CN1775971A - Mixed ammonia leaching method for deep-sea polymetallic nodule and cobalt-rich crust - Google Patents
Mixed ammonia leaching method for deep-sea polymetallic nodule and cobalt-rich crust Download PDFInfo
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Abstract
The invention relates to a mixed ammonia leaching method for deep sea polymetallic nodule and cobalt-rich crust, which is characterized by comprising the following steps in sequence: mixing the multi-metal nodule and the cobalt-rich crust, crushing the mixed ore and finely grinding; adding the ground material into an ammonium salt solution, and introducing carbon monoxide for reduction leaching; concentrating and separating, and returning supernatant of the thickener to leaching; filtering the bottom flow of the thickener to obtain a leaching solution A; washing the filter cake, and then filtering, wherein the filtrate is washing water B containing nickel, copper, cobalt and molybdenum; mixing the leachate A and the washing water B, introducing air for oxidation to oxidize and precipitate manganese and iron in the solution, and then filtering to respectively obtain a precipitate C and a solution D; returning the precipitate C to leaching to recover the coprecipitated nickel, copper and cobalt; and separating and recovering the nickel, the copper, the cobalt and the molybdenum from the solution D according to a conventional method. In the method, basic copper carbonate or other copper salts or copper powder is not required to be additionally supplemented, so that the self-catalytic reduction of the multi-metal nodule is realized, and the consumption of carbon monoxide is reduced.
Description
Technical field
A kind of deep sea polymetallic nodule and cobalt-bearing crust mixed ammonia leaching method, relate to a kind of Wet-process metallurgy method that from deep sea polymetallic nodule and cobalt-bearing crust, extracts nickel, copper, cobalt, particularly polymetallic nodule and cobalt-bearing crust are carried out the method for combination treatment with the reduction ammonia-leaching method.
Background technology
Very abundant metallic ore resource is contained in the international sea-bed area, be common heritage of humankind and 21 century the grand strategy resources base, along with the continuous expansion of global economy scale, the exhaustion day by day of land resources, the exploitation of deep-sea resources is expected to become the important industry of 21 century.
Oceanic multi-metal nodule and cobalt-bearing crust are two kinds of most important deep sea polymetallic ore deposits being familiar with at present.Polymetallic nodule claim manganese nodule or iron-manganese concretion again, be distributed widely in the marine bottom sediment top layer of each ocean, the world, depth of water 3500-6000m, the tuberculosis total resources in each ocean, the whole world is estimated above trillion tons, wherein tool business development prospect mainly is distributed in the Pacific Ocean, polymetallic nodule mainly are made up of iron and manganese oxides, and nickeliferous, copper, cobalt, molybdenum and various trace elements.Cobalt-bearing crust mainly is distributed in seamount, submarine ridge and the sunken flat of depth of water 800-3000m, the Resources Prospect that is seamount district, the Pacific Ocean equally is best, cobalt-bearing crust is rich in valuable metals such as cobalt, nickel, manganese, rare earth, particularly the cobalt contents in the cobalt-bearing crust can reach 0.4-1.2%, even part is tens of times of land primary ore cobalt grades up to 2%.
The essential mineral of deep sea polymetallic nodule and cobalt-bearing crust is the ferrimanganic hydrous oxide, next some aluminium silicate mineral, and as quartz, feldspar, mica, clay mineral, zeolite minerals etc., the mineral particle of ore is atomic thin, symbiosis closely.In the ore, valuable metals such as nickel, cobalt, copper do not have independent mineral, mainly compose with isomorphous form to be stored in the lattice of iron and manganese oxides, part is adsorbed on the surface of iron and manganese oxides, iron, manganese mineral particle are extremely tiny, often form crystallite, are cryptocrystal or amorphousness particulate dispersion state output.Above-mentioned ore characteristic decision directly adopts the physical concentration method to be difficult to separation, enrichment, and it is the prerequisite of extracting valuable metals such as nickel, cobalt, copper that iron and manganese oxides is decomposed fully.Metallurgical treatment process commonly used mainly contains smelting process, roasting method, hydrometallurgy.But the moisture height of ore, valuable metal grade are low, even under natural drying condition, its moisture still accounts for 30%～50%, adopt melting and roasting method, need the dry large quantity of moisture that remove in the polymetallic nodule, and therefore the energy consumption height is more suitable in hydrometallurgy.
