A kind of method of nickel-containing ore comprehensive utilization
Technical field
The present invention relates to a kind of methods of nickel-containing ore comprehensive utilization, belong to metallurgical technology field.
Background technique
At present to there are mainly two types of the treatment process of nickel-containing ore (such as lateritic nickel ore, garnierite): (one) wet process.Wet process
It is divided into sulfuric acid process and ammonia process again, the former mainly makees leaching agent with sulfuric acid, and the latter makees leaching agent with ammonia or ammonia salt.Wherein ammonia process because
Environmental issue seldom uses;Sulfuric acid process is difficult to recycle with generation leachate and solid, solid after sulfuric acid leaching, the heap after slag
It deposits, this part slag is because nickeliferous compound is dangerous solid waste, stockpiling pollution environment, and leachate electrolysis production after extracting is electrolysed
Nickel, being electrolysed in the solid slag of generation containing heavy metal contaminants is also dangerous solid waste, will cause environmental pollution.Therefore, sulfuric acid process is thrown
Provide that big, at high cost, leaching rate is low, water expansion, magnesium cannot open a way, particularly the metallurgical slag of a large amount of iron content calcium nickel can not utilize, ring
Packing pressure is big, has enterprise to handle lateritic nickel ore because environmental protection was once being suspended operations for consolidation with sulfuric acid process.(2) pyrogenic process.Pyrogenic process is divided into ferronickel again
Method and matte smelting method.But this method is only suitable for magnesia mine, requires height to raw ore, and head grade is generally required to be greater than 1.5% even
Greater than 2%, applicable scope of resource is very small, and investment is big, energy consumption is very high, and especially metallurgical slag can not benefit greatly for environmental pollution
With environmental protection pressure is big.
The enterprise of sulfuric acid consumption matched with copper smelting plant at present is titanium powder plant or phosphorizing treatment, but both techniques have
The critical defects such as long flow path, environmental pollution.China's titanium dioxide industry production capacity rapid growth, but the ring present in rapid growth
Border pollution problem and potential environmental risk can not be ignored really.Specifically, it is mainly manifested in following aspect.First is that unit produces
Product blowdown flow rate is big, and resource, energy consumption are high.Using traditional Titanium White Production By Sulfuric Acid Process, it is fresh to produce titanium dioxide consumption per ton
100~150 tons of water, about 1.6 tons of mark coals of comprehensive energy consumption, while 100 tons of 8 tons of Waste Sulfuric Acid, the acid waste water of about generation concentration 20%,
8 tons of waste residue, and 2.5 ten thousand stere of exhaust gas containing sulfur dioxide, acid mist and dust.Second is that factory's point is more, small scale, heavily contaminated is produced
Energy proportion is excessive.Third is that disposal of waste gas, water and industrial residue difficulty is little, but control expense is high.Production phosphate fertilizer during generate hydrogen fluoride,
Ocratation, fluorine-containing dust, phosphoric acid mist, ammonia and sulfur dioxide etc. pollute environment, wherein larger with fluorine-containing hazard of contaminant.Generally
In the case of, every production one ton of chemical fertilizer, about 40 tons of effluent, 2000 cubes of exhaust gas, dust 50mg, and a large amount of ardealite is even more pair
It is endangered caused by environmental protection bigger.
As the demand growth of rapid development of economy, especially Asia-Pacific market to nickel is very rapid, but accounts for the whole world 70% and provide
The lateritic nickel ore of source reserves but only contributes to 30% yield.It is wide, with low investment, at low cost, right that its reason is just the absence of the scope of application
Environmental-friendly enlarged production technology.
It is mishandling there are hidden danger such as social safety, environmental protection however, non-ferrous metal metallurgy enterprise by-product sulfuric acid amount is big, because
The enlarged production technology of this research nickel-containing ore comprehensive utilization has important practical significance.
