CN110964931A - Method for producing light rare earth composite heavy rare earth silicon iron alloy - Google Patents
Method for producing light rare earth composite heavy rare earth silicon iron alloy Download PDFInfo
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Abstract
The invention realizes the process for producing the heavy metal rare earth silicon-iron alloy under the carbothermic reduction condition by a new technical means, has the characteristics of obviously improved rare earth yield, simple and convenient process flow, obviously low comprehensive cost and relatively light environmental influence, and has important value on the industrial preparation and wide application of the heavy rare earth silicon-iron alloy product. Meanwhile, the application characteristics of the light rare earth silicon-iron alloy product are compounded with the heavy rare earth silicon-iron alloy, so that the light rare earth silicon-iron alloy has more comprehensive application technical characteristics of excellent spheroidization, inoculation, creeping, ageing resistance and the like, and meanwhile, the preparation cost of the heavy rare earth silicon-iron alloy product is directly reduced due to the relatively low price of the light rare earth raw material, so that the industrial application of the product is facilitated.
Description
Technical Field
The invention relates to a method for producing light rare earth composite heavy rare earth silicon iron alloy, which belongs to the technical field of rare earth pyrometallurgy; the technology relates to the technical field of comprehensive utilization of waste resources by using industrial waste residues as metallurgical raw materials.
Background
The rare earth ferrosilicon alloy is a main product in the rare earth intermediate alloy industry in China, and has been widely applied to metallurgy and casting production for a long time, and the addition of the rare earth obviously improves the mechanical property, the process property and the service performance of steel and cast iron. With the expansion of the application field, the requirements on alloy components and dosage forms are different due to different use purposes, conditions and technical equipment levels. The rare earth components in the alloy are selected differently, and the application characteristics of the product are obviously different. The light rare earth ferrosilicon alloy mainly comprises a cerium-rich type and a lanthanum-rich type, wherein Ce/TREO in the cerium-rich type is more than 70 percent, and the light rare earth ferrosilicon alloy is an excellent nodulizer and inoculant of cast iron; the latter requires that La/TREO exceed 50%, and is a good vermiculizer. Corresponding to light rare earth silicon-iron alloy, yttrium-based heavy rare earth silicon-iron alloy and corresponding nodulizer products are developed and produced by utilizing the heavy rare earth resources in the south of China, the rare earth content in the heavy rare earth silicon-iron alloy comes from yttrium heavy rare earth metal, the light rare earth silicon-iron alloy has the excellent characteristic of strong spheroidization recession resistance, and the defects of the light rare earth products in spheroidization recession resistance and other performances can be effectively overcome.
Yttrium based heavy rare earth ferrosilicon has now developed into an important class of nodulizer products. 6 heavy rare earth-silicon-iron alloy grades and 13 heavy rare earth-magnesium-silicon-iron alloy grades are specially added in rare earth-silicon-iron alloy GB/T4137-2015 and rare earth-magnesium-silicon-iron alloy GB/T4138-2015 revised in 2015 respectively. With the higher technical requirements of casting for resisting spheroidization recession, heavy rare earth silicon-iron alloy products and corresponding spheroidizing agent products are increasingly widely applied, and are widely applied in the fields of large-section iron castings, thick-section ductile iron castings, production lines, rare earth heat-resistant steel, special tool steel, cast iron welding rods and the like, so that good effects are achieved.
