CN117460855A - Method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore - Google Patents
Method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore Download PDFInfo
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- CN117460855A CN117460855A CN202380011396.7A CN202380011396A CN117460855A CN 117460855 A CN117460855 A CN 117460855A CN 202380011396 A CN202380011396 A CN 202380011396A CN 117460855 A CN117460855 A CN 117460855A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 494
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 319
- 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 68
- 238000003723 Smelting Methods 0.000 claims abstract description 109
- 238000007664 blowing Methods 0.000 claims abstract description 83
- 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 49
- 239000003546 flue gas Substances 0.000 claims abstract description 49
- 230000009467 reduction Effects 0.000 claims abstract description 45
- 238000006722 reduction reaction Methods 0.000 claims abstract description 45
- 238000004073 vulcanization Methods 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 38
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000008187 granular material Substances 0.000 claims abstract description 23
- 229910001710 laterite Inorganic materials 0.000 claims abstract description 18
- 239000011504 laterite Substances 0.000 claims abstract description 18
- 239000004615 ingredient Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000005486 sulfidation Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000010791 quenching Methods 0.000 claims description 30
- 230000000171 quenching effect Effects 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 239000002918 waste heat Substances 0.000 claims description 27
- 229910052717 sulfur Inorganic materials 0.000 claims description 22
- 239000000571 coke Substances 0.000 claims description 20
- 239000006004 Quartz sand Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 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
- 235000019738 Limestone Nutrition 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 239000006028 limestone Substances 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 36
- 239000010941 cobalt Substances 0.000 abstract description 36
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 36
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000000428 dust Substances 0.000 description 29
- 230000008569 process Effects 0.000 description 27
- 239000002689 soil Substances 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 17
- 239000010440 gypsum Substances 0.000 description 16
- 229910052602 gypsum Inorganic materials 0.000 description 16
- 239000011575 calcium Substances 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- 239000011572 manganese Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000000779 smoke Substances 0.000 description 7
- 238000003860 storage Methods 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
- 239000011651 chromium Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010248 power generation Methods 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000006243 chemical reaction Methods 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
- 239000002245 particle Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000012946 outsourcing Methods 0.000 description 4
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 238000009853 pyrometallurgy 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
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 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
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
-
- 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: (1) drying: respectively drying ternary iron aluminum slag and laterite nickel ore; (2) mixing ingredients and granulating: 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) reduction sulfidation smelting: feeding the mixed granules obtained in the step (2) into a side-blowing furnace for reduction, vulcanization and smelting to obtain low-nickel matte, smelting slag and first flue gas; (4) converting: and (3) 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 blowing to obtain high-nickel matte, blowing 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 ternary iron aluminum slag is treated by a hydrometallurgy method, so that the following defects are present: (1) the process flow is complex; (2) large reagent consumption and high production cost; (3) The process operation has high controllability difficulty, and is not beneficial to safe production; (4) high requirements on equipment. 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, mainly laterite-nickel ore and pyrite (FeS 2 ) Gypsum (CaSO) 4 ·2H 2 O) treating the nickel matte by a pyrometallurgy method, and treating the laterite-nickel ore by the pyrometallurgy method to produce the nickel matte mainly comprises an electric furnace smelting process, an RKEF process and an oxygen-enriched side-blown reduction vulcanization process. But is provided withThe electric furnace smelting and RKEF process has the following disadvantages: the energy consumption is high, and the production cost is high; (2) The process has the rotary kiln pre-reduction step, and the process cost is high; (3) the recovery rate of cobalt is low. The oxygen-enriched side-blown reduction vulcanization process can produce ferronickel and nickel matte, is a new process at present, has great advantages in various aspects, and has the following process routes: laterite nickel ore- & gt oxygen-enriched side-blown (reduction sulfidation) smelting- & gt low nickel matte- & gt side-blown converter converting- & gt high nickel matte.
