CN104232941B - A kind of method of synthetical recovery molybdenum and rhenium from high rhenium concentrated molybdenum ore - Google Patents
A kind of method of synthetical recovery molybdenum and rhenium from high rhenium concentrated molybdenum ore Download PDFInfo
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- CN104232941B CN104232941B CN201410460145.XA CN201410460145A CN104232941B CN 104232941 B CN104232941 B CN 104232941B CN 201410460145 A CN201410460145 A CN 201410460145A CN 104232941 B CN104232941 B CN 104232941B
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Abstract
The invention discloses a kind of method of rhenium-containing concentrated molybdenum ore synthetical recovery molybdenum rhenium, rhenium-containing concentrated molybdenum ore and the roasting of lime mixing granulation are obtained roasting material by the method, roasting material is by sulphuric acid soln one step Leaching Molybdenum rhenium, leach liquor adopts roasting material neutralization to obtain neutralizer, neutralizer purification dephosphorization arsenic, silicon, after again acid adjustment to pH value of solution 2.0-3.0, neutralizer after purification adopts solvent extraction synchronously to extract molybdenum rhenium, strip liquor acid is heavy obtains ammonium molybdate product, heavy molybdenum mother liquor again synchronously extracts molybdenum rhenium and obtains containing molybdenum rehenic acid ammonium, adopt calcium chloride to remove molybdenum containing molybdenum rehenic acid ammonium and be purified Ammonium rhenate solution, add Repone K after purification Ammonium rhenate solution is concentrated to sink rhenium and obtain potassium perrhenate product.The method has that technique is brief, with low cost, simple to operate, the rate of recovery is high, can obtain ammonium molybdate, potassium perrhenate product.
Description
Technical field
The present invention relates to the method for synthetical recovery molybdenum and rhenium from high rhenium concentrated molybdenum ore.
Background technology
The concentrated molybdenum ore of Shaanxi dressing-works institute of refining stone ore industry company limited output contains Mo-48%, Re-240g/t.It is low to there is Rhenium recovery rate in the technique that this raw material adopts existing multiple hearth furnace roasting to prepare molybdenum oxide, produces a large amount of low concentration SO
2,the outstanding problems such as environmental pollution is serious; The problems such as acid or alkaline oxygen leaching all exists equipment complexity, operation inconvenience.Lime-roasting---though sulfuric acid leaching process rhenium-containing concentrated molybdenum ore has research, but molybdenum rhenium segmentation in lime-roasting material is leached more by the sulfuric acid that adopts at present, obtain the leach liquor of neutral rhenium-containing and highly acidity containing molybdenum leach liquor, rhenium-containing leach liquor adopts D201 resin absorption to reclaim rhenium, rhenium-containing leach liquor rhenium concentration is low, the amount of solution that recovery rhenium need process is large, and processing cost is high; Adopt alkali neutralization containing molybdenum leach liquor, amine extractant extraction and recovery molybdenum, prepares ammonium molybdate.The patent of Shaanxi refining stone ore industry company limited, Hunan Research Institute of Non-ferrous Metals's application in 2011 adopts lime-roasting---sulfuric acid two sections of extract technologies, although technique avoids SO
2smoke pollution, but when there is meutral innersion, rhenium leaching yield is lower, and leach liquor rhenium concentration is low, and subsequent recovery rhenium difficulty is large; Slag sulphuric acid soln Leaching Molybdenum again after leaching rhenium, molybdenum leach liquor adopts alkali neutralization of waste acid, adds the consumption of technique acid-base reagent, production cost increases, and causes the loss of molybdenum rhenium to increase simultaneously.Two sections of extract technology complexity, reagent consumption is large, and facility investment is many, and cost is high, and be further improved technological process.Former technique two sections leaches and leaches rhenium, molybdenum respectively, and leaching process is complicated, and rhenium molybdenum is disperseed at leaching process, is unfavorable for subsequent recovery; Molybdenum leach liquor adopts alkali neutralization of waste acid, causes acid-base reagent consumption large; Leach liquor reclaims rhenium, molybdenum divides D201 resin absorption, amine extractant to extract molybdenum, and the Rhenium recovery after extraction molybdenum in liquid is difficult, quality product is difficult to ensure.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, provides a kind of method of synthetical recovery molybdenum and rhenium from high rhenium concentrated molybdenum ore.
