CN1757770A - Treatment method of high alkali concentration sodium tungstate solution - Google Patents
Treatment method of high alkali concentration sodium tungstate solution Download PDFInfo
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- CN1757770A CN1757770A CNA200410046815XA CN200410046815A CN1757770A CN 1757770 A CN1757770 A CN 1757770A CN A200410046815X A CNA200410046815X A CN A200410046815XA CN 200410046815 A CN200410046815 A CN 200410046815A CN 1757770 A CN1757770 A CN 1757770A
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- resin
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- naoh
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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
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Abstract
A process for treating the high-alkaline solution of sodium tungstate by ion exchange method features that when the solution is treated by high=alkaline anionic exchange resin, the saturate resin is only desorbed, the multiple exchange columns are serially connected or the compact moving bed is used for adsorption, and the high-concentration NaOH solution after exchange is concentrated by evaporating for separating the NaCl from solution and returning it back to extracting step.
Description
Technical field:
The present invention relates to hydrometallurgy, use the technology of ion exchange method processing with the alkali concn sodium tungstate solution.
Background technology:
Ion exchange method in the tungsten hydrometallurgy is used strongly basic anion exchange resin and alkaline coarse Na
2WO
4Solution generation permutoid reaction and adsorb tungsten is drained in the liquid of back and most of impurity such as phosphorus, arsenic, silicon etc. are stayed to hand over, and uses NH then
4Cl and NH
4The mixing solutions desorb of OH obtains pure (NH
4)
2WO
4Solution.Compare with original classical way, this method flow is short, can finish simultaneously and fall assorted and two tasks that make the transition, and equipment is simple, tungsten recovery rate is high, has obtained widespread use at the tungsten smelter.
But ion exchange method can only be handled the feed liquid of low alkaline concentration.For containing WO
3The sodium tungstate solution of 15-25g/l will influence the exchange capacity of tungsten more significantly when NaOH concentration during greater than 10g/l.Actual people find in production practice, and the NaOH in the solution just has a negative impact when being higher than about 4g/l.
Yet along with the black tungsten resource of high-quality consumes gradually, people have to then handle high calcium wolframite, sheelite and even low-grade complex tungsten mineral material.And when the mineral calcic is high, owing on the thermodynamics, must use more substantial NaOH (sheelite is generally more than 2.5 times of theoretical chemistry metering, and low grade ore is then also higher).Remaining alkali number is too high and have a strong impact on follow-up ion-exchange in the infusion solution that obtains like this, causes the operating capacity of resin to descend rapidly.
Owing to contain a large amount of free alkalis in the high alkaline solution, be diluted to lower concentration by traditional technology simultaneously, absorption back alkali can't reclaim, and can only discharge contaminate environment in vain.
Summary of the invention:
The objective of the invention is at this problem, a kind of technology of carrying out the ion-exchange absorption border under the high-alkalinity condition is provided, realize high-alkali high tungsten concentration (NaOH 10～100g/l, WO
3Ion-exchange under 10～200g/l) conditions realizes that high-alkalinity solution directly adsorbs, and then exchange back liquid is expected to concentrate economically to return the leaching operation.
The solution of the present invention is: use strongly basic anion exchange resin, when handling high-alkalinity solution, only saturated resin is carried out desorb.
1. use the series connection of many exchange column of fixed bed, go here and there the post operation: after the A exchange column leaked and wears, liquid flowed directly into B and changes post after the exchange of tungstenic, continued absorption; The B post further seals in the C post after leaking and wearing again; The C post further seals in the D post after leaking and wearing; Advance downstream successively; After treating that the A post reaches capacity, desorb tungsten and regenerating resin simultaneously, regenerated A post insert downstream; So hocket cycle operation.
During the operation of string post, if the linear velocity of solution below 0.1cm/min, should be operated with adverse current (solution from the bottom to top); If the linear velocity of solution is more than 0.1cm/min, then following current or counter-current operation all can.
Fixed-bed ion exchanger for present industrial use, because the whole post desorb together of actual needs in operation, then exchange zone " can only be pushed away " go out will desorb pillar, therefore at the several same exchange columns of downstream tandem, the upstream pillar leaks wears back continuation exchange, gradually exchange zone is moved on in the downstream column, after the upstream pillar is saturated, carry out desorb more separately.
2. use packed moving bed absorption: feed liquid enters continuously from the cylinder bottom, flows out from the resin bed top, and saturated resin from the bottom continuously or send out and batch emit; Simultaneously continuously or replenish the regenerating resin of equal amts at the top in batches; The desorption and regeneration of saturated resin carries out in a small ion exchange column, only needs saturated part taking-up desorb is got final product.
Advantage of the present invention and unusual effect demonstrate fully:
Handing over the main component of back liquid is NaOH and NaCl solution, and the characteristics of this mixing solutions are that NaCl solution degree concentration descends rapidly along with the raising of NaOH concentration.Utilize this characteristic, high density NaOH solution has further improved alkali concn on the one hand by evaporation concentration; can send out the NaCl in the exsolution liquid on the other hand; make superfluous free alkali can return tungsten ore and leach operation, reduced production cost, also help environment protection.
