CN102876892B - Method for leaching nickel and cobalt form low-iron and high-magnesium and high-iron and low-magnesium laterite-nickel ore by using waste dilute sulphuric acid - Google Patents
Method for leaching nickel and cobalt form low-iron and high-magnesium and high-iron and low-magnesium laterite-nickel ore by using waste dilute sulphuric acid Download PDFInfo
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- CN102876892B CN102876892B CN2012104233181A CN201210423318A CN102876892B CN 102876892 B CN102876892 B CN 102876892B CN 2012104233181 A CN2012104233181 A CN 2012104233181A CN 201210423318 A CN201210423318 A CN 201210423318A CN 102876892 B CN102876892 B CN 102876892B
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Abstract
The invention provides a method for leaching nickel and cobalt from low-iron and high-magnesium and high-iron and low-magnesium laterite-nickel ore by using waste dilute sulphuric acid. Nickelous hydroxide, cobaltous hydroxide and the like are directly extracted by leaching the laterite-nickel ore with non-concentrated decolored and desalinated waste dilute sulphuric acid. The method specially comprises the steps of: removing impurities out of the waste dilute sulphuric acid, slurrying, leaching and pre-neutralizing, filtering and washing leached ore pulp, settling nickel and cobalt from leachate, filtering and washing nickel and cobalt settled slurry, electrically depositing nickel, and post-treating and recycling iron, magnesium, manganese and the like. The method provided by the invention overcomes the technical difficulty, ensures that a technology of a direct dilute sulphuric acid atmospheric pressure leaching process route operates stably, is greatly lowered in cost, is high in production efficiency, and is high in recycling rate of nickel, cobalt, iron, magnesium, manganese and other metals. The waste dilute sulphuric acid which is an byproduct in industries such as dye industry and is difficult to treat is effectively recycled, the method is environmental-friendly, any harmful gas is not emitted, waste slag is solid materials, trees can be planted on the waste slag for greening, the waste slag can be recycled, and waste water can completely reach the standard for emission.
Description
Technical field
The invention belongs to the non-ferrous metal hydrometallurgy and with pyrometallurgy comprehensive application technology field, relate in particular to the method for the low magnesium laterite nickel mine of the high magnesium of a kind of low iron, high ferro with useless dilute sulphuric acid leaching nickel cobalt.
Background technology
Existing treatment process technical point three classes of whole world red soil nickel ore: the wet combined techniques of pyrogenic process, wet method and fire.First kind thermal process flow process: ore is broken through ore dressing, rotary kiln carries out roasting, electricity/blast furnace/electrical carbon retailoring or sulfiding smelting after dry, the thick ferronickel of output or low nickelic sulphur work in-process, then refining obtains product.The Equations of The Second Kind wet method is divided a variety of, main typical technical process is as follows: ore is with sulfuric acid, hydrochloric acid or nitric acid normal temperature or medium and high temperature, normal pressure or basic, normal, high pressure leach, and leach liquor carries out list/pair calcium method, burning soda ash sodium method, carbon/ammonia process, from ore deposit circulation method, magnesium base ore deposit method or the enrichment of sulfuration method, extracts the nickel cobalt.The 3rd wet method combined technical process of class fire divides two kinds: a kind of is reduction-beneficiating method, and raw ore is levigate and fine coal mixing briquetting, the thin slurrying of regrinding after drying and high temperature reduction roasting, and ore pulp carries out gravity concentration and magnetic concentration sub-elects Rhometal; A kind of is reduction-ammonia leaching process, leaches refining again after the heavy nickel of leach liquor sulfuration after the raw ore reducing roasting with ammoniacal liquor.
The pyrometallurgical smelting energy consumption is higher, and its economy is more difficult when the nickel valency is low.The high pressure acidleach is suitable for processing nickel 〉=1.1%, the ore of magnesium≤5%, and the nickel and cobalt recovery rate, all greater than 90%, mainly exists facility investment large, safeguards and the high problem of operational cost.Reduction-ammonia soaks can process high magnesium ore, but energy consumption is high, and the cobalt rate of recovery is low, and is superseded.The dump leaching method is suitable for processing low grade ore, but ton nickel acid consumption is too high, generally infeasible economically.Conventional normal pressure sulfuric acid agitation leach investment is lower, and raw materials cost is high, and technical process is unreasonable, can not take full advantage of that sulfuric acid mixes with water and the reaction heat of sulfuric acid and ore.In laterite nickel industry, other factory uses 98% vitriol oil to produce nickel hydroxide.
Several wet methods and wet process technology scheme are compared as follows shown in table:
| Processing method | Process characteristic | Three wastes situation | Remarks |
| Ammonia leaching process | Leach pre reduction and process difficulty, reducing atmosphere is difficult for control, and leaching yield is low, and cost is high | Pollution is large, environment is poor, the smell weight | Be only suitable for the low limonite type red soil nickel ore of Mg, Ca, industrial reality is superseded |
| The sulfuration method | Need pressurization, heating high temperature to leach, H 2S, sodium sulphite, ammonium sulfide precipitation are made the ice nickel matte and can be incorporated the smelting system into.Can obtain the high density metallic solution with concentrated sulfuric acid roasting, impurity is few, and extraction obtains high pure metal | Pollution is large, environment is poor, the smell weight | Operational condition is very harsh, pollutes very seriously, and potential safety hazard is very large, unfavorable production; |
| The high acid system of High Temperature High Pressure (HPAL) technique | Leaching yield 93～95%, scale removal accounts for duration, increases cost, water purification, circulation ammonia and steam consumption is high, zinc in nickel, manganese content are high. | Pollute less, fully utilize | Especially be suitable for the low limonite type laterite of magnesium, the foulings such as pump valve, pipe-line equipment are serious, and technology is immature |
| The high acid system of medium temperature and medium pressure | High temperature and high pressure method institute improved method, can slow down the subject matters such as fouling | Sal epsom waste water | Preliminary Applications is arranged |
| The high acid system of middle temperature low pressure | For medium temperature and medium pressure method institute modification method, technical process is more smooth and easy, and the utilization of resources is more reasonable | Sal epsom waste water | The ripe technique of improving |
| The high acid system of normal temperature and pressure | Improve technique, the relative mature and reliable of technology | Sal epsom waste water, need Tailings Dam | Relatively improve technique |
| Normal temperature and pressure hangs down acid system | Improve technique, the relative mature and reliable of technology | Have more | Relatively improve technique, application is not arranged |
| The dump leaching method | Available diluted acid, process low grade ore most economical, and ore deposit heap infiltration is difficult, and leaching yield is low, and it is difficult that iron, aluminium, nickel, cobalt removal of impurities separate | Less | Floor space is large, and extraction time approximately 30 days is fit to special process |
| Pond leaching process | Similar to dump leaching, less investment, yield is lower slightly | Less | Floor space is large, is fit to special process |
