CN102108440B - Method for extracting molybdenum from nickel-molybdenum mineral alkali leaching solution - Google Patents
Method for extracting molybdenum from nickel-molybdenum mineral alkali leaching solution Download PDFInfo
- Publication number
- CN102108440B CN102108440B CN2011100617629A CN201110061762A CN102108440B CN 102108440 B CN102108440 B CN 102108440B CN 2011100617629 A CN2011100617629 A CN 2011100617629A CN 201110061762 A CN201110061762 A CN 201110061762A CN 102108440 B CN102108440 B CN 102108440B
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- solution
- nickel
- alkali leaching
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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 discloses a method for extracting molybdenum from nickel-molybdenum mineral alkali leaching solution. The method is characterized by adding solution containing Fe<3+> to nickel-molybdenum mineral alkali leaching solution, hydrolyzing the solution to generate precipitate as a carrier for adsorbing molybdenum to extract molybdenum and adding a buffer reagent to adjust the pH of the solution, thus achieving the aim of effectively extracting molybdenum, wherein the concentration of ammonium molybdate solution obtained after the precipitate containing molybdenum is desorbed with ammonia water is more than 100g/L and the ammonium molybdate solution can be used for preparing ammonium molybdate products; and the solution containing Fe<3+> obtained through dissolving the precipitation residue after desorption with acid and regenerating the precipitation residue can be returned for use. The method has the following advantages: the extraction ratio of the molybdenum is more than 99%; the used precipitant is cheap and can be recycled for a long time, thus lowering the cost; and the whole process is simple to operate, the treatment capacity is high and the needed equipment is easy for industrialization.
Description
Technical field
The present invention relates to a kind of method of from the nickel-molybdenum ore alkali leaching liquor, extracting molybdenum.
Background technology
Extensively distributing on the western Hunan, China Hunan, zunyi, guizhou and other places a kind of reserves greatly, be rich in the ore bed of tens kinds of elements such as a large amount of organic matters and Ni, Mo, V, W, Cu, Co, Pb, Zn, P, Au, Ag, Os, Ir, Pt, Rh, Ru and Cd, Se, Ti, Rb, Cs, i.e. " many metals black shale ".This mineral economic is worth quite big, and especially the enrichment degree of molybdenum and nickel is higher relatively, and is called " nickel-molybdenum ore " by people's custom.General mining grade molybdenum is about 2～8%, and nickel is about 1～4%.
Because the molybdenum in the molybdenum nickel minerals mainly exists with the non-crystalline state sulphided form, and the mineral carbon content is high, and ore-dressing technique does not have very great technological breakthrough always, and most of smelting technologyes are all directly handled these mineral.Main technology have decarburization-roasting-alkali soak-purify-ammonium salt acid is heavy-calcining produces molybdenum oxide, roasting-soda sintering-water logging-IXization-purification and impurity removal-crystallization-productions ammonium molybdate technology and roasting-alkali soaks-IXization-purification and impurity removal-acid sinks crystallization-production ammonium molybdate technology.And the full wet processing of molybdenum nickel minerals of " molybdenum nickel minerals-NaClO+NaOH leaching-IX-purification and impurity removal-crystallization-production ammonium molybdate " and " molybdenum nickel minerals-NaOH+ atmospheric air oxidation leaching-SX-purification and impurity removal-crystallization-production ammonium molybdate ".
