RU2555741C1 - Charge for obtaining container glass - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: charge contains, wt %: quartz sand 31.25-51.72; kaolin 1.48-21.66; sulphate-containing ash 16.04-22.72; limestone 7.02-16.47; dolomite 0-4.57; portafer 0-1.04; chromium (III) oxide 0.07-0.37; titanium (IV) oxide 0.1-1.01; manganese (IV) oxide 0.01-1.02; potassium nitrate 0.02-0.27; monosubstituted sodium phosphate 0.01-0.16; barium hydroxide 0.01-0.09; sulphite liquor 8.90-9.10; birch coal 1.22-1.74. Sulphate-containing ash and sulphite liquor are wastes of trinitrotoluene production.

EFFECT: extension of the raw material base and reduction of glass production cost.

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Description

The invention relates to compositions of mixtures for producing bulk-colored glass containers and can be used for the manufacture of bottles for bottling grape, fruit and champagne wines, mineral water, as well as other containers for canned food. Glass can also be used for packaging cosmetics and perfumes.

The basis of the chemical composition of silicate industrial glasses - window, architectural, construction, packaging and others - are various combinations of oxides of Na ₂ O, CaO, SiO ₂ . To reduce the tendency to crystallization and increase the chemical resistance of glasses, magnesium and aluminum oxides are additionally introduced into their composition. It has now been established that container glass should contain up to 3-3.5% MgO and up to 3-4% Al ₂ O ₃ , which favorably affects the chemical resistance of the glass (Glass. Edited by N.M. Pavlushkin. - M.: Stroyizdat, 1973, p.375).

So, for example, in France, container glass of the following composition was developed, wt.%: SiO ₂ - 70.68; Al ₂ O ₃ - 3.20; Fe ₂ O ₃ - 0.32; CaO - 0.79; MgO - 2.20; Na ₂ O - 14.16; K ₂ O - 0.60; SO ₃ - 0.29 (Glass. Edited by N.M. Pavlushkin. - M.: Stroyizdat, 1973, p.376, table 5). However, such a glass material has insufficient strength and can only be used for narrow-necked containers. In addition, the temperature in the maximum zone of a glass melting furnace during the melting of such glass, as a rule, should be quite high, not lower than 1450-1480 ° C. Moreover, it is recommended, depending on the quality of the refractory materials used, to adhere to the upper limit and, if possible, increase it to 1500-1530 ° C. All this leads to an increase in energy costs (Glass. Edited by N.M. Pavlushkin. - M.: Stroyizdat, 1973, p. 377).

Container glass composition, wt.%: SiO ₂ 65.00-73.40; Al ₂ O ₃ 1.10-5.50; Fe ₂ O ₃ 0.20-2.50; Na ₂ O ₃ 10.00-14.00; K ₂ O 0.03-0.35; CaO 8.0-13.00; MgO 0.06-1.20; TiO ₂ 0.04-1.40; Cr ₂ O ₃ 0.10-0.50; SO ₃ 0.07-0.50; BaO 0.01-0.10; MnO 0.01-1.25; P ₂ O ₅ 0.01-0.10 is the closest analogue (prototype) of the present invention (Container glass. Rotach V.A., Ioffe V.Ya., Varzin V.F. et al. RF Patent No. 2169711 of 04/27 .1999. IPC 7 C03C 3/087. Application No. 99109209/03. Published on June 27, 2001). To prepare the mixture using this method, the following traditional charge materials are used: silica sand, soda ash, alumina, gypsum, limestone, carbon, portachrome (Cr ₂ O ₃ ), portafer (Fe ₂ O ₃ ), manganese paste (MnO ₂ ), dioxide titanium, potassium nitrate, magnesium oxide, tripolyphosphate. The disadvantage of this composition is the use of an expensive component - soda. In order to save raw materials, such as alumina, quartz sand, magnesium oxide, portafer, etc. this method of manufacturing glass melt provides an option for the preparation of a mixture using basalt of the following composition, wt.%: SiO ₂ 48-50; Al ₂ O ₃ 14-15; Fe ₂ O ₃ 4-5; CaO 8-8.5; MgO 5-5.5; Na ₂ O 12.3-13.50; K ₂ O 0.01-0.15; FeO 0.1-0.4; SO ₃ 0.05-0.20; MnO ₂ 0.01-0.10; TiO ₂ 1-2; P ₂ O ₅ 0.1-0.2. However, since basalt is one of the hardest natural minerals, its grinding will require the use of special equipment and increased energy consumption.