Ammonia leaching process has to be selected to leach, leach the advantage that medicament can recycle, and is considered to promising polymetallic nodule smelting process.Traditional ammonia leaching process is a reduction roasting-ammonia leaching, soon behind the polymetallic nodule drying and dehydrating, being reductive agent reducing roasting in multiple hearth furnace with charcoal, coal gas etc., leaches with ammonia-sal volatile then.The advantage that the tradition ammonia leaching process is handled polymetallic nodule is to have the industrial production of land laterite reduction roasting-ammonia leaching to use for reference, but the energy consumption height of drying and dehydrating.At the high shortcoming of reduction roasting-ammonia leaching method energy consumption, at United States Patent (USP) 3,983, in 017, having proposed with the cuprous ion is that catalyzer, carbon monoxide are reductive agent, and the cuprous ion ammonia soaking technology of polymetallic nodule is leached in reduction in ammonia-sal volatile, obtains good effect.Cuprous ion ammonia soaking technology is under 40 ℃～70 ℃, the manganese mineral of cuprous ion reduction polymetallic nodule, thus nickel, cobalt and copper etc. that tax is stored in the manganese mineral lattice dissociate, and become the metal ammonium complex ion and change solution over to the ammino symphysis; Cuprous ion in the solution is regenerated by-carbonoxide reduction cupric ion.And the same with the reduction roasting-ammonia leaching method, the cobalt leaching yield of cuprous ion ammonia leaching process is not higher than 70% usually
Adopt cuprous ion ammonia soaking technology to handle cobalt-bearing crust, have two main difficult technical.The one, the copper content in the cobalt-bearing crust is very low, and only about 0.1%, self can't leach for reduction enough copper catalysts are provided, and the required copper of catalysis is almost all provided by the outside, the cost height; The 2nd, the cobalt rate of recovery is low, and the cobalt contents in the cobalt-bearing crust is 2～4 times of polymetallic nodule or higher, and cobalt leaching yield height to the economic benefit influence of technology significantly.
In addition, the exploitation of deep-sea metallic ore resource have investment high, have a big risk, characteristics that the cycle is long, in case the deep-sea mining technology makes a breakthrough and the maturation on opportunity, multiple deep-sea mineral resource may enter commercial exploitation in succession, carry out the merging of polymetallic nodule and cobalt-bearing crust and handle, help to reduce plant investment, reduce risk.
Summary of the invention
The objective of the invention is the deficiency that exists in the above-mentioned prior art, provide that a kind of cost is low, cobalt rate of recovery height, economic good deep sea polymetallic nodule and cobalt-bearing crust mixed ammonia leaching method.
The objective of the invention is to be achieved through the following technical solutions.
A kind of deep sea polymetallic nodule and cobalt-bearing crust mixed ammonia leaching method is characterized in that its process is:
(1) deep sea polymetallic nodule and cobalt-bearing crust are mixed by weight 1～5: 1 after, broken, be finely ground to below the 0.2mm, wherein more than 50% less than 0.074mm;
(2) the levigated material is added in the ammonia-ammonia sulfate solution, feeding-carbonoxide reduces leaching, the ore pulp solvent and solute weight ratio that control is leached is 5～40: 1, cuprous ion concentration is greater than 4g/l, total ammonia concentration 60g/l～180g/l, sulfate concentration 20g/l～200g/l, 25 ℃～70 ℃ of temperature, extraction time 0.5h～4h, carbon monoxide flow 0.4m
3/ t tuberculosis min～4m
3/ t tuberculosis min;
(3) leach good ore pulp concentrating and separating in thickener, the supernatant liquor of thickener returns leaching;
(4) underflow of thickener filters, and obtains leach liquor A;
(5) with containing the solution pulping and washing filter cake of ammonia 40g/l～100g/l, filter then, filtrate is the wash water B of nickeliferous, copper, cobalt, aluminium;
(6) leach liquor A and wash water B are mixed, bubbling air makes manganese, the iron oxidation precipitation in the solution, filters then, obtains throw out C and solution D respectively;
(7) throw out C returns leaching, to reclaim nickel, copper, the cobalt of co-precipitation;
(8) solution D method is routinely separated and is reclaimed nickel, copper, cobalt, molybdenum.
