CN109097562A - A kind of method of lateritic nickel ore selectivity sulfidation roasting - Google Patents
A kind of method of lateritic nickel ore selectivity sulfidation roasting Download PDFInfo
- Publication number
- CN109097562A CN109097562A CN201810787258.9A CN201810787258A CN109097562A CN 109097562 A CN109097562 A CN 109097562A CN 201810787258 A CN201810787258 A CN 201810787258A CN 109097562 A CN109097562 A CN 109097562A
- Authority
- CN
- China
- Prior art keywords
- nickel ore
- lateritic nickel
- nickel
- roasting
- sulfidation
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 269
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 134
- 238000000034 method Methods 0.000 title claims abstract description 64
- 238000005486 sulfidation Methods 0.000 title claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052742 iron Inorganic materials 0.000 claims abstract description 45
- 238000005188 flotation Methods 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- -1 alkali metal salt Chemical class 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229910001710 laterite Inorganic materials 0.000 claims abstract description 6
- 239000011504 laterite Substances 0.000 claims abstract description 6
- 238000005453 pelletization Methods 0.000 claims description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000005864 Sulphur Substances 0.000 claims description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 7
- 239000003610 charcoal Substances 0.000 claims description 6
- 239000000571 coke Substances 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 239000012991 xanthate Substances 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- UOJYYXATTMQQNA-UHFFFAOYSA-N Proxan Chemical compound CC(C)OC(S)=S UOJYYXATTMQQNA-UHFFFAOYSA-N 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000000440 bentonite Substances 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052683 pyrite Inorganic materials 0.000 claims description 2
- 239000011028 pyrite Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 24
- 238000007885 magnetic separation Methods 0.000 abstract description 15
- 238000005265 energy consumption Methods 0.000 abstract description 10
- 239000008188 pellet Substances 0.000 abstract 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 22
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 16
- 239000012141 concentrate Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000004321 preservation Methods 0.000 description 12
- 229940056319 ferrosoferric oxide Drugs 0.000 description 11
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 10
- 238000002386 leaching Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 229910000863 Ferronickel Inorganic materials 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- CNJLMVZFWLNOEP-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[4.1.0]heptan-5-one Chemical compound O=C1C(C)CCC2C(C)(C)C12 CNJLMVZFWLNOEP-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910001569 aluminium mineral Inorganic materials 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- QWENMOXLTHDKDL-UHFFFAOYSA-N pentoxymethanedithioic acid Chemical compound CCCCCOC(S)=S QWENMOXLTHDKDL-UHFFFAOYSA-N 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
- C22B1/216—Sintering; Agglomerating in rotary furnaces
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
- C22B1/245—Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明公开了一种红土镍矿选择性硫化焙烧的方法，该方法是将红土镍矿与包含碳质还原剂、硫化剂、碱金属盐添加剂和粘结剂在内的原料混匀造球，所得球团料依次在低温下进行一段焙烧和在高温下进行二段焙烧；焙烧料通过浮选法回收镍产品，浮选尾矿采用磁选法回收铁产品，该方法对镍和铁回收效果好，能源消耗少、成本低、工艺简单，有利于工业化大规模生产应用。The invention discloses a method for selective sulfidation and roasting of laterite nickel ore. The method is to uniformly mix the laterite nickel ore with raw materials including carbonaceous reducing agent, vulcanizing agent, alkali metal salt additive and binder to form pellets. The obtained pellets are subjected to one-stage roasting at low temperature and second-stage roasting at high temperature in sequence; nickel products are recovered from the roasted material by flotation, and iron products are recovered from flotation tailings by magnetic separation. Well, it has less energy consumption, low cost and simple process, which is beneficial to industrialized large-scale production and application.
