CN116219198A - Preparation method of acid-soluble metallized nickel matte - Google Patents
Preparation method of acid-soluble metallized nickel matte Download PDFInfo
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- CN116219198A CN116219198A CN202310062046.5A CN202310062046A CN116219198A CN 116219198 A CN116219198 A CN 116219198A CN 202310062046 A CN202310062046 A CN 202310062046A CN 116219198 A CN116219198 A CN 116219198A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 271
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 116
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 230000008569 process Effects 0.000 claims abstract description 61
- 230000009467 reduction Effects 0.000 claims abstract description 43
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000007885 magnetic separation Methods 0.000 claims abstract description 14
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 238000006722 reduction reaction Methods 0.000 claims description 50
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 37
- 229910001710 laterite Inorganic materials 0.000 claims description 27
- 239000011504 laterite Substances 0.000 claims description 27
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 17
- 241000080590 Niso Species 0.000 claims description 11
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 229910052598 goethite Inorganic materials 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 238000004364 calculation method Methods 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000008188 pellet Substances 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 5
- 238000004073 vulcanization Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 230000006378 damage Effects 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 230000002269 spontaneous effect Effects 0.000 claims description 3
- 230000019635 sulfation Effects 0.000 claims description 3
- 238000005670 sulfation reaction Methods 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims 2
- 150000003568 thioethers Chemical class 0.000 claims 1
- 229910000863 Ferronickel Inorganic materials 0.000 abstract description 19
- 238000002386 leaching Methods 0.000 abstract description 19
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 abstract description 7
- 229910002588 FeOOH Inorganic materials 0.000 abstract description 5
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 238000003723 Smelting Methods 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 19
- 230000008901 benefit Effects 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 229910052604 silicate mineral Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- DYJOUBLHPAIUEU-UHFFFAOYSA-N nickel(2+) sulfane Chemical compound S.[Ni+2] DYJOUBLHPAIUEU-UHFFFAOYSA-N 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- 238000009853 pyrometallurgy Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910001347 Stellite Inorganic materials 0.000 description 2
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 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
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- AMULHDKUJWPBKU-UHFFFAOYSA-L nickel(2+);dichlorite Chemical compound [Ni+2].[O-]Cl=O.[O-]Cl=O AMULHDKUJWPBKU-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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
-
- 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
- C22B1/02—Roasting 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
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- Manufacturing & Machinery (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a preparation method of acid-soluble metallized nickel matte, which comprises the design of a sulfuric acid curing stage, a high-temperature reduction roasting stage and a magnetic separation step of reduction roasting materials. The nickel-iron alloy is used as a reducing agent, and simple substance nickel and iron contained in the alloy can be used for leaching Fe in limonite type laterite-nickel ore normal pressure leaching solution 3+ Reduction to Fe 2+ And nickel metal in the ferronickel is enriched in the leaching solution, and is converted into nickel sulfate through a wet process, so that the capacity conversion from the ferronickel to the nickel sulfate is realized. In addition, the addition of the nickel-iron alloy reduces the activation energy of the reaction of FeOOH and sulfuric acid in thermodynamic, and greatly promotes the leaching reaction of FeOOHThe leaching rate of FeOOH under normal pressure reaction condition is improved, so that the leaching rate of nickel in laterite-nickel ore is also promoted.
Description
Technical Field
The invention relates to a pyrometallurgical process of laterite-nickel ore, in particular to a method for preparing acid-soluble metallized nickel matte by two-stage solid phase reduction of laterite-nickel ore.
Background
Nickel resources are generally divided into two major categories, namely nickel oxide ores and nickel sulfide ores, and at present, 70% of nickel yield is derived from the nickel sulfide ores, however, the nickel sulfide ore resources are increasingly reduced, and the contradiction between supply and demand is increasingly prominent. The laterite-nickel ore reserves are rich, the exploitation is easy, the method is a main source of nickel in the future, and the method has important practical significance in fully developing and utilizing laterite-nickel ore resources.
Nickel ores can be divided into two types, laterite nickel ores and stellite. The laterite-nickel ore is mainly produced at the upper part of the laterite section of a mining area, and the main nickel-bearing minerals are iron oxides, including hematite, goethite and the like. The ore is red due to oxidation of iron and is therefore known as laterite. The attapulgite clay is produced at the middle lower part of the laterite section, the nickel-containing silicate minerals mainly comprise nickel serpentine, nickel green clay, nickel talcum, nickel chlorite and the like, and the nickel element mainly exists in the silicate minerals and other minerals in a similar and adsorbed state.
