CN115921491A - Low-radioactivity red mud-based material and preparation method thereof - Google Patents
Low-radioactivity red mud-based material and preparation method thereof Download PDFInfo
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention discloses a low-radioactivity red mud base material and a preparation method thereof, wherein the material comprises, by mole, 5.5-8.8 parts of red mud powder, 0.5-1.5 parts of TiO powder and CaSO 4 ·2H 2 0.2-1 part of O powder and SiO 2 0.2-1 part of powder and 0.3-1 part of CaO powder, and the preparation method comprises the steps of mixing the powder and sintering at the temperature of 80-200 ℃ for 10-60 parts. The internal and external radiation indexes of the low-radioactivity red mud-based material prepared by the invention are less than 0.1, the low-radioactivity red mud-based material meets the national building material radioactivity A standard, and the low-radioactivity red mud-based material can be prepared into products and products through further forming.
Description
Technical Field
The invention relates to a low-radioactivity red mud-based material and a preparation method thereof, belongs to the technical field of comprehensive utilization of resources, and can be used for the field of building materials and linings of ultrahigh-pressure hydrogen storage containers.
Background
Red mud, also known as red mud, is an industrial solid waste discharged from the extraction of alumina from bauxite. Generally contains a large amount of iron oxide, and has the appearance similar to that of red soil, so the iron oxide is named. According to the characteristics of bauxite, red mud is further classified into bayer process red mud, sintering process red mud or bayer combination process red mud. Generally, 1 ton of alumina is produced on average, and 1.0-2.0 tons of red mud are additionally produced, so that the red mud discharged each year is up to millions of tons. The main component of the red mud of the sintering method is Ca 2 SiO 4 ，Na 2 O.Al 2 O 3 .2SiO 2 .nH 2 O，3CaO. A1 2 O 3 .4SiO 2 Hydrated garnet, red mud liquid (containing Na) 2 CO 3 Water of (d). The main components of the Bayer process red mud are as follows: na (Na) 2 O.Al 2 O 3 .2SiO 2 .nH 2 O，3CaO.A1 2 O 3 .4SiO 2 ，CaO. A1 2 O 3 .2SiO 2 .nH 2 O, red mud over-flow (containing Na) 2 CO 3 Water of (d). The red mud has high pH value, the pH value of the leaching solution is 12.1-13.0, and the fluoride content is 11.5 mg.L -1 -26.7mg·L -1 (ii) a The pH value of the red mud is 10.29-11.83, and the fluoride content is 4.89 mg.L -1 -8.6mg·L -1 . In addition to the above components, red mud also contains a wide variety of trace elements, including radioactive elements such as U (uranium), th (thorium), and the like. Therefore, the red mud with high alkalinity and radioactivity can not be fully and effectively utilized, and can only be stacked by a large-area yard, thereby occupying a large amount of land and causing serious pollution to the environment. The red mud produced in the world is about 7000 million tons, and the red mud produced in China is more than 3000 million tons every year. The production of a large amount of red mud has direct and indirect influence on the production and life of human beings in various aspects, so that the yield of the red mud is reduced to the maximum extentAnd harm, and realization of multi-channel and large-scale resource utilization is urgent.
Much work has been done and progress has been made with respect to the removal and study of radioactive elements. The metal oxide material is used as a common inorganic material, and has the advantages of low price, wide source, stable property and the like. Commonly used metal oxide materials such as ferroferric oxide, bimetallic oxide, titanium dioxide, aluminum oxide, and the like are widely used for radionuclide removal, and exhibit rapid reaction kinetics and high adsorption capacity. Adsorption between radionuclides and metal oxides has been reported in the literature to be a complex physicochemical process, typically involving surface adsorption as well as internal diffusion processes. Titanium dioxide (TiO) 2 ) Due to its high chemical stability, negligible solubility over a wide pH range and ideal point of zero charge, it is widely used as a model mineral for catalytic degradation and adsorptive removal of environmental pollutants. TiO 2 2 The mechanism of removing the radionuclide can be divided into adsorption and catalysis, and the radionuclide is efficiently removed by modification or combined action with other materials. With TiO 2 Compared with the prior art, the adsorption and catalysis effects of TiO (titanium monoxide) on radionuclides are more obvious. TiO is a dielectric material with a specific structure, and the ratio of Ti to O in TiO is usually not 1:1, the literature reports that the content is between 0.7 and 1.25, so that a large number of vacancies and defects are contained in TiO. The presence of vacancies, diffusion, easily occurs, leading to radioactivity being masked. Through multiple researches, the radionuclide removal of TiO is better than that of TiO 2 。
Many researches on dealkalization of red mud have been carried out, and some progress has been made, such as lime hydrothermal method, ordinary pressure lime dealkalization method, lime soda sintering method, etc. The reduction of the radioactivity of the red mud is summarized by the following methods: the first is a beneficiation method, which separates out radioactive substances; secondly, shielding is carried out through slag such as steel slag; and thirdly, shielding by using a substance containing barium. At present, the comprehensive utilization of the red mud is not ideal, besides a high PH value, the radioactivity is also an important influence factor, and particularly, the radioactivity is a main index when being used as a raw material of building materials. Therefore, the development of various low-radioactivity red mud-based materials is a vital technology for expanding the application field and range of the red mud. Experiments show that the radioactivity of the red mud can be effectively reduced by adding a mixture of TiO and the like into the red mud and roasting at a certain temperature, so that a low-radioactivity red mud-based material is obtained, and the material can be further made into a product or a product. FIG. 1 and FIG. 2 show the original red mud material and the material calcined at 180 deg.C after adding the regulator. It can be seen that the microstructure of the material changes significantly, the primary particles become smaller in size, many fine particles are formed, and some of the primary coarse particles are encapsulated by the fine particles. The package leads the radioactive substance to release rays to be shielded, thereby reducing the radioactivity and meeting the standard of international building materials of A class.
