CN101289702A - Process for separating molybdenum and nickel form black shale containing molybdenum and nickel - Google Patents
Process for separating molybdenum and nickel form black shale containing molybdenum and nickel Download PDFInfo
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- CN101289702A CN101289702A CNA2008100581644A CN200810058164A CN101289702A CN 101289702 A CN101289702 A CN 101289702A CN A2008100581644 A CNA2008100581644 A CN A2008100581644A CN 200810058164 A CN200810058164 A CN 200810058164A CN 101289702 A CN101289702 A CN 101289702A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 54
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000011733 molybdenum Substances 0.000 title claims abstract description 53
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title abstract description 17
- 238000000605 extraction Methods 0.000 claims abstract description 49
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 24
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 24
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 24
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 24
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 24
- 235000010755 mineral Nutrition 0.000 claims abstract description 24
- 239000011707 mineral Substances 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000002386 leaching Methods 0.000 claims abstract description 15
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 5
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 53
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 239000012074 organic phase Substances 0.000 claims description 16
- 150000002815 nickel Chemical class 0.000 claims description 15
- 239000000284 extract Substances 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 6
- 238000004513 sizing Methods 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- 241000080590 Niso Species 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 abstract 2
- 150000007513 acids Chemical class 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- 238000011084 recovery Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 210000000988 bone and bone Anatomy 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 239000003978 infusion fluid Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- 229910052683 pyrite Inorganic materials 0.000 description 3
- 239000011028 pyrite Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000206602 Eukaryota Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- ADULOCGXJMPDRK-UHFFFAOYSA-N iron;sulfanylidenemolybdenum Chemical compound [Fe].[Mo]=S ADULOCGXJMPDRK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052953 millerite Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052954 pentlandite Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
The invention relates to a method for separating molybdenum and nickel from black shale containing molybdenum and nickel, belonging to the metallurgic-chemical technical field. The method is characterized in that the black shale containing molybdenum and nickel is crushed and ground and undergoes oxygen pressure leaching in a pressure pan by using diluted acids and oxidants, and leach solution containing molybdenum and nickel and leached mud are obtained after filtering; ammonium molybdate and nickel sulphate solution are obtained respectively after the leach solution undergoes extraction and back extraction by different back extraction agents. The method leaves out a calcining step existing in the conventional process, thereby avoiding the environmental pollution of gases such as SO2; by the oxygen pressure leaching, molybdenum and nickel in black carbonaceous shale containing molybdenum and nickel are directly converted and dissolved so as to generate molybdenum sulfate acyl((MoO2)SO4) and nickel sulfate(NiSO4) to enter the solution for enrichment, so that the method better realizes the separation and extraction of molybdenum and nickel and is a clean manufacturing technology with reinforced conversion; moreover, the principal process is not limited by changes of mineral compositions.
Description
Technical field
The present invention relates to a kind of from contain molybdenum nickel black look shale the method for separation molybdenum and nickel, belong to the chemical metallurgy technical field.
Background technology
The black yeath is created in the ancient stratum such as shake is adopted at the dawn, cold open system, Silurian; under the reducing environment of shallow sea, form the flammable mineral products of height matter degree by the fungus algae unicellular lower eukaryote; be characterized in ash-rich; low heat value, outward appearance such as black stone contain multiple metallic elements such as vanadium, molybdenum, nickel, phosphorus, copper, sulphur, iron, uranium.In some layer position, one or more associated elements reach industry mining grade or cut-off grade separately, can make certain mineral wealth and exploit separately, and reclaim valuable component by smelting.Exactly because the existence of these associated elements is comprehensively extracted value that valuable component creates often greater than the value that acts as a fuel.