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, and then feeding the mixture into a rotary kiln for reduction, vulcanization and roasting to obtain vulcanized calcine; then evenly mixing the sulphide calcine, the second carbon-based reducing agent and the second vulcanizing agent (sulfur), and then sending the mixture into a rotary kiln again for supplementary vulcanization reaction to obtain supplementary sulphide calcine; and feeding the supplemented sulphide calcine into an electric furnace or a side-blown furnace for smelting to obtain the low-nickel matte and slag. However, the patent application of the invention has the following disadvantages: the process flow is complex, gypsum slag and sulfur are respectively used as vulcanizing agents, the sulfur has high relative toxicity, 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-iron from laterite-nickel ore through continuous vulcanization blowing, which mainly comprises the following steps: smelting laterite nickel ore into nickel-iron alloy, performing primary water quenching and granulating, forming nickel-iron particles after the nickel-iron alloy is subjected to primary water quenching and granulating, continuously feeding nickel-iron particles, vulcanizing agent (sulfur) and flux ingredients into a converter for vulcanization, blowing to obtain molten high-nickel matte, and forming the high-nickel matte particles after the molten high-nickel matte is subjected to secondary water quenching and granulating. However, the patent application of the invention has the following disadvantages: 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, and the vulcanizing equipment and the technical requirements for production are high; 2. and converter converting is adopted, heat energy is excessive, and the heat load of a kiln is high.
The Chinese patent application CN103103352A discloses a method for producing nickel matte by combining sulfur-containing waste residues and laterite-nickel ores, which mainly comprises the following steps: uniformly mixing sulfur-containing waste residues, a reducing agent and laterite-nickel ore; then the mixture is put into a direct current electric furnace or an alternating current electric furnace to be smelted for 20 to 60 minutes at the temperature of 1200 to 1400 ℃ to obtain the nickel matte product. However, the patent application of the invention has the following disadvantages: 1. the grade and recovery rate of valuable metals nickel and cobalt of the product are low; 2. adopts electric furnace smelting, and has high process energy consumption and high production cost.
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 this, it is an object of the present disclosure to provide a method for preparing high nickel matte by combining ternary iron-aluminum slag and laterite-nickel ore, using ternary iron-aluminum slag to replace pyrite (FeS) in the prior art 2 ) Gypsum (CaSO) 4 ·2H 2 O) is used as a vulcanizing agent in the process, and a side blowing furnace is used for reducing and vulcanizing to prepare the high-nickel matte, so that valuable metals such as nickel, cobalt and the like in ternary iron aluminum slag are effectively recycled, and meanwhile, the high-nickel matte with high nickel and cobalt grades and high direct yield of nickel and cobalt is obtained.
A method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore comprises the following steps:
(1) And (3) drying: 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 ingredients and granulating: 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) Reduction and vulcanization smelting: feeding the mixed granules obtained in the step (2) into a side-blowing furnace for reduction, vulcanization and smelting to obtain low-nickel matte, smelting slag and first flue gas;
(4) Blowing: and (3) 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 blowing to obtain high-nickel matte, blowing 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.
As one of the preferable schemes, in the step (1), the ternary iron aluminum slag comprises the following components in percentage by mass: 2.1 to 2.6 percent of Ni, 1.3 to 1.5 percent of Co, 1.0 to 1.2 percent of Mn, 22.9 to 23.4 percent of Fe, 29.8 to 30.4 percent of S, 15.4 to 15.9 percent of Al, 5.2 to 5.7 percent of P, 10.7 to 11.2 percent of Ca, 6.0 to 6.9 percent of Mg, 0.2 to 0.3 percent of Si and 0.9 to 5.4 percent of other components; the laterite-nickel ore comprises the following components in percentage by mass: 1.7 to 1.8 percent of Ni, 0.05 to 0.08 percent of Co, 0.6 to 0.8 percent of Mn, 0.7 to 1.0 percent of Cr, 34.9 to 35.9 percent of Fe, 0.1 to 0.2 percent of S, 3.8 to 4.2 percent of Al, 0.2 to 0.8 percent of Ca, 23.7 to 24.1 percent of Mg, 28.8 to 29.5 percent of Si and 1.62 to 5.45 percent 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), the ternary iron aluminum slag and the laterite-nickel ore are respectively sent into a rotary kiln for drying treatment, and are dried for 3-7 h at 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 respectively reduced, 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, respectively crushing and screening the ternary iron-aluminum slag and the laterite-nickel ore which are dried in the step (1), wherein the ternary iron-aluminum slag and the laterite-nickel ore are respectively screened to 3-5 mm; the granularity of the reducing agent is 1 mm-2 mm; uniformly mixing ternary iron aluminum slag, laterite nickel ore, a first flux and a reducing agent to obtain a mixed material with the granularity of 4-6 mm, and granulating the mixed material to obtain mixed granules with the granularity of 10-15 mm. The ternary iron aluminum slag and the laterite-nickel ore are respectively screened to 3-5 mm, and the reducing agent with the granularity of 1-2 mm is selected, so that the ternary iron aluminum slag and the laterite-nickel ore can be uniformly mixed after being mixed, and the reaction can be more sufficient during the subsequent reduction, vulcanization and smelting; if the granularity is too large, the materials are unevenly mixed, and the subsequent reaction is insufficient; if the particle size is too fine, it will easily enter the soot during the subsequent reaction, causing some loss, and therefore the particle size of the material should be selected within a suitable 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 method adopts ternary iron aluminum slag, laterite-nickel ore, a first flux and a reducing agent according to the mass ratio of (20-50): 50: (4-7): (2.5-4), the Ni and Co grades of the low nickel sulfur produced in the reduction, vulcanization and smelting are high, the direct yield is also high, the slag type of smelting slag meets the requirements, the fluidity of the smelting slag is good, the viscosity is low, thereby being more beneficial to the aggregation of nickel matte, and 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 be converted into low-nickel matte.
