CN106755997B - A kind of method of nickel-containing ore comprehensive utilization - Google Patents
A kind of method of nickel-containing ore comprehensive utilization Download PDFInfo
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- CN106755997B CN106755997B CN201611097203.2A CN201611097203A CN106755997B CN 106755997 B CN106755997 B CN 106755997B CN 201611097203 A CN201611097203 A CN 201611097203A CN 106755997 B CN106755997 B CN 106755997B
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- Prior art keywords
- nickel
- containing ore
- ore
- solid
- sulfuric acid
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 188
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 60
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 72
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000002386 leaching Methods 0.000 claims abstract description 29
- 239000011777 magnesium Substances 0.000 claims abstract description 28
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 28
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000006004 Quartz sand Substances 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 239000004576 sand Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 11
- 206010016256 fatigue Diseases 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- ZGBSOTLWHZQNLH-UHFFFAOYSA-N [Mg].S(O)(O)(=O)=O Chemical compound [Mg].S(O)(O)(=O)=O ZGBSOTLWHZQNLH-UHFFFAOYSA-N 0.000 claims description 8
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- -1 ferrous metals Chemical class 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000004513 sizing Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000010334 sieve classification Methods 0.000 claims 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 8
- 238000005272 metallurgy Methods 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 4
- 238000012356 Product development Methods 0.000 abstract description 2
- 239000002440 industrial waste Substances 0.000 abstract description 2
- 230000013011 mating Effects 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 239000002893 slag Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000010669 acid-base reaction Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052928 kieserite Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052564 epsomite Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- JEZHBSJTXKKFMV-UHFFFAOYSA-N calcium nickel Chemical compound [Ca].[Ni] JEZHBSJTXKKFMV-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000011504 laterite Substances 0.000 description 1
- 229910001710 laterite Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A kind of method that the present invention discloses nickel-containing ore comprehensive utilization, it is final to realize nickel-containing ore comprehensive utilization through ore pretreatment, sulfuric acid leaching, directly heavy nickel or the heavy nickel that cleans, recycling magnesium, recycling quartz sand.The full element that the technology of the present invention is conceived to nickel-containing ore resource utilizes, the full element of silicon, magnesium, iron, nickel in nickel-containing ore is recycled, put forth effort on mating with the circulation of non-ferrous metal metallurgy enterprise, the quartz sand of the sulfuric acid this project production simultaneously of one side this project consumption non-ferrous metal metallurgy enterprise returns non-ferrous metal metallurgy enterprise to realize the purpose of resource circulation utilization again.The present invention is formd from ore pretreatment, Machine-made Sand gradation, the product development of series of quartz sand, salt recycling and water process, nickel, iron, magnesium recycling, the series such as system acid, water balance.Resource utilization of the invention is high, at low cost, small investment, without three industrial wastes discharge, generation environment pollutes；Entire technique is brief, cleans, environmentally friendly.
Description
Technical field
The present invention relates to a kind of methods of nickel-containing ore comprehensive utilization, belong to metallurgical technology field.
Background technique
At present to there are mainly two types of the treatment process of nickel-containing ore (such as lateritic nickel ore, garnierite): (one) wet process.Wet process
It is divided into sulfuric acid process and ammonia process again, the former mainly makees leaching agent with sulfuric acid, and the latter makees leaching agent with ammonia or ammonia salt.Wherein ammonia process because
Environmental issue seldom uses；Sulfuric acid process is difficult to recycle with generation leachate and solid, solid after sulfuric acid leaching, the heap after slag
It deposits, this part slag is because nickeliferous compound is dangerous solid waste, stockpiling pollution environment, and leachate electrolysis production after extracting is electrolysed
Nickel, being electrolysed in the solid slag of generation containing heavy metal contaminants is also dangerous solid waste, will cause environmental pollution.Therefore, sulfuric acid process is thrown
Provide that big, at high cost, leaching rate is low, water expansion, magnesium cannot open a way, particularly the metallurgical slag of a large amount of iron content calcium nickel can not utilize, ring
Packing pressure is big, has enterprise to handle lateritic nickel ore because environmental protection was once being suspended operations for consolidation with sulfuric acid process.(2) pyrogenic process.Pyrogenic process is divided into ferronickel again
Method and matte smelting method.But this method is only suitable for magnesia mine, requires height to raw ore, and head grade is generally required to be greater than 1.5% even
Greater than 2%, applicable scope of resource is very small, and investment is big, energy consumption is very high, and especially metallurgical slag can not benefit greatly for environmental pollution
With environmental protection pressure is big.