The ore formation rule of the laterite-nickel ore mainly comprises that the parent rock is subjected to weathering, and elements such as nickel, cobalt and the like are enriched towards the lower layer under the leaching action of the upper layer, and are generally expressed as surface limonite-type laterite-nickel ore, middle transition-type laterite-nickel ore and bottom bedrock silicon-magnesium-type laterite-nickel ore.
Limonite type laterite-nickel ore mainly consists of goethite and hematite, and a small amount of chlorite (silicate minerals containing nickel in a layered structure) and lixiviate (silicate minerals containing nickel in a net-shaped structure) are also included. The brown iron type laterite-nickel ore has the characteristics of loose and porous texture.
In general, limonite accounts for 65% -75% of the total laterite-nickel ore; 15-25% of silicon-magnesium ore; the transition ore accounts for 10 percent.
The laterite-nickel ore treatment process comprises two processes of pyrometallurgy and hydrometallurgy. Pyrometallurgy refers to various operations of separating valuable metals from a large number of gangue in a mine at elevated temperatures using a metallurgical furnace, which essentially comprises: the reduction, vulcanization and smelting of nickel matte, the rotary kiln-submerged arc furnace ferronickel and the reduction roasting-magnetic separation are applied to laterite-nickel ore smelting, but the pyrogenic process is high in energy consumption, particularly requires high ore grade, and is not suitable for treating low-grade nickel oxide ore.
The process for preparing nickel matte by sulfuration smelting comprises the following steps: the process for producing nickel matte by sulfidizing smelting is used for treating laterite nickel ore at the earliest time and is applied in the early thirties of the last century. Blast furnace smelting was used at the time. Large factories built after 70 s of the last century adopt the electric furnace smelting technology to treat laterite nickel ore to produce nickel matte. At present, several factories with the largest annual nickel yield of more than 4 ten thousand t are respectively in Indonesia and new karidonia. The nickel content of nickel matte produced from nickel oxide ore worldwide is about 12 ten thousand t. The process flow is shown in figure 1.
The sulfidizing agent for sulfidizing smelting is pyrite (FeS) 2 ) Gypsum (CaS 0) 4 ·2H 2 0) Sulfur, and sulfur-containing nickel raw materials, and the like. The process for producing nickel matte by using the laterite nickel ore through vulcanization smelting has the advantages of mature process, easiness in operation, great flexibility of the product high-nickel matte, capability of directly reducing and smelting nickel oxide subjected to roasting desulfurization to produce general nickel used in the stainless steel industry, capability of being used as a raw material for refining nickel by using a normal pressure carbonyl method to produce nickel pellets and nickel powder, low nickel recovery rate of only 70%, high energy consumption and great pollution.
The technology for preparing the ferronickel by reduction smelting comprises the following steps: the reduction smelting production of ferronickel is a process for treating laterite-nickel ore by a pyrogenic process which is relatively fast in development at present. The advantage of producing the ferronickel alloy by the reduction smelting method is obvious: the process is mature, the equipment is simple and easy to control, the production efficiency is high, but the method has the defects of large consumption of metallurgical coke or electric energy, high energy consumption, high production cost, excessive slag quantity in the smelting process, high smelting temperature (about 1600 ℃), dust pollution and the like. The process flow is shown in figure 1.
The process obtains the ferronickel by using a blast furnace or an electric furnace for reduction smelting, and has the advantages of small investment and lower energy consumption in the production of the ferronickel by using the blast furnace, and is suitable for the areas with small production scale, difficult power supply and low nickel content in the nickel oxide ore. Its advantages are low adaptability to ore and high magnesium content. In addition, the powder ore cannot be treated, and strict requirements are also imposed on the charging materials. The electric furnace smelting can reach higher temperature, the atmosphere in the furnace is easy to control, and the furnace burden is required to be dehydrated in advance, and a rotary kiln is generally adopted for drying and preheating. The process for producing the ferronickel by electric furnace smelting is suitable for treating various types of nickel oxide ores. The production scale can be determined according to the supply condition of raw materials, the storage amount of ore, etc., and can be large or small. There is no strict requirement on the granularity of the charge material. Both powder and larger blocks can be handled directly. However, only one electric power consumption of the electric furnace smelting accounts for about 50% of the operation cost, and if energy consumption of drying, roasting pretreatment and the like is added before smelting the nickel oxide ore, the energy consumption cost in the operation cost may account for more than 65%; in addition, the nickel grade of the ore has a great influence on the production cost of the pyrogenic process, and the production cost is increased by about 3-4% when the nickel grade of the ore is reduced by 0.1%.