Description
Technical field
It is the present invention relates to a kind of processing method of lateritic nickel ore, in particular to a kind of that lateritic nickel ore is passed through into reduction-vulcanization
Roasting is selectively convertered nickel at the nickel sulfide ore for being easy to FLOTATION SEPARATION, and iron is selectively convertered into the magnet for being easy to magnetic separation separation
The method of mine, belongs to non-ferrous metallurgy technology and ore dressing field.
Background technique
Nickel is a kind of important strategy metal material, is widely used in stainless steel production, alloy manufacture, new energy battery
Production etc..About 4.7 hundred million tons of world's nickel resources reserves, lateritic nickel ore accounts for 70%, and nickel sulfide ore accounts for 30%, and in the world 60%
Nickel is by extracting in nickel sulfide ore, but with increasingly depleted, the economic space structure of lateritic nickel ore of nickel sulfide ore resource
Increasingly paid attention to.Lateritic nickel ore is broadly divided into two class of limonite type and silicon magnesium types according to deposit type, at present lateritic nickel ore
Smelting process mainly have thermal process and wet processing.
Thermal process mainly has reduction melting ferronickel technique, and reduction melting prepares nickel matte technique.Ferronickel technique is by laterite
The melting at 1550 DEG C~1600 DEG C of electric furnace after nickel minerals drying, prereduction, can get nickel grade is the ferronickel on 25%, the technique
Process is short, Technological adaptability is strong, and nickel recovery is high, the high-quality ferronickel of high-grade can be mass produced, production process almost without
The advantages that waste residue, waste water generate, but energy consumption is big, and environmental pollution is serious, and can not recycle the cobalt in raw material, to cobalt content ratio
Higher mine is simultaneously not suitable with.Nickel matte technique is that vulcanizing agent is added during producing 1550 DEG C~1600 DEG C of smeltings of ferronickel technique
The low nickel matte of output, then by bessemerizing the high nickel matte of production, which realizes the comprehensive utilization of cobalt resource, can produce various
The nickel product of form, process flow are short, easy to operate；But smelting process needs to consume a large amount of good coke, and energy consumption is very high；It produces
Raw sulfur dioxide pernicious gas environmental pollution is very big, and adaptability to raw material is poor.
Wet processing mainly has reduction-ammonia soaking technology, high pressure acidleach and normal pressure acid leaching process.Reduction-ammonia soaking technology is also known as
Caron process, the technique pass through reduction roasting first and nickel in lateritic nickel ore and cobalt are reduced into metal simple-substance, then use ammonia-
Sal volatile leaching nickel and cobalt, to realize efficiently separating for nickel cobalt and gangue；Nickel quality point in the nickel block of technique production
Number is up to 90%, and the rate of recovery of whole process nickel is up to 75%~80%.Compared with pyrometallurgical smelting process, cobalt can be partially recycled, returns
Yield 40%~50%.But ammonia leaching process is only suitable for handling the laterite on lateritic nickel ore bed upper layer, is not suitable for processing lower layer's silicon magnesium and contains
Measure high ore bed.High pressure acid leaching process is at 250 DEG C~270 DEG C, under conditions of 4~5MPa, with sulfuric acid by the valuable gold such as nickel, cobalt
Belong to iron, aluminium mineral dissolve, and control leaching condition make dissolved impurity element hydrolysis enter slag in, and nickel, cobalt then enter it is molten
Liquid, the leaching rate of the technique cobalt can achieve 90% or more, but be adapted only to handle the lateritic nickel ore relatively low containing content of magnesia,
And plant investment is high, equipment corruption candle is serious, maintenance difficulty is high, causes production efficiency to be greatly reduced low.Normal pressure sulfuric acid leaching is
Lateritic nickel ore mine is filled and mixes under heating conditions leach nickel according to a certain percentage with cleaning solution, sulfuric acid, leachate neutralizes
Liquid carries out solid separation afterwards, and obtained leachate calcium oxide or vulcanized sodium do precipitating reagent coprecipitated nickel hydroxide, and simple process, low energy consumption, no
Using autoclave, investment cost is few, operating condition is easily controllable, but leachate separation is difficult, and nickel content is high in leached mud.