The enterprise of sulfuric acid consumption matched with copper smelting plant at present is titanium powder plant or phosphorizing treatment, but both techniques have
The critical defects such as long flow path, environmental pollution.China's titanium dioxide industry production capacity rapid growth, but the ring present in rapid growth
Border pollution problem and potential environmental risk can not be ignored really.Specifically, it is mainly manifested in following aspect.First is that unit produces
Product blowdown flow rate is big, and resource, energy consumption are high.Using traditional Titanium White Production By Sulfuric Acid Process, it is fresh to produce titanium dioxide consumption per ton
100~150 tons of water, about 1.6 tons of mark coals of comprehensive energy consumption, while 100 tons of 8 tons of Waste Sulfuric Acid, the acid waste water of about generation concentration 20%,
8 tons of waste residue, and 2.5 ten thousand stere of exhaust gas containing sulfur dioxide, acid mist and dust.Second is that factory's point is more, small scale, heavily contaminated is produced
Energy proportion is excessive.Third is that disposal of waste gas, water and industrial residue difficulty is little, but control expense is high.Production phosphate fertilizer during generate hydrogen fluoride,
Ocratation, fluorine-containing dust, phosphoric acid mist, ammonia and sulfur dioxide etc. pollute environment, wherein larger with fluorine-containing hazard of contaminant.Generally
In the case of, every production one ton of chemical fertilizer, about 40 tons of effluent, 2000 cubes of exhaust gas, dust 50mg, and a large amount of ardealite is even more pair
It is endangered caused by environmental protection bigger.
As the demand growth of rapid development of economy, especially Asia-Pacific market to nickel is very rapid, but accounts for the whole world 70% and provide
The lateritic nickel ore of source reserves but only contributes to 30% yield.It is wide, with low investment, at low cost, right that its reason is just the absence of the scope of application
Environmental-friendly enlarged production technology.
It is mishandling there are hidden danger such as social safety, environmental protection however, non-ferrous metal metallurgy enterprise by-product sulfuric acid amount is big, because
The enlarged production technology of this research nickel-containing ore comprehensive utilization has important practical significance.
Summary of the invention
To overcome above-mentioned the deficiencies in the prior art, the present invention provides a kind of method of nickel-containing ore comprehensive utilization, both solves
The problem that prior art investment is big, environmental pollution is big, the quantity of slag is big, and sulfuric acid and quartz sand can be realized with non-ferrous metal metallurgy enterprise
Recycle.
