CN114480840A - Preparation method of ferromolybdenum - Google Patents
Preparation method of ferromolybdenum Download PDFInfo
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- CN114480840A CN114480840A CN202210044738.2A CN202210044738A CN114480840A CN 114480840 A CN114480840 A CN 114480840A CN 202210044738 A CN202210044738 A CN 202210044738A CN 114480840 A CN114480840 A CN 114480840A
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- 229910001309 Ferromolybdenum Inorganic materials 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 29
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000003723 Smelting Methods 0.000 claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 76
- 239000008188 pellet Substances 0.000 claims description 53
- 229910052742 iron Inorganic materials 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 22
- 239000002893 slag Substances 0.000 claims description 22
- 239000000571 coke Substances 0.000 claims description 21
- 238000005453 pelletization Methods 0.000 claims description 20
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 17
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 17
- 239000004571 lime Substances 0.000 claims description 17
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 16
- 239000010436 fluorite Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 21
- 229910052750 molybdenum Inorganic materials 0.000 description 20
- 239000011733 molybdenum Substances 0.000 description 20
- 239000002994 raw material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- 239000002699 waste material Substances 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 6
- 229910000851 Alloy steel Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910000997 High-speed steel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241001417490 Sillaginidae Species 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910004647 CaMoO4 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 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 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- 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
-
- 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
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a preparation method of ferromolybdenum, which is a novel method for preparing ferromolybdenum by utilizing molybdenum oxide, calcium molybdate and a carbonaceous reducing agent, and is different from a traditional ferromolybdenum smelting mode.
Description
Technical Field
The invention belongs to the technical field of ferroalloy, and particularly relates to a preparation method of ferromolybdenum.
Background
In the steel industry, the application of molybdenum in the steel industry still occupies the most important position according to the consumption statistics of molybdenum in countries around the world. Molybdenum is used as an alloying element of the steel, so that the strength, particularly the high-temperature strength and the toughness of the steel can be improved; the corrosion resistance of the steel in acid-base solution and liquid metal is improved; improve the wear resistance of the steel and improve hardenability, weldability and heat resistance. Molybdenum is a good carbide-forming element, is not oxidized in the steel-making process, and can be used alone or together with other alloy elements. Molybdenum is used with chromium, nickel, manganese, silicon, etc. to produce various types of stainless steel, tool steel, high speed steel, alloy steel, etc. The produced stainless steel has good corrosion resistance, and can be used for corrosion-resistant steel pipes for oil exploitation, automobile shells, sewage treatment equipment and the like. A stainless steel with 6% molybdenum can also be used to replace titanium in sea water desalination equipment, ocean-going vessels, offshore oil and gas extraction pipelines. The molybdenum series high-speed steel has the advantages of non-uniformity of carbide, wear resistance, good toughness, strong high-temperature plasticity and the like, and is suitable for manufacturing a forming cutter. The molybdenum-containing alloy steel can be used for manufacturing machine tool structural components, industrial vehicles and bulldozer equipment.
Under the normal condition, molybdenum is added into alloy steel, and the currently best use benefit is the addition in the form of ferromolybdenum, so that various properties of the alloy steel are improved, and the alloy steel can be applied to various mechanical equipment or structural components.
The traditional ferromolybdenum smelting process is most widely applied to an aluminothermic reduction method, aluminum is added in the form of aluminum powder, and the heat released by reaction can be used for melting produced alloy and slag, but the traditional ferromolybdenum smelting process has many problems that the aluminum powder is expensive, the cost is too high, the intermediate process is not easy to control due to too high reaction temperature and the like; secondly, a carbon reduction method is widely applied, a carbonaceous reducing agent and iron powder are added into the roasted molybdenum sand for briquetting, and reducing gas is introduced into a closed container, so that a ferromolybdenum product with the carbon content of about 1% can be obtained, but the defect still exists. Compared with the two methods, the method has certain advantages.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of ferromolybdenum, which aims to solve the problems in ferromolybdenum production and the problem of waste utilization of waste slag calcium molybdate in the molybdenum oxide production process in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of ferromolybdenum comprises the following steps:
The invention is further improved in that:
preferably, the mixing proportion in the step 1 is as follows by mass: molybdenum oxide powder: 52.45-60%, calcium molybdate 4.82-6.5%, iron filings 9.10-10.56%, iron phosphorus 10.56-14.75%, coke 7-18%, and lime 3.28%.
