CN107056044A - A kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses - Google Patents
A kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses Download PDFInfo
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- CN107056044A CN107056044A CN201710367290.7A CN201710367290A CN107056044A CN 107056044 A CN107056044 A CN 107056044A CN 201710367290 A CN201710367290 A CN 201710367290A CN 107056044 A CN107056044 A CN 107056044A
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- liquid
- composition
- crystalline glasses
- foaming agent
- composite anti
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/225—Refining
-
- 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
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses, it mainly includes bulk composition and solvent composition, and bulk composition contains the foamicide for including titanium compound composition, tin oxide and magnesium sulfate composition steep that wall reducer and the solvent efficiency of combustion optimization iron of agent penta 2；Solvent composition contains diesel oil, aviation kerosine, heavy oil or its arbitrary proportion mixture, and flash-point >=38 DEG C of solvent, bulk composition is dissolved in solvent or is suspended in solid particle state among solvent.The present invention in the glass metal walls of floating by producing new minute bubbles to reach the effect of thinned walls, simultaneously by reducing walls local viscosity and surface tension, promote bubbles burst, to reach the maximum temperature that need not improve liquid crystal kiln, and can speed up the rupture of glass metal blibbing layer in kiln different temperatures region, efficiency is steeped with the row that this improves glass metal, the influence of liquid-crystalline glasses air blister defect is reduced.
Description
Technical field
The invention belongs to found technical field in liquid-crystalline glasses production process, specifically relate to a kind of suitable for liquid crystal glass
The composite anti-foaming agent of glass production.
Background technology
In liquid-crystalline glasses production process, because the raw materials such as silica sand, sulfate, chloride are in pyrolytic, fusion process
In can discharge SO2、H2The a large amount of gases of the gases such as O, form a large amount of bubbles in glass metal, and bubble layer almost covers liquid-crystalline glasses
The non-dispensing area of coverage in kiln, its alveolar layer thickness is that the presence of air blister defect in 10mm~100mm, glass metal has a strong impact on liquid crystal
Glass product qualification rate, as influence production efficiency key factor.
Generally, to reduce the bubble in glass metal, it can be increased by adding certain proportion fining agent in frit
Plus bubble radius, its principle is：Fining agent decomposes generation such as SO at high temperature2、O2Deng gas, the gas and above-mentioned frit
Decompose the gas produced to combine, so that bubble radius increase, in order to float up on the liquid level of glass metal；Can also be by carrying
High temperature of glass liquid, reduce the mode (such as by heating) of viscosity of glass metal to promote bubble discharge in glass metal, with this simultaneously,
The rise of temperature of glass liquid also reduces the surface tension of glass metal, promotes to swim in the rupture of the froth bed on glass metal surface.
But, although the use of fining agent can promote a large amount of bubble bubble diameter increases to float to glass metal surface, by
Do not change in the surface tension of glass metal in itself, so except a small number of king-sized bubble floatings of diameter to meeting behind glass metal surface
Rupture, most of bubble floating gathers together to glass metal surface post-concentration, and stacking is piled into froth bed, the presence one of froth bed
Aspect prevent glass metal in bubble floating efficiency, on the other hand can between glass metal and kiln top combustion heating flame shape
Into one layer of reflection, thermal insulation layer, absorption of the influence glass metal to heat.And by promoting bubble to discharge constantly to glass liquid heating
And rupture, on the one hand because froth bed presence can influence the efficiency of heating surface, on the other hand, in addition to glass metal surface tension, it is limited by
Bubble diameter size, the difference of steep that wall thickness of bubble, want to ensure the alveolate rupture of glass metal surface institute, temperature of glass liquid will add
Heat certainly will will consume the substantial amounts of energy to very high, while prolonged superhigh temperature can also influence the overall longevity of liquid-crystalline glasses kiln
Life.
The content of the invention
The technical problems to be solved by the invention are to provide one kind for the deficiency that above-mentioned prior art is present and be applied to
The composite anti-foaming agent of liquid-crystalline glasses production, is thinned walls and promotes bubbles burst, it is not necessary to improve the highest temperature of liquid crystal kiln
Degree, the row's bubble efficiency for improving glass metal, reduces the influence of liquid-crystalline glasses air blister defect.
