CN115247234A - Method for preparing ammonium metavanadate by direct sulfuric acid oxidation and acidolysis of vanadium slag - Google Patents
Method for preparing ammonium metavanadate by direct sulfuric acid oxidation and acidolysis of vanadium slag Download PDFInfo
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Abstract
The invention discloses a method for preparing ammonium metavanadate by direct sulfuric acid oxidation acidolysis of vanadium slag, which is characterized by comprising the following steps of: the invention adopts calcium fluoride as a catalyst and manganese sesquioxide as an oxidant to carry out one-time low-temperature acidolysis and deep oxidation on the acidolysis catalyst, has the advantages of low production cost, high one-time extraction proportion, low vanadium content in tailings, high comprehensive resource utilization rate, less resource consumption and low-temperature environmental protection, realizes the environmental-friendly production of vanadium in vanadium slag, can directly use the tailings without harmful elements as building materials, consumes only 20 percent of new water in the prior art, recycles waste water purification residues as acid making raw materials, directly sells iron oxide powder and calcified materials to iron mills as iron making raw materials, and directly recycles purified water as new water to the leaching process. The hidden trouble of acid-containing wastewater treatment in the production of vanadium products by sulfuric acid leaching is solved, the valuable elements in the vanadium slag are recycled to the maximum extent, and multiple benefits of environmental protection and resource saving are brought. The defects of the prior art are overcome.
Description
Technical Field
The invention relates to the technical field of ammonium metavanadate preparation, in particular to a method for preparing ammonium metavanadate by direct sulfuric acid oxidation acidolysis of vanadium slag.
Background
In the method for preparing ammonium metavanadate in the prior art, roasting and calcification roasting are carried out by adopting a vanadium slag sodium method to generate a large amount of harmful flue gas and waste water, wherein the roasting and leaching proportion of the vanadium slag is low, the roasting process of the existing sodium method and calcium method is limited to below 90%, the roasting and leaching process needs to be carried out for the second time to reach about 95%, resources and energy sources consumed by the secondary roasting are large, the generated waste gas is large in amount, more sodium salt and sulfuric acid are consumed, the excessive waste water also brings great pressure to environmental protection, the waste water is treated in a cladocera area, water enters the atmosphere by adopting a blast furnace tailing waste heat evaporation method, harmful impurities are solidified into tailings in a precipitation mode, and the influence on the environment is reduced. The waste acid is one of the biggest hidden troubles in sulfuric acid method leaching production, and the domestic main waste acid treatment method comprises the following steps: preparing calcium superphosphate fertilizer, preparing ammonium ferrous sulfate, preparing industrial magnesium sulfate, preparing polyferric from waste acid, concentrating and regenerating, purifying by diffusion dialysis membrane technology, preparing calcium hydrophosphate for agricultural use, etc., but the production cost is greatly increased.
The neutralization treatment method is adopted, so that the wastewater is purified, the acid making raw material is obtained and becomes a part of the acid making process, the purified water is directly returned to acid leaching for use, and the neutralization treatment is used in the process as an economical and reasonable method. The vanadium-precipitation waste acid is directly used as a back extraction solution for back extraction of an extracting agent for repeated use, sulfate obtained by precipitating acid-containing waste water after extraction is used as an acid making raw material, the sulfate is mixed with reducible pyrite and subjected to boiling roasting to prepare acid by using flue gas, and residual calcium-containing and iron-containing residues are used as raw materials for iron making and are sold to iron-making manufacturers; the calcium sulfate after roasting and regeneration can be used as a purifying agent for one time in neutralization treatment. In recent years, the sodium salt roasting method is adopted to extract vanadium from vanadium ores and is successively banned, and the environmental protection investment is too large in the vanadium preparation from vanadium slag; the method for roasting vanadium slag by oxygen-enriched calcification still consumes sulfuric acid for leaching, although harmful exhaust emission is reduced, energy consumption is not reduced, the amount of waste water is large, the recovery ratio is low and unstable, and tailings cannot be recycled.
Disclosure of Invention
The invention aims to provide a method for preparing ammonium metavanadate by direct sulfuric acid oxidation and acidolysis of vanadium slag, which reasonably and effectively solves the problems that the method for preparing ammonium metavanadate in the prior art generates a large amount of harmful flue gas and waste water, the roasting and leaching proportion of the vanadium slag is low, the secondary roasting consumes more resources and energy, the method for roasting vanadium slag by oxygen-enriched calcification still consumes sulfuric acid for leaching, the energy consumption is high, the waste water amount is large, the recovery proportion is low and unstable, and the tailings cannot be recycled.
The invention adopts the following technical scheme:
a method for preparing ammonium metavanadate by direct sulfuric acid oxidation acidolysis of vanadium slag is characterized by comprising the following steps: the invention mainly relates to vanadium slag produced by extracting vanadium from molten iron. When vanadium is extracted, vanadium extraction oxidation balls containing silicon, iron and oxygen are added into molten iron, the iron, silicon and vanadium crystal structures in the crystals are in a crystalline state, the physical and chemical properties of the crystals are relatively stable, the crystal structures cannot be cracked by direct acid leaching, and the chemical compositions of the crystals are as follows:
| composition (I) | TiO | SiO 2 | V 2 O 5 | TFe | MFe | p |
| Content (c) of | 6～14 | 18～28 | 16～18 | 30～35 | 14～16 | ≤0.06 |
The method for preparing the ammonium metavanadate adopts vanadium ore powder produced in the process of natural vanadium ore mining and vanadium slag produced by vanadium extraction from molten iron as main raw materials, adds a catalyst and an oxidant by using strong acid inorganic acid with high leaching proportion, wherein the strong acid inorganic acid is 90-98% concentrated sulfuric acid, carries out one-time low-temperature acidolysis and advanced oxidation, the one-time oxidative acidolysis of vanadium in the vanadium slag achieves a recovery rate of 97%, and the leached vanadium liquid is subjected to adsorption, extraction, back extraction, desorption and precipitation to prepare the ammonium metavanadate, so that the problem that trivalent vanadium cannot be completely oxidized into tetravalent vanadium because the structure of Si-Al-V-O-Fe cannot be completely destroyed by a monosulfuric acid acidolysis method is solved; the method comprises the following steps of (1) preparing sulfuric acid by boiling, carrying out boiling roasting on a mixture of sulfur-containing precipitates purified from sulfuric acid-containing wastewater, sulfates generated by extraction water precipitation and pyrite to generate sulfur dioxide flue gas, and carrying out sulfuric acid preparation process with the sulfur dioxide flue gas in an oxidation process, wherein the waste gas enters an acid preparation process in a raw material form for recycling, harmful gas is not discharged in the whole process, fresh water consumed by acid leaching is only 1;
the method for preparing ammonium metavanadate further comprises the following steps:
step one, preparing refined vanadium slag, namely crushing the crude vanadium slag, and carrying out magnetic separation to remove iron, wherein the crushing granularity is about 100 meshes, so as to prepare the refined vanadium slag for later use;
secondly, pre-oxidation acidolysis, namely adding 25-30% of concentrated sulfuric acid into a closed container, wherein a small amount of sulfuric acid is added and a certain amount of cooling material is added to control the reaction temperature due to high reaction speed and high temperature, the generated flue gas enters a circulating pipeline through a flue and flows back to the neutralizing liquid in an acid tower, the temperature is 100-150 ℃, and the flue gas is continuously stirred during the addition of the sulfuric acid to avoid hardening and hardening, so that the pre-oxidation acidolysis is completed;
step three, oxidizing and acid splitting, namely adding a catalyst, an oxidant and concentrated sulfuric acid when the temperature is reduced to 30-40 ℃, slowly adding sulfuric acid and continuously stirring, controlling the temperature to be below 150 ℃, keeping the temperature to be 80-300 ℃ for 8 hours, and carrying out heat preservation and oxidation to complete the oxidizing and acid splitting;
step four, hydrolysis and filtration, wherein the leaching ratio is 1;
step five, adsorption, adding ammonia into the filtrate to adjust the pH value to 2.0, standing for 24 hours to generate aluminum sulfate precipitate, filtering for the second time to obtain vanadium liquid, diluting the vanadium liquid to be adsorbed under the condition of 20g/L of vanadium, and separating the first extraction liquid;
extracting and desorbing, namely extracting and separating vanadium-containing extract liquor, adding the extract liquor into a dilute sulfuric acid solution with the PH of less than 1.0 for desorption, and separating the extract liquor for the second time to obtain relatively pure vanadium liquid;
seventhly, adding ammonia for precipitation, stopping adding ammonia when the temperature of the vanadium liquid is higher than 90 ℃, cooling the vanadium liquid to the normal temperature, filtering for three times, and washing precipitates twice by using purified water;
step eight, drying and packaging to obtain more than 98% of ammonium metavanadate; the method for preparing ammonium metavanadate by direct sulfuric acid oxidation acidolysis of vanadium slag is formed.
Further, the catalyst is calcium fluoride or hydrofluoric acid with the concentration of 0.5% of concentrated sulfuric acid.
Further, the oxidant is manganese sesquioxide.
Further, the acid-material ratio of the high leaching proportion is 97-98%, and the tailings are leached at one time and contain less than 0.4% of vanadium.
Furthermore, the low-temperature acidolysis temperature is not higher than 300 ℃, stone coal, electric power and coal are used as controllable energy sources to replace supplementary energy, the generated flue gas is directly recycled as a raw material for acid production, and harmful flue gas is not discharged.
Further, the method for preparing ammonium metavanadate comprises the following relevant technical parameters: the acidolysis oxidation reaction temperature of adding a catalyst and an oxidant is 80-300 ℃, the ratio of leaching feed to liquid is 1.
The beneficial technical effects of the invention are as follows:
the invention discloses a method for preparing ammonium metavanadate from vanadium slag by direct sulfuric acid oxidation acidolysis, which reasonably and effectively solves the problems that the method for preparing ammonium metavanadate in the prior art generates a large amount of harmful flue gas and waste water, the roasting and leaching proportion of the vanadium slag is low, resources and energy sources consumed by secondary roasting are more, the method for roasting vanadium slag by oxygen-enriched calcification still consumes sulfuric acid for leaching, the energy consumption is high, the waste water amount is large, the recovery proportion is low and unstable, and tailings cannot be recycled.
The method adopts the catalyst calcium fluoride (hydrofluoric acid) and the oxidant manganese sesquioxide for acidolysis to carry out one-time low-temperature acidolysis and deep oxidation, has low production cost, high one-time extraction proportion, low vanadium content in tailings, high comprehensive resource utilization rate, low resource consumption and low temperature environmental protection, realizes the environmental-friendly production of vanadium in the vanadium slag, can directly use the tailings without harmful elements as building materials, consumes only 20 percent of new water in the prior art, recycles waste water purification residues as acid making raw materials, directly sells iron oxide powder and calcified materials to ironmaking plants as iron making raw materials, and directly recycles purified water as new water in a leaching process. The hidden danger of acid-containing wastewater treatment in the production of vanadium products by sulfuric acid leaching is solved, the valuable elements in the vanadium slag are recycled to the maximum extent, and multiple benefits of environmental protection and resource saving are brought. The defects of the prior art are overcome.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention will be better understood by the following description of embodiments thereof, but the applicant is not aware of the specific embodiments thereof, which should be considered as limiting the technical solution of the invention, and any changes in the definition of parts or technical features and/or in the form of a whole structure without substantial alterations should be considered as a protection scope defined by the technical solution of the invention.
Example (b):
as shown in figure 1, a method for preparing ammonium metavanadate by direct sulfuric acid oxidation and acidolysis of vanadium slag comprises the steps of drying the vanadium slag (chemical components of V2O516.55%, caO10.73%, mgO1.81%, naO0.25%, siO212.06, tiO211.46, al2O31.61Cr2O32.24 and FeO43.7) at the temperature of 110 +/-5 ℃ for 120min to remove moisture, mixing 90g of vanadium slag, 4g of oxidant, 2g of catalyst and 10g of cooling material, adding 30g of 98% industrial sulfuric acid prepared in advance, and continuously stirring by a stirrer to fully mix the sulfuric acid and the vanadium slag, wherein the temperature can rise rapidly, and the continuous stirring can avoid material hardening and influence the next reaction. When the temperature is reduced to below 35 ℃, pouring the mixture into a closed ceramic pot, adding a catalyst and 60g of 98% industrial sulfuric acid prepared in advance, stirring, covering a pot cover, putting the ceramic pot filled with the materials into a drying furnace at the temperature of between 100 and 300 ℃, fully oxidizing and carrying out acidolysis for 8 hours, and introducing generated smoke into an alkaline solution through a pipeline.
Adding water according to the proportion of the reaction material to the leaching solution 1 (certain water is evaporated during leaching), soaking for 1 hour at the temperature of 90-95 ℃, continuously stirring, and filtering the solution after the temperature is reduced to normal temperature to obtain vanadium solution. Because the vanadium concentration of the vanadium solution is too high, the solution is not beneficial to adsorption, and the solution should be properly diluted to 5.5g/L-20g/L.
Adding ammonia water into the vanadium solution, adjusting the pH value of the vanadium solution to 2-2.3, adding the solution into an extractant prepared by 10% P204+5% of sulfonated kerosene, wherein TBP +85% of sulfonated kerosene is used for adsorption, and extracting O; a =1:1, continuously stirring for 1 hour by using a stirrer, and extracting when the vanadium content in the vanadium liquid is reduced to 0.01 g/L.
And adding the extractant which absorbs the vanadium in the vanadium slag into prepared dilute sulfuric acid for desorption, continuously stirring for 1 hour by using a stirrer, and then back-extracting and separating the extractant to obtain a vanadium precipitation solution.
Preparing refined vanadium: stirring the vanadium precipitation solution at 95 ℃ for 3 hours, continuously adding ammonia water to precipitate vanadium, adjusting the pH value of the vanadium solution to 8, stopping adding the ammonia water, cooling the vanadium precipitation solution, and filtering to obtain ammonium metavanadate with the purity of more than 98%.
Example 2: drying vanadium slag (chemical components) at the temperature of 110 +/-5 ℃ for 120min to remove moisture, mixing 100g of vanadium slag, 4g of oxidant and 2g of catalyst, adding 30g of 95% industrial sulfuric acid prepared in advance, and continuously stirring by using a stirrer to fully mix the sulfuric acid and the vanadium slag, wherein the temperature can be rapidly increased, and the stirring can avoid material hardening to influence the next reaction. When the temperature is reduced to below 35 ℃, pouring the mixture into a closed ceramic pot, adding a catalyst and 70g of prepared 95% industrial sulfuric acid, stirring, covering a pot cover, putting the ceramic pot with the materials into a drying furnace at the temperature of 150-300 ℃, fully oxidizing and carrying out acidolysis for 8 hours, and introducing generated smoke into an alkaline solution by using a pipeline.
Adding water according to the proportion of the reaction material to the leaching solution 1 (certain water is evaporated during leaching), soaking for 1 hour at the temperature of 90-95 ℃, continuously stirring, and filtering the solution after the temperature is reduced to normal temperature to obtain vanadium solution.
Because the vanadium concentration of the vanadium solution is too high to be beneficial to adsorption, the vanadium solution is concentrated to 5.5g/L-20g/L, ammonia water is added into the vanadium solution, the pH value of the vanadium solution is adjusted to 2.3-2.5, and the vanadium solution is added into an extracting agent prepared by 10 percent of P204+5 percent of sulfonated kerosene of TBP +85 percent for adsorption, and O is extracted; a =1:1, continuously stirring for 1 hour by using a stirrer, and extracting when the vanadium content in the vanadium liquid is reduced to 0.01 g/L.
And adding the extractant which adsorbs the vanadium in the vanadium slag into prepared dilute sulfuric acid for desorption, continuously stirring for 1 hour by using a stirrer, and performing back extraction to separate the extractant to obtain a vanadium precipitation solution.
Preparing refined vanadium: stirring the vanadium precipitation solution at 95 ℃ for 3 hours, continuously adding ammonia water (for recovering ammonia gas in production) to precipitate vanadium, adjusting the pH value of the vanadium solution to 8, stopping adding the ammonia water, cooling the vanadium precipitation solution, and filtering to obtain ammonium metavanadate with the purity of more than 98%.
The implementation of the method for preparing ammonium metavanadate by direct sulfuric acid oxidation and acidolysis of vanadium slag is completed.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (6)
1. A method for preparing ammonium metavanadate by direct sulfuric acid oxidation acidolysis of vanadium slag is characterized by comprising the following steps:
the method for preparing ammonium metavanadate adopts vanadium ore powder produced in the natural vanadium ore mining process and vanadium slag produced by vanadium extraction from molten iron as main raw materials, adds a catalyst and an oxidant by using strong acid inorganic acid with high leaching proportion, the strong acid inorganic acid is 90-98% concentrated sulfuric acid, carries out one-time low-temperature acidolysis and advanced oxidation, the one-time oxidation acidolysis of vanadium in the vanadium slag achieves a recovery rate of 97%, and the leached vanadium liquid is subjected to adsorption, extraction, back extraction, desorption and precipitation to prepare ammonium metavanadate, so that the problem that the structure of Si-Al-V-O-Fe cannot be completely destroyed by a monosulfuric acid acidolysis method, so that trivalent vanadium cannot be completely oxidized into tetravalent vanadium is solved, the process is simple, and a high-temperature roasting process of sodium salt roasting and oxygen-enriched calcification roasting is not needed; the method comprises the steps of preparing sulfuric acid by boiling, carrying out boiling roasting on a mixture of sulfur-containing precipitates purified by sulfuric acid-containing wastewater, sulfate produced by extraction water precipitation and pyrite to produce sulfur dioxide flue gas, and carrying out a sulfuric acid preparation process together with the sulfur dioxide flue gas in an oxidation process, wherein the waste gas enters an acid preparation process in a raw material form for cyclic utilization, harmful gas is not discharged in the whole process, fresh water consumed by acid leaching is only 1;
the method for preparing ammonium metavanadate further comprises the following steps:
step one, preparing refined vanadium slag, namely crushing the crude vanadium slag, and removing iron by magnetic separation, wherein the crushing particle size is about 100 meshes, so as to prepare the refined vanadium slag for later use;
step two, pre-oxidation acidolysis, namely adding 25-30% concentrated sulfuric acid into a closed container, wherein a small amount of sulfuric acid is added and a certain cooling material is added to control the reaction temperature because of high reaction speed and high temperature, the generated flue gas enters a circulating pipeline through a flue and flows back into a neutralization solution of an acid making tower, the temperature is 100-150 ℃, and the flue gas is continuously stirred during the sulfuric acid addition process to avoid hardening and hardening, so that the pre-oxidation acidolysis is completed;
step three, oxidizing and acid splitting, namely adding a catalyst, an oxidant and concentrated sulfuric acid when the temperature is reduced to 30-40 ℃, slowly adding sulfuric acid and continuously stirring, controlling the temperature to be below 150 ℃, keeping the temperature to be 80-300 ℃ for 8 hours, and carrying out heat preservation and oxidation to complete oxidizing and acid splitting;
step four, hydrolysis and filtration, wherein the leaching ratio is 1;
step five, adsorption, adding ammonia into the filtrate to adjust the pH value to 2.0, standing for 24 hours to generate aluminum sulfate precipitate, filtering for the second time to obtain vanadium liquid, diluting the vanadium liquid to be adsorbed under the condition of 20g/L of vanadium, and separating the first extraction liquid;
extracting and desorbing, namely extracting and separating vanadium-containing extract liquor, adding the extract liquor into a dilute sulfuric acid solution with the PH of less than 1.0 for desorption, and separating the extract liquor for the second time to obtain relatively pure vanadium liquid;
seventhly, adding ammonia for precipitation, stopping adding ammonia when the temperature of the vanadium liquid is higher than 90 ℃, cooling the vanadium liquid to the normal temperature, filtering for three times, and washing precipitates twice by using purified water;
step eight, drying and packaging to obtain more than 98% of ammonium metavanadate; the method for preparing ammonium metavanadate by direct sulfuric acid oxidation acidolysis of vanadium slag is formed.
2. The method for preparing ammonium metavanadate by direct sulfuric acid oxidation and acidolysis of vanadium slag according to claim 1, wherein the catalyst is calcium fluoride or hydrofluoric acid with a concentration ratio of 0.5% to concentrated sulfuric acid.
3. The method for preparing ammonium metavanadate by direct sulfuric acid oxidation and acidolysis of vanadium slag according to claim 1, wherein the oxidant is manganese sesquioxide.
4. The method for preparing ammonium metavanadate by direct sulfuric acid oxidation and acidolysis of vanadium slag according to claim 1, characterized in that the acid-material ratio of the high leaching proportion is 97-98%, and the tailings contain less than 0.4% of vanadium by one-time leaching.
5. The method for preparing ammonium metavanadate by direct sulfuric acid oxidation and acidolysis of vanadium slag according to claim 1, wherein the low-temperature acidolysis temperature is not higher than 300 ℃, stone coal, electric power and coal are used as controllable energy sources to replace supplementary energy, and the generated flue gas is directly recycled as a raw material for acid production without discharging harmful flue gas.
6. The method for preparing ammonium metavanadate from vanadium slag by direct sulfuric acid oxidation acidolysis according to claim 1, wherein relevant technical parameters in the method for preparing ammonium metavanadate are as follows: the acidolysis oxidation reaction temperature of adding a catalyst and an oxidant is 80-300 ℃, the leaching stock-liquid ratio is 1.
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