As for the preparation technology of the two types of rare earth ferrosilicon alloys, the production process of the light rare earth product and the heavy rare earth product has obvious difference. The light rare earth ferrosilicon alloy is mainly prepared by two processes of a silicothermic process, a carbothermic process and the like, and related technical reports are numerous, wherein the carbothermic process is a main production process due to the advantages of simple and convenient raw materials, high rare earth recovery rate and low comprehensive cost. Around the manufacture of heavy rare earth ferrosilicon products, relevant research works and technical documents are all prepared by a calcium carbide and silicothermic reduction process. The Feng drawer is introduced in the summary and progress of research and application of Yttrium-based heavy rare earth ferrosilicon alloy, and is prepared by taking heavy rare earth oxide, ferrosilicon, calcium carbide, lime and silica sand as raw materials and performing calcium carbide and silicon thermal reduction in an electric arc furnace. The aged light is introduced in the State and the prospect of yttrium-based heavy rare earth ferrosilicon alloyOn the basis of raw materials, the blanking of the heavy rare earth extraction process is fully utilized, rare earth hydroxide is used as the raw material, ferrosilicon and calcium carbide are used as composite reducing agents, and the ratio of the composite reducing agents to rare earth oxides (Ca + Si/Re)2O3) 1 to 2, and refining in an electric arc furnace. The introduction of Wang Guohai in "trial production of multiple varieties of heavy rare earth ferrosilicon alloy" is that the yttrium-based heavy rare earth ferrosilicon alloy is prepared by using heavy rare earth oxide or hydroxide extracted from ion type rare earth ore unique in south China as an aggregate, adding ferrosilicon, calcium carbide and other composite reducing agents, and smelting in an electric arc furnace. Yangqing is introduced in ZL200510019201.7, and is prepared with yttrium-base heavy rare earth mixed ore or high yttrium rare earth concentrate or yttrium oxide produced in rare earth separating enterprise as material and aluminum, ferrosilicon, calcium silicon, calcium carbide, etc. as reductant and through smelting in electric arc furnace. The preparation of the heavy rare earth silicon-iron alloy by the traditional process is inevitably accompanied by the defects of low rare earth yield (generally about 60%), incapability of continuous production, huge waste residue generation amount and the like due to the restriction of the calcium carbide and silicon thermal reduction process principle and a balanced reaction system.
Disclosure of Invention
The invention aims to provide a light rare earth composite heavy rare earth silicon-iron alloy which is used for achieving the technical purpose of enhancing yttrium base heavy rare earth silicon-iron alloy in the aspects of spheroidization and vermicular characteristics aiming at the incompleteness of the application performance of a yttrium base heavy rare earth silicon-iron alloy product only comprising yttrium group elements; meanwhile, the method for preparing the composite heavy rare earth ferrosilicon alloy adopts a carbothermic reduction process, and compared with the traditional 'calcium carbide + ferrosilicon' reduction method, the method has the characteristics of obviously improved rare earth yield, simple and convenient process flow, obviously low comprehensive cost and relatively light environmental influence. The present invention has been completed by combining the effective effects of the above aspects.
In order to more clearly express the technical scheme of the invention, the technical scheme of the reduction process of the rare earth silicon-iron alloy which is reported in China needs to be analyzed, the general rule of the technical scheme is analyzed, and key process nodes which need to be further innovated and perfected are found.
Rare earth elementAnd the basic properties of the compounds thereof. Y is a non-Ln rare earth element and has some obvious differences from the Ln rare earth element, for example, the melting point of the metal Y reaches 1509 ℃, while the melting points of the metals La and Ce are only 920 ℃ and 793 ℃. For yttrium-based heavy rare earth ferrosilicon, most of the yttrium-based heavy rare earth ferrosilicon is high yttrium rare earth enrichment produced by smelting and separating southern ion ores; most commonly in the form of carbonate, which is conventionally called "yttrium rich carbonate" in the industry, and can be converted into yttrium rich oxide after being burned; the relative ratio of yttrium group rare earth element in the high yttrium rare earth concentrate is close to 100%, wherein the ratio of Y element is more than 85% (by Y)2O3a/TREO meter). In view of rare earth wet separation, Dy/Ho is one of the most common processes, and in high yttrium rare earth enrichment such as yttrium rich carbonate, other rare earth elements except Y generally comprise Ho, Er, Tm, Yb and Lu, but do not comprise Tb, Dy and other elements; the melting point range of the metals Ho, Er, Tm, Yb and Lu is between 1461-1652 ℃. The characteristic of metal melting point also shows that if the carbon thermal reduction process is adopted to manufacture the conventional heavy rare earth silicon-iron alloy, the smelting temperature is much higher than that of the light rare earth (La, Ce) rare earth silicon-iron alloy, and the temperature difference between the light rare earth (La, Ce) rare earth silicon-iron alloy and the light rare earth silicon-iron alloy is judged to be about 600 ℃ according to the general engineering technical experience, which brings great difficulty to the design of ore smelting furnace equipment and the realization of the smelting process, and even cannot be realized. For the reasons, the traditional method for preparing the heavy rare earth ferrosilicon alloy adopts calcium carbide and ferrosilicon as a composite reducing agent and is industrially manufactured according to a two-step process.