A kind of deep sea polymetallic nodule and cobalt-bearing crust mixed ammonia leaching method is characterized in that polymetallic nodule and cobalt-bearing crust fragmentation, are finely ground to below the 0.2mm, wherein more than 70% less than 0.074mm.
A kind of deep sea polymetallic nodule and cobalt-bearing crust mixed ammonia leaching method, it is characterized in that levigated polymetallic nodule and cobalt-bearing crust by weight 1～4: 1 mixes.
A kind of deep sea polymetallic nodule and cobalt-bearing crust mixed ammonia leaching method is characterized in that compound is added to contain in total ammonia 100g/l～160g/l solution leaching.
A kind of deep sea polymetallic nodule and cobalt-bearing crust mixed ammonia leaching method, it is characterized in that the ore pulp concentrating and separating solution and the leached mud in thickener that leach, the supernatant liquor of thickener returns leaching, to keep the cuprous ion concentration that leaches in the ore pulp at 6g/L～15g/L.
A kind of deep sea polymetallic nodule and cobalt-bearing crust mixed ammonia leaching method, the ore pulp solvent and solute weight ratio that it is characterized in that leaching ore pulp is 5～20: 1.
A kind of deep sea polymetallic nodule and cobalt-bearing crust mixed ammonia leaching method is characterized in that extraction temperature is 40 ℃～55 ℃.
A kind of deep sea polymetallic nodule and cobalt-bearing crust mixed ammonia leaching method is characterized in that ore pulp concentrating and separating in thickener of leaching, and the underflow solids concn of control thickener is greater than 40%.
In the present invention, the batch mixing of polymetallic nodule and cobalt-bearing crust can carry out before fragmentation, also can carry out after fine grinding, can also be by proportioning charging respectively.
Because required catalyzer cuprous ion can't self provide when ammonia leaching process was handled cobalt-bearing crust, and the cupric ion that deep sea polymetallic nodule ammonia leaches when soaking can be reduced into cuprous ion by carbon monoxide and satisfy the needs that catalysis is leached.Polymetallic nodule and cobalt-bearing crust mixed ammonia leaching method are exactly that the cupric ion that utilizes polymetallic nodule to provide is realized both common leachings, and need add cupric ion when avoiding independent ammonia to soak cobalt-bearing crust with carrying out smoothly of guaranteeing to leach.
In the present invention, cuprous ion concentration is high more in theory, it is fast more to leach speed of response, but the restriction that the copper grade that is subjected to polymetallic nodule is lower, when adopting too high cuprous ion concentration to leach continuously, the system of removing need add a certain amount of cupric ion when beginning to start, and also requires in the production process constantly to replenish a large amount of copper by the outside, causes carbon monoxide consumption increase and cost to increase.
In the present invention, leach good ore pulp and adopt concentrating and separating, the underflow solids concn of control thickener is greater than 40%, supernatant liquor returns leaching, thereby in continuous leaching process, tuberculosis leaches spontaneous copper and just enough keeps the required cuprous ion concentration of leaching, and does not need to replenish in addition ventilation breather or other mantoquita or copper powder, thereby realize the self catalyzed reduction of polymetallic nodule, help reducing carbon monoxide consumption.
In the present invention, the thickened underflow that leaches ore pulp filters earlier, washing, and then the blowing air oxidation, and the throw out that the oxidation operation produces returns and leaches to reclaim nickel, copper, the cobalt of co-precipitation again, helps improving metal recovery rate.
Description of drawings
Fig. 1 is the principle process flow sheet of the inventive method.
