CN108059347B - Microcrystalline glass prepared from electrolytic manganese residues and preparation method thereof - Google Patents

Abstract

The invention relates to the field of materials, in particular to a glass-ceramic prepared from electrolytic manganese slag and a preparation method thereof. A glass-ceramic prepared from electrolytic manganese slag, the raw materials mainly include the following components in parts by weight: electrolytic manganese slag, phosphate rock, granite, silica lime, fly ash, mica, carbon, borax, magnesite , heavy calcium and zirconia. Calcium, silicon and aluminum in phosphate rock, granite, silica lime, fly ash, mica, carbon, heavy calcium, magnesite, etc. are glass formers. It is very beneficial to reduce the cost of raw materials, improve the degree of crystallization and shorten the crystallization time, thereby improving the production efficiency. The zirconium element in zirconia can increase the high temperature resistance, wear resistance and corrosion resistance of glass-ceramic; zirconia also acts as a nucleating agent in the nucleation process of glass-ceramic, and boron in borax is also a nucleating agent agent.

Description

A kind of glass-ceramic prepared from electrolytic manganese slag and preparation method thereof

technical field

The invention relates to the field of materials, in particular to a glass-ceramic prepared from electrolytic manganese slag and a preparation method thereof.

Background technique

my country is the world's largest producer, consumer and exporter of electrolytic manganese metal, with a production capacity of more than 2 million tons, accounting for 98% of the world's total electrolytic manganese production capacity. Electrolytic manganese slag is the filtered acid residue produced after electrolysis of metal manganese, and it is the key pollutant in the electrolytic manganese industry. The amount of electrolytic manganese slag produced reaches 7 to 11 tons/ton of manganese, and the annual production amount is about 20 million tons.

The treatment of electrolytic manganese slag is the only way to control and control the pollution of manganese slag.

The inventor has invented a glass-ceramic prepared from electrolytic manganese slag and a preparation method thereof.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a glass-ceramic prepared from electrolytic manganese slag and a preparation method thereof, which aims to improve the problems of serious accumulation and large stock of the existing electrolytic manganese slag.

The present invention provides a technical scheme:

A glass-ceramic prepared from electrolytic manganese slag, the raw material of the glass-ceramic prepared from electrolytic manganese slag mainly comprises the following components in parts by weight:

65-93 parts of electrolytic manganese slag, 10-20 parts of phosphate rock, 5-16 parts of granite, 23-35 parts of silica lime, 11-22 parts of fly ash, 10-18 parts of mica, 4-12 parts of carbon, borax 3-10 parts, 8-14 parts of magnesite, 4-15 parts of heavy calcium and 1-4 parts of zirconia.

The present invention also provides a technical solution:

A method for preparing the glass-ceramic prepared by the above-mentioned electrolytic manganese slag, comprising:

The mixed raw materials are melted into glass liquid, the melting temperature is 1500-1650 DEG C, and the melting time is 0.5-5.0 hours; the glass liquid is formed to obtain a glass plate;

The glass plate is placed at a temperature of 400-670°C for 3-7 hours, then the temperature is raised to 850-935°C for 5-10 hours, then cooled to 400-670°C, and taken out after being kept for 6-10 hours.

The present invention also provides a technical solution:

A method for preparing the glass-ceramic prepared by the above-mentioned electrolytic manganese slag, comprising:

The mixed raw materials are sieved, those with a particle size larger than 4 mm are large-sized materials, and those with a particle size smaller than 4 mm are small-sized materials;

Fill the large particle size material into the model, heat up to 1320-1450 ℃, keep warm for 1-3 hours, shake the model; cool down to 500-670 ℃, keep warm for 4-5 hours; then increase the temperature to 880-935 ℃ and keep warm for 8 -10 hours, then cool down to 500-670°C, keep warm for 8-10 hours and take it out;

Fill the small particle size material into the model, heat up to 1230-1360°C, keep warm for 1-3 hours, shake the model; cool down to 400-550°C, keep warm for 4-5 hours; then raise the temperature to 850-900°C and keep warm for 8- After 10 hours, the temperature was lowered to 400-550°C, and the temperature was kept for 8-10 hours before taking out.

