CN117403057B - Treatment method of laterite nickel ore acid leaching slag and active material - Google Patents
Treatment method of laterite nickel ore acid leaching slag and active material Download PDFInfo
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- CN117403057B CN117403057B CN202311717499.3A CN202311717499A CN117403057B CN 117403057 B CN117403057 B CN 117403057B CN 202311717499 A CN202311717499 A CN 202311717499A CN 117403057 B CN117403057 B CN 117403057B
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- slag
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- nickel ore
- leaching slag
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000002893 slag Substances 0.000 title claims abstract description 123
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 93
- 239000002253 acid Substances 0.000 title claims abstract description 82
- 238000002386 leaching Methods 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000011149 active material Substances 0.000 title claims abstract description 36
- 239000011504 laterite Substances 0.000 title abstract description 22
- 229910001710 laterite Inorganic materials 0.000 title abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000000463 material Substances 0.000 claims abstract description 82
- 229910052742 iron Inorganic materials 0.000 claims abstract description 38
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003546 flue gas Substances 0.000 claims abstract description 34
- 239000003818 cinder Substances 0.000 claims abstract description 32
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 28
- 238000002844 melting Methods 0.000 claims abstract description 17
- 230000008018 melting Effects 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 230000005284 excitation Effects 0.000 claims abstract description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 34
- 238000007885 magnetic separation Methods 0.000 claims description 24
- 239000002699 waste material Substances 0.000 claims description 20
- 239000000292 calcium oxide Substances 0.000 claims description 17
- 235000012255 calcium oxide Nutrition 0.000 claims description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 239000010440 gypsum Substances 0.000 claims description 8
- 229910052602 gypsum Inorganic materials 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- 235000019738 Limestone Nutrition 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000006028 limestone Substances 0.000 claims description 6
- 238000003672 processing method Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000004568 cement Substances 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- 239000010881 fly ash Substances 0.000 claims description 4
- 239000003345 natural gas Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 3
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000002817 coal dust Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002910 solid waste Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000863 Ferronickel Inorganic materials 0.000 description 3
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical group [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 3
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 3
- 239000003830 anthracite Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000009853 pyrometallurgy Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000009851 ferrous metallurgy Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000009868 nickel metallurgy Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010909 process residue Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/17—Mixtures thereof with other inorganic cementitious materials or other activators with calcium oxide containing activators
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate containing activators
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- 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
Abstract
The invention provides a method for treating laterite-nickel ore acid leaching slag and an active material. The method comprises the following steps: step S1, mixing laterite nickel ore acid leaching slag, material mixing, melting assisting material and reducing agent, and pressing to obtain a preform; step S2, roasting the prefabricated product to obtain hot cinder and hot flue gas, wherein the hot flue gas is used for preparing acid; s3, magnetically separating the hot burned slag to obtain a fine iron material and tailings; and S4, mixing the tailings, the active material and the excitation material, and grinding to obtain the active material. The treatment method has the characteristics of large solid waste consumption, multiple types of products, high product yield, low comprehensive production cost, high resource utilization rate and the like, and provides a more effective solution for fully recovering valuable components and recycling all components of the laterite-nickel ore acid leaching slag.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a treatment method of laterite-nickel ore acid leaching slag and an active material.
Background
Currently, nickel ores are mainly divided into two major categories worldwide, namely nickel sulfide ores and laterite nickel ores, and according to the ascertained reserves, the reserves of the two nickel ores are approximately nickel sulfide ores: laterite nickel ore=1:3. In the past, nickel sulphide ore has been mainly used worldwide, but with the gradual decrease of reserves, laterite nickel ore has been used nowadays mainly, and the proportion is gradually higher than that of nickel sulphide ore.