Embodiment
A kind of deep sea polymetallic nodule and cobalt-bearing crust mixed ammonia leaching method mix deep sea polymetallic nodule and cobalt-bearing crust by a certain percentage, and be broken, be finely ground to below the 0.2mm, wherein more than 50% less than 0.074mm; Or fragmentation, fine grinding polymetallic nodule and cobalt-bearing crust mix both more by a certain percentage separately; Or before reinforced, do not mix polymetallic nodule and cobalt-bearing crust, add in the leaching vat respectively by a certain percentage, taking a kind of fine grinding material in three kinds of mixing methods to be added in the ammonium salt solution, when starting, system, need add a certain amount of cupric ion so that system is normally moved because of catalyst-free cupric ion in the solution.Feed carbon monoxide and reduce leachings, the ore pulp solvent and solute weight ratio of control leaching is 5～40: 1, and cuprous ion concentration was greater than 4g/l when system leached continuously, total ammonia concentration 60g/l～180g/l, 25 ℃～70 ℃ of temperature, extraction time 0.5h～2h, carbon monoxide flow 0.4m
3/ tmin～2m
3/ tmin; Leach good ore pulp concentrating and separating in thickener, the supernatant liquor of thickener returns leaching; Underflow filters, washs, and filtrate and wash water merge oxidation, remove trace manganese, iron in the solution, and the throw out after the filtration returns and leaches reclaiming nickel, copper, the cobalt of co-precipitation again, and solution method is routinely separated and reclaimed nickel, copper, cobalt, molybdenum, zinc.
In the present invention, deep sea polymetallic nodule and cobalt-bearing crust are broken, are finely ground to below the 0.2mm, wherein more than 70% less than 0.074mm.
In the present invention, polymetallic nodule and cobalt-bearing crust mix by weight 1～4: 1.
In the present invention, the ammonium salt leach liquor of employing, wherein total ammonia concentration 100g/l～160g/l.
In the present invention, theoretically, keep the high cuprous ion concentration of leaching system and help accelerating reduction rate, but be subjected to the restriction of handled polymetallic nodule copper content, generally be controlled at 6g/l～15g/l.
In the present invention, for improving the processing power of leaching plant, the ore pulp solvent and solute weight ratio that control is leached is 5～20: 1.
In the present invention, the control extraction temperature is 40 ℃～55 ℃, keeping speed of response faster, and reduces the volatilization loss of ammonia.
In the present invention, leach good ore pulp concentrating and separating in thickener, the underflow solids concn of control thickener is greater than 40%, supernatant liquor stream returns leaching, keep the enough cuprous ion concentration of leaching system, and do not need from external complement ventilation breather or other mantoquita or copper powder, thus the self catalyzed reduction of realization polymetallic nodule, help reducing carbon monoxide consumption, reduce smelting cost.
In the present invention, thickener underflow filters earlier, washing, then blowing air oxidation in the leach liquor, filtration; Throw out returns and leaches, and improves metal recovery rate; Filtrate method is routinely separated and is reclaimed nickel, copper, cobalt, molybdenum, zinc etc.
With following indefiniteness embodiment method of the present invention is further described, helping understanding content of the present invention and advantage thereof, and as the qualification to protection domain of the present invention, protection scope of the present invention is determined by claims.The polymetallic nodule that embodiment adopts divide two kinds of smooth type and rough types, and its composition sees Table 1.
The chemical ingredients of table 1 polymetallic nodule (%)
| Sample | Mn | Ni | Cu | Co | Zn | Mo |
| Polymetallic nodule-1 | 25.78 | 1.39 | 1.33 | 0.22 | 0.16 | 0.049 |
| Polymetallic nodule-2 | 23.46 | 1.10 | 0.86 | 0.25 | 0.12 | 0.040 |
| Cobalt-bearing crust | 18.91 | 0.36 | 0.08 | 0.54 | 0.06 | 0.042 |
Embodiment 1
Get 3g polymetallic nodule-1 and 3g cobalt-bearing crust, be milled down to respectively-0.074mm accounts for 70.76%, is added to after the mixing to contain 120g/l NH
3, 40g/l SO
4 2-, 3g/l Co
2+, 11.3g/l Ni
2+, 8g/l Cu
+Ammonia-ammonia sulfate solution in, solvent and solute weight ratio 40: 1,45 ℃ of extraction temperatures, carbon monoxide flow 0.4m
3/ t tuberculosis min leaches 2h.The leaching yield 90.75% of cobalt.