In addition, for example, chinese patent CN108722422a discloses a method for activating and modifying red mud and application thereof, red mud powder, titanium oxide, water and acid are subjected to ultrasonic mixing stirring, filtering washing, drying and roasting, the particle size of the modified red mud is ground to 60-100 meshes, and the mass of the titanium oxide is 5-20% of the mass of the red mud; the acid is one or more of nitric acid, sulfuric acid, citric acid, acetic acid, hydrochloric acid and phosphoric acid, red mud treated by the hot acid releases more porous pores, the specific surface area is increased, more active free radicals are generated on the surface, energy released by micro jet flow released by ultrasound effectively promotes titanium oxide nano-particle microparticles to enter the red mud pores, iron which is a main component in the red mud enters titanium oxide lattices, the photoresponse range of the titanium oxide is expanded, strong interaction occurs between the activated red mud and the titanium oxide, and the weak synergistic effect of the red mud-titanium oxide prepared by a mechanical mixing method or a sol-gel method is improved. However, the recycling of red mud is not enough, and more application technologies need to be developed to increase the usage amount of red mud.
Disclosure of Invention
The invention aims to provide a low-radioactivity red mud-based material and a preparation method thereof. Compared with the original red mud, the low-radioactivity red mud-based material prepared by the invention has the internal and external illumination indexes less than 1.0, meets the radioactivity A standard of Chinese building materials, and accelerates the comprehensive utilization of the red mud.
The present invention is thus achieved.
The low-radioactivity red mud base material is prepared with red mud powder 5.5-8.8 weight portions, tiO powder 0.5-1.5 weight portions and CaSO 4 ·2H 2 0.2-1 part of O powder and SiO 2 0.2 to 1 portion of powder and 0.3 to 1 portion of CaO powder.
The low-radioactivity red mud-based material is prepared from the following raw materials in mol: 6 portions of red mud powder, 1 portion of TiO powder and CaSO 4 ·2H 2 0.3 part of O powder, siO 2 0.5 part of powder and 0.4 part of CaO powder.
A method for preparing the low-radioactivity red mud base material comprises mixing red mud powder, tiO powder, and CaSO 4 ·2H 2 O powder, siO 2 Mixing the powder and CaO powder, and sintering at 80-200 deg.C for 10-60 min.
In the preparation method of the low-radioactivity red mud-based material, the temperature is 100-180 ℃.
In the preparation method of the low-radioactivity red mud-based material, the temperature is 120-160 ℃.
In the preparation method of the low-radioactivity red mud-based material, the temperature is 140 ℃.
The sintering time of the preparation method of the low-radioactivity red mud-based material is 15-55 minutes.
The sintering time of the preparation method of the low-radioactivity red mud-based material is 20-40 minutes.
According to the preparation method of the low-radioactivity red mud-based material, the sintering time is 30 minutes.
Has the beneficial effects that:
the low-radioactivity red mud base material has lower radioactivity. The applicant takes the low-radioactivity red mud-based material prepared in example 1, the low-radioactivity red mud-based material prepared in example 2, the low-radioactivity red mud-based material prepared in example 3 and the red mud raw material to test the radioactivity (internal illumination index and external illumination index) of each material, each group is tested for 10 times, the test results are averaged, and the test results are recorded, which is shown in table 1.
Table 1 results of performance testing
It can be seen from the table that the low-radioactivity red mud-based materials prepared according to examples 1, 2 and 3 have radioactivity much lower than that of the red mud raw material, and are within the national standard range of radioactivity of the A-type building materials.
Drawings
Fig. 1 is an electron magnified view of a raw red mud material.
FIG. 2 is an enlarged view of the red mud material after being regulated by adding a regulator and roasted at 180 ℃.
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Example 1.
The raw material ratio is as follows: 7.8 mol of red mud powder, 0.6 mol of TiO powder 4 •2H 2 0.4mol of O powder 2 0.3 mol of powder and 0.4mol of CaO powder.
The process comprises the following steps: mixing red mud powder with TiO and CaSO 4 •2H 2 O、SiO 2 And CaO powder are mixed and sintered for 15 minutes at the temperature of 90 ℃ to obtain the composite material.
Example 2.
The raw material ratio is as follows: 7.2 mol of red mud powder, 0.8 mol of TiO powder 4 •2H 2 0.3 mol of O powder 2 0.4mol of powder and 0.6 mol of CaO powder.
The process comprises the following steps: mixing red mud powder with TiO and CaSO 4 •2H 2 O、SiO 2 And CaO powder are mixed and sintered for 40 minutes at the temperature of 130 ℃ to obtain the composite material.
Example 3.
The raw material ratio is as follows: 6.2 mol of red mud powder, 1 mol of TiO powder, 1 mol of CaSO 4 •2H 2 O powder 1 mol, siO 2 0.5 mol of powder and 0.7 mol of CaO powder.
The process comprises the following steps: mixing red mud powder with TiO and CaSO 4 •2H 2 O、SiO 2 And CaO powder, and sintering at 170 ℃ for 50 minutes to obtain the composite material.
Example 4.
The raw material ratio is as follows: 6 mol of red mud powder, 1.2 mol of TiO powder, caSO 4 •2H 2 0.2 mol of O powder 2 0.2 mol of powder and 0.3 mol of CaO powder.
The process comprises the following steps: mixing red mud powder with TiO and CaSO 4 •2H 2 O、SiO 2 And CaO powder, and sintering at 100 ℃ for 12 minutes to obtain the composite material.
Example 5.
The raw material ratio is as follows: 8 mol of red mud powder, 0.5 mol of TiO powder, caSO 4 •2H 2 0.2 mol of O powder 2 1 mol of powder and 0.6 mol of CaO powder.
The process comprises the following steps: mixing red mud powder with TiO and CaSO 4 •2H 2 O、SiO 2 And CaO powder are mixed and sintered for 17 minutes at the temperature of 130 ℃ to obtain the composite material.
Although the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and details may be made without departing from the spirit and scope of the invention.
Claims (9)
1. A low-radioactivity red mud-based material is characterized in that: the red mud green powder is prepared from 5.5-8.8 parts of red mud powder, 0.5-1.5 parts of TiO powder and CaSO 4 ·2H 2 0.2-1 part of O powder and SiO 2 0.2 to 1 portion of powder and 0.3 to 1 portion of CaO powder.
2. The low-emissivity red mud-based material of claim 1, wherein: the compound fertilizer is prepared from the following raw materials in molar ratio: red mud powder 6 weight portions, tiO powder 1 weight portion, caSO 4 ·2H 2 0.3 part of O powder and SiO 2 0.5 part of powder and 0.4 part of CaO powder.
3. A method for preparing a low-emissivity red mud-based material as claimed in claim 1 or 2, wherein the method comprises the following steps: mixing red mud powder, tiO powder, caSO 4 ·2H 2 O powder, siO 2 Mixing the powder and CaO powder, and sintering at 80-200 deg.C for 10-60 min.
4. The method for preparing a low-radioactivity red mud-based material according to claim 3, wherein the method comprises the following steps: the temperature is 100-180 ℃.
5. The method for preparing a low-radioactivity red mud-based material according to claim 4, wherein the method comprises the following steps: the temperature is 120-160 ℃.
6. The method for preparing a low-radioactivity red mud-based material according to claim 5, wherein the method comprises the following steps: the temperature was 140 ℃.
7. The method for preparing a low-radioactivity red mud-based material according to claim 3, wherein the method comprises the following steps: the sintering time is 15-55 minutes.
8. The method for preparing a low-radioactivity red mud-based material according to claim 7, wherein the method comprises the following steps: the sintering time is 20-40 minutes.
9. The method for preparing a low-radioactivity red mud-based material according to claim 8, wherein the method comprises the following steps: the sintering time was 30 minutes.
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| US20060066013A1 (en) * | 2004-09-30 | 2006-03-30 | Council Of Scientific & Industrial Research | Low temperature process for making radiopac materials utilizing industrial/agricultural waste as raw material |
| CN101219849A (en) * | 2008-01-22 | 2008-07-16 | 贵阳超群实业有限公司 | Method for reducing radioactivity of red mud |
| CN101468905A (en) * | 2007-12-28 | 2009-07-01 | 刘贵堂 | Red mud unburned brick and preparation thereof |
| JP5669120B1 (en) * | 2014-06-10 | 2015-02-12 | 国立大学法人山口大学 | Treatment method of contaminated water |
| CN108722422A (en) * | 2017-04-21 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of method of red mud activation modification and application |
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2022
- 2022-11-16 CN CN202211435219.5A patent/CN115921491A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060066013A1 (en) * | 2004-09-30 | 2006-03-30 | Council Of Scientific & Industrial Research | Low temperature process for making radiopac materials utilizing industrial/agricultural waste as raw material |
| CN101468905A (en) * | 2007-12-28 | 2009-07-01 | 刘贵堂 | Red mud unburned brick and preparation thereof |
| CN101219849A (en) * | 2008-01-22 | 2008-07-16 | 贵阳超群实业有限公司 | Method for reducing radioactivity of red mud |
| JP5669120B1 (en) * | 2014-06-10 | 2015-02-12 | 国立大学法人山口大学 | Treatment method of contaminated water |
| CN108722422A (en) * | 2017-04-21 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of method of red mud activation modification and application |
Non-Patent Citations (2)
| Title |
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