CN1172167A - Smelting-rusting-extraction method for extracting valuable metals from ocean polymetallic nodule - Google Patents
Smelting-rusting-extraction method for extracting valuable metals from ocean polymetallic nodule Download PDFInfo
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Abstract
A process for extracting valuable metals from the ocean polymetallic nodule includes baking and breaking the nodule, reducing and smelting the nodule to directly obtain Mn-enriched dregs, breaking molten alloy into fine powder, and ordinary-pressure rust leaching of alloy powder under the action of catalyst to obtain Fe-W deposit for gravitational separation to obtain iron oxide and coarse W powder. The leachate is extracted by different extracting agents, and is subjected to back extraction and electrodeposition under different conditions to obtain cathode copper and cathode nickel. Wherein, the back extraction solution of manganese is precipitated by ammonium bicarbonate to obtain manganese carbonate, the back extraction solution of cobalt is precipitated by ammonium oxalate to obtain cobalt oxalate, and the cobalt oxalate is calcined to obtain cobalt oxide powder. The method can effectively recover six valuable metals.
Description
The present invention relates to field of metallurgy and chemical engineering and handle a kind of novel method of oceanic multi-metal nodule.
Oceanic multi-metal nodule claims manganese nodule again, is a kind of complex oxide mineral of crystallite attitude, needs more special method to handle.For this reason, many in the world relevant scientific and technical personnel studied many treatment processs.Wherein, it is generally acknowledged the five kinds of methods that have of industrial prospect, that is:
(1), reduction ammonia-leaching method.The basic technology of this method is: the tuberculosis ore deposit is dried through fragmentation, under 625 ℃ condition, with containing CO and H
2The mixed gas reducing roasting after, use NH
3And CO
2Solution leach, soak to pile after the slag ammonia still process and abandon; Leach liquor is with 10%Lix64N-kerosene extraction copper, copper scrap electrolytic solution back extraction copper, electro deposited copper again, the surplus liquid of collection copper with 40%Lix64N-kerosene collection nickel, useless nickel electrolyte back extraction after electro deposited nickel, the surplus liquid of collection nickel is with the heavy cobalt of hydrogen sulfide.Its precipitation leaches the back under 35 normal atmosphere and 245 ℃ of conditions with sulfuric acid, goes out cobalt powder with hydrogen reduction.The product structure of this method is for reclaiming three kinds of metals.By tuberculosis to the metal recovery rate of product is (%): Ni90, Cu95, Co85.
(2) cuprous from ammonia leaching process.This direct leaching owned by France.Its principle technology is: sized mixing with seawater and the ammonia sal volatile that contains cuprous ion in levigate back, tuberculosis ore deposit, feed and be rich in CO and H
250 ℃ of mixed gass under reduce leaching.Ammonia that leached mud steams and CO
2Return the front and leach, contain manganous carbonate, iron and silicon-dioxide in the tailings; Leach liquor is with Lix64N-kerosene come together altogether copper, nickel, respectively back extraction again electrodeposition reclaim copper and mickel, raffinate leads to H
2S precipitate cobalt, cobaltous sulfide precipitate with behind the sulfuric acid dissolution, pressurized hydrogen reduce cobalt powder.
(3) High Temperature High Pressure sulfuric acid leaching [seeing that containing the dense grade in osmanthus translates, deep-sea mining technology collected works, P45, Chinese ocean Mineral resources research and development association 1995].The basic condition of this method is: behind the tuberculosis that will the wet ore grinding, mixes, under 230 ℃ and 35 normal atmosphere, leaches with sulfuric acid, and most copper, nickel and cobalt dissolving, and iron and manganese do not dissolve substantially, residue in the slag.Leach liquor is successively used Lix64N-kerosene collection copper, collection nickel, uses corresponding waste electrolyte back extraction respectively, and electrodeposition reclaims again, and the surplus liquid of collection nickel is used the hydrogen sulfide precipitate cobalt again, cobaltous sulfide with hot sulfuric acid dissolution after, adopt the pressurized hydrogen reducing process to reduce cobalt.The product structure of this technology is that pan belongs to Ni.Cu.Co.Full-range metal recovery rate (%) is: Ni92.Cu80.Co67.
