CN111705226B - Method for removing impurities from high-titanium slag - Google Patents
Method for removing impurities from high-titanium slag Download PDFInfo
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- CN111705226B CN111705226B CN202010575329.6A CN202010575329A CN111705226B CN 111705226 B CN111705226 B CN 111705226B CN 202010575329 A CN202010575329 A CN 202010575329A CN 111705226 B CN111705226 B CN 111705226B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B34/1204—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 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1213—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 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by wet processes, e.g. using leaching methods or flotation techniques
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to a method for removing impurities from high-titanium slag, which comprises the following steps: step 1, adding high titanium slag with the granularity of 0.02 mm-0.1 mm and a nitric acid solution into a reaction kettle, introducing oxygen into the reaction kettle, simultaneously heating to above 130 ℃, then preserving heat for at least 1h under the stirring condition, and cooling to obtain a first material; wherein the mass concentration of the nitric acid solution is 10-30%; the total pressure in the reaction kettle is 0.5-1.9 Mpa, and the oxygen partial pressure in the reaction kettle is more than 0.25 Mpa; the stirring speed is 250r/min to 800 r/min; and 2, filtering the first material obtained in the step 1 to obtain a filtrate and a filtrate, and washing the filtrate with water until the washing liquid is neutral to obtain the high-titanium slag after impurity removal. The inventor controls the mutual cooperation of various factors such as oxygen partial pressure, temperature, heat preservation time, nitric acid concentration, stirring speed and the like in the reaction kettle, so that the impurity removal effect is good, high-purity high-titanium slag can be obtained, and the method has the advantages of low energy consumption and low equipment requirement.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a method for removing impurities from high-titanium slag.
Background
The high titanium slag is commonly known as titanium ore concentrate formed by a physical production process, and the titanium ore is heated and melted by an electric furnace, so that titanium dioxide and iron in the titanium ore are melted and separated to obtain the titanium dioxide concentrate with high content. The high titanium slag is neither waste slag nor by-product, but is a high-quality raw material for producing titanium tetrachloride, titanium white and titanium sponge products, and the titanium slag is smelted from titanium concentrate.
The chlorination process for preparing titanium dioxide has become the main method for producing titanium dioxide at present due to its advantages of short process, low production cost and energy consumption, and less pollution of three wastes, etc., TiO2The high titanium slag with the content of more than 90 percent can be used as a production raw material of titanium white by a chlorination process, and is limited by the fact that titanium ores in China are generally not high in taste and low in purity, particularly silicon, iron and manganese in the titanium oresHigh content of impurities such as calcium, magnesium and the like and difficult purification, and seriously restricts the industrial development of titanium white and titanium sponge in China.
At present, methods for removing impurities and improving quality of high-titanium slag include an electric heating method, a roasting pretreatment two-step leaching method, a hydrochloric acid leaching method, a sulfuric acid leaching method and an alkali leaching method; the electric heating method is a mature method, has simpler process, does not produce solid and liquid waste materials, belongs to high-temperature smelting, mainly removes sulfur, phosphorus and carbon, has higher energy consumption and generates a large amount of low-price titanium; the roasting pretreatment two-step leaching method comprises the steps of firstly carrying out sodium roasting to change the phase composition of titanium slag, and then selectively removing impurities in the titanium slag through hydrochloric acid pressure leaching, wherein the silicon removal effect is not obvious; the sulfuric acid method and the hydrochloric acid leaching method mainly aim at acid-soluble titanium slag, and have weak desiliconization capability, long reaction time and large investment on pressure leaching equipment; the alkali leaching method mainly comprises a new process for cleaning and metallurgy of sub-soluble salt titanium, which is proposed by the research on process engineering of Chinese academy of sciences, and the research proposes that high-titanium slag is used as a raw material, and a sodium-alkali molten salt method is adopted to prepare a titanium-rich material; the process comprises the steps of mixing titanium slag with sodium alkali, carrying out molten salt reaction on the titanium slag and the sodium alkali at normal pressure and low temperature, efficiently and selectively converting titanium in the titanium slag into titanate, carrying out hydrolysis and precipitation on the titanate, and leaving impurity components such as iron, calcium, magnesium and the like which do not react with the sodium alkali in a non-titanium slag phase to realize effective separation of Ti from other impurities, but the problems of excessive alkali consumption, high requirement on equipment, difficulty in later-stage separation and the like exist.
