CN109734301A - A kind of depigmenting agent that removal defoaming agent colours the high turbine glass sheet of ultrawhite and application method - Google Patents
A kind of depigmenting agent that removal defoaming agent colours the high turbine glass sheet of ultrawhite and application method Download PDFInfo
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- CN109734301A CN109734301A CN201910194137.8A CN201910194137A CN109734301A CN 109734301 A CN109734301 A CN 109734301A CN 201910194137 A CN201910194137 A CN 201910194137A CN 109734301 A CN109734301 A CN 109734301A
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Abstract
The invention discloses a kind of depigmenting agent that elimination composite anti-foaming agent colours the high turbine glass sheet of ultrawhite and application methods.The composition of depigmenting agent is rubidium oxide, the cobalt oxide predominantly centainly matched, enter kiln after what depigmenting agent and appropriate glass major ingredient silica sand premixed integrally mix with other raw materials again, and eliminates the effect of coloring by the oxidisability optimization appropriate of control kiln flame zone space.
Description
Technical field
The invention belongs to ultrawhite high turbine glass sheet fields, and in particular to one kind is suitable for raw in the high turbine glass sheet of ultrawhite
Using the depigmenting agent after composite anti-foaming agent coloring during producing.
Background technique
The high turbine glass sheet of ultrawhite finds broad application in the fields such as building, solar energy, electronical display, and chemistry is main
As SiO2For 70~74.0wt%, Al2O3It is 6~10wt% for 0~2.0wt%, CaO, MgO is 2~5wt%, Na2O is 12
~15wt%, K2O is 0~2.0wt%, Fe2O3≤ 120ppm, TiO2≤ 80ppm has been achieved on a large scale by using float glass process
Batch production；There are silica sand, sulfate, carbonate etc. in its primary raw material, these raw materials carry out in special high temperature melting furnaces
It melts, in fusion process, discharges the CO of bulk gas2、SO2Equal gases, a large amount of gas are covered on the surface of glass metal, if
It takes merely and increases fusion temperature to reduce the method for viscosity of glass metal to reach elimination bubble, since froth bed adds upper part
The reflex of thermal-flame, not only fuel effective rate of utilization reduces, probably increase fuel usage amount nearly 5%~10%, and by
The heating flame heat of reflection makes the melting furnaces arch top internal surface temperature for melting glass that will increase 10 DEG C~20 DEG C, increases melting furnaces
Erosive velocity seriously affects the service life of melting furnaces.
CN107162403A have developed suitable glass production composite anti-foaming agent (main component are as follows: tetrabutyl titanate,
Titanium dioxide, sodium sulphate, calcium sulfate, ferrocene, aviation kerosine, diesel oil and heavy oil are mixed in a certain proportion), it does not need to improve super
The fusion temperature of white high turbine glass sheet production kiln, it will be able to accelerate glass metal blibbing layer in kiln different temperatures region
Rupture, essentially eliminate froth bed, do not increase fuel cost in this way, and can guarantee that the high flat glass product thoroughly of ultrawhite is qualified
Rate can also extend kiln service life.It but is necessary due to containing tetrabutyl titanate or titanium dioxide in the composite anti-foaming agent
Ingredient, while the use of composite anti-foaming agent improves the high turbine glass sheet product qualification rate of ultrawhite and extends kiln service life,
The titanium ion introduced in defoaming agent also makes glass generate " partially yellow " visual effect, causes the high turbine glass sheet of ultrawhite in solar-electricity
The application of the fields such as pond substrate and electronical display is restricted.
Meanwhile in the manufacturing process of the high turbine glass sheet of ultrawhite, silica sand accounts for 60% or more of entire raw material weight, though using
High-purity silica sand (SiO of higher cost2Content >=99.5%, TiO2Content≤80ppm, annotation: titanium ion is all with 4 valence state of ﹢
There is conversion in titanium dioxide), also still there is a certain amount of TiO2Introduce, though using ultra-pure silica sand, not only silica sand per ton at
500 yuan of this increase or more, the producing line of high-purity silica sand for using hundreds of tons daily, increased costs pressure is huge, moreover, still
The introducing that can not avoid titanium ion completely makes final glass substrate generate different degrees of " colored " visual effect.
