CN116555512A - Preparation process of high-carbon ferromanganese - Google Patents
Preparation process of high-carbon ferromanganese Download PDFInfo
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- CN116555512A CN116555512A CN202310517573.0A CN202310517573A CN116555512A CN 116555512 A CN116555512 A CN 116555512A CN 202310517573 A CN202310517573 A CN 202310517573A CN 116555512 A CN116555512 A CN 116555512A
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- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 56
- 239000008188 pellet Substances 0.000 claims abstract description 35
- 239000003245 coal Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000003723 Smelting Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000002309 gasification Methods 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 18
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 239000005997 Calcium carbide Substances 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910021538 borax Inorganic materials 0.000 claims description 9
- 235000010333 potassium nitrate Nutrition 0.000 claims description 9
- 239000004323 potassium nitrate Substances 0.000 claims description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 9
- 239000004328 sodium tetraborate Substances 0.000 claims description 9
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 8
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- 235000012255 calcium oxide Nutrition 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000010436 fluorite Substances 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 16
- 238000004939 coking Methods 0.000 abstract description 12
- 239000000571 coke Substances 0.000 abstract description 11
- 239000002912 waste gas Substances 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 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 2
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910000720 Silicomanganese Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/14—Multi-stage processes processes carried out in different vessels or furnaces
- C21B13/146—Multi-step reduction without melting
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0073—Selection or treatment of the reducing gases
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/008—Use of special additives or fluxing agents
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/12—Making spongy iron or liquid steel, by direct processes in electric furnaces
-
- 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
- C22B47/00—Obtaining manganese
-
- 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
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- 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
- C22B5/06—Dry methods smelting of sulfides or formation of mattes by carbides or the like
-
- 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
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
-
- 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
- C22B5/18—Reducing step-by-step
-
- 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 discloses a preparation process of high-carbon ferromanganese, which comprises the following steps: step one, raw material preparation: the method comprises the steps of (1) using the manganese iron ore as a raw material, performing agglomeration by a pellet method to obtain manganese iron ore pellets, and preparing reducing gas in the second step: raw coal powder is used as a raw material, the raw coal powder is added into a gasification furnace, oxygen-enriched gas and steam are introduced into the gasification furnace, reducing gas is obtained after the reaction, and the step three oxidation reaction: and (3) adding the manganese iron ore pellets obtained in the step (I) into a reaction furnace from the upper side. The invention adopts the reducing gas to replace coke for carbon reduction, the reducing gas is prepared by oxidizing raw coal powder independently, the coking coal with scarce resources is not needed to be used, the resources are saved, the cost is correspondingly reduced, the reducing gas is produced independently, the pollution waste gas is convenient to collect in production, and compared with the mode of directly adding the coke produced by the coking coal into a furnace for smelting, the waste gas is easier to collect and treat, and the pollution is avoided; the invention adopts twice heating smelting, the first heating is lower, and the phosphorus is convenient to be removed.
Description
Technical Field
The invention relates to the technical field of a process for preparing high-carbon ferromanganese from ferromanganese ores, in particular to a process for preparing high-carbon ferromanganese.
Background
The high-carbon ferromanganese is an alloy consisting of manganese and iron. 90% of the total world manganese production is consumed by the iron and steel industry. Manganese plays an important role in improving the strength, toughness, hardness and quenching performance of steel. Manganese is generally added into molten steel as an alloying element in the form of metallic manganese, ferromanganese, manganese-silicon alloy or the like in the steel production process. Manganese metal is generally produced by an electrolytic process, while ferromanganese or a silicomanganese alloy is mainly produced by a blast furnace or an ore-smelting furnace. The high-carbon ferromanganese is produced by adopting an electric furnace or a blast furnace, and corresponding products are electric furnace ferromanganese and blast furnace ferromanganese, wherein the electric furnace method is widely applied, and regardless of the production of the electric furnace or the blast furnace, the electric furnace method adopts the ferromanganese or the ferromanganese as a raw material, and carbon reduction is carried out in the furnace by using coke, so that the high-carbon ferromanganese is produced.