| Dump leaching, pond are soaked, are stirred and soak hybrid system | Be fit to special process, according to ore characteristics combination technology innovative technology, yield is higher | Less | Floor space is large, in test, and not mass-producing application |
| Full extraction process | The acidleach leach liquor extracts Ni, Co, Fe, Mn entirely after purifying, Mg can be than pure nickel, rhombohedral iron ore, sal epsom, single nickel salt | Less | Industrialization is stable need be confirmed, extraction agent is difficult, consumption indicators is difficult up to standard, is fit to special process |
| Hydrochloric acid leaching process | Normal pressure, can extract to obtain pure nickel, rhombohedral iron ore, magnesium oxide, high burn into leaches that gas is difficult to be controlled, and rhombohedral iron ore sedimentation cost is high | Environment is poor, the smell weight | Innovation separates Ni, Co, Mn, Mg special process |
| Pyrogenic process | The technology maturation production capacity is large, nickeliferous 10%, and energy consumption is high, is suitable for the low magnesium ore deposit of high ferro, the low iron of high magnesium or high aluminium ore, and furnace temperature is high, the quantity of slag is large | Waste residue can be done to build and banket, dust pollution is large | Electric furnace process less investment, cost are low.Blast furnace process is many is changed the line of production by general steel blast furnace, and the pig iron is nickeliferous low, and cost is high |
| Pyrogenic process, wet method synthetic method | The rear lump ore of the dry screening of pyrogenic process is given wet method factory heap/pond and is soaked.Available normal temperature and pressure agitation leach technique, reduced investment, yield improve | Floor space is large, must hang down the red soil nickel ore of iron with high magnesium, and normal temperature and pressure agitation leach etc. also can be adopted |
In addition, a large amount of dilute sulphuric acids of meeting by-product in the Chemical Manufacture such as dyestuff, pigment, agricultural chemicals, titanium white, however not yet there is use in the manufacturer of these industries or develops this technology.At present there are four kinds of method: ⑴ commonly used the processing of useless dilute sulphuric acid, use the Wingdale neutralisation: with high costs, the gypsum mud that by-product is a large amount of, form secondary pollution, is fit to a small amount of low acid treatment.⑵, multiple-effect evaporation and high temperature method of enrichment: investment is large, energy consumption is high.The method is at sulfuric acid concentration greater than 50%, and commodity 98% sulfuric acid price during higher than 550 yuan/tons, can break even, but for concentration lower than 25% dilute sulphuric acid, its cost of disposal is more than 700 yuan/tons.⑶, ammonia gas as byproduct absorb ammonium sulfate method processed: the ammonia of by-product is used for preparing ammoniacal liquor, nitric acid is better, and benefit is better.⑷, by-product buck absorb sodium sulphate method processed and organic products project raw material method etc., need new suitable project, and investment risk strengthens.
Summary of the invention
The present invention is in order to overcome the deficiencies in the prior art, provide a kind of direct utilization after the decolouring desalination, the give up method of dilute sulphuric acid acidleach red soil nickel ore (comprising the low magnesium laterite nickel mine of low iron high magnesium laterite nickel mine and high ferro) extraction nickel hydroxide or nickel cobalt of the industrial by-products such as the dyestuff that need not to concentrate.
To achieve these goals, the invention provides the method for a kind of low iron high magnesium laterite nickel mine with useless dilute sulphuric acid leaching nickel cobalt, comprise the steps.Useless dilute sulphuric acid removal step: will give up that dilute sulphuric acid decolours, desalination, take off after organism that to obtain mass concentration be 5～50% dilute sulphuric acid.Slurrying step: will hang down the iron high magnesium laterite nickel mine broken, after adding water or adding above-mentioned dilute sulphuric acid, with ball mill, red soil nickel ore is milled to granularity in the particle accounting below 0.075 millimeter 〉=80～95%, using Hhigh-efficient thickener, band filter or pressure filter enrichment to moisture to account for weight ratio is 30～40%, add above-mentioned dilute sulphuric acid to pull an oar, control pulp density 〉=50～60%.leach and the pre-neutralization step: slurry is put into the stirred autoclave groove, the ratio that is 0.35～0.65:1 in sulfuric acid and the dried ore deposit of low iron high magnesium laterite nickel mine mass ratio adds above-mentioned dilute sulphuric acid, difference according to the sulfuric acid additional proportion, it is 1.8～3.3:1 that washing lotion while determining with the washing of leaching slurry filtration is adjusted liquid-solid ratio, gradually be warming up to 90～175 ℃, leach approximately after 2 hours, continue to pass into air or oxygen, naturally boost 〉=0.10～0.35MPa in the still groove, after continuing to leach half an hour, be 5 ~ 30% to add magnesia ore deposit to carry out one section deironing by magnesia ore deposit and low iron high magnesium laterite nickel mine mass ratio, and continue without Ore Leaching 1～3 hour, behind pH 〉=1.3～2.3, add Wingdale, unslaked lime, white lime, magnesium oxide, magnesium hydroxide, magnesite, serpentine ore, a kind of pre-neutralization again in carbon ammonium or ammoniacal liquor is to pH=2.5～6.5, leach and finish.Leach the slurry filtration washing step: after leaching the non-ionic polyacrylamide polymeric flocculant flocculation of the ore pulp molecular weight of mass concentration 0.01～0.5% 〉=1000～1,500 ten thousand, carry out solid-liquid separation, washing with thickener, band filter, pressure filter or thickener in conjunction with band filter, pressure filter, a washing lotion part is returned while leaching to be used for adjusting and is leached liquid-solid ratio use, and a part is incorporated leaching stoste into.Leach liquor sinks nickel cobalt step: leach liquor adds the deironing of two sections, magnesium base ore deposit to pH=3.5～7.5, adopt the magnesite enrichment, in and one section heavy nickel of supernatant liquor add the heavy Ni (OH) of alkali
2To pH=7.1～9.2, crystal seed returns to heavy nickel groove, and heavy nickel material advances the thickener sedimentation, underflow press filtration, pulp, washing Ni (OH)
2, the thickener overflow is advanced two sections heavy nickel to pH=6～12, makes in mother liquor nickel less than 30～50mg/L, must sink nickel cobalt slurry.Heavy nickel cobalt slurries filtration washing step: heavy nickel cobalt slurry carries out solid-liquid separation with thickener, band filter, pressure filter or thickener in conjunction with pressure filter, band filter, wash, obtain nickel hydroxide, cobaltous hydroxide or nickelous carbonate, the cobaltous carbonate product of nickeliferous 〉=40～45%.
Preferably, also comprise heavy nickel mother liquid disposal step after heavy nickel cobalt slurries filtration washing step: during magnesium ion concentration in heavy nickel mother liquor 〉=35g/L, with magnesite, carbon ammonium, Wingdale, calcium oxide, sodium hydroxide, serpentine ore, white lime, magnesium oxide or ammonia neutralization precipitate and separate, obtain the direct fractional crystallization sal epsom of magnesiumcarbonate, magnesium basic carbonate, magnesium hydroxide and employing cryogenic film technology.
Preferably, also comprised beneficiation steps before the slurrying step: according to the difference of magnesium iron level select from red soil nickel ore iron level 〉=20% as the low magnesium laterite nickel mine of high ferro, select the low iron high magnesium laterite nickel mine of conduct of iron level＜20%.