Mainly be distributed in from the western Hunan at China's black yeath, through Jiangxi, Anhui two provinces, east is to the band in West Zhejiang Province, and wherein Yuanling-Changde district, Anhua-Ningxiang district, Linxiang-Chongyang district, Qian Xian-Shexian County district are that five in China contains vanadium black yeath area of rich ore deposits.And it is particularly abundant with the molybdenum nickel content in the ground black yeaths such as Dayong in Zhijin County, Guizhou Province, Nayong County, Jinsha County, Tongren City, Hunan Province, Zunyi ancestral home.As containing molybdenum 2.17%～4.56%, nickel 1.12%～1.67% in the bone coal ore deposit, the western Hunan, Hunan Province (Dayong celestial being's small stream), the molybdenum content in some bone coal ore deposit, Guizhou is up to 7%.
The material that contains the black carbonaceous shale ore of molybdenum nickel is formed complicated, and it is various that variation of valence is deposited in the occurrence status of molybdenum and nickel and tax, disperses tricklely, in same ore body, has multiple molybdenum ore thing and nickel mineral usually.Molybdenum in the black yeath is composed mostly and is stored in the sulfide, and in the pyrite association, is mainly molybdenum glance (MoS
2) and sulphur iron molybdenum ore ((Mo, Fe)
xS
y), other has part mainly to replace Al with class matter in-phase version
3+, Fe
3+Deng entering mica mineral and silicic acid salt face, other then are present in the organic matter with the organic form.Nickel in the bone coal is main relevant with independent mineral, sulfide (as pyrite), the clay mineral of nickel.Studies show that the nickel part in the bone coal is with millerite (NiS), two sulphur nickel minerals (NiS
2) and polydymite (Ni
3S
4) form exists, part replaces iron in the pyrite with pentlandite ((Ni, Fe) S
2) the form existence, part replaces the Al in silica octahedron " multiple stratum reticulare " and the alumina octahedral " single stratum reticulare "
3+, Fe
3+Deng the silicate, the silicoaluminate salt face that enter in the clay mineral, also there is the nickel of part and organo-functional group bonded organic in addition.Deposit with multiple valence state various ways tax just because of the molybdenum nickel in the bone coal, doping association mutually, and disseminated grain size is thinner, the argillization state is serious, the granularity thickness is extremely inhomogeneous, and microfine quartz and clay content are higher simultaneously, and the existence of molybdenum nickel presents characteristics such as complicacy, variation, changeableization, thereby the separation of the molybdenum nickel in the bone coal and enrichment are quite difficult and complicated.
At present, for the molybdenum-nickel paragenetic ore deposit because the technique of preparing horizontal constraints, extracting method mainly adopts traditional roasting-alkaline leaching or sodium carbonate roasting-water seaoning, the deficiency of these class methods is that metal recovery rate is low, cost is high, of poor benefits, environmental pollution is serious, and can only reclaim molybdenum separately, and can not reclaim nickel simultaneously, cause the serious waste of resource.
For molybdenum nickel mineral complicated and changeable in the black yeath that contains molybdenum nickel is extracted, on the principles of chemistry, must make insoluble molybdenum nickel, be converted into soluble molybdenum nickel compound or salt, from the mineral processes emphasis, then must make molybdenum nickel mineral complicated and changeable change single mineral into.At present, also there are not plant-scale technology and technology.
The patent No. is that 97107568.9 patent of invention " technology of yellow soda ash conversion processing separation molybdenum and nickel from black shale " provides a kind of technology with yellow soda ash conversion processing separation molybdenum and nickel from black shale, it is through desulphurizing roasting, size mixing, conversion, moltenly soak, purifying treatment and getting.It is characterized in that: earlier with black shale desulphurizing roasting and pulverizing, the yellow soda ash of adding 50% and 30% water are sized mixing, then through pyrolytic conversion, add water 100% molten soaking again, with clear water wash immersion liquid, the immersion liquid tailings gets nickel ore concentrate, the immersion liquid dephosphorization is purified again, filters, get clean liquid, handle promptly getting the calcium molybdate product salt through heavy molybdenum.Though this invention can realize molybdenum nickel and separate that nickel wherein still rests in the slag, fails to obtain further concentration and separation, and the desulphurizing roasting process environment is seriously polluted.
The patent No. be 99114737.5 patent of invention " extract the method for molybdenum and nickel salt from the molybdenum-nickel paragenetic ore deposit with diluted acid " and described a kind of hydrometallurgy field with diluted acid and oxygenant molybdenum-nickel paragenetic raw ore is directly leached the processing method of nickel molybdenum salt, comprise molybdenum-nickel paragenetic raw ore fragmentation ball milling, acidleach, filtration, extraction, reextraction and evaporation concentration etc.It is characterized in that raw ore through behind the ball milling, without roasting, is that molybdenum-nickel paragenetic raw ore is separated.Be specially a kind of processing method that molybdenum-nickel paragenetic raw ore is directly leached the molybdenum nickel salt with diluted acid and oxygenant, molybdenum nickel minerals raw ore is passed through broken ball milling, obtains ammonium molybdate with diluted acid and oxygenant leaching, filtration, filtrate extraction and reextraction then, raffinate solution obtains single nickel salt through extraction and reextraction again, and raffinate obtains the byproduct ferric ammonium sulfate through evaporation concentration.The grade 4.0～8.0% of raw ore molybdenum, the grade of nickel are 2.5～4.0%, sulphur～23%.The total yield of the molybdenum nickel of this inventive method is respectively 90%, 94%, but has the technological operation complexity, and reagent consumption is big, and cost is than problems such as height.
Above-mentioned treatment process at the molybdenum-nickel paragenetic ore deposit has oxidizing roasting or with the method for salt roasting process, SO
2Environmental pollution serious, produce a large amount of flue gases in the roasting process, serious environment pollution.Gu its roasting reaction of salt-roast-process is on solid-surface chemical reaction to take place substantially, and contain the low iron content sulfur content height of molybdenum nickel amount in the black yeath of molybdenum nickel (molybdenum content is 2～6%, nickel content 2.5～3% owing to contain, about iron 15%, about sulphur 20%), the addition of salt is limited, owing to molybdenum nickel mineral behavior complexity, this has just fundamentally limited the speed of response and the transformation efficiency of molybdenum nickel mineral simultaneously; Method with direct leaching, it is low that it leaches transformation efficiency, the system complexity.Thereby the deficiency that aforesaid method exists is the technical matters complexity, and metal recovery rate is low, and valuable metal disperses, and reagent consumption is big, and cost height, of poor benefits is difficult to overcome the complicacy of mineral, molybdenum nickel separation difficulty in the mineral, and environmental pollution is serious.
Summary of the invention
Technical problem to be solved by this invention provide a kind of from contain molybdenum nickel black look shale the method for separation molybdenum and nickel, its technical matters is simple, the metal recovery rate height, molybdenum nickel is easily separated, reagent consumption is little, valuable metal is concentrated, the low pollution.
Solving the scheme that technical problem of the present invention adopts is: after will containing molybdenum nickel black look shale pulverizing and jevigating, add the oxygen that acid, logical oxygen heats, pressurize and press leaching in autoclave pressure, obtain containing molybdenum, nickel leach liquor and leached mud after the filtration; Leach liquor obtains ammonium molybdate and nickel sulfate solution respectively after extraction and back extraction.
