CN103951186B - A kind of batch composition and application thereof of producing high ferrous glass - Google Patents

Abstract

The invention provides a kind of batch composition producing high ferrous glass, in frit, add simple substance Si, carbon dust and vitriol etc.; Present invention also offers and producing the concrete grammar in sheet glass with this batch composition.The glass ferrous content major part more than 31% adopting formula of the present invention to produce reaches more than 37%, can keep the character that glass is basic, and production technique is simple, and raw material is cheap.

Description

Batch component for producing high ferrous glass and its application

technical field

The invention relates to the field of soda-lime-silica glass, in particular to a batch component for producing high-ferrous-iron glass and its application.

Background technique

The best choice for building or automotive windshields is energy-saving glass. In order to make the glass energy-saving, it is usually coated with a low-reflection film on the surface of the glass, which increases the production cost of the glass, and the low-reflection film coated with time will Prolonged performance will attenuate or fall off. Therefore, it will be the best choice if the glass body can have energy-saving performance.

To make glass have energy-saving performance, it is necessary to make glass able to block infrared rays, and the cheapest substance in glass that can block infrared rays is ferrous iron, because iron is a natural impurity brought in by glass raw materials, but due to the melting process of glass kiln Limitation, about 80% of iron presents a high price state of +3 in the glass.

The US004792536 (TRANSPARENTINFRAREDABSORBINGGLASSANDMETHODOFMAKING) patent of PPG Industries Ohio Company discloses a melting furnace for producing high ferrous glass, which physically divides several processes in the glass melting process, and the melting, clarification and homogenization of the glass are respectively It is carried out in different parts, and the glass is decompressed and clarified by vacuum method, so that the reducibility of glass melting can be easily increased without affecting other processes, thereby increasing the ferrous content in the glass, but realizing This patent requires a special kiln structure, which is inconvenient to build and operate. The US003652303 (HEATABSORBINGBLUESODA-LIME-SILICAGLASS) patent of PPG industry Ohio company also discloses the method for producing high ferrous content glass by the method for adding tin, and the add-on of tin is at 0.1～15wt%, although can significantly improve the ferrous content of glass content, but the addition of tin changes the original composition elements of the glass and affects the basic properties of the glass, and the price of tin is very expensive.

Therefore, there is an urgent need for a convenient and inexpensive method for increasing the ferrous content in soda-lime glass without affecting the basic properties of the glass.

Contents of the invention

In order to increase the ferrous content in soda-lime glass without affecting the basic properties of the glass, the present invention designs a composition capable of producing high-ferrous glass.

The first aspect of the present invention is to provide a kind of batch material component that produces high ferrous iron glass, and this batch material component comprises the following composition accounting for glass weight percentage calculation:

65～80% SiO ₂ ,

0～10MgO,

5～15%CaO,

10～18Na ₂ O,

0～5%K ₂ O,

0.01～1.9% Fe ₂ O ₃ ,

0.1-0.5% elemental silicon (Si),

0.02-0.06% carbon powder (C), and

0.5-0.6% _SO3 ,

And CaO ₊ MgO is 5-15%, and Na2O ₊ K2O is 10-20%.

The above composition also contains 0-5% of Al ₂ O ₃ based on the weight percentage of the glass.

Preferably, SiO ₂ accounts for 72% by weight of the glass, Al ₂ O ₃ accounts for 1% by weight of the glass, MgO accounts for 4% by weight of the glass, CaO accounts for 8% by weight of the glass, and Na ₂ O accounts for 8% by weight of the glass 13%, K ₂ O 0.5% by weight of glass, Fe ₂ O ₃ 1% by weight of glass, Si 0.1-0.3% by weight of glass, C 0.02-0.06% by weight of glass, SO ₂ The weight percentage of the glass is 0.5-0.6%.

Optimally, SiO ₂ accounts for 72% by weight of the glass, Al ₂ O ₃ accounts for 1% by weight of the glass, MgO accounts for 4% by weight of the glass, CaO accounts for 8% by weight of the glass, and Na ₂ O accounts for 8% by weight of the glass The percentage is 13%, K ₂ O is 0.5% by weight of the glass, Fe ₂ O ₃ is 1% by weight of the glass, Si is 0.3% by weight of the glass, C is 0.02% by weight of the glass, SO ₂ is 0.02% by weight of the glass The percentage by weight is 0.5%.

