CN1872701A - Method for picking up vanadium pentexide from layer silicate without oxidation in furnace - Google Patents
Method for picking up vanadium pentexide from layer silicate without oxidation in furnace Download PDFInfo
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- CN1872701A CN1872701A CNA2006100180419A CN200610018041A CN1872701A CN 1872701 A CN1872701 A CN 1872701A CN A2006100180419 A CNA2006100180419 A CN A2006100180419A CN 200610018041 A CN200610018041 A CN 200610018041A CN 1872701 A CN1872701 A CN 1872701A
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Abstract
This invention relates to a method for extracting vanadic oxide from clay mineral without furnace oxidation process. The method comprises: (1) pulverizing crude clay ore, and adding sulfuric acid, sodium disulfate and sodium chlorate; (2) standing in a temperature tank; (3) performing solid-liquid separation; (4) adjusting the pH value of the solution containing vanadium; (5) extracting with trioctylamine; (6) back-extracting with ammonia solution; (7) adjusting the pH value of pure vanadium solution; (8) precipitating ammonium metavanadate with ammonium chloride; (9) filtering and pyrolyzing to obtain refined vanadic oxide. The method has such advantages as no waste discharge, high vanadium recovery rate of 60-70%, low cost and no pollution.
Description
Technical field
The invention belongs to and extract the rare metal technical field, be specifically related to a kind of Vanadium Pentoxide in FLAKES is extracted in the stove oxidation from clay pit method of not having.
Background technology
What the existing method of extracting Vanadium Pentoxide in FLAKES from clay pit adopted is raw ore to be pulverized the back granulate, again through the roasting of high-temp chlorination sodium, its technical process is raw ore pulverizing → mineral aggregate and salt mixing → system ball or brickmaking → 850 ℃ high temperature sodium roasting → water logging → vanadium solution clarification, when containing the vanadium massfraction in the clay pit when low, adopt the ion exchange resin absorbing process: ion absorption → desorb → clarification → precipitation → filtration → ammonium meta-vanadate → powder sheet vanadium: when containing the vanadium massfraction in the clay pit when higher, the technology of employing precipitation method: precipitation → filtration → ammonium meta-vanadate → powder vanadium or sheet vanadium.No matter this traditional technology with high-temperature roasting extraction Vanadium Pentoxide in FLAKES is direct precipitation, or the vanadium extraction of ion exchange resin absorption method, and only between 35～55%, the vanadium recovery rate is low for total rate of recovery.And in the flue gas of a large amount of energy of high temperature sodium roasting process consumption and discharge, contain a large amount of chlorine and hydrogenchloride, the severe contamination air, even all be to have lethal lethality to the plant that can touch.Adopt 6-7 that the content of ammonium chloride in the waste water that existing extracting method discharges is higher than content in the general water quality doubly, and contain detrimental impurity such as more iron, aluminium, silicon, phosphorus, the wastewater treatment burden is heavy.
China clay pit distributes mainly in the Hunan, Hubei, Henan, Shaanxi etc., and the clay mineral reserve of Xichuan County, Henan Province are very abundant, and the content of vanadium can reach about 3% in the clay pit.Vanadium is the high-melting-point rare metal, has many premium propertiess, has been widely used in industries such as metallurgy, chemical industry, and along with the adjustment development of building, the demand of vanadium and compound thereof is increasing.And vanadiumcontent is reached 3% clay pit is less, adopt this clay pit extract vanadium to collect rate higher.But gradually Chuan Xian adopts existing method to extract in Henan Province, and the waste gas of discharge, waste water will cause atmosphere and water pollution will for the waterhead area Danjiang River reservoir of the work centerline of the south water to north, causes this high-grade vanadium clay pit that contains can not obtain developing.
Summary of the invention
The objective of the invention is to overcome above-mentioned defective, provide a kind of with low cost, no waste gas discharge of wastewater, environment friendly and pollution-free, easy to operate, the method for Vanadium Pentoxide in FLAKES is extracted in the no stove oxidation that extraction yield is high from clay pit.
