WO2021197258A1 - Liant pour boulettes oxydées formé à partir de charbon de rang bas, procédé de préparation de celui-ci et ses applications - Google Patents

Liant pour boulettes oxydées formé à partir de charbon de rang bas, procédé de préparation de celui-ci et ses applications Download PDF

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WO2021197258A1
WO2021197258A1 PCT/CN2021/083574 CN2021083574W WO2021197258A1 WO 2021197258 A1 WO2021197258 A1 WO 2021197258A1 CN 2021083574 W CN2021083574 W CN 2021083574W WO 2021197258 A1 WO2021197258 A1 WO 2021197258A1
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low
oxidized
rank coal
iron ore
pellets
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PCT/CN2021/083574
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English (en)
Chinese (zh)
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李光辉
罗骏
姜涛
张鑫
饶明军
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中南大学
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Publication of WO2021197258A1 publication Critical patent/WO2021197258A1/fr

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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

Definitions

  • the invention relates to an oxidized pellet binder made from low-rank coal, a preparation method and application thereof, and belongs to the technical field of iron and steel metallurgy.
  • the main iron-containing raw materials for steel production include sinter, pellets and lump ore.
  • the lump ore resources that meet the requirements of iron smelting production are almost exhausted, and most of the iron ore fines or iron concentrates need to be agglomerated (sintered or pelletized) to meet the production requirements.
  • steel production is mainly based on the long process of blast furnace-converter, which uses sinter, pellets and coke as raw materials to obtain molten iron after blast furnace ironmaking, and then uses blast furnace molten iron as raw material to enter the converter steelmaking.
  • the long-process production of iron and steel usually uses high-basicity sinter with acidic oxide pellets as the charge. Compared with sinter, pellets have the advantages of high iron grade, good strength, uniform particle size, and good reducibility.
  • the production energy consumption of pelletizing process is low.
  • the energy consumption of pelletizing process of advanced enterprises is only 1/of the energy consumption of sintering process. About 3; less pollutant emissions, less harmful components in the exhaust gas, and low cost of subsequent end treatment.
  • the pollutant emissions of the pelletizing process are much lower than that of the sintering process.
  • the emissions of dust, sulfur dioxide, and nitrogen oxides are respectively 1/of the sintering process. 7, 1/3, 1/5.
  • the binder In the production process of iron concentrate pellets, the binder has an important influence on the pellet preparation process and the quality of the pellets.
  • the production of pellets in my country has problems such as large amount of binder and low iron grade.
  • Iron and steel plants in my country generally use bentonite as a binder to prepare oxidizing pellets.
  • the quality of bentonite in my country is poor, and the iron ore concentrate used for pellet production has a relatively high coarse-grained content.
  • a higher proportion of bentonite must be added to meet the requirements of industrial production. Because the addition of bentonite brings in a large amount of impurities such as aluminosilicate, it seriously reduces the iron grade of the pellets, and significantly increases the energy consumption and production costs of ironmaking.
  • the purpose of the invention is to provide a method for preparing an oxidized pellet binder made from low-rank coal, which uses low-rank coal as a raw material to obtain oxidized pellets through simple oxidative fermentation, and then simultaneous extraction and slurrying of humic acid.
  • Group binder cheap raw materials, wide sources, simple process, low binder content, good bonding performance, strong applicability, not only can significantly improve the spheroidizing performance of difficult-to-form nodular iron ore resources, but also for the iron of the finished ball Taste does not affect.
  • the present invention adopts the following technical solutions.
  • a method for producing oxidized pellet binder from low-rank coal The low-rank coal is crushed and oxidized and fermented, then solid caustic alkali and water are added to prepare a slurry, and the oxidized pellet binder is obtained by heating and stirring.
  • the humic acid content in the low-rank coal is not less than 25%; more preferably, the humic acid content in the low-rank coal is not less than 30%; after crushing, the particle size is less than 10 mm.
  • the temperature of the oxidative fermentation is 80 to 200° C., and the time is 2 to 10 hours, and after the oxidative fermentation is completed, low-rank coal is further ground to a particle size of less than 0.1 mm and a particle content of more than 70%.
