CN101481754A - Method for separating molybdenum and nickel in molybdenum- and nickel-containing black shale - Google Patents
Method for separating molybdenum and nickel in molybdenum- and nickel-containing black shale Download PDFInfo
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- CN101481754A CN101481754A CNA2009100941038A CN200910094103A CN101481754A CN 101481754 A CN101481754 A CN 101481754A CN A2009100941038 A CNA2009100941038 A CN A2009100941038A CN 200910094103 A CN200910094103 A CN 200910094103A CN 101481754 A CN101481754 A CN 101481754A
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- molybdenum
- nickel
- leach
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- shale
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 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 35
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 title claims description 64
- 238000000034 method Methods 0.000 title abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 12
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 12
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 12
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 238000000746 purification Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000002893 slag Substances 0.000 claims description 14
- 150000002815 nickel Chemical class 0.000 claims description 12
- 238000004513 sizing Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 7
- 238000010276 construction Methods 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 22
- 235000010755 mineral Nutrition 0.000 abstract description 22
- 239000011707 mineral Substances 0.000 abstract description 22
- 238000002386 leaching Methods 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 19
- 238000005516 engineering process Methods 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000003546 flue gas Substances 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 abstract 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 12
- 239000003245 coal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 210000000988 bone and bone Anatomy 0.000 description 7
- 239000002184 metal Substances 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
- 238000000605 extraction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 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
- 230000007812 deficiency Effects 0.000 description 3
- 238000007654 immersion 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
- 230000009466 transformation Effects 0.000 description 3
- 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
- 238000003672 processing method Methods 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 238000003723 Smelting Methods 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 238000009854 hydrometallurgy Methods 0.000 description 1
- ADULOCGXJMPDRK-UHFFFAOYSA-N iron;sulfanylidenemolybdenum Chemical compound [Fe].[Mo]=S ADULOCGXJMPDRK-UHFFFAOYSA-N 0.000 description 1
- 238000001465 metallisation 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
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052954 pentlandite Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 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
- 238000002791 soaking Methods 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 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 in black shale containing molybdenum and nickel, and belongs to the technical field of chemical metallurgy. The process of the method comprises the following steps: firstly, crushing and grinding the black shale containing molybdenum and nickel; size mixing by adding alkali materials; carrying out the process of oxygen pressure alkali leaching in a pressure kettle; filtering to obtain molybdenum-containing leaching solution and nickel-containing leaching residue; carrying out the molybdenum precipitation treatment on the one-stage molybdenum-containing leaching solution to obtain ammonium molybdate; then, size-mixing the one-stage leaching residue in the presence of sulfuric acid; carrying out the process of two-stage oxygen pressure acid leaching in the pressure kettle; filtering to obtain nickel leaching solution and two-stage leaching residue; and subjecting the two-stage nickel-containing leaching solution to iron purification and evaporating concentration to obtain nickel sulfate. The invention gets rid of the procedure of calcination, thereby preventing flue gases, such as SO2 and the like, from causing environmental pollution; the process of two-stage oxygen pressure leaching is favorable for the generation of ammonium molybdate and nickel sulfate from molybdenum and nickel respectively so as to enter different solutions for enrichment; molybdenum and nickel can be better separated and recovered; and the qualified tailings can be obtained. The method belongs to the clean production technology for intensifying the conversion, and the main process is free from the variation of the mineral composition.
Description
Technical field
The present invention relates to a kind of separation method that contains molybdenum nickel in the molybdenum nickel black look shale, belong to the chemical metallurgy technical field.
Background technology
A kind of black shale is arranged in the stratum ancient times morning on ground such as western part, China Zhejiang, south, Anhui, Jiangxi, Hunan, western part, Hubei, the west and south, Henan, south, Shaanxi, northeast, Guizhou, be commonly called as " bone coal ", " bone coal " comes down to a kind of carbon shale that contains, and do not belong to coal.The black yeath contains organism seldom, thermal value is very low, and ash content very high (far above 40%) contains valuable metal elements such as vanadium, molybdenum, nickel, phosphorus, copper, sulphur, iron, uranium simultaneously, thereby black yeath essence is a kind of complex multi-metal mineral that contain multiple metallic element.The black yeath is created in the ancient stratum such as shake is adopted at the dawn, cold open system, Silurian, forms the highly flammable mineral products of matter degree by the fungus algae unicellular lower eukaryote under the reducing environment of shallow sea.At Zhijin County, China Guizhou Province, Nayong County, Jinsha County, Tongren City, Zunyi, a large amount of black yeaths that contains molybdenum nickel is contained on ground such as the Dayong in Hunan Province.The black yeath that contains molybdenum nickel is a molybdenum nickel mineral resource, thereby the black yeath that contains molybdenum nickel also just becomes the important mineral wealth of extraction molybdenum nickel.
