CN101381810A - Extraction process of copper nickel fine alloy - Google Patents

Extraction process of copper nickel fine alloy Download PDF

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CN101381810A
CN101381810A CNA2008101199252A CN200810119925A CN101381810A CN 101381810 A CN101381810 A CN 101381810A CN A2008101199252 A CNA2008101199252 A CN A2008101199252A CN 200810119925 A CN200810119925 A CN 200810119925A CN 101381810 A CN101381810 A CN 101381810A
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leaching
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fine alloy
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顾凌霄
王魁珽
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China ENFI Engineering Corp
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Abstract

The invention provides a leaching technology for copper nickel granular alloy, which improves the leaching efficiency of the copper nickel alloy and the recovery rate of noble metal in leached mud, and avoids the environmental pollution by the vulcanized technology. The leaching technology is characterized in that the leaching technology adopts the means of sectional leaching and comprises first-stage leaching, second-stage leaching and pressure leaching which are performed in turn, wherein first-stage leached mud is taken as a raw material for second-stage leaching; second-stage leached mud is taken as a raw material for pressure leaching; and the pressure leaching is taken as a raw material of the noble metal.

Description

The extract technology of copper nickel fine alloy
Technical field
The present invention relates to the acidleach treatment process of cu-ni sulphide ore thing, belong to a kind of extract technology of the Technology, particularly a kind of copper nickel fine alloy that the fine alloy in the floating intermediates of high-sulfur mill is carried out wet processing.
Background technology
Cu-ni sulphide ore has the cu-ni sulphide ore of noble metals such as platinum, palladium, gold, rhodium, iridium, osmium, ruthenium for symbiosis, it is very important to adopt advanced and applicable technical process to reclaim these precious metals.Certain cu-ni sulphide ore in China, its platinum metals output accounts for more than 85% of national output.In existing precious metal recovery method, adopted alloy sulfiding smelting technology, this has not only caused the loss of precious metal, and has brought the serious environmental pollution.
The intermediates that cu-ni sulphide ore forms in the floating sepn process of high sulfonium mill are cupronickels, comprise coarse grain alloy and fine alloy.Precious metal floats nearly to have in the sepn process at high sulfonium mill and 90% is enriched in the intermediates cupronickel.The alloy sulfuration process carries out the high ice of sulfiding smelting output secondary nickel with this cupronickel as raw material exactly, carries out the floating output secondary alloy of secondary grinding again, and this secondary alloy is as the raw material that extracts precious metal.Production practice show, and are floating through such sulfuration and mill, precious metal only enrichment 5 times, and with a toll of more than 10%.Therefore, be necessary to adopt new technique means to improve the concentration ratio and the rate of recovery of precious metal.
In fact, not only metal loss is big, energy consumption is many but also produce the flue gas that SO2 is arranged in a large number for the sulfuration process of an alloy, is difficult for handling, and environmental pollution is serious, and labor condition is poor.As adopt then thorough decontamination source of wet processing, improve the Air quality and the Working environment of plant area.
Summary of the invention
The present invention is directed to the defective or the deficiency that exist in the prior art, a kind of extract technology of copper nickel fine alloy is provided, thereby improve noble metal recovery rate in the leached mud, and the environmental pollution of avoiding sulfuration process to bring.
Technical scheme of the present invention is as follows:
The extract technology of copper nickel fine alloy, it is characterized in that: adopt segmentation to leach mode, comprise that one section leachings carrying out successively, two sections leach and the pressurization leaching, one section leached mud is as the raw material of two sections leachings, two sections raw materials that leached mud leaches as pressurization, the pressurization leached mud is as precious metal raw material.
In described one section leaching, two sections leachings and the leaching of pressurizeing, include logical oxygen step.
The leaching agent of described one section leaching comprises the sulfuric acid of sulfuric acid or copper ions.
The leaching agent of described one section leaching comprises the sulfuric acid of copper ions, and one section leach liquor that this leaching agent leaches obtains liquid after scum and the deironing by the pressurization deironing, and liquid send the anolyte purification system after this deironing.
The leaching agent of described two sections leachings comprises sulfuric acid and cupric ion, and two sections leach liquors that this leaching agent leaches partly return in the leaching agent of one section leaching, increases cupric ion.
The leaching agent that described pressurization is leached comprises sulfuric acid, and the pressurization leach liquor that this leaching agent leaches returns in the leaching agent of one section leaching.
Technique effect of the present invention is as follows:
Experiment showed, and implement method of the present invention, but can fully realize improving the leaching yield of extracts such as Ni, Fe, Co, Cu, S, thereby improve noble metal recovery rate in the leached mud, and avoided the environmental pollution that sulfuration process brought.