  • the added amount of the solid caustic soda occupies 20%-30% of the mass of the low-rank coal; the added amount of water is 2-5 times the mass of the low-rank coal.
  • the temperature of the heating and stirring is 50 ⁇ 100°C, and the time is 1 ⁇ 5h.
  • the invention also provides the oxidized pellet binder prepared by the above preparation method, which has a high content of organic components, good bonding performance and strong applicability.
  • the present invention also provides the application of the above-mentioned oxidized pellet binder, which is added to iron ore powder for pelletizing to obtain green iron ore pellets for oxidized pellets.
  • the oxidized pellet binder of the present invention can be used for hard-to-ballite and inferior iron ore resources with poor ball-forming properties, such as vanadium-titanium magnetite, maghemite, etc., and can enhance the surface hydrophilicity of the hard-to-ballite inferior iron ore It is beneficial to the iron ore particles to form balls.
  • poor ball-forming properties such as vanadium-titanium magnetite, maghemite, etc.
  • the iron ore powder is subjected to wet grinding or high-pressure roller milling before pelletizing, which can further improve the green pellet strength.
  • the additive amount of the oxidized pellet binder accounts for 1% to 4% of the mass of the iron ore powder, and the amount of humic acid in the oxidized pellet binder accounts for 0.2% to 0.5% of the mass of the iron ore powder.
  • the prepared green iron ore pellets are oxidized and preheated and roasted at 900-1050°C for 4-12 minutes and then used for the production of oxidized pellets or direct reduced iron.
  • Humic acid contains carboxyl, hydroxyl and benzene ring structures, and has a binder molecular structure.
  • Low-rank coal is the main source of extraction of humic acid, but the content of humic acid varies greatly.
  • Existing extraction methods generally include extraction, evaporation, drying, grinding and other processes, which have high energy consumption, long process, and low extraction rate.
  • the prepared humic acid product is in a solid state. When used in the production of oxidized pellets, it is difficult to disperse and its binding effect is limited.
  • low-rank coal undergoes pre-oxidation and fermentation to increase the content of humic acid by 1.2 to 2 times, and then humic acid is extracted simultaneously and the slurry is adjusted to obtain the oxidized pellet binder, which is directly mixed with iron ore powder to prepare green pellets.
  • the dissolved humic acid forms a colloidal solution, which can evenly cover the surface of iron ore particles, significantly improve the surface hydrophilicity of iron ore particles, and increase the surface tension of iron ore; and through the long-chain structure of the binder on the surface of iron ore particles
  • the bridge function connects the iron ore particles, which is beneficial to the iron ore particles to form balls and improve the green ball strength.
  • the adhesive prepared by the invention has good bonding performance, can improve the spheroidizing performance of iron ore, has strong product adaptability, can be suitable for inferior iron ore pellets that are difficult to pelletize, and significantly improves the green spheroidizing strength.
  • Bentonite is used as the binder. Most of the bentonite is an inorganic component. After the green ball is roasted, the bentonite will remain in the finished ball, reducing the iron grade in the finished ball. According to blast furnace production practice, for every 1% increase in the iron grade of the finished ball into the furnace, the blast furnace coke ratio will decrease by 2%, the ironmaking output will increase by 3%, and the blast furnace slag will be reduced by 20kg/t. Therefore, the use of bentonite binder will greatly improve ironmaking Production costs reduce production efficiency.
  • the binder prepared by the present invention is an organic binder with a high content of organic components.
  • the organic components will all burn and volatilize during the preheating and roasting process of the oxidized pellets, which will not affect the iron grade of the finished pellets. Compared with bentonite pellets, the iron grade is improved, and the corresponding ironmaking output is significantly increased and the production cost is significantly reduced.
  • low-rank coal is oxidized and fermented to significantly increase the humic acid content in the coal, and then the humic acid is extracted simultaneously and the slurry is adjusted to obtain the oxidized pellet binder, which is directly mixed with iron ore powder to prepare green pellets.
  • the effective components of humic acid are high, and there is no need to use humic acid in conjunction with other binders; there is no need to prepare the extracted humic acid components into powder products, and the process steps such as slurry drying, crushing and grinding are omitted, and the process is short, Low energy consumption and high process efficiency.
