CN105755282A - Method for simultaneously treating submarine cobalt manganese oxide resources and multi-metal sulfides - Google Patents

Method for simultaneously treating submarine cobalt manganese oxide resources and multi-metal sulfides Download PDF

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Publication number
CN105755282A
CN105755282A CN201610320366.6A CN201610320366A CN105755282A CN 105755282 A CN105755282 A CN 105755282A CN 201610320366 A CN201610320366 A CN 201610320366A CN 105755282 A CN105755282 A CN 105755282A
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cobalt
seabed
manganese
ore deposit
copper
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Inventor
张登高
蒋训雄
汪胜东
范艳青
冯林永
蒋伟
刘巍
靳冉公
李达
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Beijing General Research Institute of Mining and Metallurgy
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Beijing General Research Institute of Mining and Metallurgy
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Priority to CN201610320366.6A priority Critical patent/CN105755282A/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • C22B47/0018—Treating ocean floor nodules
    • C22B47/0045—Treating ocean floor nodules by wet processes
    • C22B47/0054—Treating ocean floor nodules by wet processes leaching processes
    • C22B47/0063—Treating ocean floor nodules by wet processes leaching processes with acids or salt solutions

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Ocean & Marine Engineering (AREA)
  • Oceanography (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a novel method for simultaneously treating a seabed cobalt manganese oxide resource and a polymetallic sulfide, which has the main process flow of crushing. The method mainly comprises the following steps: respectively crushing the seabed cobalt manganese oxide and the polymetallic sulfide; blending the two crushed minerals according to a certain proportion; grinding the prepared minerals finely; leaching the ground ore with sulfuric acid; and after leaching, carrying out liquid-solid separation to obtain a solution containing nickel, cobalt, copper, manganese and iron, and carrying out conventional metallurgical treatment on the leaching solution to respectively obtain nickel, cobalt, copper and manganese products. The acid leaching process is carried out under normal pressure without additional additives, thereby avoiding the existence of CO and SO in the existing seabed cobalt manganese oxide wet treatment process2And ammonia volatilization and other environmental pollution problems. Meanwhile, the problem of processing seabed mineral resources with different properties by one process is solved. The new process has the advantages of environmental friendliness, cooperative development and utilization of various seabed resources with different properties and high comprehensive utilization rate of resources.