The technical scheme that the present invention is used by solution the problem of set forth above for：
A kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses, including bulk composition and solvent composition, the main body into
Dividing includes foamicide titanium-containing compound.
By such scheme, the bulk composition also includes steep that wall reducer tin oxide and/or magnesium sulfate.
By such scheme, the bulk composition also includes solvent efficiency of combustion and optimizes the iron of agent penta 2.
It is further preferred that the bulk composition is by foamicide titanium-containing compound, steep that wall reducer tin oxide and/or sulfuric acid
Magnesium, solvent efficiency of combustion optimization agent penta 2 iron composition.
Further, the mass percent that foamicide is met in the bulk composition of the composite anti-foaming agent is not less than
85%, preferably not less than 90%.
Further, the mass percent that steep that wall reducer is met in the bulk composition of the composite anti-foaming agent is not higher than
10%, preferably no greater than 3%.
Further, the quality percentage that solvent efficiency of combustion optimizes agent is met in the bulk composition of the composite anti-foaming agent
Than being not higher than 5%, preferably no greater than 2%.
By such scheme, flash-point >=38 DEG C of the solvent composition, its bulk composition is dissolved in solvent composition or with solid
Granular state is suspended among solvent composition.Preferably, the solvent composition is one in the oils such as diesel oil, aviation kerosine, heavy oil
Plant or several mixtures in any proportion.
By such scheme, described foamicide titanium-containing compound is mainly the fourth fat (C of metatitanic acid four16H36O4Ti), titanium dioxide
One or more of mixtures in any proportion in, its main function can reduce walls local surface tension, accelerate broken
Bubble.
By such scheme, described steep that wall reducer is mainly tin oxide and magnesium sulfate etc., and it can mainly make in walls
Produce new minute bubbles to reach thinned walls, make easily vanishing for bubble change.
By such scheme, described solvent efficiency of combustion optimization agent is mainly ferrocene (Fe (C5H5)2), its main function
The efficiency of combustion of solvent composition is improved, while the safety in utilization of defoamer bulk composition and solvent composition can also be optimized, and
Ensure liquid-crystalline glasses product F e2O3≤ 150ppm requirement.
By such scheme, the powder material in the bulk composition of the composite anti-foaming agent, its particle diameter must is fulfilled for 100 mesh sieves
Full by, preferably 200 mesh sieves full by.
By such scheme, the mass ratio of the composite anti-foaming agent bulk composition and solvent is 1:2-25, preferably 1:8-21.
The liquid-crystalline glasses product that composite anti-foaming agent of the present invention is mainly applicable, its representative component and its quality percentage contain
Amount：SiO256-66wt%, Al2O314-19wt%, CaO+MgO+BaO+SrO 8-22wt%, B2O31-10wt%, Na2O+
K2O+Li2O≤1wt%, Fe2O3≤150ppm。
Composite anti-foaming agent of the present invention is produced suitable for liquid-crystalline glasses, and its day usage amount is not higher than glass day fusing amount
0.06wt%, temperature in use area is not less than 1350 DEG C.
The major technique design of the present invention：Present invention is generally directed to alumina content height, alkali-free, oxygen in liquid-crystalline glasses product
Change the characteristics of iron control is strict, develop a kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses, can efficiently eliminate fusion process
In swim in the bubble layer on kiln glass metal surface, while again any bad influence can not be produced on liquid-crystalline glasses properties of product.
It is up in liquid-crystalline glasses kiln under more than 1600 DEG C of the condition of high temperature, the fourth fat (C of metatitanic acid four16H36O4Ti) occurs oxygen
Change and high temperature TiO is formed after combustion reaction2(such as foamicide directly uses titanium dioxide TiO to ultrafine dust2Then directly sprayed into solvent,
Directly obtain TiO2Ultrafine dust) descend slowly and lightly in kiln in the steep that wall of bubble layer, due to TiO2Middle Ti-O bond polarities are larger, surface
High-temperature space vaporous water and dissociate its polarization in the kiln of absorption, i.e. H-OH dissociates hydroxyl-OH, the hydroxyl dissociateed-
OH, which enters, to be formed in the glass metal of walls, reduces the viscosity and surface tension in the area, this corresponding when reaching to a certain degree, gas
Bubble is with regard to rupturing；
Meanwhile, in liquid-crystalline glasses production process, steep that wall reducer magnesium sulfate, tin oxide are injected into glass metal bubble
Layer, under the high temperature conditions, decomposed in walls reaction, MgSO4It is decomposed into MgO, SO3、O2, SnO2It is decomposed into SnO and O2,
Tiny micro MgO and SnO is entered in glass metal, and does not have any influence on glass product performance, and SO3、O2In glass metal
Many new minute bubbles are produced in walls to reach the effect of thinned walls, break the easy of walls change with the conditions of
Split.
