CN101906538A - Method for extracting nickel and molybdenum from nickel-molybdenum symbiotic ore by low-concentration composite acid and oxidizing agent - Google Patents
Method for extracting nickel and molybdenum from nickel-molybdenum symbiotic ore by low-concentration composite acid and oxidizing agent Download PDFInfo
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- CN101906538A CN101906538A CN200910062431XA CN200910062431A CN101906538A CN 101906538 A CN101906538 A CN 101906538A CN 200910062431X A CN200910062431X A CN 200910062431XA CN 200910062431 A CN200910062431 A CN 200910062431A CN 101906538 A CN101906538 A CN 101906538A
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Abstract
The invention discloses a method for extracting nickel and molybdenum from nickel-molybdenum symbiotic ore by low-concentration composite acid and an oxidizing agent, which comprises the following steps of: crushing and ball-milling the nickel-molybdenum symbiotic ore; soaking by using the low-concentration composite acid containing muriatic acid and nitric acid at the temperature of between 70 and 85 DEG C under normal pressure in the presence of the oxidizing agent, and filtering; performing extraction, reextraction, sedimentation, filtration and the like on filter liquor to obtain ammonium molybdate; and performing secondary sedimentation, filtration and the like on raffinate to obtain nickel carbonate. The method has the advantages of simple process and equipment, convenient operation and high extraction rate; the recovery rates of nickel and molybdenum are over 90 percent, and the purities of the products ammonium molybdate and nickel carbonate are over 90 percent; and the method is suitable for extracting nickel and molybdenum from black shale ore containing more carbon and oxidized or semi-oxidized symbiotic ore in a nickel silicate state.
Description
(1) technical field: the invention belongs to field of metallurgy and chemical engineering, be specifically related to a kind of method of from nickel-molybdenum symbiotic ore, extracting the nickel molybdenum with low-concentration composite acid and oxygenant.
(2) prior art: nickel-molybdenum symbiotic ore is a kind of based on appositional pattern nickel-molybdenum ore bed, low-grade, amorphous many metals symbiosis complicated ore, wherein nickeliferously is about 0.5%～5%, and molybdenum content is about 1.0%～6%.In this nickel-molybdenum ore bed, contain relatively large graphite and ferric oxide in the ore, and nickel, molybdenum exists with the form of sulfide, be distributed widely in areas such as Hunan Xiang Xibei, zunyi, guizhou and Hubei E Dong.
Because this nickel-molybdenum ore bed is often with ultra-fine granularity and the more black shale ore deposit and symbiosis such as oxidation that is silicon acid nickel state or half oxidized ore of carbon containing, adopt traditional physical concentration method to be difficult to separating nickel and molybdenum, use the pyrometallurgy technology also not reach molybdenum, nickel isolated purpose from ore.In recent years, owing to molybdenum, nickel price constantly raise up, and the scarcity day by day of nickel molybdenum rich ore, the comprehensive utilization of nickel-molybdenum symbiotic ore has caused showing great attention to of people.
At present, the extraction process of nickel molybdenum mainly contains pyrogenic process and wet method two classes in the nickel-molybdenum ore.
Thermal process is to be converted into the compound that is soluble in soda acid behind the desulfurization with roasting technique under the mineral process high temperature, thereby leaches the purpose that reaches extraction with acid-base solution then.Mainly contain methods such as oxidizing roasting, sodium roasting and acidifying slaking roasting, as Chinese patent CN1033784A, CN1177012A etc.Pyrogenic process relates to high temperature desulfurizing, and energy consumption is very high, roasting produces a large amount of SO
2Contaminate environment.
Wet processing is meant that mineral leach through pulverizing back direct oxidation in suitable acid or alkaline solution, comprise that mainly atmospheric pressure oxidation leaches (as Chinese patent CN1267739A, CN1267740A, CN1033784A, CN101086034A, CN101338365A) and high-pressure oxidation leaches modes such as (as Chinese patent CN101323915A, CN101177735A).In general, the high-pressure oxidation lixiviation process is to the equipment requirements height, and investment is big, has limited its widespread use.The atmospheric pressure oxidation lixiviation process, thereby the decomposition of utilization sulfide mineral under acidity or alkaline condition makes the nickel molybdenum enter solution and is extracted, but the acid base concentration of method employing at present is bigger, both the corrosion resistance nature to equipment had higher requirement (increasing the erosion resistance that equipment cost improves equipment), and the waste liquid after extracting needs bigger improvement input, the sulfide that polluting effect is bigger is present in the waste liquid with the form of complexity simultaneously, needs to administer.
About extract the method for nickel molybdenum from nickel-molybdenum symbiotic ore with low-concentration composite acid and oxygenant, Shang Weijian has identical bibliographical information and patented technology.