The technical result to which the invention is directed is to reduce the material and energy costs of container glass production, to expand the raw material base in the glass industry, to utilize TNT waste while preserving the quality of the resulting glass melt.

The technical result is achieved by the fact that in the mixture to obtain container glass composition, wt.%: SiO ₂ 65,00-73,40; Al ₂ O ₃ 1.10-5.50; Fe ₂ O ₃ 0.20-2.50; Na ₂ O 10.00-14.00; K ₂ O 0.03-0.35; CaO 8.0-13.00; MgO 0.06-1.20; TiO ₂ 0.04-1.40; Cr ₂ O ₃ 0.10-0.50; SO ₃ 0.07-0.50; BaO 0.01-0.10; MnO 0.01-1.25; P ₂ O ₅ 0.01-0.10, including raw materials for introducing glass-forming oxides into the glass composition: acidic (SiO ₂ , Al ₂ O ₃ ), alkaline earth (CaO, MgO, BaO), alkaline (Na ₂ O, K ₂ O) and auxiliary (TiO ₂ , Cr ₂ O ₃ , Fe ₂ O ₃ , SO ₃ , MnO, P ₂ O ₅ ), TNT waste products - sulfate-containing ash and sulfite liquor are used as a supplier of alkaline oxide - sodium oxide in the following the ratio of components, wt.%: quartz sand 31.25-51.72; kaolin 1.48-21.66; sulfate-containing ash 16.04-22.72; limestone 7.02-16.47; dolomite 0-4.57; Portafer 0-1.04; chromium oxide (III) 0.07-0.37; titanium oxide (IV) 0.1-1.01; manganese (IV) oxide 0.01-1.02; potassium nitrate 0.02-0.27; monosubstituted sodium phosphate 0.01-0.16; barium hydroxide 0.01-0.09; sulfite liquor 8.90-9.10; coal birch 1.22-1.74.

In the glass industry, sodium carbonate or sodium sulfate is used to introduce sodium oxide into the glass composition. In this regard, there are two options for glass blends containing sodium sulfate.

Sulphate charge - sodium oxide in whole or in an amount of more than 25% is introduced into the charge using sodium sulfate (Chemical technology of glass and glass metals. Artamonova M.V., Aslanova M.S., Buzhinsky I.M. et al. Ed. N .M. Pavlushkina, - M., Stroyizdat, 1983, p. 106). However, the process of making glass from a sulfate charge becomes longer and requires higher temperatures. In this case, in order to accelerate the process of silicate formation and reduce the temperature, pre-decomposition of sodium sulfate to sodium oxide is resorted to. For this, a certain amount of coal or charcoal, wood chips or shavings is introduced into the glass charge (Glass technology. Butt L.M., Polyak V.V., - M, State Publishing House of Literature on Construction, Architecture and Construction, 1960, p.64) or any organic substances (PN Grigoriev, MA Matveev. Soluble glass (preparation, properties and applications). - M .: State ed. Of literature on building materials, 1956, 444 p.) Acting as sodium sulfate reducing agents. A method of producing glass from a sulfate charge is resorted to if it is necessary to reduce the cost of production, since the original sodium sulfate is a cheap substitute for soda. The disadvantages of producing glass by the sulfate method are the complexity of the process, the need to use additional carbon fuel and a decrease in the quality of the products obtained.

