CN112593077B - Method for acid countercurrent heap leaching of vanadium titano-magnetite alkaline oxidized pellets - Google Patents
Method for acid countercurrent heap leaching of vanadium titano-magnetite alkaline oxidized pellets Download PDFInfo
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- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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Abstract
The invention belongs to the field of hydrometallurgy, and particularly relates to a method for leaching alkaline oxidized pellets of vanadium titano-magnetite in a multi-stage manner by acid countercurrent circulation. Aiming at the production process of leaching vanadium from the basic oxidized pellet of vanadium titano-magnetite, the invention provides a method for leaching the basic oxidized pellet of vanadium titano-magnetite by countercurrent circulation acid leaching, in order to improve the concentration of vanadium in mother liquor and reduce the influence of silica gel on vanadium leaching. The invention achieves the purposes of increasing the concentration of vanadium in mother liquor and controlling the leaching rate of iron to be below 0.4 percent by adjusting and controlling the acid concentration of leaching solution and adopting a method of secondary (multi-stage) leaching solution circulating countercurrent leaching. The leaching rate of silicon and aluminum is far higher than that of iron, the iron grade of the pellets after leaching is improved, the content of silicon and aluminum in the pellets is reduced, and the pellets after leaching are more suitable to be used as raw materials for blast furnace iron making. The invention adopts a method of periodically discharging the leaching solution to perform desiliconization treatment, thereby preventing the influence of silica gel on the vanadium leaching of the pellets.
Description
Technical Field
The invention belongs to the field of metallurgy, and particularly relates to a method for carrying out countercurrent circulating acid leaching on basic oxidized pellets of vanadium titano-magnetite, and carrying out desiliconization on vanadium mother liquor and returning the desiliconized mother liquor to a leaching system.
Background
At present, the main process for extracting vanadium from vanadium-titanium magnetite in China is to blow vanadium from vanadium-containing molten iron smelted from the vanadium-titanium magnetite in a blast furnace by using a converter to obtain vanadium slag, and the vanadium slag is subjected to sodium treatment or calcification roasting, water leaching or acid leaching, purification and vanadium precipitation by using a rotary kiln, and the process is linked with the steel smelting process and has the defect that the total yield of vanadium is low and is generally 43 percent. The direct vanadium extraction technology of vanadium-containing raw materials is also being studied vigorously, and the traditional vanadium extraction technology mainly comprises sodium roasting-water leaching, calcification roasting-alkali leaching and salt-free roasting-acid leaching. The sodium salt roasting-water leaching process is mature, but the subsequent iron making is adversely affected by the introduction of sodium salt; the calcification roasting-alkaline leaching process has the advantages of few applications, unsatisfactory strong base leaching effect, overhigh cost, lower ammonia leaching rate and severe operating environment; salt-free roasting-acid leaching, and the vanadium oxide can be volatilized due to the overhigh roasting temperature, so that the loss of the vanadium is serious. In view of the situation and the pressure in the vanadium industry in China, the novel process of pellet calcification roasting-acid (hydrochloric acid/sulfuric acid) leaching is a novel energy-saving, efficient and environment-friendly vanadium extraction process.
Patent application CN201910639371.7 uses vanadium-titanium-iron ore concentrate as raw material, and calcification agent is Ca (OH) 2 The binder is bentonite, and vanadium-titanium-iron ore concentrate, a calcification agent and the binder are mixed according to a certain proportion, then are pelletized and are calcified and roasted at high temperature, so that vanadium in the vanadium-titanium-iron ore concentrate is converted into acid-soluble calcium vanadate salt. And then acid leaching is carried out on the vanadium-containing solution and the solid material by hydrochloric acid/sulfuric acid solution with certain concentration. The patent not only combines the calcification agent and the alkaline pellet additive into a whole, but also combines the calcification roasting and the oxidation pellet roasting into one step, and does not influence the subsequent iron-making process of materials. The pellet heap leaching mode is adopted to keep the original chemical property and physical property of the pellets unchanged, so that the pellets after vanadium leaching can be directly sold as iron making raw materials.
Because the vanadium-titanium magnetite alkaline oxidized pellet contains less vanadium, the improvement of the concentration of vanadium in the leaching mother liquor can greatly improve the economical efficiency of the process. The cost of raising the vanadium concentration from the leaching process will be lower than the cost of subsequent extraction or ion exchange, and will also reduce the water usage of the leaching process, reducing the pressure of subsequent wastewater treatment. Along with the circulating vanadium leaching of the leaching solution, the concentration of silicon ions in the vanadium leaching mother solution is increased, and silica gel appears in the mother solution. As the leaching time further increases, the silica gel in the mother liquor continues to condense and convert to silica gel. The silica gel blocks the pores of the pellets and adheres to the surfaces of the pellets, thereby affecting the fluidity of the leaching solution, the normal operation of the leaching of vanadium and the leaching rate of vanadium. Desilication from the leachate is an essential step for industrialization.