In addition, because the solvent in the composite anti-foaming agent of the present invention is conventional fuel composition, because penta 2 iron can improve fuel combustion
Efficiency is burnt, exhaust gas volumn after burning is reduced, so introducing a certain amount of penta 2 iron in composite anti-foaming agent, but penta 2 are considered simultaneously
Iron is final to enter in the form of iron oxide or ferrous oxide in glass metal, and liquid-crystalline glasses product is to meet wanting for transmitance index
Ask, the content of iron oxide or ferrous oxide need to be controlled within 150ppm in its product, it is desirable to relatively stricter, so penta 2 iron
Usage amount need to be controlled strictly.
By above-mentioned principle, the present invention have developed the composite anti-foaming agent of suitable liquid-crystalline glasses production, and reaching need not
Improve liquid-crystalline glasses and produce the maximum temperature of kiln, and can speed up glass metal blibbing layer in kiln different temperatures region
Rupture, essentially eliminates froth bed, significantly improves liquid-crystalline glasses production qualification rate.
Compared with prior art, the beneficial effects of the invention are as follows：
First, the present invention develops one kind can promote glass metal blibbing layer in liquid-crystalline glasses production process
The composite anti-foaming agent of rupture, by producing new minute bubbles in the glass metal walls of floating to reach the work of thinned walls
With while by reducing walls local viscosity and surface tension, promoting bubbles burst, liquid crystal kiln need not being improved to reach
Maximum temperature, and can speed up the rupture of the layer of glass metal blibbing in kiln different temperatures region, glass metal improved with this
Row bubble efficiency, reduce liquid-crystalline glasses air blister defect influence.
Second, the chemical composition that composite anti-foaming agent of the present invention is introduced will not be produced in liquid-crystalline glasses product physicochemical property
It is any not influence preferably, and and kiln mode of heating (such as heating of pure electric boosting, electric boosting and pure oxygen composite heating, pure oxygen heating,
The fluxing heating of air, oxygen-enriched combustion-supporting heating) on production liquid-crystalline glasses product influence very little.
Brief description of the drawings
Fig. 1 is the sample-melting device schematic diagram of liquid-crystalline glasses, wherein, 1- sample-melting stoves, 2- platinums bowl, 3- glass melts sample, and 4- melts
Sample bowl supporting table, 5- composite anti-foaming agents spray into pipe, 6- electrically heated rods.
Fig. 2 is that liquid-crystalline glasses melt the poor normative reference sample of sample bubble.
Fig. 3 is that liquid-crystalline glasses melt the medium normative reference sample of sample bubble.
Fig. 4 is that liquid-crystalline glasses melt the preferable normative reference sample of sample bubble.
Embodiment
For a better understanding of the present invention, 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, the component and its weight/mass percentage composition of liquid-crystalline glasses chemical composition used are：SiO2
62wt%, Al2O316wt%, CaO+MgO+BaO+SrO 13wt%, B2O38wt%, Na2O+K2O+Li2O≤1wt%, Fe2O3
≤120ppm.Because mixing heavy oil etc. needs to heat it to reduce its viscosity, increase mobility, while needing at pipeline
Reason, so the solvent composition used in embodiment is to use aviation kerosine as representative illustration.
Embodiment 1-28
A kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses, including bulk composition and solvent composition, each specific group
Into and defoaming effect, the temperature process system of molten sample in initial temperature and target temperature point in as shown in table 1.
