CN115948662A - Method for leaching sulfide minerals - Google Patents
Method for leaching sulfide minerals Download PDFInfo
- Publication number
- CN115948662A CN115948662A CN202211739397.7A CN202211739397A CN115948662A CN 115948662 A CN115948662 A CN 115948662A CN 202211739397 A CN202211739397 A CN 202211739397A CN 115948662 A CN115948662 A CN 115948662A
- Authority
- CN
- China
- Prior art keywords
- leaching
- reaction
- solution
- slurry
- sulfuric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002386 leaching Methods 0.000 title claims abstract description 312
- 238000000034 method Methods 0.000 title claims abstract description 80
- 229910052569 sulfide mineral Inorganic materials 0.000 title claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 282
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 173
- 239000002002 slurry Substances 0.000 claims abstract description 98
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 73
- 230000003647 oxidation Effects 0.000 claims abstract description 63
- 239000007788 liquid Substances 0.000 claims abstract description 57
- 238000002791 soaking Methods 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000000227 grinding Methods 0.000 claims abstract description 17
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 11
- 239000011707 mineral Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 181
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 96
- 239000001301 oxygen Substances 0.000 claims description 96
- 229910052760 oxygen Inorganic materials 0.000 claims description 96
- 229910052759 nickel Inorganic materials 0.000 claims description 89
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 87
- 239000010949 copper Substances 0.000 claims description 63
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 62
- 229910052802 copper Inorganic materials 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 54
- 239000007800 oxidant agent Substances 0.000 claims description 34
- 239000012535 impurity Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000006073 displacement reaction Methods 0.000 claims description 20
- 238000004537 pulping Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 9
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 claims description 6
- NHPHQYDQKATMFU-UHFFFAOYSA-N [Cu]=S.[Co] Chemical compound [Cu]=S.[Co] NHPHQYDQKATMFU-UHFFFAOYSA-N 0.000 claims description 5
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 28
- 229910052751 metal Inorganic materials 0.000 abstract description 28
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 47
- 229910052742 iron Inorganic materials 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 19
- 230000001590 oxidative effect Effects 0.000 description 19
- 239000002253 acid Substances 0.000 description 17
- 238000007598 dipping method Methods 0.000 description 17
- 239000010941 cobalt Substances 0.000 description 16
- 229910017052 cobalt Inorganic materials 0.000 description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 11
- 238000003825 pressing Methods 0.000 description 10
- 150000004763 sulfides Chemical class 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- 238000007792 addition Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001021 Ferroalloy Inorganic materials 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a leaching method of sulfide minerals, which belongs to the field of non-ferrous metal hydrometallurgy, and particularly comprises the steps of grinding the sulfide minerals into powder, preparing the powder into slurry, adding the slurry into a sulfuric acid reaction solution prepared in advance, carrying out a pre-soaking reaction, carrying out an oxidation leaching reaction, and finally carrying out solid-liquid separation treatment to obtain a sulfate solution; wherein the concentration of the sulfuric acid in the sulfuric acid reaction solution is 30g/L-300g/L. The leaching method of the sulphide minerals provided by the invention can greatly improve the metal leaching rate of the sulphide minerals under the normal pressure condition, greatly reduce the configuration quantity of high-pressure reaction devices and greatly reduce the leaching and purifying cost of the sulphide minerals.
Description
Technical Field
The invention relates to the field of non-ferrous metal hydrometallurgy, in particular to a leaching method of sulfide minerals.
Background
The sulfide mineral reserves are abundant, and are one of the forms of the current metal raw materials. Copper and cobalt raw materials represented by copper cobalt sulfide ores and copper cobalt alloys and nickel raw materials represented by nickel sulfide ores, high nickel matte and low nickel matte occupy a considerable proportion in the hydrometallurgical industry, have the characteristics of relatively high metal grade and abundant reserves, and are easier to purify compared with other forms of minerals, so that the research on the leaching process of sulfide minerals is necessary for the development of modern metallurgy.
The general leaching process comprises the steps of crushing high nickel matte, presoaking the crushed high nickel matte in a dilute sulfuric acid reaction solution at normal pressure, carrying out acid leaching on a large amount of nickel simple substances in a presoaking stage, then pumping the presoaked slurry into an oxygen pressure leaching kettle, continuously leaching unleached nickel under the conditions of high pressure, high temperature and oxygen enrichment, then adding calcined soda into the reacted solution containing impurities such as nickel, iron, copper and the like, neutralizing water to remove iron and copper, achieving the purpose of purification, extracting the purified solution, deeply purifying other impurities, and finally producing a high-purity sulfate solution which can be directly used for producing high-purity nickel serial products.
The relevant reactions are as follows:
Ni+H 2 SO 4 ＝NiSO 4 +H 2 ↑
2Ni+2H 2 SO 4 +O 2 ＝2NiSO 4 +2H 2 O
2Ni 3 S 2 +2H 2 SO 4 +O 2 ＝4NiS+2NiSO 4 +2H 2 O
NiS+2O 2 ＝NiSO 4
Fe+H 2 SO 4 ＝FeSO 4 +H 2 ↑
4FeSO 4 +O 2 +4H 2 O＝2Fe 2 O 3 +4H 2 SO 4
Cu+O 2 +H 2 SO 4 ＝CuSO 4 +H 2 O↑
2Cu 2 S+2H 2 SO 4 +O 2 ＝2CuS+2CuSO 4 +2H 2 O
CuS+2O 2 ＝CuSO 4
in the conventional method for processing and treating nickel matte, the conventional process is to use a dilute sulfuric acid reaction solution with low concentration to perform presoaking in an atmospheric pressure leaching stage, the leaching rate of nickel is low, only part of elemental metallic nickel in the nickel matte can be leached, and the leaching reaction of nickel is slow. More than 70% of leaching reaction needs to be leached under the condition of pressurizing and oxygen-enriching, but the process needs to utilize multistage pressurizing and leaching, a large amount of high-pressure oxygen-enriching reaction equipment needs to be configured in the production treatment process of high-grade nickel matte, the equipment investment is large, the required electric energy is huge, meanwhile, the configuration of a large amount of high-pressure oxygen-enriching equipment greatly increases the potential safety hazard in the production process, the high-pressure oxygen-enriching leaching is followed by using soda ash for neutralization hydrolysis and purification, and other auxiliary material consumption is introduced, so that on one hand, the low energy consumption requirement that the production energy cost does not meet the current low carbon requirement is increased, on the other hand, new impurities can be introduced due to the introduction of new auxiliary materials, and meanwhile, the leaching and purifying process flow of the high-grade nickel matte is lengthened.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention provides a leaching method of sulfide minerals, which aims to solve the problems of low leaching rate of metals and slow leaching reaction caused by the fact that low-concentration dilute sulfuric acid is used for pre-leaching in a normal-pressure leaching stage in the prior art.
In order to solve the problems, the invention adopts the following scheme:
grinding the sulfide minerals into powder, preparing the powder into slurry, adding the slurry into a sulfuric acid reaction solution prepared in advance, performing a pre-soaking reaction, and performing an oxidation leaching reaction to obtain a sulfate solution;
wherein the concentration of the sulfuric acid in the sulfuric acid reaction solution is 30g/L-300g/L.
In the scheme, the sulfuric acid reaction solution is prepared in advance by adopting a mode of firstly preparing acid and then adding materials, the prepared slurry solution is added into the sulfuric acid reaction solution, the acid content in the sulfuric acid reaction solution in an initial state is sufficient, the slurry solution is introduced into the sulfuric acid reaction solution, the slurry solution can immediately and fully react with the sulfuric acid reaction solution, partial sulfides of metals are oxidized by utilizing the strong oxidizing property of sulfuric acid, and the metal leaching rate and the leaching reaction rate are further improved.