The present invention is realized by following technical proposal: a kind of method of nickel-containing ore comprehensive utilization, by following each step:
(1) ore pre-processes: raw material nickel-containing ore being crushed, is sized to the ore in sand form that granularity is 0.63~5mm；
(2) sulfuric acid leaching: add water to size mixing to pulp density in 20~50wt% in ore in sand form obtained by step (1), add sulfuric acid
It is 2~70% that solution, which is mixed to acidity, carries out neutralization leaching, is then separated by solid-liquid separation, obtains leachate and solid；The step
The metals such as nickel, cobalt, manganese, iron, aluminium, the chromium in nickel-containing ore (hydroxide, oxide) is set to form sulfate by the way that sulfuric acid is added
Into in leachate；And the silica in nickel-containing ore is then not involved in acid-base reaction and is completely retained in solids for giving birth to
Produce quartz sand；
(3) directly heavy nickel: in the leachate obtained by step (2) plus alkali to pH value is 8~11, using filter obtain solid and
Filtrate, obtained solid are iron-containing nickel hydroxide；Nickel content is 17~30% in the iron-containing nickel hydroxide, cobalt content 0.1
~2%, iron content is 10~20%, and manganese content is 0.5~5%, and aluminium content is 2~8%；The iron-containing nickel hydroxide can be used as stainless
The raw material of steel mill or extraordinary steel mill；Alternatively, adding sulfide (such as hydrogen sulfide, vulcanized sodium) to pH in the leachate obtained by step (2)
Value is 3.2~4.2, solid and filtrate is obtained by filtration, obtained solid is nickel sulfide；The nickel content of gained nickel sulfide be 2~
35%, cobalt content is 0.1~2%, and iron content is 1~5%；The Containing Sulfur nickel can be used as the raw material of electrolytic nickel factory；
Alternatively, the heavy nickel that cleans: it is 0.05~0.1:1 by the mass ratio of leachate and hydrogen peroxide, the leaching obtained by step (2)
After hydrogen peroxide is added in liquid, warming while stirring is to 80 DEG C, then it is 3.2~4.2 that milk of lime to pH value, which is added dropwise, then through solid-liquid point
From the removals such as impure iron, calcium, manganese, chromium, cadmium, aluminium, silicon in solids, contain magnesium and nickel, in institute in obtained solid in gained liquid
Obtaining and sodium hydroxide to pH value is added in liquid is 8~11, solids and filtrate is obtained after refiltering, obtained solid object is hydrogen-oxygen
Change nickel；The purity of gained nickel hydroxide reaches 95% or more；Gained nickel hydroxide can both produce energy storage material or can be as production
The raw material of stainless steel；
(4) recycle magnesium: sulfuric acid magnesium products be made through evaporative crystallization in filtrate obtained by step (3), at the same using distilled water as
Technique backwater circulation utilizes；The content of epsom salt is greater than 96% in gained sulfuric acid magnesium products, which effectively will can largely give up
Water is changed into distilled water return and recycles；
Alternatively, it is 11~15 that filtrate obtained by step (3), which is added alkali to adjust pH value, solid and liquid are obtained using filter,
Obtained solid is one or more of the hydroxide of magnesium, the carbonate of magnesium, the bicarbonate of magnesium；Gained liquid is as work
Skill backwater circulation utilizes；
(5) quartz sand is recycled: after technique return water washed-out sand to neutrality obtained by step (2) obtained solid step (4), screening point
Grade obtains quartz sand product.
The raw material nickel-containing ore of the step (1) is the garnierite being separated by lateritic nickel ore.
The broken of the step (1) is to be broken when the water content of nickel-containing ore is less than 15% using dry, when containing for nickel-containing ore
Using wet broken when water is greater than 15%.
The neutralization leaching of the step (2) is mixed using one or more of conventional dump leaching, soaking, leaching mode
With.
The time-consuming of the dump leaching is 15~300 days, the time-consuming of soaking is 10~1000 hours, the time-consuming of leaching is 1
~5 hours.
The sulfuric acid solution of the step (2) comes from the byproduct sulfuric acid solution of non-ferrous metal (copper, nickel, lead, zinc) smeltery.
The sulfuric acid solution of the step (2) is by being added salt in hydrochloric acid solution and/or hydrofluoric acid solution substitution or sulfuric acid solution
Acid solution and/or hydrofluoric acid solution.Wherein, the acidity of dump leaching is 2~12%, the acidity of leaching is 5~50%, the acid of soaking
Degree is 20~70%.
The alkali of the step (3) or step (4) is sodium hydroxide.
The sulfuric acid magnesium products of the step (4) include MgSO4·7H2O、MgSO4·H2O and anhydrous MgSO4。
The water outlet generated after the washed-out sand of the step (5) is back to step (2) for sizing mixing, and realizes the closed cycle benefit of water
With.
The quartz sand product of the step (5) includes porous silica, glass sand, metallurgical quartz sand and/or builds
It builds and uses sand.
