A kind of method extracting nickel from low-grade laterite nickel ore
Technical field
The present invention relates to field of hydrometallurgy, be specifically related to a kind of method extracting nickel, cobalt from low-grade laterite nickel ore with wet processing.
Background technology
Red soil nickel ore is the nickel oxide ore gone bad through extensive long-term weathering leaching in the torrid zone or subtropical zone by nickeliferous peridotites, owing to there is the difference of geographical position, weather condition and rate of decay, red soil nickel ore type is all over the world incomplete same.
Efflorescence generally produces bedded deposit, wherein also exists completely or sedentary product the most thoroughly near surface, along with degree of depth increase fades to the lighter sedentary product of degree, and finally terminates as unweathered rock at certain darker depth.
Most of nickel that height waste mantle is contained usually is trickle to be distributed in pyrrhosiderite particle in small, broken bits.This layer is commonly referred to limonite, and it generally contains silicon and the magnesium of a high proportion of iron and low ratio.
Nickel contained by the layer that weathering is lighter is generally contained in various magnesium silicate minerals more, such as serpentine.A lot of other may be had in incomplete zone of weathering to contain the silicate minerals of nickel.The height of part weathering is commonly referred to saprolite or noumeite containing magnesium ribbon.Its iron generally containing low ratio and a high proportion of silicon and magnesium.
In some mineral deposits, also have the another kind of main band containing nontonite clays be usually between limonite and saprolite, be called transition ore deposit.
Under normal circumstances, limonite is the chief component of red soil nickel ore, accounts for 65% ~ 75% of red soil nickel ore total amount; Saprolite accounts for 15% ~ 25%; Transition ore deposit accounts for 10%.
Low-grade laterite nickel ore refers to the red soil nickel ore not having saprolite ore deposit, the red soil nickel ore be namely made up of limonite and transition ore deposit.
From low-grade laterite nickel ore nickel, reclaim nickel, the where the shoe pinches of cobalt is, usually not by the useful component of the abundant enriching nickel of physics mode before carrying out chemical treatment separating metal useful component, namely cannot carry out enrichment by the technology of ore dressing, this makes the processing cost of low-grade laterite nickel ore very high.And due to different mineral and chemical constitution in the limonite in low-grade laterite nickel ore and transition ore deposit, these ores are unsuitable for using same treatment technology to process usually.Finding the method for the cost reducing process red soil nickel ore in decades always.
And the treatment process of red soil nickel ore can be divided into thermal process and the large class of wet processing two.
Fire metallurgy process is applicable to process saprolite ore deposit.This technique can only produce ferronickel usually, can not Call Provision, and its application is restricted.
Hydrometallurgical processes is applicable to process limonite.Hydrometallurgical technology comprise high pressure acidleach and reducing roasting ammonia leaching and occur in recent years as normal pressure acidleach, heap leaching method etc.
The advantage of high pressure Ore Leaching (HPAL) technique is: nickel, cobalt leaching yield are high; Speed of response is fast, the reaction times is short; Iron does not consume sulfuric acid in theory in acidleach process and hydrolysate is rhombohedral iron ore (Fe
20
3) precipitation.But the shortcoming of high pressure Ore Leaching (HPAL) technique is also very outstanding: be first that it needs the autoclave of complicated high temperature, high pressure and relevant equipment, its I&M is all very expensive; Two is that the sulfuric acid of high pressure acidleach (HPAL) processes expend is more than the sulfuric acid needed for the non-ferrous metal components stoichiometrically dissolved in ore.Because most sulfate ion provided by sulfuric acid is connected to form hydrogen sulfate ion (HSO under high pressure acidleach condition
4 -).That is sulfuric acid dissociation under high pressure acidleach condition discharges a proton (H+).Leach liquor cooling and in and time, hydrogen sulfate ion resolves into sulfate radical (SO
4 2-) and another proton.Because after this proton (acid) is inabundant for leaching, and cause excessive sulfuric acid in subsequent disposal to be carried out with and consume neutralizing agent; Three is raw materials that HPAL technique is only limited to that process is mainly limonite class, because the existence of saprolite can cause rolling up of sulfuric acid consumption.This is because the Mg content of magnesium in saprolite is higher caused; Four be HPAL technique in the easy fouling of operational process mesohigh still, need periodic shut down to clear up, working rate is low; Five is leach the quantity of slag greatly, and is the mixing slag of silicon and iron, can not cost-effectively develop.