The present invention also provides the method for the low magnesium laterite nickel mine of a kind of high ferro with useless dilute sulphuric acid leaching nickel cobalt, comprises the steps.Useless dilute sulphuric acid removal step: will give up that dilute sulphuric acid decolours, desalination, take off after organism that to obtain mass concentration be 5～50% dilute sulphuric acid.Slurrying step: the low magnesium laterite nickel mine of high ferro is broken, after adding water or adding above-mentioned dilute sulphuric acid, with ball mill, red soil nickel ore is milled to granularity in the particle accounting below 0.075 millimeter 〉=80～95%, using Hhigh-efficient thickener, band filter or pressure filter enrichment to moisture to account for weight ratio is 30～40%, add above-mentioned dilute sulphuric acid to pull an oar, control pulp density 〉=35～45%.leach and the pre-neutralization step: slurry is put into the stirred autoclave groove, the ratio that is 0.55～1.3:1 in sulfuric acid and the dried ore deposit of the low magnesium laterite nickel mine of high ferro amount mass ratio adds above-mentioned dilute sulphuric acid, difference according to the sulfuric acid additional proportion, it is 1.8～4.0:1 that washing lotion while determining with the washing of leaching slurry filtration is adjusted liquid-solid ratio, gradually be warming up to 90～175 ℃, leach approximately after 2 hours, ore amount adds low iron high magnesium laterite nickel mine ore pulp by with the low magnesium laterite nickel mine mass ratio of high ferro, being 15～90%, by with low iron high magnesium laterite nickel mine mass ratio be that 0.12～0.55:1 adds above-mentioned dilute sulphuric acid, pass into air or oxygen, certainly boost 〉=0.10～0.35MPa in the still groove, continue to leach after 1～3 hour, be 5 ~ 30% to add magnesia ore deposit to carry out one section deironing by the low magnesium laterite nickel mine mass ratio of magnesia ore deposit and high ferro, and continue without Ore Leaching 1～3 hour, behind pH 〉=1.3～2.3, add Wingdale, unslaked lime, white lime, magnesium oxide, magnesium hydroxide, magnesite, serpentine ore, a kind of pre-neutralization again in carbon ammonium or ammoniacal liquor is to pH=1.5～4.5, leach and finish.leach the slurry filtration washing step: leach that ore pulp is dense carries out liquid-solid separation, the thickener overflow flows into leaches the supernatant liquid bath, thickener underflow through pumping once, the secondary press filtration, efflux after filter cake washing, first-time filtrate is delivered to and is carried out the secondary removal of impurities except the sial groove, edulcoration purification is removed Fe, Al, Cu, Zn, Si, Cr, remove sial thickener solid-liquid separation again, after non-ionic polyacrylamide polymeric flocculant flocculation with the molecular weight of mass concentration 0.01～0.5% 〉=1000～1,500 ten thousand, use thickener, band filter, pressure filter or thickener are in conjunction with band filter, pressure filter carries out solid-liquid separation, washing, a washing lotion part is returned while leaching and is used for adjusting leaching liquid-solid ratio use, a part is incorporated leaching stoste into.Leach liquor sinks nickel cobalt step: leach liquor adds the deironing of two sections, magnesium base ore deposit to pH=3.5～7.5, adopt the magnesite enrichment, in and one section heavy nickel of supernatant liquor add the heavy Ni (OH) of alkali
2To pH=7.1～9.2, crystal seed returns to heavy nickel groove, and heavy nickel material advances the thickener sedimentation, underflow press filtration, pulp, washing Ni (OH)
2, the thickener overflow is advanced two sections heavy nickel to pH=6～12, makes in mother liquor nickel less than 30～50mg/L, must sink nickel cobalt slurry.Heavy nickel cobalt slurries filtration washing step: heavy nickel cobalt slurry carries out solid-liquid separation with thickener, band filter, pressure filter or thickener in conjunction with pressure filter, band filter, wash, obtain nickel hydroxide, cobaltous hydroxide or nickelous carbonate, the cobaltous carbonate product of nickeliferous 〉=40～45%.
Preferably, also comprise heavy nickel mother liquid disposal step after heavy nickel cobalt slurries filtration washing step: during magnesium ion concentration in heavy nickel mother liquor 〉=35g/L, with magnesite, carbon ammonium, Wingdale, calcium oxide, sodium hydroxide, serpentine ore, white lime, magnesium oxide or ammonia neutralization precipitate and separate, obtain the direct fractional crystallization sal epsom of magnesiumcarbonate, magnesium basic carbonate, magnesium hydroxide and employing cryogenic film technology.
Preferably, also comprised beneficiation steps before the slurrying step: according to the difference of magnesium iron level select from red soil nickel ore iron level 〉=20% as the low magnesium laterite nickel mine of high ferro, select the low iron high magnesium laterite nickel mine of conduct of iron level＜20%.
The present invention also provides a kind of low iron high magnesium laterite nickel mine to soak integrated approach with the heap pond of useless dilute sulphuric acid leaching nickel cobalt, comprises the steps.Useless dilute sulphuric acid removal step: will give up that dilute sulphuric acid decolours, desalination, take off after organism that to obtain mass concentration be 5～50% dilute sulphuric acid.Leach and the pre-neutralization step: first to soak the cloth liquid mode of rear spray, the ratio that is 0.35～1.1:1 in sulfuric acid and the dried ore deposit of the low magnesium laterite nickel mine of high ferro amount mass ratio adds above-mentioned dilute sulphuric acid, pond is soaked or is built the heap dump leaching and leach, and pH=1.5～4.5 after 240～360hr are soaked in the heap pond, leach and finish.Leach slurry filtration washing step: granularity＜0.075mm, the leach liquor of solid content＜8% enters thickener and carries out liquid-solid separation, the thickener underflow solid content〉33%, the solid content of thickener overflow≤1%, the thickener overflow flows into leaches the supernatant liquid bath, thickener underflow through pumping once, the secondary press filtration, efflux after filter cake washing, first-time filtrate deliver to except the sial groove carry out normal temperature or 〉=95 ℃ of secondary removal of impurities, reaction times is 2～3.5～4hr, edulcoration purification is removed Fe, Al, Cu, Zn, Si, Cr, removes sial thickener solid-liquid separation again.Leach liquor sinks nickel cobalt step: enter heavy nickel operation after solid-liquid separation, the heavy nickel time is 1.5hr, after the flocculation agent flocculation, carry out solid-liquid separation, washing with thickener, band filter, pressure filter, a washing lotion part is returned while leaching to be used for adjusting and is leached liquid-solid ratio use, and a part is incorporated leaching stoste into.Then, leach liquor adds the deironing of two sections, magnesium base ore deposit to pH=3.5～7.5, adopt the magnesite enrichment, in and one section heavy nickel of supernatant liquor add the heavy Ni (OH) of alkali
2To pH=7.1～9.2, crystal seed returns to heavy nickel groove, and heavy nickel material advances the thickener sedimentation, underflow press filtration, pulp, washing Ni (OH)
2, the thickener overflow is advanced two sections heavy nickel to pH=6～12, makes in mother liquor nickel less than 30～50mg/L, must sink nickel cobalt slurry.Heavy nickel cobalt slurries filtration washing step: heavy nickel cobalt slurry carries out solid-liquid separation with thickener, band filter, pressure filter or thickener in conjunction with pressure filter, band filter, wash, obtain nickel hydroxide, cobaltous hydroxide or nickelous carbonate, the cobaltous carbonate product of nickeliferous 〉=40～45%.
