CN109468458A - A kind of method that Gabon's manganese oxide ore leaches and recycles iron - Google Patents
A kind of method that Gabon's manganese oxide ore leaches and recycles iron Download PDFInfo
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- CN109468458A CN109468458A CN201811425704.8A CN201811425704A CN109468458A CN 109468458 A CN109468458 A CN 109468458A CN 201811425704 A CN201811425704 A CN 201811425704A CN 109468458 A CN109468458 A CN 109468458A
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- manganese
- gabon
- iron
- leaching
- sulfuric acid
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 74
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 37
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000011572 manganese Substances 0.000 claims abstract description 110
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 104
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000002386 leaching Methods 0.000 claims abstract description 81
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 22
- 239000008103 glucose Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000002893 slag Substances 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 12
- 229910052935 jarosite Inorganic materials 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims abstract description 3
- 238000000605 extraction Methods 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 230000035484 reaction time Effects 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 description 24
- 238000005516 engineering process Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000003638 chemical reducing agent Substances 0.000 description 7
- -1 iron ion Chemical class 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 229940037003 alum Drugs 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229960004887 ferric hydroxide Drugs 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- 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 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002500 ions Chemical class 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
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical group [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000219095 Vitis Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- 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
- 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
- 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
Abstract
A kind of method for being leached the invention discloses Gabon's manganese oxide ore and recycling iron, comprising the following steps: mono- section of S1. leaching: being added Gabon's manganese ore in a reservoir, and sulfuric acid and glucose is added, and stirs, and leaches；S2. two sections of leachings: first segment continuously adds sulfuric acid and iron powder into container after leaching completion, stirs, and leaches, and filtering after the completion of leaching obtains leachate；S3. the heavy iron of ihleite crystal seed is added, obtains manganese electrolyte and ammonium jarosite slag；S4. ammonium jarosite slag roasts, and recycles iron.It is able to achieve wet-leaching manganese through the invention, and a large amount of iron resource in Gabon's manganese oxide ore can be recycled.
Description
Technical field
The present invention relates to manganese ore extractive technique field, especially a kind of Gabon's manganese oxide ore leaches and the method for recycling iron.
Background technique
Electrolytic manganese metal has highly important war as a kind of important metallurgy, chemical raw material in national economy
Slightly status.China's iron and steel output accounts for about 3/4ths of Gross World Product, " no manganese not Cheng Gang ", and electrolytic manganese metal is due to purity
Height, impurity are few, are the important alloying elements of production stainless steel, Aldecor, alumal, cupromanganese etc., and
Welding rod, ferrite, permanent-magnet alloy element and many medication chemistries with manganese salt produce in indispensable raw material.With technology
Progressive and new industry rise, electrolytic manganese metal apply day metallurgy, electronics, functional material and fine manganese salt arts
Become extensive.
In China, manganese spar is the important ore raw materials of electrolytic manganese metal, is generally soaked using traditional direct acid leaching process
Manganese out.With the continuous exploitation of manganese resource, manganese spar resource day is becoming tight.Moreover, Electrolytic Manganese Product per ton discharge 8~
10 tons of waste residues, generate every year nearly ten million ton of electrolytic manganese waste residue amount of China's electrolytic manganese metal industry, only Guangxi every year just newly-increased 150
~200 ten thousand tons.Domestic enterprise only takes the mode simply stacked to dispose electrolytic manganese waste residue at present, since the improvement such as antiseep are arranged
The reasons such as undesirable are applied, so that heavy metal and ammonia nitrogen substances in waste residue is entered natural environment, harm is all brought to man and nature.