If publication number is the patent of invention of CN101001964A, propose and a kind ofly first under normal pressure (100 DEG C ~ 105 DEG C), leach limonite with enough sulfuric acid, then use the normal pressure leaching ore pulp of limonite and saprolite ore pulp to leach the method extracting nickel, cobalt under middle pressure (about 0.5MPa, 150 DEG C).The advantage of the method is: can process limonite and saprolite ore deposit simultaneously; Avoid using expensive autoclave and achieve the higher nickel leaching yield in saprolite ore deposit with relatively simple pressure exerting device under middle pressure condition.But the method exists following shortcoming and defect: first obtain the mixing slag that leached mud is silicon and iron, need to increase cost and be separated with the mixing slag of iron silicon, the economic benefit causing leached mud to develop is very poor; Two is that time of normal pressure leaching limonite is longer, is generally more than 4 hours, and therefore required normal pressure leaching equipment is huge; Three are saprolite ore deposit used amounts is 1 times of limonite amount, and the mine belt of this and red soil nickel ore forms and contradicts, it is well known that in red soil nickel ore bed, and limonite amount: saprolite ore deposit amount >=2: 1.
In a word, in the patent of invention of above-mentioned laterite nickel ore hydrometallurgical, the shortcoming of the high pressure acid leaching process of high pressure acidleach (HPAL) technique and improvement is: need the autoclave of complicated high temperature, high pressure and relevant equipment, its I&M is all very expensive; The sulfuric acid of HPAL processes expend is more than the sulfuric acid needed for the non-ferrous metal components stoichiometrically dissolved in ore; HPAL technique is only limited to the raw material that process is mainly limonite class; HPAL technique is in the easy fouling of operational process mesohigh still, and need periodic shut down to clear up, working rate is low.The shortcoming of the normal pressure acid leaching process of normal pressure acid leaching process and improvement is: sulfuric acid consumption is high; Nickel, cobalt leaching yield are low; Long reaction time, required equipment is huge.It is that to leach the quantity of slag large that high pressure acidleach comprises common drawback that the high pressure acid leaching process of improvement and normal pressure acid leaching process comprise the normal pressure acid leaching process of improvement, and is the mixing slag of silicon and iron, can not cost-effectively develop.
Summary of the invention
The present invention seeks to the shortcoming eliminating or alleviate high pressure Ore Leaching technique, obtain the nickel higher than known normal pressure leaching technique, the cobalt rate of recovery simultaneously and reclaim speed faster, the acid consumption lower than high pressure acidleach.Particularly naturally easily scum is separated with white residue very much in technological process.
In order to realize object of the present invention, the technical solution used in the present invention is:
From low-grade laterite nickel ore, extract a method for nickel, it is characterized in that being undertaken by following steps:
(1) low-grade laterite nickel ore washing classification is obtained the thicker high silicon magnesium ore of particle diameter and the thinner low silicon magnesium height iron ore of particle diameter;
(2) high silicon magnesium ore made ore pulp and synchronously add steel lining retort with enough high-concentration inorganic acids and react, to dissolve solubility non-ferrous metal and the soluble iron of the overwhelming majority, take out in loose cellular solid-state paste material from steel lining retort; By water-soluble for reaction mass rear solid-liquid separation, obtain normal pressure leaching slag A, normal pressure leaching liquid B and washings E;
(3) ore pulp that the low silicon magnesium height iron ore obtained in the normal pressure leaching liquid B obtained in step (2) and step (1) is made is added in capstan reactor, controlling pressure after sealing pressing pipeline reactor is 2.0 ~ 4.0MPa, control temperature scope is 180 ~ 240 DEG C, carry out solid-liquid separation after thermostatically heating 30 ~ 90min, obtain pressure leaching slag C, pressureleaching solution D and washings F;
(4) the pressureleaching solution D obtained in step (3) carries out process and reclaims nickel, cobalt.
