CN103243218B - A kind of from containing extracting the method for molybdenum and the application of extraction agent molybdenum high-concentration acidic wastewater leach liquor - Google Patents
A kind of from containing extracting the method for molybdenum and the application of extraction agent molybdenum high-concentration acidic wastewater leach liquor Download PDFInfo
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- CN103243218B CN103243218B CN201310136090.2A CN201310136090A CN103243218B CN 103243218 B CN103243218 B CN 103243218B CN 201310136090 A CN201310136090 A CN 201310136090A CN 103243218 B CN103243218 B CN 103243218B
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Abstract
The invention discloses a kind of from containing extracting the method for molybdenum and the application of extraction agent molybdenum high-concentration acidic wastewater leach liquor, the method directly extracts containing molybdenum high-concentration acidic wastewater leach liquor with extraction agent; Load organic phases ammoniacal liquor after extraction or NaOH solution are stripped and are obtained ammonium molybdate or sodium molybdate solution; Application above-mentioned extraction agent is applied to selective extraction containing the molybdenum in molybdenum high-concentration acidic wastewater leach liquor, realizes being separated of the impurity such as molybdenum and phosphorus, arsenic, silicon, iron, aluminium, calcium, magnesium in acidic solution; The inventive method flow process is short, simple to operate, and cost is low, and extraction agent is applied to selective extraction containing the molybdenum in molybdenum high-concentration acidic wastewater leach liquor, high to the extraction efficiency of molybdenum, can industrial applications.
Description
Technical field
The present invention relates to a kind of from containing extracting the method for molybdenum and the application of extraction agent molybdenum high-concentration acidic wastewater leach liquor, belonging to the field of extracting molybdenum.
Background technology
While adopting the method for chemical mineral processing to obtain higher-grade white tungsten fine ore containing strontium molybdate tungsten ore, a large amount of chemical mineral processing pickling liquor containing molybdenum, tungsten, phosphorus, arsenic etc. can be produced.Adopt acid decomposition to produce wolframic acid containing strontium molybdate tungsten concentrate, also containing a large amount of molybdenums in acid mother liquor, these acid solutions containing molybdenum are directly discharged and are not only wasted valuable metal, also can serious environment pollution.
To this kind for the treatment of process containing molybdic acid immersion liquid, mainly contain chemical precipitation method, ion exchange method and solvent extration at present.Chemical precipitation method needs to add the immersion liquid of alkali neutralizing acid, and products obtained therefrom is the mixture of tungsten phosphorus and calcium contents is higher, and economic benefit is lower; Ion exchange method just can be carried out after generally also needing that leach liquor is added adjusting PH with base to 3 ~ 4, consumes a large amount of alkali in process, and molybdenum can not be separated with impurity such as phosphorus, arsenic, silicon; Solvent extration occupies critical role in the process extracting molybdenum from acidic solution, but does not also adopt extraction process so far from acid concentration up to the report reclaiming molybdenum the pickling liquor of 1 ~ 6mol/L.Although have many reports to the extraction of molybdenum in acidic medium or tungsten, research objects of these reports are more weak acidic solution system, and the pH of extraction feed liquid is about 2 ~ 4.
Summary of the invention
The present invention is directed in prior art to containing molybdenum acid immersion liquid treatment process exist extract molybdenum time impurity indivisible, cost is high, the defect of process complexity, object is to provide that a kind of flow process is short, easy and simple to handle, cost is low from containing the method selected, extract molybdenum efficientibility high molybdenum high-concentration acidic wastewater leach liquor, and the method is applicable to industrial applications.
Another object of the present invention aims to provide the application of extraction agent described in a kind of above-mentioned processing method; This extraction agent is applied to selective extraction containing the molybdenum in molybdenum high-concentration acidic wastewater leach liquor, and extraction efficiency is high, and while extracting and enriching molybdenum, can also realize the high efficiency separation of the impurity such as molybdenum and phosphorus, arsenic, silicon, iron, cost is low, simple to operate, can industrial applications.
The invention provides a kind of from containing the method extracting molybdenum molybdenum high-concentration acidic wastewater leach liquor, the method directly extracts containing molybdenum high-concentration acidic wastewater leach liquor with extraction agent; Load organic phases ammoniacal liquor after extraction or NaOH solution are stripped and are obtained ammonium molybdate or sodium molybdate solution;
Described extraction agent comprises sequestrant and organic solvent; Described sequestrant has structure shown in formula I:
R
1or R
2independently be selected from C separately
6 ~ 14alkyl;
Described contains H in molybdenum high-concentration acidic wastewater leach liquor
+concentration 0.5 ~ 6.5mol/L, containing molybdenum 0.3 ~ 20g/L; Described comprise in phosphorus, arsenic, silicon, iron containing molybdenum high-concentration acidic wastewater leach liquor that one or more are at interior impurity, wherein, various impurity component concentration is not all higher than 15g/L.