Concrete processing method of the present invention is:
(1) the black yeath is broken and be crushed to-200 orders more than or equal to 90%, adding sulfuric acid sizes mixing, control sulfuric acid concentration 100～250g/L, solid-liquid mass volume ratio 1: 2～6, be pumped into after sizing mixing in the autoclave pressure, feed industrial oxygen or air, 100 ℃～220 ℃ of control invert points, under still internal pressure 0.5MPa～4.0MPa condition, generate molybdenum trisulfate acyl (MoO
2) SO
4With single nickel salt NiSO
4And enter solution, after the liquid-solid separation enrichment the leach liquor of molybdenum and nickel;
(2) solution that will be rich in molybdenum nickel joins in the reservoir, and extraction agent P204+TBP is adopted in regulator solution pH=1.8～2.2,15 ℃～35 ℃ of control extraction temperature, and extraction phase directly extracts the solution that is rich in molybdenum nickel and enters organic phase than under 1: 1～3 the condition;
(3) reverse-extraction agent adopts NH
3H
2O, 30 ℃～50 ℃ of control reextraction temperature are stripped under 10～6: 1 the condition compared, and extract 20～40 minutes, and organic phase and ammonium molybdate solution obtain stripping.Ammonium molybdate solution obtains ammonium molybdate through evaporation concentration;
(4) reverse-extraction agent adopts H
2SO
4, 30 ℃～50 ℃ of control reextraction temperature are stripped under 12～8: 1 the condition compared, and extract 20 minutes～40 minutes, obtain nickel sulfate solution.Nickel sulfate solution obtains single nickel salt through evaporation concentration;
Described mineral leach the reaction times in autoclave pressure be 60 minutes～240 minutes; The extraction time is 10 minutes～30 minutes; The reverse-extraction agent of ammonium molybdate adopts the NH that contains weight percent 20%～25%
3H
2O, the reverse-extraction agent of single nickel salt adopts the H of 1.5mol/L～2.5mol/L
2SO
4
Each composition weight percent is molybdenum in the described mineral: nickel 1%～9%: iron 0.5%～5.0%: sulphur 3%～18%: 5%～25%; Leach used sulfuric acid concentration and be 90%～93% industrial sulphuric acid.
The invention has the beneficial effects as follows:
Because the hot-pressure oxidation process is under pressurized state, the oxidising process temperature is brought up to 100～220 ℃, water is as liquid medium, under the effect of dissolved in leaching agent and water [O], elements such as molybdenum nickel in the complicated mineral composition in the black shale are carried out the oxidation conversion reaction, generate easily molten compound, to become with the method for complicated technology of selecting according to mineralogical property in the salt high-temperature roasting technology and leaching makes complicated mineral change the process of easily dissolving compound in the pressure oxidation process, the smelting metallization processes is simplified, process intensification has realized that complicated molybdenum nickel minerals in the black shale is oxidized to the molybdenum nickel compound of Yi Rong.
Method of the present invention has been saved the calcining process of traditional technology, has avoided SO
2Deng the pollution of flue gas to environment; Press acidleach to go out by oxygen, directly transform and dissolve the molybdenum and the nickel that contain in the molybdenum nickel black look yeath and generate molybdenum trisulfate acyl ((MoO
2) SO
4) and single nickel salt (NiSO
4) enter solution and enrichment, realized the separation and Extraction of molybdenum nickel preferably.Therefore, involved in the present invention from contain molybdenum nickel black look shale the method for separation molybdenum and nickel be a kind of clearer production technology of intensified transformation, and its main process is not subjected to the variation of mineral composition and restricts.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Example one:
1. raw material: molybdenum content is 6.32%, nickel content 3.05%, iron level 15.27%, sulphur content 21.58%, and is broken and pulverize-200 orders (〉=90%).
2. adding concentration and be 90～93% industrial sulphuric acid sizes mixing, control sulfuric acid concentration 200g/L, solid-liquid mass volume ratio 1: 4, be pumped into after sizing mixing in the autoclave pressure, feed industrial oxygen, 150 ℃ of control invert points, under still internal pressure 1.5MPa condition, leach reaction 240 minutes, filter and obtain leached mud and infusion solution, wherein the infusion solution enrichment molybdenum and nickel.
Molybdenum leaching yield: 90.37% nickel leaching yield: 95.69%
3. the solution that will be rich in molybdenum nickel joins in the reservoir, and regulator solution pH=2.06 adopts extraction agent P204+TBP commonly used, and 25 ℃ of control extraction temperature under the condition of extraction phase than 1: 2, extracted 20 minutes, directly extracted the solution that is rich in molybdenum nickel and entered organic phase.