In order to achieve the above object, technical scheme provided by the invention is:
The method of described synthetical recovery molybdenum and rhenium from high rhenium concentrated molybdenum ore comprises the steps:
(1) high rhenium concentrated molybdenum ore and white lime are pressed 1:0.5-2.0, the mass ratio mixing of preferred 1:1.5, granulating to particle diameter is 5-20mm, obtains roasting material in 350-680 DEG C of roasting 1-10h;
(2) to 100 orders, join quality be pulp in the water of roasting material quality 3-5 times by levigate for roasting material, add again quality be roasting material quality 55-65% and the sulfuric acid that concentration is 98% carry out leaching process, leach treatment temp and be 45-95 DEG C, the leaching treatment time is 1-8h, leaching process terminal pH is 0.4-0.6, preferably 5.0, complete after leaching process filter, washery slag obtains leach liquor containing molybdenum rhenium and leached mud;
(3) add roasting material containing the leach liquor of molybdenum rhenium and carry out neutralization reaction, in obtaining and slag and pH be the neutralizer of 2.0-5.0; Ordinary method can be adopted in neutralizer to add impurity such as vulcanizing agent removing heavy metal, Pb, As Si etc.;
(4) N235-sulfonated kerosene is adopted to carry out the extraction of molybdenum rhenium as organic phase to neutralizer, molybdenum rhenium extraction time compare O/A=1/2-1/4, load organic phases employing mass percent concentration is the ammoniacal liquor back extraction of 5-21%, obtain the first strip liquor containing ammonium molybdate, rehenic acid ammonium, during back extraction, compare O/A=1/1-3/1;
(5) in step (4) gained first strip liquor, adding volume is the first strip liquor volume 25-35%, and preferably 30%, concentration is 55-65%, and preferably the nitric acid of 60% precipitates, and obtains ammonium molybdate product and heavy molybdenum mother liquor; Containing ammonium nitrate, a small amount of molybdenum, whole rheniums in heavy molybdenum mother liquor, being the solution after precipitation ammonium molybdate filters, is the raw material reclaiming rhenium
(6) N235-sulfonated kerosene is adopted to extract heavy molybdenum mother liquor as organic phase, extraction is in a ratio of O/A=1/1-1/5, load organic phases employing mass percent concentration is the ammoniacal liquor back extraction of 5-21%, obtain the second strip liquor containing ammonium molybdate, rehenic acid ammonium, during back extraction, compare O/A=1/1-3/1;
(7) in step (6) gained second strip liquor, add quality is that the calcium chloride of molybdenum quality 1.0-1.5 times in the second strip liquor is except molybdenum, liquid after obtaining calcium molybdate and removing molybdenum, in liquid after molybdenum, add the Repone K precipitated crystal of quality for rhenium quality 2-4.5 times in liquid after molybdenum, obtain potassium perrhenate.
Preferably, in the described high rhenium concentrated molybdenum ore of step (1), the content of rhenium is 100-500g/t, and the mass percentage content of molybdenum is 35-57%.
In step (4) and the described N235-sulfonated kerosene of step (6), the volume percent content of N235 is 20-25%, preferably 25%, and the volume percent content of sulfonated kerosene is 75-80%, preferably 75%.
In described in step (3) and slag turn back in step (2), under step (2) described condition with levigate after roasting material together carry out leaching and process.In and slag do not leach completely, cause the part acid consumpting substance that make use of in mineral, so will leaching be returned.
Compared with prior art, advantage of the present invention is:
1, molybdenum rhenium one step leaches and enters leach liquor, and process is simple, and molybdenum rhenium leaching yield is high.
2, in molybdenum rhenium leach liquor, residual acid adopts roasting material neutralization, does not adopt traditional soda, leaching with sodium hydroxide or limestone vegetation method, reduces the acid consumption of technique, avoids the alkaline consumption of traditional neutralization method.
3, in leach liquor, molybdenum rhenium synchronously extracts the strip liquor prepared containing ammonium molybdate, rehenic acid ammonium, achieves the preliminary concentration of rhenium, and avoiding original technique needs to adopt resin method to reclaim rhenium from one section of leach liquor.
4, strip liquor adopts the heavy molybdenum of acid to realize the recovery of molybdenum, and rhenium is retained in heavy molybdenum mother liquor, is beneficial to the recovery of rhenium;
5, heavy molybdenum mother liquor adopts synchronous extraction to prepare the strip liquor of ammonium molybdate, rehenic acid ammonium again, adopts calcium chloride precipitation method Separation of Molybdenum rhenium, obtains the Ammonium rhenate solution of low molybdenum, realize the preparation that molybdenum rhenium is separated and is convenient to follow-up potassium perrhenate.