Preferably, in the step 2, the pellet size is larger than 10 mm.
Preferably, in the step 3, the roasting temperature is 950-1050 ℃.
Preferably, in step 3, the calcination time is 30 min.
Preferably, in the step 1, fluorite and a binder are also added into the mixed material.
Preferably, in the step 4, the smelting temperature is higher than 1475 ℃, and the heat preservation time is longer than 30 min.
Preferably, in the step 4, iron slag treatment is performed after smelting to obtain ferromolybdenum.
Preferably, the obtained ferromolybdenum comprises the following components: 56.56-61.27% of Mo, 0.023-0.037% of P, 0.038-0.041% of S, 1.35-1.89% of Si, 0.075-0.083% of C, 0.021-0.23% of Cu, 0.019-0.024% of Sb, 0.0012-0.0015% of Sn and the balance of Fe.
Preferably, the yield of ferromolybdenum is 99.05-99.57%.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of ferromolybdenum, which is a novel method for preparing ferromolybdenum by utilizing molybdenum oxide, calcium molybdate and a carbonaceous reducing agent, is different from a traditional ferromolybdenum smelting mode, utilizes industrial waste residue, namely calcium molybdate, generated by washing in a molybdenum oxide production process and molybdenum oxide as a source of molybdenum in the ferromolybdenum production, adopts iron phosphorus as a source of iron in the ferromolybdenum production, adopts coke with low price as a reducing agent, smelts at a high temperature, and smelts qualified ferromolybdenum in a melting reduction mode. In general, the method improves smelting conditions, reduces the reduction temperature, and reduces the requirements of smelting equipment on refractory materials; the raw material structure is changed, the molybdenum-containing waste generated in the molybdenum industry is solved, and the condition of large gas-solid pollution emission in the production process, smelting production working conditions, product quality and the like are improved; the reaction mechanism is perfected, and a plurality of problems such as the existing fuzzy rule and the like are solved; optimizes the smelting thermodynamics and slag system and further improves the product recovery rate.
Further, the invention discloses a novel method for preparing ferromolybdenum by utilizing molybdenum oxide, calcium molybdate and a carbonaceous reducing agent. With the increasing stricter environmental protection requirements, the molybdenum ore is poor, impure and refined, the molybdenum-containing renewable resources are increasing day by day, and the comprehensive conservation and the renewable recycling are the basic requirements for fully playing the resource benefits. The recovery of molybdenum from the ammonia leaching residue and the calcium molybdate industrial residue has positive significance for comprehensive utilization and recovery of renewable molybdenum resources
Drawings
FIG. 1 is a graph showing the temperature rise and holding curve of the calcination of the present invention;
FIG. 2 is a schematic view showing the structure of a high-temperature chamber furnace used in the calcination according to the present invention;
wherein, 1-thermocouple; 2-silicon molybdenum rod; 3-a graphite crucible; 4-a touch screen; 5-power switch
FIG. 3 is a temperature rise and holding curve diagram of the smelting process of the present invention.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
when industrial molybdenum oxide is produced, a water washing process is carried out, a large amount of waste water is generated in the process, and calcium molybdate waste residue sediment can be obtained by adding calcium oxide into the waste water. Calcium molybdate contains more chemical elements, wherein the calcium molybdate contains more harmful elements such as S, Cu, Pb and the like, and molybdenum mainly exists in the form of calcium molybdate. The molybdenum content in the calcium molybdate waste residue is generally more than 30%, the existing method for producing a large amount of molybdenum-containing waste residue calcium molybdate still adopts an open-air stacking method for treatment, which is an extreme waste of resources in all cases, and although researchers do research on the utilization of calcium molybdate, no appropriate treatment method with economic benefits still exists. The calcium molybdate contains excessive harmful elements, the yield of molybdenum oxide is increased day by day, the stacking condition of the calcium molybdate is serious day by day, the calcium molybdate can be stacked in the open air for a long time, not only occupies the land space, but also pollutes the soil and further pollutes water resources, causes environmental pollution, and is not in accordance with the concept of green development.
