CN117460855B - A method for preparing high nickel matte by using ternary iron aluminum slag and laterite nickel ore - Google Patents
A method for preparing high nickel matte by using ternary iron aluminum slag and laterite nickel ore Download PDFInfo
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- CN117460855B CN117460855B CN202380011396.7A CN202380011396A CN117460855B CN 117460855 B CN117460855 B CN 117460855B CN 202380011396 A CN202380011396 A CN 202380011396A CN 117460855 B CN117460855 B CN 117460855B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 501
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 315
- 239000002893 slag Substances 0.000 title claims abstract description 242
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 238000000034 method Methods 0.000 title claims abstract description 63
- 229910001710 laterite Inorganic materials 0.000 title claims description 21
- 239000011504 laterite Substances 0.000 title claims description 21
- 238000003723 Smelting Methods 0.000 claims abstract description 113
- 238000007664 blowing Methods 0.000 claims abstract description 89
- 230000004907 flux Effects 0.000 claims abstract description 56
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003546 flue gas Substances 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 239000008187 granular material Substances 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims description 33
- 238000010791 quenching Methods 0.000 claims description 30
- 230000000171 quenching effect Effects 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 29
- 238000004073 vulcanization Methods 0.000 claims description 29
- 239000002918 waste heat Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000779 smoke Substances 0.000 claims description 24
- 239000000571 coke Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 239000006004 Quartz sand Substances 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 235000019738 Limestone Nutrition 0.000 claims description 6
- 239000006028 limestone Substances 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 37
- 239000010941 cobalt Substances 0.000 abstract description 37
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 37
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000000428 dust Substances 0.000 description 36
- 238000006722 reduction reaction Methods 0.000 description 30
- 230000008569 process Effects 0.000 description 24
- 239000002689 soil Substances 0.000 description 19
- 239000010440 gypsum Substances 0.000 description 16
- 229910052602 gypsum Inorganic materials 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000004927 clay Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910000863 Ferronickel Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000010248 power generation Methods 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 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 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000012946 outsourcing Methods 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 238000005486 sulfidation Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241001062472 Stokellia anisodon Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000916 relative toxicity Toxicity 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
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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
-
- 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
- C22B23/02—Obtaining nickel or cobalt by dry processes
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present disclosure relates to a method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore, which belongs to the technical field of nickel matte preparation. The method comprises the following steps of (1) drying ternary iron aluminum slag and laterite-nickel ore respectively, (2) mixing and granulating, namely uniformly mixing the dried ternary iron aluminum slag, the laterite-nickel ore, a first flux and a reducing agent, granulating to obtain mixed granules, (3) reducing and vulcanizing smelting, namely sending the mixed granules obtained in the step (2) into a side blowing furnace to carry out reducing and vulcanizing smelting to obtain low-nickel matte, smelting slag and first flue gas, and (4) blowing, namely after uniformly mixing the low-nickel matte obtained in the step (3) with a second flux, sending the mixture into the side blowing furnace to carry out blowing to obtain high-nickel matte, smelting slag and second flue gas. The ternary iron aluminum slag is used as a vulcanizing agent, so that nickel and cobalt in the ternary iron aluminum slag are effectively recycled, and meanwhile, the high nickel matte with high nickel and cobalt grades and high nickel and cobalt direct yields are obtained.
Description
Technical Field
The disclosure relates to the technical field of nickel matte preparation, in particular to a method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore.
Background
Along with the continuous increase of the demand of new energy automobiles, a large number of automobile waste batteries are also generated. A large amount of iron-aluminum slag is produced in the process of treating the waste ternary cathode material battery by utilizing a wet method, and the iron-aluminum slag is called ternary iron-aluminum slag. The ternary iron-aluminum slag is rich in valuable metals such as nickel, cobalt and manganese, if the ternary iron-aluminum slag is not recycled, a great deal of valuable metals are lost, and a great deal of ternary iron-aluminum slag is piled for a long time, so that the ternary iron-aluminum slag occupies land to waste resources and pollutes the environment. In addition, the ternary iron aluminum slag is mainly recycled by hydrometallurgy at present, but the wet metallurgy method for treating the ternary iron aluminum slag has the following defects of (1) complex process flow, (2) large reagent consumption and high production cost, (3) large process operation controllability difficulty, and is not beneficial to safe production, and (4) higher equipment requirement. Therefore, a route for recycling ternary iron-aluminum slag needs to be developed.
In the existing method for preparing nickel matte by treating laterite-nickel ore, the laterite-nickel ore and pyrite (FeS 2)/gypsum (CaSO 4·2H2 O) are treated by a pyrometallurgical method to obtain nickel matte, and the nickel matte produced by treating the laterite-nickel ore by the pyrometallurgical method is mainly prepared by electric furnace smelting, RKEF (oxygen-enriched side blowing reduction and vulcanization processes. However, the electric furnace smelting and RKEF process has the following defects of (1) high energy consumption and high production cost, (2) a rotary kiln pre-reduction step, high process cost and (3) low cobalt recovery rate. The oxygen-enriched side-blown reduction vulcanization process not only can produce ferronickel, but also can produce nickel matte, is a new process at present, and has great advantages in various aspects, and the process comprises the following steps of laterite nickel ore, oxygen-enriched side-blown (reduction vulcanization) smelting, low nickel matte, side-blown furnace converting and high nickel matte.
The Chinese patent application CN115852165A discloses a method for producing low-nickel matte from laterite-nickel ore, which mainly comprises the steps of uniformly mixing laterite-nickel ore, a first vulcanizing agent (gypsum slag) and a first carbon-based reducing agent, then sending the mixture into a rotary kiln for reduction vulcanization roasting to obtain sulfide calcine, then uniformly mixing sulfide calcine, a second carbon-based reducing agent and a second vulcanizing agent (sulfur), then sending the mixture into the rotary kiln again for supplementary vulcanization reaction to obtain supplementary sulfide calcine, and sending the supplementary sulfide calcine into an electric furnace or a side blowing furnace for smelting to obtain low-nickel matte and slag. However, the invention has the following defects that the calcine is prepared by carrying out twice rotary kiln prereduction roasting, the process flow is complex, gypsum slag and sulfur are respectively used as vulcanizing agents, the relative toxicity of the sulfur is high, and the vulcanizing equipment and the technical requirements for production are high.
The Chinese patent application CN113999991A discloses a method for producing high nickel matte by smelting nickel laterite ore into ferronickel alloy and continuously vulcanizing and blowing, which mainly comprises the steps of carrying out primary water quenching granulation on the ferronickel alloy after smelting the laterite ore into the ferronickel alloy, forming ferronickel particles after the primary water quenching granulation on the ferronickel alloy, continuously entering a converter for vulcanizing after the ferronickel particles, vulcanizing agent (sulfur) and flux ingredients, and forming molten high nickel matte after blowing, wherein the molten high nickel matte is formed into high nickel matte particles after secondary water quenching granulation. The invention has the following defects that 1, sulfur is used as a vulcanizing agent, the boiling point of the sulfur is low (445 ℃), the relative toxicity of the sulfur is high, the vulcanizing equipment and technical requirements for production are high, 2, converter blowing is adopted, the heat energy is excessive, and the furnace heat load is high.