  • low-rank lignite is selected as the raw material, and its humic acid content is 32 wt%.
  • the lignite is crushed to below 10mm, fully oxidized and fermented at 120°C for 6h, and further ground to a particle size of less than 0.1mm.
  • the particle mass accounts for 85% of the total mass of pulverized coal; solid caustic which accounts for 25% of its mass is added to the pulverized coal.
  • Alkali and 400% water are used to prepare coal slurry.
  • the coal slurry is heated to a temperature of 95°C and continuously stirred for 3 hours to obtain an oxidized pellet binder.
  • vanadium-titanium magnetite which is difficult to pelletize, is selected as the iron ore raw material.
  • the main components of vanadium-titanium magnetite are shown in Table 1, and pellets are made by adding the prepared binder.
  • vanadium-titanium magnetite as raw material for pelletizing, the raw material moisture is 5.0wt%, and 3.0wt% of the binder is added to the vanadium-titanium magnetite powder to keep the moisture at 8.0wt% during pelletizing. Mix thoroughly and evenly, then sieve the mixture to less than 1mm, and use a disc pelletizer to pelletize the pellets. The pelletizing time is 10 ⁇ 12min and the pellet size is 10 ⁇ 12mm.
  • the obtained iron ore green balls were tested, the green balls falling strength was 3.5 times/(0.5m), and the compressive strength was 13.7N/piece.
  • Pellets are pelletized from vanadium-titanium magnetite with a raw material moisture of 5.0wt%, and 3.0wt% of its mass is added to the vanadium-titanium magnetite powder to keep the moisture at 8.0wt% during pelletizing.
  • the obtained iron ore green balls were tested, the green balls falling strength was 2.3 times/(0.5m), and the compressive strength was 11.7N/piece.
  • Pellets are pelletized from vanadium-titanium magnetite with a raw material moisture of 5.0wt%, and 3.0wt% of its mass is added to the vanadium-titanium magnetite powder to keep the moisture at 8.0wt% during pelletizing.
  • the pelletizing time is 10 ⁇ 12min, and the pellet size 10 ⁇ 12mm.
  • the obtained iron ore green balls were tested, the green balls falling strength was 3.3 times/(0.5m), and the compressive strength was 13.2N/piece.
  • Example 1 Comparing the green ball index data in Example 1 and Comparative Example 1-2, in Comparative Example 1-2, in order to meet the minimum requirement of iron ore green ball falling strength higher than 3.0 times/(0.5m), the bentonite binder is the lowest The dosage needs to reach more than 1.5%.
  • Example 1 when the present invention adds 3.0wt% of binder prepared from low-rank lignite (that is, the humic acid composition distribution is 0.45wt%), the green ball drop strength and compressive strength are both higher than that of bentonite Green ball strength when the amount of binder is 1.5wt%. It shows that the binder prepared by the present invention has good bonding performance and a small amount, and can improve the ball-forming performance of the hard-to-form ductile iron ore.
  • the vanadium-titanium magnetite is pretreated by high-pressure roller mill for 3 times and then pelletized.
  • the iron ore powder is mixed with 1.0wt% water and 2.0wt% binder slurry to make the water when pelletizing. Keep it at 8.0wt%, mix thoroughly, and then sieve the material to below 1mm. Use a disc pelletizer to pelletize the pellets.
  • the pelletizing time is 10-12min and the pellet size is 10-12mm.
  • the obtained iron ore green balls were tested, the green balls falling strength was 8.6 times/(0.5m), and the compressive strength was 21.3N/piece.
  • the vanadium-titanium magnetite is pelletized after being pretreated by a high-pressure roller mill for 3 times, and 3.0wt% of its mass is added to the iron ore powder to keep the moisture at 8.0wt% during pelletization, and then added
  • the bentonite binder which accounts for 1.5wt% of the iron ore powder mass, is fully mixed and evenly mixed, and then the material is sieved to below 1mm, and pelletized by a disc pelletizer.
  • the pelletizing time is 10 ⁇ 12min, and the pellet size is 10 ⁇ 12mm.
  • the obtained iron ore green balls were tested, the green balls falling strength was 5.7 times/(0.5m), and the compressive strength was 18.4N/piece.