The invention discloses a novel method for preparing ferromolybdenum by utilizing molybdenum oxide, calcium molybdate and a carbonaceous reducing agent, which comprises the following steps:
step one, molybdenum oxide is ground into powder and is uniformly mixed with calcium molybdate, lime, iron phosphorus, coke and other auxiliary materials, wherein the main auxiliary materials comprise a binder and a small amount of fluorite. The mixing proportion is as follows in parts by weight: molybdenum oxide powder: 52.45-60%, calcium molybdate 4.82-6.5%, scrap iron 9.10-10.56%, iron phosphorus 10.56-14.75%, coke 7-18%, lime 3.28%, binder 2%, and fluorite 1%.
The added binder can help molding during pelletizing, the strength can be greatly increased after roasting, the three-dimensional structure of furnace burden is guaranteed to be beneficial to uniform heating and good air permeability of materials, effective smelting is further completed, meanwhile, a small amount of fluorite is added to improve the fluidity of slag, the effective separation between slag and iron is facilitated, and the metal yield is improved.
And step two, pelletizing the mixed material on a disc pelletizer to ensure that the pellet size is uniform and mellow, spraying a proper amount of water to ensure the strength of the pellet, and measuring the moisture and cold strength of the pellet after pelletizing is finished. The pellet granularity needs to be larger than 10mm, the green pellet moisture needs to be larger than 8%, enough pelletizing time is guaranteed, and the preferable pelletizing time is 10-15 min so as to improve the pellet strength and the pelletizing performance.
And step three, referring to the figures 1 and 2, according to the temperature rise curve, placing the manufactured pellets into a corundum crucible, and respectively roasting in high-temperature furnaces of 950-1050 ℃, wherein the roasting time is 30min, and the compressive strength is greater than 310N.
And step four, referring to fig. 3, mixing the roasted pellets and scrap iron waste according to a temperature rise curve, putting the pellets and scrap iron in a graphite crucible for smelting, and performing iron slag treatment by a physical method after smelting to obtain qualified ferromolybdenum meeting the requirements. The reaction time in the smelting process is not less than 1475 ℃, and the heat preservation time is not less than 30 min.
The smelting process mainly comprises the following reduction reactions:
MoO3+3C＝Mo+3CO
MoO2+2C＝Mo+2CO
CaMoO4+3C＝Mo+CaO+3CO
the content of ferromolybdenum is obtained through the roasting reaction as follows: 56.56-61.27% of Mo, 0.023-0.037% of P, 0.038-0.041% of S, 1.35-1.89% of Si, 0.075-0.083% of C, 0.021-0.23% of Cu, 0.019-0.024% of Sb, 0.0012-0.0015% of Sn and the balance of Fe.
The present invention is further illustrated by the following examples.
Example 1
The embodiment is formed by mixing the following raw materials in percentage by weight: 52.45% of molybdenum oxide, 5% of calcium molybdate, 3.28% of lime, 10.56% of scrap iron, 10.71% of iron phosphorus, 18% of coke and 200g of total material, and 2.1g of fluorite and 4g of binder are added and placed in a disc pelletizer for pelletizing to obtain pellets. And (3) roasting the pellets in a high-temperature furnace at 1000 ℃ for 30min, wherein the compressive strength after roasting is 312.5N.
Placing the pellets in a high-temperature box furnace, preserving the heat for 30min at the temperature of 1475 ℃, and then separating slag and iron of the product to obtain reduced ferromolybdenum and slag.
Ferromolybdenum composition prepared in this example: 56.56% of Mo, 0.032% of P, 0.041% of S, 1.35% of Si, 0.083% of C, 0.22% of Cu, 0.024% of Sb, 0.0013% of Sn and the balance of Fe. The yield of Mo was 99.12%.
Comparative example 1
The comparative example is prepared by mixing the following raw materials in percentage by weight: 33% of molybdenum oxide, 21% of calcium molybdate, 20% of scrap iron, 20% of iron phosphorus, 3.28% of lime and 6% of coke, 200g of the total material, 5g of silica and 3g of fluorite, placing in a high-temperature box furnace, preserving the heat for 30min at 1475 ℃, and then carrying out slag-iron separation on the product to obtain reduced ferromolybdenum and slag.
Ferromolybdenum composition prepared in this comparative example: 40.50% of Mo, 0.046% of P, 0.040% of S, 1.86% of Si, 0.053% of C, 0.18% of Cu, 0.021% of Sb and 0.0011% of Sn. The yield of Mo was 93.65%.
Example 2
The embodiment is formed by mixing the following raw materials in percentage by weight: 58% of molybdenum oxide, 4.82% of calcium molybdate, 9.10% of scrap iron, 12.71% of iron phosphorus, 12.09% of coke, 200g of total material, 2.1g of fluorite and 4g of binder are added and placed in a disc pelletizer for pelletizing, and pellets are obtained. And (3) roasting the pellets in a high-temperature furnace at 1000 ℃ for 30min, wherein the compressive strength after roasting is 331.8N.
Placing the pellets in a high-temperature box furnace, preserving the heat for 30min at the temperature of 1500 ℃, and then carrying out slag-iron separation on the product to obtain reduced ferromolybdenum and slag.
Ferromolybdenum composition prepared in this example: 60.22% of Mo, 0.037% of P, 0.040% of S, 1.84% of Si, 0.075% of C, 0.021% of Cu, 0.023% of Sb, 0.0015% of Sn and the balance of Fe.
The yield of Mo was 99.05%.
Comparative example 2
The comparative example is prepared by mixing the following raw materials in percentage by weight: 58% of molybdenum oxide, 4.82% of calcium molybdate, 9.10% of scrap iron, 12.71% of iron phosphorus and 15.37% of coke, 200g of the total material, 5g of calcium oxide and 10g of silica are added, the mixture is placed in a high-temperature box furnace, the temperature is kept for 30min at 1475 ℃, and then the product is subjected to slag-iron separation to obtain reduced ferromolybdenum and slag.
Ferromolybdenum composition prepared in this comparative example: 57.28% of Mo, 0.086% of P, 0.038% of S, 1.32% of Si, 0.086% of C, 0.22% of Cu, 0.019% of Sb and 0.0013% of Sn. The yield of Mo was 94.63%.
Example 3
The embodiment is formed by mixing the following raw materials in percentage by weight: 60% of molybdenum oxide, 6.5% of calcium molybdate, 10% of scrap iron, 13.22% of iron phosphorus, 7.0% of coke, 3.28% of lime, 200g of total material, 2.1g of fluorite and 4g of binder are added and placed in a disc pelletizer for pelletizing, and pellets are obtained. And (3) roasting the pellets in a high-temperature furnace at 1000 ℃ for 30min, wherein the compressive strength after roasting is 347.6N.
Placing the pellets in a high-temperature box furnace, preserving the heat for 40min at the temperature of 1525 ℃, and then carrying out slag-iron separation on the product to obtain reduced ferromolybdenum and slag.
Ferromolybdenum composition prepared in this example: 61.27% of Mo, 0.023% of P, 0.038% of S, 1.89% of Si, 0.079% of C, 0.23% of Cu, 0.019% of Sb and 0.0012% of Sn. The yield of Mo was 99.57%.
Comparative example 3
The comparative example is prepared by mixing the following raw materials in percentage by weight: 60% of molybdenum oxide, 6.5% of calcium molybdate, 10% of scrap iron, 13.22% of iron phosphorus, 7.0% of coke and 3.28% of lime, wherein 200g of the total materials are placed in a high-temperature box furnace, the temperature is kept at 1500 ℃ for 30min, and then the product is subjected to slag-iron separation to obtain reduced ferromolybdenum and slag.
Ferromolybdenum composition prepared in this comparative example: the content of Mo is 58.88%, the content of P is 0.088%, the content of S is 0.054%, the content of Si is 1.93%, the content of C is 0.079%, the content of Cu is 0.23%, the content of Sb is 0.021%, and the content of Sn is 0.0016%. The yield of Mo was 98.83%.
By comparing comparative example 1 with comparative example 1, it can be seen that both the molybdenum-containing waste calcium molybdate and the waste scrap iron can be used as raw materials for producing ferromolybdenum, and reduction can be performed by using cheap coke, but the yield of Mo in the product is reduced due to the increase of the proportion of calcium molybdate in the raw materials because the calcium molybdate component is complex. Comparing example 2 with comparative example 2, it can be seen that the high-grade ferromolybdenum, for example, currently used as an additive of molybdenum alloy steel, uses the most mainstream of 60MoFe, and when the method is applied to preparation, the smelting temperature should be set to be not less than 1500 ℃ under the same heat preservation time, and the Mo yield can be seriously reduced when the temperature is lower than 1500 ℃. Compared with the comparative example 3, under the condition of high grade of the product, the heat preservation time and the smelting temperature are higher, which is beneficial to the decomposition of calcium molybdate and the reduction of molybdenum oxide, thereby improving the yield of Mo and producing high grade qualified ferromolybdenum.
