CN116426773A - Method for producing rare earth ferrosilicon alloy by using rare earth slag - Google Patents
Method for producing rare earth ferrosilicon alloy by using rare earth slag Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 205
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 201
- 239000002893 slag Substances 0.000 title claims abstract description 78
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 62
- 239000000956 alloy Substances 0.000 title claims abstract description 62
- 229910000519 Ferrosilicon Inorganic materials 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 38
- 238000003723 Smelting Methods 0.000 claims abstract description 37
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 34
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 34
- 239000010959 steel Substances 0.000 claims abstract description 34
- 239000008188 pellet Substances 0.000 claims abstract description 30
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 26
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 239000011812 mixed powder Substances 0.000 claims abstract description 22
- 239000003610 charcoal Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000010891 electric arc Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000000853 adhesive Substances 0.000 claims abstract description 3
- 230000001070 adhesive effect Effects 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 19
- 239000000571 coke Substances 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 11
- 235000019353 potassium silicate Nutrition 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002006 petroleum coke Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
- 239000004568 cement Substances 0.000 claims description 2
- 238000010079 rubber tapping Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000003034 coal gas Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 43
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000002156 mixing Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 241001062472 Stokellia anisodon Species 0.000 abstract description 2
- 238000009853 pyrometallurgy Methods 0.000 abstract description 2
- 239000012141 concentrate Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 229910001018 Cast iron Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- -1 rare earth compounds Chemical class 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- 229910001141 Ductile iron Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 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
- C22B59/00—Obtaining rare earth metals
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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
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
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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
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
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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
- 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
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/006—Making ferrous alloys compositions used for making ferrous alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention provides a method for producing rare earth ferrosilicon by using rare earth slag, which belongs to the technical field of preparing rare earth alloy by pyrometallurgy, and compared with the method for preparing rare earth ferrosilicon by using rare earth-rich slag as raw materials, the method adopts ore-dressing rare earth tailings and samarium reducing slag as raw materials and adopts a carbothermic method to smelt the rare earth ferrosilicon in an electric arc furnace, and comprises the following steps: (1) Roasting the tail, adding coke powder and charcoal powder, grinding into mixed powder, adding an adhesive into the mixed powder, adding water, mixing, granulating and drying; (2) Adding silica, a carbon reducing agent, steel scraps and pellets into an electric arc furnace together for smelting reduction; (3) And discharging and pouring furnace burden to obtain the rare earth ferrosilicon alloy and harmless glassy tailings. The method provided by the invention produces rare earth ferrosilicon alloy, and produces harmless glassy tailings, so that the tailings resources are utilized in a high value, and the environmental pressure is reduced.
Description
Technical Field
The invention belongs to the technical field of preparing rare earth alloy by pyrometallurgy, and particularly relates to a method for producing rare earth ferrosilicon alloy by using rare earth slag.
Background
Rare earth intermediate alloy is widely applied to steel production, mechanical manufacturing and military production, is mostly used as an additive of steel, and has the main effects of dephosphorizing and desulfurizing, neutralizing the harmful effects of low-melting-point impurities, refining grains and improving the mechanical properties of steel. In cast iron, the alloy cast iron is mainly used as a nodulizer of spheroidal graphite cast iron, a vermiculizer of vermicular graphite cast iron and an additive of alloy cast iron, so that the mechanical properties of various cast irons are greatly improved. Rare earth intermediate alloys are various and mainly comprise rare earth ferrosilicon alloy, rare earth magnesium alloy, rare earth aluminum alloy and the like. The rare earth intermediate alloy prepared by the thermal reduction method mainly comprises rare earth ferrosilicon alloy, rare earth ferrosilicon magnesium alloy, rare earth ferrosilicon calcium alloy, rare earth ferrosilicon titanium alloy and the like.