In above-mentioned technical process, evaporative crystallization can be substituted by multiple-effect evaporation or heat pump techniques；Being separated by solid-liquid separation can be with dense
One of machine, high-efficiency thickener, flame filter press, vacuum filter, band filter, filter press, countercurrent washing equipment or
It is several mixed；Washed-out sand can use sand washer and/or screening machine.
The advantages of present invention has and effect:
Hydroxide, oxide in nickel-containing ore is used for neutralizing acid by the present invention, generates salt and water, salinity after neutralizing acid
Step recycling magnesium and nickel, gained water is then used as process water to be recycled after recycling magnesium, and the silica in nickel-containing ore is not joined then
Magnesium, silicon, the nickel completely remained with acid-base reaction for producing building sand, in such nickel-containing ore is respectively formed magnesium
Salt/magnesium hydroxide, Machine-made Sand (brick) and nickel salt/nickel hydroxide three classes product and realize nickel-containing ore complete resource utilize,
Whole process does not generate industrial wastewater, waste residue, exhaust gas, completely environmentally protective.In the by-product sulfuric acid of consumption non-ferrous metals smelting works
Meanwhile the quartz sand of present invention process production returns to non-ferrous metals smelting works again, to realize the mesh that social resources recycle
's.
The full element that the technology of the present invention is conceived to nickel-containing ore resource utilizes, and silicon, magnesium, iron, the nickel in nickel-containing ore is complete
Element recycles, and puts forth effort on, one side this project consumption non-ferrous metal metallurgy mating with the circulation of non-ferrous metal metallurgy enterprise
The quartz sand of the sulfuric acid of enterprise this project production simultaneously returns non-ferrous metal metallurgy enterprise again to realize resource circulation utilization
Purpose.The present invention form from ore pretreatment, Machine-made Sand gradation, the product development of series of quartz sand, salt recycling and water process,
Nickel, iron, magnesium recycling, the series such as system acid, water balance, these are unique and rich creative.
Resource utilization of the invention is high, at low cost, small investment, without three industrial wastes discharge, generation environment pollutes；Entirely
Technique is brief, cleans, environmentally friendly.The present invention is to comprehensive utilization of resources, Strategy of Circular Economy and environmentally friendly sustainable development tool
It is of great importance.
Specific embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1
Raw material is lateritic nickel ore, and lateritic nickel ore is separated into the limonite of nickelic high-speed rail and the garnierite of high silicon and low iron,
Gained limonite is directly outer to be sold, and gained garnierite is as nickel-containing ore, i.e. serpentine (Ni, Mg)3Si4O10(OH)8.Laterite nickel
The specific lock out operation of mine is as follows:
Lateritic nickel ore by partial size greater than 40mm enters Three stage crushing with single closed circuit stage process, and+0.5mm is made afterwards after crushing and screening
The finished product and -0.5mm ore pulp of~10mm.Partial size less than 40mm lateritic nickel ore and ore pulp be divided into after trough washery -0.5mm ore pulp ,+
0.5mm~10mm ore in sand form and+10mm ore ,+10mm ore enter closed circuit crushing process, and it is dense that -0.5mm ore pulp enters concentrator
Contracting is concentrated as nickelic high-speed rail irony mine, and+0.5mm~10mm ore in sand form is nickel-containing ore (garnierite).Its ingredient such as the following table 1:
The grade of 1 lateritic nickel ore of table separation front and back each element
(1) ore pre-processes: above-mentioned gained nickel-containing ore being crushed, is sized to the ore in sand form that granularity is 0.63~5mm；
Wherein being crushed is to be broken when the water content of nickel-containing ore is less than 15% using dry, is used when the water content of nickel-containing ore is greater than 15%
It is wet broken；