Further, in step (3), be that 1g:0.7 ~ 1.1ml adds normal pressure leaching liquid B by the mass volume ratio of low silicon magnesium height iron ore and normal pressure leaching liquid B.
Further, it is characterized in that: in step (3), by pulp pre-heating to 80 ~ 100 DEG C that low silicon magnesium height iron ore is made, normal pressure leaching liquid B is preheated to 90 ~ 110 DEG C.
Further, described high-concentration inorganic acid to be concentration be 98% sulfuric acid.
Further, in step (2), described in the high silicon magnesium ore that adds and 98% the mass ratio of sulfuric acid be 1:0.8 ~ 1.2.
Further, in step (2), the ore pulp that high silicon magnesium ore is made is added water by high silicon magnesium ore to prepare the ore pulp of 40 ~ 60wt%.
Further, in step (3), the ore pulp that low silicon magnesium height iron ore is made is that 1g:1.5 ~ 2.5ml is prepared from by the mass volume ratio of the washings E obtained in low silicon magnesium height iron ore and step (2).
Further, in step (3), by after reaction mass fragmentation with water in mass ratio for 1:0.8 ~ 1.5 add carry out in water-soluble tank water-soluble.
Further, in step (1), low-grade laterite nickel ore is crossed 80 mesh sieve washing classifications and obtain the thicker high silicon magnesium ore of particle diameter and the thinner low silicon magnesium height iron ore of particle diameter, then high silicon magnesium ore is ground to-80 orders.
The invention has the beneficial effects as follows:
The present invention can process limonite and transition ore deposit simultaneously, and does not need separately to add sulfuric acid, by Fe in normal pressure leaching liquid in the high silicon magnesium ore pressure leaching stage
3+be hydrolyzed to and precipitate the proton that discharges and leach low silicon magnesium height iron ore again, pressurize again afterwards and Fe under the condition that heats
3+be hydrolyzed to precipitation to leach, decrease sulfuric acid consumption low, and after solid-liquid separation in pressure leaching slag iron level higher, can 58 ~ 65% be reached; Pressure leaching is medium/low-voltage equipment, avoids the shortcoming of autoclave apparatus expensive, easily fouling; Scum naturally can be separated with white residue easily by the present invention in technological process very much, and in normal pressure leaching slag, the content of silicon-dioxide reaches 65 ~ 90%, and leached mud can effectively be utilized, and achieves and utilizes the Efficient Development of low-grade laterite nickel ore; Present invention process is simple to operate, safety, the process time is short, efficiency is high.
1, existing high pressure acidleach comprises the common drawback that the high pressure acid leaching process of improvement and normal pressure acid leaching process comprise the normal pressure acid leaching process of improvement is that to leach the quantity of slag large, and is the mixing slag of silicon and iron, can not cost-effectively develop.And leached mud very naturally can be separated into available white residue and scum easily by method of the present invention in technological process.
2, sulfuric acid consumption of the present invention not only consumes far below the acid of normal pressure acidleach, and consumes lower than the acid of high pressure acidleach.Under normal circumstances, use similar red soil nickel ore and saprolite/limonite ratio, the acid consumption of normal pressure acidleach is that 600 ~ 900Kg sulfuric acid/1000Kg does ore deposit; The acid consumption of high pressure acidleach is that 250 ~ 600Kg sulfuric acid/1000Kg does ore deposit; Acid consumption of the present invention is that 180 ~ 350Kg sulfuric acid/1000Kg does ore deposit.
3, nickel leaching yield of the present invention is not only far above normal pressure acidleach, and reaches or higher than high pressure acidleach.Generally, use similar red soil nickel ore, the nickel leaching yield of normal pressure acidleach is 70 ~ 85%; The nickel leaching yield of high pressure acidleach is 90 ~ 95%; And nickel leaching yield of the present invention is more than 94%.
4, compared with normal pressure acidleach, the normal pressure leaching time of the present invention is 1 minute to 15 minutes, and normal pressure leaching time is generally 240 minutes to 2400 minutes, corresponding normal pressure pickling equipment investment of the present invention is apparent much smaller than existing normal pressure pickling equipment investment.
