CN103509955A - Two ore combined process for treatment of laterite nickel ore and pyrolusite - Google Patents
Two ore combined process for treatment of laterite nickel ore and pyrolusite Download PDFInfo
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- CN103509955A CN103509955A CN201310299709.1A CN201310299709A CN103509955A CN 103509955 A CN103509955 A CN 103509955A CN 201310299709 A CN201310299709 A CN 201310299709A CN 103509955 A CN103509955 A CN 103509955A
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- ore
- pyrolusite
- red soil
- solution
- soil nickel
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 77
- 230000008569 process Effects 0.000 title claims abstract description 43
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001710 laterite Inorganic materials 0.000 title abstract 4
- 239000011504 laterite Substances 0.000 title abstract 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000011572 manganese Substances 0.000 claims abstract description 30
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 26
- 239000010941 cobalt Substances 0.000 claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 239000003245 coal Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 10
- 229910052935 jarosite Inorganic materials 0.000 claims abstract description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 5
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002689 soil Substances 0.000 claims description 49
- 238000001556 precipitation Methods 0.000 claims description 15
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 230000002829 reductive effect Effects 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052598 goethite Inorganic materials 0.000 claims description 5
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 241000080590 Niso Species 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000006479 redox reaction Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 abstract description 19
- 238000002386 leaching Methods 0.000 abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000284 extract Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 4
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 abstract 2
- 239000011812 mixed powder Substances 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 238000006722 reduction reaction Methods 0.000 description 15
- 229940099596 manganese sulfate Drugs 0.000 description 12
- 239000011702 manganese sulphate Substances 0.000 description 12
- 235000007079 manganese sulphate Nutrition 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 235000010755 mineral Nutrition 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005987 sulfurization reaction Methods 0.000 description 6
- 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 5
- 230000001698 pyrogenic effect Effects 0.000 description 5
- -1 Manganse Dioxide Chemical compound 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical group [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- PAVJEQIFHXNOSM-UHFFFAOYSA-H manganese(3+);trisulfate Chemical compound [Mn+3].[Mn+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PAVJEQIFHXNOSM-UHFFFAOYSA-H 0.000 description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011284 combination treatment Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- VIAPNRBXEJNZKV-UHFFFAOYSA-N nickel silicic acid Chemical compound [Ni].[Si](O)(O)(O)O VIAPNRBXEJNZKV-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Images
Abstract
The invention relates to a two ore combined process for treatment of laterite nickel ore and pyrolusite. The process includes the following steps: mixing laterite nickel ore with coal and roasting to obtain a ferrous oxide powder containing nickel and cobalt; leaching the ferrous oxide powder containing nickel and cobalt with concentrated sulfuric acid; after filtering, adding ammonium sulfate to the solution, controlling the concentration of H2SO4, adding pyrolusite to oxidize Fe<2+> into Fe<3+> and reduce Mn<4+> into Mn<2+>, and filtering to obtain a MnSO4-containing solution and an ammonium jarosite precipitate; adding a vulcanizing agent to the MnSO4-containing solution to produce sulfide nickel and cobalt sulfide precipitates, drying the precipitates to obtain a mixed powder of sulfide nickel and cobalt sulfide; and roasting the obtained ammonium jarosite precipitate, washing by water and drying to obtain crude iron red. The process can extract valuable metallic elements nickel, cobalt, iron and manganese from the two ores; and compared to respective treatment on the laterite nickel ore and manganese ore, the process saves production cost and improves production efficiency.
Description
Technical field
The present invention relates to metalliferous mineral field of smelting, especially relate to a kind of method that reclaims metalliferous mineral from red soil nickel ore and pyrolusite.