The beneficial effects of the glass-ceramic prepared by the electrolytic manganese slag provided in the embodiment of the present invention and the preparation method thereof are:

Electrolytic manganese slag is a quaternary slag system of SiO ₂ -CaO-MgO-Al ₂ O ₃ , which can produce glass-ceramic, phosphate rock, granite, silica lime, fly ash, mica, carbon, heavy calcium, magnesite, etc. Calcium, silicon, aluminum, etc. are glass formers, and the rare earth elements rich in minerals are very beneficial to the glass-ceramic composition, and can greatly reduce the cost of raw materials, improve the degree of crystallization and shorten the crystallization time, thereby improving production. efficiency. The zirconium element in zirconia can increase the high temperature resistance, wear resistance and corrosion resistance of glass-ceramic; zirconia also acts as a nucleating agent in the nucleation process of glass-ceramic, and boron in borax is also a nucleating agent agent.

The preparation method provided by the invention has the advantages of simple preparation process and convenient operation, promotes the comprehensive utilization of silicon-manganese alloy slag in large quantities, not only expands the resource comprehensive utilization way of silicon-manganese alloy slag, but also reduces the environmental pollution caused by massive accumulation of slag. The obtained glass-ceramic has good wear resistance and high temperature resistance.

Detailed ways

In order to make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not indicated in the examples, it is carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used without the manufacturer's indication are conventional products that can be purchased from the market.

The glass-ceramic prepared by an electrolytic manganese slag according to the embodiment of the present invention and the preparation method thereof will be specifically described below.

In detail, a glass-ceramic prepared from electrolytic manganese slag, the raw material of the glass-ceramic prepared from electrolytic manganese slag mainly includes the following components in parts by weight:

65-93 parts of electrolytic manganese slag, 10-20 parts of phosphate rock, 5-16 parts of granite, 23-35 parts of silica lime, 11-22 parts of fly ash, 10-18 parts of mica, 4-12 parts of carbon, borax 3-10 parts, 8-14 parts of magnesite, 4-15 parts of heavy calcium and 1-4 parts of zirconia.

Further, the raw material of the glass-ceramic prepared by the above-mentioned electrolytic manganese slag mainly includes the following components in parts by weight:

68-87 parts of electrolytic manganese slag, 12-18 parts of phosphate rock, 8-15 parts of granite, 28-34 parts of silica lime, 13-26 parts of fly ash, 13-16 parts of mica, 4-10 parts of carbon, borax 5-10 parts, magnesite 10-14 parts, heavy calcium 9-15 parts and zirconia 2-4 parts.

In detail, in this embodiment, the raw material of the glass-ceramic prepared from the above-mentioned electrolytic manganese slag mainly includes the following components in parts by weight:

80 parts of electrolytic manganese slag, 16 parts of phosphate rock, 11 parts of granite, 31 parts of silica lime, 23 parts of fly ash, 15 parts of mica, 8 parts of carbon, 8 parts of borax, 11 parts of magnesite, 12 parts of heavy calcium and 3 parts of zirconia.

The electrolytic manganese slag is a quaternary slag system of SiO ₂ -CaO-MgO-Al ₂ O ₃ . The electrolytic manganese slag can be used to make glass-ceramics, and the amount of manganese slag added can reach more than 75%. The preparation method of electrolytic manganese slag glass-ceramic has the characteristics of simple process, low energy consumption and environmental protection, and can become an important direction for the resource utilization of electrolytic manganese slag.

Calcium, silicon and aluminum in phosphate rock, granite, silica lime, fly ash, mica, carbon, heavy calcium, magnesite, etc. are glass formers. It is very beneficial to reduce the cost of raw materials, improve the degree of crystallization and shorten the crystallization time, thereby improving the production efficiency. The zirconium element in zirconia can increase the high temperature resistance, wear resistance and corrosion resistance of glass-ceramic; zirconia also acts as a nucleating agent in the nucleation process of glass-ceramic, and boron in borax is also a nucleating agent agent.