The purpose of the invention is realized as follows: a method for producing light rare earth composite heavy rare earth silicon iron alloy is characterized by comprising the following steps:
(1) taking the following rare earth materials as rare earth raw materials, and mixing the materials;
a. a yttrium-rich rare earth material, wherein: the total content of RE elements calculated by REO is more than 20%, Y2O3The concentration of/TREO is more than or equal to 70 percent, and the total content of lanthanum group rare earth elements/TREO calculated by REO<5%；
b. A cerium-rich rare earth material, wherein: r in REOTotal content of E element is greater than 20%, CeO2The ratio of/TREO is more than or equal to 50 percent, and the total content of yttrium group rare earth elements/TREO calculated by REO<10%；
c. A lanthanum-rich rare earth material, wherein: RE element content calculated by REO is more than 20%, La2O3The ratio of/TREO is more than or equal to 50 percent, and the total content of yttrium group rare earth elements/TREO calculated by REO<10%；
During material mixing, the mixing proportion of each rare earth material in the rare earth raw materials must satisfy: with total of rare earth materials, Y2O3/TREO≥50%，（CeO2+La2O3）/TREO≥12%，CeO2/TREO≥4%，La2O3/TREO≥4%；
Mixing the rare earth raw material obtained by mixing the materials with a siliceous raw material and a carbonaceous reducing agent, and pressing to prepare rare earth agglomerates; adding a binding agent into each raw material to carry out batching according to the requirements of a pressing process and the characteristics of the base raw material; the dosage of the basic rare earth raw material calculated by TRE is 80-100 wt% of theoretical value; the amount of the siliceous raw material is 10-60 wt% of a theoretical value, and the siliceous raw material is calculated by total Si elements in the rare earth agglomerate and comprises Si elements brought by the adhesive; the amount of the carbonaceous reducing agent is 100-130 wt% of a theoretical value required by reducing the silicon element in the rare earth agglomerate into a simple substance, and the amount of the carbonaceous reducing agent is calculated by fixed carbon in the rare earth agglomerate;
(2) smelting silica, carbon reducing agent and the rare earth agglomerate in a furnace; if the amount of the rare earth raw material in the rare earth briquette in the step (1) is less than 100wt%, putting the rest of the rare earth raw material, silica, a carbon reducing agent and the rare earth briquette into a furnace for smelting; the amount of silica added is the remaining amount of the silica obtained by subtracting the amount of silicon contained in the rare earth agglomerates from 100 to 120wt% of the theoretical value, and the amount of silica added is SiO in the silica2Counting; the carbonaceous reducing agent is 0.80-0.96 times of the corresponding residual amount of the rare earth agglomerate after the amount of solid carbon contained in the rare earth agglomerate is deducted from the theoretical value, and the carbonaceous reducing agent is calculated by the solid carbon in the carbonaceous reducing agent; and discharging and casting to obtain the rare earth silicon-iron alloy.
The invention is further illustrated below:
the invention relates to a method for producing light rare earth composite heavy rare earth silicon-iron alloy, which is characterized in that the rare earth material is one or a mixture of more of enrichment generated by rare earth hydrometallurgy, waste generated in the production and use processes of rare earth functional materials, rare earth concentrate, single rare earth oxide, mixed rare earth oxide, single rare earth carbonate, mixed rare earth carbonate, single rare earth oxalate, mixed rare earth oxalate, single rare earth hydroxide, mixed rare earth hydroxide and rare earth smelting slag.
The invention relates to a method for producing light rare earth composite heavy rare earth ferrosilicon alloy, which is characterized in that the used yttrium-rich material is one or a mixture of more of yttrium-based heavy rare earth mixed rare earth mineral products, high yttrium rare earth concentrates produced by rare earth separation enterprises, yttrium oxide, yttrium carbonate, yttrium oxalate, yttrium hydroxide and rare earth fluorescent powder waste; the cerium-rich material is one or a mixture of more of bastnaesite products, mixed rare earth mineral products, cerium-rich rare earth concentrates produced by rare earth separation enterprises, cerium oxide, lanthanum cerium oxide, cerium carbonate, cerium oxalate, cerium hydroxide, rare earth polishing powder waste and rare earth fluorescent powder waste; the lanthanum-rich material is one or a mixture of more of bastnaesite products, rare earth mixed mineral products, high-lanthanum rare earth enrichment produced by rare earth separation enterprises, lanthanum oxide, lanthanum cerium oxide, lanthanum carbonate, lanthanum oxalate, lanthanum hydroxide, rare earth polishing powder waste and rare earth catalyst waste.