(2) sulfuric acid leaching: add water to size mixing to pulp density in 40wt% in ore in sand form obtained by step (1), add smeltery's pair
It is 45% that product sulfuric acid solution, which is mixed to acidity, neutralize using convention stir leaching and leach 1~5 hour, then carries out solid-liquid
Separation, obtains leachate and solid；Nickeliferous 0.13% in obtained solid, contain cobalt 0.0099%, nickeliferous 4.56g/L in leachate contains
Iron 4.07g/L, the leaching rate of nickel is 87.73%, the leaching rate of cobalt is 93.81%；
(3) clean heavy nickel: being 0.08:1 by the mass ratio of leachate and hydrogen peroxide, adds in the leachate obtained by step (2)
After entering hydrogen peroxide, warming while stirring is to 80 DEG C, then it is 3.2~4.2 that milk of lime to pH value, which is added dropwise, is then separated by solid-liquid separation, point
Iron rate 96.31% is removed from gained liquid；Ingredient in separating obtained liquid is shown in Table 2:
The ingredient g/L of the separating obtained liquid of table 2
It is 8~11 that sodium hydroxide to pH value is added in gained liquid, stablizes reaction 1 hour, obtains solids after refiltering
And filtrate, obtained solid object are nickel hydroxide；Nickel content is 0.32g/L in filtrate, and nickel rate of deposition is 92.28%, gained hydrogen-oxygen
The purity for changing nickel reaches 96%；
(4) it recycles magnesium: magnesium sulfate is made through evaporative crystallization in filtrate obtained by step (3) (containing magnesium ion concentration 47g/L) and is produced
Product (including MgSO4·7H2O、MgSO4·H2O and anhydrous MgSO4), while being utilized distilled water as technique backwater circulation；Its
In, 0.95 ton/ton sulfuric acid magnesium products of steam consumption, 165 KWhs/ton of sulfuric acid magnesium products of electric consumption；
(5) quartz sand is recycled: after technique return water washed-out sand to neutrality obtained by step (2) obtained solid step (4), screening point
Grade obtains quartz sand product (including porous silica, glass sand, metallurgical quartz sand and/or building sand)；After washed-out sand
The water outlet of generation is back to step (2) for sizing mixing.
Embodiment 2
(1) ore pre-processes: raw material nickel-containing ore being crushed, is sized to the ore in sand form that granularity is 0.63~5mm；
(2) sulfuric acid leaching: add water to size mixing to pulp density in 20wt% in ore in sand form obtained by step (1), add hydrochloric acid solution
Mixing with hydrofluoric acid solution to acidity is 2%, carries out in dump leaching and leaches 15~300 days, is then separated by solid-liquid separation, is soaked
Liquid and solid out；The step makes the metals such as nickel, cobalt, manganese, iron, aluminium, chromium in nickel-containing ore (hydroxide, oxide) by adding
Enter sulfuric acid formation sulfate to enter in leachate；And the silica in nickel-containing ore is then not involved in acid-base reaction and is completely protected
It stays in solids for producing quartz sand；
(3) directly heavy nickel: adding sodium hydroxide to pH value is 8~11 in the leachate obtained by step (2), is obtained using filter
Solid and filtrate, obtained solid are iron-containing nickel hydroxide；Nickel content is 17~30% in the iron-containing nickel hydroxide, and cobalt contains
Amount is 0.1~2%, and iron content is 10~20%, and manganese content is 0.5~5%, and aluminium content is 2~8%；The iron-containing nickel hydroxide can
Raw material as Stainless Steel Plant or extraordinary steel mill；
(4) recycle magnesium: it is 11~15 that filtrate obtained by step (3), which is added alkali to adjust pH value, using filter obtain solid and
Liquid, obtained solid are one or more of the hydroxide of magnesium, the carbonate of magnesium, the bicarbonate of magnesium；Gained liquid
It is utilized as technique backwater circulation；
(5) quartz sand is recycled: after technique return water washed-out sand to neutrality obtained by step (2) obtained solid step (4), screening point
Grade obtains quartz sand product (including porous silica, glass sand, metallurgical quartz sand and/or building sand)；After washed-out sand
The water outlet of generation is back to step (2) for sizing mixing, and realizes that the closed cycle of water utilizes.
