CN115386745A - Method for comprehensively utilizing manganese anode slime resources - Google Patents
Method for comprehensively utilizing manganese anode slime resources Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 98
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 95
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000002386 leaching Methods 0.000 claims abstract description 124
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 46
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002893 slag Substances 0.000 claims abstract description 32
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 12
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 24
- KJXSIXMJHKAJOD-LSDHHAIUSA-N (+)-dihydromyricetin Chemical group C1([C@@H]2[C@H](C(C3=C(O)C=C(O)C=C3O2)=O)O)=CC(O)=C(O)C(O)=C1 KJXSIXMJHKAJOD-LSDHHAIUSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 16
- 229940099596 manganese sulfate Drugs 0.000 claims description 16
- 239000011702 manganese sulphate Substances 0.000 claims description 16
- 235000007079 manganese sulphate Nutrition 0.000 claims description 16
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- KQILIWXGGKGKNX-UHFFFAOYSA-N dihydromyricetin Natural products OC1C(=C(Oc2cc(O)cc(O)c12)c3cc(O)c(O)c(O)c3)O KQILIWXGGKGKNX-UHFFFAOYSA-N 0.000 claims description 10
- 239000011656 manganese carbonate Substances 0.000 claims description 9
- 229940093474 manganese carbonate Drugs 0.000 claims description 9
- 235000006748 manganese carbonate Nutrition 0.000 claims description 9
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 9
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- -1 hydrogen ions Chemical class 0.000 claims description 8
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 63
- 239000011133 lead Substances 0.000 description 52
- 239000007788 liquid Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- 229910000003 Lead carbonate Inorganic materials 0.000 description 2
- 241001018563 Nekemias grossedentata Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000556 factor analysis Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 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
- 238000004137 mechanical activation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- 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
- 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
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- 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
-
- 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
-
- 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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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
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Abstract
The invention relates to a method for comprehensively utilizing manganese anode slime resources, and belongs to the technical field of electrolytic manganese metal. The method for comprehensively utilizing the manganese anode slime resources comprises the following specific steps: adding water into the manganese anode mud, carrying out water leaching, and filtering to obtain water leaching residues; adding an ammonium chloride solution into the obtained water leaching slag according to the liquid-solid ratio of 2-12 (1 mL/g), adjusting the pH value with a hydrochloric acid solution, heating to 50-80 ℃ under the condition that the microwave power is 300-800W, carrying out microwave chlorination leaching for 0.5-2.5h, and filtering to obtain pure manganese dioxide slag and lead leaching solution. According to the invention, the electrolytic manganese anode mud is not required to be roasted or subjected to physical state conversion, the electrolytic manganese anode mud can be subjected to water leaching to remove soluble substances in the electrolytic manganese anode mud, the wrapped lead sulfate can be exposed, and the lead can be directly leached out by adopting ammonium chloride microwave leaching subsequently.
Description
Technical Field
The invention relates to a method for comprehensively utilizing manganese anode slime resources, and belongs to the technical field of electrolytic manganese metal.
Background
During the process of electrolyzing the metal manganese, a large amount of solid waste, namely manganese anode mud, is generated on the plate surface of the anode plate or at the bottom of the electrolytic cell. The existing manganese anode slime is generally sold outside, because the manganese anode slime contains average 42-55% of Mn, 3-10% of Pb and some metals, the manganese anode slime has low economic value when sold outside, and the high-value utilization of manganese and lead in the manganese anode slime cannot be realized.
The phase structure of the manganese anode mud is compact structure, and the phase of manganese in the manganese anode mud is mainly MnO 2 The phases of the lead mainly comprise lead-manganese complex crystal type oxide and lead sulfate, and the lead sulfate is wrapped in the manganese anode slime in a micro-fine particle shape, so that the lead in the manganese anode slime is difficult to selectively leach to realize the purpose of deleading.