Chinese patent CN109182734A discloses a method for removing sodium from vanadium titano-magnetite tailings by sodium modification roasting of dilute acid heap leaching vanadium titano-magnetite, which utilizes dilute acid to remove sodium from vanadium titano-magnetite tailings after sodium modification roasting vanadium extraction by adopting a heap leaching method, and aims to integrate iron in the tailings. Chinese patent No. 103739010A discloses a method for deep desilication of silica sol in acid system, which comprises neutralizing silicate to prepare silica sol, adding silica sol into acidic solution containing silicon, aging for a certain time, adding flocculant for flocculation and settling separation.
Disclosure of Invention
The invention aims to provide a method for acid leaching of basic oxidized pellets of vanadium titano-magnetite by countercurrent circulation so as to solve the problem of too low concentration of vanadium in vanadium leaching mother liquor. The concentration of vanadium in the vanadium leaching mother liquor and the content and the type of impurities determine the subsequent vanadium precipitation process and the production cost, and if the vanadium content in the vanadium leaching mother liquor is more than 5g/L, concentration processes such as ion exchange or extraction are not needed, and the vanadium precipitation of the vanadium leaching mother liquor can be directly performed. Thus from vanadium leaching mother liquor to 99% V 2 O 5 The production cost is greatly reduced. The method adopts the methods of multistage countercurrent leaching, gradual acid addition and leaching solution circulation leaching to improve the vanadium concentration in the mother solution.
The present invention provides the following scheme:
a method for leaching basic oxidized pellets of vanadium titano-magnetite by countercurrent circulating acid comprises the following steps:
step 1, stacking the vanadium titano-magnetite alkaline oxidized pellets on an anti-seepage ground surface or in a container, and circularly performing I-level leaching by using I-level leaching solution; the grade I leaching solution is desiliconized filtrate of vanadium leaching mother liquor, acid and water;
the basic oxidized pellet of vanadium titano-magnetite is prepared by fully mixing vanadium iron material, binder and calcification agent according to the method described in Chinese patent application CN201910639371.7, adding water to prepare green pellets, and then carrying out oxidation roasting on the green pellets to form pellets.
The leaching mode of the invention can adopt heap leaching or soaking, wherein the heap leaching is to spray leaching solution on the surface of a pellet pile, the leaching solution is leached in the downward permeation process, and the leaching solution collected at the bottom of the pile is I-grade leaching mother solution. Because of the consumption of acid in the leaching process, the leaching solution is added with acid to adjust the acidity and then returns to the pellet pile, thereby realizing the circular leaching. The immersion is to put the pellet in the leaching solution in a container, and the leaching mother liquor flows out from the bottom of the container, returns to the top of the container after the acidity adjustment, and realizes the circular leaching.
The heap leaching can be placed on the acid-proof and seepage-proof ground surface, or can be in a container similar to an ore bin, the heap height of the vanadium titano-magnetite alkaline oxidized pellets is 3-20 m, and the heap height is only influenced by the heap building mode because the pellets have very good permeability and the permeability is not limited. If the pile is built on a flat ground, the pile height is influenced by the stacking angle of the pellets, and the stacking angle of the pellets is 21-23 degrees.
The grade I leaching solution is desiliconized filtrate, acid or water, the grade I leaching solution sprays the pellets from the top of the pile, grade I leaching mother liquor is collected from the bottom of the pile, and the grade I leaching mother liquor is adjusted by acid concentration and then is used as the grade I leaching solution to return to the top of the pile, so that continuous circulation and leaching are realized. Acid is continuously added in the circulating leaching process, and simultaneously, the vanadium and the silicon in the mother liquor are increased. When the concentration of Si in the I-stage leaching mother liquor is more than or equal to 8.0g/L or the leaching time reaches 72 hours, the I-stage leaching mother liquor leaves the I-stage leaching and enters a mother liquor desilication system. The additional acid of the grade I leaching solution is one or more of hydrochloric acid, sulfuric acid or desiliconized filtrate, and the acid [ H ] of the grade I leaching solution + ]The concentration is 0.3-3 mol, preferably 0.6-1.4 mol, the leaching time is less than or equal to 72h, the leaching temperature is normal temperature-70 ℃, and the leaching rainfall is 15-60L/(m) 2 ·h)；
Along with the cyclic leaching of the stage I leaching, acid is continuously supplemented, the silicon in the stage I leaching mother liquor is increased, and the silicic acid molecules (H) 4 SiO 4 ) Should a protonation process be present, the following reaction takes place:
the process of forming silicic acid gel from silicic acid solution in the leaching mother liquor comprises two stages of silicic acid molecule polymerization to form sol and further forming gel from the sol, so that the gelation time of the silicic acid solution comprises the time of forming sol from silicic acid molecule polymerization and the time of forming silica gel from silica sol. The silicon concentration increases along with the increase of the leaching time, when the silicon concentration reaches about 5.0g/L, the mother liquor starts to generate silica gel and then starts to decrease, finally, the silicon concentration in the mother liquor reaches equilibrium at about 1.0-1.8 g/L, the silicon equilibrium concentration depends on the temperature and the aging time, the higher the temperature, the lower the silicon equilibrium concentration, and the longer the aging time, the lower the silicon equilibrium concentration. Silica gel is not only formed in the leach liquor but also in the spheroidisation capillaries. The silica gel in the capillaries of the pellets prevents the leaching solution from penetrating into the pellets and thus also prevents the leaching of vanadium.
In order to avoid the formation of silica gel in the I-stage leaching solution, when the concentration of Si ions in the I-stage leaching mother liquor is more than or equal to 8.0g/L or the leaching time reaches 72 hours, the I-stage leaching mother liquor is subjected to discharge desiliconization treatment, and the filtrate after desiliconization treatment (namely desiliconized filtrate) is used as the additional acid in the step 1 and then returned to the I-stage leaching or the II-stage leaching.
Using acid (HCL or H) to the discharged grade I leaching mother liquor 2 SO 4 ) Adjusting acidity [ H +]Stirring for 5-30 min, ageing and standing for 1-7 days, adding a flocculating agent for flocculation, stirring and mixing a flocculating agent solution and the discharged I-stage leaching mother liquor after acidity adjustment, preparing a solution by using the flocculating agent according to the solid concentration of 0.1-2.0%, wherein the adding amount of the flocculating agent is 50-600 ppm, and the flocculation temperature is normal temperature-70 ℃. The flocculating agent is one or a mixture of cationic polyacrylamide, nonionic polyacrylamide or gelatin.
And (3) performing solid-liquid separation on the flocculated I-stage leaching mother liquor, wherein the solid-liquid separation method is one or combination of conventional solid-liquid separation methods such as filtration, centrifugal sedimentation, natural sedimentation and the like, the separated solid is silica gel, and the separated liquid is desiliconized filtrate and returns to I-stage leaching or II-stage leaching.
The water content of the solid silica gel after solid-liquid separation reaches more than 80 percent, in order to recover valuable element vanadium in the silica gel, the silica gel is washed by acid water with pH value less than 1.5, and the liquid after washing enters I-grade washing or III-grade leaching. The solid is a silicone gel.
The filtration performance of the silica gel flocs is affected by parameters such as acidity adjustment, aging time, flocculation temperature, and flocculant dosage of the grade I leach mother liquor. The higher the acidity of the leach mother liquor, the longer the aging time, and the higher the flocculation temperature, the more easily the silica gel flocs are filtered. The filtration time of the silica gel flocs decreases with increasing flocculant dosage, but when the flocculant dosage is excessive, the filtration time of the silica gel flocs increases conversely.
And 2, allowing the vanadium titano-magnetite alkaline oxidized pellets subjected to the grade I leaching process in the step 1 to enter a grade II leaching process, and circularly leaching the grade II pellets by using a grade II leaching solution.
Because the leaching speed of the silicon is far faster than that of vanadium and other elements, the I-stage leaching process is used as desiliconization leaching, and the silicon in the mother liquor is discharged out of the system for desiliconization before the silicon gel is formed, so that the influence of the silicon on the vanadium leaching is avoided. The II-grade leaching is used as the leaching for improving the vanadium concentration, and the vanadium concentration in the mother liquor is enabled to be more than 5.0g/L by a method of increasing the cycle times or time, so that the vanadium precipitation is facilitated.
The II-stage leaching solution is from III-stage leaching mother liquor, water, desilication filtrate and supplementary acid, the II-stage leaching solution is sprayed on the pellets from the top of the pile, the II-stage leaching mother liquor is collected from the bottom of the pile, and the II-stage leaching mother liquor is adjusted by the acid concentration and then is used as the II-stage leaching solution to return to the top of the pile, so that the circulation and the leaching are carried out continuously. Acid is continuously added in the circulating leaching process, and simultaneously, the vanadium in the mother liquor is increased. The supplementary acid of the II-level leaching solution is one or more of hydrochloric acid, sulfuric acid or desilication mother liquor, and the acid [ H ] of the II-level leaching solution + ]The concentration is 0.3 to 3 mol, preferably 0.6 to 1.4 mol, when the concentration of Si ions in the II-level leaching solution is more than or equal to 2.0g/L or reaches the II-level leaching time (3 to 20 days), the II-level leaching solution as vanadium mother solution enters a vanadium precipitation system of the subsequent vanadium precipitation process, the leaching temperature is between normal temperature and 70 ℃, and the leaching rainfall is between 15 and 60L/(m to 20L) 2 ·h)。
Step 3, the vanadium titano-magnetite alkaline oxidized pellets after the II-level leaching in the step 2 enter a III-level leaching process, and III-level leaching is carried out by using a III-level leaching solution in a circulating way;
the grade III leaching solution is prepared from grade I washing mother liquor and silica gel filtering washing liquor, and is supplemented with acid continuously in the circulating leaching process, the supplemented acid of the grade III leaching solution is one or more of hydrochloric acid, sulfuric acid, water or desiliconized washing mother liquor, and the acid [ H ] of the grade III leaching solution + ]The concentration is 0.3-3 mol, preferably 0.6-1.4 mol, the III-grade leaching time is 3-20 days, the III-grade leaching mother liquor is used as II-grade leaching liquor, the leaching temperature is normal temperature-70 ℃, and the leaching rainfall is 15-60L/(m) of leaching rain 2 ·h)。
Preferably, the invention can also add a new leaching process after the III-grade leaching process according to the requirement.
The invention has the beneficial effects that:
1) The invention avoids the formation of silica gel in the leaching mother liquor by adjusting the acidity of the leaching solution and performing three-stage (multi-stage) circulating countercurrent leaching, thereby not only increasing the leaching rate of vanadium but also increasing the concentration of vanadium in the mother liquor and reducing the consumption of water, thereby reducing the cost of subsequent vanadium precipitation, and controlling the leaching rate of iron to be below 0.4 percent by controlling the concentration of acid in the leaching solution;
2) Because the leaching rate of silicon and aluminum is far higher than that of iron, the pellets after leaching not only increase the grade of iron, but also reduce the content of silicon and aluminum impurities in the pellets;
3) Due to anions (CL) in the grade III leachate - Or SO 4 2- ) The concentration is lower than the concentration of anions in the II-level leaching solution, and the pellets are easier to wash by a countercurrent multistage leaching mode;
4) The periodic discharge desilication treatment of the I-grade leaching solution prevents the influence of silica gel on the vanadium leaching of the pellets.
Drawings
FIG. 1 is a vanadium leaching flow chart of the basic oxidized pellet of vanadium titano-magnetite according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all the embodiments. The components of the embodiments of the present application, generally described and illustrated in the figures herein, can be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present application, presented in the accompanying drawings, is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present application without making any creative effort, shall fall within the protection scope of the present application.
In the description of the embodiments of the present application, it should be noted that the terms "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings or orientations or positional relationships that the products of the present invention are usually placed in when used, and are only used for convenience of description and simplicity of description, but do not indicate or imply that the devices or elements that are referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present application. Furthermore, the terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
The experimental procedures in the following examples are all conventional ones unless otherwise specified. The test materials used in the following examples were purchased from conventional suppliers unless otherwise specified.
Hair brushThe calcified alkaline oxidized pellet selected in the working example is made of Panxi vanadium titano-magnetite concentrate according to the method of CN 201910639371.7. The pellet production conditions are as follows: the addition amount of the bentonite binder is 1.2 percent, and the calcification agent Ca (OH) 2 The addition amount is 1.8%, the roasting temperature is 1220 ℃, and the time is 30min. The chemical composition analysis is shown in table 1.
TABLE 1 chemical composition analysis of calcified alkaline oxidized pellets used in the examples of the present invention
| Composition (I) | MgO | Al 2 O 3 | SiO 2 | P 2 O 5 | CaO |
| Content (wt.) | 2.79 | 2.78 | 3.54 | 0.036 | 2.2 |
| Composition (I) | TiO 2 | V 2 O 5 | Cr 2 O 3 | SO 3 | TFe |
| Content (wt.) | 9.31 | 0.58 | 0.64 | 0.001 | 54.65 |
Example 1 pellet column impregnation
A. Stage I leaching
180 kg of pellets in the table 1 are placed in a leaching column with the diameter of 300mm and the height of 1400mm, 30L of 0.5moL of sulfuric acid solution is added for I-level leaching, the pellets are discharged after being soaked for 12 hours, and 300mL of 18.4moL of concentrated sulfuric acid is added to supplement acid to the leaching solution, and 300mL of concentrated sulfuric acid is supplemented twice a day. The acid addition system and the analysis results of the I-grade mother liquor elements are shown in the table 1-1. When the leaching is carried out to the 3 rd day, the I-grade leaching mother liquor is discharged for desilication treatment.
Table 1-1 example 1 grade I leaching acid replenishment system and grade I mother liquor elemental analysis results
| Extraction time (h) | 0 | 24 | 48 | 72 |
| H 2 SO 4 @18.4moL(mL) | 815 | 600 | 600 | 600 |
| V(g/L) | / | 1.51 | 2.75 | 3.39 |
| Si(g/L) | / | 3.15 | 5.34 | 7.12 |
| Fe(g/L) | / | 5.08 | 7.91 | 9.07 |
B. Stage II leaching
35L 0.5moL of sulfuric acid solution is prepared again for II-level leaching, the sulfuric acid solution is discharged after being soaked for 12 hours, and 18.4moL of concentrated sulfuric acid is used for adjusting the acidity of the leaching solution to ensure that the leaching solution is acidic [ H ] + ]About 1.2moL, twice a day. The elemental analysis results of the stage II leach liquor are shown in tables 1-2.
Table 1-2 example 1 elemental analysis results of grade II leach mother liquor
| Extraction time (d) | 0 | 2 | 4 | 6 | 8 | 10 |
| V(g/L) | / | 1.31 | 1.65 | 2.22 | 2.96 | 3.34 |
| Si(g/L) | / | 0.25 | 0.38 | 0.49 | 0.58 | 0.65 |
| Fe(g/L) | / | 2.63 | 4.24 | 5.96 | 7.25 | 8.19 |
| Extraction time (d) | 12 | 14 | 16 | 18 | 20 | 22 |
| V(g/L) | 3.7 | 4.14 | 4.87 | 5.4 | 5.82 | 6.12 |
| Si(g/L) | 0.71 | 0.78 | 0.85 | 0.92 | 0.99 | 1.06 |
| Fe(g/L) | 9.08 | 10.02 | 10.82 | 11.64 | 12.46 | 13.2 |
C. Stage III leaching
35L 0.5moL of sulfuric acid solution is prepared again for leaching in grade III, the solution is discharged after being soaked for 12 hours, and 18.4moL of concentrated sulfuric acid is used for adjusting the acidity of the leaching solution to ensure that the acid [ H ] in the leaching solution + ]About 1.5 moL. The adjustment is carried out twice a day. Stage III leachingThe elemental analysis results of the mother liquor are shown in tables 1 to 3.
Table 1-3 results of elemental analysis of grade III leach mother liquor from example 1
| Extraction time (d) | 0 | 2 | 4 | 6 | 8 | 10 | 12 | 14 |
| V(g/L) | / | 0.45 | 0.85 | 1.12 | 1.42 | 1.68 | 1.75 | 1.85 |
| Si(g/L) | / | 0.08 | 0.08 | 0.09 | 0.09 | 0.09 | 0.09 | 0.1 |
| Fe(g/L) | / | 1.21 | 2.13 | 2.89 | 3.46 | 4.21 | 4.98 | 5.68 |
Class D.I washes
Adding 20L of water for I-grade washing, soaking for 72h, and discharging. The pellets were dried at 140 ℃ and the washing liquid and pellet composition analyses are shown in tables 1-4 and tables 1-5, respectively. The leaching rates of vanadium, silicon and iron are respectively 61.7%,6.26% and 0.94%.
Tables 1-4 elemental analysis results for grade I wash solutions of example 1
| Extraction time (d) | 0 | 1 | 2 | 3 |
| V(g/L) | / | 0.95 | 1.28 | 1.31 |
| Si(g/L) | / | 0.01 | 0.01 | 0.01 |
| Fe(g/L) | / | 3.12 | 3.65 | 3.98 |
Tables 1-5 example 1 chemical composition analysis of calcified alkaline oxidized pellets after immersion
| Element(s) | MgO | Al 2 O 3 | SiO 2 | P 2 O 5 | CaO |
| Pellet after immersion | 2.40 | 2.19 | 3.35 | 0.04 | 2.11 |
| Element(s) | TiO 2 | V 2 O 5 | Cr 2 O 3 | SO3 | TFe |
| Pellet after immersion | 9.41 | 0.22 | 0.63 | 1.52 | 54.69 |
Example 2 pellet column impregnation
A. Stage I leaching
180 kg of pellets in the table 1 are placed in a leaching column with the diameter of 300mm and the height of 1400mm, 30L of 0.5moL of sulfuric acid solution is added for I-level leaching, the pellets are discharged after being soaked for 12 hours, and 300mL of 18.4moL of concentrated sulfuric acid is added to supplement acid to the leaching solution, and 300mL of concentrated sulfuric acid is supplemented twice a day. The results of the acid addition system and the elemental analysis of the grade I leach mother liquor are shown in Table 2-1. And when leaching is carried out for 3 days, discharging the I-stage leaching mother liquor for desiliconization.
TABLE 2-1 EXAMPLE 2 grade I leach acid replenishment System and grade I leach mother liquor elemental analysis results
B. Stage II leaching
35L 0.5mol of sulfuric acid solution is prepared by using the III leaching mother liquor (shown in tables 1-3) in example 1 to carry out II-stage leaching, and leaching solution contains 1.85g/L of vanadium, 5.68g/L of iron and 0.10g/L of silicon. Soaking for 12 hr, discharging, and regulating acidity of the extractive solution with 18.4moL concentrated sulfuric acid to ensure that the extractive solution is acidic [ H ] + ]About 1.2 moL. The adjustment is carried out twice a day. The elemental analysis results of the stage II leach liquor are shown in Table 2-2.
Table 2-2 example 2 elemental analysis results for grade II leach mother liquor
| Extraction time (d) | 0 | 2 | 4 | 6 | 8 |
| V(g/L) | 1.85 | 3.14 | 3.4 | 4.06 | 4.64 |
| Si(g/L) | 0.10 | 0.31 | 0.39 | 0.54 | 0.58 |
| Fe(g/L) | 5.68 | 8.29 | 9.72 | 11.35 | 12.63 |
| Extraction time (d) | 12 | 14 | 16 | 18 | |
| V(g/L) | 5.01 | 5.53 | 5.83 | 6.42 | |
| Si(g/L) | 0.64 | 0.72 | 0.8 | 0.85 | |
| Fe(g/L) | 13.55 | 14.46 | 14.736 | 16.03 |
C. Stage III leaching
35L 0.5moL of sulfuric acid solution is prepared again for III-level leaching, the solution is discharged after being soaked for 12 hours, and 18.4moL of concentrated sulfuric acid is used for carrying out acidity adjustment on the leaching solution to ensure that the leaching solution is acidic [ H ] + ]About 1.5 moL. Adjusting twice a day. The elemental analysis results of the grade III leach mother liquor are shown in tables 1-3.
Table 2-3 elemental analysis results of grade III leach mother liquor from example 2
| Extraction time (d) | 0 | 2 | 4 | 6 | 8 | 10 | 12 | 14 |
| V(g/L) | / | 0.55 | 0.87 | 1.23 | 1.45 | 1.87 | 2.24 | 2.67 |
| Si(g/L) | / | 0.03 | 0.03 | 0.04 | 0.04 | 0.05 | 0.06 | 0.07 |
| Fe(g/L) | / | 1.32 | 2.48 | 3.51 | 4.34 | 5.15 | 5.98 | 6.68 |
D. Class I washing
Adding 20L of water for I-grade washing, soaking for 72h, and discharging. The pellets were dried at 140 ℃ and the washing liquid and pellet composition analyses are shown in tables 2-4 and tables 2-5, respectively. The leaching rates of vanadium, silicon and iron are respectively 61.7%,6.26% and 0.94%.
Tables 2-4 elemental analysis results for grade I wash solutions of example 2
| Extraction time (d) | 0 | 1 | 2 | 3 |
| V(g/L) | / | 1.32 | 1.53 | 1.86 |
| Si(g/L) | / | 0.01 | 0.01 | 0.01 |
| Fe(g/L) | / | 3.65 | 3.97 | 4.32 |
Table 2-5 example 2 post-immersion calcified alkaline oxidized pellet chemical composition analysis
| Element(s) | MgO | Al 2 O 3 | SiO 2 | P 2 O 5 | CaO |
| Pellet after immersion | 2.23 | 2.79 | 3.31 | 0.04 | 1.92 |
| Element(s) | TiO 2 | V 2 O 5 | Cr 2 O 3 | SO 3 | TFe |
| Pellet after immersion | 9.11 | 0.23 | 0.63 | 1.44 | 54.84 |
Example 3 desilication of vanadium leach mother liquor
1000mL of vanadium leaching mother liquor of the 3 rd day of the grade I leaching of the embodiment 1, containing 7120ppm of silicon, is added into 10mL of silica gel solution, stirred for 30 minutes under the condition that the solid concentration of the silicon (Si) is 2 percent, and adjusted to the acidity of [ H ] by sulfuric acid + ]4.0moL of the mixture, aging for 96 hours, adding 20mL of 0.4 percent gelatin solution, stirring for 2 minutes, standing for 5 minutes, and filtering to obtain filtrate containing 46ppm of silicon, wherein the desilication rate is 99.35 percent.