Embodiment 2
Get 6g polymetallic nodule-2 and 3g cobalt-bearing crust and mix, be milled down to-0.074mm accounts for 84.76%, is added to contain 60g/l NH
3, 96g/l SO
4 2-, 2.5g/l Co
2+, 8.6g/l Ni
2+, 10g/l Cu
+Ammonia-ammonia sulfate solution in, solvent and solute weight ratio 30: 1,40 ℃ of extraction temperatures, carbon monoxide flow 0.8m
3/ tmin leaches 3h.The leaching yield 88.5% of cobalt.
Embodiment 3
Get 9g polymetallic nodule-1 and 3g cobalt-bearing crust, be milled down to respectively-0.074mm accounts for 70%, is added to after the mixing to contain 100g/lNH
3, 40g/l SO
4 2-, 3g/l Co
2+, 11.3g/l Ni
2+, 15g/l Cu
+Ammonia-ammonia sulfate solution in, solvent and solute weight ratio 20: 1,70 ℃ of extraction temperatures, carbon monoxide flow 1.2m
3/ tmin leaches 4h.The leaching yield 90.75% of cobalt.
Embodiment 4
Get 12g polymetallic nodule-1 and 3g cobalt-bearing crust, be milled down to respectively-0.074mm accounts for 50%, is added to respectively to contain 180g/lNH
3, 40g/l SO
4 2-, 3g/l Co
2+, 11.3g/l Ni
2+, 6g/l Cu
+Ammonia-ammonia sulfate solution in, solvent and solute weight ratio 10: 1,60 ℃ of extraction temperatures, carbon monoxide flow 2m
3/ tmin leaches 0.5h.The leaching yield 90.75% of cobalt.
Embodiment 5
Get 15g polymetallic nodule-2 and 3g cobalt-bearing crust and mix, be milled down to-0.074mm accounts for 64%, is added to contain 160g/l NH
3, 96g/l SO
4 2-, 2.5g/l Co
2+, 8.6g/l Ni
2+, 4g/l Cu
+Ammonia-ammonia sulfate solution in, solvent and solute weight ratio 5: 1,55 ℃ of extraction temperatures, carbon monoxide flow 4m
3/ tmin leaches 1h.The leaching yield 88.5% of cobalt.
Embodiment 6
Get 9g polymetallic nodule-1 and 3g cobalt-bearing crust, be milled down to respectively-0.074mm accounts for 70.76%, is added to respectively to contain 80g/lNH
3, 40g/l SO
4 2-, 3g/l Co
2+, 11.3g/l Ni
2+, 15g/l Cu
+Ammonia-ammonia sulfate solution in, solvent and solute weight ratio 30: 1,25 ℃ of extraction temperatures, carbon monoxide flow 2m
3/ tmin leaches 4h.The leaching yield 90.75% of cobalt.
Embodiment 7
Get 3g polymetallic nodule-1 and 3g cobalt-bearing crust, be milled down to respectively-0.074mm accounts for 70.76%, is added to after the mixing to contain 120g/l NH
3, 40g/l SO
4 2-, 3g/l Co
2+, 11.3g/l Ni
2+, 8g/l Cu
+Ammonia-ammonium chloride solution in, solvent and solute weight ratio 40: 1,45 ℃ of extraction temperatures, carbon monoxide flow 0.4m
3/ tmin leaches 2h.The leaching yield 90.75% of cobalt.
Embodiment 8
Get 6g polymetallic nodule-2 and 3g cobalt-bearing crust and mix, be milled down to-0.074mm accounts for 84.76%, is added to contain 60g/l NH
3, 96g/l SO
4 2-, 2.5g/l Co
2+, 8.6g/l Ni
2+, 10g/l Cu
+Ammonia-ammonium chloride solution in, solvent and solute weight ratio 30: 1,40 ℃ of extraction temperatures, carbon monoxide flow 0.8m
3/ tmin leaches 3h.The leaching yield 88.5% of cobalt.