At present, the greatest amount of laterite-nickel ore is mainly achieved by adopting RKEF pyrometallurgy to produce stainless steel raw material-ferronickel alloy, the produced waste slag is mainly ferronickel slag, most of Ni and Fe elements in the laterite-nickel ore are reduced into ferronickel, and the main components in solid slag are MgO and SiO 2 . However, the smelting process has the problems of high power consumption and high production cost, and because of MgO and SiO in the laterite-nickel ore 2 The components are easy to form high-melting-point phase in the smelting process, so that higher furnace temperature is often required for ensuring slag-iron separation, the generated slag quantity is also larger, and the recycling utilization rate is low. With the development of new energy battery materials, the market demand of nickel products is gradually increased, and with the reduction of Ni grade in laterite nickel ores, the treatment of the laterite nickel ores by adopting a wet acid leaching process is gradually becoming a development trend. In this case, various waste residues including a series of process residues including ferrite leaching residues, iron aluminum residues, gypsum residues, etc. are continuously generated. As the hydrometallurgical process of laterite nickel ore is still in the initial development stage in China, most of acid leaching residues of laterite nickel ore are still mainly piled up, and a small part of acid leaching residues are processed into iron-making raw materials or iron red pigment products, the dosage is small, the economy is low, the comprehensive utilization of waste residues in the whole process cannot be realized, and the resources are still lacked, and the products are savedVarious and no waste output.
Thus, with the use of a large amount of laterite nickel ore, a large amount of laterite nickel ore acid leaching slag tends to be produced. A large amount of laterite-nickel ore acid leaching slag is piled up, so that the environment is polluted, and residual Fe, ni and other metal elements in the slag are lost, so that the resource waste is caused. China belongs to the country with typical shortage of nickel and iron resources, a large amount of mineral resources such as nickel ore, iron ore and the like are imported from abroad every year, and the nickel ore is almost completely imported for laterite. If the metal elements such as Fe, ni and the like in the acid leaching laterite slag can be recycled, and the residual tailings are made into building materials, the utilization efficiency of laterite-nickel ore resources can be greatly improved.
Therefore, the invention provides a treatment method of laterite-nickel ore acid leaching slag, which aims to solve the problems of resource waste and environmental pollution caused by that the existing laterite-nickel ore acid leaching slag has low resource utilization rate and most of the acid leaching slag can only be piled up and the economic value of the laterite-nickel ore acid leaching slag cannot be fully exerted.
Disclosure of Invention
The invention mainly aims to provide a treatment method and an active material of laterite-nickel ore acid leaching slag, so as to solve the problem that the laterite-nickel ore acid leaching slag cannot be effectively utilized in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for treating laterite-nickel ore acid leaching slag, comprising the steps of: step S1, mixing laterite nickel ore acid leaching slag, material mixing, melting assisting material and reducing agent, and pressing to obtain a preform; step S2, roasting the prefabricated product to obtain hot cinder and hot flue gas, wherein the hot flue gas is used for preparing acid; s3, magnetically separating the hot burned slag to obtain a fine iron material and tailings; s4, mixing the tailings, the active materials and the excitation materials, and grinding to obtain the active materials; wherein the material regulating and arranging material is iron-containing waste residue; the melting aid is CaO, mgO, na 2 One or more alkaline substances in O; the active material is selected from one or more of nickel-iron slag, fly ash, blast furnace slag, furnace bottom slag or coal slag; the exciting material is one or more selected from desulfurized gypsum, steel slag tailings, carbide slag, quicklime, limestone, slaked lime or cement clinkerA kind of module is assembled in the module and the module is assembled in the module.
Further, the hot slag comprises the following components: 38-52 wt% of Fe, 4-13wt% of FeO, 8-22 wt% of SiO 2 5-23 wt% of CaO and 1-6 wt% of Al 2 O 3 And 1 to 4wt% MgO.
Further, the laterite-nickel ore acid leaching slag comprises the following components: 48-68 wt% of Fe 2 O 3 8-17 wt% of SO 3 1-5wt% of CaO and 6-25wt% of SiO 2 1-4wt% MgO and 3-8wt% Al 2 O 3 。
Further, the hot flue gas comprises SO 2 ，SO 2 The volume concentration of (2) is 4-10%.