Preferably, also comprise heavy nickel mother liquid disposal step after heavy nickel cobalt slurries filtration washing step: during magnesium ion concentration in heavy nickel mother liquor 〉=35g/L, with magnesite, carbon ammonium, Wingdale, calcium oxide, sodium hydroxide, serpentine ore, white lime, magnesium oxide or ammonia neutralization precipitate and separate, obtain the direct fractional crystallization sal epsom of magnesiumcarbonate, magnesium basic carbonate, magnesium hydroxide and employing cryogenic film technology.
Preferably, also comprised beneficiation steps before leaching and pre-neutralization step: sieving out dried ore grain size from pyrogenic process laterite nickel smelting factory is 2～5mm, and ore grade is 1.35～1.8% low iron high magnesium laterite nickel mine.
In sum, compare with wet processing with existing pyrogenic process, provided by the present invention is that a kind of direct utilization is after the decolouring desalination, the dyestuff that need not to concentrate, pigment, agricultural chemicals, titanium white, the unmanageable useless dilute sulphuric acid acidleach red soil nickel ore of chemical industry by-product extract the method for nickel hydroxide or nickel cobalt, the method overcomes various technical barriers, makes the diluted acid Technology stable.Direct dilute sulphuric acid normal pressure pickling process operational path, dilute sulphuric acid can be disregarded cost, when only this disregards the comprehensive utilization of magnesium resource ton fall these approximately 30,000 yuan, be in low level such as present nickel valency 11.5 ten thousand/ton at the nickel valency, competitive edge is fairly obvious.This method has advantages of following outstanding: Technology is advanced rationally, raw materials cost significantly reduces, production efficiency is high, mature and reliable, operating safety are stable, and the rate of recovery such as nickel, cobalt, iron, magnesium are high, the resource utilization high.Simultaneously, the present invention is environmentally friendly, does not discharge any gas that hinders environment, and waste residue is solid substance, recoverable, can plant trees, can afforest; Waste water fully can qualified discharge.
Description of drawings
Figure 1 shows that main production schema provided by the invention.
Figure 2 shows that the first production technological process provided by the invention.
Figure 3 shows that the second production technological process provided by the invention.
Figure 4 shows that the standby ginseng figure of the first technological process of production provided by the invention.
Embodiment
The invention provides the method for the high magnesium of a kind of low iron, the low magnesium of high ferro, the useless dilute sulphuric acid leaching nickel cobalt of high magnesium laterite nickel mine use.Figure 1 shows that main production schema provided by the invention.As shown in Figure 1, technical process of the present invention comprises useless dilute sulphuric acid removal step, slurrying step, leaching and pre-neutralization step, leaching slurry filtration washing step, the heavy nickel cobalt step of leach liquor and heavy nickel cobalt slurries filtration washing step.Preferably, the present invention also comprises beneficiation steps, heavy nickel mother liquid disposal step, electro deposited nickel step and aftertreatment circulation recovery iron, magnesium, manganese etc.
In practical application, the present invention collects the useless dilute sulphuric acid of by-product from the Chemical Manufacture such as dyestuff, pigment, agricultural chemicals, titanium white, and useless dilute sulphuric acid is decoloured, desalination, takes off after organism that to obtain mass concentration be 5～50% dilute sulphuric acid.Particularly, with useless dilute sulphuric acid through oil removing tower, molecular sieve resin tower with membrane filtration decolours, desalination, take off organism and obtain the qualified useless dilute sulphuric acid of water white transparency machinery-free impurity, prepare to turn material slurrying and acidleach stand-by.
The red soil nickel ore bed generally is divided into 3 layers, and upper strata is the limonite layer, and iron, cobalt contents are high, and silicon, magnesium, nickel content are lower, obtain the low magnesium laterite nickel mine of high ferro; But lower floor is lower than the low iron high magnesium laterite nickel mine of industry mining grade or claims noumeite, and silicon, Mg content are higher, and iron, cobalt contents are lower, but the content of nickel is higher; Centre is transition layer, and each major metal content is between upper strata and lower floor.Shown in its table composed as follows.
| Composition | Ni | Co | Fe | Mg | Al | SiO 2 | Zn | Cu | Pb |
| Content % | 1.4-1.9 | ≤0.029 | 15-20 | 17-40 | ≤0.64 | 33-40 | ≤0.015 | ≤0.005 | ≤0.1 |
| Composition | Mn | Cr | Ca | SO 4 2- | P | K | Na | O | Other |
| Content % | ≤0.38 | ≤0.085 | ≤0.357 | ≤0.006 | ≤0.0008 | ≤0.3 | ≤0.5 | 22.512 | ≤8.47 |
During ore dressing according to the difference of magnesium iron level, that selects iron level 〉=20% from red soil nickel ore hangs down magnesium laterite nickel mine as high ferro, also can send red soil nickel ore pyrogenic process factory floor to use, the iron high magnesium laterite nickel mine is hanged down in the conduct of iron level＜20%, enters red soil nickel ore hydrometallurgy factory and leaches the workshop use.But in the bottom of general mining nickel lower than the industry mining grade as high magnesium laterite nickel mine, stack respectively, be convenient to utilize.
with the low magnesium laterite nickel mine of high ferro, after low iron high magnesium laterite nickel mine and the fragmentation of high magnesium laterite nickel mine difference, add water or through the decolouring, desalination, after taking off organism, not concentrated, average quality concentration be 5～50% dilute sulphuric acid with grinding of ball grinder to granularity-0.075mm 〉=80～95%, use Hhigh-efficient thickener, band filter or pressure filter enrichment are to moisture 30～40%, add decolouring, desalination, take off concentration after organism and be 5～50% dilute sulphuric acid making beating, control pulp density 〉=35～45%, wherein, for low iron high magnesium laterite nickel mine and high magnesium laterite nickel mine, the pulp density of controlling respectively after ore grinding is 〉=50～60%.
when Raw Ore is low iron high magnesium laterite nickel mine, slurry is put into the stirred autoclave groove, the ratio that is 0.35～0.65:1 in sulfuric acid and the dried ore deposit of low iron high magnesium laterite nickel mine mass ratio adds above-mentioned dilute sulphuric acid, difference according to the sulfuric acid additional proportion, it is 1.8～3.3:1 that washing lotion while determining with the washing of leaching slurry filtration is adjusted liquid-solid ratio, gradually be warming up to 90～175 ℃, leach approximately after 2 hours, continue to pass into air or oxygen, naturally boost 〉=0.10～0.35MPa in the still groove, after continuing to leach half an hour, be 5 ~ 30% to add magnesia ore deposit to carry out one section deironing by magnesia ore deposit and low iron high magnesium laterite nickel mine mass ratio, and continue without Ore Leaching 1～3 hour, behind pH 〉=1.3～2.3, add Wingdale, unslaked lime, white lime, magnesium oxide, magnesium hydroxide, magnesite, a kind of pre-neutralization again in carbon ammonium or ammoniacal liquor is to pH=2.5～6.5, leach and finish.
