CN102108449A - Method for preprocessing scheelite and preparing ferro-tungsten - Google Patents
Method for preprocessing scheelite and preparing ferro-tungsten Download PDFInfo
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- CN102108449A CN102108449A CN2009103126212A CN200910312621A CN102108449A CN 102108449 A CN102108449 A CN 102108449A CN 2009103126212 A CN2009103126212 A CN 2009103126212A CN 200910312621 A CN200910312621 A CN 200910312621A CN 102108449 A CN102108449 A CN 102108449A
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- hydrochloric acid
- tungsten
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- ferro
- water
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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 relates to a method for tungsten hydrometallurgy, in particular to a method for preprocessing scheelite and preparing ferro-tungsten. The method comprises the following steps: preprocessing scheelite with hydrochloric acid and repeatedly utilizing remaining acid to decompose scheelite in an aright device having no pressure; and preprocessing slag to restore melting ferro-tungsten. Compared with the prior art, the method has the advantages as follows: in order to solve the defects in the background art, the closed circuit of hydrochloric acid is utilized to decompose scheelite, thereby reducing the consumption amount of hydrochloric acid and energy consumption, realizing the effective enrichment of CaCl2, reducing the production cost of subsidiary products, and improving the economic benefits of technology; the aright device having no pressure reduces the requirements on leaching equipment, and also reduces the investment of fixed assets; high-qualified ferro-tungsten can be prepared under the hydrogen reduction environment by just mixing iron powder and coarse tungstic acid according to a proper proportion, so that the energy consumption is reduced and the smelting process is simplified.
Description
Technical field
The present invention relates to the tungsten Wet-smelting method, be meant a kind of pre-treatment sheelite especially and produce the method for ferro-tungsten.
Background technology
In the prior art, the hydrochloric acid decompose tunstite mainly is in open reactor, adds excess acid, makes wolframic acid thereby under boiling temperature and negative pressure exhausting condition ore pulp is carried out disaggregating treatment, i.e. acid decomposition.Big and the negative pressure exhausting of this method hydrochloric acid consumption has also strengthened power loss, and consumption of raw and auxiliary materials is big, and is big for environment pollution, and productivity is lower.
Also there is report to adopt airtight acid to decompose high temperature (〉=boiling temperature) treatment process with pressure, disclosed Chinese patent CN1177944C just adopted this method as on December 1st, 2004, because it has certain pressure (0.1-0.6Mpa), thereby requirements at the higher level have been proposed pickling equipment, reaction initial acid height, it is big to react the spent acid amount that finishes, and makes production cost higher.
And other method such as electrical carbon hot reducing method and metal pyrogen method etc. all have shortcomings such as current consumption is big, auxiliary reagent consumption is big.
Summary of the invention
Main purpose of the present invention is to overcome in the prior art in the sheelite pretreatment process shortcomings such as ubiquitous energy expenditure is big, production cost height, and the method for the pre-treatment sheelite that a kind of energy consumption is lower, production cost is lower is provided.
Another object of the present invention is to provide a kind of method of producing ferro-tungsten.
By can finding to existing hydrochloric acid improved scheelite decomposing process, hydrochloric acid or be to lose in a large number in these methods, or be that utilization ratio is lower, the spent acid amount is bigger, its utilization is very insufficient, makes consumption of raw and auxiliary materials big, and productivity is lower.
Based on this thinking, the present invention adopts following technical scheme:
Hydrochloric acid pre-treatment sheelite: sheelite is milled to 325 orders accounts for more than the 75wt%, with water, hydrochloric acid in closed reactor that atmosphere communicates under heating, agitation condition, react, after-filtration is finished in reaction, and washes slag with water, with washings and filtrate mixing for standby use;
Spent acid recycle decompose tunstite: the filtrate that step 1 obtains is surveyed its spent acid amount,, in filtrate, add corresponding water and hydrochloric acid according to the amount of adding new ore deposit, repeating step one continues to react under heating, agitation condition, after reaction is finished, filter, wash, filtrate is used for circulating next time;
Pre-treatment slag retailoring ferrotungsten: the pre-treatment slag is carried out roasting, and the roasting slag adds iron powder and mixes, and changes over to fill the melting of hydrogen high temperature reduction in the atmosphere furnace and prepare ferro-tungsten.
Wherein, sheelite comprises white tungsten ore and white tungsten fine ore.
Wherein, the amount of adding hydrochloric acid in the sheelite pre-treatment is at least 1.5 times of its theoretical consumption, and its theoretical consumption is by reaction formula CaWO
4+ 2HCl=H
2WO
4+ CaCl
2Calculate gained.
