CN112250110A - Preparation method of ammonium metavanadate without wastewater discharge - Google Patents
Preparation method of ammonium metavanadate without wastewater discharge Download PDFInfo
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Abstract
The invention discloses a method for preparing ammonium metavanadate without wastewater discharge, which comprises the following steps: (1) desorption or back extraction: desorbing or back-extracting the loaded resin or loaded organic phase adsorbing vanadium by using conversion solution to obtain desorption solution or back-extraction solution; (2) and (3) vanadium precipitation: adding a certain amount of ammonium bicarbonate into the desorption solution or the strip solution in the step (1) or introducing CO into the solution2And NH3Precipitating vanadium to obtain ammonium metavanadate and crystallization mother liquor; (3) mother liquor conversion: and (3) adding the crystallization mother liquor obtained in the step (2) into one or two of calcium oxide or calcium hydroxide for conversion, and returning the converted conversion liquor for next round of desorption or back extraction. In the invention, the crystallization mother liquor can be recycled after being converted, thereby reducing the waste water discharge, avoiding the discharge of a large amount of ammonia nitrogen mixed waste water generated in the process of preparing ammonium metavanadate by the traditional ion exchange and extraction process, greatly reducing the alkali consumption in the desorption or back extraction process, reducing the production cost and being easy for industrialization.
Description
Technical Field
The invention relates to the technical field of ammonium metavanadate production, in particular to a preparation method of ammonium metavanadate without wastewater discharge.
Background
Vanadium, as a rare metal with high melting point, is widely applied to various aspects of steel, chemical industry, new energy, medicine and the like due to various excellent properties, and has the reputation of modern industrial monosodium glutamate. The vanadium is mainly used in metallurgical industry, and the vanadium is added into steel, so that the mechanical property of steel can be obviously improved, and the plasticity, the wear resistance and the corrosion resistance are improved.
The vanadium reserves and the output of China are in the top of the world, the main vanadium-containing minerals are vanadium titano-magnetite and stone coal, and the consumption of vanadium resources is continuously increased along with the development of China in the aspects of steel, vanadium batteries, vanadium-titanium alloys and the like. The vanadium extraction process in China has been mature after years of development, but with the more and more strict requirements on environmental protection, the traditional vanadium extraction process still needs to be updated and improved.
At present, the main methods for producing vanadium pentoxide at home and abroad are as follows:
sodium roasting-water leaching method: and carrying out sodium treatment roasting on the vanadium-containing resource, then carrying out water leaching to obtain a leaching solution, carrying out acid precipitation on the leaching solution to carry out coarse vanadium precipitation, wherein the coarse vanadium contains more impurities, carrying out alkali dissolution to remove the impurities, then adding ammonium chloride to precipitate vanadium, and calcining the obtained ammonium metavanadate to obtain qualified vanadium pentoxide.
Direct acid leaching-extraction method: the vanadium-containing resource is directly leached by concentrated sulfuric acid, vanadium oxygen cations are extracted by adopting P204+ TBP after the leached leaching solution is reduced, a back extraction solution is obtained by back extraction after extraction, ammonium is added for precipitating vanadium after the back extraction solution is oxidized, and vanadium pentoxide is obtained after calcination.
Calcified roasting-dilute acid leaching: the vanadium-containing resource is leached by dilute sulphuric acid after calcifying and roasting, leachate is absorbed by ion exchange or extracted by solvent, the obtained loaded resin or loaded organic phase is desorbed or back extracted by sodium hydroxide, the desorption solution or back extraction solution is purified by magnesium salt, ammonium chloride is added for precipitating vanadium after impurity removal, and vanadium pentoxide is obtained after precipitation and calcination.
Oxidizing roasting-dilute acid leaching-ion exchange/extraction: adding sulfuric acid into vanadium-containing resources after oxidizing roasting for leaching, carrying out ion exchange adsorption or extraction enrichment on leachate, desorbing or back-extracting the obtained loaded resin or loaded organic phase by using sodium hydroxide, adding ammonium chloride into the obtained solution for precipitating vanadium to obtain ammonium metavanadate, and calcining the ammonium metavanadate to obtain vanadium pentoxide.