when Raw Ore is the low magnesium laterite nickel mine of high ferro, slurry is put into the stirred autoclave groove, the ratio that is 0.55～1.3:1 in sulfuric acid and the dried ore deposit of the low magnesium laterite nickel mine of high ferro amount mass ratio adds above-mentioned dilute sulphuric acid, difference according to the sulfuric acid additional proportion, it is 1.8～4.0:1 that washing lotion while determining with the washing of leaching slurry filtration is adjusted liquid-solid ratio, gradually be warming up to 90～175 ℃, leach approximately after 2 hours, ore amount adds low iron high magnesium laterite nickel mine ore pulp by with the low magnesium laterite nickel mine mass ratio of high ferro, being 15～90%, by with low iron high magnesium laterite nickel mine mass ratio be that 0.12～0.55:1 adds above-mentioned dilute sulphuric acid, pass into air or oxygen, certainly boost 〉=0.10～0.35MPa in the still groove, continue to leach after 1～3 hour, be 5 ~ 30% to add magnesia ore deposit to carry out one section deironing by the low magnesium laterite nickel mine mass ratio of magnesia ore deposit and high ferro, and continue without Ore Leaching 1～3 hour, behind pH 〉=1.3～2.3, add Wingdale, unslaked lime, white lime, magnesium oxide, magnesium hydroxide, magnesite, a kind of pre-neutralization again in carbon ammonium or ammoniacal liquor is to pH=1.5～4.5, leach and finish, ore pulp is dense carries out liquid-solid separation, the thickener overflow flows into leaches the supernatant liquid bath, thickener underflow through pumping once, the secondary press filtration, efflux after filter cake washing, first-time filtrate is delivered to and is carried out the secondary removal of impurities except the sial groove, edulcoration purification is removed Fe, Al, Cu, Zn, Si, Cr, remove sial thickener solid-liquid separation again.
Then, after leaching non-ionic polyacrylamide (PAM) the polymeric flocculant flocculation of the ore pulp molecular weight of mass concentration 0.01～0.5% 〉=1000～1,500 ten thousand, carry out solid-liquid separation, washing with thickener, band filter, pressure filter or thickener in conjunction with band filter, pressure filter, a washing lotion part is returned while leaching to be used for adjusting and is leached liquid-solid ratio use, and a part is incorporated leaching stoste into.
Then, leach liquor adds the deironing of two sections, magnesium base ore deposit to pH=3.5～7.5, adopt the magnesite enrichment, in and one section heavy nickel of supernatant liquor add the heavy Ni (OH) of alkali
2To pH=7.1～9.2, crystal seed returns to heavy nickel groove, and heavy nickel material advances the thickener sedimentation, underflow press filtration, pulp, washing Ni (OH)
2, the thickener overflow is advanced two sections heavy nickel to pH=6～12, makes in mother liquor nickel less than 30～50mg/L, must sink nickel cobalt slurry.
Finally, heavy nickel cobalt slurry carries out solid-liquid separation with thickener, band filter, pressure filter or thickener in conjunction with pressure filter, band filter, washs, and obtains nickel hydroxide, cobaltous hydroxide or nickelous carbonate, the cobaltous carbonate product of nickeliferous 〉=40～45%.
In addition, during magnesium ion concentration in heavy nickel mother liquor 〉=35g/L, with magnesite, carbon ammonium or ammonia neutralization precipitate and separate, obtain the direct fractional crystallization sal epsom of magnesiumcarbonate, magnesium basic carbonate, magnesium hydroxide and employing cryogenic film technology.
When Raw Ore is low iron high magnesium laterite nickel mine, the present invention also buyable pyrogenic process laterite nickel smelts factory's dried low iron high magnesium laterite nickel mine of screening and enters the dilute suplhuric acid pond and soak or build the heap dump leaching, and namely soak and the low magnesium laterite nickel mine pyrogenic process synthetic method of high ferro---synthetic method is soaked in the heap pond in the heap pond of low iron high magnesium laterite nickel mine.
Sieving out dried ore grain size from pyrogenic process laterite nickel smelting factory is 2～5mm, and ore grade is 1.35～1.8% low iron high magnesium laterite nickel mine.First to soak the cloth liquid mode of rear spray, to do ore deposit amount mass ratio be that the ratio of 0.35～1.1:1 adds decolouring, desalination, takes off mass concentration after organism in the low magnesium laterite nickel mine of sulfuric acid and high ferro is 5～50% dilute sulphuric acid, pond is soaked or is built the heap dump leaching and leach, pH=1.5～4.5 after 240～360hr are soaked in the heap pond, leach and finish.
Granularity＜0.075 mm, the leach liquor of solid content＜8% enters thickener and carries out liquid-solid separation, the thickener underflow solid content〉33%, the solid content of thickener overflow≤1%, the thickener overflow flows into leaches the supernatant liquid bath, thickener underflow through pumping once, the secondary press filtration, efflux after filter cake washing, first-time filtrate deliver to except the sial groove carry out normal temperature or 〉=95 ℃ of secondary removal of impurities, reaction times is 2～3.5～4hr, edulcoration purification is removed Fe, Al, Cu, Zn, Si, Cr, except sial enters heavy nickel operation after the thickener solid-liquid separation again.
The heavy nickel time is 1.5hr, after the flocculation agent flocculation, with thickener, band filter, pressure filter, carries out solid-liquid separation, washing, and a washing lotion part is returned while leaching to be used for adjusting and leached liquid-solid ratio use, and a part is incorporated leaching stoste into.Then, leach liquor adds the deironing of two sections, magnesium base ore deposit to pH=3.5～7.5, adopt the magnesite enrichment, in and one section heavy nickel of supernatant liquor add the heavy Ni (OH) of alkali
2To pH=7.1～9.2, crystal seed returns to heavy nickel groove, and heavy nickel material advances the thickener sedimentation, underflow press filtration, pulp, washing Ni (OH)
2, the thickener overflow is advanced two sections heavy nickel to pH=6～12, makes in mother liquor nickel less than 30～50mg/L, must sink nickel cobalt slurry.
Heavy nickel cobalt slurry carries out solid-liquid separation with thickener, band filter, pressure filter, washs, and obtains nickel hydroxide, cobaltous hydroxide or nickelous carbonate, the cobaltous carbonate of nickeliferous 〉=40～45%.The heavy nickel recovery that use the method obtains 〉=98.5%, total nickel recovery 80～86%.
Being fit to best ore deposit of the present invention is low iron high magnesium laterite nickel mine, and be somebody's turn to do the producer that low iron high magnesium laterite nickel mine is the pyrometallurgical smelting technology, avoids a large amount of uses, because a large amount of existence of magnesium make the temperature of pyrometallurgical smelting higher, thereby causes cost higher., if the high magnesium laterite nickel mine that adopts pyrometallurgical smelting producer to sieve out, contain the irony ore deposit less on the one hand, make leach liquor remove iron load and greatly reduce, and greatly reduce the generation of iron mud; Also passed through on the other hand dry and pulverized, the raw material of having exempted ore dressing and washup prepares that workshop section is a large amount of takes up an area and the investment of equipment, also is more suitable for a large amount of uses in diluted acid, and the surperficial nickel content in this ore deposit is higher simultaneously, grade is relatively suitable, is the raw material of very suitable diluted acid leaching process.Avoided stirring the siderotil waste residue that can't dispose in a large number that in peracid, temperature leaches, pond soak the waste residue that produces fully can harmless treatment as building materials, building and roadbed ground banket, banket in lawn etc.
