CN86100031A - The treatment process of calcareous tungsten ore material - Google Patents
The treatment process of calcareous tungsten ore material Download PDFInfo
- Publication number
- CN86100031A CN86100031A CN 86100031 CN86100031A CN86100031A CN 86100031 A CN86100031 A CN 86100031A CN 86100031 CN86100031 CN 86100031 CN 86100031 A CN86100031 A CN 86100031A CN 86100031 A CN86100031 A CN 86100031A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- sheelite
- wolframite
- phosphoric acid
- sodium hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
The invention belongs to the method for wet method extraction tungsten from calcareous tungsten ore material.Sheelite is to contain scheelite, is difficult to dissolving in sodium hydroxide solution.Present method is to add phosphoric acid salt or phosphoric acid in sodium hydroxide leaching solution, when sodium hydroxide leaches wolframite, impel sheelite also to dissolve, wherein calcium is transformed into the calcium phosphate powder precipitation, tungsten enters solution with the sodium wolframate form, can under normal pressure wolframite and sheelite be leached simultaneously, the total leaching yield of tungsten reaches 98%.This law is applicable to the mixture of handling wolframite and sheelite, selects material and tungsten slurry, sheelite ammonia leaching residue etc. as high calcium wolframite, calcareous difficulty.
Description
The invention belongs to calcareous tungsten ore material wet method and extract the method for tungsten.
Tungsten ore with the economic exploitation value mainly is wolframite ((Fe.Mn) WO
4) and sheelite (CaWO
4) two big classes, normally draw concentrate through ore dressing earlier, extract tungsten with different metallurgical methods then.For wolframite is that the former needs the high-temperature roasting energy consumption higher with sodium carbonate roasting decomposition method or sodium hydroxide lixiviation process, the now industrial latter that adopt more.For white tungsten fine ore is to press cooking method with salt acid leaching process or yellow soda ash, and the latter then needs to use the high pressure leaching plant.
But in the tungsten deposit of reality, wolframite and sheelite usually are symbiotic, are difficult to obtain very pure single concentrate sometimes with traditional physical concentration method.For example, regular meeting is mingled with a small amount of sheelite in wolframite, and particularly some high calcium wolframite calcics mainly are because sheelite is fine grain teeth cloth in wolframite up to 3～5%, and same, also can mix in white tungsten fine ore has a small amount of wolframite.And, when tungsten ore is selected, also can produces a considerable amount of tungsten ores and (contain WO
315～45%), generally be wolframite and sheelite intergrowth form more and exist, be difficult to further sorting, be commonly referred to difficulty and select tungsten material and tungsten slurry.
For the mixture that contains wolframite simultaneously, select tungsten material and tungsten slurry, sheelite ammonia leaching residue etc. as high calcium wolframite, difficulty, if single the processing with the sodium hydroxide alkaline leaching can only be dissolved wolframite, can not leach sheelite; If single the leaching with the salt acid system can only be dissolved sheelite, can not leach wolframite.United States Patent (USP) 4320096 proposes the associating alkali pressing immersion method in wolframite and sheelite mixing ore deposit, to containing 3～75%WO
3Wolframite and contain 3～65%WO
3Sheelite mixing ore deposit.The leaching agent mixing solutions of yellow soda ash and sodium hydroxide, sodium carbonate amount Na
2CO
3/ WO
3Weight ratio is 0.9～2.0, Na
2CO
3Concentration 50～200 grams per liters, and add the NaOH of opinion calculating aequum at least according to reason, press and soak 180～310 ℃ of temperature, pressure 14～100 kilograms per centimeter
2, the total leaching yield of tungsten is more than 95%, though this method can leach wolframite and sheelite simultaneously, operate under high-temperature and high-pressure conditions, needs expensive high pressure leaching plant, and will use two kinds of alkali (Na
2CO
3And NaOH), the wherein strict control of NaOH consumption is because the FeCO that NaOH produces when being difficult to during with quantity not sufficient wolframite is leached
3And MnCO
3Hydrolysis becomes NaHCO
3, can make then when the NaOH consumption is too much that the silicon of gangue mineral dissolves in a large number in the ore.
