CN114438322B - Method for removing manganese from oxygen pressure leaching solution of high-manganese zinc concentrate - Google Patents
Method for removing manganese from oxygen pressure leaching solution of high-manganese zinc concentrate Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 79
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 71
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002386 leaching Methods 0.000 title claims abstract description 54
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 44
- 239000001301 oxygen Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000012141 concentrate Substances 0.000 title claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 58
- 239000002893 slag Substances 0.000 claims abstract description 53
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 49
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003723 Smelting Methods 0.000 claims abstract description 13
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 13
- 238000007654 immersion Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019738 Limestone Nutrition 0.000 claims abstract description 8
- 239000006028 limestone Substances 0.000 claims abstract description 8
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 8
- 239000003245 coal Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims abstract description 5
- 238000011084 recovery Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004575 stone Substances 0.000 claims abstract description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000005363 electrowinning Methods 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 229910000616 Ferromanganese Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for removing manganese from oxygen pressure leaching liquid of high manganese zinc concentrate, which comprises the following steps: s1, carrying out oxygen pressure leaching on high-manganese zinc concentrate after grinding to produce oxygen leaching liquid and oxygen leaching slag; wherein the concentration of manganese ions in the oxygen immersion liquid is more than 5g/L; s2, adding a neutralizing iron removing agent into the oxygen immersion liquid to obtain iron-removed liquid and iron-removed slag; s3, adding PbO into the deironing liquid 2 Demanganizing to obtain high-lead manganese slag and demanganizing liquid; s4, recycling crude lead and high manganese slag: and (3) drying the high-lead manganese slag, mixing the high-lead manganese slag with pulverized coal, quartz stone, limestone and ferric oxide, and carrying out reduction smelting at 1250-1350 ℃ after mixing to obtain crude lead and manganese-rich slag. The method can efficiently remove manganese ions in the zinc leaching solution, does not introduce impurity elements in the manganese removal process, ensures normal production of zinc electrowinning procedures, can be used as a fire lead smelting raw material or a lead system ingredient to obtain crude lead and manganese-rich slag, and realizes efficient recovery of manganese and lead in the process.
Description
Technical Field
The invention relates to recycling of manganese ions, in particular to a method for removing manganese from oxygen pressure leaching liquid of high manganese zinc concentrate.
Background
The high manganese zinc concentrate is mainly distributed in regions such as cloud precious plateau, south Africa and the like in China. When oxygen pressure technology is adopted to treat high manganese zinc concentrate, domestic zinc concentrate leaching material contains about 0.1% of manganese, but the manganese content in the high manganese zinc concentrate is high (about 3%), after pressure leaching, zinc and manganese in the raw materials are basically leached into solution, so that the manganese concentration in the leaching solution can reach more than 10g/L, and the high manganese concentration is difficult to meet the general requirement of controlling Mn in the subsequent zinc electrodeposition 2+ The concentration is 5 g/L. Therefore, when high manganese zinc concentrate is treated by oxygen pressure leaching, a demanganization process is required for the obtained leachate.
The demanganization method in the solution adopts potassium permanganate or persulfate to demanganize, and has better demanganizing effect. For example, patent publication No. CN112978897A discloses a method for removing iron and manganese from a solution in a zinc smelting process. The method comprises the following steps: adding a catalyst into the solution in the zinc smelting process, and introducing an oxidant into the solution to make iron ions and manganese ions in the solution in the zinc smelting process undergo catalytic oxidation reaction to form slurry containing iron-manganese slag; carrying out solid-liquid separation on the slurry containing the ferro-manganese slag to obtain ferro-manganese slag and ferro-manganese post-iron liquid; wherein the catalyst is selected from one or more of sulfur dioxide-containing gas and sulfite-containing salt. However, the method similar to the method or the actual manganese removal effect is not ideal, or a large amount of Na or K ions can be introduced, when a zinc-rich zinc sulfate solution contains a large amount of Na or K ions, the concentration of the zinc solution cannot be reduced after the zinc solution and a smelting system are circulated, and after the zinc solution is further enriched, zinc in the zinc solution can be crystallized, so that a conveying pipeline is blocked, and the production is influenced. And the demanganization cost of potassium permanganate and persulfate is higher, about 5000 yuan/tZn. When the extraction method is used for demanganizing, zn is extracted preferentially during the extraction, and the concentration of Zn ions in the leaching solution is larger than that of manganese ions, so that the extraction method is not suitable for demanganizing.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the method for removing manganese from the oxygen pressure leaching solution of the high manganese zinc concentrate, which can efficiently remove manganese ions in the zinc leaching solution, and the manganese removal process does not introduce impurity elements, so that the normal production of a zinc electrodeposition process is ensured.