Embodiment 3
(1) ore pre-processes: raw material nickel-containing ore being crushed, is sized to the ore in sand form that granularity is 0.63~5mm；
(2) sulfuric acid leaching: add water to size mixing to pulp density in 50wt% in ore in sand form obtained by step (1), add non-ferrous metal
The byproduct sulfuric acid solution and hydrochloric acid solution solution of smeltery mix to acidity be 70%, carry out soaking in and leach 10~
It 1000 hours, is then separated by solid-liquid separation, obtains leachate and solid；The step make nickel in nickel-containing ore, cobalt, manganese, iron,
The metals such as aluminium, chromium (hydroxide, oxide) are entered in leachate by the way that sulfuric acid formation sulfate is added；And in nickel-containing ore
Silica is then not involved in acid-base reaction and is completely retained in solids for producing quartz sand；
(3) directly heavy nickel: adding hydrogen sulfide or vulcanized sodium to pH value in the leachate obtained by step (2) is 3.2~4.2, warp
Solid and filtrate is obtained by filtration, obtained solid is nickel sulfide；The nickel content of gained nickel sulfide is 2~35%, cobalt content 0.1
~2%, iron content is 1~5%；The Containing Sulfur nickel can be used as the raw material of electrolytic nickel factory；
(4) it recycles magnesium: sulfuric acid magnesium products (MgSO is made through evaporative crystallization in filtrate obtained by step (3)4·7H2O、
MgSO4·H2O and anhydrous MgSO4), while being utilized distilled water as technique backwater circulation；Seven water sulphur in gained sulfuric acid magnesium products
The content of sour magnesium is greater than 96%, which effectively can be changed into distilled water return for a large amount of waste water and recycle；
(5) quartz sand is recycled: after technique return water washed-out sand to neutrality obtained by step (2) obtained solid step (4), screening point
Grade obtains quartz sand product (including porous silica, glass sand, metallurgical quartz sand and/or building sand)；After washed-out sand
The water outlet of generation is back to step (2) for sizing mixing, and realizes that the closed cycle of water utilizes.
Comparative example 1: with above-described embodiment 1, the operation of step (1) is only omitted.As a result it is unable to get quartz sand product, finally
It still will form a large amount of solid slags to stack, and be not used.
Comparative example 2: with above-described embodiment 1, the operation of step (3) is only omitted.As a result the elements such as iron can't be stainless steel
The raw material of factory or extraordinary steel mill, and stacked as solid slag, it is difficult to it recycles.
Comparative example 3: with above-described embodiment 1, the operation of step (4) is only omitted.If lime treatment filtrate is routinely added, knot
Fruit magnesium enters solid slag stacking, it is difficult to recycle.
Claims (10)
1. a kind of method of nickel-containing ore comprehensive utilization, it is characterised in that pass through following each step:
(1) ore pre-processes: raw material nickel-containing ore being crushed, is sized to the ore in sand form that granularity is 0.63-5mm；
(2) sulfuric acid leaching: add water to size mixing to pulp density in 20-50wt% in ore in sand form obtained by step (1), add sulfuric acid solution
Mixing to acidity is 2~70%, carries out neutralization leaching, is then separated by solid-liquid separation, obtains leachate and solid；
(3) directly heavy nickel: in the leachate obtained by step (2) plus alkali to pH value is 8~11, obtains solid and filter using filter
Liquid, obtained solid are iron-containing nickel hydroxide；Alternatively, in the leachate obtained by the step (2) plus sulfide to pH value be 3.2~
4.2, solid and filtrate is obtained by filtration, obtained solid is nickel sulfide；The nickel content of gained nickel sulfide is 2~35%, cobalt content
It is 0.1~2%, iron content is 1~5%；
Alternatively, the heavy nickel that cleans: being 0.05~0.1:1 by the mass ratio of leachate and hydrogen peroxide, in step (2) gained leachate
After hydrogen peroxide is added, warming while stirring is to 80 DEG C, then it is 3.2~4.2 that milk of lime to pH value, which is added dropwise, then through being separated by solid-liquid separation,
It is 8~11 that sodium hydroxide to pH value is added in gained liquid, solids and filtrate is obtained after refiltering, obtained solid object is
Nickel hydroxide；
(4) it recycles magnesium: sulfuric acid magnesium products is made through evaporative crystallization in filtrate obtained by step (3), while using distilled water as technique
Backwater circulation utilizes；
Alternatively, it is 11~15 that filtrate obtained by step (3), which is added alkali to adjust pH value, solid and liquid, gained are obtained using filter
Solid is one or more of the hydroxide of magnesium, the carbonate of magnesium, the bicarbonate of magnesium；Gained liquid is returned as technique
Water circulation use；
(5) recycle quartz sand: after technique return water washed-out sand to neutrality obtained by step (2) obtained solid step (4), sieve classification is obtained
To quartz sand product.