The invention relates to a method for producing light rare earth composite heavy rare earth silicon-iron alloy, which is characterized in that the siliceous raw material used in the step (1) is one or a mixture of more of silica, micro silicon powder, silicon micropowder, silicon powder, silicon granules, quartz sand and silicon ferroalloy smelting slag.
The invention relates to a method for producing light rare earth composite heavy rare earth ferrosilicon alloy, which is characterized in that the used carbonaceous reducing agent is one or a mixture of more of coke, carbon powder, semi-coke, charcoal, gas coal coke, bituminous coal, petroleum coke and refined coal powder; the carbonaceous reducing agent in the step (1) requires that the fixed C is more than or equal to 70wt percent and the ash content is less than 10wt percent; the carbonaceous reducing agent in the step (2) requires that the fixed C is more than or equal to 80wt percent and the ash content is less than 7wt percent.
The invention relates to a method for producing light rare earth composite heavy rare earth ferrosilicon alloy, which is characterized in that the used adhesive is one or a mixture of more of soluble glass, micro silicon powder, bentonite, paper pulp, syrup waste liquid and plant starch.
The method for producing the light rare earth composite heavy rare earth silicon-iron alloy is characterized in that the silica prepared in the step (2) contains SiO2>98wt%，Al2O3<0.4wt%，CaO<0.2wt%。
The invention relates to a method for producing light rare earth composite heavy rare earth ferrosilicon, which is characterized in that the light rare earth composite heavy rare earth ferrosilicon is discharged from a furnace and then is stood for more than 10 minutes for casting; if the upper layer of the discharged alloy melt appears suspension scum, the alloy melt is skimmed by auxiliary equipment and then is subjected to casting.
The technical principle of the invention is as follows:
1. the design idea for producing the composite rare earth silicon-iron alloy is from the difference of the application characteristics of the light and heavy rare earth silicon-iron alloys caused by the difference of rare earth elements contained in the light and heavy rare earth silicon-iron alloys. Generally, cerium-rich rare earth silicon iron alloy and related multi-element alloy products have good spheroidizing effect and inoculation characteristic, and lanthanum-rich rare earth silicon iron alloy related multi-element alloy products have unique excellent vermicular characteristics; the heavy rare earth ferrosilicon alloy has the anti-aging characteristic which is not possessed by the light rare earth products, and can effectively make up for the deficiency of the light rare earth products in the performance of resisting spheroidization recession and the like. The three rare earth silicon-iron alloy products have good complementarity in performance, so that the composite rare earth silicon-iron alloy can be more widely applied due to more comprehensive performance characteristics, and more complex application conditions and characteristic requirements are met.
At home and abroad, the rare earth concentrate is directly used as a raw material for producing rare earth silicon-iron alloy products in the early year, so that the full-spectrum rare earth silicon-iron alloy products are obtained, and the products are widely used as main products in European and American countries and have excellent performance. The reason for this is that the complementarity between the light rare earth element and the heavy rare earth element should be an important factor in the case of direct smelting production by using the concentrate product.
2. The invention starts from the characteristics of light and heavy rare earth elements, and the analysis is carried out on the heavy rare earth ferrosilicon which is difficult to smelt and produce by a carbothermic reduction process. The feasibility of realizing the breakthrough of the carbothermic reduction process is found from the point that the melting point of the mixed rare earth metal can be greatly reduced under the condition that the metal Y is compounded with the light rare earth. The characteristics of the composite rare earth-silicon-iron alloy, namely the heavy metal rare earth-silicon-iron alloy, are highlighted on the aspects of product performance design and process parameters (Y)2O3the/TREO is more than 50 percent), ensures that the composite light rare earth has excellent performance of anti-aging and anti-degradation characteristics under most application conditions, and mainly considers the content of the composite light rare earth from two aspects of product performance requirements and cost factors.
Compared with the prior art, the invention has the advantages that:
1. the invention realizes the process for producing the heavy metal rare earth silicon-iron alloy under the carbothermic reduction condition by a new technical means, has the characteristics of obviously improved rare earth yield, simple and convenient process flow, obviously low comprehensive cost and relatively light environmental influence, and has important value on the industrial preparation and wide application of the heavy rare earth silicon-iron alloy product.