In addition to the above processes, in the vanadium extraction process at the present stage, the stone coal or vanadium slag is roasted and then leached, the obtained leaching solution is subjected to ammonium salt vanadium precipitation after a series of treatments, ammonium chloride or ammonium sulfate is mostly adopted for vanadium precipitation in industry, although the vanadium precipitation effect of the method is good, the crystallization mother liquor after vanadium precipitation is a mixed solution of sodium chloride and ammonium chloride, and the method belongs to high-salt ammonia nitrogen wastewater. The industrial treatment of said waste water by evaporative crystallization is not only costly and energy intensive, but also produces large quantities of mixed salts of sodium chloride and ammonium chloride which may be dangerous solid wastes, the treatment of which will further increase costs. Secondly, in order to obtain higher vanadium precipitation rate and reduce the vanadium concentration in the crystallization mother liquor, the prior art needs to add a large amount of excessive ammonium salt, which causes reagent waste. With the increasing requirements of China on environmental protection, the problems generated by the traditional vanadium precipitation are urgently to be solved.
Disclosure of Invention
The invention aims to provide a method for preparing ammonium metavanadate without wastewater discharge, and aims to solve the problem of discharge of a large amount of ammonia nitrogen mixed wastewater generated in the process of preparing ammonium metavanadate by using the traditional ion exchange and extraction process.
In order to achieve the above object, the present invention provides a method for preparing ammonium metavanadate without wastewater discharge, comprising the following steps:
(1) desorption or back extraction: desorbing or back-extracting the loaded resin or loaded organic phase adsorbing vanadium by using conversion solution to obtain desorption solution or back-extraction solution;
(2) and (3) vanadium precipitation: adding a certain amount of ammonium bicarbonate into the desorption solution or the strip liquor obtained in the step (1) or introducing CO2 and NH3 into the solution to carry out vanadium precipitation so as to obtain ammonium metavanadate and crystallization mother liquor;
(3) mother liquor conversion: and (3) adding the crystallization mother liquor obtained in the step (2) into one or two of calcium oxide or calcium hydroxide for conversion, and returning the converted conversion liquor for next round of desorption or back extraction.
Preferably, in step (1), the support resin is a weakly basic ion exchange resin.
Preferably, in step (1), the loaded organic phase is a weakly basic extractant.
Preferably, the weakly basic extractant comprises a tertiary amine extractant, a primary amine extractant, or a secondary amine extractant.
Preferably, in the step (1), the conversion solution is one or a mixture of sodium carbonate solution and sodium hydroxide solution.
Preferably, the adding amount of ammonium bicarbonate in the step (2) is 1-3 times of the theoretical amount, the vanadium precipitation time is 0.1-5h, and the vanadium precipitation temperature is 0-60 ℃.
Preferably, in the step (3), the addition amount of one or two of calcium oxide or calcium hydroxide is 1-3 times of the theoretical amount, the conversion time is 0.5-4h, and the conversion temperature is 20-100 ℃.
Preferably, the converted conversion solution is returned to the next round of desorption or stripping process, and one or both of sodium carbonate and sodium hydroxide are supplemented.
Compared with the prior art, the method for preparing ammonium metavanadate without wastewater discharge provided by the invention has at least the following beneficial effects: does not generate ammonia nitrogen wastewater and waste salt, has low reagent consumption, simple operation, low equipment requirement and low cost, realizes the cyclic utilization of resources and is easy to realize industrialization.
Drawings
FIG. 1 is a flow chart of a method for preparing ammonium metavanadate without wastewater discharge according to the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. These examples are intended to be illustrative of the invention only and are not intended to limit the scope of the invention.
Preparation of experimental raw materials:
adjusting the pH value of a vanadium-containing raw material liquid with a certain concentration to be 2-4, wherein the vanadium-containing raw material liquid is one or more of a stone coal acid leaching liquid, a vanadium-containing waste catalyst acid leaching liquid and a vanadium-titanium magnetite slag leaching liquid.
