CN112981100B - Comprehensive utilization method of red mud by full wet method - Google Patents
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- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
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- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
- C22B34/125—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a sulfur ion as active agent
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- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/1259—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching treatment or purification of titanium containing solutions or liquors or slurries
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Abstract
The invention discloses a comprehensive utilization method of red mud by a full-wet method, which is characterized in that an inventor comprehensively recovers calcium, aluminum, titanium, scandium and iron in the red mud by reasonable process alternation, has low cost, and prepares six kinds of middle-high-end chemical products circulating in the market, such as calcium sulfate whisker, aluminum oxide, titanium dioxide, scandium oxide, ferrous sulfate, battery-grade iron phosphate and the like. In addition, the invention is completely a wet method, the main equipment only comprises a reaction tank and a filter press, no special equipment is needed, and the investment is relatively less. At present, the stockpiling of the red mud in China reaches billions of tons, each alumina plant produces millions of tons of red mud every year, the wet treatment is flexible, the production scale can be infinitely enlarged, the fire treatment equipment is special, the treatment scale is limited, the energy consumption is high, and if the method can be widely popularized and applied, the reutilization of wastes can be realized, the environmental pressure of the aluminum industry can be reduced, and certain economic benefit can be obtained.
Description
Technical Field
The invention belongs to the technical field of red mud treatment, and particularly relates to a full-wet comprehensive utilization method of red mud.
Background
The aluminum oxide production industry in China has stockpiled about billions of tons of red mud for decades, occupies a large amount of land and has potential environmental and safety hazards. At present, the policy of China is that newly-built red mud yards are prohibited, so that waste enterprises are required to promote the recycling of red mud.
On 8/10 th 2010, the Ministry of industry and informatization and the Ministry of science and technology printed the "guiding opinion on the comprehensive utilization of red mud" (the "opinion" hereinafter) in the Ministry of industry and communications [ 2010 ] 401. The opinion is divided into four parts of fully understanding the importance and urgency of comprehensive utilization of red mud, guiding thought, basic principle and target, key technology and key engineering and safeguard measures. The "opinion" stipulates that the main objectives are: by 2015, the comprehensive utilization rate of the red mud is struggled to reach 20%. Popularizing and applying a batch of advanced applicable technologies; establishing a batch of application demonstration and popularization demonstration projects with driving effects; 2-3 comprehensive utilization demonstration bases with certain scale of red mud are created to form a multi-path high-added-value comprehensive utilization development pattern of the red mud.
Although the comprehensive utilization of red mud has been studied for many years, a great number of proposals have been made by the majority of technologists. Such as:
the modified red mud is used for constructing highway subgrade by Dongwei bridge aluminum electric company in 4-month mountain in 2019, and the method has the advantages of simple process and environmental protection, but needs long-distance transportation and is not as easy as local materials, so the method is difficult to popularize.
The dongdong et al invented "a method for comprehensively recovering valuable metals such as iron, aluminum, scandium, titanium and vanadium from red mud" (patent No. 201410121083.X published as 2014 07-02), said patent adopts the combination of fire method and wet method, firstly, the red mud is fire-reduced, the iron oxide is magnetically separated, the aluminium hydroxide is alkaline-washed, then the titanium dioxide, scandium oxide and vanadium oxide are respectively recovered by acid leaching and two-step extraction, and the rest waste residue is used for producing cement. The method has the advantages that valuable metals such as iron, aluminum, titanium, scandium, vanadium and waste residues are recycled, and the method has the defects that smoke and dust are generated by a pyrogenic process, equipment is special, the scale is difficult to form, the lower end of a recovered product is high in energy consumption, benefits are difficult to generate, and the waste water contains a large amount of ammonia nitrogen and organic matters due to the use of ammonia water and two-step extraction, so that the waste water treatment cost is high. Therefore, the method has not been industrialized so far.
In addition, other methods which are disclosed and reported are mostly used for recovering single metals from red mud, such as iron recovery, scandium recovery, titanium recovery, vanadium recovery and the like, and although the methods are feasible, the single recovery is difficult to obtain benefits, and the purposes of resource utilization, reduction and harmlessness are difficult to achieve.
Disclosure of Invention
The invention aims to solve the technical problem of providing a comprehensive utilization method of red mud by a full-wet method, which is safe, environment-friendly, economical, practical and good in effect.