For example, in chinese patent 201510250414.4, the acid-soluble titanium slag is modified, subjected to acid impurity removal, and calcined by using microwaves as a heating method to meet the requirements of producing titanium white by a chlorination method, but the method requires a microwave reactor, and thus the investment on equipment is large; one or more modifiers selected from sodium carbonate, sodium hydroxide, phosphorus pentoxide, sodium phosphate or dihydrogen phosphate are added in the process of modifying the high-titanium slag, and various impurities are introduced, so that the subsequent quality improvement is difficult; the method uses sulfuric acid as pickle liquor, which causes difficulty in subsequent waste acid recovery and pollutes the environment; meanwhile, the calcination process needs to be heated to 900-1000 ℃ and has higher requirements on equipment and higher energy consumption; chinese patent 201510879416.X discloses a three-stage process for preparing high-quality titanium slag, which comprises the steps of modifying titanium slag, carrying out pressurized acid leaching and granulation, carrying out ball milling, roasting, filtering and washing, carrying out pressurized acid leaching, mixing with a binder uniformly, and carrying out microwave drying to obtain high-quality titanium slag; the process has complex operation procedures and higher equipment requirements, and other impurities can be introduced by adding the modifier to influence the upgrading process; chinese patent 201410387332.X discloses a method for preparing anatase titanium dioxide by acidolysis of clean titanium slag; the method comprises the steps of mixing and roasting common titanium slag serving as a raw material and sodium hydroxide, carrying out acidolysis by using sulfuric acid, hydrolyzing to obtain metatitanic acid precipitate, and roasting to obtain high-quality anatase titanium dioxide, wherein the process needs repeated roasting treatment to consume a large amount of energy, the acidolysis uses 15-55% sulfuric acid to seriously corrode equipment, and the subsequent waste acid is not well treated, so that the environmental hazard is large.
Disclosure of Invention
The invention aims to: aiming at the technical problems of high energy consumption, high equipment requirement, poor impurity removal effect and the like in the method for removing impurities from high-titanium slag in the prior art, the method for removing impurities from high-titanium slag is provided, and has the advantages of low energy consumption, low equipment requirement and good impurity removal effect.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for removing impurities from high-titanium slag comprises the following steps:
step 1, adding high titanium slag with the granularity of 0.02 mm-0.1 mm and a nitric acid solution into a reaction kettle, introducing oxygen into the reaction kettle, simultaneously heating to above 130 ℃, then preserving heat for at least 1h under the stirring condition, and cooling to obtain a first material; wherein the mass concentration of the nitric acid solution is 10-30%; the total pressure in the reaction kettle is 0.5-1.9 Mpa, and the oxygen partial pressure in the reaction kettle is more than 0.25 Mpa; the stirring speed is 250r/min to 800 r/min;
and 2, filtering the first material obtained in the step 1 to obtain a filtrate and a filtrate, and washing the filtrate with water until the washing liquid is neutral to obtain the high-titanium slag after impurity removal.
The invention provides a method for removing impurities from high-titanium slag. The method provided by the inventor has low requirement on equipment and low energy consumption, and the inventor controls the mutual cooperation of various factors such as oxygen partial pressure, temperature, heat preservation time, nitric acid concentration, stirring rotating speed and the like in the reaction kettle, so that the impurity removal effect is good, and high-purity high-titanium slag can be obtained.
Further, step 1 is preceded by a step a: the high titanium slag is crushed to the granularity of 0.02 mm-0.1 mm.