The Chinese patent application CN103103352A discloses a method for jointly producing nickel matte by using sulfur-containing waste residues and laterite-nickel ore, which mainly comprises the steps of uniformly mixing the sulfur-containing waste residues, a reducing agent and the laterite-nickel ore, and then introducing a direct-current electric furnace or an alternating-current electric furnace to smelt for 20-60 min at 1200-1400 ℃ to obtain a nickel matte product. The patent application of the invention has the following defects of 1, low grade and recovery rate of valuable metals nickel and cobalt of the product, 2, high process energy consumption and high production cost by adopting an electric furnace for smelting.
Therefore, a process for preparing high nickel matte by combining the aluminum slag of the three elements and the laterite-nickel ore is sought.
Disclosure of Invention
Based on the above, the present disclosure aims to provide a method for preparing high nickel matte by combining ternary iron aluminum slag and laterite nickel ore, wherein ternary iron aluminum slag is used to replace pyrite (FeS 2)/gypsum (CaSO 4·2H2 O) in the prior art as a vulcanizing agent in the process, and a side blowing furnace is used for reducing and vulcanizing to prepare high nickel matte, so that valuable metals such as nickel, cobalt and the like in ternary iron aluminum slag are effectively recycled, and meanwhile, high nickel and cobalt grades and high nickel and cobalt direct yield products of the high nickel matte are obtained.
A method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore comprises the following steps:
(1) Drying, namely respectively drying the ternary iron-aluminum slag and the laterite-nickel ore to enable the moisture content of the ternary iron-aluminum slag to be 10% -15% and the moisture content of the laterite-nickel ore to be 10% -15%;
(2) Mixing and granulating, namely uniformly mixing the dried ternary iron aluminum slag, the laterite-nickel ore, the first flux and the reducing agent, and granulating to obtain mixed granules;
(3) Reducing, vulcanizing and smelting, namely sending the mixed granules obtained in the step (2) into a side-blowing furnace for reducing, vulcanizing and smelting to obtain low-nickel matte, smelting slag and first flue gas;
(4) And (3) converting, namely uniformly mixing the low-nickel matte obtained in the step (3) with a second flux, and then feeding the mixture into a side-blowing furnace for converting to obtain high-nickel matte, converting slag and second flue gas.
According to the method for preparing the high-nickel matte by utilizing the ternary iron aluminum slag and the laterite nickel ore in a combined mode, the ternary iron aluminum slag and the laterite nickel ore are combined to prepare the high-nickel matte, because the aluminum content in the ternary iron aluminum slag is high, the aluminum content in mixed granules formed by mixing and granulating the whole ternary iron aluminum slag, the laterite nickel ore, the first flux and the reducing agent is improved, most of aluminum in the mixed granules and calcium, silicon and magnesium elements in the mixed granules form a quaternary slag system, the fluidity of smelting slag can be improved in the step (3) in the reduction, vulcanization and smelting process, the viscosity of smelting slag is reduced, so that the low-nickel matte obtained by reduction, vulcanization and smelting is easier to be aggregated, the Ni and Co grades and the direct yield in the low-nickel matte are higher, and the Ni and Co grades and the direct yield in the high-nickel matte are further improved. In addition, in the step (3), namely in the reduction vulcanization smelting process, the ternary iron aluminum slag can be used as a vulcanizing agent in the process, so that the reduction vulcanization effect in the reduction vulcanization process is improved, meanwhile, nickel and cobalt in the ternary iron aluminum slag enter the low-nickel matte and finally enter the high-nickel matte, and the grade of nickel and cobalt in the high-nickel matte is improved.
According to the method for preparing the high-nickel matte by combining the ternary iron aluminum slag and the laterite nickel ore, nickel and cobalt in the ternary iron aluminum slag enter the high-nickel matte, so that the grade of the nickel and cobalt in the high-nickel matte is improved, valuable metals such as the nickel and the cobalt in the ternary iron aluminum slag are effectively recycled, other impurity elements (manganese, aluminum, calcium, magnesium, silicon and the like) enter slag to be solidified, the ternary iron aluminum slag can be cooperatively utilized, the stock quantity of the ternary iron aluminum slag is effectively reduced, and the pollution to the land is reduced.
In the step (1), the ternary iron aluminum slag comprises, by mass, 0.9% -5.4% of ：Ni 2.1％～2.6％、Co 1.3％～1.5％、Mn 1.0％～1.2％、Fe 22.9％～23.4％、S29.8％～30.4％、Al15.4％～15.9％、P 5.2％～5.7％、Ca 10.7％～11.2％、Mg 6.0％～6.9％、Si 0.2％～0.3％、 parts of other components, and the laterite-nickel ore comprises, by mass, 1.62% -5.45% of ：Ni 1.7％～1.8％、Co 0.05％～0.08％、Mn 0.6％～0.8％、Cr 0.7％～1.0％、Fe 34.9％～35.9％、S 0.1％～0.2％、Al 3.8％～4.2％、Ca0.2％～0.8％、Mg 23.7％～24.1％、Si 28.8％～29.5％、 parts of other components. In some preferred schemes, the ternary iron-aluminum slag and the laterite-nickel ore with the above content components are adopted respectively, so that valuable metals such as rich nickel, chromium and the like in the ternary iron-aluminum slag and the laterite-nickel ore can be effectively utilized, elements such as manganese, aluminum, calcium, magnesium and silicon are provided by the ternary iron-aluminum slag and the laterite-nickel ore, slag systems can be formed in the reduction vulcanization smelting process, the fluidity of smelting slag in the reduction vulcanization smelting process in the step (3) is improved, and the viscosity of smelting slag is reduced.
In the step (1), ternary iron aluminum slag and laterite-nickel ore are respectively sent into a rotary kiln to be dried, and the ternary iron aluminum slag and the laterite-nickel ore are dried for 3-7 hours at the temperature of 100-300 ℃. And respectively conveying the ternary iron-aluminum slag and the laterite-nickel ore into a rotary kiln to be dried at the drying temperature of 100-300 ℃ for 3-7 hours, so that the moisture in the ternary iron-aluminum slag and the laterite-nickel ore can be reduced respectively, the moisture content of the ternary iron-aluminum slag is dried to 10-15%, and the moisture content of the laterite-nickel ore is dried to 10-15%.