The traditional technology is as follows: the crushed sulfide minerals are directly added with dilute sulfuric acid for leaching and leaching under normal pressure without pulping. At the initial stage of atmospheric pressure leaching, hydrophobic sulfide minerals which are not easy to be wetted by water are suspended and aggregated into lumps under the support of surface tension, the leaching effect is poor before materials are completely leached, a certain time is consumed for waiting for leaching, the leaching reaction efficiency in acid leaching equipment with high requirements on acid corrosion resistance is low, and the leaching efficiency of equipment in unit volume per unit time is low.
In addition, compare and directly let in sulfuric acid solution in the pulping liquid, the pulping liquid volume can show the volume that is greater than sulfuric acid solution in earlier stage, can't guarantee that the pulping liquid can abundant quick reaction, can't guarantee the oxidation effect to the sulphide of metal in the pulping liquid promptly, and then influence the metal leaching rate.
The sulfuric acid reaction solution with the concentration is set to be 30-300 g/L, so that the sulfuric acid reaction solution with the concentration has a better oxidation effect, the leaching rate of metal can be ensured, and the utilization efficiency of reaction raw materials can be higher.
In other preferred embodiments, the method comprises the following steps:
step a, slurry reaction: grinding the sulfide minerals into powder, and mixing the powder with the solution to prepare slurry;
step b, pre-dipping reaction: adding the slurry solution into a sulfuric acid reaction solution prepared in advance, introducing oxygen, and performing a pre-soaking reaction to obtain a reaction solution;
step c, oxidation leaching reaction: introducing oxygen into the reaction solution for oxidation leaching treatment to obtain a leaching solution and leaching residues;
preferably, when the sulfide minerals are at least one of nickel sulfide ore, nickel matte, and nickel matte, after the oxidation leaching reaction in step c is completed, the method further comprises a step d of impurity removal treatment: and removing impurities from the leachate to obtain a sulfate solution.
The leaching method of the sulfide minerals in the scheme at least comprises the steps of slurry reaction, pre-dipping reaction, oxidation leaching reaction and impurity removal treatment, the pre-dipping reaction step is independent of the step of oxidation leaching, the pre-dipping reaction of materials is carried out in a mode of firstly preparing acid and then adding materials, and sulfides of partial metals can be oxidized by using the strong oxidizing property of sulfuric acid with higher concentration.
In a preferred embodiment, step a is specifically: adding the solution into a slurrying device provided with a stirring device, grinding the sulfide minerals into powder at one time, and injecting the powder into the slurrying device in a positive pressure pneumatic conveying mode of 0.4-0.8Mpa to prepare slurry liquid.
In a more preferable scheme, the sulfide minerals are at least one of nickel sulfide ore, copper cobalt sulfide ore, cobalt copper alloy, high nickel matte and low nickel matte;
the device for grinding the sulfide minerals into powder at one time is a vertical roller mill.
Compared with the traditional ball mill, the vertical roller mill has lower energy consumption; meanwhile, the wear-resistant material of the vertical mill is higher. The method specifically comprises the following steps: the one-time grinding is vertical roller mill grinding (the treatment capacity of a vertical mill is 15 t/(h.300KW.h), the treatment capacity in unit time and energy consumption is 0.05 t/(h.KW.h), the treatment capacity of the ball mill is about 3 t/(h.100KW.h), the treatment capacity in unit time and energy consumption is 0.03 t/(h.KW.h), the energy consumption of the vertical mill is low, meanwhile, the wear rate of a wear-resistant material (ferroalloy material) of the vertical mill is about 5g/t of material, the wear rate of a wear-resistant material (ferroalloy material) of the ball mill is 1500g/t of material, the wear rate of the wear-resistant material of the vertical mill is greatly reduced, and the consumption of corresponding purification auxiliary materials for iron is greatly reduced.
The particle size D90 of the powder is less than or equal to 40 mu m, and the smaller particle size can ensure that the powder and the sulfuric acid react more fully in the subsequent leaching reaction and the oxidation leaching reaction;
d, mixing the mixture with the materials and pulping to obtain a solution, wherein the solution is water and/or a sulfate solution obtained after impurity removal treatment in the step d; the mass ratio of liquid to solid in the slurry liquid is 1.5-2:1, to meet the requirements of the subsequent steps b and c.
In other preferable schemes, when the sulfide mineral is at least one of nickel sulfide ore, high nickel matte and low nickel matte, after the oxidation leaching reaction in the step c is finished, the method further comprises a step d of impurity removal treatment: and (4) removing impurities from the leaching solution to obtain a sulfate solution.
And the solution in the step a is at least one of water, a leachate obtained by the oxidation leaching reaction in the step c and a sulfate solution obtained after impurity removal treatment in the step d.
In other preferable scheme, in the step b, the concentration of the sulfuric acid in the sulfuric acid reaction solution is 150g/L-300g/L;
the presoaking reaction temperature is 65-80 ℃; the purity of the oxygen is more than 90 percent, and the inlet flow rate of the oxygen is 10-60Nm 3 /h；
The flow ratio of the oxygen to the slurrying liquid is oxygen flow: slurry flow = (7-10 Nm) 3 /h):(8-10m 3 /h)。
In the step b, the concentration of sulfuric acid is increased in the pre-soaking process, and the pre-soaking reaction of materials is carried out in a manner of adding acid and then adding materials, so that the sulfide of partial metals can be oxidized by using strong oxidizing property of sulfuric acid with higher concentration than that of conventional leaching at a proper temperature (65-80 ℃), and meanwhile, a small amount of oxygen with higher purity (the purity is more than 90%) is supplemented to increase the oxidizing atmosphere of the pre-leaching reaction, so that the oxidizing reaction of the sulfide in sulfide minerals is accelerated, the intercrystalline structures of sulfides such as nickel sulfide and copper sulfide are damaged to the greatest extent, and the leaching reaction of elemental metals in the sulfide minerals is accelerated, so that the reaction rate of oxidizing the sulfide at normal pressure and the leaching rate of metals are indirectly increased.
In another preferred embodiment, in the step b, after the slurry liquid is added, the time of the pre-soaking reaction is 1.2 to 1.8 times of the time of adding all the slurry liquid prepared in the step a into the pre-soaking reaction device; after the slurry liquid is added, the presoaking reaction time is 0.8-1.5h. The presoaking time in the scheme is 1.2-1.8 times of the time of adding the slurry, and is mainly used for releasing hydrogen to the maximum extent.
In another preferable scheme, in the step b, the adding amount of the slurry liquid is calibrated according to the amount of sulfuric acid in the pre-soaking reaction device, and the adding amount of the slurry liquid is based on the mass of the sulfide minerals in the slurry liquid; the volume of slurry added is V = M/N;
wherein M is the mass of the sulfide minerals in the pulping liquid to be added, and N is the mass percentage content of the sulfide minerals in the pulping liquid in unit volume; m = (mass of sulfuric acid × molar mass of elemental metal/molar mass of sulfuric acid in preliminary immersion reaction apparatus) × 1.05/[ 1- (sulfur mass percentage content of sulfurized mineral × molar mass of elemental metal/molar mass of elemental sulfur)/metal content of sulfurized mineral ].
In other preferred embodiments, the step c oxidative leaching comprises an atmospheric leaching process and a pressure leaching process; the oxidation leaching reaction device comprises a normal pressure leaching reaction device and a pressure leaching reaction device; the leaching solution is divided into a first leaching solution and a second leaching solution; the leaching residues are divided into a first leaching residue and a second leaching residue.
The normal pressure leaching process comprises the following specific steps: carrying out normal-pressure oxidation leaching reaction on the reaction solution, introducing oxygen in the reaction process, wherein the reaction time of the normal-pressure oxidation leaching reaction is 2-13h, and separating the slurry solution after the reaction is finished to obtain a first leaching solution and first leaching residues; the safety coefficient of the atmospheric leaching is high, the investment is small, and the load and the investment of the pressure leaching can be reduced by the atmospheric leaching.