Technical scheme of the present invention is by following processing method:
1, original ore powder was broken to 60 mesh sieves and made breeze;
2, breeze content 80-91% and sulfuric acid 6-10%, sodium pyrosulfate 1-5%, sodium chlorate 1-5% mixes through stirrer;
3, the pondization carry out in the material that stirs is packed into the pond of sealing insulation, and time 8-20 hour, 30 ℃-150 ℃ of temperature of reaction;
4, in reacted pond, add entry, the material of Chi Huahou was soaked 2 hours, stirred 5-10 minute in 1: 5 ratio of solid-liquid;
5, stirred materials is packed into and is added filter and carry out solid-liquid separation, and isolating final slag is as material of construction;
6, isolating vanadium solution adds sodium hydroxide adjustment pH value to 2-6, and the iron in the vanadium solution, aluminium, silicon, a phosphorus part form the clarification of insoluble sedimentable matter precipitation;
7, getting clear liquor goes into extractor and extracts extraction solvent 15% trioctylamine, 10% n-Octanol, 6 grades of 75% kerosene extractions, every grade 7-8 minute, rotating speed is 200r/min, water PH1.9-2.1, extraction is than being 1: 3 water, and oil is 1, and water is 3, percentage extraction reaches 98%, poor-water after the extraction adds unslaked lime, makes iron, aluminium, silicon, phosphoric in the water-poor phase generate precipitation of hydroxide, and the water-poor phase after the processing turns back in the water soaking tank of soaking and stirring step;
8, with 3 grades of reextraction of 10% ammonia soln, being in a ratio of water oil ratio is 5: 1, time 10-20 minute, the stirrer rotating speed is 200r/min, in the reextraction process, make iron, aluminium, silicon, phosphoric in the poor organic phase generate precipitation of hydroxide, reach poor organic phase regeneration, turn back to extraction step again and use;
9, the pH value that adds the pure vanadium solution of sodium hydroxide adjustment reextraction is adjusted pH value to 8-12 and clarification;
10,4 times the ammonium chloride that adds content of vanadium in pure vanadium clear liquor forms the ammonium meta-vanadate precipitation, and the supernatant liquor after the precipitation adds unslaked lime, makes the ammonia that is contained in the supernatant liquor generate ammonium bicarbonate precipitation, turns back to soaking step again;
11, filter sedimentary ammonium meta-vanadate with filter;
12, the ammonium meta-vanadate after the filtration is made powdery V2O5 through 450 ℃ of oven dry; Ammonium meta-vanadate after the filtration dissolves 690 ℃ of following thermolysiss makes sheet V2O5;
13, packing
Beneficial effect:
According to above-mentioned V
2O
5Extraction process can find out that the present invention is easy to operate, production cost is lower than sodium method, has saved the technology of brickmaking or system ball and high-temperature roasting in the technology, has reduced manpower and has saved a large amount of fuel, has reduced cost, and do not have waste gas, poison gas produces.A large amount of waste water of being discharged during back flushing when adopting extraction process to save the resin desorb, the water-poor phase water that extraction is arranged, the use that can reflux of treated precipitation has realized zero release, has saved a large amount of waters.Avoided the sewage discharge pollution on the environment, by solvent extraction is a kind of effective ways that separate purifying substances, it is strong to have selectivity, advantages such as good separating effect, rate of recovery height, the low easy operate continuously of cost and realization automatization, percentage extraction reaches 98%, total yield reaches 60-70%, has reclaimed the vanadium in the vanadium solution basically fully.Waste residue can be used as building material after treatment, has made full use of the byproduct in extracting.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing, and a kind of do not have the stove oxidation to extract the method for Vanadium Pentoxide in FLAKES from clay pit specific as follows:
1, clay pit or ore powder are broken to 60 mesh sieves, made breeze;