The process for preparing the ferronickel by direct reduction comprises the following steps: factories that treat laterite nickel ores using a direct reduction process (a process referred to as a combination of pyrometallurgical and wet processes in the literature) currently have only the Dajiang mountain Smelter (Oyama Smelter) of Japanese metallurgy (Nippon Yakim) worldwide, as shown in FIG. 2. The main technological process is that raw ore is ground and mixed with powdered coal to form agglomerate, the agglomerate is dried and high temperature reduced and roasted in a rotary kiln, the roasted ore is ground again, ore pulp is subjected to gravity separation and magnetic separation to obtain the ferronickel alloy product. The product is suitable for AOD steelmaking process no matter how high the sulfur content is, because the AOD method has good desulfurization capability. The process is recognized as the most economical method for treating laterite-nickel ore at present, and has the most characteristic of low production cost, and 85% of energy in energy consumption is provided by coal, and 160-180 kg of coal is consumed by ton of ore. And more than 80% of the energy consumption of the electric furnace ferronickel smelting process is provided by electric energy, and the electric consumption of each ton of ore is 560-600 kw.h. However, the process has more problems, although the process technology is still unstable after a plurality of improvements in the Dajiang mountain smelting plant, the production scale of the process still stays around ten thousands of tons of annual nickel production after decades, and the nickel and iron yield of the Dajiang mountain smelting plant is continuously reduced along with the continuous reduction of the used stellite raw material with higher nickel content.
Therefore, we propose a preparation method of acid-soluble metallized nickel sulfonium to solve the problems existing in the prior art.
Disclosure of Invention
The invention aims to provide a preparation method of acid-soluble metallized nickel matte, which aims to solve the problems in the prior art in the background art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of acid-soluble metallized nickel sulfonium, which is a mutual melt of metal sulfides; formation reaction of Nickel matte 3NiSO 4 + 10C = Ni 3 S 2 + 10CO(g) + SO 2 (g) The method comprises the following steps:
and (one) a sulfuric acid curing stage: the laterite nickel ore sulfuric acid curing is a process of adding sulfuric acid into ore materials for curing, has a good sulfation effect on the ore materials, and mainly comprises the steps of reacting concentrated sulfuric acid with metal oxides in laterite to generate corresponding metal sulfate;
during the curing process, niFe is heated up 2 O、Fe 2 O 3 、Fe 3 O 4 The Gibbs free energy of the reaction with concentrated sulfuric acid slowly increases, which indicates that the reaction degree is weakened, and the selective vulcanization of nickel oxide and sulfate of nickel and iron is facilitated; the Gibbs free energy of the reaction of NiO and concentrated sulfuric acid is reduced along with the temperature rise, so that the sulfuric acid curing process of nickel is accelerated, and the conversion of Ni oxide into sulfate is facilitated;
when the curing temperature is higher than the decomposition temperature of the sulfate, the sulfate is decomposed, so that in the process of gradually increasing the curing temperature, the sulfate of iron is ideally decomposed completely to form Fe 2 O 3 While the sulfate of Ni and Co will not decompose at the curing temperature, still as NiSO 4 、CoSO 4 Is beneficial to the form of the sulfonium converted in the subsequent reduction roasting process;
(II) a high-temperature reduction stage: the spontaneous proceeding degree of the chemical reaction can be judged according to the standard gibbs free energy of the reaction, when fatg=0, the chemical reaction reaches equilibrium, when fatg < 0, the chemical reaction proceeds spontaneously forward, when fatg > 0, the chemical reaction proceeds spontaneously reversely;
(1) In the roasting process of laterite nickel ore, the solid-solid reduction reaction of nickel, oxide and sulfate of nickel and iron in the furnace occurs, and the chemical reaction is increasingly stable along with the increase of temperature;
(2) In the roasting process of the laterite nickel ore pellets, the gas-solid reduction reaction of nickel, oxide and sulfate of nickel and iron in the furnace is carried out;
(III) magnetic separation of the reduction roasting material: grinding the reduction roasting material, preparing into slurry, and carrying out wet magnetic separation under the action of a dispersing agent to obtain a magnetic product, namely the metallized nickel matte.