5, high pressure acid leaching process red soil nickel ore ore pulp and the vitriol oil is directly added autoclave leach, and in autoclave, regional area sulfuric acid concentration is very high, is easy to produce the fouling such as ferric subsulfate and alum.And the pressure leaching stage of the present invention does not have adding of the vitriol oil, the generation of foulant substantially can be avoided.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only one of them embodiment of the present invention, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Execute use in example 1
#ore, from the low-grade laterite nickel ore of New Caledonia, is crossed 80 mesh sieve washing classifications and is obtained+80 objects 2
#ore and-80 objects 3
#ore; 4
#ore, from Indonesia's low-grade laterite nickel ore, is crossed 80 mesh sieve washing classifications and is obtained+80 objects 5
#ore and-80 objects 6
#ore.The main component of ore is in table 1.+ 80 object ores are broken and be ground to-80 orders before for experiment.The vitriol oil used in the present invention is the vitriol oil of 98wt%.
Embodiment one
Get 500Kg(butt) be ground to-80 objects 2
#high silicon magnesium ore deposit adds 500Kg water and makes high silicon magnesium ore pulp, prepares the 500Kg vitriol oil (98%).Strictly controlling flow with mortar pump and vitriol oil pump synchronously adds in steel lining retort by high silicon magnesium ore pulp and the vitriol oil, and ore pulp and the vitriol oil take out after short mix reaction from steel lining retort.10 minutes total overall reaction used times.
Through cooling, leaching tank of being fallen back by the reaction mass simple crushing of loose cellular solid-state lotion, adds 1500Kg water, stir about 30 minutes.Water-soluble gained slurry is pumped into plate-and-frame filter press and carries out solid-liquid separation and residue washing, obtain normal pressure acidleach filter residue (A1) 205Kg(do), normal pressure acidleach filtrate (B1) 1450L and washings (E1) 1150L.The composition of normal pressure acidleach filter residue (A1), normal pressure acidleach filtrate (B1) and washings (E1) is in Table 1-1, table 1-2 and table 1-3.
Get 30Kg(to do) 3
#low silicon magnesium height iron ore, add washings (E1) 60L and be mixed with low silicon magnesium high ferro ore pulp, move into after being heated to 95 DEG C in the circulation tank of capstan reactor, then add normal pressure acidleach filtrate (B1) 30L of 95 DEG C in the circulation tank of capstan reactor.Open force (forcing) pump after sealing circulation tank, open the hot oil heater of capstan reactor simultaneously, control temperature heats, and pressure controls at 2.5MPa, continues thermostatically heating and within 50 minutes, stop afterwards heating and cooling when temperature is increased to 225 DEG C.From the circulation tank of capstan reactor, shift out reaction paste after being cooled to 85 DEG C carry out solid-liquid separation and wash filter residue, obtain pressure leaching slag (C1) 28Kg(do), pressureleaching solution (D1) 76L and washings (F1) 46L.The composition of pressure leaching slag (C1), pressureleaching solution (D1) and washings (F1) is in Table 1-4, table 1-5 and table 1-6.
Use mixed hydroxides precipitation to carry out process to pressureleaching solution (D1) and reclaim nickel, cobalt.
Based on the component content of residue, calculate nickel, cobalt leaching yield, slag rate and acid consumption data as follows:
Normal pressure acidleach nickel leaching yield: 98.1%; Normal pressure acidleach cobalt leaching yield: 97.2%.
Pressure leaching nickel leaching yield: 94.9%; Pressure leaching cobalt leaching yield: 93.1%.
Amount to nickel leaching yield 96.5%; Cobalt leaching yield 93.5%.
Sulfuric acid consumption: 200Kg sulfuric acid/t ore deposit.
Amount to slag rate: 82g white residue/1000g low-grade laterite nickel ore.
Embodiment two
Get 500Kg(butt) be ground to-80 objects 5
#high silicon magnesium ore deposit adds 500Kg water and makes high silicon magnesium ore pulp, prepares the 500Kg vitriol oil (98%).Strictly controlling flow with mortar pump and vitriol oil pump synchronously adds in steel lining retort by high silicon magnesium ore pulp and the vitriol oil, and ore pulp and the vitriol oil take out after short mix reaction from steel lining retort.10 minutes total overall reaction used times.
