CN114573227B - Calendaring photovoltaic glass clarifying agent and application thereof - Google Patents
Calendaring photovoltaic glass clarifying agent and application thereof Download PDFInfo
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- CN114573227B CN114573227B CN202210283552.2A CN202210283552A CN114573227B CN 114573227 B CN114573227 B CN 114573227B CN 202210283552 A CN202210283552 A CN 202210283552A CN 114573227 B CN114573227 B CN 114573227B
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- 239000011521 glass Substances 0.000 title claims abstract description 145
- 239000008395 clarifying agent Substances 0.000 title claims abstract description 47
- 238000003490 calendering Methods 0.000 title claims abstract description 31
- 239000010931 gold Substances 0.000 claims abstract description 31
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052737 gold Inorganic materials 0.000 claims abstract description 27
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002844 melting Methods 0.000 claims abstract description 20
- 230000008018 melting Effects 0.000 claims abstract description 20
- 238000002834 transmittance Methods 0.000 claims abstract description 20
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 13
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 13
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 13
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 12
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000006066 glass batch Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 24
- 239000000156 glass melt Substances 0.000 claims description 17
- 239000006025 fining agent Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- 229910001408 cation oxide Inorganic materials 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000000155 melt Substances 0.000 description 10
- 229910000420 cerium oxide Inorganic materials 0.000 description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 9
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 8
- 229910000410 antimony oxide Inorganic materials 0.000 description 8
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000005352 clarification Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000001636 atomic emission spectroscopy Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000005329 float glass Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 210000002435 tendon Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- 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
- C03B13/00—Rolling molten glass, i.e. where the molten glass is shaped by rolling
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to a calendaring photovoltaic glass clarifying agent and application thereof, wherein the glass clarifying agent comprises, by weight, 20-35% of sodium nitrate, 25-35% of ammonium sulfate, 1-1.2% of potassium permanganate and 35-50% of gold mine tailings. Mixing the glass with a dry glass batch according to the weight ratio of (1-1.5): 100, melting the glass, and preparing the photovoltaic glass product by adopting a calendaring method, wherein the prepared glass has high light transmittance. According to the invention, sodium nitrate, ammonium sulfate, potassium permanganate and gold mine tailings are mixed in different proportions to prepare the glass clarifying agent, so that not only is the light transmittance of glass improved, but also the density and elasticity of the glass improved, the defect number is reduced, the glass quality is improved, the used raw materials are environment-friendly, and the recycling of waste materials is realized.
Description
Technical Field
The invention relates to the technical field of preparation of photovoltaic glass, in particular to a calendaring photovoltaic glass clarifying agent and application thereof.
Background
The photovoltaic glass has the function of transmitting and collecting solar rays, one of the important requirements of the photovoltaic glass is that the glass has higher light transmittance, the higher light transmittance is the premise of improving the photoelectric conversion efficiency, and the national standard specifies that the light transmittance T of the photovoltaic glass is more than or equal to 91 percent. The photovoltaic glass is used as a cover plate of the photovoltaic equipment and is exposed at the outermost layer of the equipment, so that the photovoltaic glass has high light transmittance and enough mechanical properties such as impact resistance.
The composition of the photovoltaic glass produced by the calendaring method is greatly different from that of the common float glass, the composition of the photovoltaic glass produced by the calendaring method is simpler than that of the float glass, and the photovoltaic glass produced by the calendaring method has the defects which are inevitably brought into a finished glass product if the glass melt is defective and cannot be compensated because the molding is completed in a short time, so that the prior melting process is required to be perfect and any defects cannot be left in the glass melt, and the photovoltaic glass is required to be extremely high in the melting, clarifying and homogenizing stages so as to improve the quality of the glass.
In addition, the higher the viscosity of the glass melt at high temperature, the less likely the gas in the melt will overflow, and the less likely the glass beads, stones, etc. will break apart, resulting in glass defects after molding, and therefore, it is necessary to try to reduce the viscosity of the melt at high temperature. As the forming speed of the rolled glass is high, a clarifying agent is added in the production process to reduce the high-temperature viscosity, so that the melt is fully homogenized, and the uniformity of the melt is improved, thereby improving the quality of the glass.
In order to ensure the uniformity of the melt, the photovoltaic glass often needs to be additionally added with a fluxing agent and a clarifying agent in the early stage of melting to improve the quality of the melt, and even added with a decoloring agent to improve the light transmittance of the glass. Because of the limitation of the forming method, sodium carbonate with good fluxing effect and clarifier mirabilite cannot be introduced in a large amount, so that other clarifiers must be added in the production of the photovoltaic glass to help the rapid clarification of bubbles and the diffusion of non-uniform bodies in the glass melt. In the prior art, antimony oxide and cerium oxide are mostly adopted as clarifying agents, and are high-quality clarifying agents, but are toxic articles, and are expensive and pollute the environment.