In the step (2), before mixing, the ternary iron-aluminum slag and the laterite-nickel ore which are dried in the step (1) are respectively crushed and screened, the ternary iron-aluminum slag and the laterite-nickel ore are respectively screened to 3 mm-5 mm, the granularity of the reducing agent is 1 mm-2 mm, the ternary iron-aluminum slag, the laterite-nickel ore, the first flux and the reducing agent are uniformly mixed to obtain a mixed material with granularity of 4 mm-6 mm, and then the mixed material is granulated to obtain mixed granules with granularity of 10-15 mm. The three-element iron aluminum slag and the laterite nickel ore are respectively screened to 3 mm-5 mm, and the reducing agent with the granularity of 1 mm-2 mm is selected, so that the three-element iron aluminum slag and the laterite nickel ore can be uniformly mixed and can react more fully during subsequent reduction, vulcanization and smelting conveniently after being mixed, if the granularity is too large, the materials are not uniformly mixed, the subsequent reaction is insufficient, and if the granularity is too fine, the materials easily enter smoke dust in the subsequent reaction process to cause certain loss, so that the granularity of the materials is selected in a proper range.
In the step (2), the mass ratio of the ternary iron aluminum slag, the laterite-nickel ore, the first flux and the reducing agent is (20-50): 50 (4-7): 2.5-4. The mass ratio of the ternary iron-aluminum slag, the laterite-nickel ore, the first flux and the reducing agent is (20-50) 50 (4-7) 2.5-4, the grade of Ni and Co of low nickel-sulfur produced in reduction, vulcanization and smelting is high, the direct yield is also high, the slag type of smelting slag meets the requirements, the smelting slag has good fluidity and low viscosity, thereby being more beneficial to the aggregation of nickel matte, and meanwhile, the reaction temperature is also low, and the energy consumption is reduced.
As one preferable scheme, the reducing agent is at least one of pulverized coal, semi-coke, reducing coal and coke. At least one of pulverized coal, semi-coke, reducing coal and coke is used as a reducing agent, so that the high-valence sulfur in the aluminum slag of the three-element iron and the laterite nickel ore can be effectively reduced, and the aluminum slag of the three-element iron and the laterite nickel ore can be converted into nickel matte.
As one preferable scheme, the first flux is at least one of quartz sand and limestone. At least one of quartz sand and limestone is adopted as a first flux, so that the smelting effect in the reduction, vulcanization and smelting process is better.
In the step (3), the smelting temperature is 1300-1600 ℃ and the smelting time is 30-60 min. In the reduction vulcanization smelting process, smelting is carried out for 30-60 min at the smelting temperature of 1300-1600 ℃, so that the reducing agent can fully react with the aluminum slag of the three-element iron and the laterite-nickel ore, and is converted into low-nickel matte.
As one of the preferred schemes, the low nickel matte obtained in the step (3) contains the following components, by mass, 10% -28% of Ni, 0.2% -0.3% of Co, 50% -70% of Fe and 19% -21% of S, and the smelting slag obtained in the step (3) contains the following components ：Ni 0.09％～0.2％、Co 0.01％～0.04％、Mn 0.2％～0.5％、FeO 35％～40％、CaO 10％～13％、SiO2 28％～34％、Al2O3 10％～15％、MgO 10％～16％., by mass, in the low nickel sulfur obtained by adopting the preparation method of the scheme, the nickel direct yield is 93% -98% and the cobalt direct yield is 95% -98%, so that nickel and cobalt in laterite-nickel ore and ternary iron-aluminum slag can be effectively utilized.
In the step (4), the mass ratio of the second flux to the low nickel matte is (10-15) to 50. The mass ratio of the second flux to the low-nickel matte is limited to (10-15): 50, and the produced high-nickel-sulfur Ni and Co have high grade, high direct yield and better converting effect in the converting process.
In the step (4), the blowing temperature is 1350-1500 ℃ and the smelting time is 60-120 min. In the blowing process, smelting is carried out for 60-120 min at the smelting temperature of 1350-1500 ℃, so that the Fe content in the high-nickel matte can be sufficiently reduced, and the nickel and cobalt grades of the high-nickel matte are improved.
As one of the preferred schemes, the high nickel matte obtained in the step (4) contains the following components, by mass, 40% -61% of Ni, 1.3% -2.4% of Co, 7% -38% of Fe and 20% -28% of S, and the converting slag obtained in the step (4) contains the following components ：Ni 1.5％～3.3％、Co 0.5％～1.5％、Mn 1.2％～2.0％、FeO 38％～43％、CaO7％～11％、SiO2 30％～36％、Al2O3 7％～10％、MgO 8％～12％., by mass, in the high nickel matte obtained by adopting the preparation method of the scheme, the nickel direct yield is 95% -98%, the cobalt direct yield is 95% -97%, and the nickel and cobalt grades in the high nickel matte are higher.
In the step (4), the low-nickel matte and the second flux are mixed uniformly, then are sent into a side blowing furnace, compressed air is introduced into the side blowing furnace, and blowing is carried out, wherein the air supply rate of the compressed air is 10000Nm 3/h～20000Nm3/h. The compressed air is utilized to carry out converting, and the air supply rate is controlled, so that the converting effect is better.
As one preferable scheme, the second flux is at least one of quartz sand and limestone. At least one of quartz sand and limestone is adopted as a second flux, so that the blowing effect is better.
As one of the preferred schemes, the method for preparing the high nickel matte by combining the ternary iron aluminum slag and the laterite-nickel ore in the present disclosure further comprises the following steps:
(5) And (3) secondary reduction vulcanization smelting/secondary blowing, namely carrying out secondary reduction vulcanization smelting on the blowing slag obtained in the step (4) to obtain low-nickel matte, smelting slag and first smoke, adding a second flux into low-nickel sulfur to carry out blowing to obtain high-nickel matte, converting slag and second smoke, or mixing the blowing slag obtained in the step (4) with the second flux to carry out secondary blowing to obtain high-nickel matte, converting slag and second smoke.
In order to further improve the utilization rate of nickel and cobalt, the smelting slag obtained in the step (4) can be subjected to secondary reduction, vulcanization and smelting or secondary blowing, so that the nickel and cobalt in the blowing slag are effectively utilized.
As one of the preferred schemes, the method for preparing the high nickel matte by combining the ternary iron aluminum slag and the laterite-nickel ore in the present disclosure further comprises the following steps:
(6) Performing water quenching on the smelting slag, namely performing water quenching treatment on the smelting slag obtained in the step (3) and the step (5) to obtain water quenching slag, and recycling the water quenching slag;
(7) And (3) waste heat recovery, namely respectively introducing the first flue gas obtained in the step (3) and the step (4) and the second flue gas obtained in the step (5) into a waste heat boiler for cooling, and recovering waste heat.
The method comprises the steps of carrying out water quenching treatment on smelting slag to obtain water quenching slag, enabling the water quenching slag to be further recycled, respectively introducing first flue gas and second flue gas into a waste heat boiler to cool, recovering waste heat, enabling a large amount of steam generated by cooling to be used for power generation or other production purposes, introducing the cooled flue gas into an electric dust collector and a bag dust collector to collect smoke dust to achieve a dust removal effect, and enabling the dust removal smoke dust to reach a qualified emission standard after denitration and desulfurization and then to be discharged into the atmosphere.