Soda-sulfate charge - a charge currently used to produce glass. In this case, 80-95% sodium oxide is introduced into the molten glass using soda ash, the rest with sodium sulfate, which plays the role of a clarifier (Chemical technology of glass and glass metals. Artamonova M.V., Aslanova M.S., Buzhinsky I.M. . and others. Under the editorship of N.M. Pavlushkin, M., Stroyizdat, 1983, p. 106). The main disadvantage of making glass from such a mixture is the relatively high cost of soda and its scarcity, since soda is a raw material that has huge demand from various industries (Kukushkin Yu.N. Chemistry around us: Reference book. - M .: Higher school ., 1992, p. 46) and the need to use additional carbon fuel.

When raw TNT is purified (E.Yu. Orlova. Chemistry and technology of high explosives: Chemistry, 1973. - 688 p.), Tens of thousands of tons of sulfite liquor are formed containing sodium salts of sulfonic acids of asymmetric isomers of TNT, nitrophenols, nitro acids, nitrite and sodium nitrate, soda, sodium sulfate and sulfite, sodium sulfide and sodium chloride. Hydrolysis of sodium salts present in sulphite liquor leads to the fact that the pH of its solution rises to 9.0-9.5, which corresponds to slightly alkaline environments. According to the technology currently adopted, sulfite liquor after preliminary evaporation to a 30-40% concentration by solid residue is sent to incineration, and the resulting ash is dumped. Under the influence of precipitation, it turns into toxic effluents that pollute groundwater, which leads to a significant deterioration of the ecological situation.

Recycling of large-scale chemical production wastes by using them in the production of glass can improve the environmental situation in the areas of TNT production and significantly reduce the cost of glass production.

The process of preparing the mixture and making glass is as follows. TNT production waste - sulfite liquor after chemical analysis is mixed with the required amount of silica. The introduction of water with a solution of liquor into the mixture contributes to its hydration, which, along with the presence of weak alkalis in the solution, leads to the formation of a uniformly distributed film of alkaline compounds on the surface of quartz sand particles, and this, in turn, favorably affects the processes of silicate formation. In addition, the moistening of raw materials also has a beneficial effect on the uniformity of the charge (Chemical technology of glass and glass materials. Artamonova M.V., Aslanova M.S., Buzhinsky I.M. et al. Edited by N.M. Pavlushkin, - M., Stroyizdat, 1983, p. 65). The temperature of sulfite liquors should be 50-60 ° C. Silica prepared in this way is mixed with the rest of the crushed components of the charge, one of which is a waste product of trotyl production - sulfate-containing ash. It is worth noting that, thanks to the existing technology for the neutralization of sulfite liquors by burning, the resulting sulfate-containing ash is a finely divided homogeneous composition that does not require additional grinding. A typical chemical composition of sulfate ash is shown in table 1.

The mixture is fed into a continuous glass furnace. The temperature in the maximum zone of the glass melting furnace should not be lower than 1350-1400 ° C. Due to the presence in the charge of chloride and sodium sulfide, sodium carbonates and magnesium, chemical processes in the charge begin at relatively low temperatures (330-350 ° C).

Table 1 The chemical composition of sulfate-containing ash-waste of TNT production Component The content of components,% Sodium sulfate 76.49 Sodium carbonate 18.35 Sodium sulfide 2.19 Sodium chloride 1.44 Carbon 1.29 Moisture 0.16

At 780-880 ° C, the liquid phase appears due to eutectics of magnesium and sodium silicates with silica and double carbonic salts with Na ₂ CO ₃ (Chemical technology of glass and glass metals. Artamonova MV, Aslanova MS, Buzhinsky I. M. et al. Edited by N.M. Pavlushkin, M., Stroyizdat, 1983, p. 107). However, the presence of various sodium salts in the waste composition leads to the appearance of fusible compounds, the melts of which are formed earlier (Glass technology. Butt L.M., Polyak V.V. - M, State Publishing House of Literature on Construction, Architecture and Construction, 1960.S. 132-133).