Moreover, in composite anti-foaming agent containing tetrabutyl titanate or titanium dioxide be in glass furnace froth bed area from glass metal
Portion space is injected to the combustion flame space inside kiln and a series of physical-chemical reaction occurs, which is 1000
DEG C~1400 DEG C, because of the influence of temperature and kiln internal oxidation reducing atmosphere, the titanium ion after reaction exists in glass product
Form may be TiO, Ti2O3、TiO2, final glass product shows the colors such as " yellow ", " yellowish green ", " orange ", " amber "
Coloured silk, and color is deep mixed, this can also make the selection of depigmenting agent type, the proportion of depigmenting agent dosage, depigmenting agent application method
Become unstable, directly makes entire glass production that can not stablize lasting progress.
Summary of the invention
The technical problem to be solved by the present invention is to for the titanium ion introduced in ultrawhite high transparent glass raw material and using multiple
It closes the titanium ion that defoaming agent introduces to lead to the problem of on glass colour influence, the present invention provides a kind of removal defoaming agent to ultrawhite height
The depigmenting agent and application method of turbine glass sheet coloring, that is, can guarantee the normal use of defoaming agent, and reaching reduces temperature delay kiln
The purpose of furnace service life, and can handle and introduce titanium ion in defoaming agent and raw material and lead to the influence of glass whole " colored ", drop
Low cost of material.
The present invention be solve the problems, such as it is set forth above used by technical solution are as follows:
A kind of depigmenting agent that removal defoaming agent colours the high turbine glass sheet of ultrawhite, it is characterised in that the depigmenting agent is main
It is formed with rubidium oxide, cobalt oxide, mass ratio≤1:3 of cobalt oxide and rubidium oxide, while also needing to meet rubidium oxide whole with glass
Body raw material input amount ratio≤120ppm, cobalt oxide and glass entirety raw material input amount ratio≤90ppm.
According to the above scheme, the representative compositing range of the high turbine glass sheet of the ultrawhite: SiO2For 70~72.0wt%,
Al2O3It is 7~9wt% for 0.5~2.0wt%, CaO, MgO is 2~5wt%, Na2O is 13~15wt%, K2O be 0~
1.0wt%, Fe2O3≤120ppm；TiO2Content≤80ppm.The high turbine glass sheet of the ultrawhite can be used raw material and can be such that height
Pure silicon sand, alumina powder, lime stone, dolomite, soda ash, saltcake, carbon dust etc. realize above-mentioned representative compositing range.Wherein,
Each raw material specification is as follows: high-purity silica sand (SiO2>=98.5wt%, Al2O3≤ 1.1wt%, Fe2O3≤100ppm；TiO2Content≤
60ppm), alumina powder (Al2O3>=99.0wt%, Fe2O3≤200ppm；), lime stone (CaO be 55.00 ± 0.5%wt%,
Fe2O3≤80ppm；TiO2Content≤80ppm), dolomite (MgO be 21.00 ± 1.0wt%, CaO be 32.00 ± 1.0wt%,
Fe2O3≤80ppm；TiO2Content≤80ppm), soda ash (Na2CO3For >=99.5wt%, Fe2O3≤50ppm；TiO2Content≤
50ppm), saltcake (Na2SO3For >=99.0wt%, Fe2O3≤100ppm；TiO2Content≤50ppm).Wherein, carbon dust dosage is awns
2~3wt% of nitre.
According to the above scheme, the defoaming agent mainly uses the disclosed ordinary plate glass that is suitable for of CN107162403A to produce
Composite anti-foaming agent.The composite anti-foaming agent mainly includes bulk composition and solvent composition, and it includes titanium compound that bulk composition, which contains,
Foamicide, sodium sulphate and the calcium sulfate composition steep that wall reducer and solvent efficiency of combustion of composition optimize penta 2 iron of agent；Solvent at
Divide and is dissolved in solvent containing diesel oil, aviation kerosine, heavy oil or its arbitrary proportion mixture, flash-point >=38 DEG C of solvent, bulk composition
Or it is suspended among solvent with solid particle state.
