阅读说明：本技术 一种利用废弃物制备的防辐射重骨料及其制备方法 (Radiation-proof heavy aggregate prepared from wastes and preparation method thereof ) 是由 王维 李玉芝 王伟彬 张子阳 刘海涛 于 2021-09-08 设计创作，主要内容包括：本发明涉及一种利用废弃物制备的防辐射重骨料及其制备方法,所述防辐射重骨料按照重量百分比的以下原料制成：废弃阴极射线管玻璃30～35%、钡泥15～20%、高铁赤泥40～45%以及焦粉10～15%；在制备该防辐射重骨料时,按照上述比例称取原料,然后将原料分别粉碎或研磨,再将处理后的原料充分混合并造球,接着对造球得到的生坯进行烘干,再然后对烘干后的生坯进行分段焙烧,使其充分反应,最后随炉冷却降至250-350℃时出炉即可得到防辐射重骨料。本发明的防辐射重骨料以赤泥、钡泥和废弃阴极射线管玻璃为主要原料,替代了较为昂贵和稀缺的重晶石,可减轻我国建材行业对重晶石的依赖,缓解工业快速发展带来的优质重晶石匮乏的危机。(The invention relates to a radiation-proof heavy aggregate prepared from wastes and a preparation method thereof, wherein the radiation-proof heavy aggregate is prepared from the following raw materials in percentage by weight: 30-35% of waste cathode ray tube glass, 15-20% of barium mud, 40-45% of high-iron red mud and 10-15% of coke powder; when the radiation-proof heavy aggregate is prepared, the raw materials are weighed according to the proportion, then the raw materials are respectively crushed or ground, the processed raw materials are fully mixed and pelletized, then the green body obtained by pelletizing is dried, then the dried green body is subjected to sectional roasting to fully react, and finally the raw body is cooled along with the furnace to 350 ℃ and taken out of the furnace to obtain the radiation-proof heavy aggregate. The radiation-proof heavy aggregate of the invention uses red mud, barium mud and waste cathode ray tube glass as main raw materials, replaces expensive and scarce barite, can reduce the dependence of the building material industry of China on the barite, and relieves the crisis of high-quality barite shortage brought by the rapid development of the industry.)

1. The radiation-proof heavy aggregate prepared by utilizing the wastes is characterized in that: the radiation-proof heavy aggregate is prepared from the following raw materials in percentage by weight: 30-35% of waste cathode ray tube glass, 15-20% of barium mud, 40-45% of high-iron red mud and 10-15% of coke powder.

2. The radiation protective heavy aggregate according to claim 1, characterized in that: the radiation-proof heavy aggregate is prepared from the following raw materials in percentage by weight: 33% of waste cathode ray tubes, 15% of barium mud, 41% of high-iron red mud and 11% of coke powder.

3. The radiation-proof heavy aggregate according to claim 1 or 2, characterized in that: the waste cathode ray tube glass mainly comprises the following components: SiO 2₂ 45～50%、PbO 20～25%、Na₂O 8～10%、BaO 1～2%、Al₂O₃5-8% of CaO, 5-8% of CaO and K₂O 1～3%。

4. The radiation protective heavy aggregate according to claim 3, characterized in that: the high-iron red mud mainly comprises the following components: SiO 2₂20～25%、Fe₂O₃ 24～35%、Al₂O₃ 15～20%、TiO₂ 4～8%、CaO 10～15%、Na₂O5-8% and K₂O 0.1～0.3%。

5. The radiation protective heavy aggregate according to claim 4, characterized in that: the barium mud mainly comprises the following components: BaCO₃ 25～30%、BaSO₄ 25～30%、BaSO₃ 8～10%、SiO₂ 20～25%、Al₂O₃8 to 10% and Fe₂O₃ 5～8%。

6. A method for preparing radiation-proof heavy aggregate by using wastes is characterized by comprising the following steps:

(1) taking 30-35% of waste cathode ray tube glass, 15-20% of barium mud, 40-45% of high-iron red mud and 10-15% of coke powder for later use according to weight percentage;

(2) coarsely crushing the waste cathode ray tube glass into particles with the particle size of less than 5mm, and respectively grinding the high-iron red mud, the barium mud and the coke powder and then sieving the ground materials with a 160-mesh sieve;