Examples preparation of the loaded resin: taking the prepared vanadium-containing raw material liquid V2O5Adsorbing with weak base anion resin at pH 2.5 and 13.84g/L to obtain loaded resin (about 220mg V/1 ml resin)2O5)。
Fig. 1 is a flow chart of a method for preparing ammonium metavanadate without wastewater discharge.
Example one
(1) The prepared load resin is used as a raw material, and sodium carbonate with the concentration of 1mol/L is used as a desorbent for desorption.
(2) And carrying out static desorption on the obtained loaded resin under the condition that the liquid-solid ratio is 10:1, wherein the desorption time is 2h, the temperature is 25 ℃, and the desorption rate is more than 99%.
(3) Adding ammonium bicarbonate into the desorbed solution to precipitate vanadium, wherein the addition amount of the ammonium bicarbonate is 1.5 times of the theoretical amount, the temperature is 25 ℃, the vanadium precipitation time is 40min, the pH value is about 9.8, and the vanadium precipitation rate reaches 95.6%.
(4) And (3) converting the crystallization mother liquor after vanadium precipitation, adding 1 time of calcium oxide in the amount of the theoretical amount, converting at 80 ℃ for 2h, desorbing the loaded resin by adopting a liquid-solid ratio of 5:1, wherein the desorption rate is more than 99%.
Example two
(1) The prepared load resin is used as a raw material, and a mixed solution of sodium carbonate with the concentration of 0.5mol/L and sodium hydroxide with the concentration of 0.5mol/L is used as a desorbent for desorption.
(2) And carrying out static desorption on the obtained loaded resin under the condition that the liquid-solid ratio is 5:1, wherein the desorption time is 2h, the temperature is 25 ℃, and the desorption rate is more than 99%.
(3) Adding ammonium bicarbonate into the desorbed solution to precipitate vanadium, wherein the addition amount of the ammonium bicarbonate is 1.5 times of the theoretical amount, the temperature is 25 ℃, the vanadium precipitation time is 40min, the pH value is more than 10, and the vanadium precipitation rate reaches 97.7%.
(4) And (3) converting the crystallization mother liquor after vanadium precipitation, adding 1 time of calcium oxide in the amount of the theoretical amount, converting at 80 ℃ for 2h, desorbing the loaded resin by adopting a liquid-solid ratio of 5:1, wherein the desorption rate is more than 99%.
EXAMPLE III
(1) The prepared load resin is used as a raw material, and sodium hydroxide with the concentration of 1mol/L is used as a desorbent for desorption.
(2) And carrying out static desorption on the obtained loaded resin under the condition that the liquid-solid ratio is 2:1, wherein the desorption time is 2h, the temperature is 25 ℃, and the desorption rate is more than 99%.
(3) Adding ammonium bicarbonate into the desorbed solution to precipitate vanadium, wherein the addition amount of the ammonium bicarbonate is 1.6 times of the theoretical amount, the temperature is 25 ℃, the vanadium precipitation time is 40min, the pH is adjusted to be about 9, and the vanadium precipitation rate reaches 98%.
(4) And (3) converting the crystallization mother liquor after vanadium precipitation, adding 1 time of calcium oxide in the amount of the theoretical amount, converting at 80 ℃ for 2h, desorbing the loaded resin by adopting a liquid-solid ratio of 5:1, wherein the desorption rate is more than 99%.
Example four
(1) In the prepared loaded organic phase (100 mgV per 1ml extractant loading)2O5) The desorption is carried out by taking sodium hydroxide with the concentration of 1mol/L as a desorbent.
(2) And (3) carrying out back extraction on the obtained loaded organic phase under the condition that the phase ratio is 2:1, wherein the back extraction time is 10min, the temperature is 25 ℃, and the back extraction rate is more than 99%.
(3) Adding ammonium bicarbonate into the desorbed solution to precipitate vanadium, wherein the addition amount of the ammonium bicarbonate is 1.6 times of the theoretical amount, the temperature is 25 ℃, the vanadium precipitation time is 40min, the pH is adjusted to be about 9, and the vanadium precipitation rate reaches 95%.
(4) And (3) converting the crystallization mother liquor after vanadium precipitation, adding 1 time of calcium oxide based on the theoretical amount, at the conversion temperature of 80 ℃, for 2 hours, wherein the converted solution is a sodium carbonate solution, and performing back extraction on the loaded organic phase by adopting a condition of a 2:1 ratio, wherein the back extraction rate is more than 99%.
The method takes leachate of vanadium-containing resources as a raw material, and removes cationic impurities while absorbing vanadium by weak-base anion exchange resin or extracting vanadium by weak-base extracting agent. Meanwhile, the vanadium precipitation adopts ammonium bicarbonate to precipitate vanadium, so that the introduction of anions is further reduced. The crystallization mother liquor after vanadium precipitation is causticized by adding calcium oxide or calcium hydroxide, so that the cyclic utilization of the crystallization mother liquor is realized, the generation of high-salt wastewater is reduced, the environmental pollution is reduced, the reagent consumption is low, the cost is low, the operation is simple, and the industrialization is easy.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for preparing ammonium metavanadate without wastewater discharge is characterized by comprising the following steps:
(1) desorption or back extraction: desorbing or back-extracting the loaded resin or loaded organic phase adsorbing vanadium by using conversion solution to obtain desorption solution or back-extraction solution;
(2) and (3) vanadium precipitation: adding a certain amount of ammonium bicarbonate into the desorption solution or the strip solution in the step (1) or introducing CO into the solution2And NH3Precipitating vanadium to obtain ammonium metavanadate and crystallization mother liquor;
(3) mother liquor conversion: and (3) adding the crystallization mother liquor obtained in the step (2) into one or two of calcium oxide or calcium hydroxide for conversion, and returning the converted conversion liquor for next round of desorption or back extraction.
2. The method for preparing ammonium metavanadate without waste water discharge according to claim 1, wherein in the step (1), the loaded resin is a weakly basic ion exchange resin.
3. The method for preparing ammonium metavanadate without waste water discharge according to claim 1, wherein in the step (1), the loaded organic phase is a weakly alkaline extractant.
4. The method for preparing ammonium metavanadate without wastewater discharge according to claim 3, wherein the weakly basic extractant comprises a tertiary amine extractant, a primary amine extractant or a secondary amine extractant.
5. The method for preparing ammonium metavanadate without waste water discharge according to claim 1, wherein in the step (1), the conversion solution is one or a mixture of sodium carbonate solution and sodium hydroxide solution.
6. The method for preparing ammonium metavanadate without wastewater discharge according to claim 1, wherein the addition amount of ammonium bicarbonate in the step (2) is 1-3 times of the theoretical amount, the vanadium precipitation time is 0.1-5h, and the vanadium precipitation temperature is 0-60 ℃.
7. The method for preparing ammonium metavanadate without wastewater discharge according to claim 1, wherein the addition amount of one or both of calcium oxide or calcium hydroxide in the step (3) is 1 to 3 times of the theoretical amount, the conversion time is 0.5 to 4 hours, and the conversion temperature is 20 to 100 ℃.
8. The method according to claim 1, wherein one or both of sodium carbonate and sodium hydroxide are supplemented during the process of returning the converted solution to the next round of desorption or stripping.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113979474A (en) * | 2021-11-26 | 2022-01-28 | 中国科学院过程工程研究所 | Method for internal circulation of ammonium carbonate medium in process of preparing vanadium pentoxide from calcium vanadate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113979474A (en) * | 2021-11-26 | 2022-01-28 | 中国科学院过程工程研究所 | Method for internal circulation of ammonium carbonate medium in process of preparing vanadium pentoxide from calcium vanadate |
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Application publication date: 20210122 |