CN1048286C - 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 composite oxides mineral of crystallite attitude, needs more special method to handle.For this reason, the scientist of countries in the world studied many treatment processs, wherein, it is generally acknowledged that the method for industrial prospect has five kinds, that is:
(1) reduction ammonia-leaching method.The basic technology of this method is: with the broken oven dry in tuberculosis ore deposit, 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 10%Lix64N (2-hydroxyl-3-chloro-5-nonyl diphenylketoxime)-kerosene extraction copper, waste solution of copper electrolysis back extraction copper, electro deposited copper again, electro deposited nickel after the surplus liquid of collection copper 40%Lix64N-kerosene collection nickel, the back extraction of nickel electrowinning waste liquid, collection nickel surplus liquid 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 (%): Ni 90, and Cu 95, and Co 85.
(2) cuprous ion 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
2Mixed gas, under 50 ℃, reduce leaching.Ammonia that leached mud steams and CO
2Return the front and leach, contain manganous carbonate, ferric oxide and silicon-dioxide in the tailings; Leach liquor is with the Lix64N-kerosene copper and mickel that comes together altogether, 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, Chinese ocean Mineral resources research and development association, 1995.45].The primary process 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 successively with Lix64N-kerosene collection copper, collection nickel, is used corresponding waste electrolyte back extraction respectively, and electrodeposition reclaims again, the surplus liquid of collection nickel hydrogen sulfide precipitate cobalt, cobaltous sulfide with hot sulfuric acid dissolution after, employing pressurized hydrogen reducing process reduces cobalt.The product structure of this technology is that pan belongs to Ni, Cu, Co.Full-range metal recovery rate (%) is: Ni 92, and Cu 80, and Co 67.
(4) reduction salt acid leaching process.This method also belongs to direct leaching.Water spray cooling rapidly after the chlorination about 500 ℃, 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, and most of molten iron is separated precipitation.With liquid ion exchanger extracting copper from solution, back extraction electrodeposition again.Collection copper surplus liquid is with the three iso-octyl amine cobalt that comes together, water back extraction, strip liquor H
2The S precipitate cobalt 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 %:Ni 95, and Cu 90, and Co 90, and Mn 87.
(5) melting-sulfuration-lixiviation process [seeing R.Sridhar, et al, Journal of Metals, April, 1976.32～37].This method is a kind of method of studying maximum by 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 1000 ℃ temperature, melt separation about 1400 ℃, get 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 extracts nickel by Lix64N extraction, back extraction, electrodeposition process again from the surplus liquid of collection copper.The surplus liquid of collection nickel reclaims cobalt through hydrogen sulfide precipitation, sulfuric acid dissolution and High Pressure Hydrogen reduction.Whole process metal recovery rate (%) is: Ni 94, and Cu 85, and Co 85, and Mn 75.
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 selectivity under low temperature (50 ℃), normal pressure 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, 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 the equipment complexity of manganese and hydrochloric acid, and investment is high.
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, then there is the tough and tensile difficult broken problem of alloy in the direct leaching of molten 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 ℃, and smelting time 1～2 hour 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 of gained alloy is (%): Cu 3～13, and Co 2～4, and Ni 5～16, and Mn 1～4, Fe 60-85, and P 1～1.5, and W 0.05; The rate of recovery of valuable metal (%) is in the alloy: Cu 98～99, and Co 98～99.5, and Ni 98～99.5, and Mn 2～5, and Fe 85～98, and P 50～70; The composition (%) of the rich manganese slag of gained is: Cu trace～0.02, and Co trace～0.009, Ni trace～0.03, Mn 36～41, and Fe 0.6～1.5, and P 0.01～0.10.The metal in the dreg rate of recovery (%): Cu 0.5～2, and Co 0.54～1.5, and Ni 1～2, and Mn 94～98, and Fe 3～5, and P 2～4, and 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-60～320 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, is in the hydrochloric acid or sulphuric acid soln of 0.1～3N with powdered alloy in concentration, controlled temperature is in the scope 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, it is to carry out in special stirred reactor that corrosion is leached, 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 for the complete 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 the hydrochloric acid or the sulfuric acid of 0.1～3 mol.Liquid-solid ratio during leaching (L/S) is 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, comprises 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.