In order to solve the technical problems, the invention adopts the following technical scheme:
the method for comprehensively utilizing the red mud by a full-wet method comprises the following steps:
(1) Dilute hydrochloric acid is added into the red mud for primary leaching, calcium is leached, the reduction of the red mud is facilitated, the subsequent process is facilitated, meanwhile, a part of aluminum is leached, 20% of scandium is leached along with the aluminum, the scandium can be recovered in the aluminum leaching slag obtained in the step (6), and iron and titanium cannot be leached basically;
(2) Heating the filtrate treated in the step (1), and slowly adding a sodium sulfate solution while stirring to prepare calcium sulfate whisker products from calcium in the solution; sodium sulfate is concentrated and crystallized by a subsequent wastewater treatment process;
(3) Adding alkali liquor into the filtrate treated in the step (2) to ensure that aluminum is completely precipitated and aluminum slag is prepared for subsequent recovery of aluminum oxide;
(4) Adding sulfuric acid into the filter residue treated in the step (1) for secondary leaching, wherein iron, titanium, scandium and vanadium are leached together with the aluminum left in the step (1);
(5) Adding alkali liquor into the filtrate treated in the step (4) to completely precipitate iron, aluminum, titanium and scandium, and filtering to obtain filter residue and wastewater;
(6) Putting the filter residue treated in the steps (3) and (5) into alkali liquor to leach aluminum to form sodium aluminate, filtering, and recycling the alkali liquor;
(7) Heating and dissolving the filter residue treated in the step (6) by using sulfuric acid, flushing water, heating and stirring to completely hydrolyze and precipitate titanium, and filtering to obtain titanium primary hydrolysis residue;
(8) Dissolving the filter residue treated in the step (7) by using sulfuric acid, preparing titanium liquid according to the production requirement of titanium dioxide, and then hydrolyzing, washing, salinizing, drying and calcining to prepare a titanium dioxide product;
(9) Adding alkali liquor into the filtrate treated in the step (7) to enable iron and scandium to be coprecipitated, redissolving the iron and scandium coprecipitate, evaporating and concentrating to separate out ferrous sulfate, precipitating scandium hydroxide from the filtrate after iron separation, repeatedly washing, and calcining to obtain a scandium oxide crude product;
(10) Dissolving the ferrous sulfate precipitated after the treatment of the step (9) in water, adding sodium sulfide to remove impurities, filtering, adding phosphoric acid and a surfactant, adjusting the pH value with an alkaline solution, dropwise adding hydrogen peroxide to completely oxidize ferrous iron, stirring, washing and drying to obtain an iron phosphate product.
In the step (1): 1-5M of dilute hydrochloric acid is added into the red mud according to the solid-to-liquid ratio of 1.5-5.5, and the leaching temperature is 55-85 ℃.
In the step (2): heating to 70-90 deg.c and maintaining pH at 3-4.
In the step (3): adding alkali liquor to adjust the pH value to 5.3-7.
In the step (4): and (2) adding 10-45% of sulfuric acid (volume concentration) into the filter residue treated in the step (1) according to a liquid-solid ratio of 1.
In the step (5): and (3) adding alkali liquor to adjust the pH value to 6-8, and concentrating the wastewater by a multi-effect evaporator to obtain sodium sulfate as the raw material in the step (2).
In the step (6): when the sodium aluminate in the alkali liquor reaches 2mol/l, heating, stirring and precipitating to obtain aluminum hydroxide, and calcining the aluminum hydroxide to obtain an aluminum oxide product.
In the step (7): water is added and the pH value is adjusted to 1.5-2.1.
In the step (9): adding alkali liquor to adjust the pH value to 5-7.
In the step (10): the adding amount of the sodium sulfide is 1-10% (mass percentage), phosphoric acid (the mass concentration is 85%) is added according to the proportion of 1-3 of ferro-phosphorus, the adding amount of the surfactant (OP-10) is 0.5-5%, and the pH value is adjusted to 1-3 by alkali liquor.
Aiming at the problems existing in the treatment of the red mud at present, the inventor establishes a comprehensive utilization method of the red mud by a full-wet method, and the inventor comprehensively recovers calcium, aluminum, titanium, scandium and iron in the red mud by reasonable process alternation, has low cost, and prepares six kinds of middle-high-end chemical products circulating in the market, such as calcium sulfate whisker, alumina, titanium dioxide, scandium oxide, ferrous sulfate, battery-grade iron phosphate and the like. The whole process of the invention has no smoke and dust, no ammonia nitrogen and no organic matter in the wastewater, and most of the wastewater is recycled; the residue is only 50-60%, does not contain any heavy metal and harmful elements, belongs to common solid waste, can be used as bricks and tiles or used for repairing backfill soil of a pit, and really realizes 'reclamation, reduction and harmlessness'. In addition, the invention is completely a wet method, the main equipment only comprises a reaction tank and a filter press, no special equipment is needed, and the investment is relatively less. At present, the stockpiling of the red mud in China reaches billions of tons, each alumina plant produces millions of tons of red mud every year, the wet treatment is flexible, the production scale can be infinitely enlarged, the fire treatment equipment is special, the treatment scale is limited, the energy consumption is high, and if the method can be widely popularized and applied, the reutilization of wastes can be realized, the environmental pressure of the aluminum industry can be reduced, and certain economic benefit can be obtained.