Description

A kind of method simultaneously processing seabed cobalt and manganese oxide resource and Polymetallic sulphide
Technical field
The invention belongs to non-ferrous metallurgy technology field, relate to one and process seabed manganese cobalt/cobalt oxide resource and many metals sulfur simultaneously The new technology of compound.
Background technology
The grand strategy resources such as abundant mineral metal products are contained in seabed, ocean, be world development and resources must So selecting, explored metal class mineral have the seabed such as polymetallic nodules, cobalt bearing crust cobalt and manganese oxide, Polymetallic sulphide etc..
Manganese amount of metal at the bottom of the Pacific Ocean is in the manganese ore of explored land 470 times of manganese metal.Further, estimating according to J.L.Mero Calculating, the tuberculosis reserves on whole Oceanic Bottom surface reach 3,000,000,000,000 tons, and wherein 1.7 trillion tons of taxes are stored in the Pacific Ocean, and the most nickeliferous 14,600,000,000 Ton, copper 7,700,000,000 tons, cobalt 9,000,000,000 tons, 485,200,000,000 tons of manganese, simultaneously possibly together with substantial amounts of precious metals pt and rare earth compound.
The tuberculosis ore deposit that the polymetallic nodules only Pacific Ocean is just new to increase the speed output of 10,000,000 tons every year newly.With deep sea polymetallic nodule The sea-bottom deposit mineral being main are the metals resources storehouses that the following mankind are huge, are one of the most noticeable current potential mineral resources.
Cu in Co-rich crust content is usually 0.4%～1.2%, and part may be up to 2%, is land primary ore cobalt grade decades of times, Additionally rich in nickel, manganese, rare earth, titanium, platinum, molybdenum, zinc etc., according to incompletely statistics, only west of pacific ocean volcanic structure is swelled On band, the potential resources in cobalt bearing crust mineral deposit reaches 1,000,000,000 tons, and cobalt amount of metal reaches millions of tons.
Seabed Polymetallic sulphide is another seabed Polymetallic Minerals resource after polymetallic nodules, cobalt bearing crust, rich in Cu, The metallic element such as Fe, Zn, Mn, Pb and Ag, Au, Co, Mo and yttrium, the resource of single sulfide deposit Amount maximum can reach 1.0 × 108t.Have and be prone to smelt and the huge advantage of stock number is it is considered to be the most the earliest by mankind institute One of deep sea mineral resources utilized.
Polymetal Sulphide Ores can be divided into two classes by occurrence: a class is loose containing metal deposit, such as Red sea in earthy output Containing metal deposit (metal ooze)；Another kind of is the hard massive sulphide consolidated, and sprays and spoils over oceanic ridge " black smoke cylinder " hydrothermal solution Deposition is relevant, such as East Pacific ridge massive sulphide.According to chemical composition can be divided into four classes: the first kind rich in cadmium, copper and Silver, originates in Eastern Pacific's Galapagos ridge；Equations of The Second Kind, rich in silver and zinc, originates in Hu Andefuka submarine ridge and melon Asia Maas sea Basin；3rd class is enriched in copper and zinc；4th class is rich in zinc and gold, output time similar with the 3rd.
According to estimates, the whole world there are about the seabed of 100,000,000 sq-kms and is dispersed with the hydrothermal deposit of ooze shape, and they increased with every 4 years The speed development of 5 millimeters, copper one contained in metal ooze can have a net increase of 50,000 tons every year.
Up to now, having formed multiple more ripe smelting process for seabed manganese cobalt/cobalt oxide resource, representative processes has also Former roasting-ammonia leaching process, High Temperature High Pressure sulfuric acid leaching, melting sulfuration solvent extraction method, cuprous ion ammonia leaching process, Activating sulfuric acid leaching method, Normal temperature and pressure hydrochloric acid leaching process, low-temperature aqueous solution catalysis reduction ammonia-leaching method, melting corrosion extraction etc..Although seabed Manganese cobalt/cobalt oxide resource smelting process is more, but each method all cannot realize the effective process to seabed different resource.
Both at home and abroad seabed Polymetallic sulphide study and report more for its geologic feature, the origin cause of formation, submarine hydrothermal solution mineralization machanism Etc. aspect.But, for Polymetallic sulphide the most untapped go out a feasible smelting extraction process.
Summary of the invention
The present invention is directed to above process seabed cobalt and manganese oxide resources technology present situation and the deficiency of existence, it is proposed that one processes simultaneously Seabed manganese cobalt/cobalt oxide resource and the new method of Polymetallic sulphide.This technique acidleach process is carried out at ambient pressure, without additional interpolation Agent, has evaded existing seabed cobalt and manganese oxide wet processing process and there is CO, SO2And the problem of environmental pollution such as ammonia volatilization.With Time achieve a kind of PROCESS FOR TREATMENT heterogeneity Deep Sea Minerals problem.New technology has environmental friendliness, heterogeneity seabed The co-development of resource utilizes, the advantage that comprehensive resource utilization rate is high.
In the cobalt and manganese oxide resource of seabed, due to manganese mainly with δ-MnO2State exists, and manganese is with Mn4+Form exists, other gold Belong to element, as nickel, cobalt, copper be then primarily present in rich manganese mutually in；To extract nickel, cobalt, copper, the ore deposit of raw material need to be destroyed Thing structure, i.e. makes Mn with reducing agent4+It is reduced to solvable Mn2+.Based on cobalt and manganese oxide ore deposit, seabed, there is oxidisability, and many In metal sulfide, metal is many presented in sulfide, such as contains pyrite, Chalkopyrite, sphalerite and galena etc., Sulfide sulfur at a middle or low price has reproducibility.
It is an object of the invention to be achieved through the following technical solutions.
A kind of process seabed manganese cobalt/cobalt oxide resource and the new method of Polymetallic sulphide simultaneously, it is characterised in that include following step Rapid:
(1) respectively seabed manganese cobalt/cobalt oxide, Polymetallic sulphide are crushed.
(2) ore deposit is joined in two kinds of ore deposits after crushing by a certain percentage.