Article "heat treatment of electrolytic manganese anode mud and leaching of lead ions thereof", liu Lu and the like, engineering science and technology i edition, discloses that electrolytic manganese anode mud is taken as a research object, pretreated electrolytic manganese anode mud is subjected to high-temperature roasting treatment, then an ammonium acetate solution is adopted for leaching test, samples before and after roasting treatment and after leaching are subjected to Scanning Electron Microscope (SEM) characterization analysis, the leaching behavior of lead ions in the roasted electrolytic manganese anode mud is researched, and the influence of roasting temperature, ammonium acetate concentration, liquid-solid ratio and leaching time on the leaching and migration of the lead ions in the anode mud is preliminarily discussed through single-factor analysis. The test result shows that the microstructure of the electrolytic manganese anode mud particles which are not roasted is compact crystals, the electrolytic manganese anode mud particles which are roasted at high temperature all form a net structure, and the net gap size of the electrolytic manganese anode mud particles which are roasted at 750 ℃ is slightly larger than that of the electrolytic manganese anode mud particles which are roasted at 650 ℃; the microstructure of the roasted anode mud after leaching treatment is not obviously changed; the leaching rate of lead in the anode slime which is not roasted is lower than 9 percent, and the leaching rates of lead in the anode slime which is roasted at 650 ℃ and 750 ℃ can reach about 90 percent.
The patent application number is 2020108814022, and the method for deeply removing lead, selenium and arsenic from manganese electrolytic anode slime and preparing manganese dioxide. Firstly, calcining blocky electrolytic manganese anode mud to obtain calcined slag taking manganese oxide as a main body; mixing the calcined slag and water, carrying out wet grinding, and carrying out solid-liquid separation to obtain wet grinding slag and water extract; mixing the wet-milled slag with a sodium acetate solution, adding the mixture into a high-pressure kettle, stirring and leaching, cooling, and carrying out solid-liquid separation to obtain deleading slag and a lead leaching solution; uniformly mixing the deleading slag and sodium hydroxide, and carrying out oxidizing roasting to obtain roasting slag; mixing the roasting slag with water, adding the mixture into an autoclave, introducing CO2, stirring for reaction, cooling to 60 ℃ or below, and carrying out solid-liquid separation to obtain manganese dioxide and a conversion mother solution; and adding sodium sulfide into the lead leaching solution, and performing solid-liquid separation to obtain lead sulfide precipitate and lead precipitation mother liquor.
Patent application No. 2020108814060, a method for removing lead from electrolytic manganese anode slime. According to the method, through the mechanical activation and the dynamic strengthening effect in the hot ball milling process, the lead sulfate wrapped in the anode mud is fully exposed and reacts with a sodium carbonate solution to be converted into lead carbonate, and the desulfurization efficiency is remarkably improved. On the basis, the lead carbonate is decomposed and leached by nitric acid, so that the deep lead removal of the electrolytic manganese anode slime is realized. The method can lead the electrolytic manganese anode mud to be more than 99% under the condition of not changing the valence state of manganese ions.
In the process of removing lead from the electrolytic manganese anode slime, the lead in the electrolytic manganese anode slime can be leached after the treatment steps of roasting, physical transformation of the lead and the like are carried out. The pretreatment steps are complicated, and the treatment cost is increased.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention provides a method for comprehensively utilizing manganese anode slime resources. According to the invention, the electrolytic manganese anode mud is not required to be roasted or subjected to physical state conversion, the electrolytic manganese anode mud can be subjected to water leaching to remove soluble substances in the electrolytic manganese anode mud, the wrapped lead sulfate can be exposed, and the lead can be directly leached out by adopting ammonium chloride microwave leaching subsequently.
A method for comprehensively utilizing manganese anode slime resources comprises the following specific steps:
step 1, adding water into manganese anode slime, carrying out water leaching, and filtering to obtain water leaching residues;
and 2, adding an ammonium chloride solution into the water leaching slag obtained in the step 2 according to the liquid-solid ratio of 2-12 (1 mL/g), adjusting the pH value with a hydrochloric acid solution, heating to 50-80 ℃ under the condition that the microwave power is 300-800W, carrying out microwave chlorination leaching for 0.5-2.5h, and filtering to obtain pure manganese dioxide slag and lead leaching solution.
The main components of the manganese anode mud are Mn36-54wt% and lead 3-6wt%; the phase of manganese being predominantly MnO 2 The lead phase mainly comprises lead-manganese complex crystal type oxide and lead sulfate.
The water leaching process in the step 1 comprises the following specific steps: soaking in water at ultrasonic power of 400-1200W and stirring speed of 200-400r/min for 30-120min.