Background technology
At present, verified in land nickel minerals data, the industrial reserves of nickel metal is 80,000,000 tons, nickel mineral mainly exists with nickelous sulfide and two kinds of forms of red soil nickel ore, wherein nickel sulfide ore accounts for 20%, red soil nickel ore is about 75%, silicic acid nickel minerals accounts for 5%, the exploitation of nickel minerals be take nickel sulfide ore and red soil nickel ore as main, and main Chan Nie state is Canada, Russia, Australia, Philippines, Cuba, China.In nickel oxide ore, red soil nickel ore iron content is high, and siliceous magnesium is low, and nickeliferous is 1%～2%.At present, the exploitation of nickel oxide ore are to take red soil nickel ore as main, and it is formed by ultrabasic rocks weathering development, and nickel mainly exists with nickel limonite (seldom crystallization is to non crystallized ferric oxide) form.
Because continuous increase and the nickel sulfide ore reserves of nickel consumption constantly reduce in recent years, the exploitation of red soil nickel ore comes into one's own day by day, red soil nickel ore all adopts the mode of direct smelting raw ore at present, smelting process can be divided into pyrogenic process and the large class of wet method two substantially: pyrogenic process 1: primary red soil nickel ore (rotary kiln drying, electrosmelting) → ferronickel; Pyrogenic process 2: primary red soil nickel ore (sinter machine sintering, blast-furnace smelting) → Rhometal; Wet method 1: primary red soil nickel ore (adding sulfuric acid high pressure leaches) → single nickel salt (adding precipitation agent hydrogen sulfide) → nickelous sulfide (NiS); Wet method 2: the nickel in primary red soil nickel ore (also first wife burns) → ore exists (adding carbonic acid ammonia solution) → nickel hexmmine (rotary kiln drying calcining) → nickel oxide powder (reduction reaction) → metallic nickel with Rhometal structure.
Pyrogenic attack red soil nickel ore has that flow process is short, efficiency advantages of higher, but it is high to consume energy.For example adopt electrosmelting, only power consumption just accounts for 50% of production cost, the burning consumption of dry, the roasting pretreatment technique before adding red soil nickel ore melting, and the energy consumption in running cost more accounts for more than 65%.In addition, thermal process has certain requirement to the red soil nickel ore grade of processing, the nickeliferous every reduction by 1% of ore, and production cost approximately improves 30%～40%, and thermal process is mainly processed high-grade red soil nickel ore at present.
The main technique of hydrometallurgy is to leach, at present mainly by reduction-ammonia leaching process, high pressure pickling process, normal pressure pickling process and Microorganism Leaching method.The advantages such as normal pressure pickling process is to process at present red soil nickel ore to adopt more technique, and that this technique has is simple to operate, it is low to consume energy, do not use high-tension apparatus, investment cost is few, but nickel recovery is low, seriously polluted.
Manganse Dioxide in pyrolusite is insoluble to sulfuric acid, must it be reduced into manganese monoxide (MnO) by reduction reaction, could become manganous sulfate with sulfuric acid reaction.Manganese sulfate solution is the main raw material of preparing the manganese products such as industrial manganic sulfate, manganous carbonate, Manganse Dioxide, trimanganese tetroxide and electrolytic manganese.The method that manganous sulfate is prepared in present pyrolusite reduction mainly contains three kinds: coal reducing roasting---sulfuric acid leaching ,Liang ore deposit roasting method and wet reducing extract technology, coal reducing roasting---sulfuric acid leaching is traditional processing technology, this method has semicentennial history, it is traditional processing technology, technology maturation, the quality of manganous sulfate is good.But the SO that it is produced
2, serious dust pollution of the environment, coal consumption amount is large; Two ore deposit roasting methods by pyrolusite and manganous sulfate pulverize respectively, mix, 500 ℃～600 ℃ roasting temperatures 0.5～1 hour, then, with clear water leaching, after separated slag, condensing crystal obtained manganous sulfate, the method equally also can produce SO
2and dust, contaminate environment; Wet reducing extract technology, by pyrolusite, sulfuric acid and a certain amount of reductive agent hybrid reaction, can obtain manganese sulfate solution with the water extraction regular hour at a certain temperature, and the method is the developing direction that pyrolusite leaches, and is not also applied to suitability for industrialized production.