(3) summary of the invention: purpose of the present invention just provides a kind of method of extracting the nickel molybdenum with low-concentration composite acid and oxygenant from nickel-molybdenum symbiotic ore, present method can be efficiently, economy and environmental friendliness ground extract the nickel molybdenum from nickel-molybdenum symbiotic ore, extraction efficiency height, operational path and equipment are simple, easy to operate, both can realize effective extraction of nickel, molybdenum, not produce tangible environmental pollutants again.
The present invention includes following step:
A. nickel-molybdenum symbiotic ore stone cracker is worn into breeze, standby;
B. in above-mentioned breeze, add the mixed acid solution include 9～14% hydrochloric acid, 7～10% nitric acid and hydrogen peroxide or clorox and stir down in 70～85 ℃ and soaked 2～3 hours, filter, filtrate; Wherein the mass ratio of breeze and mixing acid is 1: 2～4, and the consumption of hydrogen peroxide or clorox is 5%～15% of a powdered ore quality;
C. the kerosin that in above-mentioned filtrate, adds the 2-ethylhexyl phosphoric acid of the tributyl phosphate contain 0.1～0.15 grams per liter sodium phosphate, 5%～10% volume ratio and 3%～8% volume ratio, wherein the volume ratio of filtrate and kerosin is 1.5-2: 1, stirred 15-30 minute, left standstill 40-60 minute, extraction gets extraction liquid;
D. raffinate is pending; Extraction liquid is stripped with the sodium carbonate solution of the 8%-10% mass ratio of its 1/5～1/2 times of volume again, repeat according to this 2～3 times, the amalgamation liquid of repeatedly stripping; Regulating pH with hydrochloric acid is 2～4, adds the ammonium chloride of powdered ore quality 5%～8%, boils insulation 1.5-2.0 hour, and cooled and filtered, washing, drying promptly get ammonium molybdate;
E. regulate above-mentioned raffinate pH to 4～5 with sodium hydroxide solution, left standstill 15-20 minute, filter, get filtrate, in filtrate, add the yellow soda ash of 10% mass percent until NiCO
3Precipitation left standstill 15-20 minute fully, filtered, and precipitation is through washing, be drying to obtain nickelous carbonate.
Described nickel-molybdenum symbiotic ore is a kind of in the more black shale ore deposit type of carbon containing and oxidation that is silicon acid nickel state or the half oxidized ore type symbiotic ore.
Action principle of the present invention is to be many metals symbiosis complicated ore that a kind of nickel, molybdenum exist with amorphousness, gluey sulphided form (mainly showing as ore type such as molybdenum glance, curing nickel minerals, polydymite, nickel glance NiAsS) according to nickel-molybdenum symbiotic ore.These nickel-molybdenum ore stones have bigger solubleness in certain density acidic solution, and in that have can accelerate dissolution in the presence of the oxygenant.And the solubleness of other mineral is less in the nickel-molybdenum symbiotic ore, utilizes these differences can realize separating of nickel molybdenum sulphide and other metal sulfide ore.
The purpose that adds tributyl phosphate and 2-ethylhexyl phosphoric acid in the operation is to promote effective extraction of molybdenum, and the purpose that adds sodium phosphate is to prevent being extracted of tungsten.
Add sodium hydroxide solution in the operation and regulate pH to 4～5 of raffinate, with of the influence of heavy metals such as the small amounts of iron of eliminating stripping in the ore, copper product nickelous carbonate purity.
The present invention has following characteristics:
(1) efficient height, present method can be extracted the nickel molybdenum from nickel-molybdenum symbiotic ore, and the extraction yield of nickel molybdenum is all more than 90%.
(2) product purity height, the ammonium molybdate and the nickelous carbonate of present method preparation, its purity is all more than 90%.
(3) technology, equipment are simple, easy to operate, and running cost is low, and is raw materials used cheap and easy to get.
(4) suitability is wide, present method be applicable to the more black shale ore deposit of carbon containing and be the oxidation of silicon acid nickel state or half oxidized ore in the extraction of nickel molybdenum.
(4) embodiment:
Embodiment 1:
Nickel-molybdenum symbiotic ore in the present embodiment belongs to black shale ore deposit type.After testing, contain 2.42% nickel, 3.71% molybdenum and 21.65% sulphur in this nickel-molybdenum symbiotic ore.Operation in the present embodiment is as follows:
(1) gets 200 grams, 100～150 purpose nickel-molybdenum symbiotic ore powder in beaker, under mechanical stirring, add 400 milliliters of composite acid solution that contain 9～14% hydrochloric acid, 7～10% nitric acid, 70～85 ℃ of heating in water bath and insulation were soaked 2～3 hours behind thorough mixing, divided therebetween to add the commercially available hydrogen peroxide of 30 grams for five times.Cooled and filtered discards filter residue, and filtrate is by follow-up (2) manipulation.