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 bone coal 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 Fe 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 the present invention can realize molybdenum nickel and separate, and the rate of recovery of molybdenum can reach more than 90%, and the rate of recovery of nickel can reach 98%, and nickel wherein still rests in the slag, fails to obtain further concentration and separation; 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 the technological operation complexity, reagent consumption is big, and cost is higher.
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 it is low owing to containing molybdenum nickel amount in the black yeath that contains molybdenum nickel, (molybdenum content is 2～6% to iron content sulfur content height, nickel content 2.5～3%, iron level 3～18%, sulphur content 5～23%), 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.
Therefore, contain the research of molybdenum nickel black look yeath extraction separation molybdenum nickel technical matters, exploitation is fit to the process for cleanly preparing of resource and environment demand for development, walks the sustainable development road, has crucial economy and social effect.
Summary of the invention:
The objective of the invention is to overcome the deficiency of art methods, provide a kind of technical matters simple, the metal recovery rate height, molybdenum nickel is easily separated, and reagent consumption is little, and valuable metal is concentrated, the oligosaprobic separation method that contains molybdenum nickel in the molybdenum nickel black look shale.
Technical scheme of the present invention is: after will containing molybdenum nickel black look shale pulverizing and jevigating earlier, adding alkaline material sizes mixing, one section oxygen presses alkali to leach in autoclave pressure, obtains containing molybdenum leach liquor and nickeliferous leached mud after the filtration, and one section contains the molybdenum leach liquor and promptly gets ammonium molybdate through heavy molybdenum processing; Then one section leached mud sulfuric acid is sized mixing, two sections oxygen press acidleach to go out in the autoclave pressure, obtain nickeliferous leach liquor and two sections leached muds after the filtration, and two sections nickeliferous leach liquors obtain single nickel salt through iron purification, evaporation concentration.
Concrete technical scheme of the present invention also comprises: the processing condition that described one section oxygen presses alkali to leach are, containing in the molybdenum nickel black look shale and adding mass percentage concentration is that 30%～50% calcined soda for industry and mass percentage concentration are that 10%～20% caustic soda is sized mixing, control solid-liquid mass volume ratio 1:2～4, be pumped in the autoclave pressure after sizing mixing, feed industrial oxygen or anhydrous air, 100 ℃～220 ℃ of control invert points, under still internal pressure 0.5MPa～4.0MPa condition, leach reaction 60 minutes～240 minutes, filtration obtains one section and contains molybdenum leach liquor and one section nickeliferous leached mud.
The processing condition that described two sections oxygen press acidleach to go out are: with one section nickeliferous leached mud through the two-stage washing, to filter back and concentration be that mass percentage concentration is that 90%～93% industrial sulphuric acid is sized mixing, control sulfuric acid concentration 100g/L～250g/L, solid-liquid mass volume ratio 1:2～6, be pumped in the autoclave pressure after sizing mixing, feed industrial oxygen or air, 100 ℃～200 ℃ of control invert points, under still internal pressure 0.5MPa～2.5MPa condition, leach reaction 60 minutes～240 minutes, filter and obtain two sections nickeliferous leach liquors and two sections leached muds.
The described composition that contains the black yeath raw material of molybdenum nickel is, molybdenum content is 1%～9%, nickel content is 0.5%～5.0%, iron level 3%～18%, sulphur content 5%～23%; Feed size behind the shale pulverizing and jevigating is that 200 orders are more than or equal to 90%.
The finishing slag that described two sections leached muds obtain through two-stage washing, after filtering is as waste, or is used as the starting material of material of construction.
Realize that concrete processing parameter of the present invention and step are:
(1) (molybdenum content is 1%～9% will to contain the black yeath of molybdenum nickel, nickel content is 0.5%～5.0%, iron level 3%～18%, sulphur content 5%～23%) broken and be crushed to 200 orders (〉=90%), adding mass percentage concentration and be 30%～50% calcined soda for industry and mass percentage concentration and be 10%～20% caustic soda sizes mixing, control solid-liquid mass volume ratio 1:2～4, be pumped in the autoclave pressure after sizing mixing, feed industrial oxygen or anhydrous air, 100 ℃～220 ℃ of control invert points, under still internal pressure 0.5MPa～4.0MPa condition, leach reaction 60 minutes～240 minutes, carry out one section oxygen and press alkali to leach.
(2) filter and to obtain one section and contain molybdenum leach liquor and one section nickeliferous leached mud, one section contains the molybdenum leach liquor and handles through heavy molybdenum and promptly get ammonium molybdate.
(3) with one section nickeliferous leached mud through two-stage washing, to filter back and mass percentage concentration be that 90%～93% industrial sulphuric acid is sized mixing, control sulfuric acid concentration 100g/L～250g/L, solid-liquid mass volume ratio 1:2～6, be pumped in the autoclave pressure after sizing mixing, feed industrial oxygen or air, 100～200 ℃ of control invert points are under still internal pressure 0.5MPa～2.5MPa condition, leach reaction 60 minutes～240 minutes, carry out two sections oxygen and press acidleach to go out.
(4) filtration obtains two sections nickeliferous leach liquors and two sections leached muds, and two sections nickeliferous leach liquors obtain single nickel salt through iron purification, evaporation concentration.
(5) two sections leached muds are obtained finishing slag after two-stage washing, filtration, finishing slag is a waste, or becomes the starting material of doing material of construction.
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 100～200 ℃, 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.
Two sections oxygen are pressed the method that leaches separation molybdenum and nickel from contain molybdenum nickel black look yeath, and no calcining process has been avoided SO
2Deng the pollution of flue gas to environment; Press by two sections oxygen and to leach, directly transform and dissolve that the molybdenum that contains in the molybdenum nickel black look yeath and nickel generate that Sodium orthomolybdate and single nickel salt enter different solutions and enrichment has realized the better separation and the recovery of molybdenum nickel, and obtain qualified tailings.Therefore, it is a kind of clearer production technology of intensified transformation that pressure oxidation transforms, and its main process is not subjected to the variation of mineral composition and restricts.
Specific embodiment:
Example one:
1. raw material: molybdenum content is 6.32%, nickel content 3.05%, iron level 8.27%, sulphur content 21.58%, broken 200 orders (〉=90%) that also are crushed to.
2. one section oxygen presses alkali to leach: add mass percentage concentration and be 50% calcined soda for industry and mass percentage concentration and be 10% caustic soda and size mixing, control solid-liquid mass volume ratio 1:4, be pumped in the autoclave pressure after sizing mixing, feed industrial oxygen, 150 ℃ of control invert points, under still internal pressure 1.6MPa condition, leach reaction 180 minutes.Filtration obtains one section and contains molybdenum leach liquor and one section nickeliferous leached mud, and one section contains the molybdenum leach liquor and promptly gets ammonium molybdate through heavy molybdenum processing.
Molybdenum leaching yield: the 90.37% ammonium molybdate rate of recovery: 98.69%
3. two sections oxygen press acidleach to go out: with one section nickeliferous leached mud through the two-stage washing, to filter back and mass percentage concentration be that 90～93% industrial sulphuric acid is sized mixing, control sulfuric acid concentration 200g/L, solid-liquid mass volume ratio 1:4, be pumped in the autoclave pressure after sizing mixing, feed industrial oxygen, 150 ℃ of control invert points under still internal pressure 1.5MPa condition, leach reaction 240 minutes.Filtration obtains two sections nickeliferous leach liquors and two sections leached muds, and two sections nickeliferous leach liquors obtain single nickel salt through iron purification, evaporation concentration.
Nickel leaching yield: the 97.28% single nickel salt rate of recovery: 98.91%
4. finishing slag: two sections leached muds are obtained finishing slag through the two-stage washing, after filtering, and finishing slag is a waste, or becomes the starting material of doing material of construction.
Example two:
1. raw material: molybdenum content is 5.92%, nickel content 3.17%, iron level 15.69%, sulphur content 13.88%, broken 200 orders (〉=90%) that also are crushed to.
2. one section oxygen presses alkali to leach: add mass percentage concentration and be 40% calcined soda for industry and mass percentage concentration and be 20% caustic soda and size mixing, control solid-liquid mass volume ratio 1:3, be pumped in the autoclave pressure after sizing mixing, feed industrial oxygen, 220 ℃ of control invert points, under still internal pressure 3.5MPa condition, leach reaction 90 minutes.Filtration obtains one section and contains molybdenum leach liquor and one section nickeliferous leached mud, and one section contains the molybdenum leach liquor and promptly gets ammonium molybdate through heavy molybdenum processing.
Molybdenum leaching yield: the 94.25% ammonium molybdate rate of recovery: 99.31%
3. two sections oxygen press acidleach to go out: with one section nickeliferous leached mud through the two-stage washing, to filter back and mass percentage concentration be that 90～93% industrial sulphuric acid is sized mixing, control sulfuric acid concentration 250g/L, solid-liquid mass volume ratio 1:2, be pumped in the autoclave pressure after sizing mixing, feed industrial oxygen, 100 ℃ of control invert points under still internal pressure 1.0MPa condition, leach reaction 120 minutes.Filtration obtains two sections nickeliferous leach liquors and two sections leached muds, and two sections nickeliferous leach liquors obtain single nickel salt through iron purification, evaporation concentration.
Nickel leaching yield: the 87.94% single nickel salt rate of recovery: 96.19%
4. finishing slag: two sections leached muds are obtained finishing slag through the two-stage washing, after filtering, and finishing slag is a waste, or becomes the starting material of doing material of construction.
Example three:
1. raw material: molybdenum content is 4.58%, nickel content 2.79%, iron level 17.37%, sulphur content 23.0%, broken 200 orders (〉=90%) that also are crushed to.
2. one section oxygen presses alkali to leach: add mass percentage concentration and be 30% calcined soda for industry and mass percentage concentration and be 20% caustic soda and size mixing, control solid-liquid mass volume ratio 1:2, be pumped in the autoclave pressure after sizing mixing, feed anhydrous air, 100 ℃ of control invert points, under still internal pressure 0.8MPa condition, leach reaction 120 minutes.Filtration obtains one section and contains molybdenum leach liquor and one section nickeliferous leached mud, and one section contains the molybdenum leach liquor and promptly gets ammonium molybdate through heavy molybdenum processing.
Molybdenum leaching yield: the 75.17% ammonium molybdate rate of recovery: 94.95%
3. two sections oxygen press acidleach to go out: with one section nickeliferous leached mud through the two-stage washing, to filter back and mass percentage concentration be that 90～93% industrial sulphuric acid is sized mixing, control sulfuric acid concentration 100g/L, solid-liquid mass volume ratio 1:6, be pumped in the autoclave pressure after sizing mixing, feed anhydrous air, 200 ℃ of control invert points under still internal pressure 2.5MPa condition, leach reaction 90 minutes.Filtration obtains two sections nickeliferous leach liquors and two sections leached muds, and two sections nickeliferous leach liquors obtain single nickel salt through iron purification, evaporation concentration.
Nickel leaching yield: the 91.29% single nickel salt rate of recovery: 97.55%
4. finishing slag: two sections leached muds are obtained finishing slag through the two-stage washing, after filtering, and finishing slag is a waste, or becomes the starting material of doing material of construction.
Claims (5)
1. separation method that contains molybdenum nickel in the molybdenum nickel black look shale, it is characterized in that: after will containing molybdenum nickel black look shale pulverizing and jevigating earlier, adding alkaline material sizes mixing, one section oxygen presses alkali to leach in autoclave pressure, obtain containing molybdenum leach liquor and nickeliferous leached mud after the filtration, one section contains the molybdenum leach liquor and promptly gets ammonium molybdate through heavy molybdenum processing; Then one section leached mud sulfuric acid is sized mixing, two sections oxygen press acidleach to go out in the autoclave pressure, obtain nickeliferous leach liquor and two sections leached muds after the filtration, and two sections nickeliferous leach liquors obtain single nickel salt through iron purification, evaporation concentration.