Disclosure of Invention
In order to solve the problems, the invention provides the calendaring photovoltaic glass clarifying agent and the application thereof, and sodium nitrate, ammonium sulfate, potassium permanganate and gold mine tailings are mixed in different proportions to prepare the mixed clarifying agent, so that the mixed clarifying agent not only improves the light transmittance of glass, but also reduces the defect number and improves the quality of glass because other substances contained in the tailings improve the density and the elasticity of the glass, and can be used as the clarifying agent for producing photovoltaic glass.
The invention is realized by the following technical scheme, and the calendaring photovoltaic glass clarifying agent provided by the invention comprises, by weight, 20-35% of sodium nitrate, 25-35% of ammonium sulfate, 1-1.2% of potassium permanganate and 35-50% of gold mine tailings.
Further, the sodium nitrate, the ammonium sulfate and the potassium permanganate are all industrial grade products with the weight content of more than 95 percent.
Further, the gold mine tailings are subjected to precious metal recovery and iron removal, the composition of the gold mine tailings is calculated by cationic oxides, and the chemical composition, the content and the error range of the macrocompounds are as follows:
SiO 2 (35±2)％
Fe 2 O 3 (0.8±0.1)％
Al 2 O 3 (6.50±0.5)％
CaO(25±2)％
MgO(7±0.5)％
SO 2 (1.0±0.1)％
Na 2 O(1.0±0.1)％
K 2 O(1.0±0.1)％
loss on ignition (20.+ -. 5)%
Further, the chemical composition, content and error range of the trace compounds of the gold mine tailings are (measured by atomic emission spectrometry, unit: ppm):
CuO(150±50)
Au 2 O(25±5)
Ag 2 O(25±5)
ZnO(150±50)
SnO(150±50)
Ta 2 O 5 (20±10)
MnO 2 (15.0±5)
Nd 2 O 3 (10.0±5)
further, the gold mine tailings are uniformly mixed, dried and processed until the particle size is 0.10mm, and the calendaring photovoltaic glass clarifying agent is obtained by uniformly mixing sodium nitrate, ammonium sulfate and potassium permanganate according to the weight percentage.
Further, the weight ratio of the calendared photovoltaic glass clarifying agent to the dry glass batch is (1-1.5): 100 when the calendared photovoltaic glass clarifying agent is used for glass clarification.
The invention also aims to provide an application of the calendaring photovoltaic glass clarifying agent in preparing calendaring photovoltaic glass, which specifically comprises the following steps:
dry basis glass batch and the glass fining agent were mixed at a ratio of 100: (1-1.5) and then feeding the mixture into a melting furnace for melting, and obtaining the high-performance photovoltaic glass product after melting.
Further, after the calendaring photovoltaic glass clarifying agent is mixed with a dry-based glass batch and melted, the transmittance T of the obtained photovoltaic glass sample is 91.5% -91.7%; the viscosity of the obtained photovoltaic glass melt at 1006 ℃ is 10 2.99 Pa.s, corresponding to a viscosity of 10 at 1450 DEG C 0.84 Pa.s, corresponding viscosity at 1510 ℃ of 10 0.72 Pa·s; the number of visible bubbles in each square meter of the obtained photovoltaic glass sample is 5, and the number of glass ribs is 6; the density of the obtained photovoltaic glass sample is 0.2494g/cm 3 Elastic modulus is 827×10 8 Pa。
The invention has the following beneficial effects:
the invention fully utilizes the gold mine tailings, and the constant components in the gold mine tailings comprise SiO 2 、Fe 2 O 3 、Al 2 O 3 、CaO、MgO、Na 2 O、K 2 O、SO 2 These oxides are the basic components of the glass and melt into the glass structure during the glass melting process. The gold mine tailings also contain trace amounts of CuO and Au 2 O、Ag 2 O、ZnO、SnO、Ta 2 O 5 、MnO 2 、Nd 2 O 3 . Wherein, cuO, au 2 O、Ag 2 The content of the noble metal oxides is very small, and the noble metal oxides are fused into the glass structure, so that the structure and the performance of the glass are not affected. ZnO, snO, ta 2 O 5 The glass flux is a good glass flux, can reduce the high-temperature viscosity of glass melt at high temperature, and can promote the clarification and homogenization of glass; mnO (MnO) 2 、Nd 2 O 3 Is an excellent glass colorant and can play a role in physical decolorization.
According to the invention, gold mine tailings, sodium nitrate, ammonium sulfate and potassium permanganate are mixed according to a specific proportion, the prepared glass clarifying agent can effectively improve the light transmittance of the photovoltaic glass, reduce the high-temperature viscosity of glass melt, reduce macroscopic defects such as glass ribs and bubbles, and improve the density and elastic modulus of the photovoltaic glass.
Detailed Description
In order to further describe the technical means and effects adopted by the invention to achieve the preset aim, the following is a detailed description of a specific implementation and effects of a calendaring photovoltaic glass clarifier according to the invention in combination with a preferred embodiment.
The invention relates to a calendaring photovoltaic glass clarifying agent, which belongs to a mixed clarifying agent, and comprises the following basic components in percentage by weight:
wherein, the sodium nitrate uses industrial grade sodium nitrate with the content of more than 98 percent, and the execution standard is GB/T4553-2016; the ammonium sulfate is industrial grade ammonium sulfate (wherein the dry nitrogen content is more than or equal to 20.5 percent), and the execution standard is GB/T535-2020; the potassium permanganate uses industrial potassium permanganate with the content of more than 99.1 percent, and the execution standard is GB/T1608-2017; the composition of the gold mine tailings is calculated by cation oxide, and the chemical composition, the content and the error range of the major compounds are as follows:
SiO 2 (35±2)％
Fe 2 O 3 (0.8±0.1)％
Al 2 O 3 (6.50±0.5)％
CaO(25±2)％
MgO(7±0.5)％
SO 2 (1.0±0.1)％
Na 2 O(1.0±0.1)％
K 2 O(1.0±0.1)％
loss on ignition (20.+ -. 5)%
The chemical composition, content and error range of the trace compounds of the gold mine tailings are (measured by atomic emission spectrometry, unit: ppm):
CuO(150±50)
Au 2 O(25±5)
Ag 2 O(25±5)
ZnO(150±50)
SnO(150±50)
Ta 2 O 5 (20±10)
MnO 2 (15.0±5)
Nd 2 O 3 (10.0±5)
the preparation method of the glass clarifying agent comprises the following steps: and (3) processing the uniformly mixed and dried gold mine tailings until the particle size is 0.10mm, and uniformly mixing with sodium nitrate, ammonium sulfate and potassium permanganate according to the weight percentage to obtain a powdery mixture, namely the calendaring photovoltaic glass clarifying agent.
The use method of the glass clarifying agent comprises the following steps: the dry glass batch and the glass clarifier of the invention are mixed according to the weight ratio of 100: (1-1.5) and then feeding the mixture into a melting furnace for melting, and obtaining the high-performance photovoltaic glass product after melting.
The major component in the gold mine tailing composition comprises SiO 2 、Fe 2 O 3 、Al 2 O 3 、CaO、MgO、Na 2 O、K 2 O、SO 2 These oxides are the basic components of the glass and naturally melt into the glass structure. The gold mine tailings also contain trace amounts of CuO and Au 2 O、Ag 2 O、ZnO、SnO、Ta 2 O 5 、MnO 2 、Nd 2 O 3 . Wherein CuO, au 2 O、Ag 2 The content of the noble metal oxides is very small, and the noble metal oxides are fused into the glass structure, so that the structure and the performance of the glass are not affected. ZnO, snO, ta 2 O 5 The glass flux is a good glass flux, can reduce the high-temperature viscosity of glass melt at high temperature, and can effectively promote the clarification and homogenization of glass; mnO (MnO) 2 、Nd 2 O 3 Is an excellent glass colorant and can play a role in physical decolorization.
And (3) measuring using effect:
(1) the use of the glass clarifying agent improves the light transmittance of the glass
One of the important requirements of photovoltaic glass is that the glass has higher light transmittance, which is a precondition for improving photoelectric conversion efficiency. The light transmittance T of the photovoltaic glass specified by the national standard is more than or equal to 91 percent. The main oxide affecting the light transmittance in the glass composition is iron oxide, fe 2+ 、Fe 3+ The green and yellow-green color generated by the ions affects the light transmittance of the glass. While the gold mine tailing composition contains a small amount of MnO 2 、Nd 2 O 3 Manganese dioxide MnO 2 Introduced Mn 3+ Nd introduced by ion and neodymium trioxide 3+ The ions generate mauve and the yellow-green generated by the iron is complementary color, thereby playing a role in decoloring. Through experiments, 1 to 1.2 percent of potassium permanganate is additionally added into the composite clarifying agent, so that the glass is transparentThe light efficiency can reach a maximum value.
With a rolled glass formulation of the same composition (wherein Fe 2 O 3 The content is 0.043 percent), the transmittance of the melted sample is measured, in the experiment, sample number 1# is that four glass samples with the thickness of 5mm are manufactured by melting single clarifying agent antimony oxide with high quality; sample No. 2 was four 5mm thick glass samples prepared by melting the same with the single clarifier cerium oxide, and sample No. 3 was four 5mm thick glass samples prepared by comparative melting experiments with the mixed clarifier of the present invention, and the measurement results are shown in table 1 below.
TABLE 1 transmittance of glass
From the measured data, it can be seen that the transmittance of the fining glass according to the present invention is significantly improved.
(2) The glass clarifying agent reduces the high-temperature viscosity of glass melt
The higher the viscosity of the glass melt at high temperatures, the less likely bubbles in the melt will spill out, and the less likely glass beads, stones, etc. will break apart, leading to glass defects after molding, and therefore, it is necessary to try to reduce the high temperature melt viscosity. As the forming speed of the rolled glass is high, a clarifying agent is added in the production process to reduce the high-temperature viscosity of the glass melt, so that the melt is easier to homogenize, and the uniformity of the melt is improved, thereby improving the quality of the glass.
A rolled glass formulation of the same composition (wherein Fe 2 O 3 The content is 0.043%) and a high-temperature viscosity comparison experiment is carried out. In Table 2 below, sample No. 1 is a sample obtained by melting antimony oxide as a relatively high-quality single clarifier, sample No. 2 is a sample obtained by melting cerium oxide as a single clarifier, sample No. 3 is a sample obtained by melting a mixed clarifier of the present invention, and the measurement results of the high-temperature viscosity measurement are shown in Table 2 below.
TABLE 2 high temperature viscosity of glass melts
The clarifying agent of the invention plays a role in fluxing and clarifying at low temperature Duan Xiaosuan sodium, and the medium-temperature and high-temperature sections of ammonium sulfate and ZnO, snO, ta contained in gold mine tailings 2 O 5 Plays a role in fluxing and clarifying because ZnO, snO, ta contained in the gold mine tailings 2 O 5 The cations of the oxides have smaller ionic radius, and play a role in reducing the high-temperature viscosity of the glass liquid. The high temperature viscosimetry data for the glass melt are shown in Table 2. As can be seen from the measurement data, the high-temperature viscosity of the sample corresponding to the mixed clarifying agent provided by the invention is obviously lower than that of the sample corresponding to the clarifying agent respectively prepared from antimony oxide and cerium oxide, so that the melt has a good clarifying effect.
(3) The clarifier can reduce macroscopic defects such as glass tendon bubbles in glass
The glass produced by the calendaring method cannot be compensated for because the shaping is completed in a short time, if the glass melt is defective, and these defects are necessarily brought into the finished glass product, so that the prior melting process is required to be perfect, and any defects cannot be left in the glass melt. Also because of the limitation of the forming method, sodium carbonate with good fluxing action and clarifier mirabilite can not be introduced in a large quantity, so that other clarifiers must be added in the production of the glass to help the rapid clarification of bubbles and the diffusion of non-uniform bodies in the glass melt.
In this experiment, several high quality clarifiers were selected for the melting comparison experiment, and the measurement results of the melted glass samples are shown in table 1 below.
TABLE 3 statistics of glass defects
| Sample wafer number | Clarifying agent composition | Number of visible bubbles/m 2 | Glass rib number/m 2 |
| 1# | Antimony oxide (Sb) 2 O 3 ) | 3 pieces of | 4 strips |
| 2# | Cerium oxide (CeO) 2 ) | 8 pieces of | 6 strips |
| 3# | Clarifying agent of the invention | 5 | 6 strips |
| 4# | No clarifying agent is added | 180 pieces | 25 strips |
Comparing the sample numbers 1#, 2#, 3# of the fining agent melted glass samples in table 3 with the number 4# of the fining agent not added, the comparison result clearly shows that the number 4# of the fining agent not added has more bubbles and more glass ribs, and no qualified glass can be produced. However, the glass quality of the melted samples of the clarifying agents No. 1, no. 2 and No. 3 is greatly improved, which proves that the clarifying agent can be fully popularized and used.
(4) The clarifier can improve density and elastic modulus of glass
The photovoltaic glass is used as a cover plate of the photovoltaic equipment and is exposed at the outermost layer of the equipment, so that the photovoltaic glass has high light transmittance and enough mechanical properties such as impact resistance. The mechanical properties such as density and elastic modulus were measured for sample numbers 1#, 2#, and 3# glass samples, and the results are shown in table 4 below.
TABLE 4 Density and elastic modulus of glass
| Sample wafer number | Clarifying agent composition | Density (g/cm) 3 ) | Elastic modulus (Pa/10) 8 ) |
| 1# | Antimony oxide | 0.2482 | 807 |
| 2# | Cerium oxide | 0.2481 | 810 |
| 3# | Clarifying agent of the invention | 0.2494 | 827 |
As can be seen from the measurement results, the density and the elastic modulus of the glass prepared by melting the clarifierThe density of the glass is obviously improved. This is because the use of gold mine tailings introduces CuO, au into the glass composition 2 O、Ag 2 O、ZnO、SnO、Ta 2 O 5 、MnO 2 、Nd 2 O 3 . The metal ions in the oxides have larger molecular mass, so that the density of the glass can be improved, the improvement of the density of the glass means that the microstructure of the glass is more compact, and the mechanical property and the impact resistance of the glass are improved. Al in addition in gold mine tailings 2 O 3 The content of Al in silicate glass series is about 6.50% 2 O 3 The influence on the elastic modulus is the greatest, so Al 2 O 3 The content is improved greatly, and the elastic modulus of the glass is improved greatly.
(5) The clarifier is beneficial to environmental protection and reutilization of tailing waste
The clarifying agent antimony oxide and the clarifying agent cerium oxide are both high-quality clarifying agents, but antimony oxide is a toxic substance, is high in price and pollutes the environment; cerium oxide is extremely expensive rare earth metal, and the clarifier of the invention uses nearly half of gold mine tailings, has extremely low cost and plays a role in waste utilization, and the produced clarifier is used for melting calendared photovoltaic glass to be completely qualified, thus being worthy of popularization and application.
The above embodiments of the present invention are merely examples, and the present invention is not limited in any way, and any simple modification, equivalent changes and modification made to the above embodiments according to the technical principles of the present invention without departing from the scope of the technical solutions of the present invention will still fall within the scope of the technical solutions of the present invention.
Claims (6)
1. The calendaring photovoltaic glass clarifying agent is characterized by comprising, by weight, 20-35% of sodium nitrate, 25-35% of ammonium sulfate, 1-1.2% of potassium permanganate, 35-50% of gold mine tailings,
the gold mine tailings have the following chemical composition, content and error range of major compounds calculated by cation oxides:
the chemical composition, content and error range of the trace compound of the gold mine tailings are as follows, the unit is ppm:
2. the calendaring photovoltaic glass clarifying agent according to claim 1, wherein the calendaring photovoltaic glass clarifying agent is obtained by uniformly mixing gold mine tailings, drying, processing to a particle size of 0.10mm and uniformly mixing sodium nitrate, ammonium sulfate and potassium permanganate according to weight percentage.
3. The calendered photovoltaic glass fining agent according to claim 1, wherein the weight ratio of calendered photovoltaic glass fining agent to dry glass batch material when used in glass fining is (1-1.5) 100.
4. Use of the calendered photovoltaic glass fining agent according to claim 1 in the preparation of calendered photovoltaic glass.
5. Use of a calendered photovoltaic glass fining agent according to claim 4 in the preparation of calendered photovoltaic glass wherein the dry glass batch and the glass fining agent are mixed at a ratio of 100: (1-1.5) and then feeding the mixture into a melting furnace for melting, and preparing the high-performance photovoltaic glass product by a calendaring method.
6. The use of the calendered photovoltaic glass fining agent according to claim 5 in the preparation of calendered photovoltaic glass, wherein the transmittance T of the prepared calendered photovoltaic glass article is 91.5% to 91.7%; the high-temperature viscosity of the photovoltaic glass melt is 10 2.99 Pa.s, corresponding to a viscosity of 10 at 1450 DEG C 0.84 Pa.s, corresponding to a viscosity of 10 at 1510 DEG C 0.72 Pa·s; the number of bubbles per square meter of the obtained calendared photovoltaic glass product is 5, and the number of glass ribs is 6; the density of the obtained rolled photovoltaic glass sample is 0.2494g/cm 3 Elastic modulus is 827×10 8 Pa。
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