Embodiment 9
Get 9g polymetallic nodule-1 and 3g cobalt-bearing crust, be milled down to respectively-0.074mm accounts for 70%, is added to after the mixing to contain 100g/lNH
3, 40g/l SO
4 2-, 3g/l Co
2+, 11.3g/l Ni
2+, 15g/l Cu
+Ammonia-ammonium chloride solution in, solvent and solute weight ratio 20: 1,70 ℃ of extraction temperatures, carbon monoxide flow 1.2m
3/ tmin leaches 4h.The leaching yield 90.75% of cobalt.
Embodiment 10
Get 12g polymetallic nodule-1 and 3g cobalt-bearing crust, be milled down to respectively-0.074mm accounts for 50%, is added to respectively to contain 180g/lNH
3, 40g/l SO
4 2-, 3g/l Co
2+, 11.3g/l Ni
2+, 6g/l Cu
+Ammonia-ammonium chloride solution in, solvent and solute weight ratio 10: 1,60 ℃ of extraction temperatures, carbon monoxide flow 2m
3/ tmin leaches 0.5h.The leaching yield 79.75% of cobalt.
Embodiment 11
Get 15g polymetallic nodule-2 and 3g cobalt-bearing crust and mix, be milled down to-0.074mm accounts for 64%, is added to contain 160g/l NH
3, 96g/l SO
4 2-, 2.5g/l Co
2+, 8.6g/l Ni
2+, 4g/l Cu
+Ammonia-ammonium chloride solution in, solvent and solute weight ratio 5: 1,55 ℃ of extraction temperatures, carbon monoxide flow 4m
3/ tmin leaches 1h.The leaching yield 84.5% of cobalt.
Embodiment 12
Get 9g polymetallic nodule-1 and 3g cobalt-bearing crust, be milled down to respectively-0.074mm accounts for 70.76%, is added to respectively to contain 80g/lNH
3, 40g/l SO
4 2-, 3g/l Co
2+, 11.3g/l Ni
2+, 15g/l Cu
+Ammonia-ammonium chloride solution in, solvent and solute weight ratio 30: 1,25 ℃ of extraction temperatures, carbon monoxide flow 2m
3/ tmin leaches 4h.The leaching yield 91.75% of cobalt.
Embodiment 13
Continuous leaching test.After polymetallic nodule-1 and cobalt-bearing crust difference drying, mixed the back fragmentation by weight 4: 1, the particle of using wet-type ball mill fine grinding to 75% again is less than 0.074mm; Leaching vat are used 120g/l NH in advance
3, 40g/l SO
4 2-, 3g/lCo, 10g/l Ni, 10.2g/l Cu solution fill out groove.With peristaltic pump ore pulp is transported in the leaching vat continuously then, speed is dry and hard nuclear 5kg/h, simultaneously, feeds carbon monoxide continuously in leaching vat, and flow is 1.6m
3/ tmin; Breeze is at the mean residence time 2h of leaching vat, and leaching good ore pulp, to enter thickner by the overflow port of leaching vat dense, the discharge concentration 50% of control thickener underflow, and underflow filters, washing; The thickener supernatant liquor returns leaching vat, the about 95l/h of flow; Blowing air oxidation leach liquor filters, and throw out returns and leaches.Nickel, copper, cobalt, zinc, molybdenum leaching yield the results are shown in Table 2.
Table 2 is the leaching test result continuously
| Element | Ni | Cu | Co | Zn | Mo |
| Leaching yield, % | 97.58 | 96.35 | 89.25 | 82.30 | 95.66 |
Embodiment 14
Continuous leaching test.After polymetallic nodule-2 and cobalt-bearing crust difference drying, mixed the back fragmentation by weight 3: 1, the particle of using wet-type ball mill fine grinding to 75% again is less than 0.074mm; Leaching vat are used 120g/l NH in advance
3, 40g/l SO
4 2-, 3g/lCo, 11.3g/l Ni, 7g/l Cu solution fill out groove.With peristaltic pump ore pulp is transported in the leaching vat continuously then, speed is dry and hard nuclear 5kg/h, simultaneously, feeds carbon monoxide continuously in leaching vat, and flow is 1.6m
3/ tmin; Breeze is at the mean residence time 2h of leaching vat, and leaching good ore pulp, to enter thickner by the overflow port of leaching vat dense, the discharge concentration 50% of control thickener underflow, and underflow filters, washing; The thickener supernatant liquor returns leaching vat, the about 95l/h of flow; Blowing air oxidation leach liquor filters, and throw out returns and leaches.Nickel, copper, cobalt, zinc, molybdenum leaching yield the results are shown in Table 2.