2, adding sulfuric acid, sodium pyrosulfate, sodium chlorate in breeze mixes through stirrer, it is by weight hundred than for breeze 80-91%, sulfuric acid 6-10%, sodium pyrosulfate 1-5%, sodium chlorate 1-5%, specific embodiment 1: breeze 80%, sulfuric acid 10%, sodium pyrosulfate 5%, sodium chlorate 5% phase mixing and stirring; Embodiment 2: breeze 91%, sulfuric acid 7%, sodium pyrosulfate 1%, sodium chlorate 1% phase mixing and stirring; Embodiment 3: breeze 86%, sulfuric acid 8%, sodium pyrosulfate 3%, sodium chlorate 3% phase mixing and stirring;
3, the pondization carry out in the material that stirs is packed into the pond of sealing insulation, and time 8-20 hour, 30 ℃-150 ℃ of temperature of reaction;
4, in reacted pond, add entry, the material of Chi Huahou was soaked 2 hours, stirred 5-10 minute in 1: 5 ratio of solid-liquid;
5, the stirred materials flame filter press of packing into carries out solid-liquid separation, and isolated solid final slag is used for building materials;
6, isolating vanadium solution adds sodium hydroxide adjustment pH value to 2-6, and the iron in the vanadium solution, aluminium, silicon, a phosphorus part form the clarification of insoluble sedimentable matter precipitation;
7, getting clear liquor goes into extractor and extracts extraction solvent 15% trioctylamine, 10% n-Octanol, 6 grades of 75% kerosene extractions, every grade 7-8 minute, rotating speed is 200r/min, water PH1.9-2.1, extraction is than being 1: 3 water, and oil is 1, and water is 3, percentage extraction reaches 98%, the unslaked lime that adds 5g among the every 100ml of water-poor phase after the extraction makes iron, aluminium, silicon, phosphoric in the water-poor phase generate precipitation of hydroxide, and the water-poor phase after the processing turns back in the water soaking tank of soaking and stirring step;
8, with 3 grades of reextraction of 10% ammonia soln, being in a ratio of water oil ratio is 5: 1, time 10-20 minute, the stirrer rotating speed is 200r/min, in the reextraction process, make iron, aluminium, silicon, phosphoric in the poor organic phase generate precipitation of hydroxide, reach poor organic phase regeneration, turn back to extraction step again and use;
9, the pH value that adds the pure vanadium solution of sodium hydroxide adjustment reextraction is adjusted pH value to 8-12 and clarification, and adjusting pH value to 9 is the best;
10, pure vanadium clear liquor forms the ammonium meta-vanadate precipitation with the ammonium chloride of 4 times of content of vanadium, supernatant liquor after the precipitation contains vanadium at 0.05-0.2g/L, total yield is at 60-70%, add 10g unslaked lime in the supernatant liquor of every 100ml, make the ammonia that is contained in the supernatant liquor generate ammonium bicarbonate precipitation, the clear water behind the heavy ammonia returns soaking step;
11, filter sedimentary ammonium meta-vanadate with centrifugal filter;
12, the ammonium meta-vanadate after the filtration is made powdery V through 450 ℃ of oven dry
2O
5Ammonium meta-vanadate after the filtration dissolves 690 ℃ of following thermolysiss makes sheet V
2O
5
13, packing.
Claims (1)
1, a kind of do not have Vanadium Pentoxide in FLAKES is extracted in the stove oxidation from clay pit a method, and its processing step is as follows:
1) original ore powder was broken to 60 mesh sieves and made breeze;
2) breeze content 80-91% and sulfuric acid 6-10%, sodium pyrosulfate 1-5%, sodium chlorate 1-5% mixes through stirrer;
3) pondization carry out in the material that stirs is packed into the pond of sealing insulation, and time 8-20 hour, 30 ℃-150 ℃ of temperature of reaction;
4) in reacted pond, add entry, the material of Chi Huahou was soaked 2 hours, stirred 5-10 minute in 1: 5 ratio of solid-liquid;
5) stirred materials is packed into and is added filter and carry out solid-liquid separation, and isolating final slag is as material of construction;
6) isolating vanadium solution adds sodium hydroxide adjustment pH value to 2-6, and the iron in the vanadium solution, aluminium, silicon, a phosphorus part form the clarification of insoluble sedimentable matter precipitation;