As one of the preferred embodiments, the low nickel matte obtained in step (3) contains the following components in mass percent: 10 to 28 percent of Ni, 0.2 to 0.3 percent of Co, 50 to 70 percent of Fe and 19 to 21 percent of S; the smelting slag obtained in the step (3) contains the following components in percentage by mass: 0.09 to 0.2 percent of Ni, 0.01 to 0.04 percent of Co, 0.2 to 0.5 percent of Mn, 35 to 40 percent of FeO, 10 to 13 percent of CaO and SiO 2 28％～34％、Al 2 O 3 10-15% of MgO and 10-16%. By adopting the preparation method of the scheme, the direct nickel yield is 93-98% and the direct cobalt yield is 95-98% in the obtained low nickel-sulfur, so that nickel and cobalt in laterite-nickel ore and ternary iron-aluminum slag can be effectively utilized.
As one of preferable embodiments, in the step (4), the mass ratio of the second flux to the low nickel matte is (10 to 15): 50. the mass ratio of the second flux to the low nickel matte is defined as (10-15): 50, the produced high nickel sulfur Ni and Co has high grade and high direct yield in the converting process, and the converting effect is better.
In the step (4), the blowing temperature is 1350-1500 ℃ and the smelting time is 60-120 min. In the blowing process, the Fe content in the high-nickel matte can be fully reduced by smelting for 60-120 min at the smelting temperature of 1350-1500 ℃, so that the nickel and cobalt grades of the high-nickel matte are improved.
As one of the preferred embodiments, the high nickel matte obtained in step (4) contains the following components in mass percent: 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: 1.5 to 3.3 percent of Ni, 0.5 to 1.5 percent of Co, 1.2 to 2.0 percent of Mn, 38 to 43 percent of FeO, 7 to 11 percent of CaO and SiO 2 30％～36％、Al 2 O 3 7-10% and 8-12% MgO. By adopting the preparation method of the scheme, the direct nickel yield is 95-98%, the direct cobalt yield is 95-97% and the grade of nickel and cobalt in the high nickel matte is higher.
In the step (4), the low nickel matte and the second flux are mixed uniformly and then sent into a side blowing furnace to be blown into the side blowing furnace, compressed air is introduced into the side blowing furnace, and the blowing rate of the compressed air is 10000Nm 3 /h～20000Nm 3 And/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) Secondary reduction sulfidation smelting/secondary blowing: performing secondary reduction vulcanization smelting on the converting slag obtained in the step (4) to obtain low-nickel matte, converting slag and first flue gas, adding a second flux into low-nickel sulfur to perform converting, and obtaining high-nickel matte, converting slag and second flue gas after converting; or mixing the slag obtained in the step (4) with a second flux, and then carrying out secondary blowing to obtain the high-nickel matte, slag and second flue gas.