(2) add 200 milliliters and contain 0.1～0.15 grams per liter sodium phosphate, 5%～10% (volume ratio, down together) kerosin of tributyl phosphate and 3%～8%2-ethylhexyl phosphoric acid is in the filtrate that (1) operation produces, mechanical stirring 20-30 minute, left standstill 40-60 minute, extract organic phase (extraction liquid) according to following (3) manipulation, raffinate is according to following (4) manipulation.
(3) divide secondary with 10% (mass ratio) sodium carbonate solution of 1/2 times of extraction volume extraction liquid to be stripped, organic phase recycles after washing, and merges water.The pH that regulate to merge water with hydrochloric acid is 2～4, adds 10 gram ammonium chlorides, boils insulation 1.5 hours, and cooled and filtered, washing, 100 ℃ dry 2 hours down obtain 14.48 gram ammonium molybdate products (rate of recovery of molybdenum is 95.5%).
(4) under the mechanical stirring, regulate pH to 4～5 that (2) operate the raffinate that produces with 10% (mass ratio) sodium hydroxide solution, left standstill 20 minutes, filter, sediment discards.Under the mechanical stirring, slowly add 10% sodium carbonate solution in the filtrate that this step operation produces, until precipitation fully, left standstill 20 minutes, filter, precipitation obtains 9.45 gram nickelous carbonate products (rate of recovery of nickel is 96.7%) through washing, 100 ℃ dry 2 hours down.
After testing, the purity of product ammonium molybdate is 95.08%, and the purity of product nickelous carbonate is 90.13%.
Embodiment 2
The nickel-molybdenum symbiotic ore of present embodiment is identical with embodiment 1.In the present embodiment, under other operation situation identical, in (1) step, be 800ml, and restrain commercially available chlorine bleach liquor with 25 and replace 30 to restrain hydrogen peroxide with the mixing acid consumption that adds with embodiment 1; In (2) step, add 400ml and contain 0.1～0.15 grams per liter sodium phosphate, 5%～10% (volume ratio, down together) kerosin of tributyl phosphate and 3%～8%2-ethylhexyl phosphoric acid is in the filtrate that (1) operation produces, in (3) step, replace 10 gram ammonium chlorides with 16 gram ammonium chlorides, can obtain the effect close with embodiment 1, the rate of recovery of ammonium molybdate, nickelous carbonate (purity) is respectively 95.29% (94.73%), 95.76% (90.32%).
Embodiment 3
Nickel-molybdenum symbiotic ore in the present embodiment belongs to oxidation or half oxidized ore type.After testing, contain 3.57% nickel, 4.73% molybdenum and 16.77% sulphur in this nickel-molybdenum symbiotic ore.
Press embodiment 1 identical operations program, in (1) step, add and contain 11～12% hydrochloric acid, the composite acid solution of 8～9% nitric acid, in (2) step, add and contain 0.12 grams per liter sodium phosphate, 8% (volume ratio, the kerosin of tributyl phosphate and 6%2-ethylhexyl phosphoric acid down together), in (3) step, it is stripped with 10% (mass ratio) sodium carbonate solution of 1/5 times of volume of extraction liquid, all the other processing condition and consumption be with embodiment 1, the ammonium molybdate of gained, the rate of recovery of nickelous carbonate (purity) is respectively 92.14% (92.41%), 91.76% (90.58%).
Claims (2)
1. one kind is extracted the method for nickel molybdenum with low-concentration composite acid and oxygenant from nickel-molybdenum symbiotic ore, it is characterized in that comprising the steps:
A. nickel-molybdenum symbiotic ore stone cracker is worn into breeze, standby;
B. in above-mentioned breeze, add the mixed acid solution include 9～14% hydrochloric acid, 7～10% nitric acid and hydrogen peroxide or clorox and stir down in 70～85 ℃ and soaked 2～3 hours, filter, filtrate; Wherein the mass volume ratio of breeze and mixing acid is 1: 2～4, and the consumption of hydrogen peroxide or clorox is 5%～15% of a powdered ore quality;
C. the kerosin that in above-mentioned filtrate, adds the 2-ethylhexyl phosphoric acid of the tributyl phosphate contain 0.1～0.15 grams per liter sodium phosphate, 5%～10% volume ratio and 3%～8% volume ratio, wherein the volume ratio of filtrate and kerosin is 1.5-2: 1, stirred 15-30 minute, left standstill 40-60 minute, extraction gets extraction liquid; Raffinate is pending;
D. extraction liquid is stripped with the sodium carbonate solution of the 8%-10% mass ratio of its 1/5～1/2 times of volume again, repeat according to this 2～3 times, the amalgamation liquid of repeatedly stripping; Regulating pH with hydrochloric acid is 2～4, adds the ammonium chloride of powdered ore quality 5%～8%, boils insulation 1.5-2.0 hour, and cooled and filtered, washing, drying promptly get ammonium molybdate;
E. regulate above-mentioned raffinate pH to 4～5 with sodium hydroxide solution, left standstill 15-20 minute, filter, get filtrate, in filtrate, add the yellow soda ash of 10% mass percent until NiCO
3Precipitation left standstill 15-20 minute fully, filtered, and precipitation is through washing, be drying to obtain nickelous carbonate.