Molybdenum percentage extraction: 94.38% nickel percentage extraction: 93.91%
4. extracted organic phase adopts 20～25% NH
3H
2O, 50 ℃ of control reextraction temperature are stripped under the condition of comparing 8: 1, extract 30 minutes, and organic phase and ammonium molybdate solution obtain stripping.Ammonium molybdate solution obtains ammonium molybdate through evaporation concentration.
Molybdenum back extraction ratio: the 94.25% ammonium molybdate rate of recovery: 98.33%
5. reextraction organic phase adopts the H of 2.0mol/L
2SO
4, 50 ℃ of control reextraction temperature are stripped under the condition of comparing 10: 1, extract 30 minutes, obtain nickel sulfate solution.Nickel sulfate solution obtains single nickel salt through evaporation concentration.
Nickel back extraction ratio: the 98.17% single nickel salt rate of recovery: 97.31%
Example two:
1. raw material: molybdenum content is 5.92%, nickel content 3.17%, iron level 16.69%, sulphur content 17.88%, and is broken and pulverize-200 orders (〉=90%).
2. adding concentration and be 90～93% industrial sulphuric acid sizes mixing, control sulfuric acid concentration 100g/L, solid-liquid mass volume ratio 1: 6, be pumped into after sizing mixing in the autoclave pressure, feed industrial oxygen, 200 ℃ of control invert points, under still internal pressure 3.0MPa condition, leach reaction 60 minutes, filter and obtain leached mud and infusion solution, wherein the infusion solution enrichment molybdenum and nickel.
Molybdenum leaching yield: 82.16% nickel leaching yield: 91.73%
3. the solution that will be rich in molybdenum nickel joins in the reservoir, and regulator solution pH=2.13 adopts extraction agent P204+TBP commonly used, and 15 ℃ of control extraction temperature under the condition of extraction phase than 1: 1, extracted 10 minutes, directly extracted the solution that is rich in molybdenum nickel and entered organic phase.
Molybdenum percentage extraction: 97.28% nickel percentage extraction: 96.91%
4. extracted organic phase adopts 20～25% NH
3H
2O, 30 ℃ of control reextraction temperature are stripped under the condition of comparing 10: 1, extract 40 minutes, and organic phase and ammonium molybdate solution obtain stripping.Ammonium molybdate solution obtains ammonium molybdate through evaporation concentration.
Molybdenum back extraction ratio: the 92.64% ammonium molybdate rate of recovery: 98.17%
5. reextraction organic phase adopts the H of 1.5mol/L
2SO
4, 30 ℃ of control reextraction temperature are stripped under the condition of comparing 12: 1, extract 40 minutes, obtain nickel sulfate solution.Nickel sulfate solution obtains single nickel salt through evaporation concentration.
Nickel back extraction ratio: the 95.27% single nickel salt rate of recovery: 98.08%
Example three:
1. raw material: molybdenum content is 4.58%, nickel content 2.79%, iron level 7.37%, sulphur content 23.16%, and is broken and pulverize-200 orders (〉=90%).
2. adding concentration and be 90～93% industrial sulphuric acid sizes mixing, control sulfuric acid concentration 250g/L, solid-liquid mass volume ratio 1: 2, be pumped into after sizing mixing in the autoclave pressure, feed anhydrous air, 100 ℃ of control invert points, under still internal pressure 1.0MPa condition, leach reaction 150 minutes, filter and obtain leached mud and infusion solution, wherein the infusion solution enrichment molybdenum and nickel.
Molybdenum leaching yield: 86.28% nickel leaching yield: 95.33%
3. the solution that will be rich in molybdenum nickel joins in the reservoir, and regulator solution pH=1.92 adopts extraction agent P204+TBP commonly used, and 35 ℃ of control extraction temperature under the condition of extraction phase than 1: 3, extracted 30 minutes, directly extracted the solution that is rich in molybdenum nickel and entered organic phase.