Further, in the step 1, the granularity of the high titanium slag is 0.02 mm-0.06 mm. The inventor discovers that the granularity of the crushed high-titanium slag is an important parameter influencing the impurity removal rate through a large amount of researches, and discovers that the impurity removal effect is not good due to too small or too large granularity, and the high-titanium slag is likely to agglomerate due to too small granularity, so that the oxygen dispersion effect is influenced, and the purity of the final product is not obviously improved; if the granularity is too large, impurities can not be fully contacted with the nitric acid solution, the reaction is not sufficient, the final effect can be also affected adversely, and preferably, in the step 1, the high titanium slag is crushed to the granularity of 0.05-0.06 mm.
Further, in the step 1, the mass ratio of the nitric acid solution to the high titanium slag is 3-8: 1.
On the basis of controlling the mass concentration of the nitric acid solution to be 10-30%, the inventor researches and researches the mass ratio of the nitric acid solution to the high-titanium slag through experiments, wherein the poor impurity leaching effect is caused by the excessively small mass ratio of the nitric acid solution to the high-titanium slag, but the waste of the nitric acid solution is caused by the excessively large mass ratio, the economic burden is increased,
preferably, the mass ratio of the nitric acid solution to the high-titanium slag is 4.5-6: 1.
Further, in the step 1, the stirring speed is 400 r/min-600 r/min. Through a large amount of experimental researches and researches of the inventor, the stirring rotating speed in the reaction kettle has a direct and close relation to the purity of a final product, the rotating speed is too low, the dissolved oxygen in a reaction solution is possibly dispersed unevenly, high titanium slag is not dispersed unevenly, the reaction effect is poor, the rotating speed is too high, the contact between the high titanium slag and a nitric acid solution is possibly poor, the reaction is insufficient, and the poor impurity removal effect is also caused, preferably, in the step 1, the stirring rotating speed is 400 r/min-500 r/min.
Further, in the step 1, the temperature is raised to 130 ℃ to 200 ℃. The inventor discovers through research that when the temperature in the reaction kettle needs to be controlled to be higher than 130 ℃, and lower than 130 ℃, the reaction effect of the high titanium slag and the nitric acid in the reaction kettle is poor, and the purity of the final product is affected, but if the temperature is too high, the leaching effect is not greatly improved, and the economic burden is increased, and preferably, in the step 1, the temperature is increased to 130-200 ℃.
Further, in the step 1, heat preservation is carried out for 1-4 hours under the stirring condition. The inventor discovers through exploring that the setting of holding time in the reation kettle is also very important, and when being less than 1h, the high titanium sediment of reation kettle and nitric acid can not reach the abundant reaction, influences the purity of final product, but holding time overlength not only can not promote greatly and leach the effect, can increase economic burden on the contrary.
Further, in the step 1, the oxygen partial pressure in the reaction kettle is 0.25MPa to 0.9 MPa. The inventors have found through research that a factor of oxygen partial pressure in the reaction kettle is an important factor in the whole system, and when the oxygen partial pressure is lower than 0.25Mpa, the oxygen dispersion rate in the reaction kettle is low, which affects the leaching effect of impurities, but if the oxygen partial pressure is too high, the economic cost is also increased, and preferably, in the step 1, the oxygen partial pressure in the reaction kettle is 0.25Mpa to 0.5 Mpa.
Further, the TiO in the high titanium slag after impurity removal obtained in the step 22The mass content is more than 90 percent.
Further, the method also comprises a step 3 of carrying out enrichment treatment on the filtrate obtained in the step 2, then carrying out evaporative crystallization, carrying out heating decomposition treatment on the obtained crystal, and absorbing nitrogen oxides after thermal decomposition by nitric acid absorption equipment to obtain a new nitric acid solution.
Further, the method comprises a step 3 of carrying out enrichment treatment on the filtrate obtained in the step 2, evaporating and crystallizing, adding the obtained crystals into a heat storage type circulating decomposition furnace, contacting with circulating nitric oxide gas at 800-.
In the impurity removal process of the high titanium slag in the prior art, the problems that Ti and impurities in the final filtrate are difficult to separate, the subsequent pickle liquor is difficult to recover and is difficult to treat, the environmental hazard is large and the like exist, and the problems can also limit the industrial popularization of the high titanium slag impurity removal process.