Summary of the invention
To overcome above-mentioned the deficiencies in the prior art, the present invention provides a kind of method of nickel-containing ore comprehensive utilization, both solves
The problem that prior art investment is big, environmental pollution is big, the quantity of slag is big, and sulfuric acid and quartz sand can be realized with non-ferrous metal metallurgy enterprise
Recycle.
The present invention is realized by following technical proposal: a kind of method of nickel-containing ore comprehensive utilization, by following each step:
(1) ore pre-processes: raw material nickel-containing ore being crushed, is sized to the ore in sand form that granularity is 0.63~5mm;
(2) sulfuric acid leaching: add water to size mixing to pulp density in 20~50wt% in ore in sand form obtained by step (1), add sulfuric acid
It is 2~70% that solution, which is mixed to acidity, carries out neutralization leaching, is then separated by solid-liquid separation, obtains leachate and solid;The step
The metals such as nickel, cobalt, manganese, iron, aluminium, the chromium in nickel-containing ore (hydroxide, oxide) is set to form sulfate by the way that sulfuric acid is added
Into in leachate;And the silica in nickel-containing ore is then not involved in acid-base reaction and is completely retained in solids for giving birth to
Produce quartz sand;
(3) directly heavy nickel: in the leachate obtained by step (2) plus alkali to pH value is 8~11, using filter obtain solid and
Filtrate, obtained solid are iron-containing nickel hydroxide;Nickel content is 17~30% in the iron-containing nickel hydroxide, cobalt content 0.1
~2%, iron content is 10~20%, and manganese content is 0.5~5%, and aluminium content is 2~8%;The iron-containing nickel hydroxide can be used as stainless
The raw material of steel mill or extraordinary steel mill;Alternatively, adding sulfide (such as hydrogen sulfide, vulcanized sodium) to pH in the leachate obtained by step (2)
Value is 3.2~4.2, solid and filtrate is obtained by filtration, obtained solid is nickel sulfide;The nickel content of gained nickel sulfide be 2~
35%, cobalt content is 0.1~2%, and iron content is 1~5%;The Containing Sulfur nickel can be used as the raw material of electrolytic nickel factory;
Alternatively, the heavy nickel that cleans: it is 0.05~0.1:1 by the mass ratio of leachate and hydrogen peroxide, the leaching obtained by step (2)
After hydrogen peroxide is added in liquid, warming while stirring is to 80 DEG C, then it is 3.2~4.2 that milk of lime to pH value, which is added dropwise, then through solid-liquid point
From the removals such as impure iron, calcium, manganese, chromium, cadmium, aluminium, silicon in solids, contain magnesium and nickel, in institute in obtained solid in gained liquid
Obtaining and sodium hydroxide to pH value is added in liquid is 8~11, solids and filtrate is obtained after refiltering, obtained solid object is hydrogen-oxygen
Change nickel;The purity of gained nickel hydroxide reaches 95% or more;Gained nickel hydroxide can both produce energy storage material or can be as production
The raw material of stainless steel;
(4) recycle magnesium: sulfuric acid magnesium products be made through evaporative crystallization in filtrate obtained by step (3), at the same using distilled water as
Technique backwater circulation utilizes;The content of epsom salt is greater than 96% in gained sulfuric acid magnesium products, which effectively will can largely give up
Water is changed into distilled water return and recycles;
Alternatively, it is 11~15 that filtrate obtained by step (3), which is added alkali to adjust pH value, solid and liquid are obtained using filter,
Obtained solid is one or more of the hydroxide of magnesium, the carbonate of magnesium, the bicarbonate of magnesium;Gained liquid is as work
Skill backwater circulation utilizes;
(5) quartz sand is recycled: after technique return water washed-out sand to neutrality obtained by step (2) obtained solid step (4), screening point
Grade obtains quartz sand product.
The raw material nickel-containing ore of the step (1) is the garnierite being separated by lateritic nickel ore.
The broken of the step (1) is to be broken when the water content of nickel-containing ore is less than 15% using dry, when containing for nickel-containing ore
Using wet broken when water is greater than 15%.