According to the above scheme, in the glass composition of the high turbine glass sheet of the ultrawhite between content of titanium dioxide and depigmenting agent
Mass ratio≤1:1.
Depigmenting agent of the present invention is in removal to the application in terms of the high turbine glass sheet coloring of ultrawhite, and specifically used method is such as
Under:
(1) high-purity silica sand, alumina powder, lime stone, white is weighed by the representative compositing range of the high turbine glass sheet of ultrawhite
Marble, soda ash, saltcake prepare depigmenting agent according to the ratio of depigmenting agent and glass entirety raw material as raw material；
(2) by after depigmenting agent and silica sand premix, then assimilate after aluminium powder, lime stone, dolomite, soda ash, saltcake integrally mix
It is fed machine and is sent into kiln, heated in kiln by space flame, undergone ingredient fusion zone (100~1300 DEG C), alveolar layer area
(1300~1450 DEG C), high-temperature region (1450~1500 DEG C), cooling area (1450~1200 DEG C) control the area kiln Nei Ge space gas
O in body2Volumn concentration sprays into kiln the mesh for reaching elimination bubble layer from deaeration area after making defoaming agent air atomizing
, while the titanium ion for being also conducive in kiln 95% or more can finally be converted to 4 valence of ﹢, with the form stable of titanium dioxide, there are glass
In glass product, reach and stablize the matching of depigmenting agent type, dosage and use condition.
According to the above scheme, it to guarantee that depigmenting agent is uniformly distributed in ingredient, uses depigmenting agent and part silica sand carries out in advance
Mixed, depigmenting agent accounts for 1 ‰~the 4 ‰ of premix silica sand weight when premixing, and incorporation time 2~5 minutes.
It according to the above scheme, is the matching for guaranteeing titanium ion final existing forms and defoaming agent in glass, by glass furnace
Ingredient fusion zone O in furnace2Volumn concentration is 0.5%~2%, alveolar layer area O2Volumn concentration is 3%~4%, high-temperature region
O2Volumn concentration is 5%~6%, cooling area O2Volumn concentration is 6%~10%.
Major technique design of the invention is: to ensure that stability and high efficiency produces ultra-clear glasses, passing through control kiln first
The redox condition condition degree of interior each subregion, promote titanium ion by it is a kind of it is sustainable it is stable in the form of or combination form exist
In glass (95% the above are 4 valence form presence of ﹢), then look for that " colour killing " effect can be formed with titanium ion existing for stable form
Fruit, the depigmenting agent type of atmospheric condition in kiln and dosage and usage mode can be matched again, it is same to reach stabilization production
When also stable " colour killing ".
Compared with prior art, the beneficial effects of the present invention are:
The depigmenting agent and its application method that removal defoaming agent provided by the present invention colours the high turbine glass sheet of ultrawhite, can
The normal use for guaranteeing defoaming agent achievees the purpose that reduce temperature delay kiln service life, and can handle defoaming agent and raw material
The middle titanium ion that introduces leads to the influence of glass whole " colored ", reduces cost of material.
Detailed description of the invention
Fig. 1 is test coloration distribution figure.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
In following embodiments, using spectrophotometer, (CIE1976LAB, L refer to the glass colour index measured for lightness
Mark, because the lightness and transmitance of glass are proportional, it is contemplated that the high turbine glass sheet transmitance of ultrawhite varies less, therefore
Pay close attention to chromaticity index a, b value), meetIt is preferred thatThe high turbine plate glass of its ultrawhite
The color of glass meets needs.
Embodiment 1-8
The high turbine glass sheet chemical composition of ultrawhite used in embodiment 1-8 are as follows: SiO2For 60.0wt%, Al2O3For
1.5wt%, MgO 4.0wt%, CaO 8.0wt%, Na2O is 14.0wt%, Fe2O3For 90ppm, TiO2For 50ppm.