Owing to receive the restriction (generally containing Mo2-8%) of handled nickel-molybdenum ore grade, no matter be that alkali soaks or direct alkali soaks after the roasting in the above-mentioned technology, resulting nickel-molybdenum ore alkali leaching liquor contains molybdenum concentration can be too not high, is generally 2-30g/L.So low nickel-molybdenum ore alkali leaching liquor can not directly be used for the heavy crystallization of acid or evaporative crystallization prepares the ammonium molybdate product, in addition enrichment and transition.Consider OH contained in the alkali immersion liquid
-Or CO
3 2-, and the impurity such as the PO that are leached
4 3-, AsO
4 3-, SiO
3 2-, SO
4 2-, WO
4 2-, VO
3 3-Plasma and MoO
4 2-The competition effect, directly adopt strongly basic anion exchange resin or quaternary amine extraction agent to be difficult to effectively absorption molybdenum.Generally Sodium orthomolybdate being acidified to the pH value is about 2.5～3.5, makes MoO
4 2-Be able to aggregate into Mo
7O
24-n(OH)
n (6-n)-(n=0,1,2,3) adopt weakly basic anion exchange resin or tertiary amine extraction agent to adsorb molybdenum, in the hope of reaching good adsorption effect and loading capacity then.As Li Qinggang etc. (Li Qinggang, Xiao Liansheng, Zhang Guiqing, Zhang Qi repaiies. nickel-molybdenum ore is produced full wet process technique of ammonium molybdate and practice. rare metal; 2007,31,86～88) adopt (Xu Hui, Pi Guanhua such as macroporous weakly basic anion exchange resin D314 and Pi Guanhua; Chen Baizhen, stone Xichang, Li Junli. from the alkali immersion liquid, reclaim the research of molybdenum with solvent extration. Journal of Natural Science of Hunan Normal University; 2007,30 (1), 43～46) adopt N235 to come the molybdenum in the extraction of nickel molybdenum ore leach liquor.Test discovery through us, adopt the D314 resin to adsorb molybdenum, the operating capacity of this resin has reached the 164mgMo/ml wet resin, and adsorption rate is 98.54%; Adopt the ammoniacal liquor desorb 45min of 5mol/L, desorption efficiency has reached good experiment effect up to 99.51%.Though D314 resin loading capacity is big, its mechanical property is relatively poor, in operating process, grinds easily, has caused the loss of resin and the inconvenience of operation.In addition, in ion exchange process, needing to consume a large amount of softening waters comes just to wash and the backwash resin.The method of molybdenum is simple to operate though employing N235 extracts, and the reaction times is short, and output is big etc., and general extraction agent price is mostly relatively more expensive, and organic solvent is more volatile, and certain toxicity is arranged, and in extraction process, also has the problem of third phase in addition.It is low with its cost that the precipitator method are extracted valuable metal, and efficient is high, and treatment capacity is big, simple operation and other advantages and be widely used in field of metallurgy.And the molybdenum that adopts the precipitator method to extract in the nickel-molybdenum ore alkali leaching liquor is not also seen correlative study and report.Therefore, the present invention intends that exploitation is a kind of to be adopted the precipitator method to extract the molybdenum in the nickel-molybdenum ore alkali leaching liquor and prepare the method for ammonium molybdate.
Summary of the invention
The object of the invention aims to provide a kind of simple, efficient, environmental protection, from the nickel-molybdenum ore leach liquor, extracts the method for molybdenum cheaply.
The objective of the invention is to realize in the following manner.
A kind of method of from the nickel-molybdenum ore alkali leaching liquor, extracting molybdenum: will contain Fe
3+Solution join in the nickel-molybdenum ore alkali leaching liquor (comprise after the nickel-molybdenum ore roasting that alkali soaks or directly alkali soak the alkali leaching liquor that obtains); And the pH value that adds buffer reagent adjustment solution is reacted the molybdenum deposition that contains that obtains after finishing and is obtained ammonium molybdate solution through the ammoniacal liquor desorb in 2.0～5.0 scopes.
The described Fe that contains
3+Solution be ferric chloride Solution(38 or ferrum sulfuricum oxydatum solutum, Fe
3+Concentration is 100～200g/L.
The described Fe that contains
3+The add-on of solution be Fe
3+Mol ratio with contained Mo in the nickel-molybdenum ore alkali leaching liquor: 1～3.
It is 2～30g/L that described nickel-molybdenum ore alkali leaching liquor contains molybdenum concentration.
Described buffer reagent is yellow soda ash or sodium hydrogencarbonate.
Described temperature of reaction is 20～50 ℃.
The described reaction times is 0.2～4h.
Described desorption process carries out in closed reactor.
The ammoniacal liquor mass concentration is for containing NH in the described ammoniacal liquor desorption process
310%～20%, consumption is NH
3With the mol ratio of Mo be 3～6, temperature of reaction is 60～100 ℃, reaction times 1～4h.
Deposition after the desorb obtains containing Fe through acid dissolving regeneration
3+Solution return use.
The precipitator method of the present invention are extracted the step of molybdenum and are mainly utilized Fe
3+Hydrolysis, generate the carrier of deposition as the deposition molybdenum.Fe
3+Hydrolytic process also be the acidization of nickel-molybdenum ore alkali leaching liquor, the H that hydrolysis produces
+With the MoO in the solution
4 2-Polymerization forms Mo
7O
24-n(OH)
n (6-n)-(n=0,1,2,3) are along with Fe
3+Continuation add, solution is then further by acidifying, when the pH of solution value less than 2 the time, begin to occur MoO
4 2+, with the sedimentation effect that has a strong impact on molybdenum.For this reason, need add buffer reagent yellow soda ash or sodium hydrogencarbonate simultaneously and keep pH in the heavy molybdenum process greater than 2.The CO that adds
3 2-Or HCO
3 -Can with H
+And be decomposed, whole process is not introduced new foreign ion to solution.