Further, the new nitric acid solution obtained in the step 3 is returned to the step 1 for recycling.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the invention provides a method for removing impurities from high-titanium slag, aiming at the technical problems of high energy consumption, high equipment requirement, poor impurity removal effect and the like in the impurity removal process in the prior art. The method provided by the inventor has low requirements on equipment and low energy consumption, and the inventor controls the mutual cooperation of various factors such as oxygen partial pressure, temperature, heat preservation time, nitric acid concentration, stirring speed and the like in the reaction kettle, so that the impurity removal effect is good, high-purity high-titanium slag with the purity of more than 95% can be obtained, and the content of titanium dioxide can even reach more than 98%.
2. In the impurity removal process of the high titanium slag in the prior art, the problems that Ti and impurities in final filtrate are difficult to separate, subsequent pickle liquor is difficult to recover and cannot be well treated, the environmental hazard is large and the like exist, and the problems can limit industrial popularization of the high titanium slag impurity removal process.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The percentage contents appearing in the following examples are not directly specified as percentages by mass.
Example 1
Crushing the high titanium slag to the granularity of 0.02mm, adding the high titanium slag and a nitric acid solution (the mass ratio is 1:5) with the mass concentration of 20% into a reaction kettle, introducing oxygen into the reaction kettle, simultaneously heating to 160 ℃, and then preserving heat for 2 hours under the stirring condition with the rotating speed of 600r/min, wherein the total pressure in the reaction kettle is 1.2Mpa, and the oxygen partial pressure in the reaction kettle is 0.5 Mpa.
And then filtering the mixture in the reaction kettle after cooling, and washing the filtered substance with water until the washing liquid is neutral to obtain the high titanium slag after impurity removal.
And then evaporating and crystallizing the filtrate obtained by enrichment and filtration, heating the obtained crystal, introducing the heated nitrogen oxide into nitric acid absorption equipment for absorption to obtain a new nitric acid solution, and taking the nitric acid solution as a reaction solution in a reaction kettle for recycling when the concentration of the new nitric acid solution reaches 20%.
The contents of titanium dioxide, aluminum oxide, magnesium oxide and calcium oxide in the high titanium slag before and after impurity removal by the method of example 1 were tested, and the test results are shown in table 1.
TABLE 1 test results of the content of substances in the high titanium slag after impurity removal
| Example 1 | Titanium dioxide content (%) | Alumina content (%) | Content of magnesium oxide (%) | Calcium oxide (%) |
| High titanium slag before impurity removal | 87.8 | 0.25 | 0.95 | 0.23 |
| High titanium slag after impurity removal | 95.8 | 0.05 | 0.32 | 0.08 |
Example 2
Crushing the high titanium slag to the granularity of 0.1mm, adding the high titanium slag and a nitric acid solution (the mass ratio is 1:3) with the mass concentration of 15% into a reaction kettle, introducing oxygen into the reaction kettle, simultaneously heating to 200 ℃, and then preserving heat for 1h under the stirring condition with the rotating speed of 250r/min, wherein the total pressure in the reaction kettle is 1.0Mpa, and the oxygen partial pressure in the reaction kettle is 0.4 Mpa.
And then filtering the mixture in the reaction kettle after cooling, and washing the filtered substance with water until the washing liquid is neutral to obtain the high titanium slag after impurity removal.
And then evaporating and crystallizing the filtrate obtained by enrichment and filtration, heating the obtained crystal, introducing the heated nitrogen oxide into nitric acid absorption equipment for absorption to obtain a new nitric acid solution, and taking the nitric acid solution as a reaction solution in a reaction kettle for recycling when the concentration of the new nitric acid solution reaches 15%.
The contents of titanium dioxide, aluminum oxide, magnesium oxide and calcium oxide in the high titanium slag before and after impurity removal by the method of example 2 were tested, and the test results are shown in table 2.