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) Water quenching of smelting slag: carrying out 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) Waste heat recovery: and (3) 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 water quenching treatment is carried out on the smelting slag to obtain water quenching slag, and the water quenching slag can be further recycled; the first flue gas and the second flue gas are respectively led into a waste heat boiler to cool, waste heat is recovered, and a large amount of steam generated by cooling can be used for power generation or other production purposes; the flue gas cooled by the waste heat boiler is introduced into the electric dust collector and then is collected with the bag dust collector, so that the dust removing effect is achieved; the dust and dust removed after denitration and desulfurization reach the qualified emission standard, and are 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) Replacing pyrite (FeS) with ternary iron-aluminum slag 2 ) Gypsum (CaSO) 4 ·2H 2 O) is used as a vulcanizing agent in the reduction, vulcanization and smelting process, ternary iron aluminum slag is used as the vulcanizing agent, and NiSO in the ternary iron aluminum slag 4 、CoSO 4 、Fe 2 (SO 4 ) 3 Respectively reacting with a reducing agent (pulverized coal, semi-coke, reducing coal or coke) to generate NiS, coS, feS; feO and Fe 2 (SO 4 ) 3 Reacting with a reducing agent to generate FeS; the FeS produced then reacts with NiO and CoO in laterite-nickel ore to produce NiS and CoS, respectively, 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 this embodiment, the chemical components of the ternary iron aluminum slag are: 2.1% of Ni, 1.3% of Co, 22.9% of Fe, 1.0% of Mn, 5.2% of P, 29.8% of S, 15.4% of Al, 10.7% of Ca, 6.0% of Mg, 0.2% of Si and 5.4% of other materials; the chemical components of the laterite-nickel ore in the sapropel layer are as follows: 1.7% of Ni, 0.05% of Co, 34.9% of Fe, 0.6% of Mn, 0.7% of Cr, 0.1% of S, 3.8% of Al, 0.2% of Ca, 23.7% of Mg, 28.8% of Si and 5.45% of other materials.
(1) And (3) drying: and 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:
mixing and proportioning: 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, and the reducing agent is semi-coke; the mass ratio of the ternary iron aluminum slag to the red soil nickel ore of the sapropel layer to the quartz sand to the semi-coke is 20:50:4:2.5, mixing the ternary iron aluminum slag, the red soil nickel ore of the sapropel layer, the quartz sand and the semi-coke uniformly to obtain a fine-grained mixed material with the granularity of 4mm.
Granulating: the obtained fine-granularity mixed material is granulated to obtain coarse-granularity mixed granules with granularity of 10mm, and the aim is to prevent the mixed granules entering a side-blowing furnace from being too fine in granularity, so that most of the material enters smoke dust and causes certain loss.
(3) Reduction and vulcanization smelting: and (3) sending the coarse-grain mixed granules obtained in the step (2) into a side blowing furnace for reduction, vulcanization and smelting, wherein the smelting temperature is 1300 ℃, smelting is carried out for 30min, and low-nickel matte, smelting slag and a part of flue gas 1 are obtained after natural cooling. Wherein the obtained low nickel matte contains the following components in percentage by mass: 10% of Ni, 0.2% of Co, 70% of Fe and 19% of S, wherein the direct yield of nickel is 93% and the direct yield of cobalt is 95%; the obtained smelting slag contains the following components in percentage by mass: 0.2% of Ni, 0.04% of Co, 0.5% of Mn, 36% of FeO, 10% of CaO and SiO 2 30％、Al 2 O 3 10%, mgO 11% and 2.26% of the other materials.
(4) Blowing: uniformly mixing the low-nickel matte obtained in the step (3) with a 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 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 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 has high nickel matte Ni40%, co1.3%, fe 38%, S20%, nickel direct yield 95% and cobalt direct yield 95%; the obtained blowing slag contains the following components in percentage by mass: ni 1.7%, co 0.9%, mn 1.3%, feO 39%, caO 8%, siO 2 31％、Al 2 O 3 8%, mgO 9% and 1.1% of the other.
(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:
returning the converting slag obtained in the step (4) to an oxygen-enriched side-blown furnace for secondary reduction vulcanization smelting to obtain low-nickel matte, smelting slag and flue gas 1, and adding a flux 2 into the obtained low-nickel sulfur for converting, wherein the mass ratio of the flux 2 to the low-nickel matte is 10:50, after converting is finished, obtaining the product high nickel matte, converting slag and a part of flue gas 2.