The microwave chlorination leaching process in the step 2 is twice, and specifically comprises the following steps:
step 2.1, firstly, adding an ammonium chloride solution into the water leaching residue according to a liquid-solid ratio of 2-10 (1 mL/g), wherein the concentration of the ammonium chloride solution is 2-4mol/L, adjusting the pH value by using a hydrochloric acid solution to enable the concentration of hydrogen ions in the solution to be 0.01-0.24mol/L, heating to 50-80 ℃ under the condition that the microwave power is 500-800W, performing microwave chlorination leaching for 0.4-1.5h, and performing primary microwave chlorination leaching;
and 2.2, continuously adjusting the concentration of ammonium chloride to be 1-2mol/L, continuously adjusting the pH value of the leachate leached in the step 2.1 to ensure that the concentration of hydrogen ions in the leachate is 0.01-0.24mol/L, heating to 50-80 ℃ under the condition that the microwave power is 300-500W, carrying out microwave chlorination leaching for 0.1-1.0h, carrying out secondary microwave chlorination leaching, and filtering to obtain relatively pure manganese dioxide slag and lead leachate.
And (3) concentrating, cooling and crystallizing the lead leaching solution obtained in the step 2.2 to obtain lead chloride crystals.
And (3) adding a reducing agent and a sulfuric acid solution (2-4 mol/L sulfuric acid solution or concentrated sulfuric acid) into the manganese dioxide slag obtained in the step 2.2, carrying out reduction acid leaching to obtain a manganese leaching solution, and carrying out an alkaline impurity removal-vulcanization impurity removal process on the manganese leaching solution to obtain a high-purity manganese sulfate solution.
The reducing agent is an inorganic reducing agent or an organic reducing agent.
And in the step 7, the organic reducing agent is dihydromyricetin.
And the alkaline impurity removal is performed by adding manganese carbonate to adjust the pH value to 5-6.
And the step of removing impurities by vulcanization is to add manganese sulfide for removing impurities by vulcanization.
The invention has the beneficial effects that:
(1) According to the method, by controlling specific parameters and conditions of the water leaching process, on one hand, soluble substances in the electrolytic manganese anode mud are removed, and on the other hand, the wrapped lead sulfate is exposed, so that the subsequent lead leaching is facilitated.
(2) In the process of leaching lead, the ammonium chloride solution is used as a leaching solution, the HCl solution is used for regulating the pH value, the microwave chlorination leaching is utilized, the leaching rate of lead is improved, the highest leaching rate of lead can reach 99.5%, and the main phase of manganese in manganese dioxide slag after leaching is still MnO 2 。
(3) The lead chloride crystal is obtained by concentrating, cooling and crystallizing the lead leachate obtained by microwave chlorination leaching.
(4) According to the invention, the manganese dioxide slag obtained after microwave chlorination leaching is subjected to reduction acid leaching-impurity removal to obtain a high-purity manganese sulfate solution, so that a foundation is laid for the subsequent preparation of manganese sulfate products and manganese carbonate.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
Example 1
As shown in fig. 1, the method for comprehensively utilizing manganese anode slime resources comprises the following specific steps:
step 1, 100g of manganese anode mud (the main components of the manganese anode mud are Mn36wt% and Pb 6wt%, and the phase of manganese is mainly MnO) 2 Lead phases mainly comprising lead-manganese complex crystal type oxide and lead sulfate) is added into waterSoaking in water, and filtering to obtain water-soaked residue; the water leaching process comprises the following steps: the solid-liquid ratio of the manganese anode mud to water is 1; and leaching a small amount of ammonium sulfate and manganese sulfate dissolved in water from the manganese anode slime after water leaching.
Step 2, the microwave chlorination leaching process is carried out twice, and specifically comprises the following steps:
step 2.1, firstly, adding an ammonium chloride solution into the water leaching residue according to a liquid-solid ratio of 2 to 1mL/g, wherein the concentration of the ammonium chloride solution is 2mol/L, adjusting the pH value by using a hydrochloric acid solution to enable the concentration of hydrogen ions in the solution to be 0.01mol/L, heating to 80 ℃ under the condition that the microwave power is 500W, carrying out microwave chlorination leaching for 0.4h, and carrying out primary microwave chlorination leaching;
and 2.2, continuously adjusting the concentration of ammonium chloride to 1mol/L, continuously adjusting the pH value of the leachate leached in the step 2.1 to 0.01mol/L by using hydrochloric acid, heating to 50 ℃ under the condition that the microwave power is 300W, performing microwave chlorination leaching for 1.0h, performing secondary microwave chlorination leaching, and filtering to obtain relatively pure manganese dioxide slag and lead leachate.