TABLE 2 test results of the material content in the high titanium slag after impurity removal
| Example 2 | Titanium dioxide content (%) | Alumina content (%) | Content of magnesium oxide (%) | Calcium oxide (%) |
| High titanium slag before impurity removal | 88.1 | 0.32 | 0.85 | 0.18 |
| High titanium slag after impurity removal | 96.2 | 0.07 | 0.28 | 0.06 |
Example 3
Crushing the high titanium slag to the granularity of 0.05mm, adding the high titanium slag and a nitric acid solution (the mass ratio is 1:8) with the mass concentration of 10% into a reaction kettle, introducing oxygen into the reaction kettle, simultaneously heating to 130 ℃, and then preserving heat for 4 hours under the stirring condition with the rotating speed of 800r/min, wherein the total pressure in the reaction kettle is 1.8Mpa, and the oxygen partial pressure in the reaction kettle is 0.9 Mpa.
And then filtering the mixture in the reaction kettle after cooling, and washing the filtered substance with water until the washing liquid is neutral to obtain the high titanium slag after impurity removal.
And then evaporating and crystallizing the filtrate obtained by enrichment and filtration, heating the obtained crystal, introducing the heated nitrogen oxide into nitric acid absorption equipment for absorption to obtain a new nitric acid solution, and taking the nitric acid solution as a reaction solution in a reaction kettle for recycling when the concentration of the new nitric acid solution reaches 10%.
The contents of titanium dioxide, aluminum oxide, magnesium oxide and calcium oxide in the high titanium slag before and after impurity removal by the method of example 3 were tested, and the test results are shown in table 3.
TABLE 3 test results of the content of substances in the high titanium slag after impurity removal
| Example 3 | Titanium dioxide content (%) | Alumina content (%) | Content of magnesium oxide (%) | Calcium oxide (%) |
| High titanium slag before impurity removal | 89.2 | 0.4 | 0.73 | 0.27 |
| High titanium slag after impurity removal | 95.3 | 0.08 | 0.23 | 0.09 |
Example 4
Crushing the high titanium slag to the granularity of 0.03mm, adding the high titanium slag and a nitric acid solution (the mass ratio is 1:6) with the mass concentration of 12% into a reaction kettle, introducing oxygen into the reaction kettle, simultaneously heating to 150 ℃, and then preserving heat for 3 hours under the stirring condition with the rotating speed of 400r/min, wherein the total pressure in the reaction kettle is 0.5Mpa, and the oxygen partial pressure in the reaction kettle is 0.25 Mpa.
And then filtering the mixture in the reaction kettle after cooling, and washing the filtered substance with water until the washing liquid is neutral to obtain the high titanium slag after impurity removal.
And then evaporating and crystallizing the filtrate obtained by enrichment and filtration, heating the obtained crystal, introducing the heated nitrogen oxide into nitric acid absorption equipment for absorption to obtain a new nitric acid solution, and taking the nitric acid solution as a reaction solution in a reaction kettle for recycling when the concentration of the new nitric acid solution reaches 12%.
The contents of titanium dioxide, aluminum oxide, magnesium oxide and calcium oxide in the high titanium slag before and after impurity removal by the method of example 4 were tested, and the test results are shown in table 4.
TABLE 4 test results of the content of substances in the high titanium slag after impurity removal
| Example 4 | Titanium dioxide content (%) | Alumina content (%) | Content of magnesium oxide (%) | Calcium oxide (%) |
| High titanium slag before impurity removal | 86.3 | 0.35 | 0.88 | 0.32 |
| High titanium slag after impurity removal | 96.4 | 0.06 | 0.30 | 0.09 |
Examples 5 to 10
Examples 5-10 investigate the effect of particle size after crushing of the high titanium slag on the purity of titanium dioxide in the final high titanium slag. In examples 5 to 10, only the particle size of the crushed high titanium slag was changed, the rest of the process parameters, the experimental process and the high titanium slag raw material were completely the same as those in example 1, and the content of titanium dioxide in the high titanium slag after impurity removal in examples 5 to 10 was tested, and the test results are shown in table 5.