The neutralization leaching of the step (2) is mixed using one or more of conventional dump leaching, soaking, leaching mode
With.
The time-consuming of the dump leaching is 15~300 days, the time-consuming of soaking is 10~1000 hours, the time-consuming of leaching is 1
~5 hours.
The sulfuric acid solution of the step (2) comes from the byproduct sulfuric acid solution of non-ferrous metal (copper, nickel, lead, zinc) smeltery.
The sulfuric acid solution of the step (2) is by being added salt in hydrochloric acid solution and/or hydrofluoric acid solution substitution or sulfuric acid solution
Acid solution and/or hydrofluoric acid solution.Wherein, the acidity of dump leaching is 2~12%, the acidity of leaching is 5~50%, the acid of soaking
Degree is 20~70%.
The alkali of the step (3) or step (4) is sodium hydroxide.
The sulfuric acid magnesium products of the step (4) include MgSO4·7H2O、MgSO4·H2O and anhydrous MgSO4。
The water outlet generated after the washed-out sand of the step (5) is back to step (2) for sizing mixing, and realizes the closed cycle benefit of water
With.
The quartz sand product of the step (5) includes porous silica, glass sand, metallurgical quartz sand and/or builds
It builds and uses sand.
In above-mentioned technical process, evaporative crystallization can be substituted by multiple-effect evaporation or heat pump techniques;Being separated by solid-liquid separation can be with dense
One of machine, high-efficiency thickener, flame filter press, vacuum filter, band filter, filter press, countercurrent washing equipment or
It is several mixed;Washed-out sand can use sand washer and/or screening machine.
The advantages of present invention has and effect:
Hydroxide, oxide in nickel-containing ore is used for neutralizing acid by the present invention, generates salt and water, salinity after neutralizing acid
Step recycling magnesium and nickel, gained water is then used as process water to be recycled after recycling magnesium, and the silica in nickel-containing ore is not joined then
Magnesium, silicon, the nickel completely remained with acid-base reaction for producing building sand, in such nickel-containing ore is respectively formed magnesium
Salt/magnesium hydroxide, Machine-made Sand (brick) and nickel salt/nickel hydroxide three classes product and realize nickel-containing ore complete resource utilize,
Whole process does not generate industrial wastewater, waste residue, exhaust gas, completely environmentally protective.In the by-product sulfuric acid of consumption non-ferrous metals smelting works
Meanwhile the quartz sand of present invention process production returns to non-ferrous metals smelting works again, to realize the mesh that social resources recycle
's.
The full element that the technology of the present invention is conceived to nickel-containing ore resource utilizes, and silicon, magnesium, iron, the nickel in nickel-containing ore is complete
Element recycles, and puts forth effort on, one side this project consumption non-ferrous metal metallurgy mating with the circulation of non-ferrous metal metallurgy enterprise
The quartz sand of the sulfuric acid of enterprise this project production simultaneously returns non-ferrous metal metallurgy enterprise again to realize resource circulation utilization
Purpose.The present invention form from ore pretreatment, Machine-made Sand gradation, the product development of series of quartz sand, salt recycling and water process,
Nickel, iron, magnesium recycling, the series such as system acid, water balance, these are unique and rich creative.
Resource utilization of the invention is high, at low cost, small investment, without three industrial wastes discharge, generation environment pollutes;Entirely
Technique is brief, cleans, environmentally friendly.The present invention is to comprehensive utilization of resources, Strategy of Circular Economy and environmentally friendly sustainable development tool
It is of great importance.