Wherein the purity of the oxygen is more than 90%; the flow ratio of the oxygen to the first leaching residue slurry liquid is oxygen flow: flow rate of slurrying solution of first leaching residue = (7-10 Nm) 3 /h):(8-10m 3 H); the reaction temperature of the normal pressure leaching is 60-90 ℃.
In the scheme, the oxygen flow, the slurry liquid-solid ratio and the concentration of the sulfuric acid reaction solution are accurately calculated in advance, accurate proportioning is carried out, the alkaline characteristic of hydrogen ions consumed by the material is utilized, the material is utilized as a neutralizing reagent to carry out neutralization hydrolysis iron removal purification reaction, the process flow is shortened, and the addition of auxiliary materials is reduced.
In other preferred schemes, the atmospheric leaching reaction device is provided with a stirring reactor of a super-energy oxidizer;
wherein, in the normal pressure leaching process, the stirring speed of the stirring reactor is 50-120r/min, the slurrying liquid flows out from the upper part of the stirring reactor and flows into the super-energy oxidizer, the slurrying liquid and oxygen are mixed in the super-energy oxidizer and then are injected into the stirring reactor from the bottom of the stirring reactor, and the stirring and circulating are carried out in a reciprocating way so as to ensure that the oxygen is fully contacted with the materials.
The process method is provided with the super-energy oxidizer for oxygen dispersion by using ultrasonic waves to carry out normal-pressure oxidation leaching, on one hand, oxygen with higher purity is used for oxidation reaction, on the other hand, the ultrasonic waves are used for greatly increasing the dispersion effect of the oxygen, and simultaneously, materials are ground to the particle size of 40 microns or less, so that the specific surface area of the materials and the contact area of the materials and the oxygen are greatly increased, and the reaction rate of oxidizing sulfides at normal pressure and the leaching rate of metals can be greatly increased.
In other preferred schemes, the pressure leaching process is specifically as follows: adding water into the first leaching residue obtained by the normal pressure leaching reaction for pulping into a first leaching residue pulp solution, conveying the first leaching residue pulp solution into a pressure leaching reaction device filled with a sulfuric acid reaction solution, and performing solid-liquid separation after the pressure leaching reaction is finished to obtain a second leaching solution and second filtering residue;
wherein the time for pulping the first leaching residue by adding water is 0.5-2h; the concentration of sulfuric acid in a sulfuric acid reaction solution in the pressure leaching reaction is 30-150 g/L; the internal pressure of the pressure leaching reaction device is 1-2Mpa, after the temperature in the pressure oxidation leaching reaction kettle is raised to the initial reaction temperature of 80-110 ℃, the pressure oxidation reaction starts to react violently, the reaction temperature is maintained at 140-180 ℃ by the self heat release of the reaction until the pressure oxidation reaction is finished, and the pressure leaching time is 2-5h.
In other preferred embodiments, step d is specifically: conveying the second leaching solution into an impurity removal reaction device, adding iron powder, and performing solid-liquid separation on the slurry solution after the iron powder displacement copper removal reaction is completed to obtain a sulfate solution; wherein, the pH value in the impurity removal reaction device is 1-2, and the temperature is 60-80 ℃.
Compared with the prior art, the invention has the following beneficial effects:
firstly, the equipment and the pipeline for adding the water slurry have low requirements on acid corrosion resistance, and the acid leaching process has greater requirements on the equipment and needs greater equipment investment. According to the invention, the subsequent acid leaching time can be saved by adding water for slurrying in advance, the acid leaching efficiency is improved, and the leaching efficiency of the acid leaching equipment in unit time is improved.
Secondly, the concentration of sulfuric acid is increased in the pre-soaking process, the pre-soaking reaction of materials is carried out in a mode of firstly preparing acid and then adding materials, partial sulfides of metals are oxidized by using the strong oxidizing property of the sulfuric acid with higher concentration, and meanwhile, oxygen is supplemented to improve the oxidizing atmosphere of the pre-leaching reaction, so that the oxidizing reaction of sulfides in sulfide minerals is accelerated, and the leaching reaction of elemental metals in the sulfide minerals is accelerated.
Thirdly, by adopting the mode of firstly preparing acid and then feeding, in the early stage of reaction, the viscous slurry liquid added into the acid solution is quickly diluted, the blown oxygen can also be quickly diffused into the whole reaction system, the material can quickly react with the acid and the blown oxygen, and the leaching efficiency is improved.
Fourthly, the process method is provided with an ultra-energy oxidizer for oxygen dispersion by using ultrasonic waves to carry out normal-pressure oxidation leaching, on one hand, oxygen with higher purity is used for carrying out oxidation reaction, on the other hand, the ultrasonic waves are used for greatly increasing the dispersion effect of the oxygen, meanwhile, the materials are ground to the particle size of 40 microns or less, the specific surface area of the materials and the contact area of the materials and the oxygen are greatly increased, the reaction rate of oxidizing sulfides by normal pressure and the leaching rate of metals are increased, and the leaching rate of sulfide mineral metals under normal pressure can reach more than 60 percent.
Fifthly, the process method accurately prepares the materials in the material preparation process of the normal pressure leaching reaction, utilizes the alkaline characteristic of hydrogen ion consumption of the materials, and utilizes the materials as a neutralizing reagent to perform the neutralization hydrolysis iron removal purification reaction, so that the content of impurities such as iron, copper and the like in the first leaching solution is very low, the process flow is shortened, the addition of auxiliary materials is reduced, and the processing cost of sulfide minerals is reduced.
Sixth, the process method greatly reduces the configuration quantity of high-pressure reaction equipment in the process of processing and treating the sulfide minerals, and compared with the conventional process method, the configuration quantity of the high-pressure reaction equipment in the process method is reduced by more than 60%, and the fixed investment is greatly reduced.
Seventh, the process greatly compresses the pressure oxidation leaching purification process flow of the sulfide mineral treatment in the process of processing the sulfide mineral, greatly reduces the consumption of auxiliary materials, and reduces the processing cost of the sulfide mineral.
In conclusion, the process method can greatly improve the metal leaching rate of the sulfide minerals under the normal pressure condition, greatly reduce the configuration quantity of high-pressure reaction devices and greatly reduce the leaching and purifying cost of the sulfide minerals.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart of a specific leaching method of sulfide minerals provided by the invention;
FIG. 2 is a statistical chart of parameters related to the middle filtrate in example 4 of the present invention and comparative examples 1 to 7.
Detailed Description
In order to make the aforementioned and other features and advantages of the invention more apparent, the invention is further described below with reference to the accompanying drawings. It is understood that the specific embodiments described herein are for purposes of illustration only and are not intended to be limiting, as those of ordinary skill in the art will recognize.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the specific details need not be employed to practice the present invention. In other instances, well-known steps or operations are not described in detail to avoid obscuring the invention.
In order to demonstrate the advantages of the method provided by the present invention, reference is made to the following specific examples.
Example 1 (Nickel sulfide ore)
Step a, slurry reaction: grinding nickel sulfide ore containing 50% of nickel, 0.1% of copper, 4% of iron and 18% of sulfur into powder with D90 of 40 microns by using a vertical roller mill, and adding 8m of water into a slurrying kettle with a stirring device started 3 Adding the powder into a slurrying kettle in a positive pressure pneumatic conveying mode of 0.8Mpa, wherein the ratio of liquid to solid is 2:1 preparing slurry for later use.
Step b, pre-dipping reaction: sulfate solution 8m produced by impurity removal treatment 3 (Nickel concentration 94 g/L) and 4m of water 3 Preparing a nickel-containing sulfuric acid reaction solution with sulfuric acid concentration of 100g/L in a pre-soaking reaction kettle for later use with concentrated sulfuric acid, starting a stirring device of the pre-soaking reaction kettle, and heating the prepared solution to 75 ℃ for later use.