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) Water quenching of smelting slag: and (3) 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: 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) are respectively introduced into a waste heat boiler to be cooled, waste heat is recovered, and a large amount of steam generated by cooling can be used for power generation or other production purposes; the flue gas cooled by the waste heat boiler is introduced into the electric dust collector and then is collected with the bag dust collector, so that the dust removing effect is achieved; the dust and dust removed after denitration and desulfurization reach the qualified emission standard, and are 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 this embodiment, the chemical components of the ternary iron aluminum slag are: 2.6% of Ni, 1.5% of Co, 1.2% of Mn, 23.4% of Fe, 30.4% of S, 15.9% of Al, 5.7% of P, 11.2% of Ca, 6.9% of Mg, 0.3% of Si and 0.9% of other materials; the chemical components of the laterite-nickel ore in the sapropel layer are as follows: 1.8% of Ni, 0.08% of Co, 0.8% of Mn, 1.0% of Cr, 35.9% of Fe, 0.2% of S, 4.2% of Al, 0.8% of Ca, 24.1% of Mg, 29.5% of Si and 1.62% of other materials.
(1) And (3) drying: and 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, and the reducing agent is semi-coke; the mass ratio of the ternary iron aluminum slag to the red soil nickel ore of the sapropel layer to the quartz sand to the semi-coke is 40:50:6:3.5, mixing the ternary iron aluminum slag, the red soil nickel ore of the sapropel layer, the quartz sand and the semi-coke uniformly to obtain a fine-grained mixed material with the granularity of 4mm.
Granulating: the obtained fine-granularity mixed material is granulated to obtain coarse-granularity mixed granules with granularity of 10mm, and the aim is to prevent the mixed granules entering a side-blowing furnace from being too fine in granularity, so that most of the material enters smoke dust and causes certain loss.
(3) Reduction and vulcanization smelting: and (3) sending the coarse-grain mixed granules obtained in the step (2) into a side blowing furnace for reduction, vulcanization 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 in percentage by mass: 28% of Ni, 0.3% of Co, 50% of Fe and 21% of S, wherein the direct nickel yield is 98% and the direct cobalt yield is 98%; the obtained smelting slag contains the following components in percentage by mass: 0.09% of Ni, 0.01% of Co, 0.2% of Mn, 35% of FeO, 10% of CaO and SiO 2 28％、Al 2 O 3 10% of MgO, 10% of other 6.7%.
(4) Blowing: uniformly mixing the low-nickel matte obtained in the step (3) with a 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 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 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. Wherein, the product high nickel matte contains the following components in percentage by mass: 61% of Ni, 2.4% of Co, 7% of Fe, 28% of S, 98% of nickel and 97% of cobalt; the obtained blowing slag contains the following components in percentage by mass: ni1.5%, co 0.5%, mn 1.2%, feO 38%, caO7%, siO 2 30％、Al 2 O 3 7%, mgO 8% and 6.8% of the 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:
returning the converting slag obtained in the step (4) to an oxygen-enriched side-blown 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, after converting is finished, obtaining the product high nickel matte, converting slag and a part of flue gas 1.
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) Water quenching of smelting slag: and (3) 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: 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) are respectively introduced into a waste heat boiler to be cooled, waste heat is recovered, and a large amount of steam generated by cooling can be used for power generation or other production purposes; the flue gas cooled by the waste heat boiler is introduced into the electric dust collector and then is collected with the bag dust collector, so that the dust removing effect is achieved; the dust and dust removed after denitration and desulfurization reach the qualified emission standard, and are 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 this embodiment, the chemical components of the ternary iron aluminum slag are: 2.3% of Ni, 1.4% of Co, 1.1% of Mn, 23.1% of Fe, 30.2% of S, 15.6% of Al, 5.5% of P, 10.9% of Ca, 6.6% of Mg, 0.25% of Si and 3.05% of other materials; the chemical components of the laterite-nickel ore in the sapropel layer are as follows: 1.75% of Ni, 0.06% of Co, 0.7% of Mn, 0.8% of Cr, 35.5% of Fe, 0.16% of S, 4.0% of Al, 0.6% of Ca, 23.9% of Mg, 29.3% of Si and 3.23% of other materials.
(1) And (3) drying: and 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:
mixing and proportioning: and (3) 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, and the reducing agent is semi-coke; the mass ratio of the ternary iron aluminum slag to the red soil nickel ore of the sapropel layer to the quartz sand to the semi-coke is 50:50:6:3.5, mixing the ternary iron aluminum slag, the red soil nickel ore of the sapropel layer, the quartz sand and the semi-coke uniformly to obtain a fine-grained mixed material with the granularity of 4mm.
