CN101607739A - Closed cycle process for crystalline mother solution of ammonium paratungstate - Google Patents
Closed cycle process for crystalline mother solution of ammonium paratungstate Download PDFInfo
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- CN101607739A CN101607739A CNA2008100722036A CN200810072203A CN101607739A CN 101607739 A CN101607739 A CN 101607739A CN A2008100722036 A CNA2008100722036 A CN A2008100722036A CN 200810072203 A CN200810072203 A CN 200810072203A CN 101607739 A CN101607739 A CN 101607739A
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Abstract
The present invention discloses a kind of ammonium tungstate closed cycle process for crystalline mother solution, with the primary crystallization mother liquor of conventional tungsten wet method smelting process without any processing, all return main flow, mix in an airtight steel basin with the coarse sodium tungstate after leaching, form closed cycle, utilize waste heat and surplus alkali after tungsten ore decomposes that the para-tungstate in the crystalline mother solution, metatungstate, heteropoly tungstic acid salt are changed into positive tungstate, the chemical combination ammonia in the crystalline mother solution is transformed into volatile ammonia simultaneously.This close circulation technology can be optimized technological process, turns waste into wealth, energy-saving and emission-reduction, realizes the process for cleanly preparing of tungsten hydrometallurgy closed cycle.
Description
Technical field
The invention belongs to the technical field of tungsten hydrometallurgy, relate in particular to the Technology of a kind of tungsten hydrometallurgy cleaner production, refer in particular to closed cycle process for crystalline mother solution of ammonium paratungstate.
Background technology
As shown in Figure 1, in the wet smelting process of conventional tungsten, the main flow of technology comprises alkali decomposition process, dilution burden process, ion-exchange process, evaporative crystallization operation, raw material (tungsten ore) treatment process mainly adopts base decomposing technology, make coarse sodium tungstate after the decomposition, liquid after dilution batching, ion-exchange get ammonium tungstate solution and contains the alkali friendship gets ammonium paratungstate (APT) product and primary crystallization mother liquor through evaporative crystallization again, hands over the discharging after the acid neutralization of back liquid and contain alkali.
Wherein, all contain more residue alkali in the sodium tungstate solution after the decomposition, the surplus alkali that one ton of APT of general every production produces is 45～180 kilograms; The tungsten hydrometallurgy finally all is to make the high purity tungsten acid ammonium solution, makes APT and produces a certain amount of crystalline mother solution through evaporative crystallization again, and the main component of crystalline mother solution also contains small amount of N H except that valuable element tungsten
4Cl or (NH
4)
2SO
4, WO in the general primary crystallization mother liquor
3Content is 15～30g/l, NH
4Cl content is 8～30g/l[or (NH
4)
2SO
4Content is 10～40g/l].
The treatment process of surplus alkali mainly contained after the tungsten raw material leached in the industrial production at present:
One, be in the technical process of raw material with black tungsten, the main dilution back of adopting is with liquid discharging after the friendship of ion-exchange, again with the acid neutralization.
Two, be in the technical process of raw material with white tungsten, adopting condensing crystal to separate out sodium wolframate, alkali liquor returns decomposition process, but still has part alkali to enter later process loss with sodium wolframate, needs too to neutralize with acid.
The aforesaid method surplus alkali that need neutralize with more acid, and produce inorganic salt with discharge of wastewater, the cost height has brought new pollution simultaneously.
The treatment process of ammonium para-tungstate crystal mother solution mainly contains in the industrial production at present:
First and second crystallization process.Again as shown in Figure 1, this technology with the primary crystallization mother liquor once more evaporative crystallization (concentrating) make the poor slightly substandard products APT of quality, the secondary crystal mother liquor reclaims wherein tungsten with lime precipitation again, emits ammonia-containing water.
Two, Chinese patent 99115275.1 discloses a kind of treatment process of ammonium para-tungstate crystal mother solution, and its thinking is directly to prepare the ion-exchange strippant after removing partial impurities.
Above-mentioned first method is the energy consumption height not only, and the emission problem of ammoniation does not solve yet; Though second method can reclaim tungsten and ammoniation, the problem that exists is that metatungstate and the heteropolyacid salt in the crystalline mother solution can't effectively be destroyed, and repeatedly influences the ion-exchange operation the most at last after the circulation.