Red soil nickel ore and pyrolusite are all the Mineral resources that are difficult to utilization, if combine in energy Jiang Zheliangzhong ore deposit, process, and therefrom propose useful metalliferous mineral, can greatly save production cost, and enhance productivity.
Summary of the invention
The technical problem to be solved in the present invention is to avoid above-mentioned the deficiencies in the prior art part and a kind of method that combination treatment red soil nickel ore and pyrolusite are provided, Ji Liang ore deposit integrated process, the operational path that this process using fire-wet method combines, red soil nickel ore and pyrolusite are carried out to combination treatment, therefrom extract the valuable metal elements such as nickel, cobalt, iron, manganese.
The object of the invention realizes by following technical proposals:
Two ore deposit integrated processs are processed a technique for red soil nickel ore and pyrolusite, it is characterized in that comprising the following steps:
1. red soil nickel ore is mixed by a certain percentage with coal, after oven dry, be ground into powder, then carry out roasting, maturing temperature is 750 ℃～950 ℃, and roasting time is 1～3 hour;
2. the material after roasting is ground again, obtain ferrous oxide powder nickeliferous, cobalt;
3. under normal temperature condition, adopting electrolytic manganese anolyte and the vitriol oil to leach nickeliferous, the ferrous Fen，Suan of cobalt oxidation ore deposit ratio is 0.8～1.2:1, and extraction time 1.5～3 hours, controls and leach terminal H
2sO
4concentration, at 10g/L～30g/L, after filtration, obtains containing FeSO
4, NiSO
4and CoSO
4solution and filter residue;
4. to solution, add ammonium sulfate, add the pyrolusite that grinds to form powdery, redox reaction occurs, by Fe
2+be oxidized to Fe
3+, Mn
4+be reduced into Mn
2+, by after solution filter, obtain containing MnSO
4solution and ammonium jarosite precipitation;
5. vulcanizing agent is added containing MnSO
4solution in, produce nickelous sulfide and cobaltous sulfide precipitation, after precipitation is dried, obtain mixing nickelous sulfide, cobaltous sulfide powder;
6. by the ammonium jarosite precipitation roasting obtaining, maturing temperature is 950 ℃, and the time is 2 hours, dry after washing, obtains crude iron red.
Described step 1. in the ratio of red soil nickel ore and coal be 100:16.
The maturing temperature of described step in is 1. 950 ℃, and roasting time is 2 hours.
Described step ③Zhong ore deposit liquor ratio is 1:6～10, and extraction time is 1.5 hours.
3. described step leaches terminal H
2sO
4concentration be 25g/L.
Described step 5. vulcanizing agent is that massfraction is 15% sodium sulfide solution.
5. the filtrate obtaining in to described step adds liquid SDD to carry out post cure, controls temperature at 50 ℃.
By step 6. to crude iron redly carry out again roasting, maturing temperature is 900 ℃, obtains smart iron oxide red after washing and drying.
Roasting after the filter residue washing obtaining after 3. step is filtered, then separated by magnetic separation, obtain fine chrome mine.
The further deironing of solution obtaining after 4. step is filtered adds hydrogen peroxide, by remaining Fe in solution
2+be oxidized to Fe
3+, then add ammoniacal liquor, regulate pH value between 3.5～4, controlling solution terminal pH value is 4.5, by Fe
3+become goethite precipitation and separation.