China's tungsten ore resource is abundant, and reserves and concentrate output all occupy first place in the world.But the tungsten concentrate that several important tungsten ore mountain products go out belongs to the high calcium wolframite, and a considerable amount of calcic difficulties of the equal output of each tungsten ore concentrate upgrading plant are selected the tungsten slurry material simultaneously, does not still have suitable treatment process at present.
The purpose of this invention is to provide a kind of method that can under normal pressure, leach wolframite and sheelite simultaneously, avoid using expensive high pressure leaching plant.
The present invention in the normal pressure leaching wolframite (reaction 1), adds phosphoric acid salt or phosphoric acid and impels sheelite also to dissolve in sodium hydroxide solution, and the calcium in the sheelite is transformed into the calcium phosphate powder precipitation, and tungsten then enters solution (reaction 2) with the sodium wolframate form.
In alkaline leaching liquid, add phosphoric acid salt, comprise various sodium salt (Na
3PO
4, Na
2HPO
4, NaH
2PO
4), sylvite (K
3PO
4, K
2HPO
4, KH
2PO
4) and ammonium salt ((NH
4)
3PO
4, (NH
4)
2HPO
4, NH
4H
2PO
4), and phosphoric acid (H
3PO
4).
The consumption of phosphoric acid salt or phosphoric acid is 0.5～1.0 times of the required theoretical amount of generation calcium phosphate powder, and the best is 0.6～0.9 times.
Sodium hydroxide concentration is pressed NaOH/WO
3Weight ratio is 0.5～1.1, and the best is 0.6～0.9.
NaOH concentration is 200～500 grams per liters in the alkalescence leaching liquid, and the best is 250～450 grams per liters.
Extraction temperature is 95～135 ℃, and the best is 105～130 ℃.
Extraction time is 2～6 hours, and the best is 3～5 hours.
The ore pulp liquid-solid ratio is 1.0～2.0 liters/kilogram.
Ore grain size is-320 orders.
Carry out agitation leach.
The present invention has following characteristics:
1. leach wolframite and sheelite simultaneously under normal pressure, do not need to add expensive high pressure leaching plant and high-duty boiler, the normal pressure alkali that can make full use of existing factory soaks equipment, and can reduce energy consumption, than being easier in industrial practicality.
2. only use a kind of leaching agent of sodium hydroxide, operational condition is close with the situation that present normal pressure alkali soaks wolframite, changes little to existing technical process and equipment.
3. phosphoric acid salt of Tian Jiaing or phosphoric acid, be mainly used in sheelite is transformed, its consumption is to add by generating calcium phosphate powder precipitation aequum, the close level the when phosphorus content in the leach liquor remains essentially in general normal pressure alkali and soaks wolframite.
4. this law is specially adapted to handle the mixture that contains wolframite and sheelite simultaneously, selects tungsten material and tungsten slurry, sheelite ammonia leaching residue etc. as high calcium wolframite, difficulty.
5. under above-mentioned preferable leaching condition, wolframite and sheelite can be leached simultaneously, the total leaching yield of tungsten reaches 98%.
Example one
High calcium wolframite 100 grams (contain WO
369.9%, Ca3.56%, Mn7.44%, Fe12.02%, P0.044%, As0.012%, SiO
21.85%) granularity-320 order.Add 130 milliliters in water, add Na
3PO
46 grams (be equivalent to generate the required theoretical amount of calcium phosphate powder 0.7 times).NaOH concentration 430 grams per liters in the leach liquor, sodium hydroxide concentration is NaOH/WO
30.77 of weight ratio.110 ℃ of extraction temperatures, normal pressure leaching 4 hours.The total leaching yield 98.8% of tungsten.
Example two
High calcium wolframite 100 grams are with example one.Add 130 milliliters in water, add KH
2PO
45.5 gram (be equivalent to generate the required theoretical amount of calcium phosphate powder 0.7 times).The leaching condition is with example one.The total leaching yield 99.2% of tungsten.
Example three
High calcium wolframite 100 grams are with example one.Add 130 milliliters in water, add 85%H
3PO
42.6 milliliter (be equivalent to generate the required theoretical amount of calcium phosphate powder 0.7 times).The leaching condition is with example one.The total leaching yield 98.0% of tungsten.
