CN85100350B - Method and equipment of alkali decomposition of white tungsten fine ore and raw wolframite - Google Patents
Method and equipment of alkali decomposition of white tungsten fine ore and raw wolframite Download PDFInfo
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- CN85100350B CN85100350B CN85100350A CN85100350A CN85100350B CN 85100350 B CN85100350 B CN 85100350B CN 85100350 A CN85100350 A CN 85100350A CN 85100350 A CN85100350 A CN 85100350A CN 85100350 B CN85100350 B CN 85100350B
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- ore
- tungsten
- pressurized hot
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention relates to a method and a device for alkali decomposition of scheelite concentrate and wolframite-scheelite mixed ore, which belongs to the field of tungsten extraction. The present invention is characterized in that tungsten ore is mixed with NaOH and ground in a specially designed pressurized hot grinding reactor. The combination of chemical decomposition process with ore grinding process makes full use of the mechanical activation on ore to split product films on the ore surface and hence accelerates the decomposition process. Thus, compared with conventional soda boiling method in a stirring leaching tank, the method has lower alkali consumption and higher decomposition rate, and omits the processes in the soda boiling method, such as pre-grinding, recovery of excess alkali, dissolution of Na2WO4 crystals, etc. to shorten the flow.
Description
The invention belongs to the tungsten field of extracting, promptly the raw mineral materials with NaOH decomposition tungsten therefrom extracts tungsten.The tungsten mineral material of indication comprises and contains WO
3The white tungsten fine ore of 65-78%, contain WO
365-75% is with CaWO
4The WO that form exists
3Account for total WO
3The black and white tungsten collective concentrate of the 0.5-99% of amount contains WO
3The WO that exists for 18-65%, with white tungsten form
3Account for WO
3The tungsten ore of the 0.5-99% of total amount or difficulty are selected tungsten ore (tungsten slurry) or people gallery product (tungsten ore that refers to manual exploitation gained among the people), or the tungsten tin hair concentrate in dressing-works.
In order from above-mentioned material, to extract tungsten, U.S. Pat 4353878 and China " tungsten slurry adopt normal pressure alkali soak-ion-exchange produces the production report of high-quality tungstic oxide (ammonium paratungstate) " (east, spit of fland tungsten ore tungsten slurry wet-process metallurgy craft technical expertise conference data, October nineteen eighty-two) in, proposed to use in stirred leaching tank the NaOH soda boiling respectively, the reaction of its process is:
（Fe·Mn）WO
4+2NaOH=Na
2WO
4+Fc（OH）
2
(or Mn(OH)
2(1)
CaWO
4+2NaOH=Na
2WO
4+Ca（OH）
2……（2）
Because inherent defective of stirred leaching tank own such as mass transfer velocity are limited, particularly for those reactions that produces compact solid resultant film, whipping process is very little to the effect of mass transfer; Temperature of reaction is subjected to the restriction etc. of the boiling point of handled solution.It is excessive greatly with the alkali consumption to have to when handling above-mentioned material, and correspondingly adopts tediously long flow process, their principle process as shown in Figure 1, it is through five road master operations, i.e. 1. ore grinding, raw material is levigate in advance to less than 0.074 millimeter; 2. carry out soda boiling with high excess NaOH, for concentrate, the alkali consumption is 3-8.5 a times of theoretical amount, chats is 5-9 times, and the soda boiling temperature reaches 100-145 ℃, through about 2-5 hour, rate of decomposition can reach 98-99% to concentrate, can reach 97-98% to chats; 3. filter; 4. condensing crystal since the alkali consumption too much, alkali concn is big in the leach liquor, is not suitable for the requirement of subsequent processing, therefore answers condensing crystal to make Na
2WO
4Crystal separates with NaOH; 5. Na
2WO
4Dissolution of crystals, the shortcoming of alkaline-heating method is that mainly 1. flow process is tediously long; 2. because long flow path event total yield is low; 3. owing to need carry out condensing crystal, on average whenever get one ton of WO
3Need evaporation 10-16 ton water, so energy consumption is big; The process of the alkali of condensing crystal recovery simultaneously must be repaid mistake economically often down.