Example 4 desilication of vanadium leach mother liquor
1000mL of vanadium leaching mother liquor of the 3 rd day of the I-grade leaching of the embodiment 1 is taken, the vanadium leaching mother liquor contains 7120ppm of silicon, and the acidity of the vanadium leaching mother liquor is adjusted to [ H ] + ]4.0moL, aging the vanadium leaching mother liquor at room temperature for 7 days, adding 10mL of 0.4 percent gelatin solution, stirring for 2 minutes, standing for 5 minutes, filtering, and obtaining filtrate containing 35ppm of silicon with the desilication rate of 99.51 percent.
Example 5 desilication of vanadium leach mother liquor
1000mL of vanadium leaching mother liquor of the 3 rd day of the I-grade leaching of the embodiment 2 is taken, the vanadium leaching mother liquor contains 7820ppm of silicon, and the acidity of the vanadium leaching mother liquor is adjusted to be [ H ] + ]5.0moL, aging the mother solution of the leached vanadium at room temperature for 7 days, adding 25mL of 0.4 percent gelatin solution, stirring for 2 minutes, standing for 5 minutes, and filtering, wherein the filtrate contains 54ppm of silicon, and the desilication rate is 99.31 percent.
Example 6 desilication of vanadium leach mother liquor
Taking 1000mL of vanadium leaching mother liquor of 3 days of leaching in example 2I, wherein the vanadium leaching mother liquor contains 7820ppm of silicon, and adjusting the acidity of the vanadium leaching mother liquor to [ H ] + ]4.0moL, adding 15mL of 0.4% gelatin solution, stirring for 60 minutes, aging at room temperature for 7 days, adding 15mL of 0.4% gelatin solution, stirring for 25 minutes, standing for 5 minutes, filtering, wherein the filtrate contains 38ppm of silicon, and the desilication rate is 99.51%.
The above embodiments only express specific embodiments of the present application, and the description is specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (4)
1. A method for acid leaching of basic oxidized pellets of vanadium titano-magnetite by countercurrent circulation is characterized by comprising the following steps:
step 1, stacking the vanadium titano-magnetite alkaline oxidized pellets on an anti-seepage ground surface or in a container, and circularly performing I-level leaching by using I-level leaching solution; when the concentration of Si ions in the I-stage leaching mother liquor reaches or exceeds 8.0g/L or the leaching time exceeds 72 hours, carrying out desiliconization treatment on the I-stage leaching mother liquor, and returning the desiliconized mother liquor subjected to desiliconization treatment to the I-stage leaching process or the II-stage leaching process as a supplementary acid;
step 2, after the step 1 is finished, enabling the vanadium titano-magnetite alkaline oxidized pellets leached in the stage I to enter a stage II leaching process, circularly leaching the grade II by using a stage II leaching solution, and when the concentration of Si ions in the stage II leaching solution is more than or equal to 2.0g/L or reaches the specified leaching time of the stage II leaching, taking the stage II leaching solution as a final leaching mother solution, discharging the final leaching mother solution out of a leaching system and entering a vanadium precipitation system in the next process;
step 3, after the step 2 is completed, enabling the vanadium titano-magnetite alkaline oxidized pellets leached in the level II to enter a level III leaching process, circularly leaching the grade III leaching solution by using the level III leaching solution, and taking the level III leaching mother solution as the level II leaching solution after the level III leaching solution reaches the specified leaching time of the level III leaching solution;
step 4, after the step 3 is completed, the vanadium titano-magnetite alkaline oxidized pellets leached in the level III enter a level I washing process, level I washing is carried out by using level I washing liquid in a circulating manner, and the vanadium titano-magnetite alkaline oxidized pellets after the level I washing are the pellets after leaching; the grade I washing liquid is water or desiliconized washing mother liquor, and the grade I washing mother liquor is used as a grade III leaching solution;
the grade I leaching solution in the step 1 is one or a mixture of acid and water; in the cyclic leaching of the stage I leaching process, the acidity of the stage I leaching solution is adjusted by adding acid to realize the cyclic leaching, and the added acid is one or a mixture of hydrochloric acid, sulfuric acid or desiliconized mother liquor; acid of the grade I leachate [ H + ]The concentration is 0.3 to 3 mol/L, the concentration of Si ions in the I-grade leaching solution is less than or equal to 5.0g/L, and the leaching is carried outThe time is less than or equal to 72 hours, the leaching temperature is normal temperature to 70 ℃, and the grade I leaching is soaking or heap leaching with the leaching rainfall of 15 to 60L per square meter per hour;