Moisture content waste residue self the band slightly acidic that this technique produces, neutralization is to pH=7 before discharging.Wherein heavy metal soaked 5 days through diluted acid, leached detected level and did not exceed standard.Waste residue under state of nature, does not soak institute's stripping for rainwater drenches.Can be by checkings such as country's " leaching toxicity test " standards " non-ferrous metals industry solid waste leaching toxicity test method standard ".The measure of waste residue environmental protection handling project: waste residue can harmlessly turn that building lot etc. bankets or be used for building materials, cement, brickmaking, prepare white carbon black into.Waste water: cycling utilization of wastewater and a small amount of liquid effluent pH=6.2～7.8.Reach the emission standard of GB1998 regulation after processing.Mg wherein
2+, SO
4 2-China is emission standard not yet targetedly.
Quality and the safeguard measure of efflux wastewater are as shown in the table:
The roughly technique of the schematic illustration of below giving an example for different sample ores.
Embodiment 1:
The test sample ore is low iron high magnesium laterite nickel mine, nickeliferous 2.26%, cobalt 0.09%, iron 13.8%, magnesium oxide 26.5%, adopt that grinding particle size-0.075mm accounts for 90%, dilute sulphuric acid and the dried ore deposit of pulp density 42%, mass concentration 23.5% measure mass ratio 0.85:1, liquid-solid ratio 2.5:1, leached one hour, passes into air pressurized to the still internal pressure to 0.25MPa, continue to leach half an hour, the high magnesium ore deposit that adds raw ore amount 30%, continue to leach 2.5 hours, adds magnesite to be neutralized to pH value 5.7, leach pulp liquid-solid isolation, leach liquor magnesite sinks nickel.Result: nickel recovery is 97.6%, and the cobalt rate of recovery is 95.3%.
Embodiment 2
The test sample ore is for mixing sample ore, and high ferro low magnesium laterite nickel mine in upper strata is nickeliferous 1.51%, cobalt 0.10%, and iron 25.3%, magnesium oxide 13.8%, the low iron high magnesium laterite nickel mine of lower floor is nickeliferous 1.8%, cobalt 0.02%, iron 15.4%, magnesium oxide 27.2%.The low magnesium laterite nickel mine of high ferro is milled to granularity-0.075mm and accounts for 90%, pulp density 45%, and low iron high magnesium laterite nickel mine is milled to granularity-0.075mm and accounts for 85%, pulp density 55%.dilute sulphuric acid and the low magnesium laterite nickel mine mass ratio 0.75:1 of high ferro by mass concentration 25%, the condition of liquid-solid ratio 2.5:1, leached one hour, add quality to be equivalent to the low iron high magnesium laterite nickel mine of the low magnesium laterite nickel mine 35% of high ferro, add simultaneously quality to be equivalent to the sulfuric acid of the mass concentration 25% of low iron high magnesium laterite nickel mine 40%, pass into air pressurized to still internal pressure 0.25MPa, continue to leach one hour, the high magnesium ore deposit (nickeliferous 0.5% that adds this ore deposit bottom that is equivalent to the low magnesium laterite nickel mine 10% of high ferro, cobalt＜0.01%, magnesium oxide 35.52%, grinding particle size-0.075mm accounts for 86%, pulp density 55%), continue to leach 2 hours, add magnesite to be neutralized to pH=5.5, pre-neutralization is to pH=1.5～4.5 again, leach pulp liquid-solid isolation, leach liquor magnesite sinks nickel.Result: nickel recovery is 98.2%, and the cobalt rate of recovery is 96.5%.
Embodiment 3
The test sample ore is for mixing sample ore, and high ferro low magnesium laterite nickel mine in upper strata is nickeliferous 1.80%, cobalt 0.20%, and iron 36.23%, magnesium oxide 6.21%, the low iron high magnesium laterite nickel mine of lower floor is nickeliferous 2.33%, cobalt 0.05%, iron 13.56%, magnesium oxide 21.37%.The low magnesium laterite nickel mine of high ferro is milled to granularity-0.075mm and accounts for 85%, pulp density 45%, and low iron high magnesium laterite nickel mine is milled to granularity-0.075mm and accounts for 90%, pulp density 55%.dilute sulphuric acid and the low magnesium laterite nickel mine mass ratio 0.9:1 of high ferro by mass concentration 28%, the condition of liquid-solid ratio 2.5:1, leached one hour, add the low iron high magnesium laterite nickel mine that is equivalent to the low magnesium laterite nickel mine 45% of high ferro, add simultaneously quality to be equivalent to the sulfuric acid of the mass concentration 28% of low iron high magnesium laterite nickel mine 55%, pass into air pressurized to still internal pressure 0.25MPa, leached one hour, the high magnesium of the low nickel ore deposit (nickeliferous 0.90% that adds this ore deposit bottom that is equivalent to the low magnesium laterite nickel mine 20% of high ferro, cobalt＜0.01%, magnesium oxide 33.35%, grinding particle size-0.075mm accounts for 88%, pulp density 56%), continue to leach 2 hours, add magnesite to be neutralized to pH=5.8, pre-neutralization is to pH=1.5～4.5 again, leach pulp liquid-solid isolation, the leach liquor sodium hydroxide solution sinks nickel.Result: nickel recovery is 99.0%, and the cobalt rate of recovery is 95.7%.
Figure 2 shows that the first production technological process provided by the invention.Figure 3 shows that the second production technological process provided by the invention.Figure 4 shows that the standby ginseng figure of the first technological process of production provided by the invention.Owing to clearly representing the concrete technology flow process in accompanying drawing, therefore repeat no more in specification sheets.
In sum, compare with wet processing with existing pyrogenic process, provided by the present invention is a kind of direct utilization after the decolouring desalination, and the useless dilute sulphuric acid acidleach red soil nickel ore that need not to concentrate extracts the method for nickel hydroxide or nickel cobalt, the method overcomes various technical barriers, makes the diluted acid Technology stable.Effectively utilize simultaneously useless dilute sulphuric acid, turn waste into wealth.The present invention tests and adopts red soil nickel ore almost can process all types of red soil nickel ores from Australia, from Philippines, Indonesia, and advantage is:
1) present, in laterite nickel industry, other factory uses 98% vitriol oil acidleach to produce nickel hydroxide, technique of the present invention overcomes various technical barriers, directly utilize after the decolouring desalination, the method that the useless dilute sulphuric acid acidleach red soil nickel ore that need not to concentrate extracts nickel hydroxide or nickel cobalt is a kind of brand-new Technology in nickel smelting industry, also can decompose red soil nickel ore in more efficient ground under low acidity;
2) the direct normal pressure pickling process of dilute sulphuric acid operational path, dilute sulphuric acid can be disregarded cost, and only this falls these approximately 30,000 yuan, and competitive edge is more obvious when the nickel valency is low;
3) after acidleach in leach liquor the pre-neutralization of the free acid of higher concentration adopt low iron high magnesium laterite nickel mine, effectively reduce the acid consumption of ton nickel, leaching yield improves 3% left and right than ordinary method;
4) heavy iron utilizes the moderate magnesium Ji Kuang of alkalescence, takes full advantage of the sour further leaching nickel that discharges in heavy iron process, has further improved the utilization ratio of sulfuric acid; Avoided simultaneously the formation colloids such as silicon-dioxide, ironic hydroxide in leaching ore pulp solution to be difficult to sedimentation;
5) adopt the heavy nickel of magnesite enrichment, filtrate adopt up-to-date cryogenic film concentration technique obtain pure water and sal epsom crystallization can be used for direct production magnesium salts, fertiliser containing magnesium, magnesium hydroxide, produce other magnesium products such as fire retardant, environmental protection treatment agent, sweetening agent magnesium hydroxide, water-fast closing/nanometer/activated magnesia, light/heavy/electrically molten magnesia magnesia/smart magnesia refractory materials, alkali formula/magnesiumcarbonate, MAGNESIUM METAL with the ammonia process such as carbon ammonium, iron dross removing is purer, can be used for ironmaking or production red iron oxide; Leach purer building materials or the production white carbon black of can be used for of white residue and pre-neutralization white residue, realize whole process nickel, cobalt, iron, the manganese of red soil nickel ore acidleach, recycle to extinction and the complete utilization of magnesium resource, advanced rationally, high, the mature and reliable of production efficiency, operating safety be stable, environmentally friendly, do not discharge any gas that hinders environment, waste residue is solid substance, recoverable, can plant trees, can afforest, the waste water energy qualified discharge.