In order to solve the technical problems, the invention adopts the following technical scheme: the invention discloses a method for removing manganese from oxygen pressure leaching liquid of high manganese zinc concentrate, which comprises the following steps:
s1, carrying out oxygen pressure leaching on high-manganese zinc concentrate after grinding to produce oxygen leaching liquid and oxygen leaching slag; wherein the concentration of manganese ions in the oxygen immersion liquid is more than 8g/L;
s2, adding a neutralizing iron removing agent into the oxygen immersion liquid to obtain iron-removed liquid and iron-removed slag;
s3, adding PbO into the deironing liquid 2 Removing manganese to obtain high-lead manganese slag and manganese-removed liquid.
Oxygen immersion liquid composition: (Zn-150 g/L, mn-15 g/L, residual acid about 50 g/L). Side reactions occur without neutralization and iron removal, and demanganizing agents are consumed:
2PbO 2 +2H 2 SO 4 ＝2H 2 O+O 2 +2PbSO 4 ↓
by PbO 2 The manganese ions in the zinc leaching solution can be removed efficiently, and impurity elements (Na or K ions) are not introduced in the manganese removal process, so that after further enrichment, the zinc in the zinc solution is prevented from crystallizing, the blockage of a conveying pipeline is avoided, and the normal production is ensured.
In the invention, iron is firstly removed, and PbO is adopted 2 The demanganization, na or K ions are not introduced, and the normal production of the zinc electrowinning process is guaranteed under the combined action, so that the demanganization and the K ions are indispensable. The obtained demanganization product can be used as a raw material for pyrometallurgy of lead or a burden of a lead system, and crude lead and manganese-rich slag can be prepared, thereby realizing the efficient recovery of manganese and lead in the process.
The chemical reaction principle of the invention is as follows:
PbO 2 +MnSO 4 ＝2MnO 2 ↓+PbSO 4 ↓ (1)
further, the concentration of manganese ions in the oxygen immersion liquid is 10-18 g/L.
Further, high manganese zinc concentrate and PbO 2 The mass ratio of PbO is 300:20-50 2 Adding in batches, adding 60% -80% before the reaction starts, and adding 20% -40% 2-5 min before the reaction end point. If PbO is added at one time 2 The reaction is intense just at the beginning, the later reaction is slower, and the overall reaction effect is affected. The application adopts a feeding system of adding PbO2 in batches, so that the manganese removal efficiency of PbO2 can be further improved, and the utilization rate of PbO2 is improved.
Further, pbO 2 Has a particle size of-200 mesh>95%, ensuring high reactivity.
Further, the temperature of the demanganization step in S3 is 15-50 ℃ and the time is 5-20 min.
Further, the neutralizing iron removing agent in S2 is zinc calcine or limestone, and the pH value is 4-5.
The iron removal process utilizes Fe ions to precipitate at pH 4-5. The zinc calcine is a product of boiling roasting zinc sulfide (about 50% of zinc), and the phase is mainly zinc oxide, and about 60% of zinc. The neutralization iron remover is used for neutralizing sulfuric acid with the concentration of less than 10g/L in the oxygen pressure leaching solution to pH 4-5, the neutralization iron remover cannot carry impurities and is cheap, and zinc calcine or limestone can be well met. The main purpose of this process is the purification requirements for the subsequent electrodeposition of zinc solutions. The solution after demanganization is sent to purification, electro-deposition and casting, and the pH value of the solution is basically kept unchanged (same as the pH value of the solution after deironing) during demanganization and purification, so that the pH value of the solution after deironing is controlled to be 4-5.
Further, the reaction temperature is controlled to be 70-80 ℃ in S2, and the time is controlled to be 2-3 hours.
Further, the method for removing manganese from the oxygen pressure leaching solution of the high manganese zinc concentrate also comprises the following steps:
s4, recycling crude lead and high manganese slag: and (3) drying the high-lead manganese slag, mixing the high-lead manganese slag with pulverized coal, quartz stone, limestone and ferric oxide, and carrying out reduction smelting at 1250-1350 ℃ after mixing to obtain crude lead and manganese-rich slag.
The chemical reaction principle of the recovery of the crude lead and the high manganese slag is as follows:
manganese-rich slag: mnO (MnO) 2 +C＝MnO+CO (2)
Lead bullion: pbSO 4 +C＝Pb+SO 2 +CO 2 (3)
Further, caO/SiO in S4 2 The weight ratio of FeO/SiO is 0.4-0.6 2 The weight ratio is 1.4-1.8, the addition amount of coal powder is 8-15% of the weight of the dry-based high-lead manganese slag, and the reaction time is 2-4 h.
Control of CaO/SiO 2 、FeO/SiO 2 And obtaining high-grade crude lead and manganese-rich slag products by the ratio and the proper reaction temperature. Wherein CaO, siO 2 FeO is the active ingredient in the raw materials.
Further, the technological parameters of oxygen pressure leaching in S1 are that the liquid-solid ratio is 4-7:1, the acid zinc mole ratio is 0.8-1.0, the reaction temperature is 145-155 ℃, the pressure is 1.0-1.2 Mpa, and the time is 90-180 min.
(1) The liquid-solid ratio is used for controlling the zinc concentration in the leaching solution, if the efficiency of the autoclave is low due to too thin, and the stirring resistance of the autoclave is high due to too thick, even stirring is not performed when the stirring resistance is severe; the zinc acid mole ratio (i.e. the number of moles of sulfuric acid at the beginning of the reaction: moles of zinc in the concentrate) is to control the proper final acid, if the zinc acid mole ratio is too large, the final acid will be too high, the amount of acid to be neutralized will be large, whereas if the zinc acid mole ratio is too small, the zinc leaching rate will be low. (2) The temperature is also used for ensuring the zinc leaching rate, if the temperature is too low, the leaching rate will be low, and if the temperature is too high, the S oxidation will be serious, and the final acid will be high. (3) The saturated vapor pressure of water is 0.48Mpa at 150 ℃, and the oxygen partial pressure is 0.5-0.7 Mpa when the total pressure is 1.0-1.2, so that the leaching rate of zinc can be ensured. (4) The proper leaching time is also used for ensuring the leaching rate and production efficiency of zinc.
Further, ore pulp is obtained after grinding the high-manganese zinc concentrate in the step S1, and the granularity of the ore pulp is smaller than 40 mu m.
The particle size is to ensure the leaching rate of zinc in the raw material, and the raw material of hydrometallurgy is usually controlled to a certain particle size. Ball milling media (such as steel balls, zirconium beads and the like) can be well contacted with ore, so that the ore milling efficiency is ensured, and the granularity after ball milling is smaller than 40 mu m.
S4, drying the high-lead manganese slag until the water content is 5-8%. Excessive water content and increased energy consumption affect the normal operation of the flue gas treatment system.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a method for removing manganese from oxygen pressure leaching liquid of high manganese zinc concentrate and recycling lead and manganese from demanganized products, which can efficiently remove manganese ions in zinc leaching liquid, and the demanganization process does not introduce impurity elements, so that normal production of zinc electrowinning procedures is ensured, the demanganized products can be used as raw materials for pyrometallurgy lead or ingredients of a lead system, crude lead and manganese-rich slag are obtained, and efficient recycling of manganese and lead in the process is realized.
(2) After the demanganizing slag is subjected to the pyrogenic process slagging reduction smelting, crude lead and demanganizing slag are obtained, and the demanganizing slag can be used for ferromanganese production, so that the efficient recovery of valuable metals is realized.
(3) The oxygen pressure leaching is adopted to treat the high manganese zinc concentrate independently, the zinc leaching rate is high and reaches more than 95%, sulfuric acid is not produced, and the method is suitable for areas with less sulfuric acid application and difficult sales.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Detailed Description
Example 1
300g of high manganese zinc concentrate (Zn 46%, mn 2.9%) is added with water for ore grinding, the mass concentration of ore pulp is controlled to be 65%, the granularity of ore pulp after ore grinding is smaller than 40 mu m, the ground ore pulp is added into an autoclave for oxygen pressure leaching, sulfuric acid system waste electrolyte (mainly sulfuric acid and zinc sulfate) is added, the liquid-solid ratio is controlled to be 5:1, the mole ratio of acid zinc is 0.8, the reaction temperature is 145 ℃, the pressure is 1.0Mpa, the time is 120min, and oxygen leaching liquid (wherein the concentration of manganese ions in the oxygen leaching liquid is 9.6 g/L) and oxygen leaching slag (Zn 1.07%, mn 0.46%) are produced, the leaching rate of zinc is 98.20%, and the leaching rate of manganese is 88.23%. Neutralizing oxygen immersion liquid to remove iron, adding lime milk, controlling the reaction temperature to 70 ℃ for 2 hours and the end point pH to 4, and obtaining 1.5L (Zn 118g/L and Mn 9.6 g/L) of neutralized liquid.
In 1.5L of the neutralized solution, 24g of PbO was added 2 (PbO 2 The particle size of-200 mesh was 96%), for 7min, followed by the addition of 6g PbO 2 (PbO 2 The granularity of the lead-manganese slag is 96 percent of minus 200 meshes), the lead-manganese slag is reacted for 3min at room temperature for 10min, 52g (containing 13.7 percent of Mn and 51.97 percent of Pb) of lead-manganese slag is formed after filtering, and manganese-containing post-solution (118 g/L of Zn and 5.2g/L of Mn) is sent to subsequent purification, electrodeposition and casting to produce the electro-zinc.
Washing and drying the lead-manganese slag until the water content is 100g, mixing the lead-manganese slag with 10g of coal dust, 6g of quartz stone, 5g of limestone and 10g of iron scale, and controlling CaO/SiO 2 0.4，FeO/SiO 2 1.4, the addition amount of coal powder is 10%. And (3) carrying out reduction smelting at 1300 ℃ after mixing, and cooling along with a furnace after reacting for 2 hours to obtain crude lead and manganese-rich slag. The crude Pb contains 95.2% of Pb, and the lead-rich slag contains 37.02% of Mn and 18.92% of Fe.
Example 2
300g of high manganese zinc concentrate (Zn 46%, mn 2.9%) is added with water for ore grinding, the mass concentration of ore pulp is controlled to be 65%, the granularity of ore pulp after ore grinding is smaller than 40 mu m, the ground ore pulp is added into an autoclave for oxygen pressure leaching, sulfuric acid system waste electrolyte (mainly sulfuric acid and zinc sulfate) is added, the liquid-solid ratio is controlled to be 4:1, the mole ratio of acid zinc is 0.9, the reaction temperature is 150 ℃, the pressure is 1.2Mpa, the time is 180min, and oxygen leaching liquid (wherein the concentration of manganese ions in the oxygen leaching liquid is 12.52 g/L) and oxygen leaching slag (Zn 0.52%, mn 0.31%) are produced, the leaching rate of zinc is 99.32%, and the leaching rate of manganese is 95.21%. Neutralizing oxygen immersion liquid for deironing, adding lime milk, controlling the reaction temperature to be 80 ℃, controlling the reaction time to be 3 hours, controlling the end point pH to be 4.5, and obtaining 1.2L (149.2 g/L Zn and 12.52g/L Mn) of neutralized liquid.
In 1.2L of the neutralized solution, 24g of PbO was added 2 (PbO 2 98% of a-200 mesh) for 10min, followed by the addition of 16g of PbO 2 (PbO 2 The granularity of the lead-manganese slag is 98 percent of minus 200 meshes), the lead-manganese slag is reacted for 5min, the lead-manganese slag is filtered for 15min at the temperature of 50 ℃, 69g (containing 13.56 percent of Mn and 52.02 percent of Pb) is formed, and manganese-containing post-solution (149 g/L of Zn and 5.05g/L of Mn) is sent to subsequent purification, electrodeposition and casting to produce the electro-zinc.
Washing and drying the lead-manganese slag until the water content is 100g, mixing the lead-manganese slag with 15g of coal dust, 6g of quartz stone, 6g of limestone and 12g of iron scale, and controlling CaO/SiO 2 0.5，FeO/SiO 2 1.5, the addition amount of coal powder is 15%. And (3) carrying out reduction smelting at 1350 ℃ after mixing, and cooling along with a furnace after reacting for 2 hours to obtain crude lead and manganese-rich slag. The crude Pb contains 96.5% of Pb, and the lead-rich slag contains 36.56% of Mn and 16.74% of Fe.