(3) fully mixing the raw materials sieved in the step (2);

(4) putting the mixed raw materials in the step (3) into a pelletizing disc machine for pelletizing, spraying a proper amount of water while rolling the disc, and finally forming green pellets with the diameter of 3-8 mm to prepare green bodies;

(5) drying the green body obtained in the step (4) in a drying box;

(6) and (3) placing the dried green body sample into a muffle furnace to be roasted according to the following stages:

a. the temperature is 25-750 ℃, and the heating rate is 8 ℃/min;

b. the temperature is increased at the rate of 5 ℃/min at the temperature of 750-1350 ℃, and the temperature is preserved for 120min at the temperature of 1350 ℃;

and finally, cooling naturally along with the furnace, and taking out of the furnace when the temperature is reduced to 250-350 ℃ to obtain the radiation-proof heavy aggregate.

7. The method for preparing radiation-proof heavy aggregate by using wastes as claimed in claim 6, wherein in the step (3), the mixing time of the raw materials is 12 h.

8. The method for preparing radiation-proof heavy aggregate by using wastes as claimed in claim 6, wherein the drying conditions in the step (5) are as follows: the temperature is 150 ℃ and the time is 6 h.

Technical Field

The invention belongs to the technical field of heavy aggregate manufacturing, and particularly relates to radiation-proof heavy aggregate prepared by using wastes and a preparation method thereof.

Background

In recent years, display technology is rapidly developed, and liquid crystal display technology and plasma display technology have more advantages than cathode ray tube display technology in many aspects, so that the amount of heavy metal glass of the waste cathode ray tube on computers and televisions in China is increased at a high speed. Cathode ray tube glass often contains heavy metals of barium and lead, which can seriously harm human health and ecological environment if not properly disposed. Therefore, comprehensive treatment and secondary utilization of the waste glass of the cathode ray tube become important.

The residual solid in the production process of barium salt is called barium mud, and water-soluble barium in the barium mud easily permeates into underground water to ensure that the underground water is Ba²⁺The barium mud is overproof, causes great harm to human bodies, and is very urgent to find a comprehensive utilization way of the barium mud.

The red mud is Al₂O₃The industrial solid waste generated in the production process contains Fe, Al and Si, and also contains some scattered elements such as Sc, Ti and the like and a certain amount of alkali. The pH value of the red mud is about 11, the iron content is high, the production amount is large, the conventional disposal modes such as stockpiling, sea filling and the like can cause serious pollution to peripheral drinking water, atmosphere and soil, a large amount of fertile farmlands are wasted, and the sustainable development of the iron and aluminum industry is seriously influenced. The red mud contains a large amount of useful elements, and particularly the high-iron red mud produced by the Bayer process has higher iron content and more potential utilization value.

The high-efficiency treatment of cathode ray tubes, barium mud and high-iron red mud is a new problem which troubles scientific and technological workers. The industrial waste is reasonably utilized, and the potential of secondary resources is exerted to the maximum extent. The waste is processed into high value-added products, and the method has important significance for reducing environmental risks and recycling resources.

The barite concrete is one of the most commonly used radiation-proof concretes at present, and is widely applied to medical and radiation-proof engineering. However, with continuous industrial development, high-quality single barite ore is exhausted day by day, and at present, most of barite ore in China has low grade, so that barite concrete raw materials are very lack.

Disclosure of Invention

The invention aims to solve the technical problems and provide the radiation-proof heavy aggregate prepared by using the waste and the preparation method thereof.

In order to achieve the purpose, the invention adopts the technical scheme that: the radiation-proof heavy aggregate is prepared from the following raw materials in percentage by weight: 30-35% of waste cathode ray tube glass, 15-20% of barium mud, 40-45% of high-iron red mud and 10-15% of coke powder.

Further, the radiation-proof heavy aggregate is prepared from the following raw materials in percentage by weight: 33% of waste cathode ray tube glass, 15% of barium mud, 41% of high-iron red mud and 11% of coke powder.