Although the present invention is disclosed as above by preferred embodiment; yet, not in order to limit the present invention, anyly know this skill person, without departing from the spirit and scope of the present invention; can do a little change and retouching, so protection scope of the present invention is as the criterion when looking claims scope required for protection.
Claims (9)
1. the method for the one kind low useless dilute sulphuric acid leaching nickel cobalt of iron high magnesium laterite nickel mine use, is characterized in that, comprises the steps:
Useless dilute sulphuric acid removal step: will give up that dilute sulphuric acid decolours, desalination, take off after organism that to obtain mass concentration be 5～50% dilute sulphuric acid;
Slurrying step: will hang down the iron high magnesium laterite nickel mine broken, after adding water or adding above-mentioned dilute sulphuric acid, with ball mill, red soil nickel ore is milled to granularity in the particle accounting below 0.075 millimeter 〉=80～95%, using Hhigh-efficient thickener, band filter or pressure filter enrichment to moisture to account for weight ratio is 30～40%, add above-mentioned dilute sulphuric acid to pull an oar, control pulp density 〉=50～60%;
leach and the pre-neutralization step: slurry is put into the stirred autoclave groove, the ratio that is 0.35～0.65:1 in sulfuric acid and the dried ore deposit of low iron high magnesium laterite nickel mine mass ratio adds above-mentioned dilute sulphuric acid, difference according to the sulfuric acid additional proportion, it is 1.8～3.3:1 that washing lotion while determining with the washing of leaching slurry filtration is adjusted liquid-solid ratio, gradually be warming up to 90～175 ℃, leach approximately after 2 hours, continue to pass into air or oxygen, naturally boost to 〉=0.10～0.35MPa in the still groove, after continuing to leach half an hour, be 5 ~ 30% to add magnesia ore deposit to carry out one section deironing by magnesia ore deposit and low iron high magnesium laterite nickel mine mass ratio, and continue without Ore Leaching 1～3 hour, behind pH 〉=1.3～2.3, add Wingdale, unslaked lime, white lime, magnesium oxide, magnesium hydroxide, magnesite, serpentine ore, a kind of pre-neutralization again in carbon ammonium or ammoniacal liquor is to pH=2.5～6.5, leach and finish,
Leach the slurry filtration washing step: after leaching the non-ionic polyacrylamide polymeric flocculant flocculation of the ore pulp molecular weight of mass concentration 0.01～0.5% 〉=1000～1,500 ten thousand, carry out solid-liquid separation, washing with thickener, band filter, pressure filter or thickener in conjunction with band filter, pressure filter, a washing lotion part is returned while leaching to be used for adjusting and is leached liquid-solid ratio use, and a part is incorporated leaching stoste into;
Leach liquor sinks nickel cobalt step: leach liquor adds the deironing of two sections, magnesium base ore deposit to pH=3.5～7.5, adopt the magnesite enrichment, in and one section heavy nickel of supernatant liquor add the heavy Ni (OH) of alkali
2To pH=7.1～9.2, crystal seed returns to heavy nickel groove, and heavy nickel material advances the thickener sedimentation, underflow press filtration, pulp, washing Ni (OH)
2, the thickener overflow is advanced two sections heavy nickel to pH=6～12, makes in mother liquor nickel less than 30～50mg/L, must sink nickel cobalt slurry;
Heavy nickel cobalt slurries filtration washing step: heavy nickel cobalt slurry carries out solid-liquid separation with thickener, band filter, pressure filter or thickener in conjunction with pressure filter, band filter, wash, obtain nickel hydroxide, cobaltous hydroxide or nickelous carbonate, the cobaltous carbonate product of nickeliferous 〉=40～45%.
2. low iron high magnesium laterite nickel mine according to claim 1 is with the method for useless dilute sulphuric acid leaching nickel cobalt, it is characterized in that, also comprise heavy nickel mother liquid disposal step after heavy nickel cobalt slurries filtration washing step: during magnesium ion concentration in heavy nickel mother liquor 〉=35g/L, with magnesite, carbon ammonium, Wingdale, calcium oxide, sodium hydroxide, serpentine ore, white lime, magnesium oxide or ammonia neutralization precipitate and separate, obtain the direct fractional crystallization sal epsom of magnesiumcarbonate, magnesium basic carbonate, magnesium hydroxide and employing cryogenic film technology.
3. low iron high magnesium laterite nickel mine according to claim 1 is with the method for useless dilute sulphuric acid leaching nickel cobalt, it is characterized in that, also comprised beneficiation steps before the slurrying step: according to the difference of magnesium iron level select from red soil nickel ore iron level 〉=20% as the low magnesium laterite nickel mine of high ferro, the iron high magnesium laterite nickel mine is hanged down in the conduct of iron level＜20%.