Containing the molybdenum precipitation slag separates to suck and obtains containing the above ammonium molybdate solution of molybdenum 100g/L.After this solution can be removed impurity such as phosphorus, arsenic, silicon through the magnesium salts precipitator method, the heavy crystallization of acid obtained qualified ammonium tetramolybdate product again.The removal of impurities process of the magnesium salts precipitator method and the crystallisation process of ammonium molybdate solution are the traditional method in the molybdenum smelting technology, therefore no longer detail in the present invention.
Precipitation slag after the ammoniacal liquor desorb with hydrochloric acid or sulfuric acid dissolution, finally obtains containing Fe
3+The ferric chloride Solution(38 of 100～200g/L or ferrum sulfuricum oxydatum solutum.This solution returns and is used to precipitate molybdenum.
The advantage that the present invention has is:
1. the deposition rate of molybdenum reaches more than 99%;
2. used precipitation agent is compared with ion exchange resin or extraction agent, low price, and environmental protection and can recycling has for a long time reduced cost;
3. the absorption of solution, desorption process are simple to operate, and treatment capacity is big, and required equipment is simple, is easy to industriallization.
Description of drawings:
Fig. 1 is a schematic flow sheet of the present invention.
Embodiment
Further specify present method below in conjunction with implementing profit, rather than to further restriction of the present invention.
Embodiment 1
Nickel-molybdenum ore alkali leaching liquor 10L wherein contains Mo 10.2g/L.Add and contain Fe
3+The ferric chloride Solution(38 of 150g/L, its add-on are Fe
3+With the mol ratio of Mo in the leach liquor be 2: 1, and adding sodium hydrogencarbonate, to control the pH value of solution be 3.0,25 ℃ of temperature of reaction, reaction times 1h, the precipitation slag that contains molybdenum that reaction end after-filtration obtains, the extraction yield of molybdenum is 99.3%.The precipitation slag that contains molybdenum adopts and contains NH
310% ammoniacal liquor desorb, ammonia volume are NH
3The mol ratio of/Mo 3: 1,90 ℃ of temperature of reaction, reaction 4h after scouring filters the ammonium molybdate solution that obtains containing molybdenum 154.7g/L.The desorption efficiency of molybdenum is 94.2%, and the precipitation slag after the desorb is mixed with behind dissolving with hydrochloric acid and contains Fe
3+The ferric chloride Solution(38 of 150g/L.This solution contains a small amount of Mo and together returns use.
Embodiment 2
Nickel-molybdenum ore alkali leaching liquor 10L wherein contains Mo 10.2g/L.Add and contain Fe
3+The ferric chloride Solution(38 of 200g/L, in this solution and contain the Mo of 0.08g/L, its add-on is Fe
3+With the mol ratio of Mo in the leach liquor be 2: 1, and adding sodium hydrogencarbonate, to control the pH value of solution be 5.0,50 ℃ of temperature of reaction, reaction times 4h, the extraction yield of molybdenum are 99.1%.The precipitation slag that reaction end after-filtration obtains adopts and contains NH
320% ammoniacal liquor desorb, ammonia volume are NH
3The mol ratio of/Mo 6: 1,60 ℃ of temperature of reaction, reaction 1h after scouring filters the ammonium molybdate solution that obtains containing molybdenum 203.2g/L.The desorption efficiency of molybdenum is 92.8%, and the precipitation slag after the desorb is mixed with behind dissolving with hydrochloric acid and contains Fe
3+The ferric chloride Solution(38 of 200g/L.This solution contains a small amount of Mo and together returns use.
Embodiment 3
Nickel-molybdenum ore alkali leaching liquor 10L wherein contains Mo 2.5g/L.Add and contain Fe
3+The ferric chloride Solution(38 of 200g/L, its add-on are Fe
3+With the mol ratio of Mo in the leach liquor be 1: 1, and adding sodium hydrogencarbonate, to control the pH value of solution be 2.0,20 ℃ of temperature of reaction, reaction times 1h, the extraction yield of molybdenum are 99.0%.The precipitation slag that reaction end after-filtration obtains adopts and contains NH
310% ammoniacal liquor desorb, ammonia volume are NH
3The mol ratio of/Mo 6: 1,100 ℃ of temperature of reaction, reaction 2h after scouring filters the ammonium molybdate solution that obtains containing molybdenum 114.6g/L.The desorption efficiency of molybdenum is 91.7%, and the precipitation slag after the desorb is mixed with behind dissolving with hydrochloric acid and contains Fe
3+The ferric chloride Solution(38 of 200g/L.This solution contains a small amount of Mo and together returns use.