Kerosin extracting copper with hydroxyl oximes extraction agent Lix64N (2-hydroxyl-3-chloro-5-nonyl diphenylketoxime), N510 (2-hydroxyl-5-secondary octyl diphenylketoxime) or Lix984 (2-hydroxyl-5-nonyl phenyl methyl ketone oxime and 2-hydroxyl-5-dodecyl salicylaldoxime is by the mixture of 1: 1 composition), with waste solution of copper electrolysis (anolyte) back extraction, get the sulfate liquor of copper; The surplus liquid of collection copper extracts manganese with relevant extraction agent as the kerosin that mixes 5～9 carbon fatty acids, two-(2-ethylhexyl) phosphoric acid or 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester sodium salt, 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 (＞190 grams per liter), uses the kerosin collection cobalt of N235 tertiary amines such as (three iso-octyl amine) again, and the dilute hydrochloric acid back extraction obtains purified cobalt liquor.
The surplus liquid of collection cobalt with nickel electrowinning waste liquid (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, use effective catalyst and corrosion equipment, can realize the quick mass transfer of gas, liquid, solid three-phase, accomplish at normal temperatures and pressures, ferrotungsten is thoroughly separated with other valuable metals.When the corrosion reaction times was 2～7 hours, the metal recovery rate (%) that then enters solution nickel, copper, cobalt, manganese was respectively, Ni97～99.7, Cu96.5～98.8, Co97～98.3, and Mn99～99.8.With the difference that the tuberculosis ore deposit is formed, the general composition of leach liquor (grams per liter) is Mn1～5, Fe trace, Ni6～15, Co2～4, Cu3～13; Metal content in the ferric oxide (%): Co 0.02～0.08, and Ni 0.03～0.19, and Cu 0.06～0.2, 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 extracting and separating when (D) having realized that nickel, copper, cobalt, manganese exist simultaneously in the leach liquor.That is: the percentage extraction of copper is 99～99.8%, Co, Ni in the surplus liquid, and the rate of recovery of Mn is respectively Co 99.0～99.9%, 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, and 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 fragmentation 2-join 3-electrosmelting, 4-powder by atomization, the 5-corrosion of carbon pressure group to leach 6-extracting copper 7-extraction manganese 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 6000 r.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 screen cloth, 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 0.38NHCl, and L/S (weight)=10: 1, sour consumption are 1.10 times of theoretical amount, add Fe
++(FeCl
2) 10g/l and NaCl 120g/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, and the 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 | Trace | 3.43 | 2.33 | 1.38 | 0.61 | ～100 | 99 | ～100 |
The iron oxide precipitation 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:
Leach liquor after alloy leaches adopts full extraction process to separate.The chemical ingredients that leaches gained mixing leach liquor by aforementioned condition is (grams per liter): Cu 3.80, and Co 2.06, and Ni 6.52, and Mn 3.68, Fe trace, P trace.(A) extraction of copper and back extraction.Adopt 20%2-hydroxyl-3-chloro-5 nonyl diphenylketoxime-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) extraction of manganese and back extraction.With raffinate 2,0%P,204 two-(2-ethylhexyl) phosphoric acid one 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 1NHCI, and collection surplus liquid of manganese 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, and Ni 0.005, and Mn 30.11, and HCI 15.38.The rate of recovery of this operation is respectively (%): Mn 99.75, and Co 99.44, and Ni 99.99.The strip liquor of manganese obtains one-level manganous carbonate (containing Mn 45.46%) through sulfuration removal of impurities, carbon ammonium precipitation.(C) extraction of cobalt and back extraction.With the surplus liquid of collection manganese add sodium-chlor to CI concentration greater than 190 grams per liters, the solution composition of this moment is (grams per liter): Co 1.73, Ni 5.71, Mn 0.0079, Cl
-193, pH4.1.This solution is pressed O/A=1/1.25, with 25%N235 (three iso-octyl amine), 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, the 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) extraction of nickel and back extraction.To come together the surplus liquid of cobalt with lye pH adjustment after, carry out 2 stage countercurrents extractions with 15%D2EHPA-kerosene by comparing O/A=1/1, load Ni organic phase is pressed O/A=3/1, with containing Ni 48 grams per liters, 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), nickel raffinate: Ni 0.029; Co 0.00095, and Mn 0.0001, and pH 6.2; Nickel strip liquor: Ni 63.46, Co 0.019, and Mn 0.013, H
2SO
48.53.The nickel total recovery of this operation is 99.45%, and strip liquor obtains grade greater than 99.8% cathode nickel through electrodeposition.