when the concentration of Si ions in the I-stage leaching mother liquor reaches more than or equal to 8.0g/L or the leaching time reaches 72 hours in the step 1, the I-stage leaching mother liquor leaves the I-stage leaching circulation system and enters a desiliconization system for desiliconization, and the I-stage leaching mother liquor is adjusted by mixing one or two of hydrochloric acid and sulfuric acid [ H + ]1.0-7M, standing and aging for 1-7 days, adding a flocculating agent for flocculation, wherein the flocculating agent is one or more of cationic polyacrylamide, nonionic polyacrylamide or gelatin, the flocculating agent is prepared into a flocculating agent solution according to the solid concentration of 0.1-2.0%, the flocculating agent solution and the I-stage leaching mother liquor are stirred and mixed, the adding amount of the flocculating agent is 50-600 ppm, the temperature is normal temperature-70 ℃, the stirring is carried out for 0.5-48 h, then, the solid-liquid separation is carried out, the solid-liquid separation method is one or more of filtering, centrifugal sedimentation and natural sedimentation, a filter cake is washed, the solid is silica gel, the liquid is desiliconized mother liquor, the desiliconized mother liquor returns to the I-stage leaching process or the II-stage leaching process, and the desiliconized mother liquor returns to the III-stage leaching process or the I-stage washing process;
the II-grade leaching solution in the step 2 is prepared from III-grade leaching mother liquor, water, desiliconization mother liquor or supplemented acid, the acid is continuously supplemented in the circulating leaching process, the supplemented acid is one or more of hydrochloric acid, sulfuric acid or desiliconization mother liquor, and the acid [ H ] of the II-grade leaching solution + ]The concentration is 0.3-3 mol/L, the concentration of Si ions in II-level leaching solution is less than or equal to 2.0g/L, the leaching time of II-level leaching is 3-20 days, the leaching temperature is normal temperature-70 ℃, and the soaking or leaching rainfall is 15-60L/(. Square meter.h) heap leaching; when the concentration of Si ions in the II-level leaching solution is more than or equal to 2.0g/L, the II-level leaching solution is taken as a final leaching mother solution and discharged out of the leaching system to enter a vanadium precipitation system in the next vanadium precipitation process;
the III-grade leaching solution in the step 3 is from I-grade washing mother liquor, desiliconized washing mother liquor or supplemented with acid;
the acid is continuously added in the circulating leaching process, the added acid is one or more of hydrochloric acid, sulfuric acid or desiliconized mother liquor, and the acid of grade III leaching solutionH + ]The concentration is 0.3-3 mol/L; the grade III leaching is heap leaching with leaching time of 3-20 days, normal temperature-70 ℃ and 15-60L/square meter.h of soaking or leaching rainfall, and grade III leaching mother liquor enters a grade II leaching circulation system.
2. The method of claim 1, wherein the method comprises the steps of: the basic oxidized pellet of vanadium-titanium magnetite is prepared through mixing vanadium-iron material, adhesive and calcification agent, adding water to prepare green pellet, and oxidizing roasting the green pellet into pellet.
3. The method of claim 1, wherein the method comprises the steps of: the leaching modes of the I-level leaching, the II-level leaching and the III-level leaching in the steps 1 to 3 can adopt heap leaching or soaking, wherein the heap leaching is to spray a pellet pile with leaching solution, the leaching solution permeates downwards and is collected at the bottom of the pile, and the leaching solution returns to the pellet pile after being adjusted in acidity, so that circular leaching is realized; the immersion is to put the pellet in the leaching solution in the container, the leaching solution flows out from the bottom of the container, returns to the top of the container after the acidity adjustment, and realizes the circular leaching.
4. The method of countercurrent cycle acid leaching of basic oxidized pellets of vanadium titano-magnetite as set forth in any one of claims 1 to 3, characterized in that: the grade I washing liquid in the step 4 is water, the grade I washing time is 8 h-2 days, the grade I washing temperature is normal temperature-70 ℃, and the grade I washing rainfall is 15-60L/((square meter. H)).
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