Embodiment 1-8 selects high-purity silica sand, alumina powder, lime stone, dolomite, pure according to above-mentioned glass chemistry composition
Alkali, saltcake raw material, glass raw material total amount 1kg, wherein carbon dust dosage is the 2.8wt% of saltcake.Each raw material specification is as follows: HIGH-PURITY SILICON
Sand (SiO2>=98.5wt%, Al2O3≤ 1.1wt%, Fe2O3≤100ppm；TiO2Content≤60ppm), alumina powder (Al2O3≥
99.0wt%, Fe2O3≤200ppm；), lime stone (CaO be 55.00 ± 0.5%wt%, Fe2O3≤80ppm；TiO2Content≤
80ppm), (MgO is 21.00 ± 1.0wt% to dolomite, and CaO is 32.00 ± 1.0wt%, Fe2O3≤80ppm；TiO2Content≤
80ppm), soda ash (Na2CO3For >=99.5wt%, Fe2O3≤50ppm；TiO2Content≤50ppm), saltcake (Na2SO3For >=
99.0wt%, Fe2O3≤100ppm；TiO2Content≤50ppm).
In embodiment 1-8, defoaming agent is tetrabutyl titanate and aviation kerosine is the mixture of 1:15 composition in mass ratio.?
In the case where glass raw material dosage 1kg, the specific dosage of tetrabutyl titanate is 0.05g in defoaming agent.
See Table 1 for details for the specific dosage of depigmenting agent and composition in embodiment 1-8.
It is specific as follows using the method for the preparation high turbine glass sheet of ultrawhite of depigmenting agent described in embodiment 1-8:
By the dosage of glass chemistry composition and depigmenting agent, defoaming agent, after first depigmenting agent and silica sand are premixed, then with oxidation
Aluminium powder, lime stone, dolomite, soda ash, saltcake, carbon dust enter kiln after integrally mixing, and are heated in kiln by space flame, pass through
It goes through ingredient fusion zone (100-1300 DEG C), alveolar layer area (1300-1450 DEG C), high-temperature region (1450-1500 DEG C), cooling area (1450-
1200 DEG C), and then be cooled to room temperature, obtain the high turbine glass sheet of ultrawhite；Wherein, O in the area kiln Nei Ge space gases is controlled2Body
Product percentage composition, ingredient fusion zone O2Volumn concentration is 1%~1.5%, alveolar layer area O2Volumn concentration be 3%~
4%, high-temperature region O2Volumn concentration is 5%~6%, cooling area O2Volumn concentration is 7%~8%；Defoaming agent air
It is sprayed into kiln after atomization from deaeration area.See Table 1 for details for specific performance.
Table 1
Remarks:
Embodiment 2
Chemical composition and test result based on embodiment 1, in the high float glass process plate thoroughly of 550 ton/days of ultrawhite of certain company
Glass float line is produced as a trial, used in raw material mainly have high-purity silica sand (SiO2 >=98.5wt%, Al2O3≤
1.1wt%, Fe2O3≤100ppm；TiO2Content≤60ppm), alumina powder (Al2O3>=99.0wt%, Fe2O3≤
200ppm；), lime stone (CaO be 55.00 ± 0.5%wt%, Fe2O3≤80ppm；TiO2Content≤80ppm), dolomite (MgO
It is 32.00 ± 1.0wt%, Fe for 21.00 ± 1.0wt%, CaO2O3≤80ppm；TiO2Content≤80ppm), soda ash (Na2CO3
For >=99.5wt%, Fe2O3≤50ppm；TiO2Content≤50ppm), saltcake (Na2SO3For >=99.0wt%, Fe2O3≤
100ppm；TiO2Content≤50ppm)；In view of production cost, therefore wherein using has certain titanium ion for generating glass coloration
Raw material；
Each specific dosage of raw material is as follows: 325 tons of high-purity silica sand；2.5 tons of alumina powder；90 tons of dolomite；16 tons of lime stone；
102 tons of soda ash；5 tons of saltcake；0.14 ton of carbon dust；
It is appropriate to reduce fusing maximum temperature to reduce glass blister defect on the production line, extend kiln service life,
3 pairs of flame gun regions use defoaming agent before producing line, and defoaming agent bulk composition is metatitanic acid positive fourth rouge 99wt%, sodium sulphate 1wt%, boat
The solvent that empty kerosene is done, solvent usage are 15 times of the positive fourth rouge of metatitanic acid and sodium sulphate gross mass, are sprayed into kiln after mixing, defoaming agent
Bulk composition usage amount is 25kg/ days, and solvent usage is 250kg/ days；
Whole preparation method is similar with embodiment 1-8, in the case where not adding depigmenting agent of the present invention, final gained
Glass product visual color is partially yellow, the 3mm glass plate transmitance 90.8% of measurement, and chromaticity index a is that -0.013, b is
0.25, drop point value is 4.64.