| Analytical procedure | Scanning electron microscope | Chemical analysis | |||||
| Sample number into spectrum | 1 | 2 | 3 | 4 | 5 | Compound sample | |
| Analytical results | W | 86.34 | 96.93 | 95.97 | 94.12 | 95.43 | 90.41 |
| Mo | - | - | 2.34 | 1.52 | 1.37 | 0.035 | |
| Mn | 0.49 | - | 0.01 | - | - | 0.14 | |
| Fe | 12.09 | 2.84 | 1.78 | 4.23 | 2.25 | 3.05 | |
| Ca | 1.08 | 0.23 | 0.10 | 0.13 | 0.22 | Cr 0.0084 | |
| Cu | - | - | - | - | 0.73 | Co 0.09 | |
Claims (3)
1. melting-leaching-extraction process extracts the method for multiple metal from marine manganese nodule, it is characterized in that, embody by six master operations and relevant device, master operation comprises: a, the retailoring of manganese nodule, manganese nodule is dried to moisture＜10%, be crushed to-30～60 orders, add coke powder 3～10%, ground silica 0～5% mixes briquetting, its pelletizing diameter is 10～30mm, this pelletizing reduces under 800～1000 ℃ temperature, and the recovery time is 0.5～3.0 hour, and melting is carried out in crucible oven, smelting temperature is 1300～1500 ℃, and the time is 1～2 hour; B, molten alloy separate with slag (rich manganese slag) mat difference of specific gravity; C, molten alloy pressure are the pressurized air powder by atomization of 0.4～2.0MPa; D, powdered alloy blast air under the effect of catalyzer carries out corrosion and leaches, and corrosion liquid is hydrochloric acid or the sulphuric acid soln that contains 0.1～3N, and liquid-solid ratio (L/S) is 2: 1～20: 1, and the corrosion temperature is a room temperature to 100 ℃, and pH is controlled in 2～4 the scope; E, corrosion leach liquor and soak separating of slag; The Separation and Recovery of valuable metal in f, the corrosion leach liquor is with the LiX984 Cu that comes together, electrolytic copper waste liquid back extraction Cu, electrodeposition gets electrolytic copper No. 1, and the surplus liquid of collection copper extracts Mn with P204, uses the dilute hydrochloric acid back extraction, carbon ammonium precipitation gets manganous carbonate, collection manganese surplus liquid is with the N235 Co that comes together, the dilute hydrochloric acid back extraction, and strip liquor is with the heavy cobalt of ammonium oxalate, through calcine the commodity cobalt oxide, collection Co surplus liquid is with the P204 Ni that comes together, the back extraction of electrolytic nickel waste liquid, and electrodeposition gets electric nickel.
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 catalyzer comprises sodium salt, ammonium salt, molysite, mantoquita or manganese salt, and consumption is 5～200 grams per liter corrosion liquid.
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Citations (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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Patent Citations (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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