Drawings
FIG. 1 is a process flow diagram of the comprehensive utilization method of red mud by a full-wet method.
Detailed Description
Example 1
1. Taking 100 g of perennial aluminum red mud (dry basis), adding about 200 ml of water, adding 100 ml of concentrated hydrochloric acid while stirring, flushing to 400 ml, stirring for 1 hour at 70 ℃, and filtering to obtain 175 g of filter residue (containing 60 percent of water) and 250 ml of filtrate.
2. Keeping the pH value of the filtrate in the step (1) at 3-4, heating to 70-90 ℃, slowly adding sodium sulfate until the concentration of calcium ions in the solution is less than 0.02 mol/L, slowly stirring for 2 hours, and aging for 24 hours to prepare calcium sulfate whiskers; filtering, washing and drying to obtain 21.25 g of calcium sulfate whisker, wherein the content of calcium sulfate is more than or equal to 98 percent, and the filtrate is 230 ml.
3. Adjusting the pH of the filtrate obtained in the step (2) to about 6.5 by using an alkaline solution at normal temperature, and filtering to obtain 160 g (wet) of basic aluminum chloride slag which is used as a raw material for later recovery of aluminum hydroxide, wherein the filtrate is 300 ml;
4. adding about 200 ml of water into the filter residue obtained in the step (1), adding 60 ml of sulfuric acid, flushing the water to 350 ml, leaching for 2 hours at 80-90 ℃, and filtering to obtain 120 g (wet) of filter residue, wherein the residue does not contain any harmful metal and can be used for repairing brickmaking tiles or mine pits, and the filtrate is 220 ml.
5. Adjusting the pH of the filtrate obtained in the step (4) to 6.5 by using alkali liquor, stirring for 1 hour, and filtering to obtain 150 g (wet) of filter residue and 200 ml of filtrate; concentrating the wastewater by a multi-effect evaporator to obtain sodium sulfate which is used as a raw material for preparing the calcium sulfate whisker in the step (2);
6. and (3) putting the filter residue in the step (5) and the filter residue in the step (3) into liquid caustic soda (sodium aluminate mother liquor), heating to 70-80 ℃, and stirring for 0.5 hour. Filtering to obtain 120 g of filter residue, wherein the filtrate is the mother liquor of sodium aluminate and is repeatedly used.
When the concentration of sodium aluminate in the mother liquor reaches about 2mol/l, the mother liquor is heated and stirred, aluminum hydroxide seed crystals are added to decompose sodium aluminate into aluminum hydroxide, and the aluminum hydroxide is calcined to obtain 14.5 g of alumina with the alumina content of 97.6 percent.
7. And (3) dissolving the filter residue in the step (6) by using sulfuric acid, flushing 300 ml of water, adjusting the pH value to 1.5-2.1, heating to hydrolyze titanium, and filtering to obtain 18 g (wet) of titanium residue and 280 ml of filtrate.
8. Dissolving the titanium slag obtained in the step (7) by using sulfuric acid to prepare titanium liquid, hydrolyzing, bleaching, washing, salinizing and filtering to obtain 12 g (wet) of metatitanic acid and 300 ml of filtrate. The metatitanic acid is calcined at 500 ℃ to obtain 5.2 g of titanium dioxide.
9. And (4) adding alkali liquor into the filtrate obtained in the step (7) to adjust the pH value to 5-7, coprecipitating iron and scandium, redissolving the iron and scandium coprecipitation, evaporating and concentrating to separate out ferrous sulfate, and filtering to obtain 75 g (wet) of ferrous sulfate and 80 ml of filtrate. And precipitating scandium hydroxide from the filtrate by using an alkaline solution, washing and calcining to obtain 0.013 g of coarse scandium oxide and 91% scandium oxide.
10. Dissolving ferrous sulfate (9) in water, filtering to remove impurities, purifying and removing impurities by using 1-10% of sodium sulfide, filtering to remove impurities, adding phosphoric acid (the mass concentration is 85%) with the phosphorus-iron ratio of 1.1, adjusting the pH to 1.5, adding hydrogen peroxide to completely oxidize Fe, adding 1% of surfactant OP-10 to obtain white ferric phosphate precipitate, washing and drying to obtain 21 g (dry) of ferric phosphate, wherein the ferric phosphate content is more than or equal to 99%.