Specific embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1
Raw material is lateritic nickel ore, and lateritic nickel ore is separated into the limonite of nickelic high-speed rail and the garnierite of high silicon and low iron,
Gained limonite is directly outer to be sold, and gained garnierite is as nickel-containing ore, i.e. serpentine (Ni, Mg)3Si4O10(OH)8.Laterite nickel
The specific lock out operation of mine is as follows:
Lateritic nickel ore by partial size greater than 40mm enters Three stage crushing with single closed circuit stage process, and+0.5mm is made afterwards after crushing and screening
The finished product and -0.5mm ore pulp of~10mm.Partial size less than 40mm lateritic nickel ore and ore pulp be divided into after trough washery -0.5mm ore pulp ,+
0.5mm~10mm ore in sand form and+10mm ore ,+10mm ore enter closed circuit crushing process, and it is dense that -0.5mm ore pulp enters concentrator
Contracting is concentrated as nickelic high-speed rail irony mine, and+0.5mm~10mm ore in sand form is nickel-containing ore (garnierite).Its ingredient such as the following table 1:
The grade of 1 lateritic nickel ore of table separation front and back each element
(1) ore pre-processes: above-mentioned gained nickel-containing ore being crushed, is sized to the ore in sand form that granularity is 0.63~5mm;
Wherein being crushed is to be broken when the water content of nickel-containing ore is less than 15% using dry, is used when the water content of nickel-containing ore is greater than 15%
It is wet broken;
(2) sulfuric acid leaching: add water to size mixing to pulp density in 40wt% in ore in sand form obtained by step (1), add smeltery's pair
It is 45% that product sulfuric acid solution, which is mixed to acidity, neutralize using convention stir leaching and leach 1~5 hour, then carries out solid-liquid
Separation, obtains leachate and solid;Nickeliferous 0.13% in obtained solid, contain cobalt 0.0099%, nickeliferous 4.56g/L in leachate contains
Iron 4.07g/L, the leaching rate of nickel is 87.73%, the leaching rate of cobalt is 93.81%;
(3) clean heavy nickel: being 0.08:1 by the mass ratio of leachate and hydrogen peroxide, adds in the leachate obtained by step (2)
After entering hydrogen peroxide, warming while stirring is to 80 DEG C, then it is 3.2~4.2 that milk of lime to pH value, which is added dropwise, is then separated by solid-liquid separation, point
Iron rate 96.31% is removed from gained liquid;Ingredient in separating obtained liquid is shown in Table 2:
The ingredient g/L of the separating obtained liquid of table 2
It is 8~11 that sodium hydroxide to pH value is added in gained liquid, stablizes reaction 1 hour, obtains solids after refiltering
And filtrate, obtained solid object are nickel hydroxide;Nickel content is 0.32g/L in filtrate, and nickel rate of deposition is 92.28%, gained hydrogen-oxygen
The purity for changing nickel reaches 96%;
(4) it recycles magnesium: magnesium sulfate is made through evaporative crystallization in filtrate obtained by step (3) (containing magnesium ion concentration 47g/L) and is produced
Product (including MgSO4·7H2O、MgSO4·H2O and anhydrous MgSO4), while being utilized distilled water as technique backwater circulation;Its
In, 0.95 ton/ton sulfuric acid magnesium products of steam consumption, 165 KWhs/ton of sulfuric acid magnesium products of electric consumption;
(5) quartz sand is recycled: after technique return water washed-out sand to neutrality obtained by step (2) obtained solid step (4), screening point
Grade obtains quartz sand product (including porous silica, glass sand, metallurgical quartz sand and/or building sand);After washed-out sand
The water outlet of generation is back to step (2) for sizing mixing.
Embodiment 2
(1) ore pre-processes: raw material nickel-containing ore being crushed, is sized to the ore in sand form that granularity is 0.63~5mm;
(2) sulfuric acid leaching: add water to size mixing to pulp density in 20wt% in ore in sand form obtained by step (1), add hydrochloric acid solution
Mixing with hydrofluoric acid solution to acidity is 2%, carries out in dump leaching and leaches 15~300 days, is then separated by solid-liquid separation, is soaked
Liquid and solid out;The step makes the metals such as nickel, cobalt, manganese, iron, aluminium, chromium in nickel-containing ore (hydroxide, oxide) by adding
Enter sulfuric acid formation sulfate to enter in leachate;And the silica in nickel-containing ore is then not involved in acid-base reaction and is completely protected
It stays in solids for producing quartz sand;
(3) directly heavy nickel: adding sodium hydroxide to pH value is 8~11 in the leachate obtained by step (2), is obtained using filter
Solid and filtrate, obtained solid are iron-containing nickel hydroxide;Nickel content is 17~30% in the iron-containing nickel hydroxide, and cobalt contains
Amount is 0.1~2%, and iron content is 10~20%, and manganese content is 0.5~5%, and aluminium content is 2~8%;The iron-containing nickel hydroxide can
Raw material as Stainless Steel Plant or extraordinary steel mill;
(4) recycle magnesium: it is 11~15 that filtrate obtained by step (3), which is added alkali to adjust pH value, using filter obtain solid and
Liquid, obtained solid are one or more of the hydroxide of magnesium, the carbonate of magnesium, the bicarbonate of magnesium;Gained liquid
It is utilized as technique backwater circulation;
(5) quartz sand is recycled: after technique return water washed-out sand to neutrality obtained by step (2) obtained solid step (4), screening point
Grade obtains quartz sand product (including porous silica, glass sand, metallurgical quartz sand and/or building sand);After washed-out sand
The water outlet of generation is back to step (2) for sizing mixing, and realizes that the closed cycle of water utilizes.
Embodiment 3
(1) ore pre-processes: raw material nickel-containing ore being crushed, is sized to the ore in sand form that granularity is 0.63~5mm;
(2) sulfuric acid leaching: add water to size mixing to pulp density in 50wt% in ore in sand form obtained by step (1), add non-ferrous metal
The byproduct sulfuric acid solution and hydrochloric acid solution solution of smeltery mix to acidity be 70%, carry out soaking in and leach 10~
It 1000 hours, is then separated by solid-liquid separation, obtains leachate and solid;The step make nickel in nickel-containing ore, cobalt, manganese, iron,
The metals such as aluminium, chromium (hydroxide, oxide) are entered in leachate by the way that sulfuric acid formation sulfate is added;And in nickel-containing ore
Silica is then not involved in acid-base reaction and is completely retained in solids for producing quartz sand;
(3) directly heavy nickel: adding hydrogen sulfide or vulcanized sodium to pH value in the leachate obtained by step (2) is 3.2~4.2, warp
Solid and filtrate is obtained by filtration, obtained solid is nickel sulfide;The nickel content of gained nickel sulfide is 2~35%, cobalt content 0.1
~2%, iron content is 1~5%;The Containing Sulfur nickel can be used as the raw material of electrolytic nickel factory;
(4) it recycles magnesium: sulfuric acid magnesium products (MgSO is made through evaporative crystallization in filtrate obtained by step (3)4·7H2O、
MgSO4·H2O and anhydrous MgSO4), while being utilized distilled water as technique backwater circulation;Seven water sulphur in gained sulfuric acid magnesium products
The content of sour magnesium is greater than 96%, which effectively can be changed into distilled water return for a large amount of waste water and recycle;
(5) quartz sand is recycled: after technique return water washed-out sand to neutrality obtained by step (2) obtained solid step (4), screening point
Grade obtains quartz sand product (including porous silica, glass sand, metallurgical quartz sand and/or building sand);After washed-out sand
The water outlet of generation is back to step (2) for sizing mixing, and realizes that the closed cycle of water utilizes.
Comparative example 1: with above-described embodiment 1, the operation of step (1) is only omitted.As a result it is unable to get quartz sand product, finally
It still will form a large amount of solid slags to stack, and be not used.
Comparative example 2: with above-described embodiment 1, the operation of step (3) is only omitted.As a result the elements such as iron can't be stainless steel
The raw material of factory or extraordinary steel mill, and stacked as solid slag, it is difficult to it recycles.
Comparative example 3: with above-described embodiment 1, the operation of step (4) is only omitted.If lime treatment filtrate is routinely added, knot
Fruit magnesium enters solid slag stacking, it is difficult to recycle.