Example four
The calcic difficulty selects tungsten slurry 300 grams (to contain WO
325.8%, CaO6.41%, Mn2.07%, Fe7.08%, P0.22%, As0.06%, SiO
233.94%) granularity-320 order.Add 300 milliliters in water, add Na
3PO
419 grams (be equivalent to generate the required theoretical amount of calcium phosphate powder 0.6 times).NaOH concentration 223 grams per liters in the leach liquor, sodium hydroxide concentration is NaOH/WO
30.86 of weight ratio.130 ℃ of extraction temperatures, airtight leaching 5 hours.The total leaching yield 98.0% of tungsten.
Example five
Sheelite ammonia leaching residue 50 grams (contain WO
346.9%, CaO8.54%, Mn1.10%, Fe4.09%, SiO
222.35%) granularity-320 order.Add 75 milliliters in water, add Na
3PO
46.4 gram (be equivalent to generate the required theoretical amount of calcium phosphate powder 0.85 times).NaOH concentration 350 grams per liters in the leach liquor, sodium hydroxide concentration is NaOH/WO
31.1 of weight ratio.115 ℃ of extraction temperatures, normal pressure leached 5 hours.The total leaching yield 97.3% of tungsten.
Claims (5)
1, a kind of method that tungsten is got in the lixiviate of normal pressure alkali from calcareous tungsten ore material.It is characterized in that, select calcareous tungsten ore materials such as tungsten slurry and sheelite ammonia leaching residue for high calcium wolframite, difficulty, in the immersion liquid of sodium hydroxide normal pressure alkali, add phosphoric acid salt or phosphoric acid, when wolframite leaches, impel sheelite also to dissolve, wherein calcium is transformed into the calcium phosphate powder precipitation, and tungsten enters solution with the sodium wolframate form, wolframite and sheelite can be leached simultaneously.
2, method described in claim 1 is characterized in that the phosphoric acid salt that adds comprises various sodium salt (Na
3PO
4, Na
2HPO
4, NaH
2PO
4), sylvite (K
3PO
4, K
2HPO
4, KH
2PO
4) and ammonium salt ((NH
4)
2PO
4, (NH
4)
2HPO
4, NH
4H
2PO
4), and phosphoric acid (H
3PO
4).
3, method described in claim 1 and 2, the consumption that it is characterized in that phosphoric acid salt or phosphoric acid is 0.5～1.0 times of the required theoretical amount of generation calcium phosphate powder, the best is 0.6～0.9 times.
4, method described in claim 1 is characterized in that used sodium hydroxide is by NaOH/WO
3Weight ratio is 0.5～1.1 calculating, and naoh concentration is 200～500 grams per liters, and the best is 250～450 grams per liters.
5, method described in claim 1 is characterized in that extraction temperature is 95～135 ℃, and the best is 105～130 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198686100031A CN86100031B (en) | 1986-01-07 | 1986-01-07 | Processing of calcium-contg. tungstenic ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198686100031A CN86100031B (en) | 1986-01-07 | 1986-01-07 | Processing of calcium-contg. tungstenic ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86100031A true CN86100031A (en) | 1986-09-10 |
| CN86100031B CN86100031B (en) | 1988-06-01 |
Family
ID=4800863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198686100031A Expired CN86100031B (en) | 1986-01-07 | 1986-01-07 | Processing of calcium-contg. tungstenic ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN86100031B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021327A (en) * | 2010-12-24 | 2011-04-20 | 中南大学 | Method for decomposing scheelite by using phosphoric acid |
| CN102021329A (en) * | 2010-12-24 | 2011-04-20 | 中南大学 | Method for extracting tungsten from scheelite and producing high-quality calcined gypsum |
| CN102021328A (en) * | 2010-12-24 | 2011-04-20 | 中南大学 | Method for extracting tungsten from scheelite |