The elemental silicon (Si) is derived from common chemical raw materials or wastes produced during the cutting of silicon ingots in the solar energy industry;

The carbon powder (C) has many sources, including coal dust, slag, coke and the like;

The sulfur trioxide (SO ₃ ) is derived from sulfates, including Glauber's salt or gypsum and the like.

Among the batch components for producing high-ferrous-ratio glass, the simple Si can be a chemical raw material, or industrial silicon waste produced in the process of silicon ingot processing.

Carbon and sulfate can play an important role in the melting process of glass. They cooperate with each other to adjust the melting and clarification of glass. A specific amount of carbon corresponds to a specific amount of sulfate in order to achieve the best melting and clarification. , the following chemical reactions exist in the melting process of glass:

SO ₄ ^2- +Fe ₂ O ₃ +C->Fe _x O _y +SO ₂ +CO/CO ₂

The amount of carbon and sulfate can affect the content of ferrous iron in the glass, but if the ferrous content of the glass is increased by increasing the amount of carbon, on the one hand, it will cause sulfur carbon coloring in the glass and make the glass appear brown. Excessive carbon will continue to react with oxygen to form CO ₂ bubbles after the glass is melted and clarified. The solubility of CO ₂ in glass is very low, which causes the CO ₂ bubbles formed by excess carbon to remain in the finished glass, so , It is impossible to increase the ferrous content of glass by adding carbon.

During the melting process of glass batch materials in a flame furnace, the oxidation-reduction properties of the flame will also affect the ferrous content in the glass. The ferrous content of the glass can be increased by increasing the reducibility of the flame, but in order to reduce the fuel consumption, it is necessary to The fuel is fully burned, so that the reduction of the flame cannot be greatly improved. The oxygen content in the exhaust gas after combustion is about 2%, and the lower oxygen content will cause secondary bubbles to appear during the glass melting process. The ferrous iron content in the glass produced by the traditional constant flame furnace accounts for about 18-21% of the total iron content.

The use of elemental silicon to adjust the ferrous content of glass is based on the physical and chemical properties of silicon. When elemental silicon is stored in the air for a long time, a 50-80nm SiO ₂ film will be formed on the surface. This film can protect the glass during the melting process. The protective effect of elemental silicon prevents elemental silicon from being oxidized in a low temperature stage. In the high temperature stage of glass melting, the glass is already in the clarification stage, and the temperature has reached the melting point of elemental silicon (over 1410°C). Iron has the following reaction, which greatly increases the ferrous content in the glass, and does not increase the bubble defects of the glass due to the formation of new gas products.

Si+Fe ₂ O ₃ →FeO+SiO ₂

The second aspect of the present invention is to provide a kind of application of the batch component of producing ferrous glass in the production of glass plate, the specific method of producing glass plate is as follows:

1. The batch components of the above-mentioned production high ferrous glass are mixed in proportion;

2. The uniformly mixed raw materials are put into the kiln, heated to 1300-1650°C, and become liquid glass, and then eliminate the bubbles in the glass;

3. Cooling the glass liquid (air cooling or natural cooling), the temperature of the glass liquid is 1000-1300 ℃;

4. The cooled glass liquid passes through a narrow groove flow channel on the liquid metal tin, and is pulled into a glass plate with a thickness of 1 to 10 mm by drawing equipment; the best is 4 mm.

5. Cooling and annealing the glass plate to form a glass plate.

In the application of the batch material components for the production of high ferrous glass in the production of glass plates, the elemental silicon in the batch materials is derived from common chemical raw materials or waste generated during the cutting of silicon ingots in the solar energy industry; the carbon powder is derived from Coal powder, slag or coke; SO ₃ comes from Glauber's salt or gypsum.

The ferrous content of the glass produced by adopting the formula of the invention is more than 31% and most of them are more than 37%, which can maintain the basic properties of glass, has simple production process and cheap raw materials.

detailed description

The implementation of the present invention will be described in detail below in conjunction with the embodiments of the present invention. The following embodiments are implemented under the premise of the technical solution of the present invention, and detailed implementation is provided, but the protection scope of the present invention is not limited to the following Example.