Table 3 is the leaching test result continuously
| Element | Ni | Cu | Co | Zn | Mo |
| Leaching yield, % | 96.65 | 94.87 | 87.90 | 81.00 | 94.59 |
Claims (8)
1. deep sea polymetallic nodule and cobalt-bearing crust mixed ammonia leaching method is characterized in that its process is followed successively by:
(1) with polymetallic nodule and cobalt-bearing crust by weight 1～5: 1 mixes;
(2) mix the ore deposit fragmentation, be finely ground to below the 0.2mm, wherein more than 50% less than 0.074mm;
(3) the levigated material is added in the ammonium salt solution, feed carbon monoxide and reduce leaching, the ore pulp solvent and solute weight ratio that control is leached is 5～40: 1, cuprous ion concentration was greater than 4g/l when system leached continuously, total ammonia concentration 60g/l～180g/l, 25 ℃～70 ℃ of temperature, extraction time 0.5h～4h, carbon monoxide flow 0.4m
3/ t tuberculosis min～4m
3/ t tuberculosis min;
(4) leach good ore pulp concentrating and separating in thickener, the supernatant liquor of thickener returns leaching;
(5) underflow of thickener filters, and obtains leach liquor A;
(6) with containing the solution pulping and washing filter cake of total ammonia 40g/l～100g/l, filter then, filtrate is the wash water B of nickeliferous, copper, cobalt, molybdenum;
(7) leach liquor A and wash water B are mixed, the blowing air oxidation makes manganese, the iron oxidation precipitation in the solution, filters then, obtains throw out C and solution D respectively;
(8) throw out C returns leaching, to reclaim nickel, copper, the cobalt of co-precipitation;
(9) solution D method is routinely separated and is reclaimed nickel, copper, cobalt, molybdenum.
2. a kind of deep sea polymetallic nodule according to claim 1 and cobalt-bearing crust mixed ammonia leaching method, it is characterized in that polymetallic nodule and cobalt-bearing crust by weight 1～4: 1 mixes.
3. a kind of deep sea polymetallic nodule according to claim 1 and cobalt-bearing crust mixed ammonia leaching method, it is characterized in that polymetallic nodule and cobalt-bearing crust mixing ore deposit fragmentation, be finely ground to below the 0.2mm, wherein more than 70% less than 0.074mm, or mix after broken respectively, the fine grinding and add leaching vat again, or do not mix after fragmentation, the fine grinding respectively, add respectively in the leaching vat, granularity requirements is with the ore grinding requirement in polymetallic nodule and cobalt-bearing crust mixing ore deposit again.
4. a kind of deep sea polymetallic nodule according to claim 1 and cobalt-bearing crust mixed ammonia leaching method is characterized in that compound is added to contain in ammonia 100g/l～160g/l solution leaching.
5. a kind of deep sea polymetallic nodule according to claim 1 and cobalt-bearing crust mixed ammonia leaching method, it is characterized in that the ore pulp concentrating and separating solution and the leached mud in thickener that leach, the supernatant liquor of thickener returns leaching, to keep the cuprous ion concentration that leaches in the ore pulp at 6g/l～15g/l.
6. a kind of deep sea polymetallic nodule according to claim 1 and cobalt-bearing crust mixed ammonia leaching method, the ore pulp solvent and solute weight ratio that it is characterized in that leaching ore pulp is 5～20: 1.
7. a kind of deep sea polymetallic nodule according to claim 1 and cobalt-bearing crust mixed ammonia leaching method is characterized in that extraction temperature is 40 ℃～55 ℃.
8. a kind of deep sea polymetallic nodule according to claim 1 and cobalt-bearing crust mixed ammonia leaching method is characterized in that ore pulp concentrating and separating in thickener of leaching, and the underflow solids concn of control thickener is greater than 40%.