TABLE 5 purity of titanium dioxide in the high titanium slag after impurity removal
| Particle size (mm) | Purity of titanium dioxide (%) | |
| Before removing impurities | / | 87.8 |
| Example 5 | 0.01 | 89.5 |
| Example 6 | 0.03 | 96.1 |
| Example 7 | 0.05 | 98.3 |
| Example 8 | 0.06 | 97.2 |
| Example 9 | 0.1 | 95.4 |
| Example 10 | 0.15 | 90.1 |
From the test results in table 5, the particle size of the crushed high titanium slag is an important parameter affecting the impurity removal rate, and researches show that the impurity removal effect is poor due to too small or too large particle size, and the high titanium slag is likely to agglomerate more easily due to too small particle size, so that the dispersion effect of oxygen is affected, and the purity of the final product is not obviously improved; if the granularity is too large, impurities can not be in full contact with the nitric acid solution, the reaction is not sufficient, the final effect can be affected adversely, and preferably, in the step 1, the high titanium slag is crushed to the granularity of 0.02 mm-0.06 mm.
Examples 11 to 16
Examples 11-16 investigate the effect of the rotational speed of the stirrer in the reactor on the purity of the titanium dioxide in the final high titanium slag. In examples 11 to 16, only the stirring speed was changed, the remaining process parameters, experimental procedures and high titanium slag raw materials were completely the same as those in example 1, and the content of titanium dioxide in the high titanium slag after impurity removal in examples 11 to 16 was tested, and the test results are shown in table 6.
TABLE 6 purity of titanium dioxide in the high titanium slag after impurity removal
| Rotating speed (r/min) | Purity of titanium dioxide (%) | |
| Before removing impurities | / | |
| Example 11 | 150 | 89.2 |
| Example 12 | 250 | 92.2 |
| Example 13 | 400 | 96.1 |
| Example 14 | 500 | 96.8 |
| Example 15 | 800 | 95.1 |
| Example 16 | 1000 | 92.2 |
From the test results in table 6, it can be seen that the stirring speed in the reaction kettle has a direct and close relationship with the purity of the final product, the rotation speed is too low, the dissolved oxygen in the reaction solution may not be uniformly dispersed, the high titanium slag may not be uniformly dispersed, the reaction effect is not good, the rotation speed is too high, the contact between the high titanium slag and the nitric acid solution may not be good, the reaction is not sufficient, and the impurity removal effect is also not good, preferably, in the step 3, the stirring speed is 400r/min to 500 r/min.
Comparative example 1
Comparative example 1 changes the heat preservation temperature in the reaction kettle, the temperature is set to be 100 ℃, other process parameters, experimental processes and high titanium slag raw materials are the same as those in example 1, the purity of the titanium dioxide in the high titanium slag after impurity removal in comparative example 1 is tested, and researches show that the purity of the titanium dioxide in the high titanium slag after impurity removal is 89.1%, the temperature is too low, the reaction effect of the high titanium slag and nitric acid in the reaction kettle is poor, and the purity of the final product is influenced.
Comparative example 2
Comparative example 2 changes the heat preservation time in the reaction kettle, the heat preservation time is set to be 40min, other process parameters, experimental processes and high titanium slag raw materials are the same as those in example 1, the purity of the titanium dioxide in the high titanium slag subjected to impurity removal in comparative example 2 is tested, and researches show that the purity of the titanium dioxide in the high titanium slag subjected to impurity removal is 88.3%, the heat preservation time is too short, the high titanium slag and nitric acid in the reaction kettle can not fully react, and the purity of a final product is affected.
Comparative example 3
Comparative example 3 changes the oxygen partial pressure in the reaction kettle, the oxygen partial pressure is set to be 0.15Mpa, other process parameters, experimental processes and high titanium slag raw materials are the same as those in example 1, the purity of the titanium dioxide in the high titanium slag subjected to impurity removal in comparative example 3 is tested, and researches show that the purity of the titanium dioxide in the high titanium slag subjected to impurity removal is 89.4%, the oxygen dispersion rate in the reaction kettle is low, and the leaching effect of impurities is influenced.