Then, with reference to above-mentioned preparation method, add cobalt oxide and rubidium oxide composition depigmenting agent (cobalt oxide and rubidium oxide
Mass ratio is 1:7), premix is carried out 3 minutes with 200g depigmenting agent and 80kg silica sand when being pre-mixed, and other conditions remain unchanged.
Because having about 1300 tons of glass metals in about 550 ton/days of the glass furnace of entirely feeding intake, fusing formation is carried out by being continuously added ingredient
New glass metal, is diluted original glass metal and convection current immixture, and color is gradually faded away after continuing 2 days, after a week
Substantially color is not seen.Prepared 3mm glass plate, through measuring, transmitance 90.9%, chromaticity index a is that -0.013, b is
0.17, drop point value is 0.80；Solves titanium ion coloring problem.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to of the invention
Protection scope.
Claims (6)
1. a kind of depigmenting agent for being coloured to the high turbine glass sheet of ultrawhite of removal defoaming agent, it is characterised in that the depigmenting agent mainly with
Rubidium oxide, cobalt oxide composition, mass ratio≤1:3 of cobalt oxide and rubidium oxide, while also needing to meet rubidium oxide and glass entirety
Raw material input amount ratio≤120ppm, cobalt oxide and glass entirety raw material input amount ratio≤90ppm.
2. a kind of depigmenting agent that removal defoaming agent colours the high turbine glass sheet of ultrawhite according to claim 1, feature
It is mass ratio≤1:1 in the glass composition of the high turbine glass sheet of the ultrawhite between content of titanium dioxide and depigmenting agent.
3. a kind of depigmenting agent that removal defoaming agent colours the high turbine glass sheet of ultrawhite according to claim 1, feature
It is the representative compositing range of the high turbine glass sheet of the ultrawhite: SiO2For 70 ~ 72.0wt%, Al2O3For 0.5 ~ 2.0wt%,
CaO is 7 ~ 9wt%, and MgO is 2 ~ 5wt%, Na2O is 13 ~ 15wt%, K2O is 0 ~ 1.0wt%, Fe2O3≤120ppm；TiO2Content
≤80ppm。
4. a kind of depigmenting agent that removal defoaming agent colours the high turbine glass sheet of ultrawhite according to claim 1, feature
The raw material for being that the high turbine glass sheet of the ultrawhite uses is main are as follows: HIGH-PURITY SILICON sand, alumina powder, lime stone, dolomite, pure
Alkali, saltcake, carbon dust；Wherein, part material specification is as follows: high-purity silica sand SiO2>=98.5wt%, Al2O3≤1.1wt%、 Fe2O3
≤100ppm；TiO2Content≤60ppm；Alumina powder Al2O3>=99.0wt%, Fe2O3≤200ppm；Lime stone CaO is
55.00 ± 0.5%wt%, Fe2O3≤80ppm；TiO2Content≤80ppm；Dolomite MgO is 21.00 ± 1.0wt%, and CaO is
32.00 ± 1.0wt%, Fe2O3≤80ppm；TiO2Content≤80ppm；Soda ash Na2CO3For >=99.5wt%, Fe2O3≤
50ppm；TiO2Content≤50ppm；Saltcake Na2SO3For >=99.0wt%, Fe2O3≤100ppm；TiO2Content≤50ppm.