For example, chinese patent publication No. CN102373333a discloses a method for preparing high carbon ferromanganese, comprising the steps of: a) Adding the mixed ore into an electric furnace, adding coke into the electric furnace, and smelting the mixed ore at 1400-1600 ℃ to obtain molten slurry containing high-carbon ferromanganese; and b) separating the high carbon ferromanganese from the high carbon ferromanganese-containing melt, wherein the high carbon ferromanganese comprises 75.5% manganese, 14.71% iron, 2% silicon, 0.25% phosphorus, 7% carbon and 0.03% sulfur by weight.
For another example, chinese patent publication No. CN102367516a discloses a method for preparing high carbon ferromanganese, comprising the steps of: a) Adding the first mixed ore into an electric furnace, adding the second mixed ore into the electric furnace through a central pipe at the top of the electric furnace, adding coke into the electric furnace, and smelting the first mixed ore and the second mixed ore at 1400-1600 ℃ simultaneously to obtain molten slurry containing high-carbon ferromanganese; and b) separating the high carbon ferromanganese from the high carbon ferromanganese-containing slurry, wherein the weight ratio of ferromanganese in the first mixed ore is 6.55:1; in the second mixed ore, the weight ratio of ferromanganese is 10.83:1.
The preparation method of the high-carbon ferromanganese is more traditional, and is characterized in that coke is added into a furnace to reduce the carbon of minerals, the coke is made of coking coal, the coking coal is used as a scarce coal resource, more resources are wasted by using the coking coal as a raw material, the cost is high, and the carbon reduction is carried out in the furnace, so that the collection of the polluted gas generated by the coking coal is not facilitated, and the environment protection is not facilitated.
For this reason, we propose a process for preparing high carbon ferromanganese to solve the above problems.
Disclosure of Invention
The invention aims to provide a preparation process of high-carbon ferromanganese, which aims to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: a preparation process of high-carbon ferromanganese comprises the following steps:
step one, raw material preparation: the method comprises the steps of (1) agglomerating manganese iron ore serving as a raw material by a pellet method to obtain manganese iron ore pellets;
step two, preparation of reducing gas: raw coal powder is used as a raw material, the raw coal powder is added into a gasification furnace, oxygen-enriched gas and steam are introduced into the gasification furnace, and the reduction gas is obtained after the reaction;
step three, oxidation reaction: adding the manganese iron ore pellets obtained in the step one into a reaction furnace from the upper part, deacidifying the reducing gas obtained in the step two to obtain deacidified reducing gas, heating the deacidified reducing gas, then introducing the deacidified reducing gas into the reaction furnace from the lower part, and reacting to obtain metallized pellets;
step four, circuit smelting: and (3) conveying the metallized pellets obtained in the step III into an electric furnace, adding a reducing agent, an additive, an activating agent and a catalyst to form a mixture, smelting the mixture, heating the mixture to 1000-1100 ℃ at a heating rate of 10-50 ℃/MIN during smelting, performing primary solid state reduction under an inert atmosphere, reacting at a constant temperature of 30-60MIN, heating the mixture to 1250-1350 ℃ at a heating rate of 20-60 ℃/MIN, performing secondary solid state reduction under the inert atmosphere, and reacting at a constant temperature of 40-70MIN until the reaction is complete, cooling the reaction product to 500-650 ℃ in the furnace along with the furnace after the smelting reaction is completed, rapidly cooling the reaction product to 25-50 ℃, naturally crushing the reaction product, and magnetically separating to obtain a high-carbon ferromanganese finished product, wherein the waste slag is manganese-rich slag.
Preferably, the deacidification of the reducing gas in the third step is a low-temperature methanol washing deacidification process.
Preferably, the heating temperature of the reducing gas after deacidification in the third step is 1000-1100 ℃, the heat transfer of the metallized pellets in the third step is carried out by adopting a heat preservation chute, and the temperature of the metallized pellets in the third step is higher than 600 ℃.
Preferably, the total volume of carbon monoxide and hydrogen in the reducing gas obtained in the second step is higher than 85% of the volume of the reducing gas.
Preferably, the reducing agent in the fourth step is a mixture of silicon carbide, calcium carbide and aluminum powder, and the weight ratio of the silicon carbide to the calcium carbide to the aluminum powder is as follows: 70-80 parts of silicon carbide, 18-27 parts of calcium carbide and 2-5 parts of aluminum powder.
Preferably, in the fourth step, the additive is a mixture of quicklime, quartz powder and fluorite powder, and the weight proportion of the quicklime, the quartz powder and the fluorite powder is as follows: 75-88 parts of quicklime, 0-15 parts of quartz powder, 8-20 parts of fluorite powder.