(4) reduction salt acid leaching process.This method also belongs to direct leaching.Water spray cooling rapidly after the chlorination in 50 ℃ of scopes, is carried out with hydrogen chloride gas in the tuberculosis ore deposit after levigate drying, nickel, cobalt, manganese, copper and small amounts of iron enter solution, most of molten iron dissolution precipitation.With liquid ion exchanger extracting copper from solution, back extraction electrodeposition again.Collection copper surplus liquid is with tertiary amine come together cobalt, back extraction.Use H again
2S is precipitate cobalt from anti-cobalt liquid, makes it to separate with manganese; With the liquid ion exchanger nickel that from collection cobalt surplus liquid, comes together, desorb, electro deposited nickel.Carry the surplus liquid of surplus liquid of nickel and heavy cobalt and merge, evaporative crystallization goes out Manganous chloride tetrahydrate, the Manganous chloride tetrahydrate drying, and the high temperature fused salt electrolysis gets manganese metal again.The product structure of this technology is for producing four kinds of metals.The whole process metal recovery rate is: Ni95, Cu90, Co90, Mn87.
(5) melting-sulfuration-lixiviation process [seeing R.Sridhar, et al, Journal ofMetals, April.1976, P32-37].This method is a kind of method of studying maximum, pyrogenic process and wet method combined recovery manganese, nickel, cobalt, four kinds of metals of copper.The principle technology of this method is: after the broken oven dry of tuberculosis, join carbon prereduction under, about 1400 ℃, melt separation greater than 900 ℃ temperature, the molten alloy of rich manganese slag and nickel, copper, cobalt, iron.Wherein the manganese more than 95% enters rich manganese slag (can refine manganese alloy), and alloy adds the sulfurous iron ore sulfuration about 1380 ℃, reoxidize the blowing deironing, gets nickel ice sulfonium.Nickel ice sulfonium carries out the oxygen enrichment pressurization and leaches (sulfuric acid system) through fragmentation.Leach liquor is with the Lix64N copper that comes together, and electro deposited copper after the back extraction is again by Lix64N extraction, back extraction, electrodeposition, extract nickel from the surplus liquid of collection copper.Reclaim cobalt from raffinate through hydrogen sulfide precipitation, sulfuric acid dissolution and High Pressure Hydrogen reduction then.Whole process metal recovery rate (%) is: Ni94, Cu85, Co85, Mn75.
The purpose of this invention is to provide a kind of advanced practical oceanic multi-metal nodule treatment process.Aforesaid the whole bag of tricks respectively has relative merits.Two ammonia leaching processes in low temperature (50 ℃), under the normal pressure selectivity leach nickel, cobalt, copper, do not leach ferromanganese, reagent corrosion is little, and cheaply easily reclaims.But their the cobalt leaching yield and the rate of recovery are low, can not or seldom reclaim manganese, and the kish amount is bigger, make waste residue refractory reason.After the reducing roasting ammonia leaching process is dried the tuberculosis ore deposit, roasting in 450 ℃～750 ℃ temperature range, energy consumption height; The High Temperature High Pressure sulfuric acid leaching, the ore drying-free directly leaches, Cu, Ni and Co leaching yield height, ferrimanganic leaches few, and reliability of technology is big.But its reagent expense costliness, consumption is big, and corrodibility is strong, needs to use anti-corrosion pressure-resistant equipment; The rate of recovery height of reduction salt acid leaching process cobalt, nickel, copper, four kinds of metals of manganese, reagent is cheap and easy to get.Shortcoming is to need corrosion resistant material and equipment, and reclaims the technology and equipment complexity, investment height of manganese and hydrochloric acid.
But melting-sulfuration-lixiviation process high efficiente callback manganese, nickel, cobalt and copper, wherein manganese product is worth and accounts for half.This method is applicable to different content and dissimilar tuberculosis ore deposits, and treatment capacity is big.But long flow path, the energy consumption height is if directly leaching then has the tough and tensile difficult broken problem of alloy.