2. the method for nickel-containing ore comprehensive utilization according to claim 1, it is characterised in that: the raw material of the step (1)
Nickel-containing ore is the garnierite being separated by lateritic nickel ore.
3. the method for nickel-containing ore comprehensive utilization according to claim 1, it is characterised in that: the step (1) is crushed
It is to be broken when the water content of nickel-containing ore is less than 15% using dry, when the water content of nickel-containing ore is greater than 15% using wet broken.
4. the method for nickel-containing ore comprehensive utilization according to claim 1, it is characterised in that: the neutralization of the step (2)
Leaching is mixed using one or more of conventional dump leaching, soaking, leaching mode.
5. the method for nickel-containing ore comprehensive utilization according to claim 4, it is characterised in that: the time-consuming of the dump leaching is 15
~300 days, the time-consuming of soaking be 10~1000 hours, the time-consuming of leaching is 1~5 hour.
6. the method for nickel-containing ore comprehensive utilization according to claim 1, it is characterised in that: the sulfuric acid of the step (2)
Byproduct sulfuric acid solution of the solution from non-ferrous metals smelting works.
7. the method for nickel-containing ore comprehensive utilization according to claim 1, it is characterised in that: the sulfuric acid of the step (2)
Solution is by being added hydrochloric acid solution and/or hydrofluoric acid solution in hydrochloric acid solution and/or hydrofluoric acid solution substitution or sulfuric acid solution.
8. the method for nickel-containing ore comprehensive utilization according to claim 1, it is characterised in that: the step (3) or step
(4) alkali is sodium hydroxide.
9. the method for nickel-containing ore comprehensive utilization according to claim 1, it is characterised in that: the washed-out sand of the step (5)
The water outlet generated afterwards is back to step (2) for sizing mixing.
10. the method for nickel-containing ore comprehensive utilization according to claim 1, it is characterised in that: the sulfuric acid of the step (4)
Magnesium products include MgSO47H2O, MgSO4H2O and anhydrous MgSO4.
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| CN111118285A (en) * | 2020-01-07 | 2020-05-08 | 张响 | Method for leaching valuable metals from laterite-nickel ore by sulfuric acid under normal pressure |
| CN111549219A (en) * | 2020-04-15 | 2020-08-18 | 广西赛可昱新材料科技有限公司 | Method for comprehensively treating and recycling valuable substances from nickel ore |
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| CN104789797A (en) * | 2014-12-31 | 2015-07-22 | 金川集团股份有限公司 | A novel method of recovering nickel, cobalt, iron, silicon and magnesium from low-grade lateritic nickel ore |
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| CN101289704A (en) * | 2008-06-18 | 2008-10-22 | 北京矿冶研究总院 | Treatment method of high-magnesium laterite-nickel ore |
| CN102485922A (en) * | 2009-10-23 | 2012-06-06 | 马猛 | Method for extracting nickel, cobalt, magnesium and iron from laterite-nickel ore under conditions of normal temperature and normal pressure and using waste residues |
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