In view of this, the inventor studies at the ammonium para-tungstate crystal mother solution treatment technology, has developed finally that technology is simple, cost is low, metal recovery rate is high, the close circulation technology of energy-conserving and environment-protective, and this case produces thus.
Summary of the invention
The purpose of this invention is to provide a kind of closed cycle process for crystalline mother solution of ammonium paratungstate, with optimize technological process, turn waste into wealth, energy-saving and emission-reduction, realize the process for cleanly preparing of tungsten hydrometallurgy closed cycle.
To achieve these goals, technical scheme of the present invention is:
The ammonium tungstate closed cycle process for crystalline mother solution, the primary crystallization mother liquor of conventional tungsten wet method smelting process is without any processing, all return main flow, mix in an airtight steel basin with the coarse sodium tungstate after leaching, form closed cycle, utilize waste heat and surplus alkali after tungsten ore decomposes that the para-tungstate in the crystalline mother solution, metatungstate, heteropoly tungstic acid salt are changed into positive tungstate, the chemical combination ammonia in the crystalline mother solution is transformed into volatile ammonia simultaneously.
Described mixing back pH value of solution is 8～11, temperature more than 60 ℃, stirring reaction 1～4 hour.
The ammonia that described mixing is overflowed send absorption system to be absorbed into ammonium chloride with hydrochloric acid or water is absorbed into ammoniacal liquor.
Described ammonia is used to prepare strippant after absorbing.
Described strippant returns in the main flow as the ion-exchange process or the used subsidiary material of extraction process of wet method refining tungsten.
Sodium tungstate solution directly enters the next procedure of main flow behind the described deamination.
Sodium tungstate solution directly enters the dilution burden process of main flow behind the described deamination, gets ammonium paratungstate product and primary crystallization mother liquor through ion-exchange process, evaporative crystallization operation again, and the primary crystallization mother liquor continues to return main flow, carries out closed cycle.
Liquid directly discharges after the friendship of described ion-exchange.
Advantage of the present invention is the characteristic that makes full use of material in the technological process, has optimized technological process, and without the direct Returning process of any processing, technical process is short with tungstenic solution, realizes the closed cycle of tungsten hydrometallurgy crystalline mother solution, has both reclaimed the WO in the crystalline mother solution
3And ammonia, turn waste into wealth, waste heat and surplus alkali in the technical process are utilized, energy-saving and emission-reduction, cost is low, and the metal recovery rate height reduces the secondary pollution that discharge of wastewater and end treatment bring simultaneously, realizes process for cleanly preparing.
Description of drawings
Fig. 1 is tungsten hydrometallurgy conventional process flow figure;
Fig. 2 is a process flow sheet of the present invention.
Embodiment
As shown in Figure 2, ammonium tungstate closed cycle process for crystalline mother solution of the present invention is the improvement to the conventional tungsten wet method smelting process.In the conventional tungsten wet method smelting process, tungsten ore decomposes the coarse sodium tungstate that obtains through alkali, gets ammonium tungstate solution through dilution batching, ion-exchange, gets APT product and primary crystallization mother liquor through evaporative crystallization again.Improvement of the present invention is: the primary crystallization mother liquor is directly all returned main flow, mix in an airtight steel basin with the coarse sodium tungstate after leaching, form closed cycle, mixing the back pH value of solution is 8～11, temperature is more than 60 ℃, stirring reaction 1～4 hour, waste heat after utilizing tungsten ore to decompose and surplus alkali are with the para-tungstate in the crystalline mother solution, metatungstate, heteropoly tungstic acid salt changes into positive tungstate, chemical combination ammonia in the crystalline mother solution is transformed into volatile ammonia simultaneously, the ammonia that mixing is overflowed send absorption system to be absorbed into ammonium chloride with hydrochloric acid or water is absorbed into ammoniacal liquor, be used to prepare strippant, this strippant returns in the main flow as the ion-exchange process or the used subsidiary material of extraction process of wet method refining tungsten again.Sodium tungstate solution directly enters the next procedure of main flow behind the deamination, gets ammonium paratungstate product and primary crystallization mother liquor through dilution burden process, ion-exchange process, evaporative crystallization operation again, and the primary crystallization mother liquor continues to return main flow, carries out closed cycle.And liquid does not have ammonia and can directly discharge after the friendship of ion-exchange.