(3) ore deposit prepared carries out levigate process.
(4) levigate ore deposit carries out sulfuric acid leaching.
(5) leach complete, carry out solid-liquor separation, obtain nickeliferous, the solution of cobalt, copper, manganese, ferrum, at leachate conventional metallurgical Reason respectively obtains nickel, cobalt, copper, manganese product.
In step (1), respectively seabed manganese cobalt/cobalt oxide, Polymetallic sulphide are crushed to below grain diameter 3mm.
In step (2), (butt) is by seabed manganese cobalt/cobalt oxide by weight: Polymetallic sulphide=1:0.1-1:2 carries out joining ore deposit.
In step (3), levigate rear mineral granularity at below 0.074mm not less than 50%.
In step (4), react liquid-solid ratio water by weight: ore deposit=1:1-5:1, sulphuric acid is the 0.3-1 in ore deposit weight (butt) Times, reaction temperature 50-100 DEG C, response time 1-5h.
In the present invention, unless otherwise indicated beyond, ratio, percentage ratio are quality criteria.
The present invention utilizes seabed manganese cobalt/cobalt oxide as oxidant, leaches with Polymetallic sulphide simultaneously, has both solved seabed manganese cobalt The problem of oxide reduction, solve again oxidant during Polymetallic sulphide Oxidation Leaching carrys out source problem.
The method that the present invention provides, acidleach process is carried out at ambient pressure, without outer doping, has evaded the cobalt manganese oxidation of existing seabed There is CO, SO in thing wet processing process2And the problem of environmental pollution such as ammonia volatilization；It is simultaneously achieved a kind of PROCESS FOR TREATMENT dissimilarity Matter Deep Sea Minerals；The method has environmental friendliness, and the co-development of multiple heterogeneity seabed resources utilizes, resource comprehensive The advantage that utilization rate is high.
Detailed description of the invention
The present invention provides a kind of and processes seabed manganese cobalt/cobalt oxide resource and the new method of Polymetallic sulphide, respectively by seabed manganese simultaneously Cobalt/cobalt oxide and Polymetallic sulphide are crushed to about 3mm, and the mineral after crushing are by weight by seabed manganese cobalt/cobalt oxide: golden Belonging to sulfide=1:0.1-1:2 to carry out joining ore deposit, the particle size-0.074mm after the ore deposit for preparing is levigate is not less than 50%.Leach reaction Liquid-solid ratio water by weight: ore deposit=1:1-5:1, sulphuric acid is 0.3-1 times of ore deposit weight (butt), controls reaction temperature 50 DEG C -100 DEG C, leaching under the conditions of response time 1-5h, reaction carries out solid-liquor separation after terminating, obtain nickeliferous, cobalt, copper, manganese, The solution of ferrum.Leachate conventional metallurgical processes and respectively obtains nickel, cobalt, copper, manganese product.
Embodiment 1
Seabed manganese cobalt/cobalt oxide and Polymetallic sulphide are crushed to 3mm, and the mineral after crushing are by weight by seabed manganese cobalt oxidation Thing: Polymetallic sulphide=1:0.1 carries out joining ore deposit, after the mill of the ore deposit prepared, particle diameter accounts for 60% at below 0.074mm, leaches reactant liquor Gu than water by weight: ore deposit=5:1, sulphuric acid is 0.3 times of ore deposit weight, reaction temperature 50 DEG C, under response time 1h, nickel, Cobalt, copper, manganese, ferrum leaching rate are respectively 70.47%, 51.19%, 55.31%, 53.51%, 40.65%.
Embodiment 2
Seabed manganese cobalt/cobalt oxide and Polymetallic sulphide are crushed to 3mm, and the mineral after crushing are by weight by seabed manganese cobalt oxidation Thing: Polymetallic sulphide=1:0.5 carries out joining ore deposit, after the mill of the ore deposit prepared, particle diameter accounts for 80% at below 0.074mm, leaches reactant liquor Gu than water by weight: ore deposit=5:1, sulphuric acid is 0.8 times of ore deposit weight；Reaction temperature 90 DEG C, under response time 5h, Nickel, cobalt, copper, manganese, ferrum leaching rate are respectively 99.36%, 99.04%, 47.52%, 99.82%, 40.56%.
Embodiment 3
Seabed manganese cobalt/cobalt oxide and Polymetallic sulphide are crushed to 3mm, and the mineral after crushing are by weight by seabed manganese cobalt oxidation Thing: Polymetallic sulphide=1:1.5, after the mill of the ore deposit prepared, particle diameter accounts for 85% at below 0.074mm, leaches reaction liquid-solid ratio with weight Gauge water: ore deposit=3:1, sulphuric acid is 1 times of ore deposit weight；Reaction temperature 98 DEG C, under response time 5h, nickel, cobalt, copper, Manganese, ferrum leaching rate are respectively 99.81%, 99.14%, 33.71%, 99.81%, 46.43%.
Embodiment 4
Seabed manganese cobalt/cobalt oxide and Polymetallic sulphide are crushed to 3mm, and the mineral after crushing are by weight by seabed manganese cobalt oxidation Thing: Polymetallic sulphide=1:2 carries out joining ore deposit, after the mill of the ore deposit prepared, particle diameter accounts for 90% at below 0.074mm, leaches reactant liquor Gu than water by weight: ore deposit=1:1, sulphuric acid is 1 times of ore deposit weight；Reaction temperature 98 DEG C, under response time 5h, nickel, Cobalt, copper, manganese, ferrum leaching rate are respectively 99.86%, 99.37%, 33.10%, 99.88%, 54.24%.
Embodiment 5
Seabed manganese cobalt/cobalt oxide and Polymetallic sulphide are crushed to 3mm, and the mineral after crushing are by weight by seabed manganese cobalt oxidation Thing: Polymetallic sulphide=1:0.5 carries out joining ore deposit, after the mill of the ore deposit prepared, particle diameter accounts for 95% at below 0.074mm, leaches reactant liquor Gu than water by weight: ore deposit=3:1, sulphuric acid is 0.6 times of ore deposit weight；Reaction temperature 70 DEG C, under response time 3h, Nickel, cobalt, copper, manganese, ferrum leaching rate are respectively 93.46%, 90.37%, 47.70%, 96.78%, 39.70%.
Embodiment 6
Seabed manganese cobalt/cobalt oxide and Polymetallic sulphide are crushed to 3mm, and the mineral after crushing are by weight by seabed manganese cobalt oxidation Thing: Polymetallic sulphide=1:0.5 carries out joining ore deposit, after the mill of the ore deposit prepared, particle diameter accounts for 90% at below 0.074mm, leaches reactant liquor Gu than water by weight: ore deposit=2:1, sulphuric acid is 0.6 times of ore deposit weight；Reaction temperature 90 DEG C, under response time 2h, Nickel, cobalt, copper, manganese, ferrum leaching rate are respectively 99.17%, 99.20%, 48.75%, 99.45%, 42.36%.