The method does not introduce impurity ions, namely does not influence the normal production of a zinc smelting system, and makes Mn reasonably open a circuit. In addition, the manganese-rich high-lead slag can be used as a smelting raw material of crude lead, lead and manganese can be respectively recovered, and the purpose of comprehensively recovering valuable metals is realized.
Claims (2)
1. The method for removing manganese from the oxygen pressure leaching solution of the high-manganese zinc concentrate is characterized by comprising the following steps of:
s1, carrying out oxygen pressure leaching on high-manganese zinc concentrate after grinding to produce oxygen leaching liquid and oxygen leaching slag; wherein the concentration of manganese ions in the oxygen immersion liquid is more than 8g/L;
s2, adding a neutralizing iron removing agent into the oxygen immersion liquid to obtain iron-removed liquid and iron-removed slag;
s3, adding PbO into the deironing liquid 2 The manganese is removed from the steel by the method,obtaining high lead manganese slag and demanganized liquid;
high manganese zinc concentrate and PbO 2 The mass ratio of PbO is 300:20-50 2 Adding the materials in batches, adding 60% -80% before the reaction starts, and adding 20% -40% 2% -5 min before the reaction end;
PbO 2 has a particle size of-200 mesh>95%；
S3, the temperature of the demanganization step is 15-50 ℃ and the time is 5-20 min;
the neutralizing iron removing agent in the S2 is zinc calcine or limestone, and the pH value is 4-5;
s2, controlling the reaction temperature to be 70-80 ℃ and the reaction time to be 2-3 hours;
the method for removing manganese from the oxygen pressure leaching liquid of the high-manganese zinc concentrate also comprises the following steps of S4, crude lead and high-manganese slag recovery: drying the high-lead manganese slag, mixing the high-lead manganese slag with pulverized coal, quartz stone, limestone and ferric oxide, and carrying out reduction smelting at 1250-1350 ℃ after mixing to obtain crude lead and manganese-rich slag;
CaO/SiO in S4 2 The weight ratio of FeO/SiO is 0.4-0.6 2 The weight ratio is 1.4-1.8, the addition amount of coal powder is 8-15% of the weight of the dry-basis high-lead manganese slag, and the reaction time is 2-4 hours;
the technological parameters of oxygen pressure leaching in the S1 are that the liquid-solid ratio is 4-7:1, the acid zinc mole ratio is 0.8-1.0, the reaction temperature is 145-155 ℃, the pressure is 1.0-1.2 mpa, and the time is 90-180 min.
2. The method for removing manganese from oxygen-pressed leaching solution of high-manganese zinc concentrate according to claim 1, wherein the method comprises the following steps of: grinding the high-manganese zinc concentrate in the S1 to obtain ore pulp, wherein the granularity of the ore pulp is smaller than 40 mu m.
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| US4067789A (en) * | 1975-07-09 | 1978-01-10 | Newmont Exploration Limited | Process for manganese removal from zinc metal bearing solutions |
| CN1360064A (en) * | 2001-12-10 | 2002-07-24 | 北京矿冶研究总院 | Method for extracting zinc from zinc-containing sulfide minerals |
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| CN110482592A (en) * | 2019-08-19 | 2019-11-22 | 西北矿冶研究院 | A kind of technique with steel-making cigarette ash preparing nano zinc oxide |
| CN112978897A (en) * | 2021-05-06 | 2021-06-18 | 中国恩菲工程技术有限公司 | Method for removing iron and manganese from zinc smelting process solution |
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| US4067789A (en) * | 1975-07-09 | 1978-01-10 | Newmont Exploration Limited | Process for manganese removal from zinc metal bearing solutions |
| CN1360064A (en) * | 2001-12-10 | 2002-07-24 | 北京矿冶研究总院 | Method for extracting zinc from zinc-containing sulfide minerals |
| CN102134654A (en) * | 2010-01-21 | 2011-07-27 | 云南冶金集团股份有限公司 | Treatment method of zinc sulfide ore concentrates |
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