Substance of the present invention is seen technical process shown in Figure 1.It is by several master operations and relevant device and show its characteristics.
(1) reduction-melting of manganese nodule.At reduction phase, manganese nodule is dried to moisture＜10%, be crushed to-30～60 orders, add coke powder 3～10%, ground silica 0～5% mixes the group of pressure, and its pelletizing diameter is 10～30mm.This pelletizing carries out reducing roasting under 800～1000 ℃ temperature.Roasting time was generally 0.5～3.0 hour.The melting equipment used is a crucible oven, and the temperature of fusion of material is 1300～1500 ℃, obtains the alloy and the rich manganese slag of nickeliferous, copper, cobalt, iron and a small amount of manganese of molten state, both nationality difference of specific gravity and separating.The composition range that institute gets alloy is (%): Cu 3-13, and Co 2-4, Ni 5-16, Mn 1-4, Fe 60-85, P 1-1.5, W 0.05; The rate of recovery of valuable metal (%) is in the alloy: Cu 98～99, Co 98-99.5, Ni 98-99.5, Mn 2-5, Fe 85-98, P 50-70; The composition (%) of the rich manganese slag of gained is: Cu trace-0.02, Co trace-0.009, Ni trace-0.03, Mn 36-41, Fe 0.6-1.5, P 0.01-0.10; The metal in the dreg rate of recovery (%): Cu 0.5～2, Co 0.5-1.5, Ni 1-2, Mn 94-98, Fe 3-5, P 2-4, W 0.5-2.0.
(2) preparation of powdered alloy.The alloy of molten state is sent into special atomisation unit fragmentation make powder.In this device, molten alloy is that the pressurized air of 0.4-2.0MPa carries out primary fragmentation by pressure, carry out " secondary breaking " again on the metal rotary disk of water-cooled high speed rotating, water coolant plays dual parts crushing medium and heat-eliminating medium simultaneously with the rotating disk high-speed motion.Powder size is-60～-150 orders.
(3) alloy leaches.Utilize the difference of the electrochemical activity command of different metal in the alloy, in the aqueous solution, constitute galvanic cell, with powdered alloy is (in 0.1～3N) the hydrochloric acid or sulphuric acid soln in concentration, controlled temperature is in the temperature range of room temperature to 100 ℃, blasting air or oxygen-rich air carries out corrosion and leaches and to make the iron in the alloy transfer iron oxide precipitation fully to, iron in the solution is trace, and nickel, copper, cobalt, manganese then all enter solution.PH span of control in the system is 2～4.
For improving the speed of gas---liquid---solid phase reaction, guarantee the abundant reaction of alloy, corrosion, leaching are to carry out in special stirred reactor, air evenly blasts from the stirring arm below of reactor.Agitator can be individual layer, also can be bilayer and multilayer.The pattern of agitator blades can be turbine type or propeller formula or open turbine type.Stirring velocity is that per minute 200～2000 changes.Leach fully for the corrosion that guarantees alloy, require to be reflected in the suitable medium to carry out, and add appropriate amount of catalysts.The system medium is 0.1～3 mol hydrochloric acid or sulfuric acid.Liquid-solid ratio during leaching is (L/S) 2: 1～20: 1.The consumption of acid is when nickel, copper, cobalt, manganese become divalent by zeroth order in the alloy, 50～200% of theoretical acid consumption.Catalyzer can be various salts, for example sodium salt, ammonium salt, molysite, mantoquita or manganese salt.The catalyzer add-on is 5～200 grams per liter solution, and it is different and different to look alloy ingredient.Deposited the most of tungsten in the raw material in the throw out of corrosion,, separated, obtained the black slag of rich tungsten through gravity treatment as raw material.The average tungstenic amount of this slag reaches about 90%.
(4) extracting and separating.With different extraction system separating copper, manganese, cobalt, nickel one by one from the corrosion leach liquor, obtain each monometallic pure solution.