2. The invention compounds the application characteristics of the light rare earth silicon iron alloy product with the heavy rare earth silicon iron alloy, has more comprehensive application technical characteristics of excellent spheroidization, inoculation, creeping, aging resistance, and the like, and simultaneously directly reduces the preparation cost of the heavy rare earth silicon iron alloy product because the light rare earth raw material has relatively low price, thereby being beneficial to the industrial application of the product.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The process for preparing the composite rare earth silicon-iron alloy (the lanthanum-cerium composite RESiFe-28Y is prepared by a 12500KVA ore furnace) by using the enriched substances of yttrium carbonate rich, cerium rich slag and lanthanum rich comprises the following steps:
(1) preparation of rare earth agglomerates
Taking the following rare earth materials as rare earth raw materials, and mixing the materials;
a. yttrium carbonate (from enrichment of ionic ore in south of Ganzhou by hydrometallurgy, wherein TREO is 36.12%, and Y is2O3(TREO = 85.78%), total lanthanoid rare earth element/TREO calculated as REO is 0.75%; the average particle size is 6 mm; BaO is less than or equal to 5 percent, CaO<5%，TiO2<1%）；
b. Cerium-rich slag (from waste material produced by hydrometallurgy of Sichuan bastnaesite, wherein TREO is 72.30%, CeO2(TREO = 91.12%) and total yttrium group rare earth element/TREO as REO is 1.89%; the average particle size is 6 mm; BaO is less than or equal to 5 percent, CaO<5%，TiO2<1%）；
c. Lanthanum-rich rare earth concentrate (obtained from rare earth ore from Shandong Weishan by hydrometallurgy, wherein TREO is 86.12%, and La is added2O3(TREO = 82.60%), total yttrium group rare earth element/TREO 2.33% calculated as REO; the average particle size is 5 mm; BaO is less than or equal to 5 percent, CaO<5%，TiO2<1%）。
After mixing according to the designed mixing proportion, the detection shows that Y in the rare earth raw materials2O3/TREO=74.05%， CeO2/TREO=14.01%，La2O3/TREO=8.45%。
Mixing the mixed rare earth raw materials (the quantity is 85 percent of a theoretical value), and crushed silica powder (SiO)2≥98wt%，Al2O3Less than or equal to 0.5wt%, less than or equal to 0.2wt% of CaO, and the average grain size is 3 mm; 30% of theory), blue charcoal powder (fixed carbon)>70% ash content<10% water content<5 percent, the granularity is less than or equal to 5 mm; in an amount of 120% of the theoretical value required for reducing the siliceous element to the simple substance) and water glass (SiO in the case of the silica-based material)2Not less than 25 percent, and the modulus is 3.5 cm and 0.30 cm; the dosage is 4.2 percent of the rare earth raw material), and the rare earth materials are uniformly mixed and extruded to be forcibly formed into rare earth blocks; baking to increase its strength, and using it as rare-earth block mass.
(2) The rest of rare earth raw material (the quantity is 15 percent of the theoretical value) and Silica (SiO)2>98wt%，Al2O3<0.4wt%，CaO<0.2 wt%; the amount of the residue corresponding to 108wt% of the theoretical value minus the amount of silicon contained in the rare earth agglomerate, based on the amount of silicaSiO2Calculated), coke (C is more than or equal to 80wt%, ash content<7 wt%; the amount is 0.91 times of the corresponding residual amount after the amount of solid carbon contained in the rare earth briquette is subtracted from the theoretical value, calculated by the fixed carbon in the carbonaceous reducing agent) and the rare earth briquette are put into a furnace for smelting.
The smelting process conditions in the submerged arc furnace mainly comprise the following steps: the power supply system conditions of the submerged arc furnace are that the diameter of an electrode is 900mm, the potential gradient is 1.00-1.15V/cm, the primary side current is 140-190A, and the secondary side voltage is 120-140V.
Taking out the alloy once in 3 hours on average; and standing the alloy melt for 12 minutes, skimming a small amount of suspended scum on the upper layer of the alloy melt by using a skimming device, and then performing burning casting. The analysis shows that the main component of the suspension scum is CaO & Al2O3·SiO2And (3) double salt.
The heat statistics in two days in the continuous production are taken, and the specific results are as follows:
1. 91.22 tons of rare earth ferrosilicon alloy products are produced in two days in an accumulated way, and the average power consumption level is 8130 KWh/t.