To confirm influence of the composite anti-foaming agent of the present invention to liquid-crystalline glasses defoaming effect, for the liquid under same formula
Crystal glass melts sample, and slowly lasting special sample-melting stove is injected into by the composite foamable agent of each embodiment is micro in same condition
In, by identical cooling technique, cool to room temperature, the last bubble residual volume of the molten sample of observation.Detailed process is as follows：
(1) raw material type and consumption of liquid-crystalline glasses are：High-purity 200 grams of silica sand, 56 grams of high-purity alumina powder, magnesia powder
11.8 grams, 11.6 grams of calcium oxide powder, 32 grams of strontium carbonate, 12 grams of strontium chloride；3 grams of calcium sulfate, boric acid is dry 56 grams, standby；It is compound to disappear
Infusion usage amount is 230 milligrams (using 0.06% of raw material weight)；
(2) the temperature process system of molten sample is：The first step, 1200 DEG C are increased to by sample-melting stove, and step is put at this temperature
Suddenly (1) each standby raw material；Second step, 1450 DEG C of initial temperature point is warmed to 100 DEG C/h of programming rates；3rd step,
To after 1450 DEG C, by 100 milligrams of composite anti-foaming agents with being passed through after air atomizing；4th step, continues with 100 DEG C/h of heating speed
Degree is warmed to target temperature point, by remaining 130 milligrams of composite anti-foaming agents with being passed through after air atomizing, and is incubated half an hour；5th
Step, 1450 DEG C are cooled to 100 DEG C/h of cooling rates；6th step, is reached after 1450 DEG C, continues fast cooling to normal temperature, drop
Warm speed is not to damage the prestissimo in the case of equipment；7th step, is cooled to after normal temperature, takes out gas in sample, observation sample
Blister condition, and compared with normative reference sample described in Fig. 2-4, determine defoaming effect.
Table 1
From above-described embodiment and the data of table 1：
First, using composite anti-foaming agent of the present invention, produced for liquid-crystalline glasses, preferable froth breaking effect can be obtained
Really.Wherein, it is 98% that foamicide, which accounts for bulk composition mass ratio, in composite anti-foaming agent, and steep that wall reducer accounts for foamicide mass ratio and is
When 2%, 10 DEG C of the target temperature point of deaeration can be reduced.
Moreover, the composite anti-foaming agent of the present invention produced suitable for liquid-crystalline glasses, for bulk composition, foamicide
Proportion it is bigger, defoaming effect is preferable, as shown in data above, main body shared by foamicide tetrabutyl titanate and titanium oxide
When component ratio is reduced to 87% by 100%, the overall trend of defoaming effect is with respect to variation；In foamicide tetrabutyl titanate
It is more than with bulk composition ratio shared by titanium oxide under conditions of 96%, bulk composition and solvent composition mass ratio in composite anti-foaming agent
It is unobvious to froth breaking influential effect；When being less than 96% in bulk composition ratio shared by foamicide tetrabutyl titanate and titanium oxide,
Bulk composition and solvent composition mass ratio are bigger, and defoaming effect is relatively better.Especially, bulk composition and solvent composition mass ratio
For 1：When 5, even if foamicide is reduced to 87%, moderate deaeration effect can be also obtained, and moderate defoaming effect,
It is also acceptable for actual large-scale production.
In addition, the mass ratio of steep that wall reducer tin oxide and magnesium sulfate in bulk composition is not higher than in composite anti-foaming agent
4%, it can fully optimize defoaming effect；Continue to increase its mass ratio in bulk composition, foamicide can be reduced in bulk composition
In mass ratio, so defoaming effect into reduction trend.And promote penta 2 iron of solvent efficiency of combustion in composite anti-foaming agent, offset
Bubble effect does not have obvious facilitation, and the increase of its mass ratio can cause foamicide and steep that wall reducer in defoamer main body
The reduction of mass ratio in composition, influences defoaming effect；In the production of actual liquid-crystalline glasses, it is contemplated that the solvent in composite anti-foaming agent
Composition usage amount is larger, and efficiency of combustion is also to influence a factor of defoaming effect, so not influenceing glass product quality
In the case of, it can still introduce a certain proportion of penta 2 iron.
Described above is only the preferred embodiment of the present invention, it is noted that come for one of ordinary skill in the art
Say, without departing from the concept of the premise of the invention, some modifications and variations can also be made, these belong to the present invention's
Protection domain.