  • the iron grade of the finished oxidized pellets produced by the binder prepared by the present invention is 54.65%, which is higher than the iron grade of the finished oxidized pellets produced by the bentonite binder 1%.
  • the iron grade of the finished ball into the furnace is increased by 1%, the blast furnace coke ratio is reduced by 2%, the iron production is increased by 3%, and the blast furnace slag volume is reduced by 20 kg/t. Therefore, the binder prepared by the invention can greatly reduce the refining rate. Iron production costs.
  • humic acid content is 32wt%. Grind it to a particle size of less than 0.1mm. The particle mass accounts for 85% of the total mass of pulverized coal; add 25% of the mass of solid caustic soda and 400% of water to the pulverized coal to prepare a coal slurry, and heat the coal slurry to a temperature of 95 °C and continue to stir for 3h to obtain the oxidized pellet binder.
  • the vanadium-titanium magnetite is pretreated by high-pressure roller mill for 3 times and then pelletized. The iron ore powder is mixed with 1.0wt% water and 2.0wt% binder slurry to make the water when pelletizing.
  • the obtained iron ore green balls were tested, the green balls falling strength was 2.1 times/(0.5m), the compressive strength was 8.3N/piece, and the burst temperature was 510°C.
  • an oxidized pellet binder was obtained.
  • the vanadium-titanium magnetite is pelletized after being pretreated by a high-pressure roller mill for 3 times, and a binder slurry of 4.0wt% of its mass is added to the iron ore powder to keep the water content at 8.0wt% during pelletizing. Mix evenly, then sieve the material to below 1mm, and use a disc pelletizer to pelletize the pellets.
  • the pelletizing time is 10 ⁇ 12min and the pellet size is 10 ⁇ 12mm.
  • the obtained iron ore green balls were tested and found that the falling strength of the green balls was 2.8 times/(0.5m), the compressive strength was 9.6N/piece, and the burst temperature was 460°C.
  • Example 3 Low-rank lignite was fully oxidized and fermented at a temperature of 120°C for 6 hours, and then ground to a particle size of less than 0.1 mm. The particle mass accounted for 85% of the total mass of pulverized coal; solid caustic alkali accounting for 20% of its mass was added to the pulverized coal Prepare a coal slurry with 400% water. The coal slurry is heated to a temperature of 80°C and continuously stirred for 3 hours to obtain an oxidized pellet binder. The vanadium-titanium magnetite is pretreated by high-pressure roller mill for 3 times and then pelletized.
  • the iron ore powder is mixed with 1.0wt% of its mass and 2.0wt% of binder slurry to make the water during pelletizing. Keep it at 8.0wt%, mix thoroughly, and then sieve the material to below 1mm. Use a disc pelletizer to pelletize the pellets. The pelletizing time is 10-12min and the pellet size is 10-12mm.
  • the obtained iron ore green balls were tested and found that the falling strength of the green balls was 7.3 times/(0.5m), the compressive strength was 20.6N/piece, and the burst temperature was 550°C.
  • Example 3 Using the fermented coal powder obtained in Example 3 as raw materials, adding 30% of the mass of solid caustic soda and 400% of water to prepare a coal slurry, the coal slurry is heated to a temperature of 80°C and continuously stirred for 3 hours to obtain oxidized pellets Group binder.
  • the vanadium-titanium magnetite is pretreated by high-pressure roller mill for 3 times and then pelletized.
  • the iron ore powder is mixed with 1.0wt% water and 2.0wt% binder slurry to make the water when pelletizing. Keep it at 8.0wt%, mix thoroughly, and then sieve the material to below 1mm. Use a disc pelletizer to pelletize the pellets.
  • the pelletizing time is 10-12min and the pellet size is 10-12mm.
  • the obtained iron ore green balls were tested and found that the falling strength of the green balls was 9.6 times/(0.5m), the compressive strength was 22.1N/piece, and the burst temperature was 530°C.
  • Example 3 Using the fermented coal powder obtained in Example 3 as raw materials, adding 15% of its mass of solid caustic soda and 400% of water to prepare a coal slurry, heat the coal slurry to a temperature of 80°C and continue stirring for 3 hours to obtain oxidized pellets Group binder.