The present invention also provides a technical solution:

A method for preparing the glass-ceramic prepared by the above-mentioned electrolytic manganese slag, comprising:

The mixed raw materials are melted into glass liquid, the melting temperature is 1500-1650 DEG C, and the melting time is 0.5-5.0 hours; the glass liquid is formed to obtain a glass plate;

The glass plate is placed at a temperature of 400-670°C for 3-7 hours, then the temperature is raised to 850-935°C for 5-10 hours, then cooled to 400-670°C, and taken out after being kept for 6-10 hours.

First, each mineral and raw material are mixed, and after mixing, it is melted into a liquid glass liquid, which is melted at 1500-1650 ° C for 0.5-5.0 hours, and the glass liquid is placed in a mold to form a glass plate.

To crystallize the glass plate, first nucleate at a lower temperature, 400-670°C, and then crystallize at a temperature of 850-935°C.

The inventors found that the glass-ceramic plates made of the above-mentioned raw materials have better wear resistance and high temperature resistance in the above-mentioned temperature range and temperature range.

Further, in this embodiment, before taking out, it is taken out in the furnace pit after reaching room temperature, which is beneficial to the further improvement of the crystal form.

The preparation method provided by the invention has the advantages of simple preparation process and convenient operation, promotes the comprehensive utilization of silicon-manganese alloy slag in large quantities, not only expands the resource comprehensive utilization way of silicon-manganese alloy slag, but also reduces the environmental pollution caused by massive accumulation of slag. The obtained glass-ceramic has good wear resistance and high temperature resistance.

Further, in other embodiments, drying the electrolytic manganese slag before mixing the raw materials, and pulverizing the electrolytic manganese slag to less than 3 mm after drying the electrolytic manganese slag.

The electrolytic manganese slag is pulverized, the powdered electrolytic manganese slag and the raw materials are mixed more uniformly, and the manganese and aluminum elements in the electrolytic manganese slag are prevented from agglomerating, so that they are uniformly dispersed in the whole glass liquid.

Further, the electrolytic manganese slag has acidity, and in other embodiments, calcium oxide is used to neutralize the acidity of the electrolytic manganese slag before drying.

The present invention also provides a technical solution:

A method for preparing the glass-ceramic prepared by the above-mentioned electrolytic manganese slag, comprising:

The mixed raw materials are sieved, those with a particle size larger than 4 mm are large-sized materials, and those with a particle size smaller than 4 mm are small-sized materials;

Fill the large particle size material into the model, heat up to 1320-1450 ℃, keep warm for 1-3 hours, shake the model; cool down to 500-670 ℃, keep warm for 4-5 hours; then increase the temperature to 880-935 ℃ and keep warm for 8 -10 hours, then cool down to 500-670°C, keep warm for 8-10 hours and take it out;

Fill the small particle size material into the model, heat up to 1230-1360°C, keep warm for 1-3 hours, shake the model; cool down to 400-550°C, keep warm for 4-5 hours; then raise the temperature to 850-900°C and keep warm for 8- After 10 hours, the temperature was lowered to 400-550°C, and the temperature was kept for 8-10 hours before taking out.

In the present embodiment, the raw materials are first mixed, and then sieved after mixing, into large particle size materials and small particle size materials; different particle sizes are produced by different processes.

Raw materials with large particle size use higher temperature and longer corresponding time processes, while small particle size materials use lower temperature and shorter corresponding time processes.

In detail, in the process of the experiment, in the mixed treatment method of large particle size and small particle size, the obtained glass-ceramic plates have different properties, high temperature resistance and wear resistance, which are high and bottom.

During the experiment, the raw materials with large particle size and the raw materials with small particle size were tested separately, and it was found that the temperature required for raw materials with small particle sizes was slightly lower than that of raw materials with large particle sizes.

Further, the particle size of the raw material with large particle size is 4 mm to 15 mm. Therefore, in other embodiments, after mixing the raw material, the raw material is ground to less than 15 mm, and then sieved.

Correspondingly, in this embodiment, before taking out, it is taken out in the furnace pit after reaching room temperature, which is beneficial to further perfecting the crystal form.