There are two main methods of thermal reduction in the production of rare earth ferrosilicon alloys, one is to use ferrosilicon as a reducing agent and to use an electric arc furnace for smelting, which is called the silicothermic reduction method. 75 silicon iron is used as a reducing agent in an electric arc furnace where Shanghai metallurgical research of China academy of sciences is carried out in 1956, iron-making blast furnace slag of Baotou iron and steel company with REO of 4-6% is used as a raw material, and rare earth silicon iron alloy is successfully prepared. The process is adopted first in a steel-coated rare earth factory to produce rare earth ferrosilicon alloy. The Baotou rare earth research institute of metallurgical department in 1966 successfully develops rare earth-containing medium lean iron ore and low grade rare earth concentrate pellets which are directly fed into a blast furnace to remove iron and phosphorus, so as to prepare slag rich in REO more than 10%, and then a process of smelting rare earth ferrosilicon alloy by adopting a silicothermic reduction method is adopted, so that the production of rare earth ferrosilicon alloy in China steps into a new stage, and the alloy cost is far lower than that of similar products abroad. Because of the specificity of rare earth raw materials in China, before 1990s, china has always adopted a silicon heating method as a main process for producing rare earth ferrosilicon alloy. The process has the advantages of simple operation, high yield, easy control of alloy components and the like, but has the defects of low recovery rate of rare earth elements, high content of residual rare earth in smelting slag and the like.
Another thermal reduction method for producing rare earth ferrosilicon alloy is to use carbon as a reducing agent and smelting the alloy by an ore smelting furnace, which is called as carbothermal reduction method. The method takes rare earth concentrate, silica and carbonaceous reducing agent as raw materials and continuously works in an ore smelting furnace to directly produce the rare earth ferrosilicon alloy, so that the method is also called as a one-step method. Compared with the traditional silicon heating method, the carbon heating method has the advantages of capability of directly reducing metal in one step, low cost of reducing agent, less element burning loss and the like. The method has obvious defects that in the alloy smelting process, rare earth carbide furnace nubs are extremely easy to form at the bottom of the submerged arc furnace, the furnace nubs have high melting point and are not easy to flow, and the furnace nubs can not be deposited at the bottom of the furnace along with molten iron discharged out of the furnace, so that the rising of the bottom of the furnace is caused, the smelting space of a hearth is smaller and smaller, and the furnace must be shut down for repair.
The rare earth tailings are large-scale intergrowth and associated refractory tailings generated after iron and rare earth selection, and contain a large amount of available mineral components such as rare earth, fluorite, iron, niobium and the like. The long-term piling and backlog of tailings can cause serious pollution to the surrounding environment. The tailing wastewater aggravates the salinization of soil, resulting in fluorine pollution of pasture; the tailings dust particles are finer, so that rare earth elements in the soil are continuously accumulated, and environmental pollution is caused. The rare earth tailings have considerable utilization value, and the research on how to economically, reasonably and effectively recycle the useful resources in the rare earth tailings can solve the problem of comprehensive utilization of the rare earth tailings resources, generate huge economic benefits, and effectively realize increasingly serious resources and environmental pressure. The rare earth raw material utilized in the preparation method of the rare earth ferrosilicon alloy mentioned in the patent CN201711024218.0 is bastnaesite concentrate, the REO content is more than 55 percent, the rare earth raw material belongs to the rare earth concentrate, and the method cannot be applied to low-grade rare earth tailing resources; in a method for producing rare earth ferrosilicon mentioned in patent CN201810411685.7, 886 kg of smelting slag is correspondingly produced per ton of rare earth ferrosilicon product, and the surrounding environment is seriously polluted by long-term stacking and backlog.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for producing rare earth ferrosilicon alloy by using rare earth slag, aiming at the problems of comprehensive recovery and high-value utilization of rare earth tailing resources, the rare earth slag is used as low-grade rare earth resources, and carbon reducing agent, silica, steel scraps and the like are matched for smelting in an electric arc furnace by using a carbothermic reduction method to produce the rare earth ferrosilicon alloy corresponding to target components and produce harmless glassy tailings. The invention aims to provide a feasible scheme and a solution idea for smelting rare earth ferrosilicon alloy by feeding rare earth slag into a furnace, thereby not only reducing the resource and environmental pressure, but also realizing high-efficiency comprehensive recycling of useful elements in tailings.