Among the raw materials, the waste cathode ray tube glass mainly comprises the following components: SiO 2₂45～50%、PbO 20～25%、Na₂O 8～10%、BaO 1～2%、Al₂O₃5-8% of CaO, 5-8% of CaO and K₂O 1～3%。

In the raw materials, the main components of the high-iron red mud are as follows: SiO 2₂20～25%、Fe₂O₃ 24～35%、Al₂O₃15～20%、TiO₂4～8%、CaO 10～15%、Na₂O5-8% and K₂O 0.1～0.3%。

In the raw materials, the main components of the barium mud are as follows: BaCO₃25～30%、BaSO₄25～30%、BaSO₃8～10%、SiO₂20～25%、Al₂O₃8 to 10% and Fe₂O₃5～8%。

A method for preparing radiation-proof heavy aggregate by using wastes comprises the following steps:

(1) taking 30-35% of waste cathode ray tube glass, 15-20% of barium mud, 40-45% of high-iron red mud and 10-15% of coke powder for later use according to weight percentage;

(2) coarsely crushing the waste cathode ray tube glass into particles with the particle size of less than 5mm, and respectively grinding the high-iron red mud, the barium mud and the coke powder and then sieving the ground materials with a 160-mesh sieve;

(3) fully mixing the raw materials sieved in the step (2);

(4) putting the mixed raw materials in the step (3) into a pelletizing disc machine for pelletizing, spraying a proper amount of water while rolling the disc, and finally forming green pellets with the diameter of 3-8 mm to prepare green bodies;

(5) drying the green body obtained in the step (4) in a drying box;

(6) and (3) placing the dried green body sample into a muffle furnace to be roasted according to the following stages:

a. the temperature is 25-750 ℃, and the heating rate is 8 ℃/min;

b. the temperature is increased at the rate of 5 ℃/min at the temperature of 750-1350 ℃, and the temperature is preserved for 120min at the temperature of 1350 ℃;

and finally, cooling naturally along with the furnace, and taking out of the furnace when the temperature is reduced to 250-350 ℃ to obtain the radiation-proof heavy aggregate.

In the step (3), the mixing time of the raw materials is 12 h.

The drying conditions in the step (5) are as follows: the temperature is 150 ℃ and the time is 6 h.

The invention has the beneficial effects that: 1. the radiation-proof heavy aggregate of the invention uses red mud, barium mud and waste cathode ray tube glass as main raw materials, replaces expensive and scarce barite, can reduce the dependence of the building material industry of China on the barite, and relieves the crisis of high-quality barite shortage brought by the rapid development of the industry.

2. During the high-temperature roasting process of the heavy aggregate, the coke powder reduces iron in the high-iron red mud and lead elements in barium mud, and the heavy metal elements and barium oxide or barium sulfate in the barium mud synthesize various complex oxides (BaTiO) containing barium, lead and iron in situ₃、Pb₂Fe₂O₅、BaFe₁₁Ti₃O₂₃). These complex oxides have radiation protection properties, particularly enhancing the gamma ray protection of the heavy aggregate.

3. During the high-temperature roasting process of the heavy aggregate prepared by the invention, the coke powder reduces iron in the high-iron red mud and lead elements in barium mud, and the heavy metal elements and barium oxide or barium sulfate in the barium mud in situ synthesize various barium-containing materials,Lead and iron complex oxide, improves the performance of the heavy aggregate, and the apparent density reaches 4.1 g/cm³After 28 d of maintenance, the compressive strength is higher than 35Mpa, the water absorption is lower than 0.9 percent, the abrasion rate is lower than 18.5 percent, and all the properties meet the requirements of ASTM C637.

Detailed Description

The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.