5. depigmenting agent described in claim 1 is in removal to the application in terms of the high turbine glass sheet coloring of ultrawhite, it is characterised in that tool
Body application method is as follows:
(1) by the representative compositing range of the high turbine glass sheet of ultrawhite weigh high-purity silica sand, alumina powder, lime stone, dolomite,
Soda ash, saltcake prepare depigmenting agent according to the ratio of depigmenting agent and glass entirety raw material as raw material；
(2) after premixing depigmenting agent and silica sand, then same alumina powder, lime stone, dolomite, soda ash, saltcake, carbon dust integrally mix
After be fed machine be sent into kiln, heated in kiln by space flame, undergo 100 ~ 1300 DEG C of ingredient fusion zone, alveolar layer area 1300
~ 1450 DEG C, 1450 ~ 1500 DEG C of high-temperature region, 1450 ~ 1200 DEG C of cooling area, and then be cooled to room temperature, obtain the high turbine plate glass of ultrawhite
Glass；Wherein, O in the area kiln Nei Ge space gases is controlled2Volumn concentration, ingredient fusion zone O2Volumn concentration be 0.5% ~
2%, alveolar layer area O2Volumn concentration is 3% ~ 4%, high-temperature region O2Volumn concentration is 5% ~ 6%, cooling area O2Volume basis contains
Amount is 6% ~ 10%；It is sprayed into kiln after defoaming agent air atomizing from deaeration area.
6. application according to claim 5, it is characterised in that the depigmenting agent is premixed with part silica sand, when premixing
Depigmenting agent account for premix silica sand weight 1 ‰ ~ 4 ‰, incorporation time 2 ~ 5 minutes.
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|---|---|---|---|
| CN201910194137.8A CN109734301B (en) | 2019-03-14 | 2019-03-14 | Decolorizer for removing coloring of super-white high-turbine plate glass by defoaming agent and using method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910194137.8A CN109734301B (en) | 2019-03-14 | 2019-03-14 | Decolorizer for removing coloring of super-white high-turbine plate glass by defoaming agent and using method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499184A (en) * | 2020-04-23 | 2020-08-07 | 乐平市华明玻璃增白剂有限公司 | Iron remover capable of enhancing glass strength and brightness and processing method thereof |
| CN113735452A (en) * | 2021-09-27 | 2021-12-03 | 薛四兰 | High-strength refractory fiber and preparation method thereof |
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|---|---|---|---|---|
| CN106587607A (en) * | 2016-12-10 | 2017-04-26 | 温州雏鹰科技有限公司 | Ultraviolet-proof glass for vehicle windows |
| CN107162407A (en) * | 2017-04-14 | 2017-09-15 | 中建材（宜兴）新能源有限公司 | A kind of ultra-thin photovoltaic rolled glass |
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2019
- 2019-03-14 CN CN201910194137.8A patent/CN109734301B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587607A (en) * | 2016-12-10 | 2017-04-26 | 温州雏鹰科技有限公司 | Ultraviolet-proof glass for vehicle windows |
| CN107162407A (en) * | 2017-04-14 | 2017-09-15 | 中建材（宜兴）新能源有限公司 | A kind of ultra-thin photovoltaic rolled glass |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499184A (en) * | 2020-04-23 | 2020-08-07 | 乐平市华明玻璃增白剂有限公司 | Iron remover capable of enhancing glass strength and brightness and processing method thereof |
| CN113735452A (en) * | 2021-09-27 | 2021-12-03 | 薛四兰 | High-strength refractory fiber and preparation method thereof |
| CN113735452B (en) * | 2021-09-27 | 2022-12-30 | 湖北烁砺新材料科技有限公司 | High-strength refractory fiber and preparation method thereof |
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