Embodiment 4
Nickel-molybdenum ore alkali leaching liquor 10L wherein contains Mo 19.6g/L.Add and contain Fe
3+The ferrum sulfuricum oxydatum solutum of 100g/L, its add-on are Fe
3+With the mol ratio of Mo in the leach liquor be 1.5: 1, and adding yellow soda ash, to control the pH value of solution be 4.0,30 ℃ of temperature of reaction, reaction times 2h, the extraction yield of molybdenum are 99.4%.The precipitation slag that reaction end after-filtration obtains adopts and contains NH
315% ammoniacal liquor desorb, ammonia volume are NH
3The mol ratio of/Mo 4: 1,80 ℃ of temperature of reaction, reaction 2h after scouring filters the ammonium molybdate solution that obtains containing molybdenum 185.7g/L.The desorption efficiency of molybdenum is 93.9%, and the precipitation slag after the desorb is mixed with behind sulfuric acid dissolution and contains Fe
3+The ferrum sulfuricum oxydatum solutum of 100g/L.This solution contains a small amount of Mo and together returns use.
Embodiment 5
Nickel-molybdenum ore alkali leaching liquor 10L wherein contains Mo 29.7g/L.Add and contain Fe
3+The ferric chloride Solution(38 of 150g/L, its add-on are Fe
3+With the mol ratio of Mo in the leach liquor be 2: 1, and adding sodium hydrogencarbonate, to control the pH value of solution be 3.0,25 ℃ of temperature of reaction, reaction times 1h, the extraction yield of molybdenum are 99.2%.The precipitation slag that reaction end after-filtration obtains adopts and contains NH
310% ammoniacal liquor desorb, ammonia volume are NH
3The mol ratio of/Mo 5: 1,70 ℃ of temperature of reaction, reaction 2h after scouring filters the ammonium molybdate solution that obtains containing molybdenum 174.6g/L.The desorption efficiency of molybdenum is 92.3%, and the precipitation slag after the desorb is mixed with behind dissolving with hydrochloric acid and contains Fe
3+The ferric chloride Solution(38 of 150g/L.This solution contains a small amount of Mo and together returns use.
Claims (6)
1. a method of from the nickel-molybdenum ore alkali leaching liquor, extracting molybdenum is characterized in that: will contain Fe
3+Solution join in the nickel-molybdenum ore alkali leaching liquor, and the pH value that adds buffer reagent adjustment solution is in 2.0～5.0 scopes, reaction obtains after finishing contains molybdenum and precipitates and obtain ammonium molybdate solution through the ammoniacal liquor desorb; Described buffer reagent is yellow soda ash or sodium hydrogencarbonate; The described Fe that contains
3+The add-on of solution be Fe
3+Mol ratio with contained Mo in the nickel-molybdenum ore alkali leaching liquor: 1～3; Temperature of reaction is 20～50 ℃; Reaction times is 0.2～4h.
2. method according to claim 1 is characterized in that: the described Fe of containing
3+Solution be ferric chloride Solution(38 or ferrum sulfuricum oxydatum solutum, Fe
3+Concentration is 100～200g/L.
3. method according to claim 1 is characterized in that: it is 2～30g/L that described nickel-molybdenum ore alkali leaching liquor contains molybdenum concentration.
4. method according to claim 1 is characterized in that: described desorption process carries out in closed reactor.
5. according to claim 1 or 4 described methods, it is characterized in that: the ammoniacal liquor mass concentration is for containing NH in the ammoniacal liquor desorption process
310%～20%, consumption is NH
3With the mol ratio of Mo be 3～6, temperature of reaction is 60～100 ℃, reaction times 1～4h.