Claims (10)
1. a kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses, including bulk composition and solvent composition, it is characterised in that institute
Bulk composition is stated including foamicide titanium-containing compound, the mass percent of foamicide is not less than 85% in bulk composition.
2. a kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses according to claim 1, it is characterised in that the master
The mass percent of body composition steep that wall reducer in steep that wall reducer tin oxide and/or magnesium sulfate, bulk composition is also included
Not higher than 10%.
3. a kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses according to claim 1, it is characterised in that the master
Also include the quality hundred that solvent efficiency of combustion in the solvent efficiency of combustion optimization iron of agent penta 2, bulk composition optimizes agent in body composition
Divide ratio not higher than 5%.
4. a kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses according to claim 1, it is characterised in that described molten
Flash-point >=38 DEG C of agent composition, bulk composition is dissolved in solvent composition or is suspended in solid particle state among solvent composition.
5. a kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses according to claim 1, it is characterised in that described molten
Agent composition is one or more of mixtures in any proportion in diesel oil, aviation kerosine, heavy oil.
6. a kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses according to claim 1, it is characterised in that described
Foamicide titanium-containing compound is mainly the fourth fat of metatitanic acid four and/or titanium dioxide.
7. a kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses according to claim 1, it is characterised in that described multiple
The powder material in the bulk composition of defoamer is closed, its particle diameter is no more than 100 mesh.
8. a kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses according to claim 1, it is characterised in that the master
The mass ratio of body composition and solvent composition is 1:2-25.
9. a kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses according to claim 1, it is characterised in that the liquid
The representative component and its weight/mass percentage composition of crystal glass：SiO256-66wt%, Al2O314-19wt%, CaO+MgO+BaO+
SrO 8-22wt%, B2O31-10wt%, Na2O+K2O+Li2O≤1wt%, Fe2O3≤150ppm。
10. the application method for being applied to the composite anti-foaming agent that liquid-crystalline glasses are produced described in claim 1, it is characterised in that described
When composite anti-foaming agent is used for liquid-crystalline glasses and produced, day usage amount be not higher than the 0.06wt% of glass day fusing amount, temperature in use area
It is not less than 1350 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710367290.7A CN107056044A (en) | 2017-05-23 | 2017-05-23 | A kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710367290.7A CN107056044A (en) | 2017-05-23 | 2017-05-23 | A kind of composite anti-foaming agent produced suitable for liquid-crystalline glasses |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1270934A (en) * | 1999-04-21 | 2000-10-25 | 旭硝子株式会社 | Method for glass smelting |
| CN103562147A (en) * | 2011-05-25 | 2014-02-05 | 旭硝子株式会社 | Method for producing granulated bodies, method for producing molten glass, and method for producing glass article |
| CN105948460A (en) * | 2016-06-02 | 2016-09-21 | 郑州旭飞光电科技有限公司 | Production method of liquid crystal glass substrate |
| CN206014646U (en) * | 2016-08-03 | 2017-03-15 | 合肥彩虹新能源有限公司 | A kind of defoaming device for photovoltaic glass kiln |
-
2017
- 2017-05-23 CN CN201710367290.7A patent/CN107056044A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1270934A (en) * | 1999-04-21 | 2000-10-25 | 旭硝子株式会社 | Method for glass smelting |
| CN103562147A (en) * | 2011-05-25 | 2014-02-05 | 旭硝子株式会社 | Method for producing granulated bodies, method for producing molten glass, and method for producing glass article |
| CN105948460A (en) * | 2016-06-02 | 2016-09-21 | 郑州旭飞光电科技有限公司 | Production method of liquid crystal glass substrate |
| CN206014646U (en) * | 2016-08-03 | 2017-03-15 | 合肥彩虹新能源有限公司 | A kind of defoaming device for photovoltaic glass kiln |
Non-Patent Citations (3)
| Title |
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| 乔庆东等: "《碳五烯烃的精细化工利用》", 31 January 2015, 辽宁科学技术出版社 * |
| 田英良等: "《新编玻璃工艺学》", 31 August 2013, 中国轻工业出版社 * |
| 蒋庆哲等: "《表面活性剂科学与应用》", 31 May 2006, 中国石化出版社 * |
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Application publication date: 20170818 |