The present invention is exactly at the problems referred to above, propose that a kind of NaOH consumption is few, rate of decomposition is high, flow process is short, can handle white tungsten fine ore, wolframite, black and white tungsten collective concentrate, can handle the method for the hair concentrate in tungsten ore and the tungsten tin beneficiation flowsheet again, and adapt to this method and design a kind of equipment-pressurized hot-mill reactor.
Feature of the present invention is in pressurized hot-mill reactor ore grinding and alkali cooking process to be combined, it makes full use of grinding process to the effect of mineral mechanical activation, to the effect of peeling off of ore particle surface resultant film with to the crushing effect of ore particle (the new surface that produces often has big activity), thereby improved the dynamic conditions of decomposition course greatly, reaction is quickened.Add suitable temperature and just can its ore deposit rate of decomposition be reached more than 98%, and shorten flow process greatly (flow process of the present invention as shown in Figure 2) at low alkaline consumption with in the short period.
The designed pressurized hot-mill reactor of the present invention is made up of driving part and cylindrical shell (1), the structure of shell portion as shown in Figure 3, it comprises:
1. stack shell and grinding medium: by high carbon steel, wear resisting steel materials such as cast steel or manganese steel are made, and it can be lined with or not serve as a contrast abrasion-proof backing block, interior dress sphere or clavate grinding medium, and the dressing rate of medium is 20-60%, the length-to-diameter of stack shell is 5: 1-0.8.
2. charging system: be contained on the end cap of reactor, it is made up of tapered plug (2), valve seat (3) and linkage system (4).By linkage system with the tapered plug breakdown, to feed in raw material.
3. discharge device: be contained on the end cap of reactor, center blow-off valve (5) and edge blow-off valve (6) be housed, or wherein any, can be in the process of running continuous discharge.
4. temp measuring system: go into sealed tube (7) by skewer in the mind-set grinding machine in the end cap, thermopair can stretch into and measure temperature in the sealed tube.
5. heating system: adopt modes such as common induction, resistance, fuel to heat, can be heated to about 170 ℃, if when adopting induction heating, establish ruhmkorff coil at stack shell, each parts good seal of whole shell portion, the pressure of ability 7-8 kg/cm, the driving part of pressurized hot-mill reactor is by general electric motor, deceleration device and linkage system are formed, and it makes cylindrical shell produce turning motion or vibration.
In pressurized hot-mill reactor, the alkali of tungsten mineral material soaks process to carry out as follows: with the white tungsten fine ore of granularity＜3 millimeter, black and white tungsten collective concentrate or black-and-white tungsten ore or tungsten tin hair concentrate, directly add pressurized hot-mill reactor without fine grinding with NaOH, the NaOH consumption for tungsten concentrate for the 1.3-2.2 of theoretical amount doubly, for tungsten ore for the 1.5-3.5 of theoretical amount doubly, solid-to-liquid ratio in the control process is 0.8-1.5, controlled temperature is 150-160 ℃ and carries out ore grinding and mechanical activation process in this case on the one hand, tungsten ore and NaOH effect simultaneously, above-mentioned reaction formula (1) takes place, (2) decomposition reaction, decompose after 1-3 hour, slip is drawn off filtration, reach 98.5-99% to handling the concentrate rate of decomposition, can reach 97.6-99% to handling the chats rate of decomposition, during to processing higher-grade white tungsten fine ore, residue is lime, can be used for building or other department, at this moment essentially no waste residue.
With respect to stirring alkaline-heating method, the present invention has following advantage: 1. in pressurized hot-mill reactor ore grinding and soda boiling are combined, made full use of grinding process to improving the favourable various positive factor of speed of response, thereby can be more much lower than general alkaline-heating method various tungsten mineralss being decomposed under the situation of (be about its half) rapidly at alkali consumption, rate of decomposition is than the high 1-2% of alkaline-heating method; 2. saved independent Grinding procedure on the one hand, on the other hand because the alkali consumption is few, free alkali and WO in the leach liquor
3Ratio less than 0.3-0.5, there is no need to carry out condensing crystal to separate Na
2WO
4And alkali, saved condensing crystal operation and Na
2WO
2The dissolution of crystals operation, thereby the master operation in the flow process is kept to two roads (seeing accompanying drawing 2) by five roads of alkaline-heating method; 3. can save at least 50% with respect to the alkaline-heating method energy consumption, tungsten recovery rate improves 2-3% at least.In the tungsten dressing-works, traditionally, tungsten tin hair concentrate should pass through numerous and diverse refining process, after drawing wolframite, white tungsten fine ore, tungsten ore and tin concentrate respectively, send the smeltery to handle again respectively, improve about 8% and directly handle ore dressing-smelting total yield that tungsten ore or tin hair concentrate can make tungsten with the present invention, the rate of recovery of tin improves 15-20%, the investment that can save whole selected workshops.