In this embodiment, after the glass plate is crystallized and taken out, it further includes determining the thickness, rough grinding, fine polishing and cutting of the crystallized glass plate.

High temperature resistance and wear resistance of the glass-ceramic body prepared by the above method. The difference is obtained by sieving the raw materials, and the performance of the final glass-ceramic body is the same.

The features and performances of the present invention will be further described in detail below in conjunction with the embodiments.

Example 1

The present embodiment provides a glass-ceramic prepared from electrolytic manganese slag, and the glass-ceramic prepared from electrolytic manganese slag is mainly prepared by the following arrangements:

The main raw materials are weighed: electrolytic manganese slag 93kg, phosphate rock 20kg, granite 16kg, silica lime 35kg, fly ash 22kg, mica 18kg, carbon 12kg, borax 10kg, magnesite 14kg, heavy calcium 15kg and zirconia 4kg.

The above-mentioned raw materials are mixed and melted into molten glass, the melting temperature is 1500-1650° C., and the melting time is 0.5 hour; the molten glass is introduced into the mold to form a glass plate.

Crystallize the glass plate: keep the glass plate at a temperature of 400-670 °C for 7 hours, then raise the temperature to 850-935 °C for 5 hours, then cool down to 400-670 °C, and take it out after 10 hours of heat preservation .

Thickness, rough grinding, fine polishing and cutting of the crystallized glass plate.

Example 2

The present embodiment provides a glass-ceramic prepared from electrolytic manganese slag, and the glass-ceramic prepared from electrolytic manganese slag is mainly prepared by the following arrangements:

The main raw materials are weighed: 65kg of electrolytic manganese slag, 10kg of phosphate rock, 5kg of granite, 23kg of silica lime, 11kg of fly ash, 10kg of mica, 4kg of carbon, 3kg of borax, 8kg of magnesite, 4kg of heavy calcium and 1kg of zirconia.

The above raw materials are mixed and melted into molten glass, the melting temperature is 1500-1650° C., and the melting time is 4.5 hours; the molten glass is introduced into the mold to form a glass plate.

Crystallize the glass plate: put the glass plate at a temperature of 400-670 °C for 3.5 hours, then raise the temperature to 850-935 °C for 8 hours, then cool down to 400-670 °C, and take it out after holding for 8 hours .

Thickness, rough grinding, fine polishing and cutting of the crystallized glass plate.

Example 3

The present embodiment provides a glass-ceramic prepared from electrolytic manganese slag, and the glass-ceramic prepared from electrolytic manganese slag is mainly prepared by the following arrangements:

The main raw materials are weighed: electrolytic manganese slag 87kg, phosphate rock 18kg, granite 15kg, silica lime 28kg, fly ash 26kg, mica 16kg, carbon 10kg, borax 10kg, magnesite 14kg, heavy calcium 15kg and zirconia 4kg.

The above raw materials are mixed and melted into molten glass, the melting temperature is 1500-1650° C., and the melting time is 3 hours; the molten glass is introduced into the mold to form a glass plate.

Crystallize the glass plate: put the glass plate at a temperature of 400-670 °C for 4 hours, then raise the temperature to 850-935 °C for 7 hours, then cool down to 400-670 °C, and take it out after holding for 8 hours .

Thickness, rough grinding, fine polishing and cutting of the crystallized glass plate.

Example 4

The present embodiment provides a glass-ceramic prepared from electrolytic manganese slag, and the glass-ceramic prepared from electrolytic manganese slag is mainly prepared by the following arrangements:

The main raw materials are weighed: 78kg of electrolytic manganese slag, 18kg of phosphate rock, 13kg of granite, 28kg of silica lime, 19kg of fly ash, 16kg of mica, 9kg of carbon, 8kg of borax, 11kg of magnesite, 13kg of heavy calcium and 3kg of zirconia.

