CN108118156A - A kind of electrolytic manganese anode mud separation production electrolytic manganese metal and the method for recycling lead - Google Patents
A kind of electrolytic manganese anode mud separation production electrolytic manganese metal and the method for recycling lead Download PDFInfo
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- CN108118156A CN108118156A CN201810023327.9A CN201810023327A CN108118156A CN 108118156 A CN108118156 A CN 108118156A CN 201810023327 A CN201810023327 A CN 201810023327A CN 108118156 A CN108118156 A CN 108118156A
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- electrolytic manganese
- leachate
- anode mud
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 68
- 239000011572 manganese Substances 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- 238000000926 separation method Methods 0.000 title claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 14
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 14
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 14
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000000746 purification Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 8
- 239000012141 concentrate Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims abstract description 5
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 7
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- -1 manganese metals 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
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910000859 α-Fe 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or 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)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a kind of electrolytic manganese anode muds to separate production electrolytic manganese metal and the method for recycling lead, comprises the following steps：S1. electrolytic manganese anode mud and sulfuric acid solution, blackstrap aqueous solution are mixed, and then add iron powder, separation leachate and leached mud after the completion of reaction；S2. leachate adds in H2O2, the leachate of COD must be removed；S3. the leachate for removing COD is added in into ammonium sulfide or Sodium Dimethyldithiocarbamate, and adds in ammonium hydroxide, obtain purification of manganese sulfate liquid, the electrolysis of purification of manganese sulfate liquid obtains metal manganese product.The present invention can also recycle the lead concentrate of lead tolerance more than 50% while Electrolytic Manganese Product is produced, and be utilized so as to fulfill the clean and effective of electrolytic manganese anode mud.
Description
Technical field
The present invention relates to electrolytic manganese anode mud processing technology field more particularly to a kind of electrolytic manganese anode mud separation production electricity
Solution manganese metal and the method for recycling lead.
Background technology
Manganese has highly important strategic position as a kind of important metallurgy, chemical raw material in national economy.I
State's iron and steel output accounts for 3/4ths of Gross World Product, " no manganese not Cheng Gang ", in smelting iron and steel, manganese and oxygen, sulphur it is affine
Power is all bigger, is the desulfurizing agent and deoxidier of molten steel.Electrolytic manganese metal is production stainless steel, height since purity is high, impurity is few
The important alloying element and welding rod of strength low alloy steel, alumal, cupromanganese etc., ferrite, permanent-magnet alloy member
Indispensable raw material during element and many medication chemistries are produced with manganese salt.With technological progress and the rise of new industry, electrolysis
Manganese metal is increasingly extensive in the application of metallurgy, electronics, functional material and fine manganese salt arts.
Electrolytic manganese anode mud refers to during using manganese sulfate solution in a cell electrolysis production manganese metal, in anode
Room is inevitably formed with manganese dioxide（MnO2）Or the substance based on the hydrous oxide precipitation of manganese, black easily lump,
Wherein manganese content is up to 40% ~ 50%, simultaneously containing sardinianite, cesarolite（PbMn3O7·nH2O）, tin, the multiple elements such as selenium and
Compound, it is complicated.
1 t electrolytic manganese metals are often produced, 50 ~ 100 kg electrolytic manganese anode muds are just generated, by China's electrolytic manganese metal
Yield is converted into the quantum of output of electrolytic manganese anode mud up to 100,000 tons/year or more.Mineral composition and knot due to electrolytic manganese anode mud
Structure is complicated, and the hydrous oxide symbiosis of lead and manganese therein is very close, most of manganese oxide jelly with gluey annulus
Construction, therefore manganese and recycling lead cannot be purified using simple mechanical sorting method.At present, electrolytic manganese anode mud is removed and is used on a small quantity
Than iron, the overwhelming majority is as industrial solid wastes by stockpiling disposal or cheap selling to smelting for the leaching manganese ore liquid of electrolytic manganese factory
Dispensing of the refinery as refining manganeisen raw material, however the substances such as lead, selenium in Manganese anode slime are volatile at high temperature, it is per ton
Manganese anode slime will volatilize nearly 50 kg of lead metal, not only waste lead resource, it is often more important that cause serious environmental pollution, damage
The life and health of the victimization people.