Experimental principle of the present invention:
Prepare nickel and cobalt containing ferrous oxide powder.Take red soil nickel ore as raw material, and coal dust is reductive agent, at a certain temperature iron is reduced into FeO, and nickel, cobalt are reduced into metal, thereby makes nickeliferous ferrous oxide powder (main component is FeO).Main chemical reactions equation is as follows:
2C+ O
2→2CO↑ (1)
Fe
2O
3+CO→2FeO+2CO
2 ↑
(2)
NiO+ CO→Ni+CO
2 ↑
(3)
CoO+ CO→Co+CO
2↑
(4)
Sulfuric acid leaching.At normal temperatures, with a certain amount of vitriol oil, leach the nickeliferous ferrous oxide powder of pressed powder, utilize the heat of dilution that in reaction process, the vitriol oil is emitted to maintain leaching process and complete under comparatively high temps, thereby obtain the solution of nickeliferous, cobalt, iron.Main chemical reactions equation is as follows:
FeO + H
2SO
4 →FeSO
4 + H
2O (5)
Ni + H
2SO
4→NiSO
4 + H
2↑ (6)
Co + H
2SO
4→CoSO
4 + H
2↑ (7)
Preliminary deironing.Pyrolusite main component is MnO
2, under acidic conditions, there is stronger oxidisability, and ferrous ion has stronger reductibility.First utilization redox reaction is between the two by Fe
2+be oxidized to Fe
3+, Mn
4+be reduced into Mn
2+, then, under ammoniumsulphate soln system, the pH value of regulation system, adopts ammonium jarosite method by the Fe being oxidized to
3+become ammonium jarosite precipitation and separate, main chemical reactions equation is as follows:
MnO
2+2FeSO
4+2H
2SO
4→MnSO
4+Fe
2(SO
4)
3+2H
2O （8）
3Fe
2(SO
4)
3+12H
2O+(NH
4)
2SO
4→(NH
4)
2Fe
6(SO
4)
4(OH)
12↓+6H
2SO
4 （9）
Deep iron removal.Deep iron removal first with hydrogen peroxide by remaining Fe
2+be oxidized to Fe
3+, then adopting goethite process, the pH value of the hierarchy of control, by Fe
3+become goethite precipitation and separation, main chemical reactions equation is as follows:
2Fe
2++H
2O
2 →2Fe
3++2OH
- （10）
Fe
3++3OH
- →FeOOH↓+ H
2O （11）
Sulfuration separating nickel, cobalt and manganese.At normal temperatures, by adding vulcanizing agent to make nickel cobalt form precipitation, thereby reach the object separated with manganese sulfate solution, main chemical reactions equation is as follows:
NiSO
4+Na
2S→NiS↓ + Na
2SO
4 （12）
CoSO
4+ Na
2S→CoS↓+ Na
2SO
4 （13）
Beneficial effect of the present invention: the present invention adopts two ore deposit integrated processs to process red soil nickel ore and pyrolusite, therefrom extract the valuable metal elements such as nickel, cobalt, iron, manganese, than respectively red soil nickel ore and pyrolusite being processed, this technique has been saved production cost, has improved production efficiency.The spent acid obtaining after this technology utilization acidleach red soil nickel ore directly leaches pyrolusite and heavy iron, has greatly improved the effective rate of utilization of sulfuric acid.By this technique, red soil nickel ore and pyrolusite are processed, obtain crude iron red (can further process and obtain smart iron oxide red), mix nickelous sulfide cobalt and manganese sulfate solution, as required manganese sulfate solution is prepared into the manganese products such as industrial manganic sulfate, manganous carbonate, Manganse Dioxide, trimanganese tetroxide and electrolytic manganese.The rate of recovery of this technique whole process nickel, cobalt, manganese, iron is respectively 90%, 73%, 91%, 90%, thereby has realized the comprehensive reutilization of cobalt, nickel, manganese, iron each valuable metal element.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that the present invention's two ore deposit integrated processs are processed red soil nickel ore and pyrolusite.
Embodiment
Adopting Philippines's red soil nickel ore and Gabon's pyrolusite is raw material, and main chemical compositions content (massfraction) as shown in Table 1.
Biao Yi Philippines red soil nickel ore and Gabon's pyrolusite main chemical compositions content (%)
1, pyrogenic process is prepared nickeliferous, the ferrous powder of cobalt oxidation
Raw material (comprise red soil nickel ore and go back raw coal) is placed in to electric heating constant-temperature blowing drying box, at 105 ℃ of temperature, dries.Wherein red soil nickel ore requires H
2o≤10%, goes back raw coal and dries to constant weight.(red soil nickel ore: coal=100:16) fully mix rear standby by having dried raw material according to a certain ratio.Adopt micromill that compound is milled to certain particle size, require percent of pass >=95% under 100 mesh sieves.