2. The physical and chemical analysis indexes of the product (taking a mixed sample of the product all day, the unit is wt%):
the rare earth ferrosilicon alloy product obtained in the first day comprises the following components (%): RE 29.14; Y/TRE =75.12, La/TRE =8.28, Ce/TRE = 13.72; si 49.65; ba + Ca 1.04; p < 0.01; the balance of Fe;
the rare earth ferrosilicon alloy product obtained in the next day has the following component conditions (%): RE 29.22; Y/TRE =75.18, La/TRE =8.25, Ce/TRE = 13.68; si 49.66; ba + Ca 1.09; p < 0.01; the balance of Fe.
Compared with the chemical composition table in the table 1 of rare earth-silicon-iron alloy GB/T4137-2015, the product meets the chemical composition index of RESiFe-28Y brand, but has the composition characteristics of light and heavy rare earth composition.
The RE recovery rate is calculated to be 95.12% (referring to the total RE amount in the alloy/the total RE amount in the rare earth raw material); compared with the heavy rare earth ferrosilicon alloy prepared by the traditional silicothermic reduction process, the rare earth recovery rate is greatly improved.
The total amount of the suspended slag is 1108.18Kg, and the weight ratio of the suspended slag to the rare earth ferrosilicon alloy product is 1.25%; compared with the smelting waste slag which is inevitably generated by the traditional silicothermic reduction process and is several times of the quantity of the rare earth ferrosilicon alloy, the environmental impact is obviously reduced.
Example 2
The process for preparing rare earth silicon-iron alloy (preparing lanthanum-cerium composite RESiFe-33Y by 12500KVA ore furnace) by mixing yttrium carbonate rich, rare earth polishing powder waste residue and high lanthanum rare earth enrichment comprises the following steps:
(1) preparation of rare earth agglomerates
Taking the following rare earth materials as rare earth raw materials, and mixing the materials;
a. yttrium carbonate (from enrichment of ionic ore in south of Ganzhou by hydrometallurgy, wherein TREO is 36.12%, and Y is2O3(TREO = 85.78%), total lanthanoid rare earth element/TREO calculated as REO is 0.75%; the average particle size is 6 mm; BaO is less than or equal to 5 percent, CaO<5%，TiO2<1%）；
b. The waste residue of rare earth polishing powder (derived from waste material produced after the rare earth polishing powder fails to work, wherein TREO is 84.12%, and CeO2(TREO = 88.11%), total yttrium group rare earth element/TREO 2.46% calculated as REO; the average particle size is 4 mm; BaO is less than or equal to 5 percent, CaO<5%，TiO2<1%）；
c. High lanthanum rare earth concentrate (from high lanthanum concentrate produced by hydrometallurgy of rare earth ore from Shandong Weishan, wherein TREO is 96.23%, La2O3(TREO = 92.64%) and total yttrium group rare earth element/TREO calculated as REO is 2.12%; the average particle size is 5 mm; BaO is less than or equal to 5 percent, CaO<5%，TiO2<1%）。
After mixing according to the designed mixing proportion, the detection shows that Y in the rare earth raw materials2O3/TREO=75.12%， CeO2/TREO=5.34%，La2O3/TREO=17.12%。
Mixing the mixed rare earth raw materials (the quantity is 100 percent of a theoretical value), and crushed silica powder (SiO)2≥98wt%，Al2O3Not more than 0.5wt%, CaO not more than 0.2wt%, and average grain size not more than 3 mm; 35% of theoretical value), semi-coke powder (fixed carbon)>70% ash content<10% water content<5 percent, the granularity is less than or equal to 5 mm; in an amount of siliconReducing the mass element to 120 percent of the theoretical value required by the simple substance), uniformly mixing the mass element and the wet mass element (the dosage of which is 4.2 percent of the feeding amount of the rare earth raw material), extruding and forcibly forming to prepare a rare earth briquette; baking to increase its strength, and using it as rare-earth block mass.
Mixing Silica (SiO)2>98wt%，Al2O3<0.4wt%，CaO<0.2 wt%; the amount of the residual silicon in the rare earth mass is 112wt% of the theoretical value minus the amount of silicon contained in the rare earth mass, based on SiO in the silica2Calculated), coke (C is more than or equal to 80 w%, ash content<7 wt%; the amount is 0.92 times of the corresponding residual amount after the amount of solid carbon contained in the rare earth briquette is subtracted from the theoretical value, calculated by the fixed carbon in the carbonaceous reducing agent) and the rare earth briquette are put into a furnace for smelting.