Embodiment:
Further specify the present invention below by specific embodiment.
Embodiment 1 decomposes white tungsten fine ore (WO
3Grade is 64.5%, and the NaOH consumption is 2.5 times of theoretical amount, 160 ℃ of decomposition temperatures, soaking time 4.5 hours, rate of decomposition 97.45%) the gained feed liquid contains NaOH 51.3g/l, WO
397.8g/l; Use two Φ 200 * 1400mm exchange column series connection adsorption operations, the absorption of following current is from top to bottom worn the back first pillar leakage and is inserted second pillar.After wearing, second leakage insert the 3rd pillar again, after wearing to the 3rd pillar leakage, with first independent desorb of pillar.The win working capacity of post of analysis is 125mg WO
3/ ml wet resin.Hand over back liquid to contain NaOH 47.7g/l, NaCl 24.0g/l.To hand over back liquid to be evaporated to NaOH concentration for about 250g/l, mend again solid NaOH to concentration be more than the 500g/l, be cooled to about 30 ℃ placement 4 hours; Treat NaCl from solution fully after the crystallization, centrifugation must contain the NaOH strong solution of small amount of N aCl (less than 45g/l); The NaOH that reclaims returns tungsten ore and leaches operation, has by the same terms to decompose white tungsten fine ore, and rate of decomposition is 97.17%.
Embodiment 2 decomposes high calcium black tungsten ore (tungstenic 12.8%, WO
3Grade is 43.4%, and the NaOH consumption is 3.5 times of theoretical amount, 160 ℃ of decomposition temperatures, soaking time 4.0 hours, rate of decomposition 98.45%) the gained feed liquid contains NaOH49.2g/l, WO
358.1g/l; Use two Φ 200 * 1400mm exchange column series connection adsorption operations, adverse current absorption is from bottom to top worn the back first pillar leakage and is inserted second pillar; Analyze to such an extent that working capacity is 117mgWO
3/ ml wet resin.Hand over back liquid to be evaporated to 1000g/l, cool off and placed centrifugation NaCl crystallization 8 hours; The gained concentrated NaOH solution returns and leaches batching.
Embodiment 3 feed liquids contain WO
325g/l, NaOH 20g/l, exchange column are Φ 16 * 36mm, 4 pillar series connection, following current conversion; After the upstream pillar was saturated, it was 128mg WO that independent desorb gets working capacity
3/ ml wet resin.
Embodiment 4 packed moving bed internal diameter 80mm, resin bed floor height 2000mm contains, NaOH 51.2g/l, WO
349.3g/l feed liquid flow through exchange column from bottom to top; When effluent liquid has the tungsten leakage to wear with the cinchonine check, take out the high resin of 300mm from the pillar lower end, the upper end replenishes the regenerating resin of same amount simultaneously, continuation exchange absorption.The saturated resin that takes out is packed the pillar of internal diameter 60mm into ammonia/ammonium chloride solution desorb, exchange capacity be 122mgWO
3/ ml wet resin.
Claims (8)
1. the treatment process of high-alkalinity sodium tungstate solution, use strongly basic anion exchange resin, when handling high-alkalinity solution, only saturated resin is carried out desorb, it is characterized in that: use many exchange column of fixed bed series connection, go here and there the post operation: after the A exchange column leaked and wears, liquid flowed directly into B and changes post after the exchange of tungstenic, continued absorption; The B post further seals in the C post after leaking and wearing again; The C post further seals in the D post after leaking and wearing; Advance downstream successively; After treating that the A post reaches capacity, desorb tungsten and regenerating resin simultaneously, regenerated A post insert downstream; So hocket cycle operation.
2. the treatment process of high-alkalinity sodium tungstate solution according to claim 1 is characterized in that: during the operation of string post, if the linear velocity of solution below 0.1cm/min, should be operated with adverse current (solution from the bottom to top); If the linear velocity of solution is more than 0.1cm/min, then following current or counter-current operation all can.
3. the treatment process of high-alkalinity sodium tungstate solution according to claim 1, it is characterized in that: at the several same exchange columns of downstream tandem, the upstream pillar leaks wears back continuation exchange, gradually exchange zone is moved on in the downstream column, after the upstream pillar is saturated, carry out desorb more separately.
4. the treatment process of high-alkalinity sodium tungstate solution, use strongly basic anion exchange resin, when handling high-alkalinity solution, only saturated resin is carried out desorb, it is characterized in that: use packed moving bed absorption, feed liquid enters continuously from the cylinder bottom, flows out from the resin bed top, and saturated resin from the bottom continuously or send out and batch emit; Simultaneously continuously or replenish the regenerating resin of equal amts at the top in batches; The desorption and regeneration of saturated resin carries out in a small ion exchange column, only needs saturated part taking-up desorb is got final product.