Example 4
The embodiment is formed by mixing the following raw materials in percentage by weight: 53% of molybdenum oxide, 5% of calcium molybdate, 9% of scrap iron, 12.72% of iron phosphorus, 17% of coke and 3.28% of lime, 200g of the total material, 2.0g of fluorite and 4g of binder are added and placed in a disc pelletizer for pelletizing, and pellets are obtained. The pellets are placed in a high temperature furnace for roasting at 980 ℃ for 30 min.
Placing the pellets in a high-temperature box furnace, preserving the heat for 40min at the temperature of 1525 ℃, and then carrying out slag-iron separation on the product to obtain reduced ferromolybdenum and slag.
Ferromolybdenum composition prepared in this example: 57.5% of Mo, 0.023% of P, 0.038% of S, 1.8% of Si, 0.082% of C, 0.025% of Cu, 0.022% of Sb and 0.0013% of Sn.
Example 5
The embodiment is formed by mixing the following raw materials in percentage by weight: 54% of molybdenum oxide, 4.9% of calcium molybdate, 9.82% of scrap iron, 13% of iron phosphorus, 15% of coke and 3.28% of lime, 200g of the total material, 2.1g of fluorite and 4g of binder are added and placed in a disc pelletizer for pelletizing, and pellets are obtained. The pellets were placed in a high temperature furnace and calcined at 1000 ℃ for 30 min.
Placing the pellets in a high-temperature box furnace, preserving the heat for 40min at the temperature of 1525 ℃, and then carrying out slag-iron separation on the product to obtain reduced ferromolybdenum and slag.
Ferromolybdenum composition prepared in this example: 58.3% of Mo, 0.03% of P, 0.04% of S, 1.7% of Si, 0.079% of C, 0.1% of Cu, 0.021% of Sb and 0.0012% of Sn.
Example 6
The embodiment is formed by mixing the following raw materials in percentage by weight: 58% of molybdenum oxide, 5.2% of calcium molybdate, 9.5% of scrap iron, 12.5% of iron phosphorus, 11.52% of coke, 3.28% of lime, 200g of total material, 2.1g of fluorite and 4g of binder are added and placed in a disc pelletizer for pelletizing, and pellets are obtained. The pellets were placed in a high temperature furnace and calcined at 1020 ℃ for 30 min.
Placing the pellets in a high-temperature box furnace, preserving the heat for 40min at the temperature of 1525 ℃, and then carrying out slag-iron separation on the product to obtain reduced ferromolybdenum and slag.
Ferromolybdenum composition prepared in this example: 58.8% of Mo, 0.028% of P, 0.041% of S, 1.6% of Si, 0.078% of C, 0.2% of Cu, 0.019% of Sb and 0.0015% of Sn.
Example 7
The embodiment is formed by mixing the following raw materials in percentage by weight: 58% of molybdenum oxide, 5.5% of calcium molybdate, 9.8% of scrap iron, 12% of iron phosphorus, 11.42% of coke, 3.28% of lime, 200g of total material, 2.1g of fluorite and 4g of binder are added and placed in a disc pelletizer for pelletizing, and pellets are obtained. The pellets were placed in a high temperature furnace and calcined at 1050 ℃ for 30 min.
Placing the pellets in a high-temperature box furnace, preserving the heat for 40min at the temperature of 1525 ℃, and then carrying out slag-iron separation on the product to obtain reduced ferromolybdenum and slag.
Ferromolybdenum composition prepared in this example: 59.2% of Mo, 0.03% of P, 0.039% of S, 1.5% of Si, 0.076% of C, 0.2% of Cu, 0.023% of Sb and 0.0014% of Sn.
Example 8
The embodiment is formed by mixing the following raw materials in percentage by weight: 59.82% of molybdenum oxide, 5.8% of calcium molybdate, 10% of scrap iron, 12.5% of iron phosphorus, 8.6% of coke, 3.28% of lime, 200g of total material, 2.1g of fluorite and 4g of binder are added and placed in a disc pelletizer for pelletizing, and pellets are obtained. The pellets were placed in a high temperature furnace and calcined at 950 ℃ for 30 min.
Placing the pellets in a high-temperature box furnace, preserving the heat for 40min at the temperature of 1525 ℃, and then carrying out slag-iron separation on the product to obtain reduced ferromolybdenum and slag.