In conclusion the problems such as generally existing energy consumption of thermal process is high, and environmental pollution is serious, and nickel recovery is low, wet process work
Although skill nickel, the cobalt rate of recovery are high, universal too long in flow, complex process, to equipment requirement harshness.
Summary of the invention
For lateritic nickel ore in the prior art thermal process there are long flow path, energy consumption is big, the problems such as at high cost, this
Being designed to provide for invention a kind of is converted to nickel and iron in lateritic nickel ore respectively to be easy to flotation
The nickel sulfide ore of recycling and the magnetic iron ore for being easy to magnetic separation recovery realize the side for efficiently separating recycling of nickel and iron and other metals
Method, low energy consumption for this method, at low cost, simple process, is convenient for industrialized production application.
In order to achieve the above technical purposes, the present invention provides a kind of method of lateritic nickel ore reduction-sulfidation roasting, the party
Method is to make lateritic nickel ore with comprising the raw material mixing including carbonaceous reducing agent, vulcanizing agent, alkali metal salt additive and binder
Ball, gained pelletizing feed are successively roasted at a temperature of 400 DEG C~450 DEG C and 700 DEG C~1100 DEG C；Roasting material passes through floatation
Nickel product is recycled, flotation tailing recycles iron product using magnetic method.
The roasting process of pelletizing feed is broadly divided into two sections in technical solution of the present invention, first in 430 DEG C or so of relatively low temperature
Degree is lower to carry out one section of roasting, reacts the nickel in lateritic nickel ore sufficiently with liquid-state sulfur, reduces the volatilization loss of sulphur,
Curing efficiency is improved, 700 DEG C or more is then heated to and carries out two-stage calcination, main purpose is to keep nickel sulfide and ferroso-ferric oxide brilliant
Grain agglomeration, separates convenient for subsequent flotation and magnetic separation.
Preferred scheme, the quality of the carbonaceous reducing agent are the 2.5~10% of lateritic nickel ore quality.Suitable reducing agent
It may advantageously facilitate the vulcanization of nickel and the magnetization of iron, but reducing agent additive amount excessively will lead to nickel and be reduced to metal, vulcanization effect is poor；
The very few consumption that not only will increase sulphur of reducing agent additive amount, and it is unfavorable for the magnetization of iron.
Preferred scheme, the quality of the vulcanizing agent are the 2.5%~15% of lateritic nickel ore quality.Vulcanizing agent additive amount mistake
Few, nickel vulcanization is not thorough, and additive amount is excessive, and iron also cures, poor selectivity.
Preferred scheme, the quality of the alkali metal salt additive are the 2.5%~15% of lateritic nickel ore quality.Alkali metal
The addition of salt reduces the surface tension and fusing point of nickel sulfide and ferroso-ferric oxide crystal grain, reduces vulcanization conversion and the iron of nickel
Magnetization conversion temperature, be conducive to the agglomeration of nickel sulfide and ferroso-ferric oxide crystal grain.
Preferred scheme, the quality of the binder are the 2.5%~5% of lateritic nickel ore quality.
More preferably scheme, the carbonaceous reducing agent include at least one of charcoal, coke and fine coal.
More preferably scheme, the vulcanizing agent are sulphur and/or pyrite.
More preferably scheme, the alkali metal salt additive include at least one of sodium carbonate, sodium sulphate and sodium chloride.
More preferably scheme, the binder include at least one of CMC, gelatinized starch, bentonite.
Preferred scheme, the lateritic nickel ore is dry to be lower than 5% to moisture content, is crushed and crosses 5mm sieve, take red under sieve
Native nickel minerals powder is used for pelletizing.
Preferred scheme, the lateritic nickel ore are limonite type and/or low magnesium types.
Preferred scheme, the pelletizing feed diameter are 25~50mm.