The alkali solution used for adjusting the pH is a 30% sodium hydroxide solution.
Example 2
1. 100 g of red mud (dry basis) in the Debao Hua silver aluminum industry is taken, about 200 ml of water is added, 100 ml of concentrated hydrochloric acid is added under stirring, then the mixture is flushed to 400 ml, the mixture is stirred for 1 hour at 70 ℃, and then the mixture is filtered, so that 152 g of filter residue (containing 62 percent of water) is obtained, and 265 ml of filtrate is obtained.
2. Keeping the pH value of the filtrate obtained in the step (1) at 3-4, heating to 70-90 ℃, slowly adding sodium sulfate until the concentration of calcium ions in the solution is less than 0.02 mol/L, slowly stirring for 2 hours, and aging for 24 hours to prepare calcium sulfate whiskers; filtering, washing and drying to obtain 25.3 g of calcium sulfate whisker, wherein the content of calcium sulfate is more than or equal to 98 percent, and the filtrate is 225 ml.
3. Adjusting the pH of the filtrate obtained in the step (2) to about 6.5 by using alkali liquor at normal temperature, and filtering to obtain 175 g (wet) of basic aluminum chloride slag, wherein the basic aluminum chloride slag is used for later recovery of aluminum hydroxide, and the filtrate is 310 ml;
4. adding about 200 ml of water into the filter residue in the step (1), adding 60 ml of sulfuric acid, flushing the water to 350 ml, leaching for 2 hours at 80-90 ℃, and filtering to obtain 130 g (wet) of filter residue, wherein the residue does not contain any harmful metal and can be used for repairing brickmaking tiles or mine pits, and the filtrate is 230 ml.
5. Adjusting the pH of the filtrate obtained in the step (4) to 6.5 by using alkali liquor, stirring for 1 hour, and filtering to obtain 160 g (wet) of filter residue and 220 ml of filtrate; concentrating the wastewater by a multi-effect evaporator to obtain sodium sulfate which is used as a raw material for preparing the calcium sulfate whisker in the step (2);
6. and (3) putting the filter residue in the step (5) and the filter residue in the step (3) into liquid caustic soda (sodium aluminate mother liquor), heating to 70-80 ℃, and stirring for 0.5 hour. Filtering to obtain 138 g of filter residue, wherein the filtrate is the mother liquor of sodium aluminate and is repeatedly used.
When the concentration of sodium aluminate in the mother liquor reaches about 2mol/l, the mother liquor is heated and stirred, aluminum hydroxide seed crystals are added to decompose sodium aluminate into aluminum hydroxide, and the aluminum hydroxide is calcined to obtain 15.2 g of alumina with the alumina content of 98.1%.
7. And (4) dissolving the filter residue in the step (6) by using sulfuric acid, flushing 300 ml of water, adjusting the pH value to 1.5-2.1, heating to hydrolyze titanium, and filtering to obtain 16.5 g (wet) of titanium residue and 300 ml of filtrate.
8. Dissolving the titanium slag (7) with sulfuric acid to prepare titanium liquid, hydrolyzing, bleaching, washing, salinizing, and filtering to obtain 11 g (wet) metatitanic acid and 310 ml filtrate. The metatitanic acid is calcined at 500 ℃ to obtain 5.0 g of titanium dioxide.
9. And (3) adding alkali liquor into the filtrate obtained in the step (7) to adjust the pH value to 5-7, carrying out iron-scandium coprecipitation, redissolving the iron-scandium coprecipitation, carrying out evaporation concentration to separate out ferrous sulfate, and filtering to obtain 82 g (wet) of ferrous sulfate and 90 ml of filtrate. And precipitating scandium hydroxide from the filtrate by using an alkaline solution, washing and calcining to obtain 0.009 g of coarse scandium oxide containing 95% of scandium oxide.
10. Dissolving ferrous sulfate (9) in water, filtering to remove impurities, purifying and removing impurities by using 1-10% sodium sulfide, filtering to remove impurities, adding phosphoric acid (the mass concentration is 85%) with the phosphorus-iron ratio of 1.2, adjusting the pH to 1.5, adding hydrogen peroxide to completely oxidize Fe, adding 1% of surfactant OP-10 to obtain white ferric phosphate precipitate, washing and drying to obtain 26 g (dry) of ferric phosphate, wherein the ferric phosphate content is more than or equal to 99%.
The alkali solution used for adjusting the pH is a 30% sodium hydroxide solution.