With the kerosin extracting copper of hydroxyl oximes extraction agent Lix64N or N-510, Lix984,, get the sulfate liquor of copper with copper scrap electrolytic solution (anolyte) back extraction;
The relevant extraction agent of surplus liquid of collection copper, as the kerosin that mixes 5～9 carbon fatty acids, two-(2-ethylhexyl) phosphoric acid or 2-ethylhexyl phosphonic acids list (2-ethylhexyl) ester sodium salt extracts manganese, with dilute sulphuric acid or dilute hydrochloric acid washing and back extraction, obtain purified manganese solution;
The surplus liquid of collection manganese adds muriate and adjusts chlorine ion concentration (to＞190 grams per liters), and with the kerosin collection cobalt of N235 etc., the dilute hydrochloric acid back extraction obtains purified cobalt liquor again.
The surplus liquid of collection cobalt with useless nickel electrolyte (anolyte) back extraction nickel, gets pure nickel sulfate solution with the kerosin extraction of nickel of phosphorated cationic exchange extraction agent.
(5) product is produced.The strip liquor of copper is produced cathode copper with conventional electrodeposition method after removing remaining organic phase, anolyte returns back extraction copper; The manganese strip liquor adds ammonium bicarbonate precipitation and produces manganous carbonate; The cobalt strip liquor is produced cobalt oxide through ammonium oxalate precipitation, washing and calcining; Prepare electrolytic nickel with electrodeposition method from the strip liquor of nickel, anolyte returns back extraction nickel, together with the rich manganese slag of front and ferric oxide, the recyclable six kinds of metals of rich tungsten slag, seven kinds of products.
Adopt present method to handle oceanic multi-metal nodule and have following positive effect:
(A) retailoring is produced the molten state alloy and is adopted aforesaid atomisation unit to carry out fragmentation, and the ratio of powder grade-200 order that obtains (＜74 μ m) accounts for 50～70%, has solved the tough and tensile difficult broken problem of alloy; (B) the molten alloy powder of nickeliferous, iron, cobalt, copper and a small amount of manganese directly carries out bubble method and leaches, adopt aforesaid processing condition, and under effective catalyst and corrosion equipment situation, can realize the quick mass transfer of gas, liquid, solid three-phase, accomplish at normal temperatures and pressures, ferrotungsten and the thorough of other valuable metals are separated.When the reaction times was 2～7 hours, the metal recovery rate (%) that then enters solution nickel, copper, cobalt, manganese is respectively: Ni 97～99.7, Cu96.5～98.8, Co 97～98.3 and Mn 99～99.8.With the difference that the tuberculosis ore deposit is formed, the general composition of leach liquor (grams per liter) is: Mn 1～5, the Fe trace, and Ni 6～15, Co2～4, Cu 3～13; Metal content in the ferric oxide (%): Co 0.02～0.08, Ni0.03～0.19, and Cu 0.05～0.2, and Fe 55～65.Wherein iron recovery can reach more than 98%, can further be processed into magneticsubstance or other industrial chemicals.(C) this processing method with simple condition from the tuberculosis ore deposit enriching and recovering micro-valuable metal tungsten.Tungstenic only 0.05% in the raw ore, simultaneously tungsten is reduced into metal and enters alloy in the carbon reduction fusion process, and under suitable corrosion condition, tungsten is not dissolved, and enters precipitation with metal form and ferric oxide.The throw out gravity treatment is separated, obtain thick tungsten powder, tungstenic grade 86.3～96.9%.Whole process tungsten recovery rate 80%.Efficient full collection when (D) having realized that nickel, copper, cobalt, manganese exist simultaneously in the leach liquor is separated.That is: the percentage extraction of copper is 99～99.8%, and the rate of recovery of Co, Ni, Mn is respectively Co 99.0～99.9% in the surplus liquid, and Ni 99.0～99.9%, and Mn 99.0～99.98%.Strip liquor contains Cu 25～35g/l, H
2SO
4150～180g/l, electrolytic production reach the cathode copper standard No. one; The percentage extraction of manganese reaches 99.0～99.9%, and nickel, the cobalt rate of recovery are respectively in the raffinate: Ni 99.0～99.9%, and Co 99.0～99.8%; The back extraction manganese solution is produced manganous carbonates such as I; The percentage extraction of cobalt reaches 99.0～99.9%, and the rate of recovery of nickel is 99.0～99.99% in the raffinate.With back extraction cobalt liquid is raw material, makes the universal standard that product meets GB2 cobalt oxide quality.The percentage extraction of nickel is 99.0～99.9%, gets the GB1 cathode nickel by the strip liquor electrodeposition.
The drawing explanation:
Fig. 1 is melting-corrosion-extraction process flow figure, wherein: 1-dry broken
2-joins the carbon pressure 3-of group electrosmelting 4-powder by atomization
6-extracting copper 7-extraction manganese is leached in the 5-corrosion
8-extraction cobalt 9-extraction of nickel 10-electro deposited copper
11-sulfuration removal of impurities 12-precipitation calcining 13-electro deposited nickel
Embodiment
Get the manganese nodule 20kg in C-C district, the Pacific Ocean, dry, be crushed to-0.25mm, add 5.8 parts of coke powders that contain fixed carbon 79.24% and 3 parts by 100 parts of weights (dry measure) tuberculosis and contain SiO
299% ground silica mixing reduces under 1000 ℃ temperature, and keep 1420 ℃ of fusings and separate, its alloy productive rate 8.15%, its tuberculosis ore deposit and alloying constituent are (%):
| Element | ??Mn | ??Fe | ??Cu | ??Co | ??Ni | ?Mo | ??W | ??P | ??S | |
| Content | The tuberculosis ore deposit | ??23.42 | ?10.57 | ??0.64 | ??0.30 | ??0.85 | ?0.045 | ??0.05 | ??0.30 | ??0.12 |
| Alloy | ??3.91 | ?82.50 | ??4.01 | ??2.11 | ??6.63 | ?0.65 | ??0.61 | ??1.31 | ??- | |
The condition of alloy atomization powder process is: atomising unit employing annular distance nozzle and rotating disk, water-cooled tube.The thick 15mm of dish of garden dish, diameter 600mm, card has radiation shape rill, and the rill cross section is a rectangle, dark 8mm, wide 12mm, the rotating speed of controlling board are 6000r.p.m, and used air pressure is 1.0MPa, and cooling water inlet pressure is 0.2MPa.Institute is produced the logical 100 μ m hole sizers of powder, have 75% by the sieve guiding principle, the size distribution of screen underflow is:
| Particle diameter, μ m | ?0～10 | ?10～20 | ?20～30 | ?30～40 | ?40～50 | ?50～60 | ?60～70 | ?70～80 | ?80～90 | ?90～100 |
| Allocation proportion, % | ?3.67 | ?21.0 | ?21.8 | ?17.6 | ?13.0 | ?8.14 | ?8.14 | ?2.37 | ?2.14 | ?2.14 |
| Accumulative total, % | ?3.67 | ?24.67 | ?46.47 | ?64.07 | ?77.07 | ?85.21 | ?93.35 | ?95.72 | ?97.86 | ?100.0 |
The powdered alloy of above-mentioned Chemical Composition and physical specification is carried out the corrosion leaching in hydrochloric acid medium, each charging capacity is 150 grams, and the volume of reactor is 2 liters, band temperature controlling instruments and double-deck turbine stirring arm, and rotating speed is 1000r.p.m.Leaching agent is 0.38N HCl, and L/S (weight)=10: 1, sour consumption are 1.10 times of theoretical amount, add Fe
++(FeCl
2) 10g/l and NaCl120g/l, service temperature is 85 ℃, and air velocity is 1 liter/minute, and pressure is 1kg/cm
2, in 7 hours reaction times, after-filtration is finished in reaction, gets leach liquor 1500ml washing and drying precipitation, gets ferric oxide 213 grams.Leach liquor composition (grams per liter): Cu 3.87, and Co 2.06, and Ni 6.54, and Mn 3.89, the Fe trace, and W 0.0064, the P trace.Precipitate component (%): Cu 0.097, and Co 0.035, and Ni 0.064, and Mn 0.017, and Fe 58.3, and W 0.594, and P 0.92.The metal partition ratio of leaching process is (%).
