CN111636000B - Clean and efficient barium-containing tungsten ore decomposition reagent and decomposition method thereof - Google Patents
Clean and efficient barium-containing tungsten ore decomposition reagent and decomposition method thereof Download PDFInfo
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- CN111636000B CN111636000B CN202010546153.1A CN202010546153A CN111636000B CN 111636000 B CN111636000 B CN 111636000B CN 202010546153 A CN202010546153 A CN 202010546153A CN 111636000 B CN111636000 B CN 111636000B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a clean and efficient decomposition reagent for barium-containing tungsten ore and a decomposition method thereof. According to the invention, the barium-containing tungsten ore is leached by the leaching solution containing sodium sulfate, so that barium is converted into safe and nontoxic barium sulfate while tungstate ions in the barium-containing tungsten ore enter the solution, and the method has the advantages of high leaching rate, simple process, economy, high efficiency, safety and environmental protection.
Description
Technical Field
The invention belongs to the field of extraction of rare high-melting-point metal tungsten in the field of hydrometallurgy, and particularly relates to a clean and efficient barium-containing tungsten ore decomposition reagent and a decomposition method for extracting tungsten from barium-containing tungsten ore by using the same.
Background
Tungsten and its alloys are widely used in many fields such as steel, aerospace industry, national defense military industry, machining, electronic industry and the like due to their excellent physicochemical properties, and tungsten is an important strategic material and is known as "industrial teeth". China is a resource and a large producing country of tungsten, and the reserves of China are the first place in the world.
The main smelting raw materials of tungsten are wolframite and scheelite, but with the annual exploitation of tungsten resources, the 20 th century and 80 th century, high-quality wolframite resources are consumed, and the scheelite, complex ore and low-grade refractory ore have larger and larger proportion in tungsten mineral raw materials, so that the ore dressing and smelting cost is continuously increased. The barium-containing tungsten ore is one of the refractory tungsten ores, wherein barium mainly exists in the form of barium tungstate.
The current common method for treating tungsten ore is NaOH pressure cooking method, and the process can decompose tungsten ore under the conditions of high alkali, high temperature and high pressure. However, if barium is contained in the tungsten ore, the decomposition effect is deteriorated, and the higher the content of barium is, the more difficult the decomposition is, the higher the content of tungsten in the slag is. Therefore, the conventional NaOH autoclaving method is difficult to process the barium-containing tungsten ore.
In addition, barium ions are highly toxic and can cause protein denaturation, destroying various enzymes in the human body. If the barium ions are not properly treated in the decomposition process of the barium tungstate, the barium ions are easy to cause harm to the natural environment and the human health. Therefore, when decomposing the barium-containing tungsten ore, special attention must be paid to properly handling barium ions therein.
CN110042232A discloses a method for extracting tungsten from high barium tungsten ore, which mixes sodium nitrate, sodium hydroxide and sodium carbonate as decomposers with scheelite and then carries out pressure boiling decomposition. Sodium carbonate, although it can decompose barium-containing tungsten ore, has many drawbacks. Firstly, the precipitation equilibrium constant of barium carbonate is much larger than that of barium tungstate, which indicates that the stability of barium carbonate is very low compared with that of barium tungstate, so that a large excess of carbonate ions needs to be added in the decomposition process to promote the decomposition reaction, and the waste of reagents is caused. In addition, when sodium carbonate decomposes tungsten ore, the concentration of sodium carbonate is often controlled to 230 g.L to prevent supersaturated precipitation of sodium carbonate-1Hereinafter, it is required that the content of barium tungstate in scheelite is not so high that the range of treatment objects of the method is limited. Furthermore, the need to control the concentration of sodium carbonate leads to a large liquid-solid ratio in the reaction process, which results in a large amount of acid consumed in the subsequent purification process and a large amount of sodium salt wastewater, resulting in an increase in process cost. Finally, the barium carbonate product obtained by the method has high biological toxicity and is commonly called as witherite.
Sodium phosphate can also decompose barium-containing tungsten ore, but the generated barium phosphate is unstable, easy to dissolve in acid and has larger toxicity.
Therefore, a clean, high-efficiency, safe and environment-friendly barium-containing tungsten ore decomposition reagent without generating barium toxicity and a decomposition method thereof are urgently needed.
Disclosure of Invention
In order to solve the technical problems in the existing method for extracting tungsten from barium-containing tungsten ore, the invention aims to provide a clean and efficient barium-containing tungsten ore decomposition reagent and a decomposition method thereof.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a clean and high-efficiency barium-containing tungsten ore decomposition reagent contains sodium sulfate.