Granulating: the obtained fine-granularity mixed material is granulated to obtain coarse-granularity mixed granules with the granularity of 13mm, and 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) Reduction and vulcanization smelting: and (3) sending the coarse-grain mixed granules obtained in the step (2) into a side blowing furnace for reduction, vulcanization and smelting, wherein the smelting temperature is 1500 ℃, the smelting time is 45 minutes, and the low-nickel matte, smelting slag and a part of flue gas 1 are obtained after natural cooling. Wherein the obtained low nickel matte contains the following components in percentage by mass: 26% of Ni, 0.24% of Co, 54% of Fe and 19% of S, wherein the direct nickel yield is 94% and the direct cobalt yield is 96%; the obtained smelting slag contains the following components in percentage by mass: ni 0.15%, co0.03%, mn 0.3%, feO 37%, caO 11%, siO 2 29％、Al 2 O 3 11%, 10% of MgO and 1.52% of other materials.
(4) Blowing: uniformly mixing the low-nickel matte obtained in the step (3) with a flux 2 according to a certain mass ratio, wherein the mass ratio of the flux 2 to the low-nickel matte is 13:50. mixing uniformly and then deliveringAnd (3) blowing after introducing compressed air into a side blowing furnace, wherein 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. Wherein, the product high nickel matte contains the following components in percentage by mass: the obtained blowing slag contains the following components in percentage by mass: ni 1.6%, co 1.1%, mn 1.6%, feO 40%, caO7%, siO 2 30％、Al 2 O 3 9%, mgO 8% and 1.7% of the 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:
returning the converting slag obtained in the step (4) to an oxygen-enriched side-blown 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 13:50, after converting is finished, obtaining the product high nickel matte, converting slag and a part of flue gas 2.
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) Water quenching of smelting slag: and (3) 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: 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) are respectively introduced into a waste heat boiler to be cooled, waste heat is recovered, and a large amount of steam generated by cooling can be used for power generation or other production purposes; the flue gas cooled by the waste heat boiler is introduced into the electric dust collector and then is collected with the bag dust collector, so that the dust removing effect is achieved; the dust and dust removed after denitration and desulfurization reach the qualified emission standard, and are 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 ternary iron aluminum slag is changed to gypsum (CaSO 4 ·2H 2 O)。
In this comparative example: gypsum (CaSO) 4 ·2H 2 The chemical components of O) are as follows: caO 32.6%, SO 3 46.5％、H 2 O20.9%. The chemical components of the laterite-nickel ore in the sapropel layer are as follows: 1.7% of Ni, 0.05% of Co, 34.9% of Fe, 0.6% of Mn, 0.7% of Cr, 0.1% of S, 3.8% of Al, 0.2% of Ca, 23.7% of Mg, 28.8% of Si and 5.45% of other materials.
(1) And (3) drying: gypsum (CaSO) 4 ·2H 2 Respectively feeding O) and the laterite-nickel ore of the sapropel layer into a rotary kiln for drying treatment, drying at 300 ℃ for 3h, and obtaining gypsum (CaSO) 4 ·2H 2 And O) and the laterite-nickel ore water content of the sapropel layer are both dried to 10%. After drying, gypsum (CaSO) 4 ·2H 2 O) is placed in gypsum (CaSO 4 ·2H 2 And O) storing the material bin, and placing the red soil nickel ore in the red soil nickel ore bin for storage.
(2) Mixing ingredients and granulating:
mixing and proportioning: the gypsum (CaSO) obtained in the step (1) is treated 4 ·2H 2 Crushing and sieving respectively the O) and the laterite-nickel ore in the sapropel layer, and gypsum (CaSO) 4 ·2H 2 And O) and the laterite-nickel ore of the sapropel layer are both screened to 3mm, and the granularity of the reducing agent is required to be 1mm. In the embodiment, the flux 1 is quartz sand, and the reducing agent is semi-coke; with gypsum (CaSO) 4 ·2H 2 O), the mass ratio of the laterite-nickel ore, the quartz sand and the semi-coke of the sapropel layer is 20:50:4:2.5 ingredients were applied and gypsum (CaSO 4 ·2H 2 O), laterite-nickel ore in the sapropel layer, quartz sand and semi-coke are uniformly mixed to obtain a fine-granularity mixed material, wherein the granularity is 4mm.
Granulating: granulating the fine-granularity mixed material obtained in the step (2) 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 material enters smoke dust and causes certain loss.
(3) Reduction and vulcanization smelting: and (3) sending the coarse-grain mixed granules obtained in the step (2) into a side-blowing furnace for reduction, vulcanization and 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 product low nickel matte contains the following components in percentage by mass: ni 6%, co 0.05%, fe 65%, S26%, nickel direct yield 80%, cobalt direct yield 84%, and the obtained smelting slag contains the following components in percentage by mass: ni 0.2%, co0.04%, mn 0.4%, feO 36%, caO 12%, siO 2 29％、Al 2 O 3 10%, 11% of MgO and 1.36% of the other materials.
(4) Blowing: uniformly mixing the low-nickel matte obtained in the step (3) with a flux 2 according to a certain mass ratio, wherein the mass ratio of the flux 2 to the low-nickel matte is (10): 50. and 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, the blowing slag and a part of flue gas are obtained after natural cooling. Wherein, the product high nickel matte contains the following components in percentage by mass: 28% of Ni, 0.8% of Co, 42% of Fe and 28% of S, wherein the direct nickel yield is 85% and the direct cobalt yield is 88%; the obtained blowing slag contains the following components in percentage by mass: ni 2%, co1.3%, mn 1.8%, feO 40%, caO 8%, siO 2 31％、Al 2 O 3 7%, mgO 8% and 0.9% of the other components.
(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:
returning the converting slag obtained in the step (4) to an oxygen-enriched side-blown 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 10:50, after converting is finished, obtaining the product high nickel matte, converting slag and a part of flue gas 2.
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) Water quenching of smelting slag: and (3) 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: 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) are respectively introduced into a waste heat boiler to be cooled, waste heat is recovered, and a large amount of steam generated by cooling can be used for power generation or other production purposes; the flue gas cooled by the waste heat boiler is introduced into the electric dust collector and then is collected with the bag dust collector, so that the dust removing effect is achieved; the dust and dust removed after denitration and desulfurization reach the qualified emission standard, and are discharged into 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.
Examples 1-3 of the present disclosure, relative to comparative example 1, ternary iron aluminum slag was substituted for gypsum (CaSO 4 ·2H 2 O) is used as a vulcanizing agent in the reduction, vulcanization and smelting process, 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 (15)
1. A method for preparing high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore is characterized by comprising the following steps: the method comprises the following steps:
(1) And (3) drying: 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 ingredients and granulating: 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) Reduction and vulcanization smelting: feeding the mixed granules obtained in the step (2) into a side-blowing furnace for reduction, vulcanization and smelting to obtain low-nickel matte, smelting slag and first flue gas;
(4) Blowing: and (3) 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 blowing to obtain high-nickel matte, blowing slag and second flue gas.
2. The method for preparing the high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore as claimed in claim 1, wherein: in the step (1), the ternary iron aluminum slag comprises the following components in percentage by mass: 2.1 to 2.6 percent of Ni, 1.3 to 1.5 percent of Co, 1.0 to 1.2 percent of Mn, 22.9 to 23.4 percent of Fe, 29.8 to 30.4 percent of S, 15.4 to 15.9 percent of Al, 5.2 to 5.7 percent of P, 10.7 to 11.2 percent of Ca, 6.0 to 6.9 percent of Mg, 0.2 to 0.3 percent of Si and 0.9 to 5.4 percent of other components; the laterite-nickel ore comprises the following components in percentage by mass: 1.7 to 1.8 percent of Ni, 0.05 to 0.08 percent of Co, 0.6 to 0.8 percent of Mn, 0.7 to 1.0 percent of Cr, 34.9 to 35.9 percent of Fe, 0.1 to 0.2 percent of S, 3.8 to 4.2 percent of Al, 0.2 to 0.8 percent of Ca, 23.7 to 24.1 percent of Mg, 28.8 to 29.5 percent of Si and 1.62 to 5.45 percent of other components.
3. The method for preparing the high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore as claimed in claim 1, wherein: in the step (1), the ternary iron aluminum slag and the laterite nickel ore are respectively sent into a rotary kiln for drying treatment, and are dried for 3 to 7 hours at the temperature of 100 to 300 ℃.