| Leach liquor | Throw out |
| ?Cu??????Co??????Ni??????Mn??????Fe???W????P | Cu????Co????Ni?????Mn???Fe??????W??????P |
| 96.57 97.67 98.62 99.39 trace trace traces | 3.43??2.33??1.38??0.61??～100???99???～100 |
The iron oxide precipitation thing that corrosion is leached the back output carries out the gravity treatment separation, obtains thick tungsten powder 9.80 grams, and through scanning electron microscope analysis and chemical analysis, its result is:
| Analytical procedure | Scanning electron microscope | Chemical analysis | |||||
| Sample number into spectrum | ????1 | ???2 | ???3 | ????4 | ??5 | Compound sample | |
| Analytical results | ??W ??Mo ??Mn ??Fe ??Ca ??Cu | ????86.34 ????——?? ????????0.49 ????12.09 ????1.08 ????—— | ???96.93 ???—— ??????—— ??????2.84 ???0.23 ???—— | ???95.97 ???2.34 ???0.01 ???1.78 ???0.10 ???—— | ????94.12 ????1.52 ????—— ????????4.23 ????0.13 ????—— | ??95.43 ??1.37 ??—— ????2.25 ??0.22 ??0.73 | ?????90.41 ?????0.035 ?????0.14 ?????3.05 ?Cr??0.0084 ?Co??0.09 |
Leach liquor after alloy leaches adopts full extraction process to separate.The chemical ingredients that leaches the gained leach liquor by aforementioned condition is (grams per liter): Cu 3.80, and Co 2.06, and Ni 6.52, and Mn 3.68, the Fe trace, and the P trace, (A), the extraction of copper and back extraction.Adopt 20%Lix64N-kerosene, O/A=1/2.3 carries out the extraction of three stage countercurrents under room temperature, and load copper organic phase is with containing Cu
2+20.42 grams per liter, H
2SO
4The waste electrolyte reextraction copper of 172 grams per liters, raffinate contains (grams per liter) Cu 0.029, and Co 2.04, and Ni 6.47, Mn 3.63 (pH of this liquid is 1.05).Strip liquor contains (grams per liter) Cu 28.85, and Co 0.0034, and Ni 0.007, and Mn 0.0014, H
2SO
4158.27.The copper of this section, cobalt, nickel, manganese recovery ratio (%) are respectively: 99.24,99.51,99.95,99.95.The strip liquor of copper must contain the cathode copper of Cu＞99.97% through electrodeposition.(B), the extraction of manganese and back extraction.With raffinate 20%P2O4 (two-(2-ethylhexyl phosphoric acid))-kerosene of copper, carry out the extraction of 5 stage countercurrents, the secondary washing by comparing O/A=1/1.6.Load manganese organic phase is pressed O/A=5/1, carries out 2 stage countercurrent back extractions with 1NHCl, and manganese raffinate and strip liquor composition are (grams per liter): the manganese raffinate, and Cu 0.00033, and Co 1.90, and Ni 6.01, Mn 0.0085 (pH is 4.5).The manganese strip liquor, Cu 0.23, and Co 0.093, Ni0.005, Mn 30.11, and HCl 15.38.The rate of recovery of this procedure is respectively (%): Mn99.75, and Co 99.44, Ni99.99.The strip liquor of manganese obtains one-level manganous carbonate (containing Mn 45.46%) through sulfuration removal of impurities, carbon ammonium precipitation.(C), the extraction of cobalt and back extraction.The surplus liquid of collection manganese is added sodium-chlor to Cl
-Concentration is greater than 190 grams per liters, and the solution composition of this moment is (grams per liter): Co 1.73, and Ni 5.71, and Mn 0.0079, Cl
-193, pH4.1.This solution is pressed O/A=1/1.25, use 25%N235, carry out 4 stage countercurrents in 40 ℃ and extract, negative cobalt organic phase is carried out three stage countercurrent back extractions by O/A=5/1 with the 1%HCl aqueous solution.The composition of raffinate and strip liquor is (grams per liter), cobalt raffinate: Co 0.0085, and Ni 5.70, and Mn 0.005, Cu (trace); Cobalt strip liquor: Co 11.72, Ni 0.005, and Mn 0.014.The cobalt rate of recovery 99.47% of this operation, nickel 99.99%.The strip liquor of cobalt must contain the commodity cobalt oxide of Co＞70% after ammonium oxalate precipitation and calcining.(D), the extraction of nickel and back extraction.To come together the surplus liquid of cobalt with lye pH adjustment after, use 15%D
2EHPA-kerosene carries out the extraction of 2 stage countercurrents by comparing O/A=1/1, and load Ni organic phase is pressed O/A=3/1, with containing Ni48 grams per liter, H
2SO
449.77 the waste electrolyte of grams per liter is pressed O/A=3/1 countercurrent reextraction (2 grades), gained raffinate and strip liquor composition (grams per liter): the nickel raffinate, Ni 0.029, and Co 0.00095, and Mn 0.0001, and pH 6.2; Nickel strip liquor: Ni63.46, Co 0.019, and Mn 0.013, H
2SO
48.53.The nickel total recovery of this operation is 99.45%, obtains grade greater than 99.8 cathode nickel by strip liquor through electrodeposition.
Claims (4)
1, the present invention relates to field of metallurgy and chemical engineering and handle a kind of novel method of oceanic multi-metal nodule, the method of handling this material is a lot, wherein one of representational method is melting---sulfuration---lixiviation process, its principle technology is with after the broken oven dry in tuberculosis ore deposit, joining carbon reduces under greater than 900 ℃ temperature, controlled temperature is about 1400 ℃, melts separation, gets the molten alloy of rich manganese slag and ambrose alloy ferro-cobalt, again the gained alloy is vulcanized, oxidation blowing deironing gets nickel ice sulfonium, nickel is iced the sulfonium fragmentation again, carrying out the oxygen enrichment pressurization leaches, leach liquor is respectively through extraction, back extraction, electrodeposition or high pressure reduction get electrolytic copper respectively, electricity nickel and cobalt powder.The invention is characterized in, it is embodied by eight master operations and relevant device, master operation comprises the retailoring of manganese nodule, the rich manganese slag of direct output, molten alloy is made fine grained powder, and powdered alloy carries out the normal pressure corrosion and leaches under the effect of catalyzer, gets iron tungsten sediment and carries out the gravity treatment separation, get ferric oxide and thick tungsten powder, leach liquor is through with the back extraction under extraction of different extraction agent and the different condition, electrodeposition gets cathode copper and cathode nickel, wherein, the strip liquor of manganese gets manganous carbonate through carbon ammonium precipitation, the strip liquor of cobalt gets cobalt oxalate with the heavy cobalt of ammonium oxalate, through calcining to such an extent that the commodity oxidation is bored, so far, six kinds of valuable metals obtain efficient recovery.
2, method according to claim 1, it is characterized in that: in the preparation of powdered alloy, molten alloy is that the pressurized air of 0.4～2.0MPa carries out primary fragmentation by pressure in atomisation unit, on with the metal rotary disk of water-cooled high speed rotating, carry out " secondary breaking " again, water coolant is with the rotating disk high speed rotating, play dual parts crushing medium and heat-eliminating medium simultaneously, the gained powder size is-60～320 orders (0.25～0.047mm).
3, according to the described method of claim 1, it is characterized in that: corrosion technology is atmospheric operation, and its catalyzer (as sodium salt, ammonium salt, molysite, mantoquita, manganese salt) consumption is 5～200 grams per liters, and service temperature is a room temperature to 100 ℃.
4, according to the described technology of claim 1, it is characterized in that: the throw out that corrosion is leached separates through gravity treatment, promptly gets red iron oxide and the thick tungsten that contains about W90%.
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1715873A1 (en) * | 1989-06-27 | 1992-02-28 | Всесоюзный научно-исследовательский и проектный институт механической обработки полезных ископаемых "Механобр" | Method of processing iron-manganese ores containing non-ferrous metals |
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1996
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