2. according to claim 1ly a kind ofly extracts the method for nickel molybdenum with low-concentration composite acid and oxygenant from nickel-molybdenum symbiotic ore, it is characterized in that: described nickel-molybdenum symbiotic ore is a kind of in the more black shale ore deposit type of carbon containing and oxidation that is the sour nickel state of silicon or the half oxidized ore type symbiotic ore.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910062431XA CN101906538B (en) | 2009-06-08 | 2009-06-08 | Method for extracting nickel and molybdenum from nickel-molybdenum symbiotic ore by low-concentration composite acid and oxidizing agent |
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| CN200910062431XA CN101906538B (en) | 2009-06-08 | 2009-06-08 | Method for extracting nickel and molybdenum from nickel-molybdenum symbiotic ore by low-concentration composite acid and oxidizing agent |
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| CN101906538B CN101906538B (en) | 2011-11-02 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154546A (en) * | 2011-03-11 | 2011-08-17 | 贵州大学 | Method for smelting molybdenum-nickel mineral association by wet process |
| CN102808082A (en) * | 2011-05-30 | 2012-12-05 | 深圳市格林美高新技术股份有限公司 | Method for selective leaching separation of cobalt, nickel and molybdenum from high grade cobalt-nickel-molybdenum waste material |
| CN103866116A (en) * | 2014-03-27 | 2014-06-18 | 西北有色金属研究院 | Method for oxidizing molybdenum concentrate |
| CN103993169A (en) * | 2014-06-06 | 2014-08-20 | 中南大学 | Catalytic oxidation pressure acid leaching decomposition method of nickel-molybdenum ore |
| CN105506278A (en) * | 2015-12-18 | 2016-04-20 | 中南大学 | Method for leaching nickel and molybdenum from nickel-molybdenum ore |
| CN115478179A (en) * | 2022-09-23 | 2022-12-16 | 金堆城钼业汝阳有限责任公司 | Molybdenum selection process production technology based on industry big data and method thereof |
| CN115478177A (en) * | 2022-08-30 | 2022-12-16 | 广东省科学院资源利用与稀土开发研究所 | Method for efficiently extracting vanadium, molybdenum and nickel from multi-metal vanadium shale |
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2009
- 2009-06-08 CN CN200910062431XA patent/CN101906538B/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154546A (en) * | 2011-03-11 | 2011-08-17 | 贵州大学 | Method for smelting molybdenum-nickel mineral association by wet process |
| CN102808082A (en) * | 2011-05-30 | 2012-12-05 | 深圳市格林美高新技术股份有限公司 | Method for selective leaching separation of cobalt, nickel and molybdenum from high grade cobalt-nickel-molybdenum waste material |
| CN102808082B (en) * | 2011-05-30 | 2014-07-02 | 深圳市格林美高新技术股份有限公司 | Method for selective leaching separation of cobalt, nickel and molybdenum from high grade cobalt-nickel-molybdenum waste material |
| CN103866116A (en) * | 2014-03-27 | 2014-06-18 | 西北有色金属研究院 | Method for oxidizing molybdenum concentrate |
| CN103866116B (en) * | 2014-03-27 | 2015-11-04 | 西北有色金属研究院 | A kind of method for oxidation of concentrated molybdenum ore |
| CN103993169A (en) * | 2014-06-06 | 2014-08-20 | 中南大学 | Catalytic oxidation pressure acid leaching decomposition method of nickel-molybdenum ore |
| 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 |
| CN105506278A (en) * | 2015-12-18 | 2016-04-20 | 中南大学 | Method for leaching nickel and molybdenum from nickel-molybdenum ore |
| CN105506278B (en) * | 2015-12-18 | 2018-03-06 | 中南大学 | A kind of method from nickel-molybdenum ore leaching nickel and molybdenum |
| CN115478177A (en) * | 2022-08-30 | 2022-12-16 | 广东省科学院资源利用与稀土开发研究所 | Method for efficiently extracting vanadium, molybdenum and nickel from multi-metal vanadium shale |
| CN115478179A (en) * | 2022-09-23 | 2022-12-16 | 金堆城钼业汝阳有限责任公司 | Molybdenum selection process production technology based on industry big data and method thereof |
| CN115478179B (en) * | 2022-09-23 | 2024-02-20 | 金堆城钼业汝阳有限责任公司 | Production process and method for molybdenum selection based on industry big data |
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