Molybdenum percentage extraction: 91.03% nickel percentage extraction: 90.72%
4. extracted organic phase adopts 20～25% NH
3H
2O, 40 ℃ of control reextraction temperature are stripped under the condition of comparing 6: 1, extract 20 minutes, and organic phase and ammonium molybdate solution obtain stripping.Ammonium molybdate solution obtains ammonium molybdate through evaporation concentration.
Molybdenum back extraction ratio: the 95.58% ammonium molybdate rate of recovery: 98.26%
5. reextraction organic phase adopts the H of 2.5mol/L
2SO
4, 40 ℃ of control reextraction temperature are stripped under the condition of comparing 8: 1, extract 20 minutes, obtain nickel sulfate solution.Nickel sulfate solution obtains single nickel salt through evaporation concentration.
Nickel back extraction ratio: the 98.48% single nickel salt rate of recovery: 98.50%.
Claims (4)
1. the method for a separation molybdenum and nickel from contain molybdenum nickel black look shale is characterized in that: after will containing molybdenum nickel black look shale pulverizing and jevigating, add acid in autoclave pressure, lead to the oxygen pressure leaching that oxygen heats, pressurizes, obtain containing molybdenum, nickel leach liquor and leached mud after the filtration; Leach liquor obtains ammonium molybdate and nickel sulfate solution respectively after extraction and back extraction.
2. according to claim 1 a kind of from contain molybdenum nickel black look shale the method for separation molybdenum and nickel, it is characterized in that concrete steps are:
(1) the black yeath is broken and be crushed to-200 orders more than or equal to 90%, adding sulfuric acid sizes mixing, control sulfuric acid concentration 100～250g/L, solid-liquid mass volume ratio 1: 2～6, be pumped into after sizing mixing in the autoclave pressure, feed industrial oxygen or air, 100 ℃～220 ℃ of control invert points, under still internal pressure 0.5MPa～4.0MPa condition, generate molybdenum trisulfate acyl (MoO
2) SO
4With single nickel salt NiSO
4And enter solution, after the liquid-solid separation enrichment the leach liquor of molybdenum and nickel;
(2) solution that will be rich in molybdenum nickel joins in the reservoir, and extraction agent P204+TBP is adopted in regulator solution pH=1.8～2.2,15 ℃～35 ℃ of control extraction temperature, and extraction phase directly extracts the solution that is rich in molybdenum nickel and enters organic phase than under 1: 1～3 the condition;
(3) reverse-extraction agent adopts NH
3H
2O, 30 ℃～50 ℃ of control reextraction temperature are stripped under 10～6: 1 the condition compared, and extract 20～40 minutes, and organic phase and ammonium molybdate solution obtain stripping.Ammonium molybdate solution obtains ammonium molybdate through evaporation concentration;
(4) reverse-extraction agent adopts H
2SO
4, 30 ℃～50 ℃ of control reextraction temperature are stripped under 12～8: 1 the condition compared, and extract 20 minutes～40 minutes, obtain nickel sulfate solution.Nickel sulfate solution obtains single nickel salt through evaporation concentration.
3. according to claim 2 a kind of from contain molybdenum nickel black look shale the method for separation molybdenum and nickel, it is characterized in that: mineral leach the reaction times in autoclave pressure be 60 minutes～240 minutes; The extraction time is 10～30 minutes; The reverse-extraction agent of ammonium molybdate adopts the NH that contains weight percent 20%～25%
3H
2O, the reverse-extraction agent of single nickel salt adopts the H of 1.5mol/L～2.5mol/L
2SO
4
4. according to claim 1 a kind of from contain molybdenum nickel black look shale the method for separation molybdenum and nickel, it is characterized in that: contain following component in percentage by weight in the mineral: molybdenum 1%～9%, nickel 0.5%～5.0%, iron 3～18%, sulphur 5～23%; Leach used sulfuric acid concentration and be 90%～93% industrial sulphuric acid.
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