In order to make up the deficiency of manganese spar resource, many enterprises start to be considered as manganese oxide ore as raw material production electrolysis
Manganese metal.Manganese oxide ore extract technology can be summarized as two major classes: i.e. reduction roasting-acid leaching process and wet reducing lixiviation process.It passes
The reduction roasting of system-Ore Leaching technique be by manganese oxide ore existing for the reducing agents such as coal under the conditions of carry out high temperature reduction roasting,
Make the MnO in ore2It is transformed into MnO, then uses sulfuric acid leaching.The manganese sulfate solution impurity that the method obtains is few, and removal of impurities is simple, but
There is energy consumptions it is high, operating condition is poor, environmental pollution is more serious the problems such as.Since wet reducing extract technology avoids high temperature roasting
Process is burnt, will not be generated containing SO2Exhaust gas, and be one-step leaching, technique is simplified, therefore, such method is manganese oxide ore leaching
The developing direction of technique out.
Wet reducing extract technology is to mix manganese oxide ore, reducing agent, sulfuric acid and water according to a certain ratio, in certain temperature
Lower reducing agent and MnO2Redox reaction, MnO occurs2In tetravalent manganese be reduced to bivalent manganese and enter in solution.Work at present
Common reducing agent is troilite in industry, have many advantages, such as it is cheap, operate conveniently and reduction effect is good, but the method is producing
In that there is the quantity of slag is big, brings into place of the deficiencies of impurity is more, filtering and impurity removing is difficult, be applied to power consumption and dioxy in electrolytic manganese production
The consumption for changing selenium is higher, and the sulfur content of Electrolytic Manganese Product is higher.Therefore, which is difficult at present in electrolytic manganese production
It promotes and applies.
Currently, the manganese oxide ore that Zhong Xin great manganese company exploits in African Gabon, reserves are more than 50,000,000 tons, every year can be to state
Interior 1,000,000 tons of supply ore amount or more, chemical composition is main are as follows: total Mn28.08%, MnO240.20%, Fe27.95%,
Al2O33.78%, Gabon's manganese oxide ore has manganese, iron content height, the impurity contents such as silicon, aluminium it can be seen from the above chemical composition
Low feature.If manganese oxide ore extract technology routinely, manganese therein can only be extracted, and a large amount of Tie Tong crosses hydrolysis and generates
Ferric hydroxide precipitate, which enters in solid slag, discharges.Since ferric hydroxide precipitate is colloidal substance, there are a large amount of hydroxides in slag
Iron not only leads to filtration difficulty, and causes the waste of a large amount of iron resources.
Summary of the invention
A kind of method for leaching the invention discloses Gabon's manganese oxide ore and recycling iron, is able to achieve wet-leaching manganese, and energy
Recycle a large amount of iron resource in Gabon's manganese oxide ore.
To achieve the above object, the technical solution of the present invention is as follows:
A kind of method that Gabon's manganese oxide ore leaches and recycles iron, comprising the following steps:
S1. one section of leaching: being added Gabon's manganese ore in a reservoir, and sulfuric acid and glucose, stirring, mixing speed 200 is added
~300rmin-1, sulfuric acid dosage is 10~15mL/30g Gabon manganese ore, and glucose dosage is 1.5~2.3g/30g Gabon manganese
Mine, liquid-solid ratio are 1.5~2.5mL/g, and extraction temperature is 75~95 DEG C, and extraction time is 4~6h；
S2. two sections of leachings: first segment continuously adds sulfuric acid and iron powder into container after leaching completion, stirs, mixing speed
For 300~500rmin-1, sulfuric acid dosage is 10~15mL/30g Gabon manganese ore, and iron powder dosage is 2.0~3.2g/30g Gabon
Manganese ore, extraction temperature are 60~70 DEG C, and extraction time is 40~60min, filter after the completion of leaching, obtain leachate；
S3. ihleite crystal seed, 40~60gL- of ihleite Seed charge are added in leachate1, reaction temperature 90~95
DEG C, initial pH value is 2.4~3.3, and the reaction time is 60~80min, obtains manganese electrolyte and ammonium jarosite slag；
S4. ammonium jarosite slag roasts, and recycles iron.
Preferably, in the step S1, mixing speed 200rmin-1, sulfuric acid dosage is 10mL/30g Gabon manganese ore,
Glucose dosage is 1.5g/30g Gabon manganese ore, and liquid-solid ratio 1.5mL/g, extraction temperature is 95 DEG C, extraction time 4h.