2. the separation method that contains molybdenum nickel in the molybdenum nickel black look shale according to claim 1, it is characterized in that: the processing condition that described one section oxygen presses alkali to leach are, containing in the molybdenum nickel black look shale and adding mass percentage concentration is that 30%～50% calcined soda for industry and mass percentage concentration are that 10%～20% caustic soda is sized mixing, control solid-liquid mass volume ratio 1:2～4, be pumped in the autoclave pressure after sizing mixing, feed industrial oxygen or anhydrous air, 100 ℃～220 ℃ of control invert points, under still internal pressure 0.5MPa～4.0MPa condition, leach reaction 60 minutes～240 minutes, filtration obtains one section and contains molybdenum leach liquor and one section nickeliferous leached mud.
3. the separation method that contains molybdenum nickel in the molybdenum nickel black look shale according to claim 1, it is characterized in that: the processing condition that described two sections oxygen press acidleach to go out are, one section nickeliferous leached mud is washed through two-stage, filtering back and concentration and be mass percentage concentration and be 90%～93% industrial sulphuric acid sizes mixing, control sulfuric acid concentration 100g/L～250g/L, solid-liquid mass volume ratio 1:2～6, be pumped in the autoclave pressure after sizing mixing, feed industrial oxygen or air, 100 ℃～200 ℃ of control invert points, under still internal pressure 0.5MPa～2.5MPa condition, leach reaction 60 minutes～240 minutes, filter and obtain two sections nickeliferous leach liquors and two sections leached muds.
4. according to claim 2 or the 3 described separation methods that contain molybdenum nickel in the molybdenum nickel black look shale, it is characterized in that: the described composition that contains the black yeath raw material of molybdenum nickel is, molybdenum content is 1%～9%, nickel content is 0.5%～5.0%, iron level 3%～18%, sulphur content 5%～23%; Feed size behind the shale pulverizing and jevigating is that 200 orders are more than or equal to 90%.
5. the separation method that contains molybdenum nickel in the molybdenum nickel black look shale according to claim 4 is characterized in that: the finishing slag that described two sections leached muds obtain through two-stage washing, after filtering is as waste, or is used as the starting material of material of construction.
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| CN101717858B (en) * | 2009-12-22 | 2012-10-24 | 重庆拓必拓钼业有限公司 | Method for extracting molybdenum, nickel, vanadium and ferrum from polymetallic black-shale paragentic minerals |
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| CN102000446A (en) * | 2010-10-22 | 2011-04-06 | 上海福贝宠物用品有限公司 | Preparation technique of pancake rock stock solution |
| CN102000446B (en) * | 2010-10-22 | 2012-09-19 | 上海福贝宠物用品有限公司 | Preparation technique of pancake rock stock solution |
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| CN102433433B (en) * | 2011-12-29 | 2013-06-19 | 昆明冶金研究院 | Whole-wet method treatment process for extracting and preparing Mo and Ni products from refractory Mo-Ni ore |
| CN105925796A (en) * | 2016-04-29 | 2016-09-07 | 昆明理工大学 | Method for separating and recycling nickel-molybdenum iron from black rock series nickel-molybdenum iron sulfide ores |
| CN111154977A (en) * | 2020-02-06 | 2020-05-15 | 中国恩菲工程技术有限公司 | Method for treating valuable metal sulfide concentrate |
| CN111154977B (en) * | 2020-02-06 | 2022-08-12 | 中国恩菲工程技术有限公司 | Method for treating valuable metal sulfide concentrate |
| CN111826534A (en) * | 2020-07-16 | 2020-10-27 | 江西铜业股份有限公司 | Method for recovering molybdenum from low-molybdenum ammonia leaching residue |
| CN111778404A (en) * | 2020-08-14 | 2020-10-16 | 眉山顺应动力电池材料有限公司 | Leaching separation method of nickel-cobalt-molybdenum-phosphorus-vanadium alloy material |
| CN116516148A (en) * | 2023-06-29 | 2023-08-01 | 矿冶科技集团有限公司 | Method for producing molybdic acid and high nickel matte from molybdenum-nickel ore |
| CN116516148B (en) * | 2023-06-29 | 2023-10-17 | 矿冶科技集团有限公司 | Method for producing molybdic acid and high nickel matte from nickel-molybdenum ore |
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