6. method according to claim 1 is characterized in that: the deposition after the desorb obtains containing Fe through acid dissolving regeneration
3+Solution return use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100617629A CN102108440B (en) | 2011-03-15 | 2011-03-15 | Method for extracting molybdenum from nickel-molybdenum mineral alkali leaching solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100617629A CN102108440B (en) | 2011-03-15 | 2011-03-15 | Method for extracting molybdenum from nickel-molybdenum mineral alkali leaching solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102108440A CN102108440A (en) | 2011-06-29 |
| CN102108440B true CN102108440B (en) | 2012-08-08 |
Family
ID=44172726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100617629A Expired - Fee Related CN102108440B (en) | 2011-03-15 | 2011-03-15 | Method for extracting molybdenum from nickel-molybdenum mineral alkali leaching solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102108440B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004053173A1 (en) * | 2002-12-06 | 2004-06-24 | Mitsubishi Corporation | METHOD FOR RECOVERING VALUABLE METAL FROM WASTE CONTAINING V, Mo AND Ni |
| AU2007231801A1 (en) * | 2006-11-02 | 2008-05-22 | Frank Trask | Leaching of oxidised molybdenum |
| CN101717858A (en) * | 2009-12-22 | 2010-06-02 | 重庆拓必拓钼业有限公司 | Method for extracting molybdenum, nickel, vanadium and ferrum from polymetallic black-shale paragentic minerals |
-
2011
- 2011-03-15 CN CN2011100617629A patent/CN102108440B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004053173A1 (en) * | 2002-12-06 | 2004-06-24 | Mitsubishi Corporation | METHOD FOR RECOVERING VALUABLE METAL FROM WASTE CONTAINING V, Mo AND Ni |
| AU2007231801A1 (en) * | 2006-11-02 | 2008-05-22 | Frank Trask | Leaching of oxidised molybdenum |
| CN101717858A (en) * | 2009-12-22 | 2010-06-02 | 重庆拓必拓钼业有限公司 | Method for extracting molybdenum, nickel, vanadium and ferrum from polymetallic black-shale paragentic minerals |
Non-Patent Citations (1)
| Title |
|---|
| 李青刚.《从镍钼矿中制取钼酸铵的研究》.《中国博士学位论文全文数据库 工程科技I辑》.2010,(第11期),第12页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102108440A (en) | 2011-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102206755B (en) | Method for separating and recovering valuable elements from neodymium-iron-boron wastes | |
| CN101215636B (en) | Stone coal sodication roasting and vanadium-extracting method | |
| CN101289704A (en) | Treatment method of high-magnesium laterite-nickel ore | |
| CN101880780A (en) | Method for separating and extracting tungsten-molybdenum from mixed solution of tungstate-molybdate | |
| Liu et al. | A new process of extracting vanadium from stone coal | |
| CN101838735B (en) | Method for extracting valuable metals from acid leaching solution of nickel-molybdenum multi-metal metallurgical materials by separation | |
| CN101565778A (en) | Method for depositing and separating tungsten and molybdenum in tungstate/molybdate mixed solution | |
| CN101831542B (en) | Method for extracting metallic elements of ferrum, magnesium and calcium from molybdenum milltailings | |
| CN102965506B (en) | Method for removing aluminum from rare earth solution by benzoate precipitation method | |
| CN102888515A (en) | Comprehensive utilization method of amarillite slag | |
| CN100516252C (en) | Method for treating oxidized copper ore | |
| CN103320613A (en) | Method for recovering cobalt nickel through electrolytic manganese industrial ion exchange method | |
| CN102430266A (en) | Method for purifying liquid with vanadium and method for preparing ammonium metavanadate and vanadium oxide | |
| CN101760652B (en) | Technological method for treating refractory complex molybdenum ore by combined dressing and smelting process | |
| CN107475523A (en) | A kind of method of the recovery indium from flyash | |
| CN103952550A (en) | Comprehensive method for producing ammonium paratungstate through low-tungsten tin concentrate | |
| CN102321801A (en) | Method for extracting vanadium from alkaline leaching solution containing vanadium stone coal | |
| CN104046776A (en) | Process for recovering valuable metals from high-iron alloys | |
| CN101693554A (en) | Method for extracting vanadium pentoxide from stone coal ores | |
| CN103553155B (en) | A kind of method processing laterite intermediate product | |
| CN102108440B (en) | Method for extracting molybdenum from nickel-molybdenum mineral alkali leaching solution | |
| CN102417980A (en) | Method for producing nickel sulfate by leaching Lateritic nickle ores with both sulfuric acid and ammonia | |
| CN103243226A (en) | Method for preparing rare earth concentrate from low-grade light rare earth tailings | |
| CN102154546A (en) | Method for smelting molybdenum-nickel mineral association by wet process | |
| CN103498047A (en) | Process for extracting vanadium through alkaline leaching conducted after stone coal oxidizing roasting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120808 Termination date: 20180315 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |