CN113105282B - Method for preparing silicon-potassium-calcium compound fertilizer by using calcium-containing red mud - Google Patents
Method for preparing silicon-potassium-calcium compound fertilizer by using calcium-containing red mud Download PDFInfo
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- CN113105282B CN113105282B CN202110466508.0A CN202110466508A CN113105282B CN 113105282 B CN113105282 B CN 113105282B CN 202110466508 A CN202110466508 A CN 202110466508A CN 113105282 B CN113105282 B CN 113105282B
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/02—Oxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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Abstract
A method for preparing a silicon-potassium-calcium compound fertilizer by using calcium-containing red mud comprises the following steps: (1) mixing the mother liquor containing potassium metaaluminate with the red mud containing calcium, or mixing the mixed mother liquor containing potassium metaaluminate and sodium metaaluminate with the red mud containing calcium; (2) heating the mixed slurry to 210-260 ℃, and stirring and leaching; (3) carrying out solid-liquid separation after flash evaporation on the leached materials to obtain transformation liquid and transformation slag; the solid phase in the transformation slag is mainly hydrated potassium aluminosilicate, and the hydrated potassium aluminosilicate is washed by water and dried to prepare the silicon-potassium-calcium compound fertilizer. The method can prepare the silicon-potassium-calcium compound fertilizer by using the mode of leaching the calcium-containing red mud by using the potassium metaaluminate mother liquor, thereby realizing the harmless utilization of the red mud; can extract partial alumina and a large amount of sodium oxide in the red mud, and realize valuable component recovery.
Description
The technical field is as follows:
the invention belongs to the technical field of comprehensive utilization of red mud, and particularly relates to a method for preparing a silicon-potassium-calcium compound fertilizer by utilizing calcium-containing red mud.
Technical Field
The red mud is solid waste generated in the process of producing alumina from bauxite, and because the alkali content is high and difficult to remove, most of the red mud adopts a stacking mode, the comprehensive utilization rate is insufficient, and long-term stacking treatment not only occupies a large amount of land resources, but also pollutes the environment. The red mud can be obtained by analyzing the composition of the red mud, contains some nutrient elements required by the growth of crops, has the advantages of good particle distribution and dispersibility, and can be considered to be made into fertilizer for crop production, so that the utilization rate of the fertilizer is improved.
In recent years, relevant practitioners have performed a great deal of research work on the comprehensive utilization of red mud, such as "a fertilizer for soil remediation assisted by red mud, which is proposed by grandson: the method of CN 105330476A ", the main steps include: (1) drying orange peel and kapok shell, mixing with siderite slag, calcining, and sieving to obtain magnetic charcoal powder; (2) mixing wheat gluten powder, humus soil and cottonseed cakes, and fermenting to obtain fermented solid residues and fermented liquid; (3) mixing and heating the fermentation liquor, potassium selenite and ammonium humate, and then adding charcoal powder for impregnation to obtain impregnated charcoal; (4) calcining and crushing the red mud, and then sieving the red mud with a 50-mesh sieve to obtain red mud particles; (5) mixing the impregnated biochar with fermentation solid residues, red mud particles, an EM composite microbial agent and other residual materials, and granulating; (6) and (5) irradiating the particles obtained in the step (5) for 40-60 minutes by using ultrasonic waves to obtain the soil remediation fertilizer.
' a compound fertilizer prepared by red mud and a preparation method thereof, which are proposed by Liukai Ping, and the publication number is as follows: the scheme of CN 110590461A "comprises the following main steps: (1) drying the red mud, mixing the dried red mud with furnace slag, crushing, adding organic acid and organic liquid fertilizer, uniformly stirring, adjusting the pH value to 7-9, adding coal ash, and controlling the temperature and the moisture to obtain a red mud mixture; (2) mixing the red mud mixture with wormcast or soil, rice hull powder, sweet potato powder, straw powder, saw dust and mixed strains, controlling the moisture and the temperature, fermenting, adding the rest raw materials after the fermentation is finished, uniformly mixing and granulating to obtain the compound fertilizer.
The' red mud particle soil remediation agent and the preparation method thereof proposed by Zhao Guangli et al, the publication number is: the scheme of CN 105316001A "comprises the following main steps: s1, mixing and crushing red mud, gypsum and a cementing material according to a proportion, stirring for 2-4 hours, and then sieving with a 60-mesh sieve to obtain mixed powder; s2, granulating the mixed powder into balls; s3, drying the balls obtained in the step S2 for 12-48 hours; and S4, drying the green balls dried in the air of the S3, and naturally cooling to obtain the red mud granular soil remediation agent.
Although the existing method can also realize the comprehensive utilization of the red mud, the problems of complex flow, long production period, more raw materials, increased production cost and the like exist, the red mud generated by producing alumina has strong alkalinity, and sodium oxide can bring harm to the growth of crops if dealkalization treatment is not carried out.
Disclosure of Invention
The invention aims to provide a method for preparing a silicon-potassium-calcium compound fertilizer by using calcium-containing red mud, which overcomes the defects in the prior art and improves the comprehensive utilization rate of the red mud.
The method of the invention comprises the following steps:
1. mixing the mother liquor containing potassium metaaluminate with the red mud containing calcium, or mixing the mixed mother liquor containing potassium metaaluminate and sodium metaaluminate with the red mud containing calcium, wherein the mixing ratio is 3-4.5 mL/g according to the liquid-solid ratio to obtain mixed slurry; the calcium-containing red mud contains Al according to mass percentage 2 O 3 10～25％，CaO 10～50％，SiO 2 15～25％，Na 2 O 4～10％，K 2 O 0.5～2.0％；
2. Heating the mixed slurry to 210-260 ℃, and carrying out leaching reaction under the stirring condition for 10-55 min to obtain a leaching material;
3. carrying out flash evaporation on the leached materials, and carrying out solid-liquid separation to obtain transformation liquid and transformation slag; the solid phase in the transformation slag is mainly hydrated potassium aluminosilicate, and the silicon-potassium-calcium compound fertilizer is prepared after washing and drying.
In the step 2, the main reaction formula of the leaching reaction is as follows:
Na 2 O·Al 2 O 3 ·SiO 2 ·nH 2 O+2KAl(OH) 4 →2KAl SiO 4 +2NaAl(OH) 4 +n H 2 O (1)。
in the step 3, the silicon-potassium-calcium compound fertilizer contains K according to the mass percentage 2 O≥15％。
In the step 3, the transformation liquid is cooled to separate out partial sodium hydroxide and aluminum hydroxide, and then a solid phase and a liquid phase are separated by filtration; the solid phase is used for producing alumina by a Bayer process, the liquid phase is used as mother liquor containing potassium perchlorate, and after potassium hydroxide solution is added, the solution returns to the step 1 for recycling.
The reaction formula of the temperature reduction and precipitation is as follows:
Al(OH) 4 + →Al(OH) 3 ↓+OH - (2)。
in the method, the recovery rate of the aluminum oxide is 10-25%, and the recovery rate of the sodium oxide is 93-96%.
In the method, the washing liquid is washed until the washing liquid is neutral, and the obtained washing liquid is mixed with the filtrate and then cooled to separate out.
The method of the invention leaches the K in the transformation slag through the mother liquor 2 The content of O is increased, and Al in the red mud 2 O 3 After being dissolved by the alkali, part of the solution enters a liquid phase, the solution containing part of the alkali and aluminum is recovered, is crystallized by cooling to separate out aluminum hydroxide and sodium hydroxide, and is returned to a Bayer process system for producing aluminum oxide, and the mother solution after being separated out by cooling is supplemented with potassium hydroxide solution and is returned to the process for recycling; cooling, crystallizing and separating out partial sodium hydroxide and aluminum hydroxide solids, and returning the sodium hydroxide and aluminum hydroxide solids to a Bayer process system to produce aluminum oxide, so as to achieve the purpose of removing sodium and extracting aluminum from the calcium-containing red mud; the invention adopts the potassium metaaluminate mother liquor to directly leach the red mud containing calcium, and realizes the harmless treatment of the red mud by combining the Bayer process to produce alumina.
Compared with the prior art, the invention has the characteristics and beneficial effects that: (1) by utilizing the mode of leaching the calcium-containing red mud by the potassium metaaluminate mother liquor, the silicon-potassium-calcium compound fertilizer can be prepared, and the harmless utilization of the red mud is realized; (2) the calcium-containing red mud is leached by the potassium metaaluminate mother liquor, partial alumina and a large amount of sodium oxide in the red mud can be extracted, and valuable component recovery is realized.
Drawings
FIG. 1 is a schematic flow chart of the method for preparing the silicon-potassium-calcium compound fertilizer by using the calcium-containing red mud.
Detailed Description
The calcium-containing red mud in the embodiment of the invention is red mud generated in the process of producing alumina by a Bayer process.
The solute of the potassium metaaluminate mother liquor in the embodiment of the invention comprises KOH and KAl (OH) 4 KOH concentration of 200-240 g/L, K in solution + And Al (OH) 4 - The molar ratio of (A) to (B) is 3 to 7.
The solute of the mixed mother liquor containing potassium metaaluminate and sodium metaaluminate in the embodiment of the invention comprises KOH, NaOH, KAl (OH) 4 And NaAl (OH) 4 The concentration of KOH is 200-240 g/L, (K) + +Na + ) And Al (OH) 4 - The molar ratio of (A) to (B) is 3 to 7.
In the embodiment of the invention, the stirring speed of the leaching reaction is 200-400 rpm.
In the embodiment of the invention, the washing liquid is washed until the washing liquid is neutral, and the obtained washing liquid is mixed with the filtrate and then cooled to separate out.
The recovery rate of alumina in the embodiment of the invention is the yield of converting alumina in red mud into alumina in a solid phase.
In the embodiment of the invention, the recovery rate of the sodium oxide is the yield of converting the sodium oxide in the red mud into the sodium hydroxide in the liquid phase.
In the embodiment of the invention, the material after flash evaporation is subjected to solid-liquid separation in a filtering or settling mode.
Example 1
The flow is shown in figure 1;
mixing the mixed mother liquor containing potassium metaaluminate and sodium metaaluminate with the calcium-containing red mud according to the mixing ratio of 3mL/g to obtain mixed slurry;
the red mud containing calcium contains Al according to the mass percentage 2 O 3 22.25％，CaO 13.31％，SiO 2 19.58％，Na 2 O 6.85％，K 2 O1.82％；
The potassium hydroxide concentration of the mixed mother liquor containing potassium metaaluminate and sodium metaaluminate is 200 g/L;
heating the mixed slurry to 210 ℃, and carrying out leaching reaction under the stirring condition for 55min to obtain a leaching material;
after the leaching material is subjected to flash evaporation, filtering and solid-liquid separation (a filtering mode is selected) to obtain transformation liquid and transformation slag; the solid phase in the transformation slag is mainly hydrated potassium aluminosilicate, and the silicon-potassium-calcium compound fertilizer is prepared after washing and drying, and contains 15% of potassium oxide, 21.91% of silicon oxide, 15.69% of calcium oxide, 0.33% of sodium oxide and 18.82% of aluminum oxide according to mass percentage;
cooling the transformation liquid to separate out partial sodium hydroxide and aluminum hydroxide, and then filtering and separating out a solid phase and a liquid phase; the solid phase is used for producing alumina by a Bayer process, the liquid phase is used as mother liquor containing potassium perchlorate, and after potassium hydroxide solution is added, the mother liquor returns to the preparation process of the mixed slurry for recycling;
the recovery of alumina was 24% and the recovery of sodium oxide was 93%.
Example 2
The method is the same as example 1, except that:
(1) mixing the mother liquor containing potassium metaaluminate with the red mud containing calcium according to the liquid-solid ratio of 4 mL/g;
(2) the concentration of potassium hydroxide in the mother liquor containing potassium metaaluminate is 220 g/L;
(3) heating the mixed slurry to 230 ℃ for leaching reaction for 30 min;
(4) the silicon-potassium-calcium compound fertilizer comprises 20.69 percent of silicon oxide, 15.49 percent of potassium oxide, 14.47 percent of calcium oxide, 0.5 percent of sodium oxide and 19.37 percent of aluminum oxide by mass percent;
(5) the recovery rate of alumina was 17.6% and the recovery rate of sodium oxide was 95%.
Example 3
The method is the same as example 1, except that:
(1) mixing the mother liquor containing potassium metaaluminate with the red mud containing calcium according to the liquid-solid ratio of 4.5 mL/g;
(2) the concentration of potassium hydroxide in the mother liquor containing potassium metaaluminate is 240 g/L;
(3) heating the mixed slurry to 260 ℃ for leaching reaction for 10 min;
(4) the silicon-potassium-calcium compound fertilizer comprises 21.65 percent of silicon oxide, 15.35 percent of potassium oxide, 14.23 percent of calcium oxide, 0.51 percent of sodium oxide and 19.78 percent of aluminum oxide by mass percent
(5) The recovery rate of alumina was 19.6% and the recovery rate of sodium oxide was 96%.
Claims (1)
1. A method for preparing a silicon-potassium-calcium compound fertilizer by using calcium-containing red mud is characterized by comprising the following steps:
(1) mixing the mother liquor containing potassium metaaluminate with the red mud containing calcium, or mixing the mixed mother liquor containing potassium metaaluminate and sodium metaaluminate with the red mud containing calcium, wherein the mixing ratio is 3-4.5 mL/g according to the liquid-solid ratio to obtain mixed slurry; the calcium-containing red mud contains Al according to mass percentage 2 O 3 10~25%，CaO 10~50%，SiO 2 15~25%，Na 2 O 4~10%，K 2 O 0.5~2.0%；
(2) Heating the mixed slurry to 210-260 ℃, and carrying out leaching reaction under the stirring condition for 10-55 min to obtain a leaching material;
(3) carrying out flash evaporation on the leached materials, and carrying out solid-liquid separation to obtain transformation liquid and transformation slag; the solid phase in the transformation slag is mainly hydrated potassium aluminosilicate, and the hydrated potassium aluminosilicate is washed and dried to prepare a silicon-potassium-calcium compound fertilizer; cooling the transformation liquid to separate out partial sodium hydroxide and aluminum hydroxide, and then filtering and separating out a solid phase and a liquid phase; the solid phase is used for producing alumina by a Bayer process, the liquid phase is used as mother liquor containing potassium metaaluminate, and after potassium hydroxide solution is added, the liquid phase returns to the step (1) for recycling; the silicon-potassium-calcium compound fertilizer contains K according to the mass percentage 2 O is more than or equal to 15 percent; the recovery rate of the aluminum oxide is 10-25%, and the recovery rate of the sodium oxide is 93-96%.
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| CN202110466508.0A CN113105282B (en) | 2021-04-28 | 2021-04-28 | Method for preparing silicon-potassium-calcium compound fertilizer by using calcium-containing red mud |
| PCT/CN2021/096795 WO2022227181A1 (en) | 2021-04-28 | 2021-05-28 | Method for preparing silicon-potassium-calcium compound fertilizer by using calcium-containing red mud |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030160A (en) * | 2012-12-11 | 2013-04-10 | 中国科学院过程工程研究所 | Method for recycling alumina and sodium oxide from bayer process red mud |
| CN103934258A (en) * | 2014-04-30 | 2014-07-23 | 东北大学 | Method for recycling alkali and aluminum in process of treating bayer red mud by calcification-carbonization method |
| 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 |
| CN109250741A (en) * | 2018-10-08 | 2019-01-22 | 东北大学 | A method of comprehensive utilization iron red mud |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| AU563304B2 (en) * | 1984-12-21 | 1987-07-02 | Comalco Aluminium Limited | Soz leach to recover soda and alumina from red mud with recycle to bayer process |
| CN101607725B (en) * | 2008-06-19 | 2011-04-20 | 中国科学院过程工程研究所 | Method for reclaiming alumina and sodium oxide in red mud of Bayer process |
| CN106187550B (en) * | 2016-08-02 | 2019-02-22 | 中国地质大学（北京） | A method of siliceous fertilizer is prepared using red mud flocculation agent acid leaching residue |
| CN107298452A (en) * | 2017-06-23 | 2017-10-27 | 东北大学 | The method that the hot method of the step alkali of andradite one handles Bayer process red mud production metallurgy grade aluminum oxide |
| CN107892630A (en) * | 2017-11-20 | 2018-04-10 | 曲方圆 | A kind of humic acid calcium silicate fertilizer based on red mud and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030160A (en) * | 2012-12-11 | 2013-04-10 | 中国科学院过程工程研究所 | Method for recycling alumina and sodium oxide from bayer process red mud |
| CN103934258A (en) * | 2014-04-30 | 2014-07-23 | 东北大学 | Method for recycling alkali and aluminum in process of treating bayer red mud by calcification-carbonization method |
| 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 |
| CN109250741A (en) * | 2018-10-08 | 2019-01-22 | 东北大学 | A method of comprehensive utilization iron red mud |
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