Example 1: certain difficulty selects tungsten ore to contain 36.89%WO
3, 4.42%Ca, with CaWO
4The WO that form exists
3Account for total WO
325% of amount, granularity accounts for 41.75% for the 0.074-3 millimeter.With 35 kilograms in above-mentioned ore deposit, add the NaOH of 2.6 times of theoretical amount, in the pressurized hot-mill reactor of 400 * 600 millimeters of φ, decompose, solid-to-liquid ratio is about 1 in the control process, 155 ℃ of temperature, about 5 kg/cm of pressure, after 2 hours, ore pulp is drawn off filtration, contain WO in the dried slag
3Be 0.79%, rate of decomposition reaches 98.74%.
Example 2: the intermediates-tungsten ore in certain dressing-works (being commonly called as a mao concentrate), its composition is 44.01%WO
3, 21.10%Sn, with CaWO
4The WO that form exists
3Account for total WO
334.26% of amount, granularity accounts for 89.77% for the 0.074-3 millimeter.Directly with 35 kilograms in this ore deposit, in example 1 described equipment, add the NaOH of 2.6 times of theoretical amount by the present invention, 150 ℃ of temperature, pressure is less than 5 kg/cm, and solid-to-liquid ratio is about 1 in the process, decomposes 1.5 hours, filters the dried slag in back and contains WO
3Be 0.82%, rate of decomposition is 99.06%, and tin tin grade reaches 34.50% in the slag, and the rate of recovery that tin enters slag is 96.06%.
Example 3: the white tungsten slurry composition of certain dressing-works output is 44.98%WO
3, with CaWO
4The WO that form exists
3Account for total WO
387.50% of amount with 35 kilograms in this ore deposit, in example 1 described equipment, adds the NaOH of 2.9 times of theoretical amount, and the control solid-to-liquid ratio is about 1, and 160 ℃ of temperature were decomposed 2 hours, and dried slag contains WO
3Be 2.03%, rate of decomposition is 97.65%.
In addition, behind the leach liquor mixed diluting of above-mentioned example 1,2,3 gained, contain WO
3Be 15 gram liters, free alkali 5 grams per liters exchange purification with 717 type strongly basic anion exchange resins, and exchange capacity is 249 a milligrams/gram dried resin as a result, and the peak liquid of desorb gained gets ammonium paratungstate behind evaporative crystallization.Wherein except that molybdenum content was high slightly, other foreign matter contents all were lower than standard GB 3457-82FWO
3-1 regulation.
Claims (11)
1, a kind of method of decomposing white tungsten fine ore and Scheelite-Wolframite Mixed Mine extraction tungsten, it is characterized in that ore grinding and soda boiling are combined with sodium hydroxide heating digestion, the ore deposit is added pressurized hot-mill reactor with alkali, control proper temperature, pressure, in ore grinding, carry out the decomposition of mineral.
2, method according to claim 1 is characterized in that handled tungsten minerals comprises that granularity less than 3 millimeters, contains WO
3For the white tungsten fine ore of 65-78% with contain WO
3 Be 65-75%, with CaWO
4The WO that form exists
3Account for total WO
3The black and white tungsten mixing tungsten concentrate of the 0.5-99% of amount, and granularity contains WO less than 3 millimeters
3Be 18-65%, with CaWO
4The WO that form exists
3Account for total WO
3Tungsten ore dressing intermediates, tungsten ore or the people gallery product of the 0.5-99% of amount (tungsten ore of manual exploitation gained among the people).
3, method according to claim 1 is characterized in that for used alkali is the NaOHNaOH consumption, for white tungsten fine ore or black and white tungsten collective concentrate, for the 1.3-2.2 of theoretical amount doubly, for tungsten ore, for the 1.5-3.5 of theoretical amount doubly.
4, method according to claim 1 is characterized in that the decomposition course controlled temperature is 150 ℃-160 ℃.