Ferromolybdenum composition prepared in this example: 59.5% of Mo, 0.035% of P, 0.038% of S, 1.4% of Si, 0.075% of C, 0.023% of Cu, 0.024% of Sb and 0.0013% of Sn.
Example 9
The embodiment is formed by mixing the following raw materials in percentage by weight: 58% of molybdenum oxide, 6.5% of calcium molybdate, 9.6% of scrap iron, 10.56% of iron phosphorus, 12.06% of coke, 3.28% of lime, 200g of total material, 2.1g of fluorite and 4g of binder are added and placed in a disc pelletizer for pelletizing, and pellets are obtained. The pellets were baked in a high temperature furnace at 990 ℃ for 30 min.
Placing the pellets in a high-temperature box type furnace, preserving the heat for 40min at the temperature of 1525 ℃, and then carrying out slag-iron separation on the product to obtain reduced ferromolybdenum and slag.
Ferromolybdenum composition prepared in this example: 60.5% of Mo, 0.037% of P, 0.039% of S, 1.35% of Si, 0.079% of C, 0.15% of Cu, 0.022% of Sb and 0.0012% of Sn.
Example 10
The embodiment is formed by mixing the following raw materials in percentage by weight: 55% of molybdenum oxide, 5% of calcium molybdate, 10.56% of scrap iron, 10% of iron phosphorus, 16.16% of coke and 3.28% of lime, 200g of the total material, 2.1g of fluorite and 4g of binder are added and placed in a disc pelletizer for pelletizing, and pellets are obtained. The pellets were placed in a high temperature furnace and calcined at 1030 ℃ for 30 min.
Placing the pellets in a high-temperature box furnace, preserving the heat for 40min at the temperature of 1525 ℃, and then carrying out slag-iron separation on the product to obtain reduced ferromolybdenum and slag.
Ferromolybdenum composition prepared in this example: 61% of Mo, 0.032% of P, 0.04% of S, 1.55% of Si, 0.08% of C, 0.08% of Cu, 0.019% of Sb and 0.0015% of Sn.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of ferromolybdenum is characterized by comprising the following steps:
step 1, uniformly mixing molybdenum oxide powder, calcium molybdate, lime, iron phosphorus, scrap iron and coke to obtain a mixed material;
step 2, pelletizing the mixed material on a disc pelletizer, determining the moisture and cold strength of the pellets after pelletizing, and obtaining the pellets when the moisture of the green pellets is more than 8%;
step 3, roasting the pellets to obtain roasted pellets;
step 4, smelting the roasted pellets and the scrap iron to obtain ferromolybdenum; the temperature in the smelting process is more than or equal to 1475 ℃, and the heat preservation time is more than or equal to 30 min.
2. The preparation method of ferromolybdenum according to claim 1, wherein the mixing ratio in step 1 is, in parts by mass: molybdenum oxide powder: 52.45-60%, calcium molybdate 4.82-6.5%, iron filings 9.10-10.56%, iron phosphorus 10.56-14.75%, coke 7-18%, and lime 3.28%.
3. The method for preparing ferromolybdenum as claimed in claim 1, wherein in step 2, pellet size is larger than 10 mm.
4. The method for preparing ferromolybdenum according to claim 1, wherein in the step 3, the roasting temperature is 950 to 1050 ℃.
5. The method for preparing ferromolybdenum as claimed in claim 1, wherein in step 3, the calcination time is 30 min.
6. The method of claim 1, wherein in step 1, fluorite and a binder are further added to the mixture.
7. The method for preparing ferromolybdenum according to claim 1, wherein in step 4, the melting temperature is higher than 1475 ℃ and the holding time is longer than 30 min.
8. The method for preparing ferromolybdenum according to claim 1, wherein in step 4, ferromolybdenum is obtained by performing iron slag treatment after smelting.
9. The method of preparing ferromolybdenum according to any one of claims 1 to 8, wherein the composition of the obtained ferromolybdenum is: 56.56-61.27% of Mo, 0.023-0.037% of P, 0.038-0.041% of S, 1.35-1.89% of Si, 0.075-0.083% of C, 0.021-0.23% of Cu, 0.019-0.024% of Sb, 0.0012-0.0015% of Sn and the balance of Fe.
10. The method for producing ferromolybdenum according to any one of claims 1 to 8, wherein yield of ferromolybdenum is 99.05 to 99.57%.
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