Example 1 black tungsten coarse sodium tungstate slip 6m after alkali decomposes leaching
3(WO
3Concentration 198g/l, NaOH concentration 32g/l) and primary crystallization mother liquor 5m
3(WO
3Concentration 27g/l, NH
4Cl concentration 21g/l) mix, mix back pH and be 10～11,68 ℃ of temperature, stirring reaction is after 3 hours, and pH value of solution is 10.2, ammonia content is (with NH
3Meter) be 102mg/l, the ammonia that overflows makes NH after absorbing with hydrochloric acid
4Cl solution 0.98m
3(NH
4Cl concentration 267g/l).
Example 2 white tungsten are coarse sodium tungstate 9m after alkali decomposes leaching
3(WO
3Concentration 246g/l, NaOH concentration 22g/l) and primary crystallization mother liquor 5m
3(WO
3Concentration 27g/l, NH
4Cl concentration 21g/l) mix, mix back PH and be 10～11,60 ℃ of temperature, stirring reaction is after 4 hours, and solution PH is 10.0, ammonia content is (with NH
3Meter) be 96mg/l, the ammonia that overflows makes NH after absorbing with hydrochloric acid
4Cl solution 0.96m
3(NH
4Cl concentration 271g/l).
Claims (8)
1, closed cycle process for crystalline mother solution of ammonium paratungstate, it is characterized in that: the primary crystallization mother liquor of conventional tungsten wet method smelting process is without any processing, all return main flow, mix in an airtight steel basin with the coarse sodium tungstate after leaching, form closed cycle, para-tungstate in the crystalline mother solution, metatungstate, heteropoly tungstic acid salt are changed into positive tungstate, and the chemical combination ammonia in the crystalline mother solution is transformed into volatile ammonia simultaneously.
2, closed cycle process for crystalline mother solution of ammonium paratungstate according to claim 1 is characterized in that: control mixes that the back pH value of solution is 8～11, temperature more than 60 ℃, stirring reaction 1～4 hour.
3, closed cycle process for crystalline mother solution of ammonium paratungstate according to claim 1 is characterized in that: the ammonia that mixing is overflowed send absorption system to be absorbed into ammonium chloride with hydrochloric acid or water is absorbed into ammoniacal liquor.
4, closed cycle process for crystalline mother solution of ammonium paratungstate according to claim 3 is characterized in that: ammonia is used to prepare strippant after absorbing.
5, closed cycle process for crystalline mother solution of ammonium paratungstate according to claim 4 is characterized in that: strippant returns in the main flow as the ion-exchange process or the used subsidiary material of extraction process of wet method refining tungsten.
6, closed cycle process for crystalline mother solution of ammonium paratungstate according to claim 1 is characterized in that: sodium tungstate solution directly enters the next procedure of main flow behind the deamination.
7, closed cycle process for crystalline mother solution of ammonium paratungstate according to claim 6, it is characterized in that: sodium tungstate solution directly enters the dilution burden process of main flow behind the deamination, get ammonium paratungstate product and primary crystallization mother liquor through ion-exchange process, evaporative crystallization operation again, the primary crystallization mother liquor continues to return main flow, carries out closed cycle.
8, closed cycle process for crystalline mother solution of ammonium paratungstate according to claim 1 is characterized in that: liquid directly discharges after the friendship of ion-exchange.