Described is preferably hydrochloric acid or sulfuric acid containing the acid in molybdenum high-concentration acidic wastewater leach liquor.
In described extraction agent, the mass percentage of sequestrant is 5% ~ 25%, the mass percentage 65% ~ 95% of organic solvent.
Described organic solvent is sulfonated kerosene or more than 260# solvent oil.
Described extraction agent comprises volumn concentration and is not more than the TBP of 10%, the one of nonyl phenol or Pyrogentisinic Acid and several.
In aforesaid method, the remaining liquid of extraction directly returns Ore Leaching operation.
Described extraction temperature is 10 ~ 40 DEG C; Phase volume ratio O/A=1/1 ~ 1/3; Extraction time is 3 ~ 10min.
In described reextraction, ammoniacal liquor or NaOH solution concentration are 1 ~ 6mol/L; Phase volume ratio O/A=1/1 ~ 10/1; Reextraction temperature is 10 ~ 40 DEG C, back-extraction time 5 ~ 10min.
Preferred containing molybdenum high-concentration acidic wastewater leach liquor comprise nickel-molybdenum ore high-concentration acidic wastewater leach liquor, dephosphorization sheelite high-concentration acidic wastewater leach liquor or other is containing molybdenum high-concentration acidic wastewater leach liquor.
Present invention also offers a kind of application of extraction agent, this application is that the compound with structure shown in formula I is applied to selective extraction containing the molybdenum in molybdenum high-concentration acidic wastewater leach liquor as extraction agent.
Described containing H in molybdenum high-concentration acidic wastewater leach liquor
+concentration 0.5 ~ 6.5mol/L, containing molybdenum 0.3 ~ 20g/L; Described comprise in phosphorus, arsenic, silicon or iron containing molybdenum high-concentration acidic wastewater leach liquor that one or more are at interior impurity, wherein, various impurity component concentration is not all higher than 15g/L.
More than extraction in aforesaid method, liquid is high concentrated acid, does not need, through process, can directly return Ore Leaching operation, with reuse acid wherein.
The ammonium molybdate of gained or sodium molybdate solution in aforesaid method, usable acid sinks legal system and gets ammonium molybdate or Sodium orthomolybdate; After stripping, organic phase does not need regeneration, directly can return extraction process.
Beneficial effect of the present invention:
Contrast with existing chemical precipitation method and ion exchange method, technical solution of the present invention decreases in acid decomposition liquid and operation, and technique is simple, easy and simple to handle; Because this extraction process is that organic phase directly extracts molybdenum from high-concentration acidic wastewater solution, raffinate containing acid can return sour decomposition process with reuse acid wherein, compared with chemical precipitation method traditional at present, save a large amount of acid, and there is no the consumption of neutralizing agent, thus reduce the production cost of ammonium molybdate or Sodium orthomolybdate by a relatively large margin; Metal recovery rate is high, and from containing molybdic acid decomposed solution to strip liquor process, molybdenum recovery can reach more than 98%; This solvent selection is excellent, and extraction process can realize being separated of the impurity such as molybdenum and phosphorus, arsenic, silicon, chromium.
The bright book of accompanying drawing
[Fig. 1] is process flow sheet of the present invention.
Embodiment
Further illustrate the present invention in conjunction with the embodiments, and do not limit the present invention
Embodiment 1
Operate according to technical process described in Fig. 1;
Feed liquid is dephosphorization sheelite acid decomposition liquid, containing molybdenum 8.328g/L, and free H
+concentration is 6.189mol/L;
Organic phase is 10% extraction agent+5%TBP+ sulfonated kerosene;
Carry out single-stage extraction with separating funnel, extraction phase ratio (O/A)=1/1, extraction time 10min, temperature is 30 DEG C, phase-splitting 1min, and raffinate is containing molybdenum 1.252g/L, and molybdenum percentage extraction reaches 85.0%.
Embodiment 2
Operate according to technical process described in Fig. 1;
Feed liquid is dephosphorization sheelite acid decomposition liquid, containing molybdenum 8.328g/L, and free H
+concentration is 6.189mol/L;
Organic phase is 10% extraction agent+5%+85% sulfonated kerosene;
Carry out single-stage extraction with separating funnel, extraction phase ratio (O/A)=1/1.5, extraction time 10min, temperature is 30 DEG C, phase-splitting 1min, and raffinate is containing molybdenum 1.362g/L, and molybdenum percentage extraction reaches 89.1%.