In recent years, researcher finds different processing methods for the characteristic of electrolytic manganese anode mud, mainly studies
By the use of Manganese anode slime as production manganese sulfate, manganese carbonate, the pure manganese dioxide of chemistry or battery, aoxidize manganese systems product and LiMn2O4 etc.
The raw material of new material, but there are still production cost is higher, the valuable element rate of recovery is low or energy consumption is big, process route is long, very
Secondary pollution problems can extremely be formed.On the premise of national environmental protection energy saving policy is increasingly stringent, it can not generally be adopted by factory.
Therefore, in view of manganese utilizes present situation, a kind of economic, environmental protection of searching in the critical role in China and the processing of electrolytic manganese anode mud at present
Mode handle and had important practical significance using electrolytic manganese anode mud and urgent.
The content of the invention
The invention discloses a kind of electrolytic manganese anode muds to separate production electrolytic manganese metal and the method for recycling lead, in production electricity
The lead concentrate of lead tolerance more than 50% can also be recycled while solving metal manganese product, it is high so as to fulfill the cleaning of electrolytic manganese anode mud
Effect utilizes.
To achieve the above object, the technical scheme is that：
A kind of electrolytic manganese anode mud separation production electrolytic manganese metal and the method for recycling lead, comprise the following steps：
S1. electrolytic manganese anode mud and 2.5 ~ 3.5molL-1Sulfuric acid solution mixes, and adds in 65 ~ 70 gL-1Blackstrap is water-soluble
Liquid stirs, and the dosage of blackstrap is the 85 ~ 90% of reducing agent theoretical amount, 150 ~ 250 rmin of stir speed (S.S.)-1, above-mentioned electrolysis
In the mixture of Manganese anode slime, sulfuric acid solution and blackstrap aqueous solution, liquid-solid ratio is 3.8 ~ 4.2: 1, keeps the temperature of mixture
For 70 ~ 80 DEG C, 30 ~ 50min is reacted, then adds in iron powder, the dosage of iron powder is more than the theoretical amount of remaining reducing agent, reaction 10
~ 20min separates leachate and leached mud after the completion of reaction with filter press；
S2. leachate adds in H2O2, oxidizing condition is:ρ(H2O2)/ρ (COD)=2.0 ~ 2.5, controlling reaction temperature are 48 ~ 52 DEG C,
The leachate of COD must be removed；
S3. the leachate that COD will be removed adds in ammonium sulfide or Sodium Dimethyldithiocarbamate, and add in ammonium hydroxide adjust the pH of leachate for 5.5 ~
6.0, removing heavy metals are removed, obtain purification of manganese sulfate liquid, the electrolysis of purification of manganese sulfate liquid obtains metal manganese product.
Preferably, in the step S1, the concentration of sulfuric acid solution is 3.5molL-1, blackstrap concentration of aqueous solution is 70
g·L-1, liquid-solid ratio 4:1.
Preferably, 190 ~ 210 rmin of stir speed (S.S.)-1。
Preferably, in the step S1, the temperature of mixture is 70 DEG C.
Preferably, in the step S2, ρ (H2O2)/ρ(COD)=2.5。
Preferably, in the step S2, reaction temperature is 50 DEG C, and the reaction time is 2 ~ 2.5h.
Preferably, in the step S3, the temperature for adding in ammonium hydroxide reaction is 45 ~ 55 DEG C.
Preferably, in the step S1, leached mud takes out after being cleaned in filter press to be dried, and obtains lead concentrate product.
The present invention has the following advantages：
（1）The present invention by electrolytic manganese anode mud directly as reactant carry out manganese metal recycling, add in sulfuric acid, first using blackstrap as
Reducing agent, then using iron powder as reducing agent, the manganese leaching rate in the earth of positive pole can be made to reach more than 99%, and blackstrap is discarded for production
Object by carrying out recycling to blackstrap, can substantially reduce production cost, realize refuse reclamation, energy conservation and environmental protection.
（2）Lead in the earth of positive pole is all stayed in filter residue through separation to be separated and recovered, and the present invention is directly to being deposited in pressure
Filter residue in filter aluminium sheet is cleaned, and processing procedure is quick, and cleaning is completed to dry.