In a preferred embodiment, the decomposition reagent is sodium sulfate; or sodium hydroxide and sodium sulfate; or sodium carbonate and sodium sulphate; or sodium phosphate and sodium sulfate.
A clean and efficient decomposition method of barium-containing tungsten ore comprises mixing decomposition reagent containing sodium sulfate with barium-containing tungsten ore, placing in a reaction kettle, and hot-dipping under alkaline condition.
In a preferred scheme, the hydrothermal leaching conditions are as follows: pH is not lower than 7.8, temperature is 90-200 deg.C, time is 1-5h, and liquid-solid ratio is 0.8:1-2:1m3/t。
In a preferable scheme, when the barium-containing tungsten ore only contains barium tungstate, the decomposition reagent is sodium sulfate, and the molar weight of the sodium sulfate is 1.8-5.0 times of the molar weight of the total tungsten in the barium-containing tungsten ore.
Preferably, when the barium-containing tungsten ore further contains calcium tungstate, the decomposition reagent is sodium hydroxide and sodium sulfate, the molar weight of the sodium hydroxide is 4.0-10.0 times of the molar weight of the total tungsten in the barium-containing tungsten ore, and the molar weight of the sodium sulfate is 1.8-5.0 times of the molar weight of the total tungsten in the barium-containing tungsten ore.
Preferably, when the barium-containing tungsten ore further contains calcium tungstate, the decomposition reagents are sodium carbonate and sodium sulfate, the molar weight of the sodium carbonate is 2.5-5.0 times of the molar weight of the total tungsten in the barium-containing tungsten ore, the molar weight of the sodium sulfate is 1.8-5.0 times of the molar weight of the total tungsten in the barium-containing tungsten ore, and the initial concentration of the sodium carbonate is controlled to be 50-200 g/L.
Preferably, when the barium-containing tungsten ore also contains calcium tungstate, the decomposition reagent is sodium phosphate and sodium sulfate, the molar weight of the sodium phosphate is 1.0-1.5 times of the molar weight of the total tungsten in the barium-containing tungsten ore, the molar weight of the sodium sulfate is 1.8-5.0 times of the molar weight of the total tungsten in the barium-containing tungsten ore, and the initial concentration of the sodium phosphate is controlled to be 30-150 g/L.
The invention has the following advantages:
1. according to the invention, the barium-containing tungsten ore is leached by the leaching solution containing sodium sulfate, the sodium sulfate can be effectively combined with barium, so that barium tungstate in the barium-containing tungsten ore cannot stably exist, and the decomposition rate of the tungsten ore is high.
2. In the leaching residue obtained after leaching, barium exists in the form of barium sulfate, and the leaching residue is safe and non-toxic.
3. The method only mixes the decomposition reagent containing sodium sulfate and the barium-containing tungsten ore and then carries out hydrothermal leaching under the alkaline condition, and has the advantages of simple process, easy implementation, high efficiency and environmental protection.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Certain barium-containing tungsten ore containing WO355.36%, Ca4.2% and Ba26.4%, and barium exists in the form of barium tungstate by phase analysis.
The weight of the ore is 1000g, the ore is pre-ground to less than 75 mu m, and 0.8L, NaOH952g and Na are added into the water2SO4608g, put into an autoclave, the reaction temperature is 200 ℃, and leaching is carried out for 5 hours. After unloading and filtering, the decomposition rate of the obtained tungsten ore is 98.73 percent.
Example 2
Certain barium-containing tungsten ore containing WO355.36%, Ca4.2% and Ba26.4%, and barium exists in the form of barium tungstate by phase analysis.
The weight of the ore is 1000g, the ore is pre-ground to be less than 75 mu m, and 2L, NaOH382g and Na are added into the water2SO41690g, placing in an autoclave, and leaching for 5 hours at the reaction temperature of 200 ℃. After unloading and filtering, the decomposition rate of the obtained tungsten ore is 99.21 percent.
Example 3
Certain barium-containing tungsten ore containing WO351.13% and Ba 37%, wherein barium exists in the form of barium tungstate and tungsten exists in the form of barium tungstate through phase analysis. Taking 1000g of the material, pre-grinding to less than 75 μm, adding 2L, NaOH10 waterg、Na2SO4564g was placed in a round bottom flask and leached at 90 ℃ for 1 hour. After unloading and filtering, the decomposition rate of the obtained tungsten ore is 99.71 percent.