Through cooling, leaching tank of being fallen back by the reaction mass simple crushing of loose cellular solid-state lotion, adds 1500Kg water, stir about 30 minutes.Water-soluble gained slurry is pumped into plate-and-frame filter press and carries out solid-liquid separation and residue washing, obtain normal pressure acidleach filter residue (A2) 230Kg(do), normal pressure acidleach filtrate (B2) 1400L and washings (E2) 1180L.The composition of normal pressure acidleach filter residue (A2), normal pressure acidleach filtrate (B2) and washings (E2) is in Table 2-1, table 2-2 and table 2-3.
Get 40Kg(to do) 6
#low silicon magnesium height iron ore, add washings (E2) 80L and be mixed with low silicon magnesium high ferro ore pulp, move into after being heated to 80 DEG C in the circulation tank of capstan reactor, then add normal pressure acidleach filtrate (B2) 30L of 100 DEG C in the circulation tank of capstan reactor.Open force (forcing) pump after sealing circulation tank, open the hot oil heater of capstan reactor simultaneously, control temperature heats, and pressure controls at 3.0MPa
,temperature continues thermostatically heating and within 55 minutes, stops afterwards heating and cooling when being increased to 230 DEG C.From the circulation tank of capstan reactor, shift out reaction paste after being cooled to 85 DEG C carry out solid-liquid separation and wash filter residue, obtain pressure leaching slag (C2) 34Kg(do), pressureleaching solution (D2) 94L and washings (F2) 55L.The composition of pressure leaching slag (C2), pressureleaching solution (D2) and washings (F2) is in Table 2-4, table 2-5 and table 2-6.
Use mixed hydroxides precipitation to carry out process to pressureleaching solution (D2) and reclaim nickel, cobalt.
Based on the component content of residue, calculate nickel, cobalt leaching yield, slag rate and acid consumption data as follows:
Normal pressure acidleach nickel leaching yield: 97.8%; Normal pressure acidleach cobalt leaching yield: 94.9%.
Pressure leaching nickel leaching yield: 95.2%; Pressure leaching cobalt leaching yield: 94.3%.
Amount to nickel leaching yield 95.4%; Cobalt leaching yield 93.5%.
Sulfuric acid consumption: 200Kg sulfuric acid/t ore deposit.
Amount to slag rate: 92.0g white residue/1000g low-grade laterite nickel ore.
Embodiment three
Get 500Kg(butt) be ground to-80 objects 2
#high silicon magnesium ore deposit adds 500Kg water and makes high silicon magnesium ore pulp, prepares the 500Kg vitriol oil (98%).Strictly controlling flow with mortar pump and vitriol oil pump synchronously adds in steel lining retort by high silicon magnesium ore pulp and the vitriol oil, and ore pulp and the vitriol oil take out after short mix reaction from steel lining retort.10 minutes total overall reaction used times.
Through cooling, leaching tank of being fallen back by the reaction mass simple crushing of loose cellular solid-state lotion, adds 1500Kg water, stir about 30 minutes.Water-soluble gained slurry is pumped into plate-and-frame filter press and carries out solid-liquid separation and residue washing, obtain normal pressure acidleach filter residue (A3) 205Kg(do), normal pressure acidleach filtrate (B3) 1450L and washings (E3) 1150L.The composition of normal pressure acidleach filter residue (A3), normal pressure acidleach filtrate (B3) and washings (E3) is in Table 3-1, table 3-2 and table 3-3.