（3）The present invention is handled leachate by hydrogen peroxide, aoxidizes organic matter therein so that electrolytic manganese anode mud
Generated electrolyte COD concentration is leached between 60-160mg/L, manganese electrolytic process is caused so as to reduce organic substance residues
It influences, improves the efficiency and quality of electrolytic manganese metal.
（4）Generated manganese electrolyte production electrolysis manganese product is leached with electrolytic manganese anode mud, ton product power consumption is about
6200kwh/t, energy consumption are greatly reduced, remarkable in economical benefits.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, but protection scope of the present invention is not limited to following reality
Apply example.
Embodiment 1
A kind of electrolytic manganese anode mud separation production electrolytic manganese metal and the method for recycling lead, comprise the following steps：
S1. electrolytic manganese anode mud and 3.5molL-1Sulfuric acid solution mixes, and adds in 70 gL-1Blackstrap aqueous solution stirs,
The dosage of blackstrap is the 90% of reducing agent theoretical amount, 200 rmin of stir speed (S.S.)-1, above-mentioned electrolytic manganese anode mud, sulfuric acid are molten
In the mixture of liquid and blackstrap aqueous solution, liquid-solid ratio 4: 1 keeps the temperature of mixture to react 40min, then for 70 DEG C
Iron powder is added in, the dosage of iron powder is more than the theoretical amount of remaining reducing agent, reacts 15min, separated after the completion of reaction with filter press
Leachate and leached mud；
S2. leachate adds in H2O2, oxidizing condition is:ρ(H2O2)/ρ (COD)=2.5, controlling reaction temperature is 50 DEG C, during reaction
Between for 2h, the leachate of COD must be removed；
S3. the leachate for removing COD is added in into Sodium Dimethyldithiocarbamate, and the pH for adding in ammonium hydroxide adjusting leachate is 5.5 ~ 6.0, reaction temperature
For 50 DEG C, removing heavy metals are removed, obtain purification of manganese sulfate liquid, the electrolysis of purification of manganese sulfate liquid obtains metal manganese product.
To be recycled to lead, leached mud takes out after being cleaned in filter press to be dried, and obtains lead concentrate product.
Embodiment 2
A kind of electrolytic manganese anode mud separation production electrolytic manganese metal and the method for recycling lead, comprise the following steps：
S1. electrolytic manganese anode mud and 3.5molL-1Sulfuric acid solution mixes, and adds in 65 gL-1Blackstrap aqueous solution stirs,
The dosage of blackstrap is the 90% of reducing agent theoretical amount, 150 rmin of stir speed (S.S.)-1, above-mentioned electrolytic manganese anode mud, sulfuric acid are molten
In the mixture of liquid and blackstrap aqueous solution, liquid-solid ratio 4.2: 1 keeps the temperature of mixture to react 50min, so for 75 DEG C
After add in iron powder, the dosage of iron powder is more than the theoretical amount of remaining reducing agent, reacts 10min, with filter press point after the completion of reaction
From leachate and leached mud；
S2. leachate adds in H2O2, oxidizing condition is:ρ(H2O2)/ρ (COD)=2, controlling reaction temperature are 48 DEG C, the reaction time
For 2h, the leachate of COD must be removed；
S3. the leachate for removing COD is added in into ammonium sulfide, and the pH for adding in ammonium hydroxide adjusting leachate is 5.5 ~ 6.0, reaction temperature
For 45 DEG C, removing heavy metals are removed, obtain purification of manganese sulfate liquid, the electrolysis of purification of manganese sulfate liquid obtains metal manganese product.
To be recycled to lead, leached mud takes out after being cleaned in filter press to be dried, and obtains lead concentrate product.