The specific technical scheme of the invention is as follows:
a method for producing rare earth ferrosilicon alloy by using rare earth slag comprises the following steps:
(1) Roasting the rare earth slag, adding coke powder and charcoal powder, and grinding into mixed powder; adding an adhesive into the mixed powder, adding water, mixing to prepare pellets, and drying;
(2) Adding pellets, silica, carbonaceous reducing agent and steel scraps into an electric arc furnace for smelting reduction to obtain furnace burden;
(3) And discharging and pouring furnace burden to obtain the rare earth ferrosilicon alloy and harmless glassy tailings.
In the step (1), the rare earth slag is rare earth tailings or rare earth tailings and samarium reducing slag, and when the rare earth slag is the rare earth tailings and samarium reducing slag, the mass ratio of the rare earth tailings to the samarium reducing slag is 4: (1-1.5);
the components and mass percentages of the rare earth tailings in the step (1) are respectively re=4-8%, ce/re=50-55%, la/re=20-30%, nd/re=10-15%, pr/re=10-15%;
the samarium reducing slag in the step (1) comprises the following components in percentage by mass of Sm=8-12%wt, and La=55-65%wt;
the roasting temperature of the roasting in the step (1) is 500-600 ℃ and the roasting time is 3-5h;
the binder in the step (1) is one or a mixture of a plurality of water glass, bentonite, pulp waste liquid and plant starch;
when the rare earth slag is the rare earth tailings, the binder accounts for 1-5% of the mass of the mixed powder; when the rare earth slag is the rare earth tailings and samarium reducing slag, the binder accounts for 3-5% of the mass of the mixed powder;
the granularity of the coke powder in the step (1) is 5-30mm, and the fixed carbon content is more than or equal to 75%;
the fixed carbon content of the charcoal powder in the step (1) is more than or equal to 75 percent, the volatile component is less than or equal to 12 percent, and the ash content is less than or equal to 12 percent;
the total mass of the coke powder and the charcoal powder in the step (1) is 10-25% of that of the rare earth slag; the mass ratio of the coke powder to the charcoal powder is 2:1, a step of;
the drying temperature of the drying in the step (1) is 100-120 ℃ and the drying time is 1-2h; the water content of the dried pellets is less than or equal to 4 percent, the pellets freely fall to the cement ground from 1.5-2m in height, and the pellets are not crushed;
the silica particle size in step (2) is 5-20mm, wherein SiO 2 The content is more than or equal to 98 percent;
the carbonaceous reducing agent in the step (2) is one or a mixture of more than one of coke, semi-coke, gas coke, petroleum coke, charcoal and wood blocks, wherein the fixed carbon content is more than or equal to 75%;
the mass percentage of the pellets, the silica, the carbonaceous reducing agent and the steel scraps in the step (2) is that the pellets (40-50%), the silica (20-30%), the carbonaceous reducing agent (15-20%) and the steel scraps (10-15%);
the smelting reduction in the step (2) is specifically that furnace burden is fed into an arc furnace for smelting reduction at 1500-2000 ℃;
the tapping and casting in the step (3) is specifically to pour the completely melted furnace burden into an ingot mould for slag-iron separation;
in the step (3), si=30-40%wt in the rare earth ferrosilicon alloy component, and the balance is iron, wherein when the rare earth slag is rare earth tailings, re=10-15%wt, and when the rare earth slag is rare earth tailings and samarium reducing slag, re=15-20%wt;
the smelting slag separated in the step (3) is harmless glassy tailings, and the components and the mass content of the smelting slag are SiO 2 ＝40-45％wt，Al 2 O 3 30-35%wt, 3-5%wt of MgO and 1-3%wt of Fe, wherein when the rare earth slag is rare earth tailings, caO=25-30%wt, and when the rare earth slag is rare earth tailings and samarium reducing slag, caO=20-25%wt.
The technical principle of the invention is as follows:
1. the rare earth content in the rare earth tailings is about 4-8%, and the rare earth tailings can be used as a low-grade rare earth raw material, and can be reduced and smelted by a carbothermic method, so that the production of the rare earth ferrosilicon alloy with the rare earth content of about 10-15% is realized. As a method for producing rare earth ferrosilicon, the carbothermic method has the advantages of low cost of reducing agent, less element burning loss, capability of directly reducing metal in one step and the like compared with the traditional carbothermic method.