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| CNB2005101345132A CN1333092C (en) | 2005-12-15 | 2005-12-15 | Mixed ammonia leaching method for deep-sea polymetallic nodule and cobalt-rich crust |
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| CNB2005101345132A CN1333092C (en) | 2005-12-15 | 2005-12-15 | Mixed ammonia leaching method for deep-sea polymetallic nodule and cobalt-rich crust |
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| CN1333092C CN1333092C (en) | 2007-08-22 |
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| CNB2005101345132A Active CN1333092C (en) | 2005-12-15 | 2005-12-15 | Mixed ammonia leaching method for deep-sea polymetallic nodule and cobalt-rich crust |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358919A (en) * | 2011-11-02 | 2012-02-22 | 长沙矿冶研究院有限责任公司 | Method for extracting valuable metal from submarine metallic ore |
| CN103555968A (en) * | 2013-10-23 | 2014-02-05 | 北京矿冶研究总院 | Novel smelting process of cobalt-manganese multi-metal ore |
| CN104831065A (en) * | 2015-04-09 | 2015-08-12 | 长沙矿冶研究院有限责任公司 | Method for separating nickel and cobalt from manganese in high manganese-cobalt ratio nickel-cobalt-manganese raw material |
| CN105903561A (en) * | 2016-04-16 | 2016-08-31 | 北京矿冶研究总院 | Method for recovering manganese from cobalt-manganese multi-metal oxidized ore |
| CN111286605A (en) * | 2018-12-06 | 2020-06-16 | 深圳市金航深海矿产开发集团有限公司 | Method for recovering valuable metals of seabed polymetallic nodule and co-producing NCM precursor |
| CN113528815A (en) * | 2021-07-28 | 2021-10-22 | 矿冶科技集团有限公司 | Method for recovering valuable metals from cobalt-manganese multi-metal oxide ores and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4018866A (en) * | 1972-12-01 | 1977-04-19 | Kennecott Copper Corporation | Metal carbonate recycle to reduction circuit in the cuprion process |
| US3983017A (en) * | 1972-12-01 | 1976-09-28 | Kennecott Copper Corporation | Recovery of metal values from manganese deep sea nodules using ammoniacal cuprous leach solutions |
| US4137291A (en) * | 1976-10-18 | 1979-01-30 | Deepsea Ventures, Inc. | Extraction of metal values from manganese nodules |
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2005
- 2005-12-15 CN CNB2005101345132A patent/CN1333092C/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358919A (en) * | 2011-11-02 | 2012-02-22 | 长沙矿冶研究院有限责任公司 | Method for extracting valuable metal from submarine metallic ore |
| CN103555968A (en) * | 2013-10-23 | 2014-02-05 | 北京矿冶研究总院 | Novel smelting process of cobalt-manganese multi-metal ore |
| CN103555968B (en) * | 2013-10-23 | 2015-11-25 | 北京矿冶研究总院 | Novel smelting process of cobalt-manganese multi-metal ore |
| CN104831065A (en) * | 2015-04-09 | 2015-08-12 | 长沙矿冶研究院有限责任公司 | Method for separating nickel and cobalt from manganese in high manganese-cobalt ratio nickel-cobalt-manganese raw material |
| CN105903561A (en) * | 2016-04-16 | 2016-08-31 | 北京矿冶研究总院 | Method for recovering manganese from cobalt-manganese multi-metal oxidized ore |
| CN105903561B (en) * | 2016-04-16 | 2018-06-29 | 北京矿冶研究总院 | Method for recovering manganese from cobalt-manganese multi-metal oxidized ore |
| CN111286605A (en) * | 2018-12-06 | 2020-06-16 | 深圳市金航深海矿产开发集团有限公司 | Method for recovering valuable metals of seabed polymetallic nodule and co-producing NCM precursor |
| CN113528815A (en) * | 2021-07-28 | 2021-10-22 | 矿冶科技集团有限公司 | Method for recovering valuable metals from cobalt-manganese multi-metal oxide ores and application |
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|---|---|
| CN1333092C (en) | 2007-08-22 |
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