Example 1: a method for preparing radiation-proof heavy aggregate by using wastes comprises the following steps:

(1) taking 33% of waste cathode ray tube glass, 15% of barium mud, 41% of high-iron red mud and 11% of coke powder for later use according to the weight percentage;

(2) coarsely crushing the waste cathode ray tube glass into particles with the particle size of less than 5mm, respectively putting the high-iron red mud, the barium mud and the coke powder into a ball mill for ball milling, and then sieving the materials through a 160-mesh sieve;

(3) putting the raw materials sieved in the step (2) into a three-dimensional mixer to mix for 12 hours;

(4) putting the mixed raw materials obtained in the step (3) into a pelletizing disc machine with a certain inclination angle for pelletizing, spraying a proper amount of water while rolling the disc to bond the mixed raw materials, and finally forming green pellets with the diameter of 3-8 mm to obtain green bodies;

(5) drying the green body obtained in the step (4) in a drying oven at 150 ℃ for 6 h;

(6) and (3) placing the dried green body sample into a muffle furnace to be roasted according to the following stages:

a. the temperature is 25-750 ℃, and the heating rate is 8 ℃/min;

b. the temperature is increased at the rate of 5 ℃/min at the temperature of 750-1350 ℃, and the temperature is preserved for 120min at the temperature of 1350 ℃;

and finally, cooling naturally along with the furnace, and taking out of the furnace when the temperature is reduced to 250-350 ℃ to obtain the radiation-proof heavy aggregate.

The final green body roasting in the invention adopts sectional roasting, which is beneficial to the roasting, so that the related reaction can be thoroughly carried out, and more complex oxides can be formed.

The main composition of the waste cathode ray tube glassComprises the following steps: SiO 2₂45～50%、PbO 20～25%、Na₂O 8～10%、BaO 1～2%、Al₂O₃5-8% of CaO, 5-8% of CaO and K₂O 1～3%。

The high-iron red mud mainly comprises the following components: SiO 2₂20～25%、Fe₂O₃ 24～35%、Al₂O₃15～20%、TiO₂4～8%、CaO 10～15%、Na₂O5-8% and K₂O 0.1～0.3%。

The barium mud mainly comprises the following components: BaCO₃25～30%、BaSO₄25～30%、BaSO₃8～10%、SiO₂20～25%、Al₂O₃8 to 10% and Fe₂O₃5～8%。

Detecting various properties of the obtained heavy aggregate: water absorption of 0.83%, volume density of 4.2g/cm³After 28 days of maintenance, the compressive strength is 36Mpa, the volume abrasion rate is 17.86 percent, and the performance test of the whole heavy aggregate meets the ASTM C637 standard.

Example 2: the difference between this example and example 1 is that the composition of raw materials used for the preparation is different, and in this example, 35% by weight of waste cathode ray tube glass, 15% by weight of barium mud, 40% by weight of high-iron red mud, and 10% by weight of coke powder are taken. The other steps are the same as in example 1.

Detecting various properties of the obtained heavy aggregate: water absorption of 0.85% and volume density of 4.3g/cm³After 28 days of maintenance, the compressive strength is 37 Mpa, the volume abrasion rate is 18.16 percent, and the performance test of the whole heavy aggregate meets the ASTM C637 standard.

Example 3: the difference between this example and example 1 is that the composition of the raw materials used for the preparation is different, and in this example, 30% of waste cathode ray tube glass, 17% of barium mud, 40% of high-iron red mud and 13% of coke powder are taken according to the weight percentage. The other steps are the same as in example 1.

Detecting various properties of the obtained heavy aggregate: water absorption of 0.86% and volume density of 4.2g/cm³After 28 days of maintenance, the compressive strength is 36Mpa, the volume abrasion rate is 17.68 percent, and the performance test of the whole heavy aggregate meets the ASTM C637 standard.

Example 4: the difference between this example and example 1 is that the composition of raw materials used for preparation is different, and in this example, 30% of waste cathode ray tube glass, 15% of barium mud, 45% of high-iron red mud and 10% of coke powder are taken according to weight percentage. The other steps are the same as in example 1.

Detecting various properties of the obtained heavy aggregate: water absorption of 0.83%, volume density of 4.1 g/cm³After 28 days of maintenance, the compressive strength is 37 Mpa, the volume abrasion rate is 17.75 percent, and the performance test of the whole heavy aggregate meets the ASTM C637 standard.

The above embodiments are only intended to illustrate the technical solution of the present invention and not to limit the same, and it should be understood by those of ordinary skill in the art that the specific embodiments of the present invention can be modified or substituted with equivalents with reference to the above embodiments, and any modifications or equivalents without departing from the spirit and scope of the present invention are within the scope of the claims to be appended.