Claims (5)

1. one kind processes seabed cobalt and manganese oxide resource and the method for Polymetallic sulphide simultaneously, it is characterised in that comprise the following steps:
(1) respectively seabed cobalt and manganese oxide, Polymetallic sulphide are crushed；
(2) two kinds of mineral after crushing join ore deposit by a certain percentage；
(3) mineral prepared carry out levigate；
(4) levigate ore deposit is carried out sulfuric acid leaching；
(5) leach complete, solid-liquor separation, obtain nickeliferous, the solution of cobalt, copper, manganese, ferrum, leachate conventional metallurgical process respectively obtain nickel, Cobalt, copper, manganese product.
Method the most according to claim 1, it is characterised in that in step (1), seabed manganese cobalt/cobalt oxide, Polymetallic sulphide are crushed to Grain diameter is at below 3mm.
Method the most according to claim 1, it is characterised in that in step (2), described ratio is, with dry basis: seabed manganese cobalt Oxide: Polymetallic sulphide=1:0.1-1:2.
Method the most according to claim 1, it is characterised in that the levigate rear grain diameter of mineral prepared in step (3) 0.074mm with Under not less than 50%.
Method the most according to claim 1, it is characterised in that in step (4), leaches and reacts liquid-solid ratio water by weight: ore deposit=1:1-5:1, Sulphuric acid is 0.3-1 times of butt ore deposit weight, reaction temperature 50-100 DEG C, response time 1-5h.
CN201610320366.6A 2016-05-14 2016-05-14 Method for simultaneously treating submarine cobalt manganese oxide resources and multi-metal sulfides Pending CN105755282A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106282600A (en) * 2016-08-30 2017-01-04 北京矿冶研究总院 Novel metallurgy process of deep-sea polymetallic sulfide
CN110923441A (en) * 2019-12-10 2020-03-27 北京矿冶科技集团有限公司 Co-Mn multi-metal oxidized ore and seabed multi-metal sulfide combined metallization recovery method
CN111172412A (en) * 2020-01-17 2020-05-19 北京矿冶科技集团有限公司 Method for extracting manganese and comprehensively recovering nickel, cobalt and copper by cobalt-manganese multi-metal oxide ore dressing and smelting
CN116624152A (en) * 2023-06-29 2023-08-22 自然资源部第一海洋研究所 In-situ separation device for deep sea polymetallic nodules and loose sediments

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CN104805310A (en) * 2015-04-17 2015-07-29 北京矿冶研究总院 Method for leaching cobalt from high-valence cobalt oxide-containing raw material

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106282600A (en) * 2016-08-30 2017-01-04 北京矿冶研究总院 Novel metallurgy process of deep-sea polymetallic sulfide
CN110923441A (en) * 2019-12-10 2020-03-27 北京矿冶科技集团有限公司 Co-Mn multi-metal oxidized ore and seabed multi-metal sulfide combined metallization recovery method
CN110923441B (en) * 2019-12-10 2021-08-24 矿冶科技集团有限公司 Co-Mn multi-metal oxidized ore and seabed multi-metal sulfide combined metallization recovery method
CN111172412A (en) * 2020-01-17 2020-05-19 北京矿冶科技集团有限公司 Method for extracting manganese and comprehensively recovering nickel, cobalt and copper by cobalt-manganese multi-metal oxide ore dressing and smelting
CN116624152A (en) * 2023-06-29 2023-08-22 自然资源部第一海洋研究所 In-situ separation device for deep sea polymetallic nodules and loose sediments

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