4. The method for preparing the high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore as claimed in claim 1, wherein: in the step (2), before mixing, respectively crushing and screening the ternary iron-aluminum slag and the laterite-nickel ore which are dried in the step (1) until the ternary iron-aluminum slag and the laterite-nickel ore are respectively screened to 3-5 mm; the granularity of the reducing agent is 1 mm-2 mm; uniformly mixing ternary iron aluminum slag, laterite nickel ore, a first flux and a reducing agent to obtain a mixed material with the granularity of 4-6 mm, and granulating the mixed material to obtain mixed granules with the granularity of 10-15 mm.
5. The method for preparing the high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore as claimed in claim 1, wherein: 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).
6. The method for preparing the high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore as claimed in claim 1, wherein: the reducing agent is at least one of pulverized coal, semi-coke, reducing coal and coke.
7. The method for preparing the high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore as claimed in claim 1, wherein: in the step (3), the smelting temperature is 1300-1600 ℃ and the smelting time is 30-60 min.
8. The method for preparing the high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore as claimed in claim 1, wherein: the low nickel matte obtained in step (3) contains the following components in percentage by mass: 10 to 28 percent of Ni, 0.2 to 0.3 percent of Co, 50 to 70 percent of Fe and 19 to 21 percent of S; the smelting slag obtained in the step (3) contains the following mass percentThe components are as follows: 0.09 to 0.2 percent of Ni, 0.01 to 0.04 percent of Co, 0.2 to 0.5 percent of Mn, 35 to 40 percent of FeO, 10 to 13 percent of CaO and SiO 2 28％～34％、Al 2 O 3 10％～15％、MgO 10％～16％。
9. The method for preparing the 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.
10. the method for preparing the high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore as claimed in claim 1, wherein: in the step (4), the blowing temperature is 1350-1500 ℃ and the smelting time is 60-120 min.
11. The method for preparing the high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore as claimed in claim 1, wherein: the high nickel matte obtained in step (4) contains the following components in mass percent: 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: 1.5 to 3.3 percent of Ni, 0.5 to 1.5 percent of Co, 1.2 to 2.0 percent of Mn, 38 to 43 percent of FeO, 7 to 11 percent of CaO and SiO 2 30％～36％、Al 2 O 3 7％～10％、MgO 8％～12％。
12. The method for preparing the high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore as claimed in claim 1, wherein: in the step (4), the low nickel matte and the second flux are mixed uniformly and then sent into a side blowing furnace to be blown after compressed air is introduced, and the air supply rate of the compressed air is 10000Nm 3 /h～20000Nm 3 /h。
13. The method for preparing the high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore as claimed in claim 1, wherein: in the step (2), the first flux is at least one of quartz sand and limestone; in the step (4), the second flux is at least one of quartz sand and limestone.
14. The method for preparing the high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore as claimed in claim 1, wherein: the method also comprises the following steps:
(5) Secondary reduction sulfidation smelting/secondary blowing: performing secondary reduction vulcanization smelting on the converting slag obtained in the step (4) to obtain low-nickel matte, converting slag and first flue gas, adding a second flux into low-nickel sulfur to perform converting, and obtaining high-nickel matte, converting slag and second flue gas after converting; or mixing the slag obtained in the step (4) with a second flux, and then carrying out secondary blowing to obtain the high-nickel matte, slag and second flue gas.
15. The method for preparing the high nickel matte by combining ternary iron aluminum slag and laterite-nickel ore as claimed in claim 1, wherein: the method also comprises the following steps:
(6) Water quenching of smelting slag: carrying out 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) Waste heat recovery: and (3) 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.
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| Application Number | Priority Date | Filing Date | Title |
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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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| CN114761587B (en) * | 2019-11-27 | 2023-11-28 | 尤米科尔公司 | Pyrometallurgical process for recovery of nickel, manganese and cobalt |
| 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 |
| 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 |
| CN115386736B (en) * | 2022-08-04 | 2024-03-12 | 广东邦普循环科技有限公司 | Method for treating laterite-nickel ore by oxygen-enriched side-blown furnace |
| CN116083737A (en) * | 2023-01-13 | 2023-05-09 | 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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