Mixing the above-mentioned raw materials, those with a particle size greater than 4mm are large particle size materials, and those with particle diameters less than 4mm are small particle size materials;

Processing of large particle size materials:

Fill the large particle size material into the model, heat up to 1320-1450°C, keep the temperature for 2.5 hours, and shake the model; cool down to 500-670°C, keep the temperature for 3 hours; then increase the temperature to 880-935°C, keep the temperature for 9 hours, and then cool down To 500-670 ℃, after 9 hours of incubation, take out;

Processing of small particle size materials:

Fill the small particle size material into the model, heat it up to 1230-1360°C, hold it for 2 hours, and shake the model; cool it down to 400-550°C, hold it for 4.5 hours; then raise the temperature to 850-900°C, hold it for 9 hours, and then cool down to 400-550 ℃, take out after 9 hours of incubation.

Example 5

The present embodiment provides a glass-ceramic prepared from electrolytic manganese slag, and the glass-ceramic prepared from electrolytic manganese slag is mainly prepared by the following arrangements:

The main raw materials are weighed: 80kg of electrolytic manganese slag, 16kg of phosphate rock, 11kg of granite, 31kg of silica lime, 23kg of fly ash, 15kg of mica, 8kg of carbon, 8kg of borax, 11kg of magnesite, 12kg of heavy calcium and 3kg of zirconia.

Mixing the above-mentioned raw materials, those with a particle size greater than 4mm are large particle size materials, and those with particle diameters less than 4mm are small particle size materials;

Processing of large particle size materials:

Fill the large particle size material into the model, heat up to 1320-1450°C, keep the temperature for 2.5 hours, and shake the model; cool down to 500-670°C, keep the temperature for 3 hours; then increase the temperature to 880-935°C, keep the temperature for 9 hours, and then cool down To 500-670 ℃, after 9 hours of incubation, take out;

Processing of small particle size materials:

Fill the small particle size material into the model, heat it up to 1230-1360 °C, keep it for 2 hours, and shake the model; cool it down to 400-550 °C, keep it warm for 4.5 hours; then increase the temperature to 850-900 °C for 9 hours, and then cool down to 400-550 ℃, take out after 9 hours of incubation.

The products prepared in Example 1-Example 5 can all obtain glass-ceramic; compared with Example 1-Example 3, the high-temperature resistance and resistance of the glass-ceramic prepared in Example 4 and Example 5 The grinding performance is more uniform.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (4)

1. a method for preparing the glass-ceramic prepared by electrolytic manganese slag, is characterized in that, The raw materials of the glass-ceramic prepared from electrolytic manganese slag mainly include the following components in parts by weight: 68-87 parts of electrolytic manganese slag, 12-18 parts of phosphate rock, 8-15 parts of granite, 28-34 parts of silica lime, 13-26 parts of fly ash, 13-16 parts of mica, 4-10 parts of carbon, borax 5-10 parts, 10-14 parts of magnesite, 9-15 parts of heavy calcium and 2-4 parts of zirconia; Preparation methods include: The mixed raw materials are sieved, and those with a particle size greater than 4 mm are large-sized materials, and those with a particle size less than 4 mm are small-sized materials; Fill the large particle size material into the model, heat up to 1320-1450 ℃, keep warm for 1-3 hours, shake the model; cool down to 500-670 ℃, keep warm for 4-5 hours; then increase the temperature to 880- Incubate at 935°C for 8-10 hours, then cool down to 500-670°C, and take it out after keeping for 8-10 hours; Fill the small particle size material into the model, heat up to 1230-1360°C, keep warm for 1-3 hours, shake the model; cool down to 400-550°C, keep warm for 4-5 hours; then the temperature is raised to 850- 900 for 8-10 hours, then cool down to 400-550°C, and take out after 8-10 hours of incubation. 2 . The method for preparing glass-ceramics from electrolytic manganese slag according to claim 1 , wherein before mixing the raw materials, it further comprises pulverizing the raw materials to a particle size of less than 15 mm. 3 . 3 . The method for preparing glass-ceramics from electrolytic manganese slag according to claim 1 , wherein the method further comprises determining the thickness of the taken out glass plate, rough grinding, fine polishing and cutting. 4 . 4 . The method for preparing glass-ceramics from electrolytic manganese slag according to claim 1 , wherein, before taking out, the glass plate is naturally cooled in a furnace and then taken out. 5 .