2. The production of rare earth ferrosilicon by carbothermic processes can be mainly described as two processes, namely, reduction of silicon dioxide to silicon by carbon and carbonization of silicon monoxide with rare earth compounds to form carbides and reduction of rare earth carbides to rare earth metals by silicon monoxide.
Compared with the prior art, the invention has the advantages that:
1. compared with the traditional method which uses rare earth concentrate as raw material, the invention selects rare earth slag (the rare earth content is about 4-8%) as smelting raw material, and the rare earth ferrosilicon alloy with the rare earth content of 10-15% and the silicon content of 30-40% is produced by proportioning silica, carbonaceous reducing agent and steel scraps. The low-grade rare earth tailings are selected, so that useful elements in the tailings can be comprehensively recycled, the high-value utilization of the tailings is realized, and the resource and environmental pressure are reduced; but also explore a new raw material and a new process for smelting the rare earth ferrosilicon alloy by a carbothermic method.
2. The invention adopts a carbothermic reduction method to smelt rare earth ferrosilicon alloy in an electric arc furnace, can realize direct reduction of metal, reduce element burning loss and improve rare earth recovery rate.
3. The tailings generated in the production flow of the invention are harmless glassy tailings, and the components of the tailings are SiO 2 ＝40-45％wt，Al 2 O 3 ＝30-35％wt，MgO＝3-5％wt，Fe＝1-3％wt。
Drawings
Fig. 1 is a process flow chart of a method for producing rare earth ferrosilicon alloy by using rare earth tailings.
Detailed Description
The invention is further illustrated below with reference to examples.
In the embodiment of the invention, the components and the mass percentages of the rare earth tailings are respectively RE=4-8%, ce/RE=50-55%, la/RE=20-30%, nd/RE=10-15%, pr/RE=10-15%; the samarium reducing slag comprises the following components in percentage by mass of Sm=8-12%wt, and La=55-65%wt;
the binder is one or a mixture of a plurality of sodium silicate, bentonite, paper pulp waste liquid and plant starch;
silica particle size of 5-20mm, wherein SiO 2 The content is more than or equal to 98 percent;
the carbonaceous reducing agent is one or a mixture of more than 75% of coke, semi-coke, gas coke, petroleum coke, charcoal and wood blocks;
si=30-40%wt in the rare earth ferrosilicon alloy component prepared in the embodiment, and the balance is iron, wherein re=10-15%wt when the rare earth slag is rare earth tailings, and re=15-20%wt when the rare earth slag is rare earth tailings and samarium reducing slag; the separated smelting slag is harmless glassy tailings, and the components and mass contents of the smelting slag are SiO 2 ＝40-45％wt，Al 2 O 3 30-35%wt, 3-5%wt of MgO and 1-3%wt of Fe, wherein when the rare earth slag is rare earth tailings, caO=25-30%wt, and when the rare earth slag is rare earth tailings and samarium reducing slag, caO=20-25%wt.
Example 1
The process flow chart is shown in figure 1The burden of alloy smelting is shown as follows: rare earth tailings, carbonaceous reducing agents, silica and steel scraps. The burden is prepared by taking the total weight of the burden as 100%, and the burden comprises the following components: rare earth tailings of about 68%, carbonaceous reducing agent of about 11% (fixed carbon content not less than 75%), silica of about 12% (SiO) 2 Not less than 98%) and about 9% steel chip. The binder water glass was about 5%.
The method comprises the following steps:
(1) Roasting the rare earth tailings for 3 hours at 550 ℃, adding coke powder and charcoal powder accounting for 10% of the mass of the rare earth tailings, grinding into mixed powder, adding a binder accounting for 5% of the total weight of the mixed powder into the mixed powder, adding water, mixing, granulating, and drying for 2 hours at 100 ℃;
(2) Adding silica, coke, steel scraps and pellets into an electric arc furnace together for smelting reduction at 1500 ℃;
(3) And discharging and pouring furnace burden to obtain the rare earth ferrosilicon alloy and harmless glassy tailings.
Example 2
The furnace burden for alloy smelting is as follows: rare earth tailings, carbonaceous reducing agents, silica and steel scraps. The burden is prepared by taking the total weight of the burden as 100%, and the burden comprises the following components: the rare earth pellet is about 66 percent, the carbonaceous reducing agent is about 13 percent (fixed carbon content is more than or equal to 75 percent), and the silica is about 14 percent (SiO) 2 Not less than 98%) and about 7% steel chip. The binder water glass was about 2%.
The method comprises the following steps:
(1) Roasting the rare earth tailings for 4 hours at the temperature of 500 ℃, adding coke powder and charcoal powder accounting for 15% of the mass of the rare earth tailings, grinding into mixed powder, adding a binder accounting for 5% of the total weight of the mixed powder into the mixed powder, adding water, mixing, granulating, and drying for 1 hour at 110 ℃;
(2) Adding silica, charcoal, steel scraps and pellets into an electric arc furnace together for smelting reduction at 2000 ℃;
(3) And discharging and pouring furnace burden to obtain the rare earth ferrosilicon alloy and harmless glassy tailings.
Example 3
The furnace burden for alloy smelting is as follows: rare earth tailings, carbonaceous reducing agents, silica and steel scraps. In the form of a chargeThe total weight of the furnace burden is 100 percent: the rare earth pellet is about 64%, the carbonaceous reducing agent is about 14% (fixed carbon content is more than or equal to 75%), the silica is about 17% (SiO) 2 Not less than 98%) and steel scraps of about 5%. Wherein the Bayan obo rare earth tailings in the rare earth pellets are about 85%, the coke is about 10% (the fixed carbon content is more than or equal to 75%), and the binder water glass is about 5%.
The method comprises the following steps:
(1) Roasting the rare earth tailings for 4 hours at 600 ℃, adding coke powder and charcoal powder accounting for 20% of the mass of the rare earth tailings, grinding into mixed powder, adding a binder accounting for 5% of the total weight of the mixed powder into the mixed powder, adding water, mixing, granulating, and drying for 2 hours at 100 ℃;
(2) Adding silica, coke, charcoal, steel scraps and pellets into an electric arc furnace together for smelting reduction at 1800 ℃;
(3) And discharging and pouring furnace burden to obtain the rare earth ferrosilicon alloy and harmless glassy tailings.
Example 4
The furnace burden for alloy smelting is as follows: rare earth tailings, carbonaceous reducing agents, silica and steel scraps. The burden is prepared by taking the total weight of the burden as 100%, and the burden comprises the following components: the rare earth pellet is about 64%, the carbonaceous reducing agent is about 14% (fixed carbon content is more than or equal to 75%), the silica is about 17% (SiO) 2 Not less than 98%) and steel scraps of about 5%. Wherein the Bayan obo rare earth tailings in the rare earth pellets are about 85%, the coke is about 10% (the fixed carbon content is more than or equal to 75%), and the binder water glass is about 5%.
The method comprises the following steps:
(1) Roasting the rare earth tailings for 4 hours at the temperature of 550 ℃, adding coke powder and charcoal powder accounting for 15% of the mass of the rare earth tailings, grinding into mixed powder, adding a binder accounting for 3% of the total weight of the mixed powder into the mixed powder, adding water, mixing, granulating, and drying for 1 hour at 110 ℃;
(2) Adding silica, charcoal, steel scraps and pellets into an electric arc furnace together for smelting reduction at 2000 ℃;
(3) And discharging and pouring furnace burden to obtain the rare earth ferrosilicon alloy and harmless glassy tailings.
Example 5
The furnace burden for alloy smelting is as follows: rare earth tailings, samarium reducing slag, carbonaceous reducing agent, silica and steel scraps. The burden is prepared by taking the total weight of the burden as 100 percent, and the burden comprises the following components: the weight ratio of the rare earth tailings to the samarium reducing slag is 4:1, the carbonaceous reducing agent is 17 percent (the fixed carbon content is more than or equal to 75 percent), the silica is 24 percent (the SiO2 is more than or equal to 98 percent), and the steel scraps are 15 percent. Wherein the rare earth pellets contain about 75% of rare earth raw materials, about 20% of coke (the fixed carbon content is more than or equal to 75%) and about 5% of binder water glass. The specific procedure is as in example 1.
Example 6
The furnace burden for alloy smelting is as follows: rare earth tailings, samarium reducing slag, carbonaceous reducing agent, silica and steel scraps. The burden is prepared by taking the total weight of the burden as 100 percent, and the burden comprises the following components: the rare earth pellets are about 46 percent (the weight ratio of the Bayan obo rare earth tailings to the samarium reducing slag is 4:1), the carbonaceous reducing agent is about 16 percent (the fixed carbon content is more than or equal to 75 percent), the silica is about 27 percent (the SiO2 is more than or equal to 98 percent), and the steel scraps are about 11 percent. Wherein the rare earth pellets contain about 75% of rare earth raw materials, about 20% of coke (the fixed carbon content is more than or equal to 75%) and about 5% of binder water glass. The specific procedure is as in example 2.
Example 7
The furnace burden for alloy smelting is as follows: rare earth tailings, samarium reducing slag, carbonaceous reducing agent, silica and steel scraps. The burden is prepared by taking the total weight of the burden as 100 percent, and the burden comprises the following components: the weight ratio of the rare earth tailings and the samarium reducing slag in the Bayan Obo is 4:1, the carbonaceous reducing agent is 16 percent (the fixed carbon content is more than or equal to 75 percent), the silica is 21 percent (the SiO2 is more than or equal to 98 percent), and the steel scraps are 13 percent. Wherein the rare earth pellets contain about 75% of rare earth raw materials, about 20% of coke (the fixed carbon content is more than or equal to 75%) and about 5% of binder water glass. The specific procedure is the same as in example 3.
Example 8
The furnace burden for alloy smelting is as follows: rare earth tailings, samarium reducing slag, carbonaceous reducing agent, silica and steel scraps. The burden is prepared by taking the total weight of the burden as 100 percent, and the burden comprises the following components: the weight ratio of the rare earth tailings and the samarium reducing slag in the Bayan Obo is 4:1, the carbonaceous reducing agent is 16 percent (the fixed carbon content is more than or equal to 75 percent), the silica is 21 percent (the SiO2 is more than or equal to 98 percent), and the steel scraps are 13 percent. Wherein the rare earth pellets contain about 75% of rare earth raw materials, about 20% of coke (the fixed carbon content is more than or equal to 75%) and about 5% of binder water glass. The specific procedure is the same as in example 3. The specific procedure is the same as in example 4.
Claims (10)
1. A method for producing rare earth ferrosilicon alloy by using rare earth slag, which is characterized by comprising the following steps:
(1) Roasting the rare earth slag, adding coke powder and charcoal powder, and grinding into mixed powder; adding an adhesive into the mixed powder to be synthesized into pellets, and then drying;
(2) Adding pellets, silica, carbonaceous reducing agent and steel scraps into an electric arc furnace for smelting reduction to obtain furnace burden;
(3) And discharging and pouring furnace burden to obtain the rare earth ferrosilicon alloy and harmless glassy tailings.
2. The method for producing rare earth ferrosilicon alloy with rare earth slag according to claim 1, wherein the rare earth slag in step (1) is rare earth tailings or rare earth tailings and samarium reducing slag; when the rare earth slag is the rare earth tailings and the samarium reducing slag, the mass ratio of the rare earth tailings to the samarium reducing slag is 4: (1-1.5).
3. The method for producing rare earth ferrosilicon alloy with rare earth slag according to claim 1, wherein the components and mass percentages in the rare earth tailings in the step (1) are re=4% -8%, ce/re=50-55%, la/re=20% -30%, nd/re=10% -15%, pr/re=10% -15%, respectively; the samarium reducing slag comprises the following components in percentage by mass of Sm=8-12%wt and La=55-65%wt.
4. The method for producing rare earth ferrosilicon alloy with rare earth slag according to claim 1, wherein the roasting temperature for roasting in the step (1) is 500-600 ℃ and the roasting time is 3-5 hours; the total mass of the coke powder and the charcoal powder is 10-25% of the rare earth slag, and the mass ratio of the coke powder to the charcoal powder is 2:1, a step of; the granularity of the coke powder is 5-30mm, and the fixed carbon content is more than or equal to 75%; the fixed carbon content of the charcoal powder is more than or equal to 75%, the volatile component is less than or equal to 12% and the ash content is less than or equal to 12%.
5. The method for producing rare earth ferrosilicon alloy with rare earth slag according to claim 1, wherein the binder in the step (1) is one or a mixture of several of water glass, bentonite, pulp waste liquid and plant starch; when the rare earth slag is the rare earth tailings, the binder accounts for 1-5% of the mass of the mixed powder; when the rare earth slag is the rare earth tailings and samarium reducing slag, the binder accounts for 3-5% of the mass of the mixed powder.
6. The method for producing rare earth ferrosilicon alloy with rare earth slag according to claim 1, wherein the drying temperature in the step (1) is 100-120 ℃ and the drying time is 1-2h; the water content of the dried pellets is less than or equal to 4 percent, the pellets freely fall to the cement ground from 1.5-2m in height, and the pellets are not crushed.
7. The method for producing rare earth ferrosilicon alloy with rare earth slag according to claim 1, wherein the silica particle size in step (2) is 5-20mm, wherein SiO 2 The content is more than or equal to 98 percent; the carbonaceous reducing agent is one or a mixture of more than one of coke, semi-coke, coal gas coke, petroleum coke, charcoal and wood blocks, wherein the fixed carbon content is more than or equal to 75%; the mass percentage of the pellets, the silica, the carbonaceous reducing agent and the steel scraps is 40-50 percent of the pellets, 20-30 percent of the silica, 15-20 percent of the carbonaceous reducing agent and 10-15 percent of the steel scraps.
8. The method for producing rare earth ferrosilicon alloy with rare earth slag according to claim 1, wherein the smelting reduction in step (2) is specifically smelting reduction of furnace burden in an arc furnace at 1500-2000 ℃.
9. The method for producing rare earth ferrosilicon alloy according to claim 1, wherein the tapping and casting in step (3) is specifically to pour the totally melted charge into an ingot mold for slag-iron separation.
10. The method for producing a rare earth ferrosilicon alloy with rare earth slag according to claim 1, wherein si=30-40%wt in the rare earth ferrosilicon alloy composition in step (3), the balance being iron, wherein re=10-15%wt when the rare earth slag is rare earth tailings, and re=15-20%wt when the rare earth slag is rare earth tailings and samarium reducing slag; the separated smelting slag is harmless glassy tailings, and comprises the following components in percentage by mass 2 ＝40-45％wt，Al 2 O 3 30-35%wt, 3-5%wt of MgO and 1-3%wt of Fe, wherein when the rare earth slag is rare earth tailings, caO=25-30%wt, and when the rare earth slag is rare earth tailings and samarium reducing slag, caO=20-25%wt.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5002733A (en) * | 1989-07-26 | 1991-03-26 | American Alloys, Inc. | Silicon alloys containing calcium and method of making same |
| CN1071205A (en) * | 1992-10-27 | 1993-04-21 | 东北工学院 | The technology of preparation of rareearth ferro-silicon alloy by carbon thermal reduction to ore bearing O, C and Ce |
| CN1389586A (en) * | 2001-06-05 | 2003-01-08 | 四川红佳瑞稀土金属材料厂 | Method of compounding furnace charge for one-step process of producing RE ferro-silicon alloy |
| CN104878289A (en) * | 2015-06-29 | 2015-09-02 | 理县岷江稀土新材料开发有限公司 | Ceric rare earth ferrosilicon alloy and production method thereof |
-
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- 2023-04-28 CN CN202310480046.7A patent/CN116426773A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5002733A (en) * | 1989-07-26 | 1991-03-26 | American Alloys, Inc. | Silicon alloys containing calcium and method of making same |
| CN1071205A (en) * | 1992-10-27 | 1993-04-21 | 东北工学院 | The technology of preparation of rareearth ferro-silicon alloy by carbon thermal reduction to ore bearing O, C and Ce |
| CN1389586A (en) * | 2001-06-05 | 2003-01-08 | 四川红佳瑞稀土金属材料厂 | Method of compounding furnace charge for one-step process of producing RE ferro-silicon alloy |
| CN104878289A (en) * | 2015-06-29 | 2015-09-02 | 理县岷江稀土新材料开发有限公司 | Ceric rare earth ferrosilicon alloy and production method thereof |
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