Uniformly adding the prepared slurry liquid into a pre-dipping reaction kettle for pre-dipping reaction, wherein the pre-dipping reaction process is 7m 3 Introducing oxygen (the oxygen purity is 95%, the same applies below) at a flow rate of/h, adding the slurry while introducing the oxygen, and controlling the flow ratio of the oxygen to the slurry at an oxygen flow rate: slurry flow = (7 Nm) 3 /h):(8m 3 H), after the slurry liquid is added, the presoaking reaction time is 1.5 times of the time for adding the slurry liquid into the presoaking reaction device.
Step c, oxidation leaching reaction: conveying reaction liquid which completes the presoaking reaction in the presoaking reaction kettle into a normal-pressure leaching reaction device, starting a stirring reactor, wherein the stirring speed of the stirring reactor is 100r/min, starting an oxygen valve, starting a super-energy oxidizer of the oxidation leaching reaction kettle, enabling slurry liquid to flow out of the upper part of the stirring reactor and flow into the super-energy oxidizer, mixing the slurry liquid and oxygen in the super-energy oxidizer, injecting the mixture into the stirring reactor from the bottom of the stirring reactor, and repeating the steps in such a way to ensure that the oxygen is fully contacted with materials for 3 hours. Filter pressing to obtain a first leaching solution with a thickness of 15.7m 3 And 3.15 tons of first leaching residues; the pH value of the first leaching solution is 5.0, the nickel concentration is 92g/L, the iron concentration is 0.005g/L, the copper concentration is 0.002g/L, and the nickel leaching rate is 52 percent; the first leaching residue comprises NiS and Fe (OH) as main components 3 、Cu(OH) 2 。
Adding the first leaching residue into the solution containing 2m of the first leaching residue 3 Slurrying in water slurrying kettle for 1 hr to obtain first leaching residue slurry, and transferring to a tank containing 12m 3 The sulfuric acid reaction solution with the sulfuric acid concentration of 50g/L is pressurized, oxidized and leached in the reaction device; increasing the gas pressure in the pressure oxidation leaching reaction kettle to 1.6Mpa by using high-pressure oxygen, starting a steam valve of the pressure oxidation leaching reaction kettle, increasing the temperature in the pressure oxidation leaching reaction kettle to 100 ℃, starting a violent reaction of the pressure oxidation reaction, closing the steam valve, maintaining the reaction temperature at 165 ℃ by means of self heat release of the reaction, continuously introducing oxygen to maintain the gas pressure in the reaction kettle, finishing the reaction for 3 hours, and performing filter pressing to obtain a second leaching solution and second leaching residues. Wherein the second leaching solution is 12m 3 109g/L of nickel, 4.07 percent of nickel in second leaching slagIron content is 52.03%, dry weight is about 0.76 ton, and nickel comprehensive leaching rate is 98.9%.
D, impurity removal treatment: conveying the second leaching solution to an iron powder displacement copper removal reaction kettle; and starting a stirring device of the iron powder displacement copper removal reaction kettle, quantitatively adding 50 kg of iron powder according to the copper content of the second leaching solution, carrying out iron powder displacement copper removal reaction, and reacting for 1 hour.
And conveying the sulfate solution which completes the iron powder displacement copper removal reaction in the iron powder displacement copper removal reaction kettle to an iron powder displacement copper removal filtering device, and filtering to obtain a sulfate solution, wherein the solution contains 0.01g/L of copper.
Example 2 (copper cobalt sulfide ore)
Step a, slurry reaction: grinding copper-cobalt sulfide ore containing copper 30%, iron 20%, cobalt 15% and sulfur 13% 4.05t into powder with D90 of 30 μm by vertical roller mill, adding water 8m in a pulping kettle with stirring device 3 Adding the powder into a slurrying kettle in a positive pressure pneumatic conveying mode of 0.4Mpa, wherein the ratio of liquid to solid is 2:1 preparing slurry for later use.
Step b, pre-dipping reaction: sulfate solution 8m produced by impurity removal treatment 3 (containing 28g/L cobalt and 16g/L copper) and 4m water 3 And preparing a cobalt-copper-containing sulfuric acid reaction solution with sulfuric acid concentration of 100g/L in the pre-soaking reaction kettle for later use with concentrated sulfuric acid, starting a stirring device of the pre-soaking reaction kettle, and heating the prepared solution to 80 ℃ for later use.
Uniformly adding the prepared slurry liquid into a pre-dipping reaction kettle for pre-dipping reaction, wherein the pre-dipping reaction process is 10m 3 Introducing oxygen at the flow rate of/h, adding the slurry while introducing the oxygen, and controlling the flow ratio of the oxygen to the slurry at the oxygen flow rate: slurry flow = (10 Nm) 3 /h):(10m 3 And h), the presoaking reaction time is 1.2 times of the time for adding the slurry into the presoaking reaction device.
Step c, oxidation leaching reaction: conveying the reaction liquid in the pre-soaking reaction kettle after the pre-soaking reaction into a normal-pressure leaching reaction device, starting a stirring reactor, wherein the stirring speed of the stirring reactor is 80r/min, starting an oxygen valve, starting a super-energy oxidizer of an oxidation leaching reaction kettle,the slurry flowed out of the upper part of the stirred reactor and flowed into the super oxidizer, and the slurry was mixed with oxygen in the super oxidizer and then injected into the stirred reactor from the bottom of the stirred reactor to react for 13 hours. Filter pressing to obtain a first leaching solution of 18m 3 And first leaching residue; the pH value of the first leaching solution reaches 2.0, the copper concentration is 46.01g/L, the cobalt concentration is 26.2g/L, the iron concentration is 3.05g/L, the copper leaching rate is 54 percent, and the cobalt leaching rate is 65 percent.
Adding the first leached slag into the solution containing 8m of the first leached slag 3 Slurrying in water slurrying kettle for 1 hr to obtain first leaching residue slurry, and transferring to a tank containing 12m 3 The sulfuric acid reaction solution with the sulfuric acid concentration of 90g/L is pressurized, oxidized and leached in the reaction device; increasing the gas pressure in the pressure oxidation leaching reaction kettle to 2.0Mpa by using high-pressure oxygen, starting a steam valve of the pressure oxidation leaching reaction kettle, increasing the temperature in the pressure oxidation leaching reaction kettle to 80 ℃, starting a violent reaction of the pressure oxidation reaction, closing the steam valve, maintaining the reaction temperature at 180 ℃ by means of self heat release of the reaction, continuously introducing oxygen to maintain the gas pressure in the reaction kettle, finishing the reaction for 5 hours, and performing filter pressing to obtain a second leaching solution and second leaching residues. Wherein the second leaching solution is 17m 3 The copper concentration in the second leaching solution is 40.12g/L, the cobalt concentration is 14.31g/L, the second leaching residue contains 1% of copper, 0.5% of cobalt, 48.06% of iron, and about 2.5 tons of dry weight, the comprehensive leaching rate of copper is 98.4%, and the comprehensive leaching rate of cobalt is 98.3%.
Example 3 (cobalt copper alloy)
Step a, slurry reaction: grinding 2.0t of cobalt-copper alloy containing 5.5% of cobalt, 70% of copper, 18% of iron and 2% of sulfur into powder with D90 reaching 35 microns by using a vertical roller mill, and adding 4m of water into a slurrying kettle with a stirring device started 3 Adding the powder into a slurrying kettle in a positive pressure pneumatic conveying mode of 0.6Mpa, wherein the ratio of liquid to solid is 2:1 preparing slurry with solid content more than 30% for standby.
Step b, pre-dipping reaction: sulfate solution 8m produced by impurity removal treatment 3 (copper concentration 17.5g/L, cobalt 1.4 g/L), water 8m 3 Preparing a sulfuric acid reaction solution containing cobalt and copper with the sulfuric acid concentration of 180g/L in a pre-soaking reaction kettle for later use, and startingAnd (3) pre-soaking a reaction kettle stirring device, and heating the prepared solution to 65 ℃ for later use.
Uniformly adding the prepared slurry liquid into a pre-soaking reaction kettle for pre-soaking reaction, wherein the pre-soaking reaction process is 9m 3 Introducing oxygen in the amount of/h. The slurry is added while oxygen is introduced, and the flow ratio of the oxygen to the slurry is controlled to be the following oxygen flow: slurry flow = (9 Nm) 3 /h):(9m 3 And h), the presoaking reaction time is 1.8 times of the time for adding the slurry into the presoaking reaction device.
Step c, oxidation leaching reaction: conveying reaction liquid which completes the presoaking reaction in the presoaking reaction kettle into the normal-pressure leaching reaction device, starting a stirring reactor, wherein the stirring speed of the stirring reactor is 50r/min, starting an oxygen valve, starting a super-energy oxidizer of the oxidation leaching reaction kettle, enabling slurry liquid to flow out of the upper part of the stirring reactor, then flowing into the super-energy oxidizer, mixing the slurry liquid and oxygen in the super-energy oxidizer, then injecting the mixture into the stirring reactor from the bottom of the stirring reactor, and reacting for 2.1 hours. Filter pressing to obtain a first leaching solution with a thickness of 15.7m 3 And 1.1t of first leaching residue; the pH value of the first leaching solution is 3.0, the copper concentration is 70.01g/L, the cobalt concentration is 5.94g/L, the iron concentration is 2.5g/L, the copper leaching rate is 90.9 percent, and the cobalt leaching rate is 98.0 percent.
Adding the first leaching residue into the solution containing 2m of the first leaching residue 3 Pulping in water pulping kettle for 1 hr to obtain first leached residue pulp liquid, and transferring to 8m 3 The sulfuric acid reaction solution with the sulfuric acid concentration of 30g/L is pressurized, oxidized and leached in the reaction device; increasing the gas pressure in the pressure oxidation leaching reaction kettle to 1.0Mpa by using high-pressure oxygen, starting a steam valve of the pressure oxidation leaching reaction kettle, increasing the temperature in the pressure oxidation leaching reaction kettle to 110 ℃, starting a violent reaction of the pressure oxidation reaction, closing the steam valve, maintaining the reaction temperature at 140 ℃ by means of self heat release of the reaction, continuously introducing oxygen to maintain the gas pressure in the reaction kettle, finishing the reaction for 2 hours, and performing filter pressing to obtain a second leaching solution and second leaching residues. Wherein the second leaching solution is 7.5m 3 The copper concentration in the second leaching solution is 17.6g/L, the cobalt concentration is 0.22g/L, the copper content in the second leaching residue is 1%, the cobalt content in the filter residue is 0.1%, and the filter residue contains iron46 percent, dry weight of about 0.78 ton, comprehensive leaching rate of cobalt of 99.4 percent and comprehensive leaching rate of copper of 99.5 percent.
Example 4 (high nickel matte)
Step a, slurry reaction: grinding high nickel matte particles which are produced by pyrometallurgy and contain 65 percent of nickel, 8 percent of copper, 3 percent of iron and 18 percent of sulfur into powder with D90 reaching 20 micrometers by using a vertical roller mill, and adding 8m of water into a slurrying kettle with a stirring device started 3 Adding the powder into a slurrying kettle in a positive pressure pneumatic conveying mode of 0.5Mpa, wherein the ratio of liquid to solid is 2:1 preparing slurry with solid content more than 30% for standby.
Step b, presoaking reaction: sulfate solution 8m produced by impurity removal treatment 3 (Nickel concentration 109 g/L) and 4m of water 3 And concentrated sulfuric acid are prepared into a nickel-containing sulfuric acid reaction solution with the concentration of 204g/L in the pre-soaking reaction kettle for standby, and a stirring device of the pre-soaking reaction kettle is started to heat the prepared solution to 70 ℃ for standby.
Uniformly adding the prepared slurry liquid into a pre-soaking reaction kettle for pre-soaking reaction, wherein the pre-soaking reaction process is 8m 3 Introducing oxygen in the amount of/h. Oxygen is introduced into the reactor while the slurry liquid is added, and the flow ratio of the oxygen to the slurry liquid is controlled to be that the oxygen flow is as follows: slurry flow = (8 Nm) 3 /h):(9m 3 And h), the presoaking reaction time is 1.2 times of the time for adding the slurry into the presoaking reaction device.
Step c, oxidation leaching reaction: conveying reaction liquid which completes the presoaking reaction in the presoaking reaction kettle into a normal-pressure leaching reaction device, starting a stirring reactor, wherein the stirring speed of the stirring reactor is 120r/min, starting an oxygen valve, starting a super-energy oxidizer of the oxidation leaching reaction kettle, enabling slurry liquid to flow out of the upper part of the stirring reactor and flow into the super-energy oxidizer, mixing the slurry liquid and oxygen in the super-energy oxidizer, injecting the mixture into the stirring reactor from the bottom of the stirring reactor, and repeating the steps in such a way to ensure that the oxygen is fully contacted with materials for 3 hours. Filter pressing to obtain a first leaching solution with a thickness of 17.5m 3 And the first leaching residue is 2.87t; the pH value of the first leaching solution is 5.0, the nickel concentration is 128g/L, the iron concentration is 0.011g/L, the copper concentration is 0.008g/L, and the nickel leaching rate is 64.13%.
Adding the first leaching residue into the solution containing 2m of the first leaching residue 3 Slurrying in water slurrying kettle for 1 hr to obtain first leaching residue slurry, and transferring to a tank containing 12m 3 The sulfuric acid reaction solution with the sulfuric acid concentration of 100g/L is pressurized, oxidized and leached in the reaction device; increasing the gas pressure in the pressure oxidation leaching reaction kettle to 1.6Mpa by using high-pressure oxygen, starting a steam valve of the pressure oxidation leaching reaction kettle, increasing the temperature in the pressure oxidation leaching reaction kettle to 110 ℃, starting a violent reaction of the pressure oxidation reaction, closing the steam valve, maintaining the reaction temperature at 165 ℃ by means of self heat release of the reaction, continuously introducing oxygen to maintain the gas pressure in the reaction kettle, finishing the reaction for 3 hours, and performing filter pressing to obtain a second leaching solution and second leaching residues. Wherein the second leaching solution is 11m 3 The concentration of nickel in the second leaching solution is 109g/L, the second leaching residue contains 4.07 percent of nickel, 52.03 percent of iron and 0.76 ton of dry weight, and the comprehensive leaching rate of nickel is 99.1 percent.
D, impurity removal treatment: conveying the second leaching solution into an iron powder displacement copper removal reaction kettle; and (3) starting a stirring device of the iron powder displacement copper removal reaction kettle, quantitatively adding 550 kg of iron powder according to the copper content of the second leaching solution, carrying out iron powder displacement copper removal reaction, and reacting for 1 hour.
And conveying the sulfate solution which completes the iron powder displacement copper removal reaction in the iron powder displacement copper removal reaction kettle to an iron powder displacement copper removal filtering device, and filtering to obtain the sulfate solution, wherein the solution contains 0.03g/L of copper.
Example 5 (Low Nickel matte)
Step a, slurry reaction: grinding low grade nickel matte particles (containing 30% of nickel, 2% of copper, 36% of iron and 7% of sulfur) produced by pyrometallurgy into powder with D90 of 40 microns by using a vertical roller mill, and adding 8m of water into a slurrying kettle with a stirring device started 3 Adding the powder into a slurrying kettle in a positive pressure pneumatic conveying mode of 0.6Mpa, wherein the ratio of liquid to solid is 2:1 preparing slurry with solid content more than 30% for standby.
Step b, pre-dipping reaction: sulfate solution 8m produced by impurity removal treatment 3 (Nickel concentration 58.5 g/L) and 4m of water 3 And concentrated sulfuric acid in a pre-soaking reaction kettle to prepare the solution with the sulfuric acid concentration of 100g/LThe sulfuric acid reaction solution of nickel is reserved, a stirring device of the pre-immersion reaction kettle is started, and the prepared solution is heated to 75 ℃ for reservation.
Uniformly adding the prepared slurry liquid into a pre-dipping reaction kettle for pre-dipping reaction, wherein the pre-dipping reaction process is 7m 3 Introducing oxygen at the flow rate of/h, adding the slurry while introducing the oxygen, and controlling the flow ratio of the oxygen to the slurry at the oxygen flow rate: slurry flow = (7 Nm) 3 /h):(8m 3 And h), the presoaking reaction time is 1.3 times of the time for adding the slurry into the presoaking reaction device.
Step c, oxidation leaching reaction: conveying reaction liquid which finishes the presoaking reaction in the presoaking reaction kettle into a normal pressure leaching reaction device, starting a stirring reactor, wherein the stirring speed of the stirring reactor is 110r/min, starting an oxygen valve, starting a super-energy oxidizer of the oxidation leaching reaction kettle, enabling slurry liquid to flow out of the upper part of the stirring reactor and flow into the super-energy oxidizer, mixing the slurry liquid and oxygen in the super-energy oxidizer, injecting the mixture into the stirring reactor from the bottom of the stirring reactor, and reacting for 4 hours. Filter pressing to obtain a first leaching solution with a length of 18m 3 And 2.34t of first leaching residue; the pH value of the first leaching solution is 5.0, the nickel concentration is 60g/L, the iron concentration is 0.038g/L, the copper concentration is 0.005g/L, and the nickel leaching rate is 61%.
Adding the first leaching residue into the solution containing 2m of the first leaching residue 3 Slurrying in water slurrying kettle for 1 hr to obtain first leaching residue slurry, and transferring to a tank containing 12m 3 The sulfuric acid reaction solution with the sulfuric acid concentration of 50g/L is pressurized, oxidized and leached in the reaction device; increasing the gas pressure in the pressure oxidation leaching reaction kettle to 1.4Mpa by using high-pressure oxygen, starting a steam valve of the pressure oxidation leaching reaction kettle, increasing the temperature in the pressure oxidation leaching reaction kettle to 90 ℃, starting a violent reaction of the pressure oxidation reaction, closing the steam valve, maintaining the reaction temperature at 155 ℃ by relying on the self heat release of the reaction, continuously introducing oxygen to maintain the gas pressure in the reaction kettle, finishing the reaction for 3.5 hours, and performing filter pressing to obtain a second leaching solution and second leaching residues. Wherein the second leaching solution is 12m 3 The concentration of nickel in the second leaching solution is 57g/L, the second leaching slag contains 1.2% of nickel, 50.08% of iron and 2.88 tons of dry weight, and the nickel content is comprehensiveThe combined leaching rate is 97.9 percent.
D, impurity removal treatment: conveying the second leaching solution into an iron powder displacement copper removal reaction kettle; and starting a stirring device of the iron powder displacement copper removal reaction kettle, quantitatively adding 200 kg of iron powder according to the copper content of the second leaching solution, carrying out iron powder displacement copper removal reaction, and reacting for 1 hour.
And conveying the sulfate solution which completes the iron powder displacement copper removal reaction in the iron powder displacement copper removal reaction kettle to an iron powder displacement copper removal filtering device, and filtering to obtain the sulfate solution, wherein the solution contains 0.01g/L of copper.
The effect of the present application is demonstrated below in conjunction with related comparative examples, all of which are compared to example 4 in order to facilitate the unification of the comparison criteria.
Comparative example 1 (sulfuric acid addition sequence)
A comparative test was conducted using a high nickel matte material as an example, and this comparative example was different from example 4 in that: in the pretreatment step, the slurry is added firstly and then the sulfuric acid is slowly added (in example 4, the slurry is added after the acid is added), and the first leaching solution with the length of 14.5m is produced by atmospheric pressure oxidation leaching 3 The pH value is 1.5, the nickel concentration is 96.01g/L, the iron concentration is 3.36g/L, the copper concentration is 14.04g/L, and the comprehensive leaching rate of nickel is 39.8%.
Compared with the embodiment 4, the method can be obtained by firstly adding the slurry into water, then adding concentrated sulfuric acid, and changing the adding sequence of the sulfuric acid and the slurry, so that the overall sulfuric acid concentration of the reaction system is basically lower, the sulfuric acid concentration of the system is lower in the whole reaction process, the oxidation is low, the oxidation of sulfides in the nickel matte is not facilitated, and the leaching rate of nickel is greatly reduced from 64.13% to 39.8%.
Comparative example 2 (grinding particle size not meeting the requirements)
A comparative test was conducted using a high nickel matte material as an example, except that: grinding the materials into fine particles with D90 of 130 microns, pulping, and leaching under normal pressure to obtain a first leachate with a particle size of 13.5m 3 The pH value reaches 1.05, the nickel concentration is 89.6g/L, the iron concentration is 4.56g/L, the copper concentration is 12.89g/L, and the comprehensive nickel leaching rate is 34.5 percent.
By comparison with example 4, the finer the particle size, the larger the specific surface area, the larger the reaction contact area and the faster the reaction rate, while the finer the particle size, the more favorable the leaching of sulfide-coated metallic nickel, i.e. the smaller the particle size of the nickel matte particles, the more favorable the oxidative leaching of nickel.
COMPARATIVE EXAMPLE 3 (oxidizing agent)
To investigate the effect of different oxidants on the leaching rate of nickel, comparative example 3 was a reaction process of atmospheric pressure oxidative leaching using air as the oxidant.
The difference lies in that: the atmospheric pressure and pressurization process uses air instead of oxygen as oxidant to carry out reaction, and the first leaching solution 15m produced by atmospheric pressure leaching 3 The pH value is detected to reach 0.89, the nickel concentration is 96.7g/L, the iron concentration is 6.75g/L, the copper concentration is 8.44g/L, and the comprehensive leaching rate of nickel is 41.33%.
By comparison with example 4, the use of high purity oxygen as the oxidant is more efficient than air, due to: the air contains oxidants such as oxygen and the like, and also contains other reducing gases and protective inert nitrogen, so that the oxidation of sulfides is not facilitated, the air serving as the oxidant has large ventilation capacity and is not beneficial to gas dispersion and dissolution, and the pure oxygen serving as the oxidant has strong oxidizability, can reduce the gas introduction volume and is beneficial to the dispersion of oxygen and dissolution in a reaction system, so that the oxidation leaching rate of sulfides in the nickel matte is accelerated.
Comparative example 4 (oxygen dispersing mode)
In order to study the influence of different oxygen dispersion modes on the leaching rate of nickel, the oxygen is directly introduced into the atmospheric pressure oxidation leaching reaction kettle to carry out atmospheric pressure oxidation leaching in the comparative example 15.
The difference lies in that: in the atmospheric leaching process, the ultrasonic oxidizer is removed, oxygen is directly introduced into the atmospheric oxidation leaching reaction kettle to carry out atmospheric oxidation leaching reaction, and the first leaching solution 15m produced in the atmospheric leaching process 3 The pH value reaches 4.5, the nickel concentration is 104.3g/L, the iron concentration is 0.045g/L, the copper concentration is 0.15g/L and the comprehensive nickel leaching rate is 44.6 percent.
As compared with example 4, the leaching rate of oxidation by the ultrasonic oxidizer is about 20% higher than that by the conventional oxygen introduction, because: the ultrasonic oxidizer utilizes the high-frequency vibration of ultrasonic waves, is favorable for dispersing and dissolving bubbles of oxygen, can greatly increase the oxygen dissolution rate and the gas dissolution rate of a solution system, and is favorable for improving the reaction speed of the oxidation leaching reaction.
Comparative example 5 (sulfuric acid addition)
To investigate the effect of different sulfuric acid additions on the copper and iron purification reactions, the reaction process was carried out at different sulfuric acid additions.
The difference lies in that: in the pretreatment of comparative example 5, the amount of sulfuric acid added was adjusted to 2.8t, and 14.5m of the first leachate obtained in the atmospheric pressure leaching step was obtained 3 The pH value reaches 1.02, the nickel concentration is 130.4g/L, the iron concentration is 3.45g/L, the copper concentration is 9.12g/L, and the comprehensive nickel leaching rate is 65.1 percent.
As can be seen by comparison with example 4, when the amount of sulfuric acid added is greater than the theoretical amount, the reaction end point pH is too low and there is a large amount of leached iron and copper in the solution, resulting in an increase in post-leach liquor impurities due to: the sulfuric acid can only be consumed by the metallic nickel, the oxidation leaching of the sulfide of the nickel does not consume the sulfuric acid, and when the addition amount of the sulfuric acid is excessive, the excessive sulfuric acid can consume acid-consuming impurities such as copper, iron and the like, so that the impurities in the leaching solution are increased, and the aim of selective leaching cannot be fulfilled.
COMPARATIVE EXAMPLE 6 (addition of dilute sulfuric acid)
In order to study the influence of different sulfuric acid concentrations on the nickel leaching rate under the same total amount of sulfuric acid added.
The difference lies in that: the concentration of the nickel-containing sulfuric acid solution in comparative example 6 was 120g/L. 17.5m of first leaching solution produced in the atmospheric pressure leaching process 3 When the pH value reaches 4.5, the nickel concentration is 101g/L, the iron concentration is 0.03g/L, the copper concentration is 0.05g/L, and the nickel comprehensive leaching rate is 50.6%.
When compared with example 4, the concentration of the sulfuric acid solution is too low, which affects the leaching rate of nickel.
COMPARATIVE EXAMPLE 7 (Leaching time combination)
In order to study the effect of leaching time on leaching rate under the same conditions.
The difference is as follows: the preliminary immersion time in comparative example 7 was 0.5h. 17.5m of first leachate produced in the atmospheric pressure leaching process 3 When the pH value is detected to reach 5.0, the nickel concentration is 115g/L, the iron concentration is 0.02g/L, the copper concentration is 0.005g/L, and the comprehensive nickel leaching rate is 57.6 percent.
Compared with example 4, the method can affect the oxidation reaction rate of raw materials, reduce the nickel leaching rate and finally reduce the nickel comprehensive leaching rate.
The pH, nickel concentration, iron concentration, copper concentration and nickel leaching rate of the first leachate filtrate in example 4 and comparative examples 1 to 7 are shown in table 1, and fig. 2 is plotted according to table 1.
TABLE 1 statistical tables of parameters related to the first leach solution in example 4 and comparative examples 1 to 7
The traditional process is to perform presoaking in an atmospheric pressure leaching stage, and to perform presoaking by using a low-concentration dilute sulfuric acid solution, the leaching rate of nickel is low, only part of elemental metal nickel in high nickel matte can be leached, more than 70% of leaching reaction needs to be leached under a pressurized oxygen-enriched condition, multi-stage pressurized leaching needs to be utilized, a large amount of high-pressure oxygen-enriched reaction equipment needs to be configured in the production treatment process of the high nickel matte, the equipment investment is large, the required electric energy is huge, meanwhile, the configuration of a large amount of high-pressure oxygen-enriched equipment greatly increases the potential safety hazard in the production process, sodium carbonate needs to be used for neutralization, hydrolysis and purification after the high-pressure oxygen-enriched leaching, other auxiliary material consumption is introduced, on one hand, the production energy cost is increased, the low energy consumption requirement which does not meet the low carbon requirement at present, on the other hand, new auxiliary material introduction may introduce new impurities, and on the other hand, the leaching and purification process flow of the high nickel matte is lengthened.
Compared with the prior art, the leaching rate of the metal under the normal pressure condition is greatly improved in the technical process of processing the sulfide mineral, and the leaching rate of the sulfide mineral metal under the normal pressure condition can reach more than 52%; the method greatly reduces the configuration quantity of high-pressure reaction equipment in the technical process of processing and treating the sulfide minerals, and compared with a conventional technical method, the configuration quantity of the high-pressure reaction equipment in the method is reduced by more than 60%, so that the fixed investment is greatly reduced; the leaching and purifying process flow for treating the sulfide minerals is greatly compressed in the technical process of processing the sulfide minerals, so that the consumption of auxiliary materials is greatly reduced, and the processing cost of the sulfide minerals is reduced.
In conclusion, the process method can greatly improve the metal leaching rate of the sulfide minerals under the normal pressure condition, greatly reduce the configuration quantity of high-pressure reaction devices and greatly reduce the leaching and purifying cost of the sulfide minerals.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The leaching method of the sulfide minerals is characterized in that the sulfide minerals are ground into powder and prepared into slurry, the slurry is added into a sulfuric acid reaction solution prepared in advance for a pre-soaking reaction, and then an oxidation leaching reaction is carried out to obtain a sulfate solution;
wherein the concentration of the sulfuric acid in the sulfuric acid reaction solution is 30g/L-300g/L.
2. The method of leaching a sulphide mineral according to claim 1, comprising the steps of:
step a, slurry reaction: grinding the sulfide minerals into powder, and mixing the powder with a solution to prepare a slurry;
step b, presoaking reaction: adding the slurry solution into a pre-prepared sulfuric acid reaction solution, and introducing oxygen to carry out a pre-soaking reaction to obtain a reaction solution;
step c, oxidation leaching reaction: introducing oxygen into the reaction solution to carry out oxidation leaching treatment to obtain a leaching solution and leaching residues;
preferably, when the sulfide minerals are at least one of nickel sulfide ore, nickel matte, and nickel matte, after the oxidation leaching reaction in step c is completed, the method further comprises a step d of impurity removal treatment: and removing impurities from the leachate to obtain a sulfate solution.
3. The method for leaching sulphide minerals according to claim 2, wherein step a is in particular: adding a solution into a slurrying device provided with a stirring device, grinding the sulfide minerals into powder, and injecting the powder into the slurrying device in a positive pressure pneumatic transmission mode of 0.4-0.8Mpa to prepare the slurrying liquid;
wherein the sulfide minerals are at least one of nickel sulfide ore, copper cobalt sulfide ore, cobalt copper alloy, high nickel matte and low nickel matte;
the device for grinding the sulfide minerals into powder is a vertical roller mill;
the grain diameter D90 of the powder is less than or equal to 40 mu m;
the solution is water and/or the sulfate solution obtained after impurity removal treatment in the step d;
the mass ratio of liquid to solid in the slurry is 1.5-2:1;
the solution in the step a is at least one of water, leachate obtained by the oxidation leaching reaction in the step c and sulfate solution obtained after impurity removal treatment in the step d.
4. The method for leaching sulfide minerals according to claim 2 or 3, wherein in the step b, the concentration of sulfuric acid in the sulfuric acid reaction solution is 150g/L-300g/L;
the presoaking reaction temperature is 65-80 ℃;
the purity of the oxygen is more than 90 percent, and the inlet flow rate of the oxygen is 10-60Nm 3 /h；
The flow ratio of the oxygen to the slurry liquid is oxygen flow: slurry flow = (7-10 Nm) 3 /h):(8-10m 3 /h)。
5. The method for leaching sulfide minerals according to claim 4, wherein in the step b, after the slurry solution is added, the presoaking reaction time is 1.2-1.8 times of the time for adding the slurry solution into the presoaking reaction device completely.
6. The process of leaching a sulphide mineral according to any one of claims 2, 3 or 5, wherein step c comprises an atmospheric leaching process and a pressure leaching process;
the leachate is divided into a first leachate and a second leachate; the leaching residues are divided into a first leaching residue and a second leaching residue.