Embodiment 1 - Embodiment 6

Prepare the soda-lime-silica glass batch material (by weight percentage) according to the ratio in Table 1

Table 1 Example 1-6 Soda-lime-silica glass batch ratio table

The preparation process is as follows:

1. The batch components of the above-mentioned production high ferrous glass are mixed in proportion;

2. The uniformly mixed raw materials are put into the kiln, heated to 1300-1650°C, and become liquid glass, and then eliminate the bubbles in the glass;

3. Cooling the glass liquid (air cooling or natural cooling), the temperature of the glass liquid is 1000-1300 ℃;

4. The cooled glass liquid passes through a narrow groove flow channel on the liquid metal tin, and is pulled into a 4mm thick glass plate by pulling equipment;

5. Cooling and annealing the glass plate to form a glass plate.

Embodiment 7: the mensuration of iron content in the sample (the sample is the glass that preceding embodiment produces)

The content of ferrous iron in the glass is to measure the transmittance of the sample at a wavelength of 1060nm with a spectrophotometer, and enter the following formula to calculate the optical density:

Optical density OD＝Log ₁₀ T ₀ /T

T ₀ =100 - estimated reflection loss ≈92

T = transmittance at 1060nm

Ferrous content (Fe ²⁺ )=110×optical density/(glass thickness (in mm)×total iron (in Fe ₂ O ₃ ) weight %)

Example Fe ²⁺ (%) 1 31.2 2 38.4 3 47.1 4 39.5 5 37.1 6 38.9

Note: Fe ²⁺ in the table refers to the ratio of ferrous iron to total iron.

The above examples are preferred implementations of the present invention, but the implementation of the present invention is not limited by the above examples. Any other modifications made without departing from the spirit and principle of the present invention shall be considered within the protection scope of the present invention.

Claims (8)

1. a batch component of producing high ferrous iron glass, it is characterized in that, this batch component, comprises and accounts for the following composition of glass weight percentage calculation: 65～80% SiO ₂ , 0～10%MgO, 5～15%CaO, 10～ ₁₈ %Na2O, 0～5%K ₂ O, 0.01～1.9% Fe ₂ O ₃ , 0.1-0.5% elemental silicon, 0.02-0.06% toner, and 0.5-0.6% _SO3 , And CaO+MgO is 5-15%, Na ₂ O+K ₂ O is 10-20%; Wherein, the _SO3 is derived from Glauber's salt or gypsum. 2 . A batch component for producing high-ferrous-iron glass according to claim 1 , characterized in that the batch component further comprises 0-5% Al ₂ O ₃ by weight percentage. 3. a kind of batch component of producing high ferrous ferrous glass according to claim 2, is characterized in that, this batch component, is the following composition that accounts for glass weight percentage calculation: 72% SiO ₂ , 1% Al ₂ O ₃ 4% MgO, 8% CaO, ₁₃ %Na2O, _0.5 %K2O, 1% Fe ₂ O ₃ , 0.1～0.3% elemental silicon, 0.02-0.06% carbon powder, and _0.5-0.6 % SO3. 4. a kind of batch composition of producing high ferrous iron glass according to claim 3, is characterized in that, this batch composition, is the following composition that accounts for glass weight percent calculation: 72% SiO ₂ , 1% Al ₂ O ₃ 4% MgO, 8% CaO, ₁₃ %Na2O, _0.5 %K2O, 1% Fe ₂ O ₃ , 0.3% elemental silicon, 0.02% toner, and 0.5% _SO3 . 5. according to claim 1-4 arbitrary described a kind of batch material component of producing high ferrous glass, it is characterized in that, described elemental silicon originates from common chemical raw material or solar industry silicon ingot cutting process produces waste. 6. A batch component for producing ferrous ferrous glass according to any one of claims 1-4, characterized in that said carbon powder is derived from coal powder, slag or coke. 7. the application of a batch component in the production of glass plates as described in any one of claims 1-4, is characterized in that, the specific method of producing glass plates is as follows: A mixes the batch components of the above-mentioned production high ferrous glass in proportion; B The uniformly mixed raw materials are put into the kiln, heated to 1300-1650°C, and become liquid glass, and then eliminate the bubbles in the glass; C Cool the molten glass so that the temperature of the molten glass is between 1000 and 1300°C; D. The cooled glass liquid flows to the liquid metal tin through a narrow groove, and is pulled into a glass plate with a thickness of 1 to 10 mm by drawing equipment; E cooling and annealing the glass plate to form a glass plate. 8. the application of a batch material component for producing high ferrous glass according to claim 7 in the production of glass plates, is characterized in that, in the described batch material, elemental silicon originates from common chemical raw materials or solar energy industry Waste produced during the cutting of silicon ingots; carbon powder is derived from coal dust, slag or coke.