4. a high ferro is hanged down the method for magnesium laterite nickel mine with useless dilute sulphuric acid leaching nickel cobalt, it is characterized in that, comprises the steps:
Useless dilute sulphuric acid removal step: will give up that dilute sulphuric acid decolours, desalination, take off after organism that to obtain mass concentration be 5～50% dilute sulphuric acid;
Slurrying step: the low magnesium laterite nickel mine of high ferro is broken, after adding water or adding above-mentioned dilute sulphuric acid, with ball mill, red soil nickel ore is milled to granularity in the particle accounting below 0.075 millimeter 〉=80～95%, using Hhigh-efficient thickener, band filter or pressure filter enrichment to moisture to account for weight ratio is 30～40%, add above-mentioned dilute sulphuric acid to pull an oar, control pulp density 〉=35～45%;
leach and the pre-neutralization step: slurry is put into the stirred autoclave groove, the ratio that is 0.55～1.3:1 in sulfuric acid and the dried ore deposit of the low magnesium laterite nickel mine of high ferro amount mass ratio adds above-mentioned dilute sulphuric acid, difference according to the sulfuric acid additional proportion, it is 1.8～4.0:1 that washing lotion while determining with the washing of leaching slurry filtration is adjusted liquid-solid ratio, gradually be warming up to 90～175 ℃, leach approximately after 2 hours, ore amount adds low iron high magnesium laterite nickel mine ore pulp by with the low magnesium laterite nickel mine mass ratio of high ferro, being 15～90%, by with low iron high magnesium laterite nickel mine mass ratio be that 0.12～0.55:1 adds above-mentioned dilute sulphuric acid, pass into air or oxygen, certainly boost 〉=0.10～0.35MPa in the still groove, continue to leach after 1～3 hour, be 5 ~ 30% to add magnesia ore deposit to carry out one section deironing by the low magnesium laterite nickel mine mass ratio of magnesia ore deposit and high ferro, and continue without Ore Leaching 1～3 hour, behind pH 〉=1.3～2.3, add Wingdale, unslaked lime, white lime, magnesium oxide, magnesium hydroxide, magnesite, serpentine ore, a kind of pre-neutralization again in carbon ammonium or ammoniacal liquor is to pH=1.5～4.5, leach and finish,
leach the slurry filtration washing step: leach that ore pulp is dense carries out liquid-solid separation, the thickener overflow flows into leaches the supernatant liquid bath, thickener underflow through pumping once, the secondary press filtration, efflux after filter cake washing, first-time filtrate is delivered to and is carried out the secondary removal of impurities except the sial groove, edulcoration purification is removed Fe, Al, Cu, Zn, Si, Cr, remove sial thickener solid-liquid separation again, after non-ionic polyacrylamide polymeric flocculant flocculation with the molecular weight of mass concentration 0.01～0.5% 〉=1000～1,500 ten thousand, use thickener, band filter, pressure filter or thickener are in conjunction with band filter, pressure filter carries out solid-liquid separation, washing, a washing lotion part is returned while leaching and is used for adjusting leaching liquid-solid ratio use, a part is incorporated leaching stoste into,
Leach liquor sinks nickel cobalt step: leach liquor adds the deironing of two sections, magnesium base ore deposit to pH=3.5～7.5, adopt the magnesite enrichment, in and one section heavy nickel of supernatant liquor add the heavy Ni (OH) of alkali
2To pH=7.1～9.2, crystal seed returns to heavy nickel groove, and heavy nickel material advances the thickener sedimentation, underflow press filtration, pulp, washing Ni (OH)
2, the thickener overflow is advanced two sections heavy nickel to pH=6～12, makes in mother liquor nickel less than 30～50mg/L, must sink nickel cobalt slurry;
Heavy nickel cobalt slurries filtration washing step: heavy nickel cobalt slurry carries out solid-liquid separation with thickener, band filter, pressure filter or thickener in conjunction with pressure filter, band filter, wash, obtain nickel hydroxide, cobaltous hydroxide or nickelous carbonate, the cobaltous carbonate product of nickeliferous 〉=40～45%.
5. high ferro according to claim 4 is hanged down the method for magnesium laterite nickel mine with useless dilute sulphuric acid leaching nickel cobalt, it is characterized in that, also comprise heavy nickel mother liquid disposal step after heavy nickel cobalt slurries filtration washing step: during magnesium ion concentration in heavy nickel mother liquor 〉=35g/L, with magnesite, carbon ammonium, Wingdale, calcium oxide, sodium hydroxide, serpentine ore, white lime, magnesium oxide or ammonia neutralization precipitate and separate, obtain the direct fractional crystallization sal epsom of magnesiumcarbonate, magnesium basic carbonate, magnesium hydroxide and employing cryogenic film technology.
6. high ferro according to claim 4 is hanged down the method for magnesium laterite nickel mine with useless dilute sulphuric acid leaching nickel cobalt, it is characterized in that, also comprised beneficiation steps before the slurrying step: according to the difference of magnesium iron level select from red soil nickel ore iron level 〉=20% as the low magnesium laterite nickel mine of high ferro, select the low iron high magnesium laterite nickel mine of conduct of iron level＜20%.
7. one kind low iron high magnesium laterite nickel mine soaks integrated approach with the heap pond of useless dilute sulphuric acid leaching nickel cobalt, it is characterized in that, comprises the steps:
Useless dilute sulphuric acid removal step: will give up that dilute sulphuric acid decolours, desalination, take off after organism that to obtain mass concentration be 5～50% dilute sulphuric acid;
Leach and the pre-neutralization step: beneficiation steps is smelted factory at pyrogenic process laterite nickel and is completed, through sieving the dried high magnesium ore of low iron, need not slurrying, first to soak the cloth liquid mode of rear spray, the ratio that is 0.35～1.1:1 in sulfuric acid and the dried ore deposit of the low magnesium laterite nickel mine of high ferro amount mass ratio adds above-mentioned dilute sulphuric acid, pond is soaked or is built the heap dump leaching and leach, and pH=1.5～4.5 after 240～360hr are soaked in the heap pond, leach and finish;
Leach slurry filtration washing step: granularity＜0.075mm, the leach liquor of solid content＜8% enters thickener and carries out liquid-solid separation, the thickener underflow solid content〉33%, the solid content of thickener overflow≤1%, the thickener overflow flows into leaches the supernatant liquid bath, thickener underflow through pumping once, the secondary press filtration, efflux after filter cake washing, first-time filtrate deliver to except the sial groove carry out normal temperature or 〉=95 ℃ of secondary removal of impurities, reaction times is 2～3.5～4hr, edulcoration purification is removed Fe, Al, Cu, Zn, Si, Cr, removes sial thickener solid-liquid separation again;
Leach liquor sinks nickel cobalt step: enter heavy nickel operation after solid-liquid separation, the heavy nickel time is 1.5hr, after the flocculation agent flocculation, carry out solid-liquid separation, washing with thickener, band filter, pressure filter, a washing lotion part is returned while leaching to be used for adjusting and is leached liquid-solid ratio use, and a part is incorporated leaching stoste into, then, leach liquor adds the deironing of two sections, magnesium base ore deposit to pH=3.5～7.5, adopt the magnesite enrichment, in and one section heavy nickel of supernatant liquor add the heavy Ni (OH) of alkali
2To pH=7.1～9.2, crystal seed returns to heavy nickel groove, and heavy nickel material advances the thickener sedimentation, underflow press filtration, pulp, washing Ni (OH)
2, the thickener overflow is advanced two sections heavy nickel to pH=6～12, makes in mother liquor nickel less than 30～50mg/L, must sink nickel cobalt slurry;
Heavy nickel cobalt slurries filtration washing step: heavy nickel cobalt slurry carries out solid-liquid separation with thickener, band filter, pressure filter or thickener in conjunction with pressure filter, band filter, wash, obtain nickel hydroxide, cobaltous hydroxide or nickelous carbonate, the cobaltous carbonate product of nickeliferous 〉=40～45%.
8. low iron high magnesium laterite nickel mine according to claim 7 is with the method for useless dilute sulphuric acid leaching nickel cobalt, it is characterized in that, also comprise heavy nickel mother liquid disposal step after heavy nickel cobalt slurries filtration washing step: during magnesium ion concentration in heavy nickel mother liquor 〉=35g/L, with magnesite, carbon ammonium, Wingdale, calcium oxide, sodium hydroxide, serpentine ore, white lime, magnesium oxide or ammonia neutralization precipitate and separate, obtain the direct fractional crystallization sal epsom of magnesiumcarbonate, magnesium basic carbonate, magnesium hydroxide and employing cryogenic film technology.
9. low iron high magnesium laterite nickel mine according to claim 7 is with the method for useless dilute sulphuric acid leaching nickel cobalt, it is characterized in that, also comprised beneficiation steps before leaching and pre-neutralization step: sieving out dried ore grain size from pyrogenic process laterite nickel smelting factory is 2～5mm, and ore grade is 1.35～1.8% low iron high magnesium laterite nickel mine.
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