Further, in the step S1, according to the weight parts of dry ore, the laterite-nickel ore acid leaching slag is 100 parts, the material adjusting and arranging is 3-28 parts, the melting assisting material is 0.5-22 parts, and the reducing agent is 5-20 parts.
Further, in the step S4, the tailings are 20-40 parts by weight of dry ore, the active materials are 50-70 parts by weight of dry ore, and the excitation materials are 3-10 parts by weight of dry ore.
Further, in the step S2, the roasting temperature is 900-1250 ℃, and the roasting time is 1-2 hours.
Further, in the combustion-supporting gas adopted in the roasting process, O 2 The volume concentration of (2) is 40-60%.
Further, the fuel used in the calcination process is selected from natural gas and/or coal dust.
Further, O in hot flue gas 2 The volume concentration of the flue gas is less than or equal to 5 percent, and the temperature of the hot flue gas is more than or equal to 300 ℃.
Further, the iron-containing waste slag is selected from one or more of steel slag, wet iron aluminum slag or nickel smelting slag.
Further, the alkaline substance is selected from one or more of limestone, dolomite, quicklime, gypsum slag, carbide slag or magnesium slag.
Further, the reducing agent is selected from solid reducing agents with carbon content of 40-90% and calorific value of more than or equal to 3000 kcal/kg.
Further, the reducing agent is selected from one or more of anthracite, lignite, coke, waste graphite electrode and biomass waste.
Further, in step S1, the treatment method further comprises the steps of carrying out first crushing treatment on laterite-nickel ore acid leaching slag, material adjustment and fluxing materials before pressing so as to control the granularity of the materials to be less than or equal to 10mm.
Further, in step S3, the treatment method further includes a step of air-cooling the hot cinder to obtain cinder before the magnetic separation.
Further, in step S3, the second crushing treatment and grinding treatment are sequentially performed on the cinder, and the granularity of the cinder after the grinding treatment meets the following requirements: the grain size of the cinder which exceeds 35 percent by mass in the cinder after the grinding treatment is less than or equal to 0.074mm.
Further, in the step S3, the magnetic separation comprises two magnetic separation processes which are sequentially carried out, and the magnetic field intensity of the two magnetic separation processes is respectively and independently 80-250 kA/m.
Further, the magnetic field intensity of the first magnetic separation process is higher than that of the second magnetic separation process, the first magnetic separation intensity is 150-250 kA/m, and the second magnetic separation intensity is 80-150 kA/m.
In order to achieve the above object, according to one aspect of the present invention, there is provided an active material obtained by the aforementioned treatment method of laterite-nickel ore acid leaching slag, the specific surface area of the active material being not less than 350m 2 /kg。
By applying the technical scheme of the invention, the Fe element in the laterite-nickel ore acid leaching slag can be further effectively recovered through mutual cooperative coordination among the material adjusting body, the melting assisting material and the reducing agent. The processing method of the laterite-nickel ore acid leaching slag realizes the full-resource comprehensive utilization of the laterite-nickel ore acid leaching slag, has high recovery rate of residual valuable Fe metal, realizes the full utilization of valuable metals (such as Fe, ni, sulfur and the like), realizes the recycling of valuable metals, realizes the recycling of sulfur resources, and reduces the purchase cost of sulfuric acid. Meanwhile, the processing method of the laterite-nickel ore acid leaching slag can realize the aim of the synergistic processing and utilization of various iron-containing waste slag generated in other peripheral matched industrial production of nickel metallurgy (including wet metallurgy and pyrometallurgy), ferrous metallurgy, thermal power and the like. The treatment method has the characteristics of large solid waste consumption, multiple types of products, high product yield, low comprehensive production cost, high resource utilization rate and the like, and provides a more effective solution for fully recovering valuable components and recycling all components of the laterite-nickel ore acid leaching slag.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 shows a flow chart of a method for treating laterite-nickel ore acid leaching residue in one embodiment of the invention.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As described in the background section of this application, the prior art does not effectively utilize the problems of laterite nickel ore acid leaching residues. In order to solve the problem, the application provides a treatment method of laterite-nickel ore acid leaching slag, which comprises the following steps: step S1, mixing laterite nickel ore acid leaching slag, material mixing, melting assisting material and reducing agent, and pressing to obtain a preform; step S2, roasting the prefabricated product to obtain hot cinder and hot flue gas, wherein the hot flue gas is used for preparing acid; s3, magnetically separating the hot burned slag to obtain a fine iron material and tailings; s4, mixing the tailings, the active materials and the excitation materials, and grinding to obtain the active materials; wherein the material regulating and arranging material is iron-containing waste residue; the fluxing agent is alkaline substance containing one or more of CaO, mgO, na 2O; the active material is selected from one or more of nickel-iron slag, fly ash, blast furnace slag, furnace bottom slag or coal slag; the exciting material is one or more selected from desulfurized gypsum, steel slag tailings, carbide slag, quicklime, limestone, slaked lime or cement clinker.
The method comprises the steps of firstly mixing and pressing laterite nickel ore acid leaching slag, material adjustment, material assisting and reducing agent to obtain a prefabricated product, then roasting the prefabricated product to obtain hot cinder and hot flue gas (the hot flue gas is sent to an acid making system to prepare concentrated sulfuric acid and the like), and then carrying out magnetic separation on the hot cinder to obtain fine iron materials and tailings. Wherein, the refined iron material can be directly used as iron raw material. Through the operation steps, the recycling of residual Fe and Ni elements in the laterite-nickel ore acid leaching slag is realized; the tailings can be mixed with active materials and exciting materials for grinding to obtain active materials, and the active materials are applied to the field of building materials, so that the recycling of calcium element in laterite-nickel ore acid leaching residues is effectively realized.
Wherein the adjusting material is mainly used for adjusting each chemical component (alkaline component MgO, caO and acid component SiO) in the laterite-nickel ore acid leaching slag 2 、Al 2 O 3 ) The proportion of the materials can lead some weak magnetic iron-containing materials in the materials to form magnetic iron-containing minerals, and the Fe material can be recovered and obtained through simple magnetic separation, thereby improving the recovery rate of Fe metal. Meanwhile, the adjusting materials are selected from the iron-containing waste residues, so that the iron-containing solid waste can be effectively utilized, and resource waste is avoided. The melting aid is CaO, mgO, na 2 One or more alkaline substances in O, which can be combined with SiO in laterite-nickel ore acid leaching slag 2 Reacting with isoacidic oxide and reacting with SiO 2 Bound Fe 2 O 3 And released, thereby improving the reduction reaction activity of the iron oxide and increasing the yield of metallic iron.
In sum, the Fe element in the laterite nickel ore acid leaching slag can be further effectively recovered through the mutual cooperative coordination among the material adjusting body, the melting aid and the reducing agent. The processing method of the laterite-nickel ore acid leaching slag realizes the full-resource comprehensive utilization of the laterite-nickel ore acid leaching slag, has high recovery rate of residual valuable Fe metal, realizes the full utilization of valuable metals (such as Fe, ni, sulfur and the like), realizes the recycling of valuable metals, realizes the recycling of sulfur resources, and reduces the purchase cost of sulfuric acid. Meanwhile, the processing method of the laterite-nickel ore acid leaching slag can realize the aim of the synergistic processing and utilization of various iron-containing waste slag generated in other peripheral matched industrial production of nickel metallurgy (including wet metallurgy and pyrometallurgy), ferrous metallurgy, thermal power and the like. The treatment method has the characteristics of large solid waste consumption, multiple types of products, high product yield, low comprehensive production cost, high resource utilization rate and the like, and provides a more effective solution for fully recovering valuable components and recycling all components of the laterite-nickel ore acid leaching slag.
The laterite-nickel ore acid leaching slag disclosed by the invention is waste slag generated after laterite-nickel ore is subjected to wet acid leaching process treatment, and comprises the following components: 38-52 wt% of Fe, 4-13wt% of FeO, 8-22 wt% of SiO 2 5-23 wt% of CaO and 1-6 wt% of Al 2 O 3 And 1 to 4wt% MgO. The hot cinder comprises the following components: 48-68 wt% of Fe 2 O 3 8-17 wt% of SO 3 1-5wt% of CaO and 6-25wt% of SiO 2 1-4wt% MgO and 3-8wt% Al 2 O 3 . The hot flue gas comprising SO 2 ，SO 2 The volume concentration of (2) is 4-10%.
In a preferred embodiment, the laterite-nickel ore acid leaching slag is 100 parts by weight of dry ore, the material adjusting and arranging is 3-28 parts, the melting assisting material is 0.5-22 parts, and the reducing agent is 5-20 parts. Based on the method, the synergistic effect of the laterite-nickel ore acid leaching slag, the material regulating body, the material assisting body and the reducing agent is more remarkable, so that Fe element of the laterite-nickel ore acid leaching slag can be promoted to be fully reduced, more laterite-nickel ore acid leaching slag can be subjected to effective treatment, the iron content of the subsequently obtained refined iron material is higher, the performance of the tailings active material is better, and meanwhile, the reduction efficiency of roasting metal can be improved by the laterite-nickel ore acid leaching slag, the material regulating body, the material assisting body and the reducing agent in the proportion range, and the energy consumption and the cost are reduced.
In order to further obtain an active material with better activity performance, preferably, the tailing is 20-40 parts, the active material is 50-70 parts, and the exciting material is 3-10 parts by weight based on the dry ore.
In order to further improve the resource utilization rate of the laterite-nickel ore acid leaching slag and fully recycle the iron element, in the step S2, the roasting temperature is 900-1250 ℃ and the roasting time is 1-2 hours. When the roasting temperature is too high, the liquid phase content is increased and the roasting is excessively sintered, so that the stable operation of the roasting furnace is not facilitated, meanwhile, the energy consumption is increased, and when the roasting temperature is too low, the iron element cannot be fully reduced.
In order to further improve the roasting efficiency, preferably, the mixture of the laterite nickel ore acid leaching slag, the material conditioning, the melting aid and the reducing agent is pressed into blocks or balls for roasting; preferably, the fuel used in the calcination process is selected from natural gas and/or coal fines; preferably, the preform firing process may be firing reduction in a rotary kiln, rotary hearth furnace, sintering vehicle, belt calciner, or tunnel kiln. In a preferred embodiment, the combustion gas employed in the calcination process is O 2 The volume concentration of (2) is 40-60%. The invention adds O in combustion-supporting gas 2 The volume concentration of the fuel is controlled within the range, so that oxygen-enriched combustion can be realized, and the energy consumption is further reduced.
In a preferred embodiment, O in the hot flue gas 2 The volume concentration of the flue gas is less than or equal to 5 percent, and the temperature of the hot flue gas is more than or equal to 300 ℃. The hot flue gas can be recycled and used as an acid making raw material, so that the recycling of sulfur resources of the laterite-nickel ore acid leaching slag is realized, and the sulfuric acid purchasing cost in the laterite-nickel ore wet acid leaching process is reduced. The invention controls the O of hot flue gas discharged from the furnace 2 The volume concentration and the temperature of the slag can fully ensure the reducing atmosphere required by the reduction of the metal oxide in the slag, and simultaneously reduce the increase of production energy consumption caused by the generation of excessive CO and the excessive flue gas temperature. Preferably, O in hot flue gas 2 The volume concentration of the hot flue gas is 2-4%, and the temperature of the hot flue gas is 300-350 ℃.
In some alternative embodiments, the iron-containing slag is selected from one or more of steel slag, wet iron aluminum slag, or nickel smelting slag. The alkaline substance can be raw materials for processing natural ore resources, such as limestone, dolomite, quicklime and the like, and can also be metallurgical chemical waste residues from the viewpoint of changing waste into valuables, such as gypsum residues, carbide residues, magnesium residues and the like.
In a preferred embodiment, the reducing agent is selected from solid reducing agents having a carbon content of 40-90% and a calorific value of not less than 3000 kcal/kg. The solid reducing agent can promote the reduction of iron element in the laterite-nickel ore acid leaching slag on one hand, can be used as fuel on the other hand, improves the roasting efficiency, and further improves the recovery rate of iron element in the laterite-nickel ore acid leaching slag. Preferably, the reducing agent is selected from fossil fuels such as anthracite, lignite, coke and the like, and also selected from waste graphite electrodes and biomass wastes (for example, straw, carbonized rice hulls and the like). Preferably, the particle size of the reducing agent is controlled to be less than or equal to 10mm.
In a preferred embodiment, in step S1, the treatment method further comprises the steps of subjecting the laterite-nickel ore acid leaching slag, the monolith adjustment and the fluxing material to a first crushing treatment to control the particle size of the material to be less than or equal to 10mm before pressing. According to the invention, the materials are crushed, the granularity of the materials is controlled to be less than or equal to 10mm, the materials can be fully mixed and contacted, the reaction efficiency is improved, and the granularity of the materials is preferably 3-7 mm.
In a preferred embodiment, in step S3, the treatment method further comprises the step of air-cooling the hot cinder to obtain cinder before the magnetic separation. The invention is treated by the steps, not only can recover the waste heat of the hot slag to form cooling hot air, but also can be used as combustion air continuously, promote the formation of a glass phase of the cinder tailings, and improve the potential hydration gelation activity of the tailings. When the hot cinder and air are used for cooling, the residual heat of the hot cinder converts cold air into hot air, and the hot air is returned to a part of combustion-supporting gas in the roasting process of the prefabricated product for use, so that the residual heat of flue gas is fully utilized, and the energy consumption is saved.
In order to facilitate the subsequent magnetic separation treatment, the separation of tailings and fine iron materials is improved. Preferably, in the step S3, the second crushing treatment and the grinding treatment are sequentially performed on the cinder, wherein the grain size of the cinder exceeding 35% by mass in the cinder after the grinding treatment is less than or equal to 0.074mm.
In order to further improve the separation degree of tailings and fine iron materials, the performance of the product is improved. In the step S3, the magnetic separation comprises two magnetic separation processes which are sequentially carried out, and the magnetic field intensity of the two magnetic separation processes is respectively and independently 80-250 kA/m. Preferably, the magnetic field intensity of the first magnetic separation process is higher than that of the second magnetic separation process, the first magnetic separation intensity is 150-250 kA/m, and the second magnetic separation intensity is 80-150 kA/m.
The invention also provides an active material which is prepared from the laterite-nickel oreThe specific surface area of the active material is more than or equal to 350m, which is obtained by the processing method of acid leaching slag 2 /kg。
Based on the reasons, the active material obtained by the treatment method has potential hydration activity and better activity. The material can be used as an active mixed material by virtue of better hydration activity, and can be directly used as an active admixture for being sold to production enterprises such as concrete, cement products and the like.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
The components of the laterite nickel ore acid leaching slag are as follows: fe (Fe) 2 O 3 57wt% of SiO 2 15wt%, caO 4wt%, al 2 O 3 3.7wt% MgO 1.7wt% SO 3 11wt% of other impurities.
Crushing laterite-nickel ore acid leaching slag, adjustment materials (steel slag) and fluxing materials (quicklime) to a granularity smaller than 10mm, mixing with a reducing agent (anthracite), and pressing into balls to obtain a preform; wherein, according to the weight portion of dry ore, laterite nickel ore acid leaching slag is 100 portions, the material adjusting is 15 portions, the melting aid is 2 portions, and the reducing agent is 15 portions.
The prefabricated product is sent into a rotary kiln to be roasted, the roasting temperature is controlled within the range of 1100-1150 ℃ and the roasting time is 2 hours, wherein natural gas is used as fuel in the roasting process, and oxygen-enriched combustion-supporting air with the oxygen volume concentration of 50% is blown in (wherein the volume concentration of each gas is O 2 50%, N 2 49%, H 2 O1%) to obtain hot burned slag (Fe 43wt%, feO 6wt%, caO 8.1wt%, siO) 2 12.3% wt% of Al 2 O 3 2.3wt%, mgO 1.4 wt%) and hot flue gas. Wherein the hot flue gas is flue gas discharged from a roasting furnace, SO 2 The component content is 7%, the temperature of the flue gas is 340 ℃, O 2 The concentration of (2) was 5%. And cooling and dedusting the recovered hot flue gas to obtain a raw material for preparing concentrated sulfuric acid.
Cooling the hot cinder after discharging the furnace to 300 ℃ by air, obtaining cinder, crushing and grinding the cinder, wherein the granularity distribution of the cinder after grinding is as follows: the burned slag passes through a sieve with the screen residue weight of 25% after 0.074 and mm, then the burned slag is subjected to two magnetic selections, the magnetic field intensity of the primary magnetic selection is 240kA/m, middlings and tailings are obtained, the secondary magnetic selection is performed on the middlings, the magnetic field intensity is 100kA/m, and the fine iron (TFe content is 78%, and Fe recovery rate is 92%) and tailings are obtained.
According to the weight parts of dry ore, 30 parts of tailings, 65 parts of active material (fly ash) and 5 parts of exciting material (desulfurized gypsum) are mixed and ground, and the specific surface area reaches 400-450 m 2 At/kg, the active material is obtained.
Example 2
The difference from example 1 is that the laterite-nickel ore acid leaching slag is 100 parts, the material adjusting and arranging is 28 parts, the melting assisting material is 22 parts, and the reducing agent is 20 parts.
Example 3
The difference from example 1 is that the laterite-nickel ore acid leaching slag is 100 parts, the material adjusting and mixing is 3 parts, the melting aid is 0.5 part, and the reducing agent is 5 parts.
Example 4
The difference from example 1 is that the laterite-nickel ore acid leaching slag is 100 parts, the material adjusting and arranging is 15 parts, the melting assisting material is 2 parts, and the reducing agent is 2 parts.
Example 5
The difference from example 1 is that the baking temperature is 780-800 ℃ and the baking time is 2h.
Example 6
The difference from example 1 is that the baking temperature is 1380 to 1400 ℃ and the baking time is 2 hours.
Example 7
Unlike example 1, O in the combustion-supporting gas 2 Is 20% by volume.
Example 8
The difference from example 1 is that 20 parts of tailings, 70 parts of active material and 10 parts of exciting material are mixed and ground according to the weight parts of dry ore.
Example 9
The difference from example 1 is that 37 parts of tailings, 50 parts of active material and 3 parts of exciting material are mixed and ground according to the weight parts of dry ore.
Example 10
The difference from example 1 is that 50 parts of tailings, 30 parts of active material and 20 parts of exciting material are mixed and ground according to the weight parts of dry ore.
Characterization of Performance
TFe test: fe recovery = weight of fine iron ore x Fe content of fine iron ore/(Σamount of each input material x Fe content of each input material) x 100%.
Activity index test: the test is performed with reference to GB/T18046-2017. The test results of the above examples are shown in Table 1.
TABLE 1
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The processing method of the laterite-nickel ore acid leaching slag is characterized by comprising the following steps of:
step S1, mixing and pressing the laterite-nickel ore acid leaching slag, the material adjusting material, the melting aid and the reducing agent to obtain a preform;
step S2, roasting the prefabricated product to obtain hot cinder and hot flue gas, wherein the hot flue gas is used for preparing acid;
s3, carrying out magnetic separation on the hot cinder to obtain a fine iron material and tailings;
s4, mixing the tailings, the active materials and the excitation materials for grinding to obtain active materials;
wherein the material regulating and arranging is iron-containing waste residue; the melting aid contains CaO, mgO, na 2 One or more alkaline substances in O; the active material is selected from one or more of nickel-iron slag, fly ash, blast furnace slag, furnace bottom slag or coal slag; the exciting material is selected from one or more of desulfurized gypsum, steel slag tailings, carbide slag, quicklime, limestone, slaked lime or cement clinker;
the laterite-nickel ore acid leaching slag comprises the following components: 48-68 wt% of Fe 2 O 3 8-17 wt% of SO 3 1-5wt% of CaO and 6-25wt% of SiO 2 1-4wt% MgO and 3-8wt% Al 2 O 3 ；
In the step S4, the tailings are 20-40 parts by weight of dry ore, the active materials are 50-70 parts by weight of dry ore, and the excitation materials are 3-10 parts by weight of dry ore;
in the step S2, the roasting temperature is 900-1250 ℃ and the roasting time is 1-2 h; o in combustion-supporting gas adopted in the roasting process 2 The volume concentration of (2) is 40-60%; the fuel used in the roasting process is selected from natural gas and/or coal dust.
2. The method for treating laterite-nickel ore acid leaching slag according to claim 1, wherein the hot slag comprises the following components: 38-52 wt% of Fe, 4-13wt% of FeO, 8-22 wt% of SiO 2 5-23 wt% of CaO and 1-6 wt% of Al 2 O 3 And 1-4wt% MgO;
the hot flue gas comprises SO 2 The SO 2 The volume concentration of (2) is 4-10%.
3. The method for treating laterite-nickel ore acid leaching slag according to claim 1, wherein in the step S1, 100 parts by weight of laterite-nickel ore acid leaching slag are calculated according to dry ore, 3-28 parts by weight of the adjusting material are calculated according to dry ore, 0.5-22 parts by weight of the melting aid is calculated according to dry ore, and 5-20 parts by weight of the reducing agent are calculated according to dry ore.
4. The method for treating laterite-nickel ore acid leaching slag according to claim 1, wherein the hot flue gas contains O 2 The volume concentration of the flue gas is less than or equal to 5 percent, and the temperature of the hot flue gas is more than or equal to 300 ℃.
5. A method of treating laterite-nickel ore acid leaching slag according to any one of claims 1 to 3, wherein the iron-containing slag is selected from one or more of steel slag, wet process iron aluminium slag or nickel smelting slag;
the alkaline substance is selected from one or more of limestone, dolomite, quick lime, gypsum slag, carbide slag or magnesium slag;
the reducing agent is selected from solid reducing agents with carbon content of 40-90% and calorific value of more than or equal to 3000 kcal/kg.
6. A method of treating laterite-nickel ore acid leaching slag according to any one of claims 1 to 3, characterized in that in step S1, before the pressing, the method of treating further comprises subjecting the laterite-nickel ore acid leaching slag, the monolith, and the fluxing material to a first crushing treatment to control the particle size of the material to 10mm or less;
in the step S3, before the magnetic separation, the treatment method further includes a step of air-cooling the hot cinder to obtain cinder.
7. The method according to claim 6, wherein in the step S3, the second crushing treatment and grinding treatment are sequentially performed on the cinder, and the granularity of the cinder after the grinding treatment meets the following requirements: the grain size of the cinder which exceeds 35% by mass in the cinder after the grinding treatment is less than or equal to 0.074mm;
in the step S3, the magnetic separation comprises two magnetic separation processes which are sequentially carried out, wherein the magnetic field intensity of the two magnetic separation processes is independent, and the value range is 80-250 kA/m.
8. An active material obtained by the treatment method of laterite-nickel ore acid leaching slag according to any one of claims 1 to 7, wherein the specific surface area of the active material is not less than 350m 2 /kg。
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