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| CNA2008100722036A CN101607739A (en) | 2008-11-20 | 2008-11-20 | Closed cycle process for crystalline mother solution of ammonium paratungstate |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071313A (en) * | 2011-01-29 | 2011-05-25 | 湖南辰州矿业股份有限公司 | Method for treating tungsten-containing and molybdenum-containing slag produced in ammonium paratungstate production process |
| CN102923805A (en) * | 2012-11-01 | 2013-02-13 | 厦门钨业股份有限公司 | Method for treating ammonia nitrogen in tungsten smelting by using extraction absorption |
| CN102963911A (en) * | 2012-11-14 | 2013-03-13 | 中湘钨业股份有限公司 | Method of recycling residual alkali from sodium tungstate solution in tungsten smelting |
| CN103395841A (en) * | 2013-08-08 | 2013-11-20 | 北京赛科康仑环保科技有限公司 | Process of resource comprehensive utilization of tungsten crystal-containing mother solution and washing water |
| CN104263975A (en) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | Metallurgical technology with multiple closed cycles for tungsten mineral raw materials |
| CN104263972A (en) * | 2014-10-09 | 2015-01-07 | 中南大学 | Metallurgy system with multiple closed cycles for tungsten mineral raw materials |
| CN104263974A (en) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | Method for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material with zero waste water discharge |
| CN104263976A (en) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | Tungsten mineral raw material metallurgical process capable of realizing no pollution discharge in whole process |
| CN104263973A (en) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | Method for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material by multiple closed loops |
| CN104263971A (en) * | 2014-10-09 | 2015-01-07 | 中南大学 | System for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material with zero pollution |
| CN107089685A (en) * | 2017-06-26 | 2017-08-25 | 江西省修水赣北钨业有限公司 | A kind of circulation utilization method for producing ammine in ammonium paratungstate gas |
| CN107638712A (en) * | 2017-09-30 | 2018-01-30 | 洛阳栾川钼业集团股份有限公司 | A kind of device and method administered ammonium para-tungstate crystal and blocked |
| CN114525415A (en) * | 2022-02-09 | 2022-05-24 | 信丰华锐钨钼新材料有限公司 | High-low molybdenum coupling system for tungsten smelting |
-
2008
- 2008-11-20 CN CNA2008100722036A patent/CN101607739A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071313A (en) * | 2011-01-29 | 2011-05-25 | 湖南辰州矿业股份有限公司 | Method for treating tungsten-containing and molybdenum-containing slag produced in ammonium paratungstate production process |
| CN102923805A (en) * | 2012-11-01 | 2013-02-13 | 厦门钨业股份有限公司 | Method for treating ammonia nitrogen in tungsten smelting by using extraction absorption |
| CN102923805B (en) * | 2012-11-01 | 2014-03-05 | 厦门钨业股份有限公司 | Method for treating ammonia nitrogen in tungsten smelting by using extraction absorption |
| CN102963911A (en) * | 2012-11-14 | 2013-03-13 | 中湘钨业股份有限公司 | Method of recycling residual alkali from sodium tungstate solution in tungsten smelting |
| CN103395841A (en) * | 2013-08-08 | 2013-11-20 | 北京赛科康仑环保科技有限公司 | Process of resource comprehensive utilization of tungsten crystal-containing mother solution and washing water |
| CN103395841B (en) * | 2013-08-08 | 2015-08-05 | 北京赛科康仑环保科技有限公司 | The comprehensive utilization of resources technique of a kind of tungstenic crystalline mother solution and wash water |
| CN104263976A (en) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | Tungsten mineral raw material metallurgical process capable of realizing no pollution discharge in whole process |
| CN104263974A (en) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | Method for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material with zero waste water discharge |
| CN104263972A (en) * | 2014-10-09 | 2015-01-07 | 中南大学 | Metallurgy system with multiple closed cycles for tungsten mineral raw materials |
| CN104263973A (en) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | Method for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material by multiple closed loops |
| CN104263971A (en) * | 2014-10-09 | 2015-01-07 | 中南大学 | System for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material with zero pollution |
| CN104263975A (en) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | Metallurgical technology with multiple closed cycles for tungsten mineral raw materials |
| CN104263972B (en) * | 2014-10-09 | 2016-03-16 | 中南大学 | There is the tungsten mineral material metallurgical system of multiple closed loop |
| CN104263976B (en) * | 2014-10-09 | 2016-07-27 | 江西稀有金属钨业控股集团有限公司 | The tungsten mineral material metallurgical technology of omnidistance non-pollution discharge |
| CN104263971B (en) * | 2014-10-09 | 2016-08-24 | 中南大学 | The system of APT is prepared by tungsten mineral material no pollution |
| CN107089685A (en) * | 2017-06-26 | 2017-08-25 | 江西省修水赣北钨业有限公司 | A kind of circulation utilization method for producing ammine in ammonium paratungstate gas |
| CN107638712A (en) * | 2017-09-30 | 2018-01-30 | 洛阳栾川钼业集团股份有限公司 | A kind of device and method administered ammonium para-tungstate crystal and blocked |
| CN114525415A (en) * | 2022-02-09 | 2022-05-24 | 信丰华锐钨钼新材料有限公司 | High-low molybdenum coupling system for tungsten smelting |
| CN114525415B (en) * | 2022-02-09 | 2024-01-02 | 信丰华锐钨钼新材料有限公司 | Tungsten smelting high-low molybdenum coupling system |
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Open date: 20091223 |