Raw material after grinding is put into chamber type electric resistance furnace reducing roasting 2h, and reduction temperature is set as respectively 750 ℃, 850 ℃, 950 ℃, according to Fe
3+reduction degree select best temperature condition, roasting sample analytical results is in Table two.
Table two temperature condition test-results
From table two data, can find out, along with the rising of reduction temperature, burn out rate, Fe
3+reduction degree increases successively, illustrates that high temperature is more conducive to the carrying out of reduction reaction.Known by contrasting, 750 ℃ differ nearly 70% with the reduction degree of 950 ℃, temperature are described on reduction effect impact significantly, therefore for making Fe
3+the Fe that is converted into as much as possible
2+, 950 ℃ of this process choice are as optimum calcination temperature.
By red soil nickel ore with go back raw coal in mass ratio 100:16 mix, at 950 ℃ of temperature, carry out reducing roasting, the time is respectively 1 hour, 2 hours, 3 hours, according to Fe
3+reduction degree select best roasting time, test-results is in Table three.
Table three roasting time condition test result
From table three, data can be found out, Fe
3+reduction degree at 2 hours, reached maximum value, along with the prolongation of roasting time, Fe
3+reduction degree not only do not improve on the contrary and decline to some extent, be mainly because along with the weakening of reducing atmosphere, this has been reduced the Fe of generation
2+oxidized generation Fe gradually again
3+, so the best recovery time of this process choice conduct in 2 hours.
According to the top condition of above-mentioned test: proportioning (red soil nickel ore: go back raw coal) is 100:16,950 ℃ of maturing temperatures, 2 hours recovery times, carry out circulation ratio proof test, the results are shown in Table four.
Table four circulation ratio proof test result
As can be seen from Table IV, under top condition, carry out roasting test, Fe
3+reduction degree in 99% left and right, burn out rate 23.68%, nickeliferous, the ferrous powder of cobalt oxidation that after roasting, obtain can meet subsequent handling requirement.
2, wet-leaching extracts each valuable metal element
To nickeliferous, the ferrous powder of cobalt oxidation, adding the electrolytic manganese anolyte and the concentration that after manganese sulfate solution electrolysis, obtain is 98% vitriol oil (analytical pure), ore deposit liquor ratio is 1:6～10, An Suan ore deposit is than testing respectively for 1:1,1.1:1,1.2:1, extraction time is all 1.5 hours, and test-results is compared in Biao Wushisuan ore deposit.
Test-results is compared in Biao Wusuan ore deposit
Test-results shows, increase along with acid amount, each metal leaching rate is all in rising trend, subsequent processing (soaking manganese deironing) need to remain under certain acidity condition and complete in addition, spent acid is very few to be difficult to meet and to soak the required acidity of manganese, spent acid too much can increase the consumption of neutralizing agent, to sum up considers to select best sour ore deposit than being 1.1:1.
Extraction time test.In temperature of reaction 55℃Xia， ore deposit liquor ratio, be that 1:10 ，Suan ore deposit is than being 1.2:1, after adding ore deposit, every 30min gets sample one time, extraction time is 3 hours, investigates the changing conditions of Fe, Co, Ni and spent acid in leach liquor, and (this condition is nickeliferous, the ferrous grade powder of cobalt oxidation: Fe to the results are shown in Table six
2+: 48.21%, Co:0.14%, Ni:1.12%).
Table six extraction time test-results
From table 3.6, can find out: adding ore deposit, reaction reaches 1.5 hours, except Co, the leaching yield of Fe, Ni has all surpassed 93%, when extraction time reaches 2 hours, only have the leaching yield of cobalt to change greatly, the leaching yield of Fe, Ni is substantially unchanged, due to Co denier, from the viewpoint of reducing the energy and improving product economy benefit two, selecting best extraction time is 1.5 hours; Control and leach terminal H
2sO
4concentration is at 10g/L～30g/L.