Preferred scheme is 1~3h in the time of 400 DEG C~450 DEG C roasting temperatures.
Preferred scheme is 0.5~2h in 700 DEG C~1100 DEG C roasting temperature times.
Preferred scheme, product of roasting wet-milling accounts for 75%~85% to pulp granularity -74um when the flotation, using amyl
Xanthate and/or isopropyl xanthate are as flotation collector.
Preferred scheme, the magnetic field strength that the magnetic method uses is 0.4~1.2KGs.
A kind of method of lateritic nickel ore reduction-sulfidation roasting of the invention, including following specific steps:
Step 1: dry, broken and screening
Lateritic nickel ore drying to moisture content is lower than 5%, is then crushed and crosses the sieve of 5mm；The lateritic nickel ore is brown
Iron ore type and low magnesium types；
Step 2: pelletizing
Lateritic nickel ore dry, broken in step 1, after screening and carbonaceous reducing agent, vulcanizing agent, alkali metal salt are added
Agent and binder are mixed evenly to prepare pelletizing；The reducing agent is the one kind of charcoal, coke or fine coal at least within, and reducing agent adds
Dosage is 2.5%~10%；The additive is that sodium sulphate or sodium carbonate are one of, additive amount 2.5%~15%；It is described
The additive amount of vulcanizing agent sulphur is 2.5%~15%；The additive amount of the binder CMC, bentonite or gelatinized starch are 2.5%
~5%；The pelletizing diameter is 25~50mm；
Step 3: sulfidation roasting
Pelletizing in step 2 is placed in rotary kiln, the first stage roasts 1~3h, second stage at 400~450 DEG C
700 DEG C~1100 DEG C are warming up to, 0.5~2h is roasted；
Step 4: flotation
Step 3 product of roasting wet-milling to pulp granularity -74um is accounted for 75%~85%, is then returned using conventional flotation method
Receive nickel sulfide；Collecting agent is that amyl group xanthate or isopropyl xanthate are one of；
Step 5: magnetic separation
The flotation tailing of step 4 is used into magnetic separation recovery iron；The flotation tailing magnetic separation magnetic field strength be 0.4~
1.2KGs。
The present invention adapts to that poor, energy consumption is big, the problems such as at high cost for existing lateritic nickel ore thermal process raw material, for the first time
It is proposed to realize that nickel and iron are selectively convertered in lateritic nickel ore by reduction-sulfidation roasting, nickel is converted to nickel sulfide ore, and iron converts
At magnetic iron ore, and promote by alkali metal salt additive the generation of liquid phase in high-temperature reaction process, iron sulfide and four are provided
Effective channel of Fe 3 O crystal grain aggregation growth, to obtain the nickel sulfide and ferroso-ferric oxide crystal grain of greater particle size, more favorably
Method for floating recycling nickel sulfide ore in the prior art is used for reference in subsequent, magnetic iron ore is recycled using magnetic selection method, to realize nickel
Recycling is efficiently separated with iron and other metals.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
1) nickel in lateritic nickel ore and iron can be converted to by the present invention respectively by reduction-sulfidation roasting technique is easy to flotation
Recycling nickel sulfide ore and the magnetic iron ore for being easy to magnetic separation recovery, while being realized by alkali metal salt additive and control reaction temperature
The regulation of nickel and Fe clusters crystal grain, so as to realize the height of nickel and iron and other metals by existing magnetic separation and method for floating
Effect separation and recovery.
2) present invention is carried out in the case where being lower than sulphur boiling temperature, can effectively be subtracted by two-stage roasting, first stage roasting
The volatilization of few sulphur improves the utilization rate of sulphur, and second stage increases temperature calcination, promotes the agglomeration of ferronickel crystal grain, has
Conducive to the raising of the rate of recovery of nickel and iron, relatively traditional nickel matte technique, maturing temperature is low, and energy consumption is few, and sulfur consumption is small,
Environmental pollution is small.