Extraction and back-extraction is got in the past for extracting separately molybdenum, extraction rhenium, and the present invention adopts extraction and back-extraction synchronously to extract molybdenum rhenium, that is, one section of lixiviation process Leaching Molybdenum rhenium simultaneously.Its process is simple, and molybdenum rhenium leaching yield is high.The present invention to adopt in roasting material and residual acid in leach liquor, decreases technique acid and alkali consumption, and completely avoid the loss of molybdenum rhenium.The present invention adopts molybdenum rhenium hybrid extraction, enormously simplify molybdenum Rhenium recovery operation; Nitric acid to sink after molybdenum extraction and recovery rhenium again.This invention simplifies technical process, improve molybdenum rhenium metal recovery rate, reduce reagent consumption, production cost significantly reduces, and quality product is secure.Belong to a kind of novel method of synthetical recovery rhenium-containing concentrated molybdenum ore.
Embodiment
embodiment 1
The concentrated molybdenum ore of Shaanxi mining industry company limited output is containing Mo-48%, and Re-240g/t, adopts the inventive method to process it.
Get the rhenium-containing concentrated molybdenum ore (Mo 47.38%, Re 240g/t) that 100g Shaanxi refining stone ore industry provides, add 130g white lime mixing granulation, control particle diameter Φ 6-12mm, then control temperature is 650 DEG C of roasting 3h, obtain roasting material, roasting material is levigate, add 800ml water slurry, then add 138g concentration be 98% sulfuric acid leach, extraction temperature is 90 DEG C, time is 3h, and filtration, washery slag obtain 1200ml leach liquor (containing wash water) and leached mud, and molybdenum rhenium leaching yield is respectively 98.66%, 98.12%.Leach liquor adds 150g roasting material stirring at normal temperature 1h, in obtaining and slag and pH value be the neutralizer of 3.5, in and slag directly return and leach next time.
Neutralizer (Mo 39.20g/L, Re 21.0 mg/L, pH3.5) (N235 content is 25% directly to adopt N235-sulfonated kerosene to carry out extracting, sulfonated kerosene is 75%), extraction time is 5min, extraction progression is 3 grades, extraction is in a ratio of 1/2.5, and molybdenum rhenium percentage extraction is respectively 99.4%, 97.5%, and load organic phases adopts concentration to be that 12% ammoniacal liquor carries out back extraction, control Stripping times is 5min, back extraction progression is 3 grades, and back extraction is in a ratio of 1/2.0, and molybdenum rhenium back extraction ratio is respectively 99.0%, 96.55%, strip liquor composition is Mo192.85g/L, Re98.8g/L.
Strip liquor composition is Mo192.85g/L, Re98.8g/L, and add the nitric acid that concentration is 60%, pH is 2.0 to terminal, and obtain ammonium molybdate product and heavy molybdenum mother liquor, mother liquor composition is Mo2.0g/L, Re70.50, and molybdenum rhenium deposition rate is respectively 98.54%, 0.10%.
Heavy mother liquor (the Mo2.0g/L of acid, Re70.50, pH2.0) (N235 content is 25% to adopt N235-sulfonated kerosene to carry out extracting, sulfonated kerosene is 75%), extraction time is 5min, extraction progression is 3 grades, extraction is in a ratio of 1/5, and molybdenum rhenium percentage extraction is respectively 99.5%, 99.8%, and load organic phases adopts concentration to be that 12% ammoniacal liquor carries out back extraction, control Stripping times is 5min, back extraction progression is 3 grades, and back extraction is in a ratio of 1/10, and molybdenum rhenium back extraction ratio is respectively 99.0%, 99.0%, strip liquor composition is Mo98.505g/L, Re3.48g/L.
Strip liquor (Mo98.505g/L, Re3.48g/L) adds the calcium chloride that quality is molybdenum quality 1.1 times in strip liquor, and 40 DEG C are stirred 2h, liquid after obtaining calcium molybdate and precipitating molybdenum, molybdenum deposition rate is 99.89%, and rhenium deposition rate is 3%, after heavy molybdenum, liquid composition is Mo0.1g/L, Re3.37g/L.After heavy molybdenum, liquid is long-pending is concentrated into 1/10, and rhenium concentration is to 33.7g/L, and adding quality is except the Repone K precipitation of rhenium quality 2.0 times in liquid after molybdenum obtains potassium perrhenate.
