41B is set as 0.5m, the distance on the fore-and-aft direction between venting port 25B and burner 42B is set as 1.5m.Further, in each example 13 ~ 14, by multiple burner 31B ~ 33B, 41B ~ 42B separately horal heat output be set as identical.It should be noted that, the burner 31B ~ 33B of example 13,41B ~ 42B only use oxygen-fired burners, and burner 31B ~ 33B, the 41B ~ 42B of example 14 use oxygen-fired burners and air-breathing burner.
[table 4]
As shown in Table 4, in example 14, with direction backwards of venting port 24B, 25B in the region of more than 0.6L, be provided with at least one air-breathing burner and at least one oxygen-fired burners, compared with the situation of example 13, the β-OH in sheet glass reduces more than 10%.Therefore distinguishing, in example 14, by regulating the horal heat output ratio of air-breathing burner and oxygen-fired burners, can fully regulate the amount of moisture dissolved in the melten glass in melting chamber 10B.
With reference to specific embodiment, the present invention is illustrated in detail, but without departing from the spirit and scope of the present invention, can make various changes and modifications, this will be apparent to those skilled in the art.
The Japanese patent application 2010-101312 that the application proposed based on April 26th, 2010, quotes its content in this specification sheets with the form of reference.
Utilizability in industry
According to the present invention, can provide and can suppress NO
xthe increase of output and fully can regulate the glass furnace of the amount of moisture dissolved in melten glass.This glass furnace is effective especially when heating fully melten glass, when making amount of moisture reduce simultaneously.
Label declaration
1 smelting furnace
10 melting chambers
11 antethecas
12 rear walls
13 sidewalls (left side wall)
14 sidewalls (right side wall)
21 material pouring inlet
22 conveying ends
23 streams
24 venting ports
25 venting ports
31 ~ 50 burners
Claims (4)
1. a manufacture method for glasswork, has and frit is melted and obtains the melting process of melten glass; The melten glass obtained in this melting process is supplied in clarifying tank, the bubble of removing melten glass and clarification operation that melten glass is clarified; And the melten glass after clarification is configured as the forming process of predetermined shape,
Described melting process the composition according to glasswork is weighed plurality of raw materials the frit mixed to put in smelting furnace and the operation being heated to the temperature corresponding to the kind of glass and making it melt,
The feature of the manufacture method of described glasswork is,
Described glass furnace possesses melting chamber that frit is melted and is arranged on from the antetheca of this melting chamber to the multiple burners the sidewall of the stream of rear wall, described multiple burner jets out flames and heats the glass in described melting chamber and make it melt in described melting chamber
Described multiple burner uses the oxygen-fired burners spraying the flame making fuel and oxygenous gas and vapor permeation burn and be formed and these the two kinds of burners of air-breathing burner spraying the flame making fuel and air mixed burn and be formed,
Each configuration one on each sidewall in an opposing fashion in the two side of described melting chamber of venting port that the gas after the burning in described melting chamber is discharged to the outside, or a sidewall only in the two side of described melting chamber configures one, or be configured in antetheca or the rear wall of described melting chamber
When ultimate range in distance on fore-and-aft direction described in Distance geometry on fore-and-aft direction between described venting port and described antetheca between venting port and described rear wall is set to L, with the direction of described venting port forward and/or direction backwards at a distance of more than 0.6L region in arrange oxygen-fired burners described at least one and at least one described in air-breathing burner
In described melting process,
The contribution rate of described oxygen-fired burners to the horal gross heat of combustion amount of described multiple burner is set as more than 30% and less than 90%,
The contribution rate of described air-breathing burner to the horal gross heat of combustion amount of the described burner be arranged in described region is set as more than 5% and less than 95%, thus the amount of moisture dissolved in the melten glass in described melting chamber is regulated.
2. the manufacture method of glasswork as claimed in claim 1, wherein, when ultimate range in distance on fore-and-aft direction described in Distance geometry on fore-and-aft direction between described venting port and described antetheca between venting port and described rear wall is set to L, with the direction of described venting port forward and/or direction backwards at a distance of 0.6L ~ 0.73L region in arrange oxygen-fired burners described at least one and at least one described in air-breathing burner.
3. the manufacture method of glasswork as claimed in claim 1, wherein, the value of the β-OH in manufactured glass is 0.25 ~ 0.52/mm.
4. the manufacture method of glasswork as claimed in claim 1, wherein, when the sidewall of described melting chamber is arranged with at least two described air-breathing burners, arranges oxygen-fired burners described at least one between these two air-breathing burners.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-101312 | 2010-04-26 | ||
| JP2010101312 | 2010-04-26 | ||
| PCT/JP2011/059621 WO2011136086A1 (en) | 2010-04-26 | 2011-04-19 | Glass melting furnace and method for melting glass |
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| CN102858697A CN102858697A (en) | 2013-01-02 |
| CN102858697B true CN102858697B (en) | 2016-01-20 |
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| KR (1) | KR101453639B1 (en) |
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| CN103771686A (en) * | 2014-01-15 | 2014-05-07 | 温州市康尔微晶器皿有限公司 | Microcrystalline glass melting tank furnace |
| JP6292090B2 (en) * | 2014-09-03 | 2018-03-14 | 旭硝子株式会社 | Melting kiln, melting method, and alkali-free glass plate manufacturing method |
| EP3313791B1 (en) * | 2015-06-26 | 2021-03-24 | Owens Corning Intellectual Capital, LLC | Submerged combustion glass melter with oxygen/gas heat-up burner system |
| JP6749123B2 (en) * | 2016-03-31 | 2020-09-02 | ＡｖａｎＳｔｒａｔｅ株式会社 | Glass substrate manufacturing method and glass substrate manufacturing apparatus |
| JP6631372B2 (en) * | 2016-04-08 | 2020-01-15 | Ａｇｃ株式会社 | Melting method and method for producing alkali-free glass plate |
| JP2023121646A (en) | 2022-02-21 | 2023-08-31 | Ａｇｃ株式会社 | Glass melting furnace, and facility and method for manufacturing glass product |
| JP2023121645A (en) | 2022-02-21 | 2023-08-31 | Ａｇｃ株式会社 | Glass melting furnace, and facility and method for manufacturing glass product |
| WO2023199909A1 (en) | 2022-04-15 | 2023-10-19 | 日本電気硝子株式会社 | Method for producing glass article |
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| WO2009118336A1 (en) * | 2008-03-25 | 2009-10-01 | Agc Flat Glass Europe Sa | Glass melting furnace |
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| US5147438A (en) * | 1991-09-18 | 1992-09-15 | Union Carbide Industrial Gases Technology Corporation | Auxiliary oxygen burners technique in glass melting cross-fired regenerative furnaces |
| US6519973B1 (en) * | 2000-03-23 | 2003-02-18 | Air Products And Chemicals, Inc. | Glass melting process and furnace therefor with oxy-fuel combustion over melting zone and air-fuel combustion over fining zone |
| DE10055924B4 (en) * | 2000-08-19 | 2006-03-23 | Horn Glasanlagen Gmbh | Method for operating a glass melting furnace |
| JP4245424B2 (en) * | 2003-07-18 | 2009-03-25 | 日本エア・リキード株式会社 | Glass melting kiln |
| JP5793419B2 (en) * | 2008-06-05 | 2015-10-14 | エージーシー グラス ユーロップ | Glass melting furnace |
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| WO2009118336A1 (en) * | 2008-03-25 | 2009-10-01 | Agc Flat Glass Europe Sa | Glass melting furnace |
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| KR101453639B1 (en) | 2014-11-03 |
| JPWO2011136086A1 (en) | 2013-07-18 |
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| TWI498301B (en) | 2015-09-01 |
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