Comparative example 4
Comparative example 4 changes the mass ratio of the nitric acid solution to the second material in the reaction kettle, the mass ratio is set to be 2:1, other process parameters, experimental processes and high titanium slag raw materials are the same as those in example 1, the purity of the titanium dioxide in the high titanium slag after impurity removal in comparative example 4 is tested, and researches show that the purity of the titanium dioxide in the high titanium slag after impurity removal is 90.3%, and the impurity leaching effect is poor due to the fact that the mass ratio of the titanium dioxide to the high titanium slag is too small.
The invention provides a method for removing impurities from high-titanium slag. The method provided by the inventor has low requirements on equipment and low energy consumption, and the inventor controls the mutual cooperation of various factors such as oxygen partial pressure, temperature, heat preservation time, nitric acid concentration, stirring speed and the like in the reaction kettle, so that the impurity removal effect is good, high-purity high-titanium slag with the purity of more than 95% can be obtained, and the content of titanium dioxide can even reach more than 98%. The nitric acid solution is concentrated continuously, so that the new nitric acid solution can be applied in a targeted manner, acid liquor can be recycled in the impurity removal process, industrial wastewater and waste residues are not generated, and green production is realized.
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 within the scope of the present invention.
Claims (9)
1. The method for removing impurities from high-titanium slag is characterized by comprising the following steps of:
step 1, adding high titanium slag with the granularity of 0.02-0.1 mm and a nitric acid solution into a reaction kettle, introducing oxygen into the reaction kettle, simultaneously heating to above 130 ℃, then preserving heat for at least 1h under the stirring condition, and cooling to obtain a first material; wherein the mass concentration of the nitric acid solution is 10-30%; the total pressure in the reaction kettle is 0.5-1.9 Mpa, and the oxygen partial pressure in the reaction kettle is more than 0.25 Mpa; the stirring speed is 250r/min to 800 r/min;
step 2, filtering the first material obtained in the step 1 to obtain a filtrate and a filtrate, and washing the filtrate with water until the washing liquid is neutral to obtain the high titanium slag after impurity removal;
wherein, TiO in the high titanium slag after impurity removal2The mass content is more than 90 percent.
2. An impurity removal method for high titanium slag according to claim 1, wherein in the step 1, the granularity of the high titanium slag is 0.02 mm-0.06 mm.
3. A method for removing impurities from high-titanium slag according to claim 1, wherein in the step 1, the mass ratio of the nitric acid solution to the high-titanium slag is 3-8: 1.
4. A method for removing impurities from high-titanium slag according to claim 1, wherein in the step 1, the stirring speed is 400-600 r/min.
5. The method for removing impurities from high-titanium slag according to claim 1, wherein in the step 1, the temperature is increased to 130-200 ℃.
6. An impurity removal method for high titanium slag according to claim 1, wherein in the step 1, the oxygen partial pressure in the reaction kettle is 0.25MPa to 0.9 MPa.
7. The method for removing impurities from high titanium slag according to any one of claims 1 to 6, further comprising the step 3 of carrying out enrichment treatment on the filtrate obtained in the step 2, then carrying out evaporation crystallization, carrying out thermal decomposition treatment on the obtained crystal, and absorbing nitrogen oxides obtained by thermal decomposition by nitric acid absorption equipment to obtain a new nitric acid solution.
8. An impurity removing method for high titanium slag according to claim 7, wherein in the step 3, the specific steps of the heating decomposition treatment of the obtained crystal are as follows: and adding the obtained crystal into a heat accumulating type circulating decomposing furnace, contacting with circulating nitric oxide gas at 800-1100 ℃, decomposing for 1-3min, and decomposing to obtain oxide and nitric oxide gas.
9. A method for removing impurities from high-titanium slag according to claim 7, wherein the new nitric acid solution obtained in the step 3 is returned to the step 1 for recycling.
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