Preferably, in the step S2, mixing speed 300rmin-1, sulfuric acid dosage is 15mL/30g Gabon manganese ore,
Iron powder dosage is 2.4g/30g Gabon manganese ore, and extraction temperature is 60 DEG C, extraction time 40min.
Preferably, in the step S3, ihleite Seed charge 40gL-1, 95 DEG C of reaction temperature, initial pH value 3,
Reaction time is 60min.
Further, in the step S4, maturing temperature is 800~1000 DEG C, and calcining time is 15~60min.It is preferred that
, 1000 DEG C of maturing temperature, calcining time 60min.
First glucose is added in one section of extract technology in the method that above-described Gabon's manganese oxide ore leaches and recycles iron
As reducing agent, by MnO2In tetravalent manganese be reduced to bivalent manganese and enter in leachate, and when leachate is in certain
When under acid condition, the reduction efficiency of glucose is then in lower state, at this point, iron powder is added, it further will be remaining
MnO2In tetravalent manganese be reduced to bivalent manganese and enter into liquid, so manganese leaching rate can be made to reach 95.10%.Due to above-mentioned
Extract technology is not added with the reducing agent of sulfur-bearing, therefore the problem higher there is no the sulfur content of Electrolytic Manganese Product.
The leachate that above two sections of extract technologies obtain, wherein containing a large amount of Fe, the present invention further uses yellow ammonium iron
Alum method carries out heavy iron, is roasted again after heavy iron, and the content of slag Fe may be up to 60.32% after roasting, be so able to achieve plus
The recycling of iron resource in fluffy manganese oxide ore, while avoiding and leading to the problem of a large amount of iron-containing solid slags when being electrolysed.
Detailed description of the invention
Fig. 1 is the manganese leaching rate result figure of one section of leaching orthogonal experiment.
Fig. 2 a is the figure of changing of manganese leaching rate and COD content under different sulfuric acid dosages in one section of leaching experiment.
Fig. 2 b is the figure of changing of manganese leaching rate and COD content under different glucose dosages in one section of leaching experiment.
Fig. 3 be in two sections of leaching experiments Mn leaching rate with the figure of changing of mixing speed.
Fig. 4 be in two sections of leaching experiments Mn leaching rate with the figure of changing of iron powder dosage.
Fig. 5 be in two sections of leaching experiments Mn leaching rate with the figure of changing of sulfuric acid dosage.
Fig. 6 be in two sections of leaching experiments Mn leaching rate with the figure of changing of extraction time.
Fig. 7 be in two sections of leaching experiments Mn leaching rate with the figure of changing of extraction temperature.
Fig. 8 a is the electron microscope of Gabon's manganese ore, and Fig. 8 b is the electron microscope of two sections of leached muds.
Fig. 9 be in three sections of heavy iron experiments iron ion removal efficiency with the figure of changing of Seed charge.
Figure 10 be in three sections of heavy iron experiments iron ion removal efficiency with the figure of changing of pH value.
Figure 11 be in three sections of heavy iron experiments iron ion removal efficiency with the figure of changing of reaction temperature.
Figure 12 be in three sections of heavy iron experiments iron ion removal efficiency with the figure of changing in reaction time.
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.
The process study leached about step S1 first segment:
S1-1. to explore the suitable process conditions that first segment leaches, using manganese leaching rate as objective function, fixed Gabon's manganese ore
Dosage is 30.0g, mixing speed 200rmin-1, the other factors for influencing manganese leaching rate are considered, such as liquid-solid ratio A/mLg-1, sulfuric acid dosage B/mL, extraction time C/h and glucose dosage D/g, E/ DEG C of extraction temperature.Design the examination of five factors, four horizontal quadrature
Test L16(45), it tests the factor and level is shown in Table 1.