7. The method for leaching sulfide minerals according to claim 6, wherein the atmospheric leaching process is specifically as follows: carrying out normal-pressure oxidation leaching reaction on the reaction solution, introducing oxygen in the reaction process, wherein the reaction time of the normal-pressure oxidation leaching reaction is 2-13h, and separating after the reaction is finished to obtain a first leaching solution and first leaching residues;
wherein the purity of the oxygen is greater than 90%; the flow ratio of the oxygen to the first leaching residue slurry liquid is oxygen flow: flow rate of slurrying solution of first leaching residue = (7-10 Nm) 3 /h):(8-10m 3 H); the temperature of the slurry liquid is 60-90 ℃.
8. The sulfide mineral leaching method of claim 7, wherein the atmospheric leaching reaction device is provided with a stirred reactor of a super oxidizer;
wherein, in the atmospheric pressure leaching process, the stirring speed of the stirring reactor is 50-120r/min, the slurry liquid flows out from the upper part of the stirring reactor and flows into the super oxidizer, and the slurry liquid and oxygen are mixed in the super oxidizer and then are injected into the stirring reactor from the bottom of the stirring reactor.
9. The method for leaching sulphide minerals according to claim 7 or 8, wherein the pressure leaching process is in particular: adding water into the first leaching residue obtained by the normal pressure leaching reaction, pulping to obtain a first leaching residue pulp liquid, conveying to a pressure leaching reaction device filled with the sulfuric acid reaction solution, and performing solid-liquid separation after the pressure leaching reaction is finished to obtain a second leaching solution and second filter residue;
wherein the time for pulping the first leaching residue by adding water is 0.5-2h; the concentration of sulfuric acid in a sulfuric acid reaction solution in the pressure leaching reaction is 30-150 g/L; the internal pressure of the pressure leaching reaction device is 1-2Mpa, the initial reaction temperature is 80-110 ℃, the reaction temperature is 140-180 ℃, and the pressure leaching time is 2-5h.
10. The method for leaching sulphide minerals according to claim 9, wherein step d is in particular: conveying the second leaching solution into an impurity removal reaction device, adding iron powder, and performing solid-liquid separation on slurry liquid which is subjected to iron powder displacement copper removal reaction to obtain a sulfate solution;
wherein the pH value in the impurity removal reaction device is 1-2, and the temperature is 60-80 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211739397.7A CN115948662A (en) | 2022-12-31 | 2022-12-31 | Method for leaching sulfide minerals |
| PCT/CN2023/142522 WO2024140857A1 (en) | 2022-12-31 | 2023-12-27 | Leaching method for sulfide minerals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211739397.7A CN115948662A (en) | 2022-12-31 | 2022-12-31 | Method for leaching sulfide minerals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115948662A true CN115948662A (en) | 2023-04-11 |
Family
ID=87285774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211739397.7A Pending CN115948662A (en) | 2022-12-31 | 2022-12-31 | Method for leaching sulfide minerals |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115948662A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024140857A1 (en) * | 2022-12-31 | 2024-07-04 | 贵州中伟资源循环产业发展有限公司 | Leaching method for sulfide minerals |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2252270C1 (en) * | 2003-11-11 | 2005-05-20 | ОАО "Горно-металлургическая компания "Норильский никель" | Method for reprocessing of fused copper-nickel sulfide ores containing cobalt, iron and platinum group metals |
| CN109971953A (en) * | 2019-03-18 | 2019-07-05 | 中国科学院过程工程研究所 | A method of enhanced oxidation extracts valuable metal from the sulfide mineral containing non-ferrous metal |
| CN113526576A (en) * | 2021-05-31 | 2021-10-22 | 金川集团股份有限公司 | Preparation method of high-nickel low-acid low-sodium nickel sulfate solution |
| CN113584314A (en) * | 2021-07-29 | 2021-11-02 | 湖南中伟新能源科技有限公司 | High nickel matte normal pressure leaching method and nickel sulfate |
| CN114921647A (en) * | 2022-06-01 | 2022-08-19 | 长沙有色冶金设计研究院有限公司 | Oxygen pressure leaching method of nickel matte under sulfuric acid |
-
2022
- 2022-12-31 CN CN202211739397.7A patent/CN115948662A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2252270C1 (en) * | 2003-11-11 | 2005-05-20 | ОАО "Горно-металлургическая компания "Норильский никель" | Method for reprocessing of fused copper-nickel sulfide ores containing cobalt, iron and platinum group metals |
| CN109971953A (en) * | 2019-03-18 | 2019-07-05 | 中国科学院过程工程研究所 | A method of enhanced oxidation extracts valuable metal from the sulfide mineral containing non-ferrous metal |
| CN113526576A (en) * | 2021-05-31 | 2021-10-22 | 金川集团股份有限公司 | Preparation method of high-nickel low-acid low-sodium nickel sulfate solution |
| CN113584314A (en) * | 2021-07-29 | 2021-11-02 | 湖南中伟新能源科技有限公司 | High nickel matte normal pressure leaching method and nickel sulfate |
| CN114921647A (en) * | 2022-06-01 | 2022-08-19 | 长沙有色冶金设计研究院有限公司 | Oxygen pressure leaching method of nickel matte under sulfuric acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024140857A1 (en) * | 2022-12-31 | 2024-07-04 | 贵州中伟资源循环产业发展有限公司 | Leaching method for sulfide minerals |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020253733A1 (en) | Method for selective oxygen pressure leaching of precious metal enrichment using nickeliferous material with high iron and copper contents | |
| CN1333089C (en) | Method for processing cobalt copper alloy | |
| CN113215398B (en) | Oxygen pressure leaching method of nickel sulfide concentrate | |
| CN113957243B (en) | Method for realizing open circuit of nickel, copper and iron in high-nickel matte and enriching noble metals | |
| CN113416843A (en) | Superfine grinding-oxygen pressure leaching process for nickel sulfide concentrate | |
| CN113526576B (en) | Preparation method of high-nickel low-acid low-sodium nickel sulfate solution | |
| WO2023273264A1 (en) | Method for preparing high-nickel type ternary precursor by means of ferronickel production conversion and application thereof | |
| WO2018155114A1 (en) | Method for producing sulfide, and method for hydrometallurgically refining nickel oxide ore | |
| CN115948662A (en) | Method for leaching sulfide minerals | |
| CN111057847A (en) | Green method for preparing battery-grade nickel sulfate from nickel salt | |
| CN112342377A (en) | Treatment process of nickel concentrate | |
| WO2020073411A1 (en) | Method for extracting nickel, cobalt, and iron from low-grade laterite nickel ore | |
| CN111225988B (en) | Oxygen pressure leaching method of copper sulfide concentrate and copper smelting method | |
| CN117926027A (en) | Comprehensive utilization method of laterite nickel ore | |
| CN112456461B (en) | Method for preparing battery-grade flaky iron phosphate by using cobalt-iron leaching solution | |
| WO2016139858A1 (en) | Method for producing nickel sulfide and hydrometallurgical method for nickel oxide ore | |
| CN116004983A (en) | Leaching method of sulfide minerals | |
| CN116144947A (en) | Leaching method of sulfide minerals | |
| CN116287683A (en) | Leaching method of sulfide minerals | |
| CN104775027A (en) | Method for recovering nickel, iron, silicon and magnesium from low grade laterite-nickel ore | |
| CN116254410A (en) | Leaching method of sulfide minerals | |
| CN116287703A (en) | Leaching method of sulfide minerals | |
| CN114214521B (en) | Method for recycling iron and copper in copper slag | |
| CN112646976B (en) | Method for synergistically leaching nickel, cobalt and manganese by utilizing waste lithium ion battery black powder and nickel cobalt sulfide ore and application | |
| CN112760480B (en) | Method for improving oxygen pressure leaching efficiency of copper sulfide cobalt concentrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |