CN113087328A - Method for removing sodium and potassium in red mud by using manganese slag leachate - Google Patents
Method for removing sodium and potassium in red mud by using manganese slag leachate Download PDFInfo
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- CN113087328A CN113087328A CN202110451851.8A CN202110451851A CN113087328A CN 113087328 A CN113087328 A CN 113087328A CN 202110451851 A CN202110451851 A CN 202110451851A CN 113087328 A CN113087328 A CN 113087328A
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a method for removing sodium and potassium in red mud by using manganese slag leachate, which comprises the following steps: (1) drying, grinding and sieving the red mud and the manganese slag respectively; (2) adding water into the treated manganese slag for leaching reaction, and filtering to obtain manganese slag leachate; (3) adding manganese slag leachate into the treated red mud, carrying out five-stage leaching reaction again, centrifuging, washing and filtering to obtain the red mud after dealkalization of the manganese slag leachate. The invention provides a new process for dealkalizing red mud by utilizing manganese slag leachate, which has high effect of removing sodium and potassium in the red mud, does not change the main chemical composition of the dealkalized red mud greatly, is beneficial to adding and using the red mud in building materials, and is a method for regulating and controlling the alkalinity of the red mud by treating waste with waste.
Description
Technical Field
The invention relates to the field of harmless treatment of industrial solid wastes, in particular to a method for removing sodium and potassium in red mud by using manganese slag percolate.
Background
The red mud is industrial solid waste produced in an alumina refining process, and about 1.5 tons of red mud is produced when 1 ton of alumina is produced. By 2018, the accumulated stock of red mud in the world already exceeds 46 hundred million tons; the annual output of the red mud in the world exceeds 1.6 million tons, wherein the annual increase of the red mud in China is about 1 million tons. The accumulated amount of the Chinese red mud also exceeds 7.9 million tons. Moreover, as the discharge and stockpiling of the red mud are gradually increased, the safe disposal of the red mud brings huge challenges, and the development of the alumina industry is restricted. The high yield and low consumption of red mud result in an increase in the amount of red mud stockpiled year by year. On one hand, the strong alkalinity and high salinity of the red mud bring serious environmental problems in the stacking process, on the other hand, the comprehensive utilization of the red mud is also limited, and the red mud becomes a bottleneck which restricts the sustainable development of aluminum industry of various countries in the world. Therefore, dealkalization of the red mud is the main direction for solving the problem of red mud stockpiling and the problem of comprehensive utilization. The manganese slag leachate is weakly acidic wastewater generated after manganese slag is stockpiled, has the pH value of about 5.9, and pollutants such as soluble manganese in the wastewater migrate into surrounding soil, underground water and rivers, thereby causing serious threats to the ecological environment and human health. Therefore, the red mud is dealkalized by utilizing the manganese slag percolate, so that the alkalinity of the red mud is reduced, the problem of discharge of the manganese slag percolate is solved, the environmental impact caused by the red mud and the manganese slag percolate is reduced, and reference is provided for the basic idea of regulating and controlling the alkalinity of the red mud by using waste to treat waste.
The existing red mud dealkalization process mainly comprises a water washing method, an acid neutralization method, a seawater method and a gypsum method. The water consumption of the water washing method is large and the dealkalization efficiency is low; the acid neutralization method causes silicon, aluminum and iron in the red mud to dissolve in a liquid phase and form a colloid, causing a problem of difficulty in filtration. In addition, the acid neutralization process results in a reduced yield of dealkalized red mud and is acidic, which is not beneficial for subsequent utilization, and the seawater process requires a higher liquid-to-solid ratio and is not suitable for the alumina industry in non-coastal areas. The gypsum method is difficult to be widely used because of the slow dissolution rate of gypsum.
Therefore, how to develop a new dealkalization method for red mud is a technical problem which needs to be solved urgently.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for removing sodium and potassium in red mud by utilizing manganese slag percolate, which is characterized in that the red mud is dealkalized by utilizing the manganese slag percolate containing elements such as manganese, calcium and the like, so that the sodium and potassium in the red mud are released, and diaspore ([ Mn ] Al-Mn-Fe-B) is generated in the dealkalized red mud4Al2(OH)12CO3·3H2O]) Is beneficial to the addition and use of the building material.
In order to achieve the technical purpose, the invention provides the following technical scheme:
a method for removing sodium and potassium in red mud by utilizing manganese slag leachate comprises the following steps:
(1) drying, grinding and sieving the red mud and the manganese slag respectively;
(2) adding water into the treated manganese slag, placing the manganese slag in a constant-temperature water bath oscillator for leaching reaction, and filtering to obtain manganese slag leachate;
(3) adding the manganese slag leachate into the treated red mud, placing the red mud in a constant-temperature water bath oscillator for leaching reaction again, repeatedly leaching, centrifuging, washing and filtering to obtain the red mud after dealkalization of the manganese slag leachate.
Preferably, the drying temperature in the step (1) is 70-90 ℃, and the drying time is 24 h.
Preferably, the sieving in step (1) is 80-120 mesh sieving.
Preferably, the manganese slag in the step (2) is electrolytic manganese slag or manganese sulfate slag discharged in manganese sulfate production.
Preferably, the liquid-solid ratio of the water to the manganese slag in the step (2) is 1-3 mL/g.
Preferably, the leaching conditions in step (2) are as follows: reacting for 1.5-2.5h at room temperature, and oscillating at 240 r/min.
Preferably, the leaching reaction conditions in the step (3) are as follows: reacting for 1-2h at the temperature of 90-95 ℃, and the oscillation speed is 240 r/min.
Preferably, the liquid-solid ratio of the manganese slag leachate to the red mud in the step (3) is 8-12 mL/g.
Preferably, the number of repetitions of step (3) is 4 to 6. Preferably 5 times.
The invention also provides dealkalized red mud prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
during the dealkalization by the traditional acid method, components such as aluminum, iron, calcium and the like in the red mud are often dissolved out, the generated colloid is not beneficial to filtration and separation, and the dealkalized red mud is acidic and is not beneficial to subsequent addition and use in the building material field. The method adopts the idea of treating waste by waste, and takes manganese slag leachate as dealkalization raw material to remove potassium and sodium in the red mud, so that the content of alkaline substances in the red mud is effectively reduced, simultaneously, the content of alumina, silica, ferric oxide and other components in the dealkalization process is basically unchanged, the filtration and separation are facilitated, and the red mud after dealkalization almost does not release heavy metals after being soaked in water, and is basically harmless to the environment. In addition, the method dealkalizes the red mud by the leachate containing elements such as manganese, calcium and the like, so that sodium and potassium of the red mud are released, and the diaspore is generated in the dealkalized red mud, thereby being beneficial to the addition and use of the diaspore in building materials.
The invention adopts manganese slag leachate and red mud to react, mainly utilizes manganese ions in the red mud to exchange sodium and potassium in the red mud, does not simply mix acid waste slag and red mud and carry out dealkalization by utilizing an acid-base neutralization mode, and provides a new route for dealkalizing the red mud.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
(1) Drying the red mud and the electrolytic manganese slag at 80 ℃ for 24h respectively and sieving the dried red mud and the electrolytic manganese slag with a 100-mesh sieve;
(2) adding water (the liquid-solid ratio of the water to the manganese slag is 2mL/g) into the treated electrolytic manganese slag, carrying out leaching reaction for 2h in a constant-temperature water bath oscillator at the rotating speed of 240r/min at room temperature, and filtering to obtain electrolytic manganese slag leachate;
(3) placing 5g of sieved red mud sample into a conical flask, adding the electrolytic manganese slag percolate according to the liquid-solid ratio of 10mL/g of the electrolytic manganese slag percolate to the red mud, and reacting for 2h in a constant-temperature water bath oscillator at the rotating speed of 240r/min and the temperature of 95 ℃. And (4) performing circulating leaching for five times, and performing centrifugation, washing and filtration to obtain a sodium and potassium-containing leachate and dealkalized red mud of the electrolytic manganese residue leachate.
The leaching rates of sodium and potassium can respectively reach 78.31 percent and 80.78 percent, and the pH value of the leaching solution is 7.96.
Example 2
The difference from example 1 is that the electrolytic manganese residue was replaced with manganese sulfate residue.
The leaching rates of sodium and potassium can respectively reach 80.48% and 73.77%, and the pH of the leaching solution is 7.61.
Example 3
The difference from example 2 is that the reaction temperature in step (3) is 90 ℃.
The leaching rates of sodium and potassium can respectively reach 72.84% and 70%, and the pH value of the leaching solution is 7.71.
Example 4
(1) Drying the red mud and the electrolytic manganese slag at 70 ℃ for 24h respectively and sieving the dried red mud and the electrolytic manganese slag with a 120-mesh sieve;
(2) adding water (the liquid-solid ratio of the water to the manganese slag is 1mL/g) into the treated electrolytic manganese slag, carrying out leaching reaction for 2h in a constant-temperature water bath oscillator at the rotating speed of 240r/min at room temperature, and filtering to obtain electrolytic manganese slag leachate;
(3) placing 5g of sieved red mud sample into a conical flask, adding the electrolytic manganese slag percolate according to the liquid-solid ratio of 8mL/g of the electrolytic manganese slag percolate to the red mud, and reacting for 2h in a constant-temperature water bath oscillator at the rotating speed of 240r/min and the temperature of 95 ℃. And circularly leaching for six times, centrifuging, washing and filtering to obtain sodium and potassium-containing leachate and dealkalized red mud of electrolytic manganese residue leachate.
The leaching rates of sodium and potassium can respectively reach 74.12% and 72.3%, and the pH value of the leaching solution is 7.46.
Example 5
(1) Drying the red mud and the electrolytic manganese slag at 90 ℃ for 24h respectively and sieving the dried red mud and the electrolytic manganese slag with a 80-mesh sieve;
(2) adding water (the liquid-solid ratio of the water to the manganese slag is 2mL/g) into the treated electrolytic manganese slag, carrying out leaching reaction for 2h in a constant-temperature water bath oscillator at the rotating speed of 240r/min at room temperature, and filtering to obtain electrolytic manganese slag leachate;
(3) placing 5g of sieved red mud sample into a conical flask, adding the electrolytic manganese slag percolate according to the liquid-solid ratio of the electrolytic manganese slag percolate to the red mud of 12mL/g, and reacting for 2h in a constant-temperature water bath oscillator at the rotating speed of 240r/min and the temperature of 92 ℃. And (4) circularly leaching for four times, and centrifuging, washing and filtering to obtain a sodium and potassium-containing leachate and the dealkalized red mud of the electrolytic manganese residue leachate.
The leaching rates of sodium and potassium can respectively reach 75.4% and 76.3%, and the pH value of the leaching solution is 7.11.
Test 1
The samples of examples 1-2 were soaked in water at room temperature for 2 hours at a liquid-solid ratio of 10 mL/g. After filtration, the concentration of heavy metal ions was measured by inductively coupled plasma emission spectroscopy (ICP-OES), and the results are shown in table 1.
TABLE 1 concentration (mg/L) of heavy metal ions in the dealkalized red mud in examples 1-2 in the aqueous solution
As can be seen from Table 1, the heavy metal ion concentration of the dealkalized red mud is very low after the red mud is immersed in water, and the influence on the environment is very small, so that the alkalinity of the red mud can be effectively reduced by using the dealkalization of the manganese slag leachate, and the influence on the environment is hardly caused.
Comparative example 1
The difference from example 1 is that the electrolytic manganese residue was directly mixed with red mud and water.
As a result, it was found that: the leaching rates of sodium and potassium are respectively 62.1% and 71.4%, and the pH of the leaching solution is 7.23. The electrolytic manganese residue leachate is obtained without leaching reaction of the non-electrolytic manganese residue, so that the removal efficiency is seriously reduced.
Comparative example 2
The difference from example 1 is that the liquid-solid ratio of water to manganese slag was 5 mL/g.
As a result, it was found that: the leaching rates of sodium and potassium were 73.6% and 79.4%, respectively.
Comparative example 3
The difference of the method is that the liquid-solid ratio of the electrolytic manganese slag percolate to the red mud is 15mL/g as in example 1.
As a result, it was found that: the leaching rates of sodium and potassium are 78.33% and 80.93%, respectively. Compared with the embodiment 1 in which the liquid-solid ratio is 10mL/g, the leaching rate of sodium and potassium is not obviously improved, which indicates that the electrolytic manganese slag leachate does not need to be added too much, and the production cost is increased by adding too much.
Comparative example 4
The same as example 1 except that the reaction temperature in step (3) was 90 ℃.
As a result, it was found that: the leaching rates of sodium and potassium are 71.4% and 76.5%, respectively.
Comparative example 5
The same as example 1 except that the reaction temperature in step (3) was 100 ℃.
As a result, it was found that: the leaching rates of sodium and potassium are 69.23% and 71.09%, respectively.
Comparative example 6
The difference from example 1 is that step (3) is carried out 3 times of cyclic leaching.
As a result, it was found that: the leaching rates of sodium and potassium are 76.45% and 78.52%, respectively.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for removing sodium and potassium in red mud by utilizing manganese slag leachate is characterized by comprising the following steps:
(1) drying, grinding and sieving the red mud and the manganese slag respectively;
(2) adding water into the treated manganese slag for leaching reaction, and filtering to obtain manganese slag leachate;
(3) and adding the manganese slag leachate into the treated red mud for leaching reaction again, repeatedly leaching, centrifuging, washing and filtering to obtain the red mud after dealkalization of the manganese slag leachate.
2. The method according to claim 1, wherein the drying temperature in step (1) is 70-90 ℃ and the drying time is 24 h.
3. The method of claim 1, wherein the sieving in step (1) is through an 80-120 mesh sieve.
4. The method according to claim 1, wherein the manganese slag in the step (2) is electrolytic manganese slag or manganese sulfate slag discharged in manganese sulfate production.
5. The method according to claim 1, wherein the liquid-solid ratio of the water to the manganese slag in the step (2) is 1-3 mL/g.
6. The method of claim 1, wherein the leaching conditions of step (2) are: reacting for 1.5-2.5h at room temperature, and oscillating at 240 r/min.
7. The method as claimed in claim 1, wherein the leaching reaction conditions of step (3) are as follows: reacting for 1-2h at the temperature of 90-95 ℃, and the oscillation speed is 240 r/min.
8. The method according to claim 1, wherein the liquid-solid ratio of the manganese slag leachate to the red mud in the step (3) is 8-12 mL/g.
9. The method of claim 1, wherein the number of repetitions of step (3) is 4-6.
10. Dealkalized red mud prepared by the method of any one of claims 1 to 9.
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- 2021-04-26 CN CN202110451851.8A patent/CN113087328B/en active Active
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| CN108975364A (en) * | 2018-07-30 | 2018-12-11 | 中南大学 | A kind of method that the processing of Bayer process red mud acid removes alkali collection sodium |
| CN109608073A (en) * | 2018-12-26 | 2019-04-12 | 中国科学院地球化学研究所 | A method of light-weight aggregate is prepared using manganese sulfate slag and red mud |
| CN109987639A (en) * | 2019-03-22 | 2019-07-09 | 昆明理工大学 | A kind of method that aluminium strengthens red mud dealkalization and separates and recovers aluminium, iron |
| CN109970368A (en) * | 2019-04-11 | 2019-07-05 | 东北大学 | A kind of method that the melting and reducing dealkalize of iron red mud vortex mentions the direct cement of iron |
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