By above-mentioned load organic phases with 12.5% ammoniacal liquor by comparing (O/A)=4:1 back extraction, Stripping times 10min, temperature is 40 DEG C, and strip liquor is containing molybdenum 32.58g/L, and molybdenum back extraction ratio reaches 73.2%.
Embodiment 3
Operate according to technical process described in Fig. 1;
Feed liquid is scheelite middling dephosphorization mother liquor, containing molybdenum 0.374g/L, and phosphorous 5.451g/L, free H
+concentration is 0.912mol/L;
Organic phase is 10% extraction agent+5%TBP+ sulfonated kerosene;
Carry out single-stage extraction with separating funnel, extraction phase ratio (O/A)=1/1, extraction time 10min, temperature is 30 DEG C, phase-splitting 1min, and raffinate is containing molybdenum 0.0092g/L, phosphorous 5.385g/L, and molybdenum percentage extraction reaches 97.5%, and phosphorus percentage extraction is only 1.2%.
Embodiment 4
Operate according to technical process described in Fig. 1;
The immersion liquid of nickel-molybdenum ore oxidizing acid, containing molybdenum 13.327g/L, H
+concentration is 3.96mol/L, containing As2.543g/L, P3.04g/L, Al3.63g/L, Cu0.45g/L, Ni5.03g/L, Zn0.45g/L, Fe13.46g/L, Mg2.43g/L.Organic phase is 10% extraction agent+5%TBP+260# solvent oil, carries out cascade extraction, compares 1.5/1, mixing time 5min with separating funnel, and temperature is 30 DEG C, does not all extract iron, arsenic, silicon, phosphorus, calcium, magnesium.Through secondary counter-current extraction, in raffinate, molybdenum is 0.0358g/L, and percentage extraction reaches 99.7%, and load organic phases uses the back extraction of 6mol/L ammoniacal liquor, one-level back extraction ratio 91.89% again through the washing of pure water one-level.Through three stage countercurrent back extractions, back extraction ratio reaches 99.96%, and in strip liquor, molybdenum concentration is 36.3g/L.This strip liquor is used further to the back extraction that refluxes, and in the final strip liquor obtained, molybdenum concentration reaches 111.07g/L, and the arsenic in analysis strip liquor, phosphorus, iron, aluminium, nickel, zinc, copper, magnesium are trace, good separating effect, and the enrichment of molybdenum is high.
Embodiment 5
Operate according to technical process described in Fig. 1;
Containing seyrigite acid decomposition nut liquid, containing molybdenum 10.32g/L, H
+concentration is 6.5mol/L, phosphorous 0.16g/L, silicon 2.38g/L; Organic phase is 10% extraction agent+10%TBP+ sulfonated kerosene.Carry out two-stage countercurrent extraction with separating funnel, compare 1/1, mixing time 5min, temperature is 30 DEG C, and in raffinate, molybdenum is less than 0.004g/L, and percentage extraction reaches 99.96%, phosphorus, silica-based be not extracted.Load organic phases carries out three stage countercurrent back extractions with the ammoniacal liquor of 1:1 to compare 4:1 again after the washing of pure water one-level, and back extraction ratio is greater than 97%, and in strip liquor, molybdenum concentration is 47.9g/L.This strip liquor is used further to the back extraction that refluxes, and in the final strip liquor obtained, molybdenum concentration reaches 99.5g/L, and in strip liquor, Mo/P and Mo/Si concentration ratio is increased to 1043 and 185 by 64 in stock liquid and 4 respectively, good separating effect, and the enrichment of molybdenum is high.
Claims (8)
1., from containing the method extracting molybdenum molybdenum high-concentration acidic wastewater leach liquor, it is characterized in that, directly will extract with extraction agent containing molybdenum high-concentration acidic wastewater leach liquor; Load organic phases ammoniacal liquor after extraction or NaOH solution are stripped and are obtained ammonium molybdate or sodium molybdate solution;
Described extraction agent comprises sequestrant and organic solvent; Described sequestrant has structure shown in formula I:
R
1or R
2independently be selected from C separately
6 ~ 14alkyl;
Described contains H in molybdenum high-concentration acidic wastewater leach liquor
+concentration 3.96 ~ 6.5mol/L, containing molybdenum 0.3 ~ 20g/L; Described comprises phosphorus, arsenic, silicon and iron at interior impurity containing molybdenum high-concentration acidic wastewater leach liquor, and wherein, various impurity component concentration is not all higher than 15g/L; The described high-concentration acidic wastewater leach liquor comprising nickel-molybdenum ore high-concentration acidic wastewater leach liquor or dephosphorization sheelite containing molybdenum high-concentration acidic wastewater leach liquor.