Example 4
Certain barium-containing tungsten ore containing WO351.13% and Ba 37%, wherein barium exists in the form of barium tungstate and tungsten exists in the form of barium tungstate through phase analysis. Extracting 1000g, pre-grinding to less than 75 μm, adding water 2L, NaOH10g and Na2SO41565g, placing in a round-bottom flask, reacting at 90 deg.C, leaching for 1 hr. After unloading and filtering, the decomposition rate of the obtained tungsten ore is 99.63 percent.
Example 5
Certain barium-containing tungsten ore containing WO343.2%, Ca3.51%, Ba23.5%, by phase analysis, barium was present as barium tungstate.
The weight of the ore is 1000g, the ore is pre-ground to be less than 75 mu m, and 10L, NaOH74, 74g and Na are added into the water3PO4305g、Na2SO41322g, placing in a high-pressure autoclave, and leaching for 5 hours at the reaction temperature of 180 ℃. After unloading and filtering, the decomposition rate of the obtained tungsten ore is 98.97 percent.
Example 6
Certain barium-containing tungsten ore containing WO343.2%, Ca3.51%, Ba23.5%, by phase analysis, barium was present as barium tungstate.
The weight of the ore is 1000g, the ore is pre-ground to be less than 75 mu m, 3L of water, 14.89g of NaOH14 and Na are added3PO4458g、Na2SO4476g, placing in an autoclave, the reaction temperature is 180 ℃, and leaching for 5 hours. After unloading and filtering, the decomposition rate of the obtained tungsten ore is 98.43 percent.
Example 7
Certain barium-containing tungsten ore containing WO310.2%, Ca3.2%, Ba5.5%, by phase analysis, barium was present as barium tungstate. The weight of the ore is 1000g, the ore is pre-ground to less than 75 mu m, 2.33L of water, 8.8g of NaOH8 and Na are added2CO3116.5g、Na2SO4312g, and placing the mixture into an autoclave, wherein the reaction temperature is 200 ℃, and leaching is carried out for 5 hours. After unloading and filtering, the decomposition rate of the obtained tungsten ore is 98.15 percent.
Example 8
Certain barium-containing tungsten ore containing WO310.2%, Ca3.2%, Ba5.5%, by phase analysis, barium was present as barium tungstate.
The weight of the ore is 1000g, the ore is pre-ground to be less than 75 mu m, 1.165L of water, 3.5g of NaOH3 and Na are added2CO3233g、Na2SO4112.5g, and placing the mixture into an autoclave, wherein the reaction temperature is 200 ℃, and leaching is carried out for 5 hours. After unloading and filtering, the decomposition rate of the obtained tungsten ore is 98.77 percent.
Example 9
Certain barium-containing tungsten ore containing WO335.73 percent of Mn2.1 percent, Ca1.5 percent and Ba16.5 percent, and the barium mainly exists in the form of barium tungstate through phase analysis.
1000g of the material is taken, and 1L, NaOH246g and Na are added into the material2SO4875g, placing in a high-pressure kettle, and leaching for 3 hours at the reaction temperature of 200 ℃. After unloading and filtering, the decomposition rate of the obtained tungsten ore is 98.94 percent.
Comparative example 1
The experimental raw materials and experimental conditions were the same as in example 1 except that sodium sulfate was not added, and the amount of sodium hydroxide added was adjusted to 1925g, the tungsten ore decomposition rate was decreased to 19.35%.
Comparative example 2
The experimental raw materials and experimental conditions were the same as in example 3, except that 880g of NaOH was used as a decomposition reagent without adding sodium sulfate, and the tungsten ore decomposition rate was only 3.73%.
Comparative example 3
The experimental raw materials and experimental conditions were the same as those of example 5 except that sodium sulfate was not added, and the decomposition rate of tungsten ore was reduced to 83.61% by adjusting the amount of sodium phosphate to 1322 g.
Comparative example 4
The experimental raw materials and experimental conditions were the same as those of example 7 except that sodium sulfate was not added, the amount of sodium carbonate added was adjusted to 350g, and the decomposition rate of tungsten ore was only 47.83%.
Comparative example 5
The experimental raw materials and experimental conditions were the same as in example 1 except that the amount of sodium sulfate was adjusted to 508g, and the decomposition rate of tungsten ore was reduced to 86.37%.