Table 1 leaches Gabon's manganese ore orthogonal experiment factor and level
| A/mL·g-1 | B/mL | C/h | D/g | E/℃ | |
| 1 | 1.5 | 6.00 | 1 | 1.40 | 65 |
| 2 | 2.5 | 9.00 | 2 | 1.70 | 75 |
| 3 | 3.5 | 12.00 | 3 | 2.00 | 85 |
| 4 | 4.5 | 15.00 | 4 | 2.30 | 95 |
The results are shown in Table 2 for orthogonal design table:
Table 2 leaches Gabon's manganese ore orthogonal experiments
Fig. 1 is drawn according to the result of table 3, from table 3 and Fig. 1 it is found that liquid-solid ratio, sulfuric acid dosage, extraction time, glucose are used
Amount, extraction temperature, the influence size that this five factors leach manganese in Gabon's manganese ore are as follows:
Liquid-solid ratio > extraction temperature > sulfuric acid dosage > extraction time > glucose dosage.
The optimal case of Gabon's leaching manganese ore are as follows: A1B4C4D4E4。
I.e. according to above-mentioned orthogonal experiment as a result, Gabon's manganese ore dosage is 30.0g, mixing speed 200rmin-1Shi Meng
Optimal leaching scheme it is as follows: liquid-solid ratio 1.5mLg-1, 95 DEG C of extraction temperature, sulfuric acid dosage 15mL, extraction time 4h, grape
Sugared dosage is 2.4g, leaching rate 86.4%.
S2-2. the optimal case based on above-mentioned orthogonal experiment leaches Gabon's manganese ore, organic in resulting leachate
Object concentration (being characterized with COD) and spent acid concentration are excessively high.Excessively high organic concentration will affect the electrolytic efficiency of manganese, corrode anode
Plate is unfavorable for the electrolysis production of manganese.And spent acid excessive concentration can then consume a large amount of neutralizer in subsequent iron removal step, increase
Addition sheet.Therefore this step advanced optimizes extract technology, reduces organic concentration and spent acid concentration in leachate.Organic matter
Concentration, mainly related with glucose dosage, spent acid concentration are mainly related with sulfuric acid dosage.
Fix other experimental conditions: mixing speed 200rmin-1, liquid-solid ratio 1.5mLg-1, 95 DEG C of extraction temperature, Portugal
Grape sugar dosage 2g, extraction time 4h.Selection sulfuric acid dosage is respectively 6,8,10,12,14mL tested, as a result such as Fig. 2 a institute
Show.
From Fig. 2 a it can be seen that with sulfuric acid dosage increase, the leaching rate of manganese gradually rises, and COD is gradually reduced.
When sulfuric acid dosage is 10mL, manganese leaching rate is higher and leachate COD is lower, therefore sulfuric acid dosage selection 10mL carries out subsequent reality
It tests.
Fix other experimental conditions: mixing speed 200rmin-1, liquid-solid ratio 1.5mLg-1, 95 DEG C of extraction temperature, sulphur
Sour dosage 10mL, extraction time 4h.Selection glucose dosage is respectively 1.00,1.25,1.50,1.75,2.00g tested,
As a result as shown in Figure 2 b.
From Fig. 2 b it can be seen that with glucose dosage increase, although the leaching rate of manganese gradually rises, simultaneously
COD is also synchronous to be risen, therefore not the higher the better for glucose dosage, but to take into account manganese leaching rate and COD.It can be with from Fig. 2 b
Find out: when glucose dosage is 1.50g, leachate COD is lower and manganese leaching rate is higher, achieves preferable balance, therefore
Glucose dosage selects 1.50g.
Comprehensively consider manganese leaching rate, COD and spent acid content, it is final to determine one section after having carried out series of optimum test
Extract technology are as follows: Gabon's manganese ore dosage is 30.0g, mixing speed 200rmin-1The optimal leaching scheme of Shi Meng is as follows: liquid
Admittedly comparing 1.5mLg-1, 95 DEG C of extraction temperature, sulfuric acid dosage 10mL, extraction time 4h, glucose dosage is 1.5g, manganese leaching rate
Up to 60.4%, leachate COD is 517.81mgL-1, leachate spent acid is 18.68gL-1。
The process study leached about step S2 second segment:
The influence of S2-1 stirring rate.