The smelting process conditions in the submerged arc furnace mainly comprise the following steps: the power supply system conditions of the submerged arc furnace are that the diameter of an electrode is 900mm, the potential gradient is 1.00-1.15V/cm, the primary side current is 150-210A, and the secondary side voltage is 126-148V.
The alloy is divided once in 3 hours and 10 hours on average; and standing the alloy melt for 12 minutes, skimming a small amount of suspended scum on the upper layer of the alloy melt by using a skimming device, and then performing burning casting. The analysis shows that the main component of the suspension scum is CaO & Al2O3·SiO2And (3) double salt.
The heat statistics in two days in the continuous production are taken, and the specific results are as follows:
1. 92.53 tons of rare earth ferrosilicon alloy products are produced in two days in an accumulated way, and the average power consumption level is 8443 KWh/t.
2. The physical and chemical analysis indexes of the product (taking a mixed sample of the product all day, the unit is wt%):
the rare earth ferrosilicon alloy product obtained in the first day comprises the following components (%): RE 32.17; Y/TRE =76.02, La/TRE =16.91, Ce/TRE = 5.27; si 49.15; ba + Ca 1.04; p < 0.01; the balance of Fe;
the rare earth ferrosilicon alloy product obtained in the next day has the following component conditions (%): RE 32.26; Y/TRE =76.17, La/TRE =16.88, Ce/TRE = 5.25; si 49.06; ba + Ca 1.09; p < 0.01; the balance of Fe.
Compared with the chemical composition table in the table 1 of rare earth-silicon-iron alloy GB/T4137-2015, the product meets the chemical composition index of RESiFe-33Y brand, but has the composition characteristics of light and heavy rare earth composition.
The RE recovery rate is calculated to be 94.39% (referring to the total RE amount in the alloy/the total RE amount in the rare earth raw material); compared with the heavy rare earth ferrosilicon alloy prepared by the traditional silicothermic reduction process, the rare earth recovery rate is greatly improved.
The total amount of the suspended slag is 1116.60Kg, and the weight ratio of the suspended slag to the rare earth ferrosilicon alloy product is 1.21%; compared with the smelting waste slag which is inevitably generated by the traditional silicothermic reduction process and is several times of the quantity of the rare earth ferrosilicon alloy, the environmental impact is obviously reduced.
The applicant carries out continuous production on two 12500KWA ore furnaces according to the embodiment 1 and the embodiment 2 respectively, and the continuous production lasts for more than 20 months, and the product quality is stable.
While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that the foregoing is illustrative and not limiting. Without departing from the principle of the invention, several improvements and modifications can be made, and these improvements and modifications are also considered to be within the scope of the invention.
Claims (8)
1. A method for producing light rare earth composite heavy rare earth silicon iron alloy is characterized by comprising the following steps:
(1) taking the following rare earth materials as rare earth raw materials, and mixing the materials;
a. a yttrium-rich rare earth material, wherein: the total content of RE elements calculated by REO is more than 20%, Y2O3The concentration of/TREO is more than or equal to 70 percent, and the total content of lanthanum group rare earth elements/TREO calculated by REO<5%；
b. A cerium-rich rare earth material, wherein: RE element accounting for REO accounting for more than 20 percent, CeO2The ratio of/TREO is more than or equal to 50 percent, and the total content of yttrium group rare earth elements/TREO calculated by REO<10%；
c. A lanthanum-rich rare earth material, wherein: RE element content calculated by REO is more than 20%, La2O3The ratio of/TREO is more than or equal to 50 percent, and the total content of yttrium group rare earth elements/TREO calculated by REO<10%；
When mixing, the mixing proportion of each rare earth material in the rare earth raw materials needs to be fullFoot: with total of rare earth materials, Y2O3/TREO≥50%，（CeO2+La2O3）/TREO≥12%，CeO2/TREO≥4%，La2O3/TREO≥4%；
Mixing the rare earth raw material obtained by mixing the materials with a siliceous raw material and a carbonaceous reducing agent, and pressing to prepare rare earth agglomerates; adding a binding agent into each raw material to carry out batching according to the requirements of a pressing process and the characteristics of the base raw material; the dosage of the basic rare earth raw material calculated by TRE is 80-100 wt% of theoretical value; the amount of the siliceous raw material is 10-60 wt% of a theoretical value, and the siliceous raw material is calculated by total Si elements in the rare earth agglomerate and comprises Si elements brought by the adhesive; the amount of the carbonaceous reducing agent is 100-130 wt% of a theoretical value required by reducing the silicon element in the rare earth agglomerate into a simple substance, and the amount of the carbonaceous reducing agent is calculated by fixed carbon in the rare earth agglomerate;
(2) smelting silica, carbon reducing agent and the rare earth agglomerate in a furnace; if the amount of the rare earth raw material in the rare earth briquette in the step (1) is less than 100wt%, putting the rest of the rare earth raw material, silica, a carbon reducing agent and the rare earth briquette into a furnace for smelting; the amount of silica added is the remaining amount of the silica obtained by subtracting the amount of silicon contained in the rare earth agglomerates from 100 to 120wt% of the theoretical value, and the amount of silica added is SiO in the silica2Counting; the carbonaceous reducing agent is 0.80-0.96 times of the corresponding residual amount of the rare earth agglomerate after the amount of solid carbon contained in the rare earth agglomerate is deducted from the theoretical value, and the carbonaceous reducing agent is calculated by the solid carbon in the carbonaceous reducing agent; and discharging and casting to obtain the rare earth silicon-iron alloy.