Embodiment 3
A kind of electrolytic manganese anode mud separation production electrolytic manganese metal and the method for recycling lead, comprise the following steps：
S1. electrolytic manganese anode mud and 3.5molL-1Sulfuric acid solution mixes, and adds in 70 gL-1Blackstrap aqueous solution stirs,
The dosage of blackstrap is the 85% of reducing agent theoretical amount, 250 rmin of stir speed (S.S.)-1, above-mentioned electrolytic manganese anode mud, sulfuric acid are molten
In the mixture of liquid and blackstrap aqueous solution, liquid-solid ratio 3.8: 1 keeps the temperature of mixture to react 30min, so for 80 DEG C
After add in iron powder, the dosage of iron powder is more than the theoretical amount of remaining reducing agent, reacts 20min, with filter press point after the completion of reaction
From leachate and leached mud, leached mud takes out after being cleaned in filter press to be dried, and obtains lead concentrate product；
S2. leachate adds in H2O2, oxidizing condition is:ρ(H2O2)/ρ (COD)=2.5, controlling reaction temperature is 52 DEG C, during reaction
Between for 2h, the leachate of COD must be removed；
S3. the leachate that COD will be removed adds in ammonium sulfide or Sodium Dimethyldithiocarbamate, and add in ammonium hydroxide adjust the pH of leachate for 5.5 ~
6.0, reaction temperature is 55 DEG C, removes removing heavy metals, obtains purification of manganese sulfate liquid, and the electrolysis of purification of manganese sulfate liquid obtains metal manganese product.
To be recycled to lead, leached mud takes out after being cleaned in filter press to be dried, and obtains lead concentrate product.
Table 1
Claims (8)
1. a kind of electrolytic manganese anode mud separation production electrolytic manganese metal and the method for recycling lead, it is characterised in that including following step
Suddenly：
S1. electrolytic manganese anode mud and 2.5 ~ 3.5molL-1Sulfuric acid solution mixes, and adds in 65 ~ 70 gL-1Blackstrap is water-soluble
Liquid stirs, and the dosage of blackstrap is the 85 ~ 90% of reducing agent theoretical amount, 150 ~ 250 rmin of stir speed (S.S.)-1, above-mentioned electrolysis
In the mixture of Manganese anode slime, sulfuric acid solution and blackstrap aqueous solution, liquid-solid ratio is 3.8 ~ 4.2: 1, keeps the temperature of mixture
For 70 ~ 80 DEG C, 30 ~ 50min is reacted, then adds in iron powder, the dosage of iron powder is more than the theoretical amount of remaining reducing agent, reaction 10
~ 20min separates leachate and leached mud after the completion of reaction with filter press；
S2. leachate adds in H2O2, oxidizing condition is:ρ(H2O2)/ρ (COD)=2.0 ~ 2.5, controlling reaction temperature are 48 ~ 52 DEG C,
The leachate of COD must be removed；
S3. the leachate that COD will be removed adds in ammonium sulfide or Sodium Dimethyldithiocarbamate, and add in ammonium hydroxide adjust the pH of leachate for 5.5 ~
6.0, removing heavy metals are removed, obtain purification of manganese sulfate liquid, the electrolysis of purification of manganese sulfate liquid obtains metal manganese product.
2. electrolytic manganese anode mud separation production electrolytic manganese metal according to claim 1 and the method for recycling lead, feature
It is：
In the step S1, the concentration of sulfuric acid solution is 3.5molL-1, blackstrap concentration of aqueous solution is 70 gL-1, liquid-solid ratio
For 4:1.
3. electrolytic manganese anode mud separation production electrolytic manganese metal according to claim 1 and the method for recycling lead, feature
It is：
In the step S1,190 ~ 210 rmin of stir speed (S.S.)-1。
4. electrolytic manganese anode mud separation production electrolytic manganese metal according to claim 1 and the method for recycling lead, feature
It is：
In the step S1, the temperature of mixture is 70 DEG C.
5. electrolytic manganese anode mud separation production electrolytic manganese metal according to claim 1 and the method for recycling lead, feature
It is：
In the step S2, ρ (H2O2)/ρ(COD)=2.5。
6. electrolytic manganese anode mud separation production electrolytic manganese metal according to claim 1 and the method for recycling lead, feature
It is：
In the step S2, reaction temperature is 50 DEG C, and the reaction time is 2 ~ 2.5h.
7. electrolytic manganese anode mud separation production electrolytic manganese metal according to claim 1 and the method for recycling lead, feature
It is：
In the step S3, the temperature for adding in ammonium hydroxide reaction is 45 ~ 55 DEG C.
8. electrolytic manganese anode mud separation production electrolytic manganese metal according to claim 1 and the method for recycling lead, feature
It is：
In the step S1, leached mud takes out after being cleaned in filter press to be dried, and obtains lead concentrate product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810023327.9A CN108118156B (en) | 2018-01-10 | 2018-01-10 | A kind of method that electrolytic manganese anode mud separation produces electrolytic manganese metal and recycles lead |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810023327.9A CN108118156B (en) | 2018-01-10 | 2018-01-10 | A kind of method that electrolytic manganese anode mud separation produces electrolytic manganese metal and recycles lead |
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| Publication Number | Publication Date |
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| CN108118156A true CN108118156A (en) | 2018-06-05 |
| CN108118156B CN108118156B (en) | 2019-11-26 |
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Cited By (7)
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| CN109455677A (en) * | 2018-11-27 | 2019-03-12 | 中信大锰矿业有限责任公司 | The method of selenium is recycled in a kind of electrolytic manganese anolyte |
| CN110408786A (en) * | 2019-08-29 | 2019-11-05 | 贵州大学 | A kind of electrolytic manganese anode slag catalysis prepares the method for manganese sulfate solution and recovers lead |
| CN112553468A (en) * | 2020-12-18 | 2021-03-26 | 中信大锰矿业有限责任公司 | Method for producing high-purity manganese sulfate by adopting metal manganese anode mud |
| CN112551591A (en) * | 2020-12-18 | 2021-03-26 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for preparing high-purity manganese sulfate qualified liquid by electrolyzing metal manganese anode slime |
| CN112607782A (en) * | 2020-12-18 | 2021-04-06 | 中信大锰矿业有限责任公司 | Method for preparing battery-grade high-purity manganese sulfate by using metal manganese anode slime |
| CN112795773A (en) * | 2020-12-18 | 2021-05-14 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for removing Ca and Mg in electrolytic manganese metal anode mud |
| CN115724470A (en) * | 2022-09-26 | 2023-03-03 | 广西科技师范学院 | A kind of purification method of manganese sulfate solution |
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| NO20211136A1 (en) * | 2021-09-22 | 2023-03-23 | Eramet | Metallic manganese production from ore without CO2 emission |
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| CN109455677A (en) * | 2018-11-27 | 2019-03-12 | 中信大锰矿业有限责任公司 | The method of selenium is recycled in a kind of electrolytic manganese anolyte |
| CN110408786A (en) * | 2019-08-29 | 2019-11-05 | 贵州大学 | A kind of electrolytic manganese anode slag catalysis prepares the method for manganese sulfate solution and recovers lead |
| CN112553468A (en) * | 2020-12-18 | 2021-03-26 | 中信大锰矿业有限责任公司 | Method for producing high-purity manganese sulfate by adopting metal manganese anode mud |
| CN112551591A (en) * | 2020-12-18 | 2021-03-26 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for preparing high-purity manganese sulfate qualified liquid by electrolyzing metal manganese anode slime |
| CN112607782A (en) * | 2020-12-18 | 2021-04-06 | 中信大锰矿业有限责任公司 | Method for preparing battery-grade high-purity manganese sulfate by using metal manganese anode slime |
| CN112795773A (en) * | 2020-12-18 | 2021-05-14 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for removing Ca and Mg in electrolytic manganese metal anode mud |
| CN112795773B (en) * | 2020-12-18 | 2022-10-14 | 南方锰业集团有限责任公司大新锰矿分公司 | Method for removing Ca and Mg in electrolytic manganese metal anode mud |
| CN112607782B (en) * | 2020-12-18 | 2022-10-14 | 南方锰业集团有限责任公司 | Method for preparing battery-grade high-purity manganese sulfate by using metal manganese anode slime |
| CN112551591B (en) * | 2020-12-18 | 2022-12-06 | 南方锰业集团有限责任公司大新锰矿分公司 | Method for preparing high-purity manganese sulfate qualified liquid by electrolyzing metal manganese anode slime |
| CN115724470A (en) * | 2022-09-26 | 2023-03-03 | 广西科技师范学院 | A kind of purification method of manganese sulfate solution |
| CN115724470B (en) * | 2022-09-26 | 2024-05-07 | 广西科技师范学院 | A method for purifying manganese sulfate solution |
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