In order to meet the actual production requirements, the acid consumption is kept to be proper, the leaching rate of each metal is kept to be about 80%, the yield is higher than the cost, if the leaching rate is overhigh, the acid consumption is increased, and the cost is infinitely increased.
Claims (9)
1. A method for comprehensively utilizing red mud by a full-wet method is characterized by comprising the following steps:
(1) 1-5M of dilute hydrochloric acid is added into the red mud according to the solid-to-liquid ratio of 1.5-5.5, the leaching temperature is 55-85 ℃, and primary leaching is carried out;
(2) Heating the filtrate treated in the step (1), and slowly adding a sodium sulfate solution while stirring to prepare calcium sulfate whisker products from calcium in the solution;
(3) Adding alkali liquor into the filtrate treated in the step (2) to ensure that aluminum is completely precipitated and is prepared into aluminum slag for subsequent recovery of aluminum oxide;
(4) Adding sulfuric acid into the filter residue treated in the step (1) for secondary leaching;
(5) Adding alkali liquor into the filtrate treated in the step (4) to completely precipitate iron, aluminum, titanium and scandium, and filtering to obtain filter residue and wastewater;
(6) Putting the filter residue treated in the steps (3) and (5) into alkali liquor to leach aluminum to form sodium aluminate, and filtering to recycle the alkali liquor;
(7) Heating and dissolving the filter residue treated in the step (6) by using sulfuric acid, flushing water, heating and stirring to completely hydrolyze and precipitate titanium, and filtering to obtain titanium primary hydrolysis residue;
(8) Dissolving the filter residue treated in the step (7) by using sulfuric acid, preparing titanium liquid according to the production requirement of titanium dioxide, and then hydrolyzing, washing, salinizing, drying and calcining to obtain a titanium dioxide product;
(9) Adding alkali liquor into the filtrate treated in the step (7) to enable iron and scandium to be coprecipitated, redissolving the iron and scandium coprecipitate, evaporating and concentrating to separate out ferrous sulfate, precipitating scandium hydroxide from the filtrate after iron separation, repeatedly washing, and calcining to obtain a scandium oxide crude product;
(10) Dissolving the ferrous sulfate precipitated after the treatment in the step (9) with water, adding sodium sulfide to remove impurities, filtering, adding phosphoric acid and a surfactant, adjusting the pH value with an alkaline solution, dropwise adding hydrogen peroxide to completely oxidize ferrous iron, stirring, washing and drying to obtain an iron phosphate product.
2. The full-wet comprehensive utilization method of red mud according to claim 1, characterized in that in step (2): heating to 70-90 deg.c and maintaining pH 3-4.
3. The full-wet comprehensive utilization method of red mud according to claim 1, characterized in that in step (3): adding alkali liquor to adjust the pH value to 5.3-7.
4. The full-wet comprehensive utilization method of red mud according to claim 1, characterized in that in step (4): adding 10-45% of sulfuric acid into the filter residue treated in the step (1) according to a liquid-solid ratio of 1.
5. The full-wet comprehensive utilization method of red mud according to claim 1, characterized in that in the step (5): and (3) adding alkali liquor to adjust the pH value to 6-8, and concentrating the wastewater by a multi-effect evaporator to obtain sodium sulfate as the raw material in the step (2).
6. The full-wet comprehensive utilization method of red mud according to claim 1, characterized in that in step (6): when the sodium aluminate in the alkali liquor reaches 2mol/l, heating, stirring and precipitating to obtain aluminum hydroxide, and calcining the aluminum hydroxide to obtain an aluminum oxide product.
7. The full-wet comprehensive utilization method of red mud according to claim 1, characterized in that in step (7): water is added and the pH is adjusted to 1.5 to 2.1.
8. The full-wet comprehensive utilization method of red mud according to claim 1, characterized in that in step (9): adding alkali liquor to adjust the pH value to 5-7.
9. The full-wet comprehensive utilization method of red mud according to claim 1, characterized in that in the step (10): the addition amount of the sodium sulfide is 1-10%, phosphoric acid is added according to the proportion of phosphorus to iron of 1-3, the addition amount of the surfactant is 0.5-5%, and the pH value is adjusted to 1-3 by alkali liquor.
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| CN116002647B (en) * | 2023-01-30 | 2024-08-27 | 昆明理工大学 | Method for preparing ferric phosphate by taking high-iron Bayer process red mud as iron source |
| CN118022855A (en) * | 2024-04-15 | 2024-05-14 | 昆明理工大学 | Chemical looping combustion enriched CO of blast furnace gas2Is a method of (2) |
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