| CN103451434A (en) * | 2013-08-29 | 2013-12-18 | 湖南辰州矿业股份有限公司 | Treatment method for dephosphorized slag in tungsten metallurgy |
| CN103526052A (en) * | 2013-10-23 | 2014-01-22 | 北京矿冶研究总院 | Method for recovering tungsten from tungsten-containing fluorite ore |
| CN106319212A (en) * | 2016-09-27 | 2017-01-11 | 中南大学 | Method for resolving scheelite at normal pressure in alkaline system |
| CN106636632A (en) * | 2016-09-27 | 2017-05-10 | 中南大学 | Method for conducting normal-pressure decomposition on wolframite or scheelite and wolframite mixture ores in alkali system |
| CN108913884A (en) * | 2018-07-23 | 2018-11-30 | 中国有色集团（广西）平桂飞碟股份有限公司 | Low alkali high temperature and pressure decomposes the method that wolframite prepares coarse sodium tungstate |
| CN108998655A (en) * | 2018-08-24 | 2018-12-14 | 赣州海创钨业有限公司 | The Acid-Base of high calcium low-grade scheelite combines smelting process |
| CN109439929A (en) * | 2018-12-17 | 2019-03-08 | 江西理工大学 | A kind of method that alkaline system decomposes Scheelite-Wolframite Mixed Mine |
| CN110878393A (en) * | 2019-12-17 | 2020-03-13 | 中南大学 | Environment-friendly and efficient tungsten smelting method |
-
1986
- 1986-01-07 CN CN198686100031A patent/CN86100031B/en not_active Expired
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021327A (en) * | 2010-12-24 | 2011-04-20 | 中南大学 | Method for decomposing scheelite by using phosphoric acid |
| CN102021329A (en) * | 2010-12-24 | 2011-04-20 | 中南大学 | Method for extracting tungsten from scheelite and producing high-quality calcined gypsum |
| CN102021328A (en) * | 2010-12-24 | 2011-04-20 | 中南大学 | Method for extracting tungsten from scheelite |
| CN102021328B (en) * | 2010-12-24 | 2012-03-21 | 中南大学 | Method for extracting tungsten from scheelite |
| CN102021329B (en) * | 2010-12-24 | 2012-03-21 | 中南大学 | Method for extracting tungsten from scheelite and producing high-quality calcined gypsum |
| CN102021327B (en) * | 2010-12-24 | 2012-07-25 | 中南大学 | Method for decomposing scheelite by using phosphoric acid |
| CN103451434A (en) * | 2013-08-29 | 2013-12-18 | 湖南辰州矿业股份有限公司 | Treatment method for dephosphorized slag in tungsten metallurgy |
| CN103451434B (en) * | 2013-08-29 | 2016-03-02 | 湖南辰州矿业有限责任公司 | A kind for the treatment of process of Tungsten smelting dephosphorization slag |
| CN103526052B (en) * | 2013-10-23 | 2014-12-03 | 北京矿冶研究总院 | Method for recovering tungsten from tungsten-containing fluorite ore |
| CN103526052A (en) * | 2013-10-23 | 2014-01-22 | 北京矿冶研究总院 | Method for recovering tungsten from tungsten-containing fluorite ore |
| CN106319212A (en) * | 2016-09-27 | 2017-01-11 | 中南大学 | Method for resolving scheelite at normal pressure in alkaline system |
| CN106636632A (en) * | 2016-09-27 | 2017-05-10 | 中南大学 | Method for conducting normal-pressure decomposition on wolframite or scheelite and wolframite mixture ores in alkali system |
| CN108913884A (en) * | 2018-07-23 | 2018-11-30 | 中国有色集团（广西）平桂飞碟股份有限公司 | Low alkali high temperature and pressure decomposes the method that wolframite prepares coarse sodium tungstate |
| CN108998655A (en) * | 2018-08-24 | 2018-12-14 | 赣州海创钨业有限公司 | The Acid-Base of high calcium low-grade scheelite combines smelting process |
| CN109439929A (en) * | 2018-12-17 | 2019-03-08 | 江西理工大学 | A kind of method that alkaline system decomposes Scheelite-Wolframite Mixed Mine |
| CN109439929B (en) * | 2018-12-17 | 2020-07-28 | 江西理工大学 | Method for decomposing wolframite and wolframite mixed ore by alkaline system |
| CN110878393A (en) * | 2019-12-17 | 2020-03-13 | 中南大学 | Environment-friendly and efficient tungsten smelting method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN86100031B (en) | 1988-06-01 |
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