Embodiment
The leaching existing repeatedly experimental study and the industrial practice of copper nickel ice nickel, for example: adopt the sulfuric acid pressure leaching process to handle high ice nickel, the normal pressure and the pressurization of nickel ore concentrate, fine alloy mixture are leached or the like.What the present invention studied floats product to liking the high-sulfur mill: coarse grain alloy and fine alloy.Big for this granularity, take which kind of wet processing flow process than great, the difficult material that grinds, also do not have studying and testing of system, the applicant has proposed " using acid leaching process processing cupronickel instead to improve precious metal rate of recovery conductive suggestion about abolishing the alloy sulfuration " for this reason.According to this suggestion, coarse grain alloy and fine alloy carry out sulfuric acid respectively and leach; Fine alloy also will increase by one section pressurization and leaches because sulfur-bearing is higher; In the normal pressure leaching process, introduce cupric ion to strengthen leaching velocity; Leach solution that a kind of nickeliferous height of output and impurity are few and the another kind of high and nickeliferous low solution (Cu:Ni 〉=2:1), handle nickel and copper in the recovery raw material respectively of Cu that contains simultaneously by one section leachings, precipitation and two sections oxygen.Particulate pressurization leached mud and two sections leached muds of coarse grain, because of the quantity of slag seldom, can directly send the precious metal workshop.
1. coarse grain alloy and fine alloy are taked the mode that leaches respectively.The advantage of this mode is can obtain copper, nickel than higher solution.
2.1 the technical process that fine alloy leaches is described below:
Two sections leach liquors with the pressurization leach liquor that contains sulfuric acid and cupric ion and about 70% leach fine alloy, nickel, iron, cobalt dissolving, the cupric ion precipitation obtains containing Ni〉80g/l, Cu＜0.5g/l, H 2SO 4The nickel sulfate solution of＜10g/l is incorporated the anolyte purification system into after deironing.Leached mud carries out two sections normal pressure oxygen and leaches, and leaching agent is a sulphuric acid soln.In two sections one section leached muds when leaching in sedimentary copper and the alloy copper bearing major part leached, this leach liquor major part is returned one section leaching, about 30% delivers to one section leaching of coarse grain, wherein contained copper equals the whole of fine alloy leaching copper.Two sections leached muds advance pressurization and leach, and adopt to contain H 2SO 4The aqueous solution of＜10g/l is as leaching agent.Leach liquor all returns one section leaching, and the leached mud trial of strength seldom, can be used as the raw material that extracts precious metal.In order to accelerate leaching velocity, logical oxygen is as oxygenant during leaching.
2.2 the chemical principle that fine alloy leaches:
One section leaching of fine alloy divides two stages: oxidation period and locomorphic stage.Lead to oxygen oxidation period, mainly leach Cu, Fe, Ni, Co in the alloy.When the ph value reaches certain numerical value, stop oxygen, leach and enter locomorphic stage.Mainly utilize the Ni, the Fe metal replacement copper that are not leached in the alloy.Ni, Fe, Co mainly exist with metallic state in the coarse grain alloy.According to their character, in oxidation period following reaction may take place:
Fe 0+H 2SO 4＝FeSO 4+H 2↑ (1)
Ni 0+H 2SO 4＝NiSO 4+H 2↑ (2)
Fe 0+1/2O 2+H 2SO 4＝FeSO 4+H 2O (3)
Ni 0+1/2O 2+H 2SO 4＝NiSO 4+H 2O (4)
Fe 0+CuSO 4＝FeSO 4+Cu 0 (5)
Ni 0+CuSO 4＝NiSO 4+Cu 0 (6)
Fe 0+Fe 2(SO 4) 3＝3FeSO 4 (7)
Ni 0+Fe 2(SO 4) 3＝NiSO 4+2FeSO 4 (8)
(1), (2) reaction exists, this can observe from experiment, when leaching obstructed oxygen, slag has poly-and rising phenomenon, obviously is due to the slag particle surface adsorption hydrogen.It is very little changing slowly the contribution of reaction (1), (2) as can be seen leaching velocity being done from pH, does not exist with alloy state because iron, nickel are with simple substance.Fe when leading to oxygen 0And Ni 0Mainly generated water with (3), the oxidation of (4) formula reactive hydrogen.
Reaction (3), (4) are leached in the reaction at all and are occupied certain weight proportion, but speed of response is limited, and when not adding copper leaching only logical oxygen, the leaching yield of 4 hours nickel has only 54%.
When aerobic, sulfuric acid and cupric ion existed, that carries out in the oxidising process was very fast, and this is because (5), (6), (7), (8) these 4 reactions have taken place.Because Cu 2+And Fe 3+Participate in displacement and oxidizing reaction, leaching process is quickened greatly.
Fe 3+Be by Fe 2+Oxidation and come.Fe 2+Can react by following formula:
2FeSO 4+1/2O 2+H 2SO 4＝Fe 2(SO 4) 3+H 2O (9)
In fact, this reaction is carried out quite slowly.As Cu 2+When existing, Fe 2+Oxidation rate will accelerate:
Fe 2++Cu 2+＝Fe 3++Cu + (10)
Cu ++1/4O 2+H 2＝Cu 2++1/2H 2O (11)
The katalysis of cupric ion is carried out according to top two reaction formula just.
By (5), (6), two Cu that reaction generates 0Also can be oxidized to Cu 2+:
Cu 0+1/2O 2+H 2SO 4＝CuSO 4+H 2O (12)
Cu 0+Fe 2(SO 4) 3＝CuSO 4+2FeSO 4 (13)
In oxidising process, copper is played the effect of an acid by repeated precipitation and dissolving.Because sedimentation speed is greater than oxidation rate, how on a declining curve copper ion concentration is.The obvious example of the oxidized dissolved of copper is, copper ion concentration descends earlier, rises in the back, even surpasses starting point concentration.This is because oxidation rate has surpassed sedimentation speed.
In the fine alloy, alloy content is about 50%, and sulfur-bearing is higher, thereby contains more nickelous sulfide, and the method the same with coarse grain alloy adopted in one, two section leaching.So the chemical reaction and the coarse grain of leaching process are basic identical, promptly the both carries out the chemical reaction of above-mentioned (1)～(13).Because following reaction when normal pressure leaches particularly two sections leachings of fine alloy, also can take place in the existence of nickelous sulfide:
Ni 3S 2+CuSO 4＝NiSO 4+Cu 0+2NiS (14)
Ni 3S 2+1/2O 2+H 2SO 4＝NiSO 4++2NiS+ (15)
H 2O
The Cu that reaction (14) generates 0Can continue to be oxidized to Cu 2+
Two sections leached muds find to have a large amount of NiS to exist by pin check, and Ni is described 3S 2In Ni 0Can be partly dissolved.
In the pressurization leaching process, main chemical reaction is the dissolving of the sulfide of nickel and copper, and its reaction formula is as follows;
NiS+2O 2＝NiSO 4 (16)
Ni 3S 2+H 2SO 4+9/2O 2＝3NiSO 4+H 2O (17)
CuS+2O 2＝CuSO 4 (18)
CuS+1/2O 2+H 2SO 4＝CuSO 4+H 2O+ (19)
S 0
The sulfide of a spot of cobalt, iron is also equally oxidized with NiS, leaches.
In the pressurization leached mud with on the wall, there is sulphur to exist, illustrates to generate S in the leaching process 0, generate reason most possible be autoclave when heating up, produce sulphur when high through low-temperature zone and acidity.Under this experiment condition, sulphur becomes SO 2- 4Transformation efficiency be 98%, so S 0Production rate very little.
3. test-results
Be the checking such scheme, we have carried out necessary test, comprise the test of coarse grain alloy and fine alloy.
3.1 the physicochemical property of coarse grain alloy
The physicochemical property of the coarse grain alloy that test is adopted are as follows:
1) size-grade distribution
Size-grade distribution sees Table 3-1
The size-grade distribution of table 3-1 coarse grain alloy
Grain warp/mm >1 1-0.5 0.5-0.25 0.25-0.154 0.154-0.074 <0.074
Distribution/% 0.8 12.7 26.9 25.9 19.9 13.8
2) density
After measured: the true density of coarse grain alloy is 7.75g/cm 3
The loose density of coarse grain alloy is 2.25g/cm 3
The tap density of coarse grain alloy is 2.65g/cm 3
3) chemical ingredients
Chemical ingredients sees Table 3-2
The chemical ingredients of table 3-2 coarse grain alloy
Element Ni Fe Co Cu S Al 2O 3 SiO 2 CaO MgO
Content % 72.56 10.03 1.26 11.29 1.25 1.00 0.77 <0.02 <0.02
3.2 the physicochemical property of fine alloy
The physicochemical property of the fine alloy that test is adopted are as follows:
1) size-grade distribution of fine alloy sees Table 3-3
The size-grade distribution of table 3-3 fine alloy
Grain warp/mm >0.154 0.154-0.074 0.074-0. 0.05 0.05-0.045 <0.045
Distribution/% 5.8 12.6 15.2 13.8 13.8 38.7
2) Chemical Composition of fine alloy
We used two batch materials at the trial, and its Chemical Composition is as table 3-4,3-5.
The Chemical Composition of table 3-4 fine alloy
Figure A200810119925D00081
3) the thing phase of alloy
The thing phase composite of fine alloy is as follows:
Table 3-5 material dosing analytical results
The thing phase Nickelous sulfide Cupric sulfide Alloy Magnetite Gangue
Composition/% 39.0 1.1 48.9 6.0 5.0
3.3 investigation about metallographic phase in two sections leached muds
We utilize microscope, and means such as electronic probe have been carried out examination of product to two sections leached muds, and the result is as follows:
(1) material in the product is formed
Mainly be NiS in the product, next has metallic copper, chalcopyrite, pentlandite, the Ni of copper glance, magnetite, trace 3S 2, slag, CuS, (FeNiCu) S, ferric oxide etc.Wherein NiS is Ni 3S 2After two sections leachings, change and come, see the electron probe microanalysis result:
Table 3-6 nickelous sulfide electron probe microanalysis result/%
Content S Fe Co Ni Cu Add up to
Soak preceding nickelous sulfide 25.8 0.70 0.96 71.89 0.36 99.71
Soak postcure nickel 35.67 0.22 1.30 60.32 2.16 99.67
Soak the residual Ni in back 3S 2 25.34 0.61 0.92 72.86 0.15 99.88
The content and the existence form of (2) two sections leached mud interalloies
Utilize the microscope statistical technique that the residual alloys in the product has been carried out quantitative analysis, its result is 14ppm (14g/t).
The existence form of alloy in product has following several:
A, independent alloy with other particle adhesion or symbiosis, can not divide two kinds again: a kind of because mechanical sneaking into; Another kind of is corrosion remnants.The former quantity is few but granularity is bigger, is 0.06 * 0.012 to the maximum.The latter is main residual alloys, and granularity does not wait.
B, with other particle adhesion or symbiosis, as with adhesion or symbiosis such as magnetite, metallic copper, copper glance, NiS.
Composition before and after alloy leaches changes little, sees the electron probe microanalysis result:
Table 3-7 alloying constituent electron probe microanalysis result/%
Content S Fe Co Ni Cu Add up to
Before the leaching 0.19 10.61 1.57 78.22 8.87 99.46
After the leaching 0.18 8.75 1.38 79.42 10.02 99.75
(3) conclusion
Two sections leached mud interalloy content are few, even whole nickel wherein, iron, cobalt and acid-respons generate hydrogen, its content also is safe.
3.4 concentration effect about precious metal
Duration of test was once analyzed one, two sections leached muds of normal pressure thick, fine alloy, and its bullion content is as table 3-8.
Table 3-8 precious metal grade/g/t
Title P t P d A u
One section leached mud of coarse grain 502 187 139
Two sections leached muds of coarse grain 8680 2890 1090
One section leached mud of particulate 10.4 50.8 43.5
Two sections leached muds of particulate 198 91.8 90.3
According to two sections slag rates of coarse grain is 3.3% reckoning, and concentration of precious metal can reach 30 times.