Preferably, the metal oxide in the laterite ore in the sulphuric acid maturation stage comprises Fe, ni, co, and XRD analysis of the raw ore shows that Fe is mainly in the form of goethite and reacts with concentrated sulphuric acid to form Fe 2 (SO 4 ) 3 Ni reacts with concentrated sulfuric acid to generate NiSO 4 Co reacts with sulfuric acid to form CoSO 4 。
Preferably, the relevant thermodynamic calculations are performed using HSC6.0 software, the following equation shows the chemical reactions that may occur during the sulfate ripening of laterite nickel ores:
2FeOOH+3H 2 SO 4 =Fe 2 (SO 4 ) 3 +4H 2 O
Fe 2 O 3 +3H 2 SO 4 =Fe 2 (SO 4 ) 3 +3H 2 O
NiO+H 2 SO 4 =NiSO 4 +H 2 O
Fe 3 O 4 (s)+4H 2 SO 4 (l)=Fe 2 (SO 4 ) 3 (s)+FeSO 4 (s)+4H 2 O(g)
CoO+H 2 SO 4 =CoSO 4 +H 2 O。
preferably, the thermodynamic data related to the above equation are plotted as a graph, from which it can be seen that: in the temperature range studied, the gibbs free energy is mostly less than zero with increasing temperature, indicating that the reaction proceeds very spontaneously; meanwhile, a large amount of heat released in the reaction can promote the destruction of goethite structures which are main components in the ore, so that nickel and cobalt which are endowed in the goethite structures are exposed, and the goethite structures react with concentrated sulfuric acid to generate nickel sulfate and cobalt sulfate.
Preferably, the gibbs free energy-temperature line of the reaction in the graph plotted on the thermodynamic data relating to the reaction formula shows that the reaction of mainly goethite with concentrated sulfuric acid proceeds spontaneously with little effect on temperature.
Preferably, the solid-solid reduction reaction of nickel, oxide and sulfate of nickel and iron in the furnace in the roasting process of laterite nickel ore comprises the following steps:
NiO+C=Ni+CO∆Gθ=126013-178.06TJ/mol
3Fe 2 O 3 +C=2Fe 3 O 4 +CO∆Gθ=129861-228.227TJ/mol
Fe 3 O 4 +C=3FeO+CO∆Gθ=181155-188.991TJ/mol
FeO+C=Fe+CO∆Gθ=153000-154.195TJ/mol
it is known from calculation that the temperatures at which the above chemical reactions occur are 710K, 573K, 956K, 993K, respectively, and the chemical reactions proceed more and more steadily as the temperature increases.
Preferably, the gas-solid reduction reaction of nickel, oxide and sulfate of nickel and iron in the furnace during the roasting process of the laterite-nickel ore pellet comprises the following steps:
C+CO 2 =2CO∆G=170857-175.587TJ/mol
NiO+CO=Ni+CO 2 ∆G=-40590-0.4TJ/mol
3Fe 2 O 3 +CO=2Fe 3 O 4 +CO 2 ∆G46550-47.46TJ/mol
Fe 3 O 4 +CO=3FeO+CO 2 ∆G=40960-46.62T/mol
FeO+CO=Fe+CO 2 ∆G=-7580+10.75TJ/mol。
preferably, it can be seen from the chemical reaction equation that the metal oxides NiO and Fe at very low reduction temperatures 2 O 3 Can be reduced by CO, which indicates that NiO and Fe 2 O 3 Is extremely easy to be reduced by CO gas; the reduction roasting temperature is higher than 800 ℃, and the sulfate of nickel and iron is also easy to be reduced into corresponding low-valence sulfidesThe roasting temperature is set at 1000-1250 ℃ in the designed experimental scheme, so that the experiment can be ensured to be carried out smoothly.
Preferably, the process conditions in the sulfuric acid curing stage are the amount of concentrated sulfuric acid (98 percent concentration): 200-350 kg of acid/ton of ore; curing time: piling and curing for 24-72 hours;
high-temperature reduction roasting process conditions, and roasting temperature: 950-1250 ℃; roasting time: 30-60 minutes; carbon blending amount of reducing agent: c/o=0.8 to 1.2;
the magnetic separation process conditions of the reduction roasting material are as follows: 100-300 milli-dtex; roasting material grinding granularity: -0.043mm is more than or equal to 80%; dispersant dosage: 80-150 g/ton of dry material.
The invention has the technical effects and advantages that: compared with the prior art, the preparation method of the acid-soluble metallized nickel matte provided by the invention has the following advantages:
according to the preparation method of the metallized nickel matte, which comprises the steps of sulfuric acid curing, high-temperature reduction and magnetic separation of the reduction roasting material, in the normal-pressure sulfuric acid leaching process of brown iron type laterite nickel ore, reduction leaching is needed in order to improve leaching rate and control ferrous ions in the solution to be divalent. The nickel-iron alloy is used as a reducing agent, and simple substance nickel and iron contained in the alloy can be used for leaching Fe in brown iron type laterite-nickel ore normal pressure leaching solution 3+ Reduction to Fe 2+ And nickel metal in the ferronickel is enriched in the leaching solution, and is converted into nickel sulfate through a wet process, so that the capacity conversion from the ferronickel to the nickel sulfate is realized. In addition, the addition of the ferronickel reduces the activation energy of the reaction of FeOOH and sulfuric acid in thermodynamic, greatly promotes the leaching reaction of FeOOH, and improves the leaching rate of FeOOH under normal pressure reaction conditions, so that the leaching rate of nickel in laterite-nickel ore is promoted.
Because the nickel-iron alloy has the property of corrosion resistance similar to stainless steel, and is difficult to break and grind, the dynamic condition of chemical reaction is poor when the nickel-iron alloy and laterite-nickel ore are subjected to collaborative leaching, and the reaction rate is low, so that the method has significance in producing the acid-soluble nickel-iron alloy.
The production of the nickel-iron alloy is usually carried out at a furnace temperature of not lower than 1550 ℃, the production conditions are harsh, the production cost is high, in order to reduce the cost of the reducing agent containing simple substance nickel-iron for the production synergistic leaching, and meanwhile, the reducing agent is fragile and easy to grind, so that the production cost can be reduced, and the product can meet the wet leaching process.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
FIG. 1 is a flow chart of a process for preparing ferronickel by reduction smelting in the prior art;
FIG. 2 is a flow chart of a ferronickel process in a Dajiangshan smelting plant in the prior art;
FIG. 3 is a flow chart of the preparation principle of the metallized nickel matte alloy according to the preparation method of the metallized nickel matte of the invention;
FIG. 4 is a diagram showing the relationship of the fatting reaction in the sulfuric acid curing process according to the embodiment of the present invention;
FIG. 5 is a schematic diagram of a 3NiSO according to the invention 4 + 10C = Ni 3 S 2 + 10CO(g) + SO 2 (g) Is a reaction scheme of (2);
FIG. 6 is a diagram of a 3NiSO according to the invention 4 + 10CO(g) = Ni 3 S 2 + 10CO 2 (g) + SO 2 (g) A reaction scheme in (a);
FIG. 7 shows Fe in the present invention 2 (SO 4 ) 3 + 10CO(g) = 2FeS + 10CO 2 (g) + SO 2 (g) Is a reaction scheme of (2);
FIG. 8 is a diagram of Fe in the present invention 2 (SO 4 ) 3 + 10C = 2FeS + 10CO(g) + SO 2 (g) Is a reaction scheme of (2);
FIG. 9 is a diagram of Fe in the present invention 2 (SO 4 ) 3 = Fe 2 O 3 + 3 SO 3 (g) Is a reaction scheme of (2);
FIG. 10 is a diagram of NiSO according to the invention 4 = NiO + SO 3 (g) Is a reaction scheme of (2);
FIG. 11 is 3 NiO+2SO in the invention 3 (g) + 9C = Ni 3 S 2 A reaction scheme of +9CO (g);
FIG. 12 shows the 3 NiO+2SO in the present invention 3 (g) + 9CO(g) = Ni 3 S 2 + 9CO 2 (g) Is a reaction scheme of (2).
Description of the embodiments
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. The specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The present invention provides embodiments as shown in the drawings:
and (one) a sulfuric acid curing stage: the sulfuric acid curing of laterite nickel ore is a process of adding sulfuric acid to mineral aggregate for curing, and has a good sulfation effect on the mineral aggregate. The main reaction is that concentrated sulfuric acid reacts with metal oxides of Fe, ni, co and the like in laterite to generate corresponding metal sulfate.
XRD analysis of raw ore shows that Fe exists mainly in the form of goethite and reacts with concentrated sulfuric acid to generate Fe 2 (SO 4 ) 3 Ni reacts with concentrated sulfuric acid to generate NiSO 4 Co reacts with sulfuric acid to form CoSO 4 . Relevant thermodynamic calculations were performed using HSC6.0 software. The following formula shows the chemical reactions that may occur during the sulfuric acid curing of laterite nickel ores:
2FeOOH+3H 2 SO 4 =Fe 2 (SO 4 ) 3 +4H 2 O
Fe 2 O 3 +3H 2 SO 4 =Fe 2 (SO 4 ) 3 +3H 2 O
NiO+H 2 SO 4 =NiSO 4 +H 2 O
Fe 3 O 4 (s)+4H 2 SO 4 (l)=Fe 2 (SO 4 ) 3 (s)+FeSO 4 (s)+4H 2 O(g)
CoO+H 2 SO 4 =CoSO 4 +H 2 O
the above equation-related thermodynamic data is plotted as shown in fig. 4.
1) As can be seen from fig. 4: in the temperature range studied, the gibbs free energy is mostly less than zero with increasing temperature, indicating that the reaction proceeds very spontaneously; meanwhile, a large amount of heat released in the reaction can promote the destruction of goethite structures which are main components in ores, so that nickel and cobalt which are endowed in the goethite structures are exposed, and the goethite structures react with concentrated sulfuric acid to generate nickel sulfate and cobalt sulfate;
2) As seen from the free energy-temperature line of the reactive gibbs in FIG. 4, the reaction of the main reaction goethite with concentrated sulfuric acid proceeds spontaneously, the temperature having little effect thereon;
3) During the curing process, niFe is heated up 2 O、Fe 2 O 3 、Fe 3 O 4 The Gibbs free energy of the reaction with concentrated sulfuric acid slowly increases, which indicates that the reaction degree is weakened, and the selective vulcanization of nickel oxide and sulfate of nickel and iron is facilitated; as the temperature increases, the Gibbs free energy of the reaction of NiO and concentrated sulfuric acid is reduced, the sulfuric acid curing process of nickel is accelerated, and the conversion of Ni oxide into sulfate is facilitated.
4) When the curing temperature is higher than the decomposition temperature of the sulfate, the sulfate is decomposed, so that in the process of gradually increasing the curing temperature, the sulfate of iron is ideally decomposed completely to form Fe 2 O 3 While the sulfate of Ni and Co will not decompose at the curing temperature, still as NiSO 4 、CoSO 4 Is beneficial to the form of the sulfonium converted in the subsequent reduction roasting process. The equation for its associated reaction is as follows:
(II) a high-temperature reduction stage: the spontaneous extent of the chemical reaction can be judged from the standard gibbs free energy of the reaction, and when fatg=0, the chemical reaction reaches equilibrium, when fatg < 0, the chemical reaction spontaneously proceeds in the forward direction, and when fatg > 0, the chemical reaction spontaneously proceeds in the reverse direction.
(1) The solid-solid reduction reaction of nickel, oxide and sulfate of nickel and iron in the furnace in the roasting process of laterite nickel ore comprises the following steps:
NiO+C=Ni+CO∆Gθ=126013-178.06TJ/mol(2.1)
3Fe 2 O 3 +C=2Fe 3 O 4 +CO∆Gθ=129861-228.227TJ/mol(2.2)
Fe 3 O 4 +C=3FeO+CO∆Gθ=181155-188.991TJ/mol(2.3)
FeO+C=Fe+CO∆Gθ=153000-154.195TJ/mol(2.4)
3NiSO 4 +10C=Ni 3 S 2 +10CO+SO 2
Fe 2 (SO 4 ) 3 +10C=2FeS+10CO+SO 2
as can be seen by calculation, the temperatures at which the above six sets of chemical reactions occur are 710K, 573K, 956K, 993K, respectively. And as the temperature increases, the chemical reaction proceeds more and more steadily.
(2) The gas-solid reduction reaction of nickel, oxide and sulfate of nickel and iron in the furnace in the roasting process of the laterite-nickel ore pellets comprises the following steps:
C+CO 2 =2CO ∆G=170857-175.587TJ/mol (2.5)
NiO+CO=Ni+CO 2 ∆G=-40590-0.4TJ/mol (2.6)
3Fe 2 O 3 +CO=2Fe 3 O 4 +CO 2 ∆G46550-47.46TJ/mol (2.7)
Fe 3 O 4 +CO=3FeO+CO 2 ∆G=40960-46.62T/mol (2.8)
FeO+CO=Fe+CO 2 ∆G=-7580+10.75TJ/mol (2.9)
3NiSO 4 +10CO=Ni 3 S 2 +10CO 2 +SO 2
Fe2(SO 4 ) 3 +10CO=2FeS+10CO 2 +SO 2
from the above chemical reaction equation, it can be seen that the metal oxides NiO and Fe at very low reduction temperatures 2 O 3 Can be reduced by CO, which indicates that NiO and Fe 2 O 3 Is very easy to be CO gasReducing the body; the reduction roasting temperature is higher than 800 ℃, and the sulfate of nickel and iron is easily reduced into corresponding low-valence sulfides, and the roasting temperature is set at 1000-1250 ℃ in the experimental scheme designed below, so that the smooth performance of the experiment can be ensured.
(III) magnetic separation of the reduction roasting material: grinding the reduction roasting material, preparing into slurry, and carrying out wet magnetic separation under the action of a dispersing agent to obtain a magnetic product, namely the metallized nickel matte.
Specifically, the technological conditions in the sulfuric acid curing stage are the dosage of concentrated sulfuric acid (the concentration is 98 percent): 200-350 kg of acid/ton of ore; curing time: piling and curing for 24-72 hours;
high-temperature reduction roasting process conditions, and roasting temperature: 950-1250 ℃; roasting time: 30-60 minutes; carbon blending amount of reducing agent: c/o=0.8 to 1.2;
the magnetic separation process conditions of the reduction roasting material are as follows: 100-300 milli-dtex; roasting material grinding granularity: -0.043mm is more than or equal to 80%; dispersant dosage: 80-150 g/ton of dry material.
Sulfonium is a mutual melt of metal sulfides and the formation reaction of nickel sulfonium is as follows:
3NiSO 4 + 10C = Ni 3 S 2 + 10CO(g) + SO 2 (g) As shown in fig. 5;
3NiSO 4 + 10CO(g) = Ni 3 S 2 + 10CO 2 (g) + SO 2 (g) As shown in fig. 6;
Fe 2 (SO 4 ) 3 + 10CO(g) = 2FeS + 10CO 2 (g) + SO 2 (g) As shown in fig. 7;
Fe 2 (SO 4 ) 3 + 10C = 2FeS + 10CO(g) + SO 2 (g) As shown in fig. 8;
iron sulfate easily decomposes Fe 2 (SO 4 ) 3 = Fe 2 O 3 + 3SO 3 (g) As shown in fig. 9;
the sulfate of nickel is not easy to decompose NiSO 4 = NiO + SO 3 (g) As shown in fig. 10;
the SO released by ferric sulfate separation 3 Is effectively utilized, and the following reactions exist:
3NiO + 2SO 3 (g) + 9C = Ni 3 S 2 +9 CO (g), as shown in FIG. 11;
3NiO + 2SO 3 (g) + 9CO(g) = Ni 3 S 2 + 9CO 2 (g) As shown in fig. 12;
in summary, the technology has the advantages that the sulfuric acid used for the sulfuric acid curing is only 50-70% of that of the conventional sulfuric acid curing technology, so that the selective curing is realized. Although solid phase reduction is carried out, low-melting-point sulfonium appears, so that the aggregation of elementary ferronickel generated in furnace burden is promoted, the particle growth of valuable components is promoted, and the dissociation with gangue is facilitated, and the recovery rate is improved. The ferronickel with mixed matte has good acid solubility and strong magnetism, and is favorable for magnetic separation recovery.
Finally, it should be noted that: the foregoing description is only illustrative of the preferred embodiments of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principles of the present invention.
Claims (9)
1. The preparation method of the acid-soluble metallized nickel matte is characterized by comprising the following steps of:
and (one) a sulfuric acid curing stage: the laterite nickel ore sulfuric acid curing is a process that mineral materials are added with sulfuric acid to react with elements such as iron, nickel, cobalt and the like, and has better sulfation effect on the mineral materials, and the main reaction is that concentrated sulfuric acid reacts with metal oxides in the laterite ore to generate corresponding metal sulfate;
during the curing process, niFe is heated up 2 O、Fe 2 O 3 、Fe 3 O 4 The Gibbs free energy of the reaction with concentrated sulfuric acid slowly increases, which indicates that the reaction degree is weakened, and the selective vulcanization of nickel oxide and sulfate of nickel and iron is facilitated; gibbs free energy reduction of NiO reaction with concentrated sulfuric acid with increasing temperatureThe sulfuric acid curing process of nickel is accelerated, and the conversion of the oxide of Ni into sulfate is facilitated;
when the curing temperature is higher than the decomposition temperature of the sulfate, the sulfate is decomposed, so that in the process of gradually increasing the curing temperature, the sulfate of iron is ideally decomposed completely to form Fe 2 O 3 While the sulfate of Ni and Co will not decompose at the curing temperature, still as NiSO 4 、CoSO 4 Is beneficial to the form of the sulfonium converted in the subsequent reduction roasting process;
(II) a high-temperature reduction stage: the spontaneous proceeding degree of the chemical reaction can be judged according to the standard gibbs free energy of the reaction, when fatg=0, the chemical reaction reaches equilibrium, when fatg < 0, the chemical reaction proceeds spontaneously forward, when fatg > 0, the chemical reaction proceeds spontaneously reversely;
(1) In the roasting process of laterite nickel ore, the solid-solid reduction reaction of nickel, oxide and sulfate of nickel and iron in the furnace occurs, and the chemical reaction is increasingly stable along with the increase of temperature;
(2) In the roasting process of the laterite nickel ore pellets, the gas-solid reduction reaction of nickel, oxide and sulfate of nickel and iron in the furnace is carried out;
(III) magnetic separation of the reduction roasting material: grinding the reduction roasting material, preparing into slurry, and carrying out wet magnetic separation under the action of a dispersing agent to obtain a magnetic product, namely the metallized nickel matte.