On the basis of one section of extract technology, other experiment conditions are fixed: two sections 60 DEG C of extraction temperature, sulfuric acid dosage
15mL, two sections of extraction time 1h, iron powder dosage are 2.4g.Choose stirring rate be respectively 100,200,300,400,500,
600r·min-1It is tested, the leaching rate of manganese is as shown in Figure 3.
From the figure 3, it may be seen that manganese leaching rate first rises with the increase of stirring rate, after be gradually reduced.This is because stirring rate
Increase, reduce resistance to mass tranfer, reduce external diffusion influence, enhance leaching effect.Manganese leaching rate is with stirring speed at this time
The increase of rate and rise.But stirring rate is excessively high to will lead to the attachment of part miberal powder on the reactor wall, is detached from solution, Wu Facan
With leaching, lead to the reduction of manganese leaching rate.It can be seen that stirring rate is 300~500rmin-1Preferable Mn leaching can be obtained
Extracting rate, from the angle of save the cost, selection stirring rate is 300rmin-1Carry out subsequent experimental.
S2-2. the influence of iron powder dosage.
On the basis of one section of extract technology, other experiment conditions are fixed: two sections 60 DEG C of extraction temperature, sulfuric acid dosage
15mL, two sections of extraction time 1h, stirring rate 300rmin-1.Choose iron powder dosage be respectively 0.80,1.60,2.00,
2.40,3.20,4.00,4.80g is tested, and the leaching rate of manganese is as shown in Figure 4.
As seen from Figure 4, manganese leaching rate increases rapidly with the increase of iron powder dosage.When iron powder dosage increases from 0.80g
When being added to 2.00g, manganese leaching rate is increased to 96.88% from 69.47%.The dosage of iron powder is continued growing, manganese leaching rate is only omited
There is rising, but iron powder utilization rate reduces, cost of material rises.Therefore, from fig. 4, it can be seen that iron powder dosage is that 2.0~3.2g can
Preferable manganese leaching rate is obtained, but is best with iron powder dosage 2.00g from the angle of save the cost.
The influence of S2-3 sulfuric acid dosage.
On the basis of one section of extract technology, other experiment conditions are fixed: two sections 60 DEG C of extraction temperature, iron powder dosage
2.00g, two sections of extraction time 1h, stirring rate 300rmin-1.Choose sulfuric acid dosage be respectively 3.00,6.00,9.00,
10.00,12.00,15.00,18.00mL is tested, and the leaching rate of manganese is as shown in Figure 5.
As seen from Figure 5, manganese leaching rate is significantly increased with the increase of sulfuric acid dosage.When sulfuric acid dosage increases from 3.00mL
When being added to 10.00mL, manganese leaching rate is increased to 95.59% from 63.70%.The dosage of sulfuric acid is continued growing, manganese leaching rate is
Slightly rise.Therefore, sulfuric acid dosage is that 10~15mL can obtain preferable manganese leaching rate, from the angle of spent acid, with sulfuric acid
Dosage 10.00mL is best.
The influence of bis- sections of extraction times of S2-4.
On the basis of one section of extract technology, other experiment conditions are fixed: two sections 60 DEG C of extraction temperature, iron powder dosage
2.00g, sulfuric acid dosage 10.00mL, stirring rate 300rmin-1.Choose two sections of extraction times be respectively 10,20,40,60,
80,100,120min is tested, and the leaching rate of manganese is as shown in Figure 6.
As seen from Figure 6, in preceding 10min, manganese ore and iron powder vigorous reaction, manganese leaching rate is rapidly from 60.70% liter
Up to 86.83%.As reaction continues, from 10min to 20min, manganese leaching rate still has faster raising.But when reaction
It carries out to 40min, manganese leaching rate only slightly rises, until no longer changing substantially with the increase in reaction time when 60min.Cause
This, extraction time is that 40~60min can obtain preferable manganese leaching rate, take energy consumption of reaction into consideration, two sections of extraction times with
40min is best.At this point, manganese leaching rate is 95.10%.