Wherein, the amount of adding water in the sheelite pre-treatment is according to weight liquid-solid ratio 1-4: 1 carries out.
Wherein, in the sheelite pre-treatment heating and temperature control at 80-100 ℃, reaction times 〉=60min.
Wherein, the recycle number of times of hydrochloric acid requires<3 times, if 〉=3 times, though the CaCl of filtrate
2Concentration can be increased to 110g/L, but the thick wolframic acid grade of filter residue can be lower than 80% slightly.
Wherein, pre-treatment slag maturing temperature is 400-600 ℃, roasting time 〉=60min; The temperature that the high temperature reduction melting prepares ferrotungsten is controlled to be<and 1600 ℃.
By the above-mentioned description of this invention as can be known, the present invention is directed to the disadvantage that background technology exists,, reduced hydrochloric acid consumption and energy consumption, and realize CaCl with hydrochloric acid sealing and circulating decompose tunstite
2Effective enrichment, reduced the production cost of byproduct, improved the economic benefit of technology.Airtight but do not reduced requirement to leaching plant with pressure device, also reduced investment in fixed assets.And only mix with certain proportioning with iron powder and thick wolframic acid, under the hydrogen reducing environment, just can produce the fine ferro-tungsten, reduced energy consumption, simplified smelting technology.
Embodiment
Embodiment 1
Use the 1L reactor, give ore deposit 150g tungsten concentrate ,-325 orders account for 75%, L/S=4: 1, the concentrated hydrochloric acid consumption be theoretical 1.5 times (102ml), with encloses container that atmosphere communicates in stir pre-treatment 3 hours, filtration.Add new ore deposit, aforementioned filtrate is surveyed the acid amount, according to 1.5 times of the theoretical acid consumption, adds insufficient acid, continues to leach, and circulates after twice tungsten concentrate WO
3Grade maintains about 83%.And after twice circulation leaching, the pretreatment fluid calcium concn significantly improves.
500 ℃ of roastings of pre-treatment slag generated thick wolframic acid in 1 hour, and thick wolframic acid and iron powder are by Fe: the W ratio is to mix at 1: 4, changes over to fill 1600 ℃ of retailoring of hydrogen in the atmosphere furnace and prepare and can get the fine ferro-tungsten.
Embodiment 2
Use the 1L reactor, give ore deposit 300g tungsten concentrate ,-325 orders account for 85%, L/S=2: 1, the concentrated hydrochloric acid consumption be theoretical 2 times (272ml), with encloses container that atmosphere communicates in stir pre-treatment 2 hours, filtration.Filtrate is added acid, and Jia Xinkuang continues to leach.After the circulation like this three times, tungsten concentrate WO
3Grade maintains about 77%, and through after three circulation leachings, the pretreatment fluid calcium concn is increased to 110g/L.
400 ℃ of roastings of pre-treatment slag generated thick wolframic acid in 2 hours, and thick wolframic acid and iron powder are by Fe: the W ratio is to mix at 2: 3, changes over to fill 1500 ℃ of retailoring of hydrogen in the atmosphere furnace and prepare and can get the fine ferro-tungsten.
Embodiment 3
Use the 1L reactor, give ore deposit 300g tungsten concentrate ,-325 orders 95%, L/S=1: 1, the concentrated hydrochloric acid consumption be theoretical 2 times (272ml), with encloses container that atmosphere communicates in stir pre-treatment 1 hour, filtration.Filtrate is added acid, and Jia Xinkuang continue to leach, and circulates after twice tungsten concentrate WO
3Grade maintains about 82%.
500 ℃ of roastings of pre-treatment slag generated thick wolframic acid in 2 hours, and thick wolframic acid and iron powder are by Fe: the W ratio is to mix at 2: 3, changes over to fill 1600 ℃ of retailoring of hydrogen in the atmosphere furnace and prepare and can get the fine ferro-tungsten.
Above-mentioned only is several embodiment of the present invention, but design concept of the present invention is not limited thereto, and allly utilizes this design that the present invention is carried out the change of unsubstantiality, all should belong to the behavior of invading protection domain of the present invention.
Claims (9)
1. the method for a pre-treatment sheelite is characterized in that comprising the steps:
Step 1 is milled to sheelite in-325 orders and accounts for more than the 75wt%, with water, hydrochloric acid in closed reactor that atmosphere communicates under heating, agitation condition, react, after-filtration is finished in reaction, and washes slag with water, with washings and filtrate mixing for standby use;
Step 2 is surveyed its spent acid amount with the filtrate that step 1 obtains, and according to the amount of adding new ore deposit, adds corresponding water and hydrochloric acid in filtrate, and repeating step one continues to react under heating, agitation condition, after reaction is finished, and filtration, washing, filtrate is used for circulating next time.