And 3, concentrating, cooling and crystallizing the lead leachate obtained in the step 2.2 to obtain lead chloride crystals.
Step 4, the concrete process is as follows:
step 4.1, adding a reducing agent and a concentrated sulfuric acid solution into the manganese dioxide slag to perform reduction acid leaching to obtain a manganese leaching solution, which specifically comprises the following steps:
manganese dioxide slag is determined according to n (MnO) in manganese dioxide slag 2 ) Reducing agent n (Fe) in iron powder and n (H) in 2mol/L sulfuric acid solution 2 SO 4 ) Molar mass ratio of n (MnO) 2 ）：n（Fe）：n（H 2 SO 4 ) 1.2, adding water to control the liquid-solid ratio to be 4;
step 4.2, adding manganese carbonate into the manganese leaching solution obtained in the step 4.2 to adjust the pH value of the manganese leaching solution to 5, reacting for 30min, and filtering to obtain a filtrate A;
and 4.3, regulating the pH value of the filtrate A obtained in the step 4.2 to 3.9 by adopting a sulfuric acid solution, adding manganese sulfide, reacting for 120min at 85 ℃, and filtering to obtain a high-purity manganese sulfate solution, wherein the adding amount of ammonium sulfide is the stoichiometric ratio of the theoretical contents of lead, copper and zinc in the filtrate A of 1:1.
by the treatment of the invention, the leaching rate of lead in the lead leaching process of the step 2 reaches 99.0 percent. And 4.3, laying a foundation for the subsequent preparation of manganese sulfate products and manganese carbonate by using the high-purity manganese sulfate solution obtained in the step 4.3.
Example 2
As shown in fig. 1, the method for comprehensively utilizing manganese anode slime resources comprises the following specific steps:
step 1, 100g of manganese anode mud (the main components of the manganese anode mud are 49wt% of Mn and 4.8wt% of lead, and the phase of manganese is mainly MnO) 2 Lead phases mainly comprise lead-manganese complex crystal type oxides and lead sulfate) is added into water, water leaching is carried out, and water leaching residue is obtained through filtering; the water leaching process comprises the following steps: the solid-liquid ratio of the manganese anode mud to water is 1; and leaching a small amount of ammonium sulfate and manganese sulfate dissolved in water from the manganese anode slime after water leaching.
Step 2, the microwave chlorination leaching process is carried out twice, and specifically comprises the following steps:
step 2.1, firstly, adding an ammonium chloride solution into the water leaching residue according to a liquid-solid ratio of 8 to 1mL/g, wherein the concentration of the ammonium chloride solution is 3.5mol/L, adjusting the pH value by using a hydrochloric acid solution to enable the concentration of hydrogen ions in the solution to be 0.18mol/L, heating to 70 ℃ under the condition that the microwave power is 700W, carrying out microwave chlorination leaching for 1.0h, and carrying out primary microwave chlorination leaching;
and 2.2, continuously adjusting the concentration of ammonium chloride to 2mol/L, continuously adjusting the pH value of the leachate leached in the step 2.1 to 0.18mol/L by using hydrochloric acid, heating to 60 ℃ under the condition that the microwave power is 400W, performing microwave chlorination leaching for 0.5h, performing secondary microwave chlorination leaching, and filtering to obtain relatively pure manganese dioxide slag and lead leachate.
And 3, concentrating, cooling and crystallizing the lead leaching solution obtained in the step 2.2 to obtain lead chloride crystals.
Step 4, the concrete process is as follows:
step 4.1, heating a solvent (water) to 85 ℃, then adding dihydromyricetin, stirring until the dihydromyricetin is completely dissolved, dropwise adding concentrated sulfuric acid while the mixture is hot, and then naturally cooling to a temperature of 65 ℃ to obtain an organic reduction acid leaching solution, wherein the dihydromyricetin is extracted from the ampelopsis grossedentata and has a purity of more than 95%; the concentration of concentrated sulfuric acid is more than 70wt%, the sulfuric acid concentration of the organic reducing acid leaching solution is 1.5mol/L, and the dropping amount of concentrated sulfuric acid is 0.01mol/min; adding the manganese dioxide slag into the organic reducing acid leaching liquid for reducing acid leaching for 180min to obtain a manganese leaching liquid, wherein the solid-to-solid ratio of the manganese dioxide slag to the organic reducing acid leaching liquid is 3 mL/g, and the mass ratio of the manganese dioxide slag to dihydromyricetin in the organic reducing acid leaching liquid is 10.5;
step 4.2, adding manganese carbonate into the manganese leaching solution obtained in the step 4.2 to adjust the pH value of the manganese leaching solution to 5, reacting for 30min, and filtering to obtain a filtrate A;
and 4.3, regulating the pH value of the filtrate A obtained in the step 4.2 to 3.9 by adopting a sulfuric acid solution, adding manganese sulfide, reacting at 85 ℃ for 120min, and filtering to obtain a high-purity manganese sulfate solution, wherein the adding amount of ammonium sulfide is the stoichiometric ratio of the theoretical contents of lead, copper and zinc in the filtrate A of 1:1.
by the treatment of the invention, the leaching rate of lead in the lead leaching process of the step 2 reaches 99.5 percent. And 4.3, laying a foundation for the subsequent preparation of manganese sulfate products and manganese carbonate by using the high-purity manganese sulfate solution obtained in the step 4.3.
Example 3
As shown in fig. 1, the method for comprehensively utilizing manganese anode slime resources comprises the following specific steps:
step 1, 100g of manganese anode mud (the main components of the manganese anode mud are 54wt% of Mn and 3.6wt% of lead, and the phase of manganese is mainly MnO) 2 Lead phases mainly comprise lead manganese complex crystal type oxides and lead sulfate) is added into water, and water leaching is carried out and filtered to obtain water leaching residue; the water leaching process comprises the following steps: the solid-liquid ratio of the manganese anode mud to water is 1; and leaching a small amount of ammonium sulfate and manganese sulfate dissolved in water from the manganese anode slime after water leaching.
Step 2, the microwave chlorination leaching process is carried out twice, and specifically comprises the following steps:
step 2.1, firstly, adding an ammonium chloride solution into the water leaching residues according to a liquid-solid ratio of 10 mL/g, wherein the concentration of the ammonium chloride solution is 4mol/L, adjusting the pH value by using a hydrochloric acid solution to enable the concentration of hydrogen ions in the solution to be 0.24mol/L, heating to 50 ℃ under the condition that the microwave power is 800W, and carrying out microwave chlorination leaching for 1.5h for primary microwave chlorination leaching;
and 2.2, continuously adjusting the concentration of ammonium chloride to 1.5mol/L, continuously adjusting the pH value of the leachate leached in the step 2.1 to ensure that the concentration of hydrogen ions in the leachate is 0.24mol/L, heating to 80 ℃ under the condition of 500W of microwave power, carrying out microwave chlorination leaching for 0.1h, carrying out secondary microwave chlorination leaching, and filtering to obtain pure manganese dioxide slag and lead leachate.
And 3, concentrating, cooling and crystallizing the lead leaching solution obtained in the step 2.2 to obtain lead chloride crystals.
Step 4, the concrete process is as follows:
step 4.1, heating a solvent (water) to 85 ℃, adding dihydromyricetin, stirring until the dihydromyricetin is completely dissolved, dropwise adding concentrated sulfuric acid for mixing while the solution is hot, and naturally cooling to the temperature of 65 ℃ to obtain an organic reduction acid leaching solution, wherein the dihydromyricetin is extracted from the ampelopsis grossedentata and has the purity of more than 95%; the concentration of concentrated sulfuric acid is more than 70wt%, the sulfuric acid concentration of the organic reducing acid leaching solution is 1.5mol/L, and the dropping amount of concentrated sulfuric acid is 0.01mol/min; adding the manganese dioxide slag into the organic reducing acid leaching solution for reducing acid leaching for 180min to obtain a manganese leaching solution, wherein the solid-to-solid ratio of the manganese dioxide slag to the organic reducing acid leaching solution is 3 mL/g, and the mass ratio of the manganese dioxide slag to dihydromyricetin in the organic reducing acid leaching solution is 10.5;
step 4.2, adding manganese carbonate into the manganese leaching solution obtained in the step 4.2 to adjust the pH value of the manganese leaching solution to 5, reacting for 30min, and filtering to obtain a filtrate A;
and 4.3, regulating the pH value of the filtrate A obtained in the step 4.2 to 3.9 by adopting a sulfuric acid solution, adding manganese sulfide, reacting for 120min at 85 ℃, and filtering to obtain a high-purity manganese sulfate solution, wherein the adding amount of ammonium sulfide is the stoichiometric ratio of the theoretical contents of lead, copper and zinc in the filtrate A of 1:1.
by the treatment of the invention, the leaching rate of lead in the lead leaching process of the step 2 reaches 99.2 percent. The high-purity manganese sulfate solution obtained in the step 4.3 lays a foundation for the subsequent preparation of manganese sulfate products and manganese carbonate.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (10)
1. A method for comprehensively utilizing manganese anode slime resources is characterized by comprising the following specific steps:
step 1, adding water into manganese anode slime, carrying out water leaching, and filtering to obtain water leaching residues;
and 2, adding an ammonium chloride solution into the water leaching slag obtained in the step 2 according to the liquid-solid ratio of 2-12 (1 mL/g), adjusting the pH value with a hydrochloric acid solution, heating to 50-80 ℃ under the condition that the microwave power is 300-800W, carrying out microwave chlorination leaching for 0.5-2.5h, and filtering to obtain manganese dioxide slag and lead leaching solution.
2. The method for comprehensively utilizing manganese anode slime resources according to claim 1, characterized in that: the main components of the manganese anode mud are Mn36-54wt% and lead 3-6wt%; the phase of manganese being predominantly MnO 2 The lead phase mainly comprises lead-manganese complex crystal type oxide and lead sulfate.
3. The method for comprehensively utilizing manganese anode slime resources according to claim 1, characterized in that: the water leaching process in the step 1 comprises the following specific steps: soaking in water at ultrasonic power of 400-1200W and stirring speed of 200-400r/min for 30-120min.
4. The method for comprehensively utilizing manganese anode slime resources according to claim 1, characterized in that: the microwave chlorination leaching process in the step 2 is twice, and specifically comprises the following steps:
step 2.1, firstly, adding an ammonium chloride solution into the water leaching residue according to a liquid-solid ratio of 2-10 (1 mL/g), wherein the concentration of the ammonium chloride solution is 2-4mol/L, adjusting the pH value by using a hydrochloric acid solution to enable the concentration of hydrogen ions in the solution to be 0.01-0.24mol/L, heating to 50-80 ℃ under the condition that the microwave power is 500-800W, performing microwave chlorination leaching for 0.4-1.5h, and performing primary microwave chlorination leaching;
and 2.2, continuously adjusting the concentration of ammonium chloride to be 1-2mol/L, continuously adjusting the pH value of the leachate leached in the step 2.1 to ensure that the concentration of hydrogen ions in the leachate is 0.01-0.24mol/L, heating to 50-80 ℃ under the condition that the microwave power is 300-500W, carrying out microwave chlorination leaching for 0.1-1.0h, carrying out secondary microwave chlorination leaching, and filtering to obtain manganese dioxide slag and lead leachate.
5. The method for comprehensively utilizing manganese anode slime resources according to claim 4, characterized in that: and (3) concentrating, cooling and crystallizing the lead leaching solution obtained in the step 2.2 to obtain lead chloride crystals.
6. The method for comprehensively utilizing manganese anode slime resource according to claim 4, characterized by comprising the following steps: and (3) adding a reducing agent and a sulfuric acid solution into the manganese dioxide slag obtained in the step 2.2, carrying out reduction acid leaching to obtain a manganese leaching solution, and carrying out an alkaline impurity removal-vulcanization impurity removal process on the manganese leaching solution to obtain a high-purity manganese sulfate solution.
7. The method for comprehensively utilizing manganese anode slime resources of claim 6, wherein: the reducing agent is an inorganic reducing agent or an organic reducing agent.
8. The method for comprehensively utilizing manganese anode slime resources of claim 7, wherein: the organic reducing agent is dihydromyricetin.
9. The method for comprehensively utilizing manganese anode slime resources of claim 6, wherein: and the alkaline impurity removal is performed by adding manganese carbonate to adjust the pH value to 5-6.
10. The method for comprehensively utilizing manganese anode slime resources of claim 6, wherein: and the step of removing impurities by vulcanization is to add manganese sulfide for removing impurities by vulcanization.
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