Claims (7)
1. A clean and efficient method for decomposing barium-containing tungsten ore is characterized by comprising the following steps: mixing a decomposition reagent containing sodium sulfate and the barium-containing tungsten ore, putting the mixture into a reaction kettle, and carrying out hot dipping under an alkaline condition;
in the barium-containing tungsten ore, barium exists in a barium tungstate form.
2. The method for decomposing barium-containing tungsten ore according to claim 1, characterized in that: the decomposition reagent is sodium sulfate; or sodium hydroxide and sodium sulfate; or sodium carbonate and sodium sulphate; or sodium phosphate and sodium sulfate.
3. The barium-containing tungsten ore decomposition method according to claim 2, characterized in that: the conditions of the hydrothermal leaching are as follows: pH is not lower than 7.8, temperature is 90-200 deg.C, time is 1-5h, and liquid-solid ratio is 0.8:1-2:1m3/t。
4. The method for decomposing barium-containing tungsten ore according to claim 3, characterized in that: when the barium-containing tungsten ore only contains barium tungstate, the decomposition reagent is sodium sulfate, and the molar weight of the sodium sulfate is 1.8-5.0 times of the total molar weight of tungsten in the barium-containing tungsten ore.
5. The method for decomposing barium-containing tungsten ore according to claim 3, characterized in that: when the barium-containing tungsten ore also contains calcium tungstate, the decomposition reagent is sodium hydroxide and sodium sulfate, the molar weight of the sodium hydroxide is 4.0-10.0 times of the molar weight of the total tungsten in the barium-containing tungsten ore, and the molar weight of the sodium sulfate is 1.8-5.0 times of the molar weight of the total tungsten in the barium-containing tungsten ore.
6. The method for decomposing barium-containing tungsten ore according to claim 3, characterized in that: when the barium-containing tungsten ore also contains calcium tungstate, the decomposition reagents are sodium carbonate and sodium sulfate, the molar weight of the sodium carbonate is 2.5-5.0 times of the molar weight of the total tungsten in the barium-containing tungsten ore, the molar weight of the sodium sulfate is 1.8-5.0 times of the molar weight of the total tungsten in the barium-containing tungsten ore, and the initial concentration of the sodium carbonate is controlled to be 50-200 g/L.
7. The method for decomposing barium-containing tungsten ore according to claim 3, characterized in that: when the barium-containing tungsten ore also contains calcium tungstate, the decomposition reagents are sodium phosphate and sodium sulfate, the molar weight of the sodium phosphate is 1.0-1.5 times of the molar weight of the total tungsten in the barium-containing tungsten ore, the molar weight of the sodium sulfate is 1.8-5.0 times of the molar weight of the total tungsten in the barium-containing tungsten ore, and the initial concentration of the sodium phosphate is controlled to be 30-150 g/L.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614545A (en) * | 2013-11-22 | 2014-03-05 | 中南大学 | Method for treating low-grade tungsten concentrate and tungsten slag |
| CN105296749A (en) * | 2015-10-29 | 2016-02-03 | 江西稀有稀土金属钨业集团有限公司 | Method and system for dissolving barium-containing tungsten ores |
| CN106319212A (en) * | 2016-09-27 | 2017-01-11 | 中南大学 | Method for resolving scheelite at normal pressure in alkaline system |
| CN109468453A (en) * | 2018-12-14 | 2019-03-15 | 中南大学 | A method of tungsten being extracted from tungstenic raw material using cullet |
| CN110042232A (en) * | 2019-04-30 | 2019-07-23 | 江西理工大学 | A kind of scheelite distintegrant and its method that tungsten is extracted from scheelite |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614545A (en) * | 2013-11-22 | 2014-03-05 | 中南大学 | Method for treating low-grade tungsten concentrate and tungsten slag |
| CN105296749A (en) * | 2015-10-29 | 2016-02-03 | 江西稀有稀土金属钨业集团有限公司 | Method and system for dissolving barium-containing tungsten ores |
| CN106319212A (en) * | 2016-09-27 | 2017-01-11 | 中南大学 | Method for resolving scheelite at normal pressure in alkaline system |
| CN109468453A (en) * | 2018-12-14 | 2019-03-15 | 中南大学 | A method of tungsten being extracted from tungstenic raw material using cullet |
| CN110042232A (en) * | 2019-04-30 | 2019-07-23 | 江西理工大学 | A kind of scheelite distintegrant and its method that tungsten is extracted from scheelite |
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