Carbon (in the form of soot), which is present in sulfate-containing ash (1.1 to 5%), as well as organic reducing agents introduced into the mixture as a part of sulfite liquor and gaseous products of its decomposition CO, are directly involved in the reactions of sodium sulfate reduction. H ₂ , CH ₄ , etc., which create a reducing atmosphere in the mixture. In the case of a low soot content in sulfate-containing ash, a carbon-containing material in the form of coal or sawdust is additionally introduced into the charge.

Sodium sulfate reduction starts at 740-800 ° C by reaction

Na ₂ SO ₄ + 2C = Na ₂ S + 2CO ₂

It is worth noting that the water present in the ash and sulfite liquor accelerates the formation of silicates. This is due to the formation of caustic soda, which interacts with silica more energetically than soda

Na ₂ S + 2H ₂ O = 2NaOH + H ₂ S;

2NaOH + SiO ₂ = 2Na ₂ SiO ₃ + H ₂ O

Silicate formation starts at 865 ° C

Na ₂ SO ₄ + Na ₂ S + ₂ SiO ₂ = ₂ Na ₂ SiO ₃ + SO ₂ + S

CaO + SiO ₂ = CaSiO ₃

Clarification of the glass melt and its homogenization require an increase in the temperature of the glass melt to 1450-1500 ° C. The presence of sulfate and sodium chloride in the mixture accelerates the manufacturing process of glass melt, its clarification and homogenization (Handbook for the production of glass. Edited by I.I.Kitaygorodsky. A.I. Berezhnoy, Yu.A. Brodsky, Z.I. Bronstein and etc., - M., State Publishing House of Literature on Construction, Architecture and Construction, 1963, p. 160-162).

From the working part of the glass melting furnace, special feeders supply portions of glass melt for molding to glass forming machines. Molded glass products are installed on a transport conveyor and transferred using it and special rearrangements to annealing furnaces (lehrs). After leaving the annealing furnace, the glass containers are sorted and packaged.

To assess the feasibility of manufacturing container glass melt based on TNT waste, laboratory melting of glass blends according to the invention was carried out. Laboratory melting was carried out under rather severe conditions: the maximum temperature of the glass melt heating was 1350-1400 ° C, and the exposure time of the molten glass melt at the maximum heating temperature was 35-60 min. The glass blends were designed to produce glass containers of green and brown tones with uniform intense color, the compositions of which are given in table 2. Under the same conditions, samples of glass material were made from traditional materials in accordance with option No. 4 of table 1 of the description of the patent of the Russian Federation No. 2169711 dated April 27, .1999 (prototype).

table 2 Glass Container Compositions Glass Components The content of components in the compositions of the glasses, wt.% one 2 3 four SiO ₂ 65.00 65.39 72.5 73.40 Al ₂ O ₃ 5.35 5.50 1,53 1.10 Fe ₂ O ₃ 2,35 2,50 0.21 0.20 Na ₂ O 13.28 10.00 13.50 14.00 K ₂ O 0.30 0.10 0,03 0.35 Cao 10.96 13.00 11.00 8.00 MgO 1.10 0.06 0.83 1.20 TiO ₂ 1.10 1.40 0.04 0.14 Cr ₂ O ₃ 0.35 0.10 0.25 0.50 SO ₃ 0.10 0.50 0,07 0,07 Bao 0.05 0.10 0.01 0.01 MnO 0.01 1.25 0.02 1,02 P ₂ O ₅ 0.05 0.10 0.01 0.01

The compositions of the glass blends that were used to obtain the experimental container glass melt are shown in table 3.

The quality of the obtained glasses was evaluated by specific gravity, solubility in water and uniformity. The obtained average results are shown in table 4.