5. the treatment process of high-alkalinity sodium tungstate solution according to claim 1 is characterized in that: decompose white tungsten fine ore (WO
3Grade is 64.5%, and the NaOH consumption is 2.5 times of theoretical amount, 160 ℃ of decomposition temperatures, soaking time 4.5 hours, rate of decomposition 97.45%) the gained feed liquid contains NaOH 51.3g/l, WO
397.8g/l; Use two Φ 200 * 1400mm exchange column series connection adsorption operations, the absorption of following current is from top to bottom worn the back first pillar leakage and is inserted second pillar.After wearing, second leakage insert the 3rd pillar again, after wearing to the 3rd pillar leakage, with first independent desorb of pillar.The win working capacity of post of analysis is 125mgWO
3/ ml wet resin.Hand over back liquid to contain NaOH 47.7g/l, NaCl 24.0g/l.To hand over back liquid to be evaporated to NaOH concentration for about 250g/l, mend again solid NaOH to concentration be more than the 500g/l, be cooled to about 30 ℃ placement 4 hours; Treat NaCl from solution fully after the crystallization, centrifugation must contain the NaOH strong solution of small amount of N aCl (less than 45g/l); The NaOH that reclaims returns tungsten ore and leaches operation, has by the same terms to decompose white tungsten fine ore, and rate of decomposition is 97.17%.
6. the treatment process of high-alkalinity sodium tungstate solution according to claim 1 is characterized in that: decompose high calcium black tungsten ore (tungstenic 12.8%, WO
3Grade is 43.4%, and the NaOH consumption is 3.5 times of theoretical amount, 160 ℃ of decomposition temperatures, soaking time 4.0 hours, rate of decomposition 98.45%) the gained feed liquid contains NaOH49.2g/l, WO
358.1g/l; Use two Φ 200 * 1400mm exchange column series connection adsorption operations, adverse current absorption is from bottom to top worn the back first pillar leakage and is inserted second pillar; Analyze to such an extent that working capacity is 117mgWO
3/ ml wet resin.Hand over back liquid to be evaporated to 1000g/l, cool off and placed centrifugation NaCl crystallization 8 hours; The gained concentrated NaOH solution returns and leaches batching.
7. the treatment process of high-alkalinity sodium tungstate solution according to claim 1 is characterized in that: feed liquid contains WO
325g/l, NaOH 20g/l, exchange column are Φ 16 * 36mm, 4 pillar series connection, following current exchange; After the upstream pillar was saturated, it was 128mg WO that independent desorb gets working capacity
3/ ml wet resin.
8. the treatment process of high-alkalinity sodium tungstate solution according to claim 4 is characterized in that: packed moving bed internal diameter 80mm, resin bed floor height 2000mm contains, NaOH51.2g/l, WO
349.3g/l feed liquid flow through exchange column from bottom to top; When effluent liquid has the tungsten leakage to wear with the cinchonine check, take out the high resin of 300mm from the pillar lower end, the upper end replenishes the regenerating resin of same amount simultaneously, continuation exchange absorption.The saturated resin that takes out is packed the pillar of internal diameter 60mm into ammonia/ammonium chloride solution desorb, exchange capacity be 122mg WO
3/ ml wet resin.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410046815XA CN100348751C (en) | 2004-10-09 | 2004-10-09 | Treatment method of high alkali concentration sodium tungstate solution |
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|---|---|---|---|
| CNB200410046815XA CN100348751C (en) | 2004-10-09 | 2004-10-09 | Treatment method of high alkali concentration sodium tungstate solution |
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| CN1757770A true CN1757770A (en) | 2006-04-12 |
| CN100348751C CN100348751C (en) | 2007-11-14 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329962A (en) * | 2011-10-17 | 2012-01-25 | 中南大学 | Method for deeply separating tungsten and molybdenum from high-tungsten and high-molybdenum mixed solution |
| 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 |
| 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 |
| CN111617810A (en) * | 2020-05-11 | 2020-09-04 | 厦门钨业股份有限公司 | Method for decomposing tungsten by using weak-base anion exchange resin |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1003441B (en) * | 1986-12-13 | 1989-03-01 | 核工业部北京第五研究所 | Preparating of secondary ammonium tungstate with high purity using two-steption exchange method |
-
2004
- 2004-10-09 CN CNB200410046815XA patent/CN100348751C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329962A (en) * | 2011-10-17 | 2012-01-25 | 中南大学 | Method for deeply separating tungsten and molybdenum from high-tungsten and high-molybdenum mixed solution |
| CN102329962B (en) * | 2011-10-17 | 2014-04-09 | 中南大学 | Method for deeply separating tungsten and molybdenum from high-tungsten and high-molybdenum mixed solution |
| 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 |
| 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 |
| CN104263972B (en) * | 2014-10-09 | 2016-03-16 | 中南大学 | There is the tungsten mineral material metallurgical system of multiple closed loop |
| CN104263971B (en) * | 2014-10-09 | 2016-08-24 | 中南大学 | The system of APT is prepared by tungsten mineral material no pollution |
| CN111617810A (en) * | 2020-05-11 | 2020-09-04 | 厦门钨业股份有限公司 | Method for decomposing tungsten by using weak-base anion exchange resin |
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|---|---|
| CN100348751C (en) | 2007-11-14 |
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