2. The method of claim 1, wherein the rare earth materials are selected from the group consisting of concentrates from hydrometallurgy of rare earth, scrap from production and use of functional rare earth materials, rare earth concentrates, single rare earth oxides, mixed rare earth oxides, single rare earth carbonates, mixed rare earth carbonates, single rare earth oxalates, mixed rare earth oxalates, single rare earth hydroxides, mixed rare earth hydroxides, and slag from smelting rare earth.
3. The method for producing light rare earth composite heavy rare earth silicon-iron alloy according to claim 1, wherein the yttrium-rich material is one or a mixture of more of yttrium-based heavy rare earth mixed rare earth mineral products, high yttrium rare earth concentrates produced by rare earth separation enterprises, yttrium oxide, yttrium carbonate, yttrium oxalate, yttrium hydroxide and rare earth fluorescent powder waste; the cerium-rich material is one or a mixture of more of bastnaesite products, mixed rare earth mineral products, cerium-rich rare earth concentrates produced by rare earth separation enterprises, cerium oxide, lanthanum cerium oxide, cerium carbonate, cerium oxalate, cerium hydroxide, rare earth polishing powder waste and rare earth fluorescent powder waste; the lanthanum-rich material is one or a mixture of more of bastnaesite products, rare earth mixed mineral products, high-lanthanum rare earth enrichment produced by rare earth separation enterprises, lanthanum oxide, lanthanum cerium oxide, lanthanum carbonate, lanthanum oxalate, lanthanum hydroxide, rare earth polishing powder waste and rare earth catalyst waste.
4. The method for producing the light rare earth composite heavy rare earth silicon-iron alloy according to claim 1, wherein the siliceous raw material used in the step (1) is one or a mixture of more of silica, micro silicon powder, silicon granules, quartz sand and silicon ferroalloy smelting slag.
5. The method for producing light rare earth composite heavy rare earth ferrosilicon alloy according to claim 1, wherein the carbonaceous reducing agent is one or a mixture of more of coke, carbon powder, semi-coke, charcoal, gas coal coke, bituminous coal, petroleum coke and refined coal powder; the carbonaceous reducing agent in the step (1) requires that the fixed C is more than or equal to 70wt percent and the ash content is less than 10wt percent; the carbonaceous reducing agent in the step (2) requires that the fixed C is more than or equal to 80wt percent and the ash content is less than 7wt percent.
6. The method for producing the light rare earth composite heavy rare earth ferrosilicon alloy according to claim 1, wherein the binder is one or a mixture of water glass, silica fume, bentonite, paper pulp, syrup waste liquid and plant starch.
7. The method for producing a light rare earth complex heavy rare earth-Si-Fe alloy as claimed in claim 1, wherein the silica of the step (2) contains SiO2>98wt%，Al2O3<0.4wt%，CaO<0.2wt%。
8. The method for producing the light rare earth composite heavy rare earth silicon-iron alloy according to claim 1, wherein the casting is carried out after the discharging in the step (2) and the standing for more than 10 minutes; if the upper layer of the discharged alloy melt appears suspension scum, the alloy melt is skimmed by auxiliary equipment and then is subjected to casting.
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