Table 3 Compositions of glass blends Charge components The content of components in the mixture, wt.%, one 2 3 four Quartz sand 31.25 31.87 49.26 51.72 Kaolin 20.62 21.69 3.26 1.48 Portafer 0.96 1,04 0 0 Sulphated Ash 21.43 16.05 21.76 22.72 Potassium nitrate 0.26 0.08 0.02 0.27 Limestone 11.10 16.47 11.85 7.02 Dolomite 2,55 0 2.85 4,57 Titanium oxide 0.80 1.01 0,03 0.10 Chromium oxide 0.36 0,07 0.19 0.37 Barium hydroxide 0.04 0.09 0.01 0.01 Manganese (IV) oxide 0.02 1,02 0.01 0.89 Monosubstituted sodium phosphate 0.08 0.16 0.01 0.01 Birch coal 1,63 1.22 1,67 1.74 Sulphite liquor 8.90 9.23 9.08 9.10

Table 4 Glass container quality Glass Option Number Specific gravity, g / cm ³ Solubility in water,% Color intensity one 2.60 2.9 Uniform 2 2,58 2,8 Uniform 3 2.61 2,8 Uniform four 2.63 2.9 Uniform Option 4 prototype 2,52 2.83 Uniform

The quality of the obtained glass samples in laboratory conditions was slightly lower than the quality of the samples obtained in industrial conditions according to the prototype (RF Patent No. 2169711 dated 04/27/1999, table 2). This, apparently, is due to the fact that the maximum temperature in an industrial furnace in the manufacture of glass melt according to the prototype was 100-150 ° C higher than in a laboratory furnace. In addition, in accordance with industrial technologies, the exposure time of the glass melt at maximum temperatures is several hours, in contrast to the exposure under laboratory conditions - 35-60 minutes. More favorable conditions of industrial technologies increase the degree of glass formation and glass mass homogenization, which ultimately leads to an increase in the quality of the resulting glass.

As it turned out, the quality of the molten glass obtained in the same conditions from the mixture using waste TNT production and based on traditional materials (option 4 of the prototype), practically coincides. Although, the specific gravity of the glass melt samples obtained using waste (2.63 g / cm ³ ) is slightly higher than that of samples obtained without them (2.52 g / cm ³ ).

Based on the foregoing, we can say that the manufacture of glass from laboratory charges according to this invention, in an industrial environment will lead to the production of glass having a quality not lower than that of glass obtained by the prototype.

Thus, the use of TNT waste in the manufacture of glass can reduce the cost of the glass charge without compromising the quality of the glass material.

The total content of trotyl production waste in the experimental batch used to produce glass according to this invention is more than 30%, which significantly reduces the cost of the whole process and allows you to completely utilize the waste of trotyl production.

Claims (1)

The mixture to obtain container glass composition, wt.%: SiO ₂ 65,00-73,40; Al ₂ O ₃ 1.10-5.50; Fe ₂ O ₃ 0.20-2.50; Na ₂ O 10.00-14.00; K ₂ O 0.03-0.35; CaO 8.0-13.00; MgO 0.06-1.20; TiO ₂ 0.04-1.40; Cr ₂ O ₃ 0.10-0.50; SO ₃ 0.07-0.50; BaO 0.01-0.10; MnO 0.01-1.25; P ₂ O ₅ 0.01-0.10, including raw materials for introducing glass-forming oxides into the glass: acidic (SiO ₂ , Al ₂ O ₃ ), alkaline earth (CaO, MgO, BaO), alkaline (Na ₂ O, K ₂ O) and auxiliary (TiO ₂ , Cr ₂ O ₃ , Fe ₂ O ₃ , SO ₃ , MnO, P ₂ O ₅ ), characterized in that as a raw material supplier of alkaline oxide - sodium oxide, waste of trotyl production is used - sulfate-containing ash and sulfite liquor in the following ratio of components, wt.%: silica sand 31.25-51.72; kaolin 1.48-21.66; sulfate-containing ash 16.04-22.72; limestone 7.02-16.47; dolomite 0-4.57; Portafer 0-1.04; chromium oxide (III) 0.07-0.37; titanium oxide (IV) 0.1-1.01; manganese (IV) oxide 0.01-1.02; potassium nitrate 0.02-0.27; monosubstituted sodium phosphate 0.01-0.16; barium hydroxide 0.01-0.09; sulfite liquor 8.90-9.10; coal birch 1.22-1.74.