2. method according to claim 1, is characterized in that, in described extraction agent, the mass percentage of sequestrant is 5% ~ 25%, the mass percentage 65% ~ 95% of organic solvent.
3. method according to claim 2, is characterized in that, described organic solvent is sulfonated kerosene or more than 260# solvent oil.
4. method according to claim 1, is characterized in that, described extraction agent comprises volumn concentration and is not more than the TBP of 10%, the one of nonyl phenol or Pyrogentisinic Acid and several.
5. the method according to any one of Claims 1 to 4, is characterized in that, the remaining liquid of extraction directly returns Ore Leaching operation.
6. method according to claim 1, is characterized in that, described extraction temperature is 10 ~ 40 DEG C; Phase volume ratio O/A=1/1 ~ 1/3; Extraction time is 3 ~ 10min.
7. method according to claim 1, is characterized in that, in described reextraction, the concentration of ammoniacal liquor or NaOH solution is 1 ~ 6mol/L; Phase volume ratio O/A=1/1 ~ 10/1; Reextraction temperature is 10 ~ 40 DEG C, back-extraction time 5 ~ 10min.
8. an application for extraction agent, is characterized in that, the compound with structure shown in formula I is applied to selective extraction containing the molybdenum in molybdenum high-concentration acidic wastewater leach liquor as extraction agent;
R
1or R
2for being independently selected from C separately
6 ~ 14alkyl;
Described containing H in molybdenum high-concentration acidic wastewater leach liquor
+concentration 3.96 ~ 6.5mol/L, containing molybdenum 0.3 ~ 20g/L; Described comprises phosphorus, arsenic, silicon and iron at interior impurity containing molybdenum high-concentration acidic wastewater leach liquor, and wherein, various impurity component concentration is not all higher than 15g/L.
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| CN103993169B (en) * | 2014-06-06 | 2015-12-30 | 中南大学 | A kind of nickel-molybdenum ore catalyzed oxidation pressurized acid leaching decomposition method |
| CN104711422B (en) * | 2015-03-16 | 2016-09-07 | 中南大学 | A kind of method extracting and separating tungsten in high phosphorus is containing tungsten mixed solution |
| CN105567958B (en) * | 2016-01-12 | 2018-03-16 | 东华理工大学 | Uranium molybdenum extraction separating method in high uranium molybdenum ore solution leachate |
| CN105838908B (en) * | 2016-04-08 | 2018-05-11 | 中南大学 | A kind of molybdenum smelting process of high-efficiency cleaning |
| CN106591603A (en) * | 2016-11-14 | 2017-04-26 | 核工业北京化工冶金研究院 | Back extraction method for molybdenum-containing organic phase |
| CN108342597B (en) * | 2017-01-24 | 2020-05-08 | 中南大学 | Method for decomposing scheelite by using hydrochloric acid with mother liquor circulation |
| CN108677036A (en) * | 2018-05-05 | 2018-10-19 | 广西大学 | A method of it is disseminated in raw ore from molybdenum oxide particulate and directly recycles molybdenum |
| CN109022787B (en) * | 2018-11-05 | 2020-07-14 | 中南大学 | Method for extracting nickel and molybdenum from nickel-molybdenum ore acidic leaching solution |
| CN110791656B (en) * | 2019-12-03 | 2021-05-04 | 浙江大学 | Method for extracting and separating molybdenum in waste catalyst leaching solution by multi-field synergistic enhancement |
| CN112062112B (en) * | 2020-09-08 | 2021-10-29 | 绍兴市九鑫环保有限公司 | Comprehensive utilization method of phosphorus-containing waste acid |
| CN112813287B (en) * | 2020-12-29 | 2022-05-13 | 常州大学 | Method for recovering molybdenum from waste hydrogenation catalyst |
| CN115403071A (en) * | 2022-08-23 | 2022-11-29 | 安庆市月铜钼业有限公司 | Production method of low-tungsten ammonium dimolybdate and ammonium dimolybdate produced by same |
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| CN102851500A (en) * | 2012-09-19 | 2013-01-02 | 中南大学 | Method for extracting vanadium from vanadium-containing highly concentrated sulfuric acid solution and application of extracting agent |
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