Claims (3)
1. the method for synthetical recovery molybdenum and rhenium from high rhenium concentrated molybdenum ore, it is characterized in that, described method comprises the steps:
(1) high rhenium concentrated molybdenum ore is mixed with the mass ratio of white lime by 1:0.5-2.0, granulate, obtain roasting material in 350-680 DEG C of roastings; In described high rhenium concentrated molybdenum ore, the content of rhenium is 100-500g/t, and the mass percentage content of molybdenum is 35-57%;
(2) joining quality after roasting material is levigate is pulp in the water of roasting material quality 3-5 times, add again quality be roasting material quality 55-65% and the sulfuric acid that concentration is 98% carry out leaching process, leach treatment temp and be 45-95 DEG C, the leaching treatment time is 1-8h, it is 0.4-0.6 that leaching processes terminal pH, and filtration after completing leaching process, washery slag obtain the leach liquor and the leached mud that contain molybdenum rhenium;
(3) add roasting material containing the leach liquor of molybdenum rhenium and carry out neutralization reaction, in obtaining and slag and pH be the neutralizer of 2.0-5.0;
(4) N235-sulfonated kerosene is adopted to carry out the extraction of molybdenum rhenium as organic phase to neutralizer, molybdenum rhenium extraction time compare O/A=1/2-1/4, load organic phases employing mass percent concentration is the ammoniacal liquor back extraction of 5-21%, obtain the first strip liquor containing ammonium molybdate, rehenic acid ammonium, during back extraction, compare O/A=1/1-3/1;
(5) in step (4) gained first strip liquor, add the nitric acid that volume is the first strip liquor volume 25-35%, concentration is 55-65% to precipitate, obtain ammonium molybdate product and heavy molybdenum mother liquor;
(6) N235-sulfonated kerosene is adopted to extract heavy molybdenum mother liquor as organic phase, extraction is in a ratio of O/A=1/1-1/5, load organic phases employing mass percent concentration is the ammoniacal liquor back extraction of 5-21%, obtain the second strip liquor containing ammonium molybdate, rehenic acid ammonium, during back extraction, compare O/A=1/1-3/1;
(7) in step (6) gained second strip liquor, add quality is that the calcium chloride of molybdenum quality 1.0-1.5 times in the second strip liquor is except molybdenum, liquid after obtaining calcium molybdate and removing molybdenum, in liquid after molybdenum, add the Repone K precipitated crystal of quality for rhenium quality 2-4.5 times in liquid after molybdenum, obtain potassium perrhenate.
2. the method for claim 1, is characterized in that, in step (4) and the described N235-sulfonated kerosene of step (6), the volume percent content of N235 is 20-25%, and the volume percent content of sulfonated kerosene is 75-80%.
3. the method for claim 1, is characterized in that, in described in step (3) and slag turn back in step (2), under step (2) described condition with levigate after roasting material together carry out leaching and process.
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| CN105087962B (en) * | 2015-09-09 | 2017-11-10 | 中南大学 | The method of high efficiency extraction molybdenum and rhenium from rhenium-containing Low Grade Molybdenum Concentrates |
| CN105866112A (en) * | 2016-03-30 | 2016-08-17 | 商洛学院 | Method for determining content of rhenium in rhenium-containing material |
| CN105714123B (en) * | 2016-05-04 | 2018-03-09 | 中条山有色金属集团有限公司 | A kind of method that rehenic acid ammonium is prepared from rich rhenium slag |
| CN107779590B (en) * | 2017-10-31 | 2020-01-14 | 中南大学 | Method for extracting molybdenum and rhenium |
| CN108588446B (en) * | 2018-04-28 | 2020-09-04 | 西安鑫城投资有限公司 | Method for extracting molybdenum and rhenium from rhenium-containing molybdenum concentrate |
| CN109055747B (en) * | 2018-10-08 | 2020-06-26 | 河南科技大学 | Method for extracting and separating molybdenum and rhenium under acidic condition |
| CN113249594B (en) * | 2020-12-24 | 2022-09-06 | 国家地质实验测试中心 | Method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore |
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| CN103924081A (en) * | 2014-04-28 | 2014-07-16 | 北京矿冶研究总院 | Method for recovering molybdenum and rhenium from molybdenum concentrate pressurized leaching solution |
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