Compared with the prior art, the beneficial effects of the present disclosure are:
(1) According to the method disclosed by the invention, the ternary iron aluminum slag and the laterite nickel ore are combined to prepare the high nickel matte, so that nickel and cobalt in the ternary iron aluminum slag enter the high nickel matte, the grade of nickel and cobalt in the nickel matte is improved, valuable metals such as nickel and cobalt in the ternary iron aluminum slag are effectively recycled, other impurity elements (manganese, aluminum, calcium, magnesium, silicon and the like) enter smelting slag to be solidified, and the ternary iron aluminum slag and the laterite nickel ore are combined to cooperatively realize the resource utilization of the ternary iron aluminum slag, so that the stock quantity of the ternary iron aluminum slag is effectively reduced, and the pollution to the land is reduced.
(2) When the ternary iron aluminum slag and the laterite nickel ore are combined to prepare the high nickel matte, because the aluminum content in the ternary iron aluminum slag is higher, the aluminum content in the whole mixed material system of the ternary iron aluminum slag and the laterite nickel ore is improved, most of aluminum and calcium, silicon and magnesium elements in the mixed material form a quaternary slag system, the fluidity of smelting slag is further improved, the viscosity of smelting slag is reduced, and thus the reduced and vulcanized low nickel matte is easier to agglomerate, and the Ni and Co grades and the direct yield in the low nickel matte are higher, so that the Ni and Co grades and the direct yield in the low nickel matte are improved.
(3) The method comprises the steps of replacing pyrite (FeS 2)/gypsum (CaSO 4·2H2 O) with ternary iron aluminum slag as a vulcanizing agent in a reduction vulcanization smelting process, enabling NiSO 4、CoSO4、Fe2(SO4)3 in the ternary iron aluminum slag to react with a reducing agent (pulverized coal, semi-coke, reducing coal or coke) respectively to generate NiS, coS, feS, enabling FeO to react with Fe 2(SO4)3 and the reducing agent to generate FeS, and enabling the FeS generated later to react with NiO and CoO in laterite nickel ore respectively to generate NiS and CoS, wherein NiS, coS, feS is the main component of nickel matte.
(4) The method adopts the side-blown furnace to smelt and generate the low-nickel matte, and then utilizes the side-blown furnace to blow and generate the high-nickel matte, so that the process flow is simple, the energy consumption is low, and the smelting equipment with high grade and direct yield of valuable metal nickel and cobalt in the product nickel matte is changed from an electric furnace to the side-blown furnace, thereby reducing the equipment investment cost.
(5) The flue gas utilizes a waste heat boiler to recycle waste heat, and the obtained steam can be used for power generation or other production purposes.
For a better understanding and implementation, the present disclosure is described in detail below with reference to the drawings.
Drawings
Fig. 1 is a process flow diagram of the combined preparation of high nickel matte from ternary iron aluminum slag and laterite-nickel ore of the present disclosure.
Detailed Description
To better illustrate the contents of the present disclosure, the following examples are provided. Unless otherwise specified, the following examples were carried out using the process flow shown in FIG. 1.
Example 1
The embodiment is a method for preparing high nickel matte by combining three-element iron aluminum slag and laterite-nickel ore with a saprolite layer, referring to fig. 1, comprising the following steps:
In the embodiment, the chemical components of the ternary iron-aluminum slag are Ni 2.1%, co 1.3%, fe 22.9%, mn 1.0%, P5.2%, S29.8%, al 15.4%, ca 10.7%, mg 6.0%, si 0.2%, other 5.4%, and the chemical components of the red soil nickel ore of the sapropel layer are Ni 1.7%, co 0.05%, fe 34.9%, mn 0.6%, cr 0.7%, S0.1%, al 3.8%, ca 0.2%, mg 23.7%, si 28.8% and other 5.45%.
(1) And (3) drying, namely respectively conveying the ternary iron-aluminum slag and the red soil nickel ore in the sapropel layer into a rotary kiln for drying treatment, and drying for 3 hours at 300 ℃, wherein the moisture of the ternary iron-aluminum slag and the red soil nickel ore in the sapropel layer is dried to 10%. And after the drying is finished, placing the dried ternary iron aluminum slag in a ternary iron aluminum slag material bin for storage, and placing the dried laterite-nickel ore in a laterite-nickel ore bin for storage.
(2) Mixing ingredients and granulating:
And (3) mixing, namely respectively crushing and screening the ternary iron-aluminum slag and the red soil nickel ore in the sapropel layer obtained in the step (1), wherein the ternary iron-aluminum slag and the red soil nickel ore in the sapropel layer are screened to 3mm, and the granularity of the reducing agent is required to be 1mm. In the embodiment, the flux 1 is quartz sand, the reducing agent is semi-coke, the mixture is prepared by mixing ternary iron aluminum slag, the red clay nickel ore with a saprolite layer, the quartz sand and the semi-coke in a mass ratio of 20:50:4:2.5, and the ternary iron aluminum slag, the red clay nickel ore with a saprolite layer, the quartz sand and the semi-coke are uniformly mixed to obtain a fine-grained mixed material with a granularity of 4mm.
Granulating, namely granulating the obtained fine-granularity mixed material to obtain coarse-granularity mixed granules with granularity of 10mm, wherein the aim is to prevent the mixed granules entering a side-blowing furnace from being too fine in granularity, so that most of the materials enter smoke dust and cause certain loss.
(3) And (3) reducing, vulcanizing and smelting, namely sending the coarse-grain mixed granules obtained in the step (2) into a side blowing furnace for reducing, vulcanizing and smelting, wherein the smelting temperature is 1300 ℃, smelting is 30min, and naturally cooling to obtain the low-nickel matte, smelting slag and a part of flue gas 1. Wherein the obtained low nickel matte contains the following components by mass percent of Ni 10%, co 0.2%, fe 70%, S19%, the direct yield of nickel is 93% and the direct yield of cobalt is 95%, and the obtained smelting slag contains the following components by mass percent of Ni 0.2%, co0.04%, mn 0.5%, feO 36%, caO 10%, siO 2 30％、Al2O3%, mgO 11% and other 2.26%.
(4) And (3) blowing, namely uniformly mixing the low-nickel matte obtained in the step (3) with the flux 2 according to a certain mass ratio, wherein the mass ratio of the flux 2 to the low-nickel matte is 10:50. After being mixed uniformly, the mixture is sent into a side blowing furnace, compressed air is introduced into the side blowing furnace, blowing is carried out, the air supply rate of the compressed air is 10000L/h, the blowing temperature is 1350 ℃, smelting is carried out for 60min, and the product high nickel matte, blowing slag and a part of smoke 2 are obtained after natural cooling. Wherein, the product contains Ni 40%, co 1.3%, fe 38%, S20%, nickel direct yield 95% and cobalt direct yield 95% in percentage by mass, and the obtained blowing slag contains the following components of Ni 1.7%, co 0.9%, mn 1.3%, feO 39%, caO 8%, siO 2 31％、Al2O3%, mgO 9% and other 1.1%.