Preferably, the activating agent in the fourth step is a mixture of sodium carbonate, potassium nitrate and borax, and the weight proportion of the sodium carbonate, the potassium nitrate and the borax is as follows: 20-65 parts of sodium carbonate, 20-53 parts of potassium nitrate and 2-38 parts of borax.
Preferably, the catalyst in the fourth step is a mixture of manganese oxide, metal manganese powder, metal iron powder and vanadium pentoxide, wherein the weight proportion of the manganese oxide, the metal manganese powder, the metal iron powder and the vanadium pentoxide is as follows: 17-50 parts of manganese oxide, 19-50 parts of metal manganese powder, 18-45 parts of metal iron powder and 4-16 parts of vanadium pentoxide.
Preferably, in the fourth step, the weight portion ratio of the metallized pellets, the reducing agent, the additive, the activating agent and the catalyst is: 88-96 parts of metallized pellets, 1-5 parts of reducing agent, 1-4 parts of additive, 1-4 parts of activator and 1-4 parts of catalyst.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts the reducing gas to replace coke for carbon reduction, the reducing gas is prepared by oxidizing raw coal powder independently, the coking coal with scarce resources is not needed to be used, the resources are saved, the cost is correspondingly reduced, the reducing gas is produced independently, the pollution waste gas is convenient to collect in production, and compared with the mode of directly adding the coke produced by the coking coal into a furnace for smelting, the waste gas is easier to collect and treat, and the pollution is avoided; the invention adopts twice heating smelting, the first heating is lower, and the phosphorus is convenient to be removed.
Drawings
FIG. 1 is a schematic illustration of a preparation process of the present invention;
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
referring to fig. 1, the present invention provides a technical solution: a preparation process of high-carbon ferromanganese comprises the following steps:
step one, raw material preparation: the method comprises the steps of (1) agglomerating manganese iron ore serving as a raw material by a pellet method to obtain manganese iron ore pellets;
step two, preparation of reducing gas: raw coal powder is used as a raw material, the raw coal powder is added into a gasification furnace, oxygen-enriched gas and steam are introduced into the gasification furnace, the reduction gas is obtained after the reaction, the reduction gas is used for replacing coking coal as a carbon reduction substance, the reduction gas is prepared by grinding and oxidizing raw coal, the coking coal with scarce resources is not needed, the environmental protection cost is lower, the raw coal is produced by reaction in the gasification furnace when being used for producing the reduction gas, and the polluted flue gas generated by the raw coal is easier to collect and treat;
step three, oxidation reaction: adding the manganese iron ore pellets obtained in the step one into a reaction furnace from the upper part, deacidifying the reducing gas obtained in the step two to obtain deacidified reducing gas, heating the deacidified reducing gas, then introducing the deacidified reducing gas into the reaction furnace from the lower part, and reacting to obtain metallized pellets;
step four, circuit smelting: and (3) conveying the metallized pellets obtained in the step III into an electric furnace, adding a reducing agent, an additive, an activating agent and a catalyst to form a mixture, smelting the mixture, heating the mixture to 1000-1100 ℃ at a heating rate of 10-50 ℃/MIN during smelting, performing primary solid state reduction under an inert atmosphere, reacting at a constant temperature of 30-60MIN, heating the mixture to 1250-1350 ℃ at a heating rate of 20-60 ℃/MIN, performing secondary solid state reduction under the inert atmosphere, and reacting at a constant temperature of 40-70MIN until the reaction is complete, cooling the reaction product in the furnace to 500-650 ℃ along with the furnace after the smelting reaction is completed, rapidly cooling to 25-50 ℃, naturally crushing the reactant, and obtaining a high-carbon ferromanganese finished product through magnetic separation, wherein waste residues are manganese-rich slag, smelting is performed at two sections of temperature, the first temperature is lower, phosphorus removal is convenient, and the whole reaction time is not long.
Example 2:
in a second embodiment of the present invention, the embodiment is based on the previous embodiment, wherein the deacidification of the reducing gas in the third step is a low-temperature methanol deacidification process.
The heating temperature of the reducing gas after deacidification is 1000-1100 ℃, the heat transfer of the metallized pellets is carried by adopting a heat preservation chute, and the heat transfer temperature of the metallized pellets is higher than 600 ℃.
The total volume of carbon monoxide and hydrogen in the reducing gas obtained in the second step is higher than 85% of the volume of the reducing gas.
In the fourth step, the reducing agent is a mixture of silicon carbide, calcium carbide and aluminum powder, and the weight proportion of the silicon carbide, the calcium carbide and the aluminum powder is as follows: 70-80 parts of silicon carbide, 18-27 parts of calcium carbide and 2-5 parts of aluminum powder.
And step four, the mixture of the additive quicklime, quartz powder and fluorite powder comprises the following components in parts by weight: 75-88 parts of quicklime, 0-15 parts of quartz powder, 8-20 parts of fluorite powder.
In the fourth step, the activator is a mixture of sodium carbonate, potassium nitrate and borax, and the weight proportion of the sodium carbonate, the potassium nitrate and the borax is as follows: 20-65 parts of sodium carbonate, 20-53 parts of potassium nitrate and 2-38 parts of borax.
In the fourth step, the catalyst is mixed by manganese oxide, metal manganese powder, metal iron powder and vanadium pentoxide, wherein the weight proportion of the manganese oxide, the metal manganese powder, the metal iron powder and the vanadium pentoxide is as follows: 17-50 parts of manganese oxide, 19-50 parts of metal manganese powder, 18-45 parts of metal iron powder and 4-16 parts of vanadium pentoxide.
In the fourth step, the weight proportion of the metallized pellets, the reducing agent, the additive, the activating agent and the catalyst is as follows: 88-96 parts of metallized pellets, 1-5 parts of reducing agent, 1-4 parts of additive, 1-4 parts of activator and 1-4 parts of catalyst.
Example 3:
referring to fig. 1, a third embodiment of the present invention is based on the above two embodiments, and the preparation process of the present invention is as follows: step one, raw material preparation: the method comprises the steps of (1) agglomerating manganese iron ore serving as a raw material by a pellet method to obtain manganese iron ore pellets; step two, preparation of reducing gas: raw coal powder is used as a raw material, the raw coal powder is added into a gasification furnace, oxygen-enriched gas and steam are introduced into the gasification furnace, and the reduction gas is obtained after the reaction; step three, oxidation reaction: adding the manganese iron ore pellets obtained in the step one into a reaction furnace from the upper part, deacidifying the reducing gas obtained in the step two to obtain deacidified reducing gas, heating the deacidified reducing gas, then introducing the deacidified reducing gas into the reaction furnace from the lower part, and reacting to obtain metallized pellets; step four, circuit smelting: and (3) conveying the metallized pellets obtained in the step III into an electric furnace, adding a reducing agent, an additive, an activating agent and a catalyst to form a mixture, smelting the mixture, heating the mixture to 1000-1100 ℃ at a heating rate of 10-50 ℃/MIN during smelting, performing primary solid state reduction under an inert atmosphere, reacting at a constant temperature of 30-60MIN, heating the mixture to 1250-1350 ℃ at a heating rate of 20-60 ℃/MIN, performing secondary solid state reduction under the inert atmosphere, and reacting at a constant temperature of 40-70MIN until the reaction is complete, cooling the reaction product to 500-650 ℃ in the furnace along with the furnace after the smelting reaction is completed, rapidly cooling the reaction product to 25-50 ℃, naturally crushing the reaction product, and magnetically separating to obtain a high-carbon ferromanganese finished product, wherein the waste slag is manganese-rich slag. The invention adopts the reducing gas to replace coke for carbon reduction, the reducing gas is prepared by oxidizing raw coal powder independently, the coking coal with scarce resources is not needed to be used, the resources are saved, the cost is correspondingly reduced, the reducing gas is produced independently, the pollution waste gas is convenient to collect in production, and compared with the mode of directly adding the coke produced by the coking coal into a furnace for smelting, the waste gas is easier to collect and treat, and the pollution is avoided; the invention adopts twice heating smelting, the first heating is lower, and the phosphorus is convenient to be removed.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The preparation process of the high-carbon ferromanganese is characterized by comprising the following steps of:
step one, raw material preparation: the method comprises the steps of (1) agglomerating manganese iron ore serving as a raw material by a pellet method to obtain manganese iron ore pellets;
step two, preparation of reducing gas: raw coal powder is used as a raw material, the raw coal powder is added into a gasification furnace, oxygen-enriched gas and steam are introduced into the gasification furnace, and the reduction gas is obtained after the reaction;
step three, oxidation reaction: adding the manganese iron ore pellets obtained in the step one into a reaction furnace from the upper part, deacidifying the reducing gas obtained in the step two to obtain deacidified reducing gas, heating the deacidified reducing gas, then introducing the deacidified reducing gas into the reaction furnace from the lower part, and reacting to obtain metallized pellets;
step four, circuit smelting: and (3) conveying the metallized pellets obtained in the step III into an electric furnace, adding a reducing agent, an additive, an activating agent and a catalyst to form a mixture, smelting the mixture, heating the mixture to 1000-1100 ℃ at a heating rate of 10-50 ℃/MIN during smelting, performing primary solid state reduction under an inert atmosphere, reacting at a constant temperature of 30-60MIN, heating the mixture to 1250-1350 ℃ at a heating rate of 20-60 ℃/MIN, performing secondary solid state reduction under the inert atmosphere, and reacting at a constant temperature of 40-70MIN until the reaction is complete, cooling the reaction product to 500-650 ℃ in the furnace along with the furnace after the smelting reaction is completed, rapidly cooling the reaction product to 25-50 ℃, naturally crushing the reaction product, and magnetically separating to obtain a high-carbon ferromanganese finished product, wherein the waste slag is manganese-rich slag.
2. The process for preparing high-carbon ferromanganese according to claim 1, wherein the process is characterized in that: and in the third step, the deacidification of the reducing gas is a low-temperature methanol washing deacidification process.
3. The process for preparing high-carbon ferromanganese according to claim 1, wherein the process is characterized in that: the heating temperature of the reducing gas after deacidification in the step III is 1000-1100 ℃, the heat transfer of the metallized pellets in the step III is carried out by adopting a heat preservation chute, and the temperature of the metallized pellets in the step III is higher than 600 ℃.
4. The process for preparing high-carbon ferromanganese according to claim 1, wherein the process is characterized in that: and in the second step, the total volume of carbon monoxide and hydrogen in the reducing gas is higher than 85% of the volume of the reducing gas.
5. The process for preparing high-carbon ferromanganese according to claim 1, wherein the process is characterized in that: in the fourth step, the reducing agent is a mixture of silicon carbide, calcium carbide and aluminum powder, and the weight proportion of the silicon carbide, the calcium carbide and the aluminum powder is as follows: 70-80 parts of silicon carbide, 18-27 parts of calcium carbide and 2-5 parts of aluminum powder.
6. The process for preparing high-carbon ferromanganese according to claim 1, wherein the process is characterized in that: the additive in the fourth step is a mixture of quicklime, quartz powder and fluorite powder, wherein the weight proportion of the quicklime, the quartz powder and the fluorite powder is as follows: 75-88 parts of quicklime, 0-15 parts of quartz powder, 8-20 parts of fluorite powder.
7. The process for preparing high-carbon ferromanganese according to claim 1, wherein the process is characterized in that: in the fourth step, the activator is a mixture of sodium carbonate, potassium nitrate and borax, and the weight proportion of the sodium carbonate, the potassium nitrate and the borax is as follows: 20-65 parts of sodium carbonate, 20-53 parts of potassium nitrate and 2-38 parts of borax.
8. The process for preparing high-carbon ferromanganese according to claim 1, wherein the process is characterized in that: in the fourth step, the catalyst is a mixture of manganese oxide, metal manganese powder, metal iron powder and vanadium pentoxide, wherein the weight proportion of the manganese oxide, the metal manganese powder, the metal iron powder and the vanadium pentoxide is as follows: 17-50 parts of manganese oxide, 19-50 parts of metal manganese powder, 18-45 parts of metal iron powder and 4-16 parts of vanadium pentoxide.
9. The process for preparing high-carbon ferromanganese according to claim 1, wherein the process is characterized in that: in the fourth step, the weight proportion of the metallized pellets, the reducing agent, the additive, the activating agent and the catalyst is as follows: 88-96 parts of metallized pellets, 1-5 parts of reducing agent, 1-4 parts of additive, 1-4 parts of activator and 1-4 parts of catalyst.
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