2. the method for claim 1 is characterized in that: the amount of adding hydrochloric acid in described step 1 and the step 2 is at least 1.5 times of its theoretical consumption.
3. the method for claim 1 is characterized in that: the amount of adding water in described step 1 and the step 2 is according to weight liquid-solid ratio 1-4: 1 carries out.
4. the method for claim 1, it is characterized in that: heating and temperature control is at 80-100 ℃ in described step 1 and the step 2.
5. the method for claim 1 is characterized in that: the reaction times 〉=60min in described step 1 and the step 2.
6. the method for claim 1 is characterized in that: recycle number of times<3 of described hydrochloric acid time.
7. method of producing ferro-tungsten is characterized in that:
Step 1 is milled to sheelite in-325 orders and accounts for more than the 75wt%, with water, hydrochloric acid in closed reactor that atmosphere communicates under heating, agitation condition, react, after-filtration is finished in reaction, and washes slag with water, with washings and filtrate mixing for standby use;
Step 2 is surveyed its spent acid amount with the filtrate that step 1 obtains, and according to the amount of adding new ore deposit, adds corresponding water and hydrochloric acid in filtrate, and repeating step one continues to react under heating, agitation condition, after reaction is finished, and filtration, washing, filtrate is used for circulating next time;
Step 3 is carried out roasting with the pre-treatment slag, and the roasting slag adds iron powder and mixes, and changes over to fill the melting of hydrogen high temperature reduction in the atmosphere furnace and prepare ferro-tungsten.
8. method as claimed in claim 7 is characterized in that: wherein the high temperature reduction melting temperature for preparing ferrotungsten be controlled to be<1600 ℃.
9. method as claimed in claim 7 is characterized in that: wherein pre-treatment slag maturing temperature is 400-600 ℃, roasting time 〉=60min.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105907993A (en) * | 2016-07-05 | 2016-08-31 | 江西理工大学 | Method for extracting tungsten from fluorine-containing scheelite |
CN106011504A (en) * | 2016-07-05 | 2016-10-12 | 江西理工大学 | Method for resolving scheelite |
CN108342597A (en) * | 2017-01-24 | 2018-07-31 | 中南大学 | A kind of method that the hydrochloric acid of Recycling Mother Solution decomposes scheelite |
CN108642277A (en) * | 2018-05-08 | 2018-10-12 | 中南大学 | A kind of preprocess method containing tungsten mineral |
CN108642279A (en) * | 2018-04-13 | 2018-10-12 | 中南大学 | A kind of method that mixture of sulfuric phosphoric acid pressurization adverse current decomposes wolframite |
CN108796226A (en) * | 2018-07-04 | 2018-11-13 | 赣州有色冶金研究所 | A method of it recycling alkali and soaks tungsten slag |
-
2009
- 2009-12-29 CN CN2009103126212A patent/CN102108449A/en active Pending
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105907993A (en) * | 2016-07-05 | 2016-08-31 | 江西理工大学 | Method for extracting tungsten from fluorine-containing scheelite |
CN106011504A (en) * | 2016-07-05 | 2016-10-12 | 江西理工大学 | Method for resolving scheelite |
CN105907993B (en) * | 2016-07-05 | 2018-01-02 | 江西理工大学 | A kind of method that tungsten is extracted from fluorine-containing scheelite |
CN108342597A (en) * | 2017-01-24 | 2018-07-31 | 中南大学 | A kind of method that the hydrochloric acid of Recycling Mother Solution decomposes scheelite |
CN108642279A (en) * | 2018-04-13 | 2018-10-12 | 中南大学 | A kind of method that mixture of sulfuric phosphoric acid pressurization adverse current decomposes wolframite |
CN108642279B (en) * | 2018-04-13 | 2020-05-26 | 中南大学 | Method for decomposing wolframite by pressurizing and countercurrent sulfur and phosphorus mixed acid |
CN108642277A (en) * | 2018-05-08 | 2018-10-12 | 中南大学 | A kind of preprocess method containing tungsten mineral |
CN108796226A (en) * | 2018-07-04 | 2018-11-13 | 赣州有色冶金研究所 | A method of it recycling alkali and soaks tungsten slag |
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Application publication date: 20110629 |