Preliminary deironing.To the solution leaching after filtering, add ammonium sulfate, add the pyrolusite that grinds to form powdery, redox reaction occurs, by Fe
2+be oxidized to Fe
3+, Mn
4+be reduced into Mn
2+, by after solution filter, obtain containing MnSO
4solution and ammonium jarosite precipitation.Table seven is H
2sO
4concentration is to Mn
4+the impact of leaching yield.
Table seven H
2sO
4concentration is to Mn
4+the impact of leaching yield
As can be seen from Table VII, when initial acid is 25g/l, Mn
4+leaching yield reached 97.86%, the Fe in solution system
2+≤ 2g/L, has met follow-up deep iron removal requirement, if by Fe in system
2+concentration is down to lower, not only can increase acid consumption, and crosses the formation that lower concentration is unfavorable for deep iron removal crystal grain, and therefore selecting best initial acid is 25 g/L.
To the ammonium jarosite obtaining is precipitated to roasting, maturing temperature is 950 ℃, and the time is 2 hours, dry after washing, obtains crude iron red.
Deep iron removal.To the solution obtaining after preliminary deironing is filtered, add hydrogen peroxide, be oxidized remaining Fe
2+, then, under 85 ℃ of temperature condition, adopt goethite process to carry out deep iron removal, in experimentation, with ammoniacal liquor, regulate acidity to make pH between 3.5～4.0, control solution terminal pH=4.5 left and right, experimental result is in Table shown in eight.
Table eight deep iron removal liquid analytical results
As can be seen from Table VIII, after deep iron removal, in solution, residual iron amount has reached trace, meets deironing requirement.
Sulfuration separating nickel, cobalt.Once sulfuration: under normal temperature condition, the solution of the vulcanizing agent that adopts theoretical amount after to deep iron removal vulcanizes, and wherein vulcanizing agent adopts the sodium sulfide solution that concentration is 15%, filters and obtains vulcanized slag and manganese sulfate solution.Post cure: under normal temperature condition, the solution after once vulcanizing adds SDD(Sodium dimethyldithiocarbamate 40min) carry out deep impurity-removing.Take qualitative is reaction end without nickel, filters and obtains qualified manganese sulfate solution.Table nine is the rear liquid analytical results of sulfuration, and table ten is slag analytical results after vulcanizing.
Liquid analytical results after table nine sulfuration
Slag analytical results after table ten sulfuration
From manganese sulfate solution and the vulcanized slag composition analysis result of above-mentioned two table gained, can find out, nickel, cobalt, manganese separating effect are more satisfactory, both obtain meeting electrolytic metal Mn and produced required qualified manganese sulfate solution, make again Co, Ni in solution obtain effective enrichment, obtained the high-quality vulcanized slag of high cobalt, nickelic, low manganese, in two kinds of dissimilar vulcanized slags, Co, Ni content have reached respectively the heavy nickel cobalt of 4.5%, 29. 5%(sodium sulphite) and 0.15%, 14%(SDD sinks nickel cobalt).
This technique can also be entered the filter residue obtaining after rear filtration by nickeliferous, the ferrous powder acid of cobalt oxidation and washes, and carries out magnetic separation separation after roasting again, finally can access fine chrome mine.By electrolyzing manganese sulfate solution, obtain manganese metal and electrolytic manganese anolyte, electrolytic manganese anolyte can be used for again leaching nickeliferous, the ferrous powder of cobalt oxidation; Manganese sulfate solution also can be prepared the manganese products such as industrial manganic sulfate, manganous carbonate, Manganse Dioxide, trimanganese tetroxide as required.
Although above the present invention is described in detail in conjunction with the embodiments; but described those skilled in the art can understand, do not departing under the prerequisite of aim of the present invention; in claim protection domain, can also more become or change etc. above-described embodiment.