3) floatation and magnetic method recycling nickel and iron is respectively adopted in reduction of the invention-sulfidation roasting product, and process is short, at
This is low, and concentration ratio is big.
4) nickel in flotation concentrate of the invention exists with sulphided form, and the high nickel matte obtained after bessemerizing is available
In producing general nickel, the raw material production nickel rondelle and nickel powder of atmospheric pressure carbonyl process Refining Nickel can also be used as；Magnetic concentrate can directly be made
For iron-smelting raw material.
5) the reducing agents dosage such as reduction of the invention-sulfidation roasting charcoal, coke or fine coal is few, and energy consumption is few, cost
It is low.
6) after reduced sulphur of the invention-change roasting is used as roasting additive by addition sodium carbonate or sodium sulphate etc., significantly
The surface tension and fusing point for reducing nickel sulfide and ferroso-ferric oxide crystal grain, the vulcanization conversion and the magnetization of iron for reducing nickel turn
Change temperature.
Detailed description of the invention
[Fig. 1] process flow chart of the invention.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention
It encloses.
Specific implementation of the invention is described in further detail below with reference to Fig. 1.
Limonite type lateritic nickel ore main chemical elements used are shown in Table 1.
1 limonite type lateritic nickel ore (butt) main chemical compositions composition of table/%
Embodiment 1
Lateritic nickel ore is dry to be lower than 5% to moisture content, and it is 10% that its mass fraction is crossed after the sieve of 5mm and accounted for after broken
Sodium carbonate, 7.5% charcoal, 5% sulphur, 3% CMC mix pelletizing, pelletizing diameter is 25~50mm, and pelletizing is placed in self-control
In rotary kiln, 2h is roasted at 400 DEG C first, then raises temperature to 1000 DEG C of roasting 1.5h, nitrogen protection is cooled to room temperature；Object phase
Analysis the result shows that, 90% nickel is in calcining with sulphided form preservation, 85% or more iron preservation in the form of ferroso-ferric oxide；
Product of roasting is finely ground to pulp granularity in grinding machine and accounts for 80% for -74 μm, makees collecting agent flotation nickel using amyl group xanthate, can get
Nickeliferous 8.3%, the nickel ore concentrate that nickel recovery is 78.6%；Flotation tailing magnetic separation in the case where magnetic field strength is 0.5KGs, can get iron
Grade is 79.4%, the iron ore concentrate that the rate of recovery is 78.5%.
Embodiment 2
Lateritic nickel ore is dry to be lower than 5% to moisture content, and it is 5% that its mass fraction is crossed after the sieve of 5mm and accounted for after broken
Sodium sulphate, 5% coke, 15% sulphur, 5% bentonite mix pelletizing, pelletizing diameter be 25~50mm, pelletizing be placed in from
In rotary kiln processed, 3h is roasted at 400 DEG C first, then raises temperature to 950 DEG C of roasting 1h, nitrogen protection is cooled to room temperature；Object phase
Analysis the result shows that, 95% or more nickel is in calcining with sulphided form preservation, and 78% or more iron is in the form of ferroso-ferric oxide
Preservation；Product of roasting is finely ground to pulp granularity in grinding machine and accounts for 75% for -74 μm, makees collecting agent flotation using isopropyl xanthate
Nickel can get nickeliferous 6.8%, the nickel ore concentrate that nickel recovery is 84.3%；Flotation tailing magnetic separation in the case where magnetic field strength is 0.8KGs,
Can get Iron grade is 71.6%, the iron ore concentrate that the rate of recovery is 73.1%.
Embodiment 3
Lateritic nickel ore is dry to be lower than 5% to moisture content, and it is 5% that its mass fraction is crossed after the sieve of 5mm and accounted for after broken
Sodium sulphate, 5% sodium carbonate, 10% fine coal, 7.5% sulphur, 2.5% gelatinized starch mix pelletizing, and pelletizing diameter is
25~50mm, pelletizing are placed in self-control rotary kiln, roast 2h at 400 DEG C first, then raise temperature to 950 DEG C of roasting 2h, nitrogen
Protection is cooled to room temperature；Material phase analysis the result shows that, in product of roasting 92% or more nickel with sulphided form preservation, 82% with
On iron in the form of ferroso-ferric oxide preservation；Product of roasting is finely ground to pulp granularity in grinding machine and accounts for 85% for -74 μm, and use is different
Propyl xanthate makees collecting agent flotation nickel sulfide, can get nickeliferous 7.8%, the nickel ore concentrate that nickel recovery is 81.8%；Flotation tailing
The magnetic separation in the case where magnetic field strength is 0.4KGs, can get Iron grade is 79.5%, the iron ore concentrate that the rate of recovery is 81.1%.
Comparative example 1
Lateritic nickel ore is dry to be lower than 5% to moisture content, and the powder of its mass fraction 10% is crossed after the sieve of 5mm and accounted for after broken
Coal, 7.5% sulphur, 2.5% bentonite mix pelletizing, and pelletizing diameter is 25~50mm, and pelletizing is placed in self-control rotary kiln,
2h is roasted at 400 DEG C first, then raises temperature to 750 DEG C of roasting 2h, nitrogen protection is cooled to room temperature；Material phase analysis result table
Bright, 78% nickel is in calcining with sulphided form preservation, and 85% iron preservation in the form of ferroso-ferric oxide, product of roasting is in grinding machine
In be finely ground to pulp granularity be -74 μm account for 80%, collecting agent flotation nickel sulfide, obtained nickel ore concentrate nickel product are made using isopropyl xanthate
Position is only 3.9%, and the rate of recovery is only 69.2%；Flotation tailing magnetic separation in the case where magnetic field strength is 0.6KGs, obtained iron ore concentrate iron
Grade is 65.6%, the rate of recovery 70.1%；When not adding alkali metal salt roasting, the vulcanization conversion ratio of nickel is low, product of roasting nickel
The rate of recovery it is undesirable.
Comparative example 2
Lateritic nickel ore is dry to be lower than 5% to moisture content, and it is 10% that its mass fraction is crossed after the sieve of 5mm and accounted for after broken
Sodium carbonate, 10% charcoal, 5% sulphur, 3% gelatinized starch mix pelletizing, pelletizing diameter is 25~50mm, and pelletizing is placed in
It makes by oneself in rotary kiln, is warming up to 1000 DEG C of roasting 3h, nitrogen protection is cooled to room temperature；Material phase analysis the result shows that, in calcining
53% nickel is finely ground in grinding machine with sulphided form preservation, 88% iron preservation in the form of ferroso-ferric oxide, product of roasting
Pulp granularity is -74 μm and accounts for 80%, makees collecting agent flotation nickel, nickel ore concentrate nickeliferous 5.1% using amyl group xanthate, the rate of recovery is only
42.3%；Flotation tailing magnetic separation in the case where magnetic field strength is 0.3KGs, the grade for obtaining iron ore concentrate iron is 76.4%, and the rate of recovery is
79.5%；It is roasted when roasting only with one section, sulphur largely volatilizees, and the vulcanization rate of nickel is low, and flotation effect is poor.
Comparative example 3
Lateritic nickel ore is dry to be lower than 5% to moisture content, and it is 10% that its mass fraction is crossed after the sieve of 5mm and accounted for after broken
Sodium carbonate, 10% sulphur, 3% CMC mix pelletizing, and pelletizing diameter is 25~50mm, and pelletizing is placed in self-control rotary kiln, first
2h first is roasted at 400 DEG C, then raises temperature to 1000 DEG C of roasting 1.5h, nitrogen protection is cooled to room temperature；Material phase analysis result table
Bright, 45% nickel is in product of roasting with sulphided form preservation, 35% iron preservation in the form of ferroso-ferric oxide；Product of roasting exists
It is finely ground to pulp granularity in grinding machine and accounts for 80% for -74 μm, collecting agent flotation nickel, obtained nickel ore concentrate nickel grade are made using amyl group xanthate
It is 4.6%, the rate of recovery is only 28.6%；Flotation tailing magnetic separation in the case where magnetic field strength is 0.5KGs, iron ore concentrate Iron grade are only
63.2%, the rate of recovery 58.5%；Reducing agent is not added when roasting, the vulcanization effect of nickel and the magnetic efficiency of iron are undesirable.
Comparative example 4 (reduction roasting-ammonia leaching technique)
Lateritic nickel ore is placed in rotary kiln, the reduction roasting at 1000 DEG C through drying with fine coal mixing after sieving approach
90min leaches 120min in ammonia-sal volatile after reduction roasting product is cooling；The leaching rate of nickel is 87.5%, leached mud
The mass fraction of middle iron is 62%.
Claims (10)
1. a kind of method of lateritic nickel ore selectivity sulfidation roasting, it is characterised in that: by lateritic nickel ore with comprising carbonaceous reducing agent,
Raw material including vulcanizing agent, alkali metal salt additive and binder mixes pelletizing, and gained pelletizing feed is successively at 400 DEG C~450 DEG C
It is roasted at a temperature of with 700 DEG C~1100 DEG C；Roasting material recycles nickel product by floatation, and flotation tailing is returned using magnetic method
Receive iron product.
2. a kind of method of lateritic nickel ore selectivity sulfidation roasting according to claim 1, it is characterised in that: the carbonaceous
The quality of reducing agent is the 2.5~10% of lateritic nickel ore quality；
The quality of the vulcanizing agent is the 2.5%~15% of lateritic nickel ore quality；
The quality of the alkali metal salt additive is the 2.5%~15% of lateritic nickel ore quality；
The quality of the binder is the 2.5%~5% of lateritic nickel ore quality.
3. a kind of method of lateritic nickel ore selectivity sulfidation roasting according to claim 2, it is characterised in that: the carbonaceous
Reducing agent includes at least one of charcoal, coke and fine coal；
The vulcanizing agent is sulphur and/or pyrite；
The alkali metal salt additive includes at least one of sodium carbonate, sodium sulphate and sodium chloride；
The binder includes at least one of CMC, gelatinized starch, bentonite.
4. a kind of method of lateritic nickel ore selectivity sulfidation roasting according to claim 1, it is characterised in that: the laterite
Nickel minerals drying to moisture content is lower than 5%, then is crushed and crosses 5mm sieve, takes the lower lateritic nickel ore powder of sieve for pelletizing.
5. a kind of method of lateritic nickel ore selectivity sulfidation roasting according to claim 4, it is characterised in that: the laterite
Nickel minerals is limonite type and/or low magnesium types.
6. a kind of method of lateritic nickel ore selectivity sulfidation roasting according to claim 1, it is characterised in that: the pelletizing
Material diameter is 25~50mm.
7. a kind of method of described in any item lateritic nickel ore selectivity sulfidation roastings, feature exist according to claim 1~6
In: it is 1~3h in the time of 400 DEG C~450 DEG C roasting temperatures.
8. a kind of method of described in any item lateritic nickel ore selectivity sulfidation roastings, feature exist according to claim 1~6
In: the time of 700 DEG C~1100 DEG C roasting temperatures is 0.5~2h.
9. a kind of method of lateritic nickel ore selectivity sulfidation roasting according to claim 1, it is characterised in that: the flotation
Using amyl group xanthate and/or isopropyl xanthate as flotation collector.
10. a kind of method of lateritic nickel ore selectivity sulfidation roasting according to claim 1, it is characterised in that: the magnetic
Select the magnetic field strength used for 0.4~1.2KGs.
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