(5) Secondary reduction sulfidation smelting/secondary blowing:
in this embodiment, one of the following two modes may be adopted, and for convenience in describing this embodiment, both modes of this embodiment are implemented:
And (3) returning the converting slag obtained in the step (4) to an oxygen-enriched side-blowing furnace for secondary reduction and vulcanization smelting to obtain low-nickel matte, smelting slag and flue gas 1, and adding a flux 2 into the obtained low-nickel matte for converting, wherein the mass ratio of the flux 2 to the low-nickel matte is 10:50, and obtaining the high-nickel matte, converting slag and a part of flue gas 2 after converting is finished.
Or mixing the converting slag obtained in the step (4) with the flux 2 according to a certain mass ratio, wherein the mass ratio of the flux 2 to the converting slag is 5:50. And returning the uniformly mixed materials to a side blowing furnace for secondary blowing to obtain the product high-nickel matte, blowing slag and a part of flue gas 2.
(6) And (3) water quenching the smelting slag, namely carrying out water quenching treatment on the smelting slag obtained in the step (3) to obtain water quenching slag, wherein the water quenching slag accords with the technical specification of outsourcing and can be outsourced.
(7) Waste heat recovery, namely respectively introducing the flue gas 1 obtained in the step (3) and the step (5) and the flue gas 2 obtained in the step (4) and the step (5) into a waste heat boiler for cooling, recovering waste heat, wherein a large amount of steam generated by cooling can be used for power generation or other production purposes, introducing the flue gas cooled by the waste heat boiler into an electric dust collector and a cloth bag dust collector for collecting smoke dust to achieve a dust removal effect, and then, after denitration and desulfurization, the dust removal smoke dust reaches a qualified emission standard and is discharged into the atmosphere.
Example 2
The embodiment is a method for preparing high nickel matte by combining three-element iron aluminum slag and laterite-nickel ore with a saprolite layer, referring to fig. 1, comprising the following steps:
In the embodiment, the chemical components of the ternary iron-aluminum slag are Ni 2.6%, co 1.5%, mn 1.2%, fe 23.4%, S30.4%, al 15.9%, P5.7%, ca 11.2%, mg 6.9%, si 0.3% and other 0.9%, and the chemical components of the red clay nickel ore of the saprolite layer are Ni 1.8%, co 0.08%, mn 0.8%, cr 1.0%, fe 35.9%, S0.2%, al 4.2%, ca 0.8%, mg 24.1%, si 29.5% and other 1.62%.
(1) And (3) drying, namely respectively conveying the ternary iron-aluminum slag and the red soil nickel ore in the sapropel layer into a rotary kiln for drying treatment, and drying for 3 hours at 300 ℃, wherein the moisture of the ternary iron-aluminum slag and the red soil nickel ore in the sapropel layer is dried to 10%. And after the drying is finished, placing the ternary iron aluminum slag in a ternary iron aluminum slag material bin for storage, and placing the red soil nickel ore in the sapropel layer in a red soil nickel mineral bin for storage.
(2) Mixing ingredients and granulating:
Crushing and screening the ternary iron aluminum slag and the red soil nickel ore with the sapropel layer obtained in the step (1) respectively, wherein the ternary iron aluminum slag and the red soil nickel ore with the sapropel layer are screened to 3mm, and the granularity of the reducing agent is required to be 1mm. In the embodiment, the flux 1 is quartz sand, the reducing agent is semi-coke, the mixture is prepared by mixing ternary iron aluminum slag, the red clay nickel ore with a saprolite layer, the quartz sand and the semi-coke in a mass ratio of 40:50:6:3.5, and the ternary iron aluminum slag, the red clay nickel ore with a saprolite layer, the quartz sand and the semi-coke are uniformly mixed to obtain a fine-grained mixed material with a granularity of 4mm.
Granulating, namely granulating the obtained fine-granularity mixed material to obtain coarse-granularity mixed granules with granularity of 10mm, wherein the aim is to prevent the mixed granules entering a side-blowing furnace from being too fine in granularity, so that most of the materials enter smoke dust and cause certain loss.
(3) And (3) reducing, vulcanizing and smelting, namely sending the coarse-grain mixed granules obtained in the step (2) into a side blowing furnace for reducing, vulcanizing and smelting, wherein the smelting temperature is 1600 ℃, smelting is carried out for 60min, and low-nickel matte, smelting slag and a part of flue gas 1 are obtained after natural cooling. Wherein the obtained low nickel-sulfur contains the following components by mass percent of Ni 28%, co 0.3%, fe 50%, S21%, nickel direct yield 98% and cobalt direct yield 98%, and the obtained smelting slag contains the following components by mass percent of Ni 0.09%, co0.01%, mn 0.2%, feO 35%, caO 10%, siO 2 28％、Al2O3%, mgO 10% and other 6.7%.
(4) And (3) blowing, namely uniformly mixing the low-nickel matte obtained in the step (3) with the flux 2 according to a certain mass ratio, wherein the mass ratio of the flux 2 to the low-nickel matte is 15:50. After being mixed uniformly, the mixture is sent into a side blowing furnace, compressed air is introduced into the side blowing furnace, blowing is carried out, the air supply rate of the compressed air is 20000L/h, the blowing temperature is 1500 ℃, smelting is carried out for 120min, and the product high nickel matte, blowing slag and a part of smoke 2 are obtained after natural cooling. The high nickel matte product contains, by mass, 61% of Ni, 2.4% of Co, 7% of Fe, 28% of S, 98% of nickel and 97% of cobalt, and the obtained blowing slag contains, by mass, 1.5% of Ni, 0.5% of Co, 1.2% of Mn, 38% of FeO, 7% of CaO, 2 30％、Al2O3% of SiO, 8% of MgO and 6.8% of other components.
(5) Secondary reduction sulfidation smelting/secondary blowing:
in this embodiment, one of the following two modes may be adopted, and for convenience in describing this embodiment, both modes of this embodiment are implemented:
and (3) returning the converting slag obtained in the step (4) to an oxygen-enriched side-blowing furnace for secondary reduction vulcanization smelting to obtain low-nickel matte, smelting slag and flue gas 1, and adding a flux 2 into low-nickel sulfur for converting, wherein the mass ratio of the flux 2 to the low-nickel matte is 15:50, and obtaining the high-nickel matte, the converting slag and a part of flue gas 1 after converting.
Or mixing the converting slag obtained in the step (4) with the flux 2 according to a certain mass ratio, wherein the mass ratio of the flux 2 to the converting slag is 7:50. And returning the uniformly mixed materials to a side blowing furnace for secondary blowing to obtain the product high-nickel matte, blowing slag and a part of flue gas 2.
(6) And (3) water quenching the smelting slag, namely carrying out water quenching treatment on the smelting slag obtained in the step (3) to obtain water quenching slag, wherein the water quenching slag accords with the technical specification of outsourcing and can be outsourced.
(7) Waste heat recovery, namely respectively introducing the flue gas 1 obtained in the step (3) and the step (5) and the flue gas 2 obtained in the step (4) and the step (5) into a waste heat boiler for cooling, recovering waste heat, wherein a large amount of steam generated by cooling can be used for power generation or other production purposes, introducing the flue gas cooled by the waste heat boiler into an electric dust collector and a cloth bag dust collector for collecting smoke dust to achieve a dust removal effect, and then, after denitration and desulfurization, the dust removal smoke dust reaches a qualified emission standard and is discharged into the atmosphere.
Example 3
The embodiment is a method for preparing high nickel matte by combining three-element iron aluminum slag and laterite-nickel ore with a saprolite layer, referring to fig. 1, comprising the following steps:
In the embodiment, the chemical components of the ternary iron-aluminum slag are Ni 2.3%, co 1.4%, mn 1.1%, fe 23.1%, S30.2%, al 15.6%, P5.5%, ca 10.9%, mg 6.6%, si 0.25% and other 3.05%, and the chemical components of the red clay nickel ore of the saprolite layer are Ni 1.75%, co 0.06%, mn 0.7%, cr 0.8%, fe 35.5%, S0.16%, al 4.0%, ca 0.6%, mg 23.9%, si 29.3% and other 3.23%.
(1) And (3) drying, namely respectively conveying the ternary iron-aluminum slag and the red soil nickel ore in the sapropel layer into a rotary kiln for drying treatment, and drying for 4 hours at 200 ℃, wherein the moisture content of the ternary iron-aluminum slag and the red soil nickel ore in the sapropel layer is 12 percent. And after the drying is finished, placing the ternary iron aluminum slag in a ternary iron aluminum slag material bin for storage, and placing the red soil nickel ore in the sapropel layer in a red soil nickel mineral bin for storage.
(2) Mixing ingredients and granulating:
And (3) mixing ingredients, namely respectively crushing and screening the ternary iron aluminum slag and the red soil nickel ore in the sapropel layer obtained in the step (1), wherein the ternary iron aluminum slag and the red soil nickel ore in the sapropel layer are screened to 4mm, and the granularity of the reducing agent is required to be 1.5mm. In the embodiment, the flux 1 is quartz sand, the reducing agent is semi-coke, the mixture is prepared by mixing ternary iron aluminum slag, the red clay nickel ore with a saprolite layer, the quartz sand and the semi-coke in a mass ratio of 50:50:6:3.5, and the ternary iron aluminum slag, the red clay nickel ore with a saprolite layer, the quartz sand and the semi-coke are uniformly mixed to obtain a fine-grained mixed material with a granularity of 4mm.
Granulating, namely granulating the obtained fine-granularity mixed material to obtain coarse-granularity mixed granules with the granularity of 13mm, and aiming at preventing the mixed granules entering a side-blowing furnace from being too fine in granularity, so that most of the materials enter smoke dust and cause certain loss.
(3) And (3) reducing, vulcanizing and smelting, namely sending the coarse-grain mixed granules obtained in the step (2) into a side blowing furnace for reducing, vulcanizing and smelting, wherein the smelting temperature is 1500 ℃, smelting is 45min, and naturally cooling to obtain low-nickel matte, smelting slag and a part of flue gas 1. The obtained low-nickel matte contains the following components in percentage by mass of Ni 26%, co 0.24%, fe 54%, S19%, nickel direct yield 94% and cobalt direct yield 96%, and the obtained smelting slag contains the following components in percentage by mass of Ni 0.15%, co0.03%, mn 0.3%, feO 37%, caO 11%, siO 2 29％、Al2O3%, mgO 10% and other 1.52%.
(4) And (3) blowing, namely uniformly mixing the low-nickel matte obtained in the step (3) with the flux 2 according to a certain mass ratio, wherein the mass ratio of the flux 2 to the low-nickel matte is 13:50. After being mixed evenly, the mixture is sent into a side blowing furnace, compressed air is introduced into the side blowing furnace, blowing is carried out, the air supply rate of the compressed air is 20000L/h, the blowing temperature is 1450 ℃, smelting is carried out for 90min, and the product high nickel matte, blowing slag and a part of smoke 2 are obtained after natural cooling. The high nickel matte product contains, by mass, 53% of Ni, 2.1% of Co, 16% of Fe, 27% of S, 97% of nickel in direct yield and 96% of cobalt in direct yield, and the obtained blowing slag contains, by mass, 1.6% of Ni, 1.1% of Co, 1.6% of Mn, 40% of FeO, 7% of CaO, 2 30％、Al2O3% of SiO, 8% of MgO and other 1.7%.
(5) Secondary reduction sulfidation smelting/secondary blowing:
in this embodiment, one of the following two modes may be adopted, and for convenience in describing this embodiment, both modes of this embodiment are implemented:
And (3) returning the converting slag obtained in the step (4) to an oxygen-enriched side blowing furnace for secondary reduction and vulcanization smelting to obtain low-nickel matte, smelting slag and flue gas 1, and adding a flux 2 into low-nickel sulfur for converting, wherein the mass ratio of the flux 2 to the low-nickel matte is 13:50, and obtaining the high-nickel matte, converting slag and a part of flue gas 2 after converting.
Or mixing the converting slag obtained in the step (4) with the flux 2 according to a certain mass ratio, wherein the mass ratio of the flux 2 to the converting slag is 6:50. And returning the uniformly mixed materials to a side blowing furnace for secondary blowing to obtain the product high-nickel matte, blowing slag and a part of flue gas 2.
(6) And (3) water quenching the smelting slag, namely carrying out water quenching treatment on the smelting slag obtained in the step (3) to obtain water quenching slag, wherein the water quenching slag accords with the technical specification of outsourcing and can be outsourced.
(7) Waste heat recovery, namely respectively introducing the flue gas 1 obtained in the step (3) and the step (5) and the flue gas 2 obtained in the step (4) and the step (5) into a waste heat boiler for cooling, recovering waste heat, wherein a large amount of steam generated by cooling can be used for power generation or other production purposes, introducing the flue gas cooled by the waste heat boiler into an electric dust collector and a cloth bag dust collector for collecting smoke dust to achieve a dust removal effect, and then, after denitration and desulfurization, the dust removal smoke dust reaches a qualified emission standard and is discharged into the atmosphere.
Comparative example 1
The method for preparing high nickel matte of this comparative example is different from example 1 in that the ternary iron aluminum slag is changed to gypsum (CaSO 4·2H2 O).
In the comparative example, the chemical components of gypsum (CaSO 4·2H2 O) are 32.6% of CaO and 20.9% of SO 3 46.5％、H2 O. The chemical components of the laterite-nickel ore in the sapropel layer are Ni 1.7%, co 0.05%, fe 34.9%, mn 0.6%, cr 0.7%, S0.1%, al 3.8%, ca 0.2%, mg 23.7%, si 28.8% and other 5.45%.
(1) And (3) drying, namely respectively conveying gypsum (CaSO 4·2H2 O) and the laterite-nickel ore in the sapropel layer into a rotary kiln for drying treatment, and drying at 300 ℃ for 3 hours, wherein the moisture of the gypsum (CaSO 4·2H2 O) and the laterite-nickel ore in the sapropel layer are both dried to 10%. After the drying is finished, placing gypsum (CaSO 4·2H2 O) in a gypsum (CaSO 4·2H2 O) material bin for storage, and placing the red soil nickel ore in the sapropel layer in a red soil nickel mineral bin for storage.
(2) Mixing ingredients and granulating:
and (3) mixing, namely respectively crushing and screening the gypsum (CaSO 4·2H2 O) and the laterite-nickel ore in the sapropel layer obtained in the step (1), wherein the gypsum (CaSO 4·2H2 O) and the laterite-nickel ore in the sapropel layer are screened to 3mm, and the granularity of the reducing agent is required to be 1mm. In the embodiment, the flux 1 is quartz sand, the reducing agent is semi-coke, the ingredients are mixed by the mass ratio of gypsum (CaSO 4·2H2 O), the laterite-nickel ore of the saprolite layer, the quartz sand and the semi-coke being 20:50:4:2.5, and the gypsum (CaSO 4·2H2 O), the laterite-nickel ore of the saprolite layer, the quartz sand and the semi-coke are uniformly mixed to obtain a fine-granularity mixed material, and the granularity is 4mm.
Granulating, namely granulating the fine-granularity mixed material obtained in the step (2) to obtain coarse-granularity mixed granules with the granularity of 10mm, and aiming at preventing the mixed granules entering a side-blowing furnace from being too fine in granularity, so that most of the material enters smoke dust and causing certain loss.
(3) And (3) reduction vulcanization smelting, namely sending the coarse-grain mixed granules obtained in the step (2) into a side blowing furnace for reduction vulcanization smelting, wherein the smelting temperature is 1300 ℃, smelting is 30min, and naturally cooling to obtain low-nickel matte and smelting slag, so as to generate a part of flue gas 1. Wherein the low nickel matte product contains the following components by mass percent of Ni 6%, co 0.05%, fe 65%, S26%, nickel direct yield 80% and cobalt direct yield 84%, and the obtained smelting slag contains the following components by mass percent of Ni 0.2%, co0.04%, mn 0.4%, feO 36%, caO 12%, siO 2 29％、Al2O3%, mgO 11% and other 1.36%.
(4) And (3) blowing, namely uniformly mixing the low-nickel matte obtained in the step (3) with the flux 2 according to a certain mass ratio, wherein the mass ratio of the flux 2 to the low-nickel matte is (10): 50. After being mixed uniformly, the mixture is sent into a side blowing furnace, compressed air is introduced into the side blowing furnace, blowing is carried out, the air supply rate of the compressed air is 10000L/h, the blowing temperature is 1350 ℃, smelting is carried out for 60min, and the product high nickel matte, blowing slag and part of flue gas are obtained after natural cooling. The high nickel matte product contains, by mass, ni 28%, co 0.8%, fe 42%, S28%, nickel direct yield 85% and cobalt direct yield 88%, and the obtained blow-smelting slag contains, by mass, ni 2%, co 1.3%, mn 1.8%, feO 40%, caO 8%, siO 2 31％、Al2O3%, mgO 8% and other 0.9%.
(5) Secondary reduction sulfidation smelting/secondary blowing:
In the comparative example, one of the following two modes is adopted, and for convenience of comparison, the two modes of the comparative example are both compared and implemented:
and (3) returning the converting slag obtained in the step (4) to an oxygen-enriched side blowing furnace for secondary reduction and vulcanization smelting to obtain low-nickel matte, smelting slag and flue gas 1, and adding a flux 2 into low-nickel sulfur for converting, wherein the mass ratio of the flux 2 to the low-nickel matte is 10:50, and obtaining the high-nickel matte, converting slag and a part of flue gas 2 after converting.
Or mixing the converting slag obtained in the step (4) with the flux 2 according to a certain mass ratio, wherein the mass ratio of the flux 2 to the converting slag is 5:50. And returning the uniformly mixed materials to a side blowing furnace for secondary blowing to obtain the product high-nickel matte, blowing slag and a part of flue gas 2.
(6) And (3) water quenching the smelting slag, namely carrying out water quenching treatment on the smelting slag obtained in the step (5) to obtain water quenching slag, wherein the water quenching slag accords with the technical specification of outsourcing and can be outsourced.
(7) Waste heat recovery, namely respectively introducing the flue gas 1 obtained in the step (3) and the step (5) and the flue gas 2 obtained in the step (4) and the step (5) into a waste heat boiler for cooling, recovering waste heat, and enabling a large amount of steam generated by cooling to be used for power generation or other production purposes, introducing the flue gas cooled by the waste heat boiler into an electric dust collector and a cloth bag dust collector for collecting smoke dust to achieve a dust removal effect, and then, after denitration and desulfurization, enabling the dust removal smoke dust to reach a qualified emission standard and discharging the dust to the atmosphere.
In the embodiment 1-3, the ternary iron aluminum slag and the laterite nickel ore are combined to prepare the high nickel matte, so that nickel and cobalt in the ternary iron aluminum slag enter the high nickel matte, the grade of nickel and cobalt in the nickel matte is improved, valuable metals such as nickel and cobalt in the ternary iron aluminum slag are effectively recycled, other impurity elements (manganese, aluminum, calcium, magnesium, silicon and the like) enter smelting slag to be solidified, and the ternary iron aluminum slag and the laterite nickel ore are combined to realize the resource utilization of the ternary iron aluminum slag in a synergic manner, so that the stock quantity of the ternary iron aluminum slag is effectively reduced, and the pollution to the land is reduced.
In the embodiments 1-3 of the disclosure, compared with the comparative example 1, the ternary iron aluminum slag is used as the vulcanizing agent in the reduction, vulcanization and smelting process instead of gypsum (CaSO 4·2H2 O), firstly, the ternary iron aluminum slag can be reused, the process production cost is reduced, and secondly, the ternary iron aluminum slag can improve the grade of nickel and cobalt in the nickel matte, and has certain beneficial effects.
The foregoing examples represent only a few embodiments of the present disclosure, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the disclosure, and the disclosure is intended to encompass such modifications and improvements as well.
Claims (14)
1. The method for preparing the high-nickel matte by combining the ternary iron aluminum slag and the laterite-nickel ore is characterized by comprising the following steps of:
(1) Drying, namely respectively drying the ternary iron-aluminum slag and the laterite-nickel ore to enable the moisture content of the ternary iron-aluminum slag to be 10% -15% and the moisture content of the laterite-nickel ore to be 10% -15%;
Wherein the ternary iron-aluminum slag comprises the following components ：Ni 2.1％～2.6％、Co 1.3％～1.5％、Mn 1.0％～1.2％、Fe 22.9％～23.4％、S29.8％～30.4％、Al 15.4％～15.9％、P 5.2％～5.7％、Ca10.7％～11.2％、Mg 6.0％～6.9％、Si 0.2％～0.3％、 in percentage by mass and 0.9% -5.4% of other components;
(2) Mixing and granulating, namely uniformly mixing the dried ternary iron aluminum slag, the laterite-nickel ore, the first flux and the reducing agent, and granulating to obtain mixed granules;
wherein the mass ratio of the ternary iron aluminum slag to the laterite nickel ore to the first flux to the reducing agent is (20-50) 50 (4-7) 2.5-4;
(3) Reducing, vulcanizing and smelting, namely sending the mixed granules obtained in the step (2) into a side-blowing furnace for reducing, vulcanizing and smelting to obtain low-nickel matte, smelting slag and first flue gas;
(4) And (3) converting, namely uniformly mixing the low-nickel matte obtained in the step (3) with a second flux, and then feeding the mixture into a side-blowing furnace for converting to obtain high-nickel matte, converting slag and second flue gas.
2. The method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore, as claimed in claim 1, wherein in the step (1), the laterite-nickel ore comprises the following components ：Ni 1.7％～1.8％、Co 0.05％～0.08％、Mn 0.6％～0.8％、Cr 0.7％～1.0％、Fe 34.9％～35.9％、S 0.1％～0.2％、Al 3.8％～4.2％、Ca 0.2％～0.8％、Mg 23.7％～24.1％、Si 28.8％～29.5％、 in mass percent and other components 1.62% -5.45%.
3. The method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore, which is characterized in that in the step (1), the ternary iron aluminum slag and the laterite-nickel ore are respectively sent into a rotary kiln to be dried, and the ternary iron aluminum slag and the laterite-nickel ore are dried for 3-7 hours at 100-300 ℃.
4. The method for preparing the high nickel matte by utilizing the ternary iron aluminum slag and the laterite-nickel ore in a combined mode, which is disclosed by claim 1, is characterized in that in the step (2), before mixing, the ternary iron aluminum slag and the laterite-nickel ore which are dried in the step (1) are respectively crushed and screened, the ternary iron aluminum slag and the laterite-nickel ore are respectively screened to 3 mm-5 mm, the granularity of the reducing agent is 1 mm-2 mm, the ternary iron aluminum slag, the laterite-nickel ore, the first flux and the reducing agent are uniformly mixed to obtain a mixed material with the granularity of 4 mm-6 mm, and then the mixed material is granulated to obtain mixed granules with the granularity of 10-15 mm.
5. The method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore according to claim 1, wherein the reducing agent is at least one of pulverized coal, semi-coke, reduced coal and coke.
6. The method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore, which is characterized in that in the step (3), the smelting temperature is 1300-1600 ℃ and the smelting time is 30-60 min.
7. The method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore, which is characterized in that the low nickel matte obtained in the step (3) contains the following components, by mass, 10% -28% of Ni, 0.2% -0.3% of Co, 50% -70% of Fe and 19% -21% of S; the smelting slag obtained in the step (3) contains the following components in percentage by mass ：Ni0.09％～0.2％、Co 0.01％～0.04％、Mn 0.2％～0.5％、FeO 35％～40％、CaO 10％～13％、SiO228％～34％、Al2O3 10％～15％、MgO 10％～16％.
8. The method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore, as claimed in claim 1, wherein in the step (4), the mass ratio of the second flux to the low nickel matte is (10-15): 50.
9. The method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore, which is characterized in that in the step (4), the converting temperature is 1350-1500 ℃ and the converting time is 60-120 min.
10. The method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore, which is characterized in that the high nickel matte obtained in the step (4) contains the following components, by mass, 40% -61% of Ni, 1.3% -2.4% of Co, 7% -38% of Fe and 20% -28% of S; the converting slag obtained in the step (4) contains the following components in percentage by mass ：Ni1.5％～3.3％、Co 0.5％～1.5％、Mn 1.2％～2.0％、FeO 38％～43％、CaO 7％～11％、SiO2 30％～36％、Al2O3 7％～10％、MgO 8％～12％.
11. The method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore according to claim 1, wherein in the step (4), the low nickel matte and the second flux are mixed uniformly, and then are fed into a side blowing furnace to be blown with compressed air, and the blowing rate of the compressed air is 10000Nm 3/h～20000Nm3/h.
12. The method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore according to claim 1, wherein in the step (2), the first flux is at least one of quartz sand and limestone, and in the step (4), the second flux is at least one of quartz sand and limestone.
13. The method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore according to claim 1, further comprising the following steps:
(5) And (3) secondary reduction vulcanization smelting/secondary blowing, namely carrying out secondary reduction vulcanization smelting on the blowing slag obtained in the step (4) to obtain low-nickel matte, smelting slag and first smoke, adding a second flux into low-nickel sulfur to carry out blowing to obtain high-nickel matte, converting slag and second smoke, or mixing the blowing slag obtained in the step (4) with the second flux to carry out secondary blowing to obtain high-nickel matte, converting slag and second smoke.
14. The method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore according to claim 13, further comprising the steps of:
(6) Performing water quenching on the smelting slag, namely performing water quenching treatment on the smelting slag obtained in the step (3) and the step (5) to obtain water quenching slag, and recycling the water quenching slag;
(7) And (3) waste heat recovery, namely respectively introducing the first flue gas obtained in the step (3) and the step (5) and the second flue gas obtained in the step (4) and the step (5) into a waste heat boiler for cooling, and recovering waste heat.
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| PCT/CN2023/119430 WO2024037659A1 (en) | 2023-09-18 | 2023-09-18 | Method for preparing high-nickel matte by combining ternary iron-aluminum slag with laterite-nickel ore |
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| CN111996377A (en) * | 2020-08-13 | 2020-11-27 | 衢州华友资源再生科技有限公司 | Method for recovering nickel, cobalt and manganese metal from lithium extracted from waste batteries |
| CN115386736A (en) * | 2022-08-04 | 2022-11-25 | 广东邦普循环科技有限公司 | Method for treating laterite-nickel ore by oxygen-enriched side-blown converter |
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| CN114350977B (en) * | 2021-12-13 | 2024-04-16 | 中南大学 | Method for extracting nickel and cobalt by circular sulfuration of laterite-nickel ore |
| CN114317991B (en) * | 2021-12-31 | 2023-05-09 | 金川镍钴研究设计院有限责任公司 | Method for recycling valuable metals through carbonless smelting of iron-aluminum dangerous waste residues and wet desulphurization residues |
| CN116083737B (en) * | 2023-01-13 | 2024-10-22 | 中国恩菲工程技术有限公司 | Method and system for producing nickel matte by nickel-containing solid waste |
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| CN111996377A (en) * | 2020-08-13 | 2020-11-27 | 衢州华友资源再生科技有限公司 | Method for recovering nickel, cobalt and manganese metal from lithium extracted from waste batteries |
| CN115386736A (en) * | 2022-08-04 | 2022-11-25 | 广东邦普循环科技有限公司 | Method for treating laterite-nickel ore by oxygen-enriched side-blown converter |
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