7) getting clear liquor goes into extractor and extracts extraction solvent 15% trioctylamine, 10% n-Octanol, 6 grades of 75% kerosene extractions, every grade 7-8 minute, rotating speed is 200r/min, water PH1.9-2.1, extraction is than being 1: 3 water, and oil is 1, and water is 3, percentage extraction reaches 98%, water-poor phase after the extraction adds unslaked lime, makes iron, aluminium, silicon, phosphoric in the water-poor phase generate precipitation of hydroxide, and the water-poor phase after the processing turns back in the water soaking tank of soaking and stirring step;
8) with 3 grades of reextraction of 10% ammonia soln, being in a ratio of water oil ratio is 5: 1, time 10-20 minute, the stirrer rotating speed is 200r/min, in the reextraction process, make iron, aluminium, silicon, phosphoric in the poor organic phase generate precipitation of hydroxide, poor organic phase regeneration turns back to extraction step again;
9) pH value of the pure vanadium solution of adding sodium hydroxide adjustment reextraction is adjusted pH value to 8-12 and clarification;
10) add 4 times ammonium chloride of content of vanadium in pure vanadium clear liquor, form the ammonium meta-vanadate precipitation, supernatant liquor adds unslaked lime, makes the ammonia that is contained in the supernatant liquor generate the ammonium hydrogencarbonate precipitation, and the supernatant liquor behind the heavy ammonia turns back to soaking step;
11) filter sedimentary ammonium meta-vanadate with filter;
12) ammonium meta-vanadate after the filtration is made powdery V through 450 ℃ of oven dry
2O
5Ammonium meta-vanadate after the filtration dissolves 690 ℃ of following thermolysiss makes sheet V
2O
5
13) packing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100180419A CN100360428C (en) | 2006-06-22 | 2006-06-22 | Method for picking up vanadium pentexide from layer silicate without oxidation in furnace |
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| CNB2006100180419A CN100360428C (en) | 2006-06-22 | 2006-06-22 | Method for picking up vanadium pentexide from layer silicate without oxidation in furnace |
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| CN1872701A true CN1872701A (en) | 2006-12-06 |
| CN100360428C CN100360428C (en) | 2008-01-09 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289705B (en) * | 2007-04-20 | 2010-07-14 | 北京化工大学 | Process for abstracting vanadium from iron-smelting waste slag of vanadium -containing iron ore |
| CN101117238B (en) * | 2007-07-12 | 2010-07-21 | 中国铝业股份有限公司 | Method for extracting vanadium pentoxide from bayer process seed precipitation solution by extraction process |
| CN103515642A (en) * | 2012-06-25 | 2014-01-15 | 中国人民解放军63971部队 | Preparation method of vanadium battery electrolyte solution with high purity and high concentration |
| CN109852820A (en) * | 2019-02-22 | 2019-06-07 | 梁刘友 | A method of producing vanadic anhydride |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1023693C (en) * | 1990-07-12 | 1994-02-09 | 江西省煤炭工业科学研究所 | Process for extracting of vanadium pentoxide by water immersion from cured mixture of stone coal ash with surfuric acid by heating |
| CN1059885A (en) * | 1990-07-24 | 1992-04-01 | 湖南省煤炭科学研究所 | A kind of novel method of from contain the scherbinaite coal, extracting Vanadium Pentoxide in FLAKES |
| CN1057130C (en) * | 1996-12-06 | 2000-10-04 | 湖南省安化县东坪钒冶炼厂 | Vanadium pentoxide extracting method from stone coal vanadium ore |
-
2006
- 2006-06-22 CN CNB2006100180419A patent/CN100360428C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289705B (en) * | 2007-04-20 | 2010-07-14 | 北京化工大学 | Process for abstracting vanadium from iron-smelting waste slag of vanadium -containing iron ore |
| CN101117238B (en) * | 2007-07-12 | 2010-07-21 | 中国铝业股份有限公司 | Method for extracting vanadium pentoxide from bayer process seed precipitation solution by extraction process |
| CN103515642A (en) * | 2012-06-25 | 2014-01-15 | 中国人民解放军63971部队 | Preparation method of vanadium battery electrolyte solution with high purity and high concentration |
| CN109852820A (en) * | 2019-02-22 | 2019-06-07 | 梁刘友 | A method of producing vanadic anhydride |
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| CN100360428C (en) | 2008-01-09 |
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Granted publication date: 20080109 Termination date: 20110622 |