Get 30Kg(to do) 6
#low silicon magnesium height iron ore, add washings (E3) 60L and be mixed with low silicon magnesium high ferro ore pulp, move into after being heated to 100 DEG C in the circulation tank of capstan reactor, then add normal pressure acidleach filtrate (B3) 30L of 90 DEG C in the circulation tank of capstan reactor.Open force (forcing) pump after sealing circulation tank, open the hot oil heater of capstan reactor simultaneously, control temperature heats, and pressure controls at 3.5MPa
,temperature continues thermostatically heating and within 60 minutes, stops afterwards heating and cooling when being increased to 225 DEG C.From the circulation tank of capstan reactor, shift out reaction paste after being cooled to 85 DEG C carry out solid-liquid separation and wash filter residue, obtain pressure leaching slag (C3) 29Kg(do), pressureleaching solution (D3) 76L and washings (F3) 44L.The composition of pressure leaching slag (C3), pressureleaching solution (D3) and washings (F3) is in Table 3-4, table 3-5 and table 3-6.
Use mixed hydroxides precipitation to carry out process to pressureleaching solution (D3) and reclaim nickel, cobalt.
Based on the component content of residue, calculate nickel, cobalt leaching yield, slag rate and acid consumption data as follows:
Normal pressure acidleach nickel leaching yield: 98.1%; Normal pressure acidleach cobalt leaching yield: 97.2%.
Pressure leaching nickel leaching yield: 95.5%; Pressure leaching cobalt leaching yield: 96.3%.
Amount to nickel leaching yield 96.0%; Cobalt leaching yield 95.7%.
Sulfuric acid consumption: 200Kg sulfuric acid/t ore deposit.
Amount to slag rate: 82.0g white residue/1000g low-grade laterite nickel ore.
Embodiment four
Get 500Kg(butt) be ground to-80 objects 5
#high silicon magnesium ore deposit adds 500Kg water and makes high silicon magnesium ore pulp, prepares the 500Kg vitriol oil (98%).Strictly controlling flow with mortar pump and vitriol oil pump synchronously adds in steel lining retort by high silicon magnesium ore pulp and the vitriol oil, and ore pulp and the vitriol oil take out after short mix reaction from steel lining retort.10 minutes total overall reaction used times.
Through cooling, leaching tank of being fallen back by the reaction mass simple crushing of loose cellular solid-state lotion, adds 1500Kg water, stir about 30 minutes.Water-soluble gained slurry is pumped into plate-and-frame filter press and carries out solid-liquid separation and residue washing, obtain normal pressure acidleach filter residue (A4) 230Kg(do), normal pressure acidleach filtrate (B4) 1400L and washings (E4) 1180L.The composition of normal pressure acidleach filter residue (A4), normal pressure acidleach filtrate (B4) and washings (E4) is in Table 4-1, table 4-2 and table 4-3.
Get 40Kg(to do) 3
#low silicon magnesium height iron ore, add washings (E4) 80L and be mixed with low silicon magnesium high ferro ore pulp, move into after being heated to 95 DEG C in the circulation tank of capstan reactor, then add normal pressure acidleach filtrate (B4) 30L of 95 DEG C in the circulation tank of capstan reactor.Open force (forcing) pump after sealing circulation tank, open the hot oil heater of capstan reactor simultaneously, control temperature heats, and pressure controls at 4.0MPa
,temperature continues thermostatically heating and within 55 minutes, stops afterwards heating and cooling when being increased to 230 DEG C.From the circulation tank of capstan reactor, shift out reaction paste after being cooled to 85 DEG C carry out solid-liquid separation and wash filter residue, obtain pressure leaching slag (C4) 38Kg(do), pressureleaching solution (D4) 94L and washings (F4) 55L.The composition of pressure leaching slag (C4), pressureleaching solution (D4) and washings (F4) is in Table 4-4, table 4-5 and table 4-6.
Use mixed hydroxides precipitation to carry out process to pressureleaching solution (D4) and reclaim nickel, cobalt.
Based on the component content of residue, calculate nickel, cobalt leaching yield, slag rate and acid consumption data as follows:
Normal pressure acidleach nickel leaching yield: 97.8%; Normal pressure acidleach cobalt leaching yield: 94.9%.
Pressure leaching nickel leaching yield: 96.2%; Pressure leaching cobalt leaching yield: 90.7%.
Amount to nickel leaching yield 96.4%; Cobalt leaching yield 90.6%.
Sulfuric acid consumption: 200Kg sulfuric acid/t ore deposit.
Amount to slag rate: 92.0g white residue/1000g low-grade laterite nickel ore.