5, method according to claim 1 is characterized in that decomposition course control solid-to-liquid ratio is 0.8-1.5.
6, decompose white tungsten fine ore and the used pressurized hot-mill reactor of Scheelite-Wolframite Mixed Mine, it is characterized in that equipment this as a grinding machine that has the feeding in raw material of heating unit and good seal, a discharge device, but its not only ore grinding but also have mechanical agitating tank concurrently or the effect of autoclave.
7, pressurized hot-mill reactor according to claim 6, it is characterized in that pressurized hot-mill reactor has shell portion, it can be lined with or not serve as a contrast abrasion-proof backing block, adorn spherical or bar-shaped grinding medium in the cylindrical shell, medium dressing rate is 20-60%, and the stack shell length-to-diameter is 5: 1-0.8, cylindrical shell carries out turning motion or vibration by transmission rig, the cylindrical shell good seal, ability 7-8 kilogram, cm2 pressure.
8, pressurized hot-mill reactor according to claim 6 is characterized in that pressurized hot-mill reactor has induction or resistance or fuelizer, can carry out work with interior at 170 ℃.
9, pressurized hot-mill reactor according to claim 6 is characterized in that charging system is contained on the end cap of reactor, and it is made up of tapered plug (2), valve seat (3) and linkage system (4), the tapered plug breakdown can be fed in raw material by linkage system.
10, pressurized hot-mill reactor according to claim 6 is characterized in that discharge system is contained on the end cap of reactor, and center blow-off valve (5) and edge blow-off valve (6) are housed, by wherein any, can be in operation process continuous pulp discharge.
11, pressurized hot-mill reactor according to claim 6 is characterized in that temp measuring system by inserting sealed tube (7) in the mind-set reactor in the end cap, and thermopair can stretch into and measure temperature in the sealed tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100350A CN85100350B (en) | 1985-04-01 | 1985-04-01 | Method and equipment of alkali decomposition of white tungsten fine ore and raw wolframite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100350A CN85100350B (en) | 1985-04-01 | 1985-04-01 | Method and equipment of alkali decomposition of white tungsten fine ore and raw wolframite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85100350A CN85100350A (en) | 1986-08-27 |
| CN85100350B true CN85100350B (en) | 1987-03-04 |
Family
ID=4791086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85100350A Expired CN85100350B (en) | 1985-04-01 | 1985-04-01 | Method and equipment of alkali decomposition of white tungsten fine ore and raw wolframite |
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|---|---|
| CN (1) | CN85100350B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2757774C2 (en) * | 2020-10-07 | 2021-10-21 | Виталий Евгеньевич Дьяков | Method for leaching tungsten from tin raw material smelting slag and an apparatus for its implementation |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103484672A (en) * | 2013-09-09 | 2014-01-01 | 昆明贵金属研究所 | Method for removing SnS3<2-> damage in tungsten ion exchange process |
| KR101466928B1 (en) * | 2014-03-05 | 2014-12-03 | 한국지질자원연구원 | Leaching method of valuable metal in spent catalyst of denitrification using high pressured leaching process |
| CN104843791B (en) * | 2015-05-06 | 2017-06-13 | 江西稀有金属钨业控股集团有限公司 | A kind of method for processing tungsten contained material |
| CN105642448B (en) * | 2015-12-30 | 2018-07-27 | 中南大学 | A method of efficiently separating wolframite and white tungsten fine ore from tungsten ore |
| CN105586487A (en) * | 2016-03-14 | 2016-05-18 | 江西稀有金属钨业控股集团有限公司 | Method for treating scheelite and wolframite mixture ore |
| CN107881339A (en) * | 2017-12-05 | 2018-04-06 | 赣州华兴钨制品有限公司 | A kind of ball milling soda boiling integral type reaction system |
| CN113737025B (en) * | 2021-07-23 | 2022-05-17 | 中南大学 | Vanadium extraction method and vanadium extraction device for high-silicon refractory stone coal vanadium ore |
-
1985
- 1985-04-01 CN CN85100350A patent/CN85100350B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2757774C2 (en) * | 2020-10-07 | 2021-10-21 | Виталий Евгеньевич Дьяков | Method for leaching tungsten from tin raw material smelting slag and an apparatus for its implementation |
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| Publication number | Publication date |
|---|---|
| CN85100350A (en) | 1986-08-27 |
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