Claims (10)
1.Yi Zhongliang ore deposit integrated process is processed the technique of red soil nickel ore and pyrolusite, it is characterized in that comprising the following steps:
1. red soil nickel ore is mixed by a certain percentage with coal, after oven dry, be ground into powder, then carry out roasting, maturing temperature is 750 ℃～950 ℃, and roasting time is 1～3 hour;
2. the material after roasting is ground again, obtain ferrous oxide powder nickeliferous, cobalt;
3. under normal temperature condition, adopting electrolytic manganese anolyte and the vitriol oil to leach nickeliferous, the ferrous Fen，Suan of cobalt oxidation ore deposit ratio is 0.8～1.2:1, and extraction time 1.5～3 hours, controls and leach terminal H
2sO
4concentration, at 10g/L～30g/L, after filtration, obtains containing FeSO
4, NiSO
4and CoSO
4solution and filter residue;
4. in solution, add ammonium sulfate, add the pyrolusite that grinds to form powdery, redox reaction occurs, by Fe
2+be oxidized to Fe
3+, Mn
4+be reduced into Mn
2+, by after solution filter, obtain containing MnSO
4solution and ammonium jarosite precipitation;
5. vulcanizing agent is added containing MnSO
4solution in, produce nickelous sulfide and cobaltous sulfide precipitation, after precipitation is dried, obtain mixing nickelous sulfide, cobaltous sulfide powder;
6. by the ammonium jarosite precipitation roasting obtaining, maturing temperature is 950 ℃, and the time is 2 hours, dry after washing, obtains crude iron red.
2. a kind of two ore deposit integrated processs according to claim 1 are processed the technique of red soil nickel ores and pyrolusite, it is characterized in that: described step 1. in the ratio of red soil nickel ore and coal be 100:16.
3. a kind of two ore deposit integrated processs according to claim 2 are processed the technique of red soil nickel ores and pyrolusite, it is characterized in that: the maturing temperature of described step in is 1. 950 ℃, and roasting time is 2 hours.
4. a kind of two ore deposit integrated processs according to claim 3 are processed the technique of red soil nickel ore and pyrolusite, it is characterized in that: described step ③Zhong ore deposit liquor ratio is 1:6～10, and extraction time is 1.5 hours.
5. a kind of two ore deposit integrated processs according to claim 4 are processed the technique of red soil nickel ore and pyrolusite, it is characterized in that: 3. described step leaches terminal H
2sO
4concentration be 25g/L.
6. a kind of two ore deposit integrated processs according to claim 5 are processed the technique of red soil nickel ore and pyrolusite, it is characterized in that: described step 5. vulcanizing agent is that massfraction is 15% sodium sulfide solution.
7. a kind of two ore deposit integrated processs according to claim 6 are processed the technique of red soil nickel ores and pyrolusite, it is characterized in that: the filtrate obtaining in 5. to described step adds liquid SDD to carry out post cure, controls temperature at 50 ℃.
8. a kind of two ore deposit integrated processs according to claim 7 are processed the technique of red soil nickel ores and pyrolusite, it is characterized in that: by step 6. to crude iron redly carry out again roasting, maturing temperature is 900 ℃, obtains smart iron oxide red after washing and drying.
9. a kind of two ore deposit integrated processs according to claim 1 are processed the technique of red soil nickel ore and pyrolusite, it is characterized in that: roasting after the filter residue washing obtaining after 3. step is filtered, and then separated by magnetic separation, obtain fine chrome mine.
10. a kind of two ore deposit integrated processs according to claim 1 are processed the technique of red soil nickel ore and pyrolusite, it is characterized in that: the further deironing of solution obtaining after 4. step is filtered adds hydrogen peroxide, by remaining Fe in solution
2+be oxidized to Fe
3+, then add ammoniacal liquor, regulate pH value between 3.5～4, controlling solution terminal pH value is 4.5, by Fe
3+become goethite precipitation and separation.
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