2. The method for preparing the acid-soluble metallized nickel matte according to claim 1, which is characterized in that: XRD analysis of laterite metal oxides including Fe, ni, co in the sulfuric acid aging stage shows that Fe exists mainly in the form of goethite and reacts with concentrated sulfuric acid to produce Fe 2 (SO 4 ) 3 Ni reacts with concentrated sulfuric acid to generate NiSO 4 Co reacts with sulfuric acid to form CoSO 4 。
3. The method for preparing the acid-soluble metallized nickel matte according to claim 2, which is characterized in that: the following equation shows the chemical reactions that may occur during the sulfate aging process of laterite nickel ore using HSC6.0 software for the relevant thermodynamic calculations:
2FeOOH+3H 2 SO 4 =Fe 2 (SO 4 ) 3 +4H 2 O
Fe 2 O 3 +3H 2 SO 4 =Fe 2 (SO 4 ) 3 +3H 2 O
NiO+H 2 SO 4 =NiSO 4 +H 2 O
Fe 3 O 4 (s)+4H 2 SO 4 (l)=Fe 2 (SO 4 ) 3 (s)+FeSO 4 (s)+4H 2 O(g)
CoO+H 2 SO 4 =CoSO 4 +H 2 O。
4. a method for preparing acid-soluble metallized nickel matte according to claim 3, wherein: the thermodynamic data related to the above equation are plotted as a graph, from which it can be seen that: in the temperature range studied, the gibbs free energy is mostly less than zero with increasing temperature, indicating that the reaction proceeds very spontaneously; meanwhile, a large amount of heat released in the reaction can promote the destruction of goethite structures which are main components in the ore, so that nickel and cobalt which are endowed in the goethite structures are exposed, and the goethite structures react with concentrated sulfuric acid to generate nickel sulfate and cobalt sulfate.
5. The method for preparing the acid-soluble metallized nickel matte according to claim 4, which is characterized in that: the gibbs free energy-temperature line of the reaction in the graph plotted on the thermodynamic data relating to the reaction scheme shows that the reaction of mainly goethite with concentrated sulfuric acid proceeds spontaneously with little effect on temperature.
6. The method for preparing the acid-soluble metallized nickel matte according to claim 1, which is characterized in that: the solid-solid reduction reaction of nickel, oxide and sulfate of nickel and iron in the furnace in the roasting process of laterite nickel ore comprises the following steps:
NiO+C=Ni+CO∆Gθ=126013-178.06TJ/mol
3Fe 2 O 3 +C=2Fe 3 O 4 +CO∆Gθ=129861-228.227TJ/mol
Fe 3 O 4 +C=3FeO+CO∆Gθ=181155-188.991TJ/mol
FeO+C=Fe+CO∆Gθ=153000-154.195TJ/mol
it is known from calculation that the temperatures at which the above chemical reactions occur are 710K, 573K, 956K, 993K, respectively, and the chemical reactions proceed more and more steadily as the temperature increases.
7. The method for preparing the acid-soluble metallized nickel matte according to claim 1, which is characterized in that: the gas-solid reduction reaction of nickel, oxide and sulfate of nickel and iron in the furnace in the roasting process of the laterite-nickel ore pellets comprises the following steps:
C+CO 2 =2CO∆G=170857-175.587TJ/mol
NiO+CO=Ni+CO 2 ∆G=-40590-0.4TJ/mol
3Fe 2 O 3 +CO=2Fe 3 O 4 +CO 2 ∆G46550-47.46TJ/mol
Fe 3 O 4 +CO=3FeO+CO 2 ∆G=40960-46.62T/mol
FeO+CO=Fe+CO 2 ∆G=-7580+10.75TJ/mol。
8. the method for preparing acid-soluble metallized nickel matte according to claim 7, wherein: it can be seen from the chemical reaction equation that the metal oxides NiO and Fe at very low reduction temperatures 2 O 3 Can be reduced by CO, which indicates that NiO and Fe 2 O 3 Is extremely easy to be reduced by CO gas; the reduction roasting temperature is higher than 800 ℃, and the sulfate of nickel and iron is easily reduced into corresponding low-valence sulfides, so that the roasting temperature is set at 1000-1250 ℃ in the designed experimental scheme, and the smooth performance of the experiment can be ensured.
9. The method for preparing the acid-soluble metallized nickel matte according to claim 1, which is characterized in that:
the technological conditions in the sulfuric acid curing stage are the dosage of concentrated sulfuric acid (the concentration is 98 percent): 200-350 kg of acid/ton of ore; curing time: piling and curing for 24-72 hours;
high-temperature reduction roasting process conditions, and roasting temperature: 950-1250 ℃; roasting time: 30-60 minutes; carbon blending amount of reducing agent: c/o=0.8 to 1.2;
the magnetic separation process conditions of the reduction roasting material are as follows: 100-300 milli-dtex; roasting material grinding granularity: -0.043mm is more than or equal to 80%; dispersant dosage: 80-150 g/ton of dry material.
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