The influence of bis- sections of extraction temperatures of S2-5.
On the basis of one section of extract technology, other experiment conditions: two sections of extraction time 40min, iron powder dosage are fixed
2.00g, sulfuric acid dosage 10.00mL, stirring rate 300rmin-1.Choose two sections of extraction temperatures be respectively 40,50,60,70,
80, it is tested for 90 DEG C, the leaching rate of manganese is as shown in Figure 7.
As seen from Figure 7, manganese leaching rate gradually rises with the raising of temperature, when extraction temperature is improved from 30 DEG C to 60
DEG C when, manganese leaching rate is correspondingly increased to 95.10% from 87.15%.Meanwhile the experimental results showed that, in lower reaction temperature
Under, reaction can also obtain higher manganese leaching rate.This is because the reactivity of iron powder is very high, even if the situation lower in temperature
Under, also the manganese in manganese ore can be restored well.After extraction temperature is more than 70 DEG C, with the raising of temperature, manganese is leached
Rate is basically unchanged.Considering cost factor, reaction temperature are best with 60 DEG C.
S2-6 leached mud sem analysis.
The microcosmic knot of front and back is leached to Gabon's ferric manganese ore using Hitachi, Japan S-3400N scanning electron microscope (SEM)
Structure is detected, as a result as shown in Fig. 8 a, 8b.
Fig. 8 a, 8b are respectively that Gabon's ferric manganese ore leaches front and back micro-structure diagram.As can be seen that Gabon is high from SEM figure
Ferromanganese Ore is after leaching, by the convert of rough surface densification at the particle with smooth loose hole configurations.It therefore can be with
Think, in leaching process, sulfuric acid and reducing agent are entered inside manganese ore particle, and manganese therein and iron are leached.
Brief summary: best extract technology condition are as follows: first segment, Gabon manganese ore 30.00g, sulfuric acid dosage 10.00mL, glucose
Dosage 1.50g, liquid-solid ratio 1.5,95 DEG C of extraction temperature, extraction time 4h, stirring rate 200rmin-1；Second segment, iron powder are used
Measure 2.00g, two sections 60 DEG C of extraction temperature, two sections of extraction time 40min.With this condition, manganese leaching rate is up to 95.10%.
Research about step S3.
S3-1. influence of the Seed charge to iron removal rate.
Seed charge has a major impact heavy alum process, needs to investigate it.Fix other experimental conditions: stirring
Speed 300rmin-1, initial pH value 3,90 DEG C of reaction temperature, the additional additional amount 0gL of ammonium sulfate-1, the reaction time
60min.Choosing Seed charge is respectively 0,20,40,60,80,100gL-1It is tested, the removal efficiency of leachate iron is as schemed
Shown in 9.
As seen from Figure 9: with the increase of Seed charge, the removal efficiency of iron is continuously improved, especially when crystal seed adds
Enter amount 0gL-1Increase to 40gL-1When, the removal efficiency of iron sharply increases and basically reaches peak value, continues to increase crystal seed later
Additional amount, until 60gL-1When have slow rising, the removal efficiency of later period iron is substantially unchanged.The result shows that Seed charge is to iron
Removal efficiency have considerable influence.The result shows that 40~60gL of Seed charge-1Preferably heavy iron effect can be obtained,
Considering cost factor, selects Seed charge for 40gL-1It is best.
S3-2. influence of the initial pH value to iron removal rate.
During heavy iron, initial pH value is to influence one of the principal element of iron removal efficiency, fixes other experimental conditions: stirring
Mix speed 300rmin-1, 90 DEG C of reaction temperature, the additional additional amount 0gL of ammonium sulfate-1, reaction time 60min.Early period is explored
Experiment shows that after initial pH is greater than 3.3, the extremely difficult filtering of solution seriously affects test effect, therefore chooses initial pH value difference
It is tested for 1.5,1.8,2.1,2.4,2.7,3,3.3, the removal efficiency of leachate iron is as shown in Figure 10.
As seen from Figure 10: with the increase of initial pH value, the removal efficiency of iron is continuously improved, and is 2.4 in initial pH value
When, iron effect of sinking is preferable, is maximum when reaching 3, up to 93.22%.This is because the generating process of ammonium jarosite is one
The process for producing acid, can be such that the pH value of solution in reaction process constantly declines, and increase the generation that initial pH value is conducive to ammonium jarosite.
But when pH value is 3.3 in leachate, the filter residue of generation is reacted in colloidal, it is extremely difficult to filter.Infer that initial pH value is at this moment
Under conditions of 3.3, generation is ferric hydroxide colloid, not ammonium jarosite.Therefore, it can be obtained when pH value is 2.4~3.3 preferably
Heavy iron effect, and with initial pH value be 3 when effect it is best.
Influence of the S3-3 reaction temperature to iron removal rate.
Fixed other conditions are constant, and initial pH value 3, investigating reaction temperature is respectively 50,60,70,80,90,95 DEG C of feelings
Under condition, the removing situation of iron in leachate, as a result as shown in figure 11.
As seen from Figure 11, in the case where lower than 60 DEG C, the removal efficiency of iron says that this bright low temperature is unfavorable less than 22.51%
Filtration difficulty is found at alum, and in separation.With the increase of temperature, the removal efficiency of iron is continuously improved, when temperature reaches 90
DEG C, iron removal efficiency reaches 90% or more, and when temperature reaches 95 DEG C, iron ion removal efficiency reaches 96.32%, illustrates that temperature raising has
Conducive to the progress of heavy alum.Therefore, 90~95 DEG C of reaction temperature when can obtain preferably heavy iron effect, and with reaction temperature for 95 DEG C
Shi Xiaoguo is best.
Influence of the S3-4 reaction time to iron removal rate.
Other conditions are constant, iron ion in leachate when the investigation reaction time is 20,40,60,80,100,120min respectively
Removing situation, as a result as shown in figure 12.
As seen from Figure 12: with the increase in reaction time, the removal efficiency of iron is to increase.But after reaching 60min,
Extend the reaction time again, the removal efficiency of iron is declined slightly.This is because the iron ion with the increase in reaction time, in solution
Constantly reaction generates ammonium jarosite slag, so that iron removal efficiency constantly rises.But when continuing to extend the reaction time, the sulfuric acid of generation will
Anti- molten iron vitriol slag, causes iron removal efficiency to be declined slightly, and therefore, when 60~80min of reaction time can obtain preferably heavy iron effect,
And effect is best when being 60min with the reaction time.
Solution composition is analyzed after S3-5 removes iron.
Using optimum process condition, iron in leachate is removed, through filtering, solution composition is analyzed, as a result
As shown in table 3.
Table 3 sinks solution composition after iron
From table 3 it is observed that after ferriammonium sulfate method sinks alum, manganese content 23.64gL-1, compared to former leachate,
4.25% is lost, Fe ion concentration is down to 233.90mgL in solution-1, removal efficiency up to 96.32%, be down to by COD value
55.27mg·L-1, removal efficiency illustrates that content of organics in solution can be effectively reduced in heavy iron process up to 90.33%.It simultaneously can also be with
Find out, there there are the constituent contents such as Mg, Ca, Pb, Cu in solution declines to a certain degree, this is because the yellow ammonium generated during heavy iron
Siderotil has certain suction-operated to foreign ion.
Brief summary: carrying out except iron leachate using ferriammonium sulfate method, in leachate the removal efficiency of iron increased with reaction temperature,
The increase of pH in a certain range and increase.Experiment of single factor shows in Seed charge 40gL-1, 95 DEG C of reaction temperature, initially
PH value is 3, and under conditions of reacting 1h and in addition not adding ammonium sulfate, de-ferrous effect is best, with this condition except iron rate is reachable
96.32%.
Research about step S4.
Using L16 (45) orthogonal arrage studies step S4, the arrangement of orthogonal experiment factor and experimental result are shown in Table 4.
As shown in Table 4, maturing temperature and the two factors of calcining time influence size order to the roasting of ammonium jarosite slag
Are as follows: maturing temperature > calcining time.Maturing temperature reaches 800 DEG C or more, and the content of slag Fe is easier to reach 50% or more, roasting
Burning the time can select according to temperature in 15~60min, wherein best roasting condition are as follows: and 1000 DEG C of maturing temperature, calcining time
60min, with this condition, the content of slag Fe is up to 60.32%.
Claims (6)
1. a kind of method that Gabon's manganese oxide ore leaches and recycles iron, it is characterised in that the following steps are included:
S1. one section of leaching: being added Gabon's manganese ore in a reservoir, and sulfuric acid and glucose, stirring is added, and mixing speed is 200 ~ 300
r·min-1, sulfuric acid dosage is 10 ~ 15 mL/30g Gabon manganese ore, and glucose dosage is 1.5 ~ 2.3g/30g Gabon manganese ore, liquid
Gu extraction temperature is 75 ~ 95 DEG C, and extraction time is 4 ~ 6 h than being 1.5 ~ 2.5 mL/g；
S2. two sections of leachings: first segment continuously adds sulfuric acid and iron powder into container after leaching completion, stirs, mixing speed 300
~500 r·min-1, sulfuric acid dosage is 10 ~ 15 mL/30g Gabon manganese ore, and iron powder dosage is 2.0 ~ 3.2 g/30g Gabon manganese ores,
Extraction temperature is 60 ~ 70 DEG C, and extraction time is 40 ~ 60min, filters after the completion of leaching, obtains leachate；
S3. ihleite crystal seed, 40 ~ 60gL of ihleite Seed charge are added in leachate-1, 90 ~ 95 DEG C of reaction temperature, just
Beginning pH value is 2.4 ~ 3.3, and the reaction time is 60 ~ 80min, obtains manganese electrolyte and ammonium jarosite slag；
S4. ammonium jarosite slag roasts, and recycles iron.
2. the method that Gabon's manganese oxide ore according to claim 1 leaches and recycles iron, it is characterised in that:
In the step S1, mixing speed is 200 rmin-1, sulfuric acid dosage is 10 mL/30g Gabon manganese ore, and glucose is used
Amount is 1.5 g/30g Gabon manganese ores, and liquid-solid ratio is 1.5 mL/g, and extraction temperature is 95 DEG C, and extraction time is 4 h.
3. the method that Gabon's manganese oxide ore according to claim 1 leaches and recycles iron, it is characterised in that:
In the step S2, mixing speed is 300 rmin-1, sulfuric acid dosage is 15 mL/30g Gabon manganese ore, iron powder dosage
For 2.4 g/30g Gabon manganese ores, extraction temperature is 60 DEG C, extraction time 40min.
4. the method that Gabon's manganese oxide ore according to claim 1 leaches and recycles iron, it is characterised in that:
In the step S3,40 gL of ihleite Seed charge-1, 95 DEG C of reaction temperature, initial pH value 3, the reaction time
For 60min.
5. the method that Gabon's manganese oxide ore according to claim 1 leaches and recycles iron, it is characterised in that:
In the step S4, maturing temperature is 800 ~ 1000 DEG C, and calcining time is 15 ~ 60min.
6. the method that Gabon's manganese oxide ore according to claim 5 leaches and recycles iron, it is characterised in that:
1000 DEG C of maturing temperature, 60 min of calcining time.
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| CN102851498A (en) * | 2012-09-26 | 2013-01-02 | 中信锦州金属股份有限公司 | Preparation method of sintering manganese ore to leach electrolytic manganese |
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| CN108660326A (en) * | 2018-05-25 | 2018-10-16 | 东北大学 | A method of reduction acidolysis-leaching is simultaneously except iron handles manganese oxide ore |
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| CN102851498A (en) * | 2012-09-26 | 2013-01-02 | 中信锦州金属股份有限公司 | Preparation method of sintering manganese ore to leach electrolytic manganese |
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