Claims (6)

1. the extract technology of copper nickel fine alloy, it is characterized in that: adopt segmentation to leach mode, comprise one section leaching carrying out successively, two sections leachings and the leaching of pressurizeing, one section leached mud is as the raw material of two sections leachings, two sections raw materials that leached mud leaches as pressurization, the pressurization leached mud is as precious metal raw material.
2. the extract technology of copper nickel fine alloy according to claim 1 is characterized in that: in described one section leaching, two sections leachings and the leaching of pressurizeing, include logical oxygen step.
3. the extract technology of copper nickel fine alloy according to claim 1, it is characterized in that: the leaching agent of described one section leaching comprises the sulfuric acid of sulfuric acid or copper ions.
4. the extract technology of copper nickel fine alloy according to claim 1, it is characterized in that: the leaching agent of described one section leaching comprises the sulfuric acid of copper ions, one section leach liquor that this leaching agent leaches obtains liquid after scum and the deironing by the pressurization deironing, and liquid send the anolyte purification system after this deironing.
5. the extract technology of copper nickel fine alloy according to claim 1, it is characterized in that: the leaching agent of described two sections leachings comprises sulfuric acid and cupric ion, two sections leach liquors that this leaching agent leaches partly return in the leaching agent of one section leaching, increase cupric ion.
6. the extract technology of copper nickel fine alloy according to claim 1 is characterized in that: the leaching agent that described pressurization is leached comprises sulfuric acid, and the pressurization leach liquor that this leaching agent leaches returns in the leaching agent of one section leaching.
CNA2008101199252A 2008-09-10 2008-09-10 Extraction process of copper nickel fine alloy Pending CN101381810A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023005428A1 (en) * 2021-07-29 2023-02-02 广东邦普循环科技有限公司 Method for extracting nickel from high matte nickel leaching residue
US12000012B2 (en) 2021-07-29 2024-06-04 Guangdong Brunp Recycling Technology Co, Ltd. Method for extracting nickel from high matte nickel leaching residue

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023005428A1 (en) * 2021-07-29 2023-02-02 广东邦普循环科技有限公司 Method for extracting nickel from high matte nickel leaching residue
US12000012B2 (en) 2021-07-29 2024-06-04 Guangdong Brunp Recycling Technology Co, Ltd. Method for extracting nickel from high matte nickel leaching residue

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