  • the vanadium-titanium magnetite is pretreated by high-pressure roller mill for 3 times and then pelletized.
  • the iron ore powder is mixed with 1.0wt% water and 2.0wt% binder slurry to make the water when pelletizing. Keep it at 8.0wt%, mix thoroughly, and then sieve the material to below 1mm. Use a disc pelletizer to pelletize the pellets.
  • the pelletizing time is 10-12min and the pellet size is 10-12mm.
  • the obtained iron ore green balls were tested, and the green balls had a falling strength of 2.8 times/(0.5m), a compressive strength of 12.8N/piece, and a burst temperature of 480°C.
  • Example 3 Using the fermented coal powder obtained in Example 3 as raw materials, adding 35% of the mass of solid caustic soda and 400% water to prepare a coal slurry.
  • the coal slurry is heated to a temperature of 80°C and continuously stirred for 3 hours to obtain oxidized pellets.
  • Group binder The vanadium-titanium magnetite is pretreated by high-pressure roller mill for 3 times and then pelletized.
  • the iron ore powder is mixed with 1.0wt% water and 2.0wt% binder slurry to make the water when pelletizing. Keep it at 8.0wt%, mix thoroughly, and then sieve the material to below 1mm. Use a disc pelletizer to pelletize the pellets.
  • the pelletizing time is 10-12min and the pellet size is 10-12mm.
  • the obtained iron ore green balls were tested, and the green balls had a falling strength of 3.2 times/(0.5m), a compressive strength of 13.2N/piece, and a burst temperature of 390°C.
  • Example 3-4 Comparing the green ball index data in Example 3-4 and Comparative Example 6-7, when the dosage of solid caustic alkali is outside the preferred range, the prepared binder slurry cannot satisfy the iron ore green ball falling strength at the same time.
  • the minimum requirement is higher than 3.0 times/(0.5m) and burst temperature higher than 450°C.
  • a coal slurry is prepared by adding 20% of the mass of solid caustic soda and 200% of the coal powder to the coal powder.
  • the coal slurry is heated to a temperature of 60°C and continuously stirred for 5 hours to obtain an oxidized pellet binder slurry.
  • the binder is used to pelletize the magnetite concentrate.
  • the binder content is 1%, and the pellets are pelletized after high-pressure roller milling.
  • the pelletizing time is 10-12 minutes, and the green pellet size is 14-16mm.
  • the green ball has a drop strength of 8.1 times/(0.5m), a compressive strength of 27.8N, and a burst temperature of 570°C, which all meet the requirements of pellet production.
  • the oxidized pellet binder slurry prepared in Example 5 Take the oxidized pellet binder slurry prepared in Example 5 and use it to pelletize hematite concentrate.
  • the binder content is 1.5%.
  • the pellets are pelletized after high-pressure roller milling.
  • the pelletizing time is 10-12 minutes.
  • the ball size is 14 ⁇ 16mm.
  • the drop strength of the green ball is 9.2 times/(0.5m), the compressive strength is 25.2N, and the burst temperature is 520°C, which all meet the requirements of pellet production.
  • the prepared qualified green balls are oxidized and preheated and roasted at a preheating temperature of 1000°C, a preheating time of 4 minutes, and a compressive strength of 1050N/piece.
  • the oxidized preheated pellets are used for direct reduced iron production.
  • the oxidized pellet binder slurry prepared in Example 5 was used to pelletize ordinary iron fine powder, the binder content was 1.0%, the pelletizing time was 10-12 minutes, and the green pellet size was 14-16mm.
  • the green ball has a drop strength of 8.7 times/(0.5m), a compressive strength of 23.2N, and a burst temperature of 580°C, which all meet the requirements of pellet production.
  • the prepared qualified green pellets are oxidized and preheated and roasted at a preheating temperature of 900°C, a preheating time of 5 minutes, and a compressive strength of 970N/piece.
  • the oxidized preheated pellets are used for the production of direct reduced iron.

Abstract

L'invention concerne un liant pour boulettes oxydées formé à partir de charbon de rang bas, un procédé de préparation de celui-ci et ses applications. Le charbon de rang bas est concassé puis oxydé et fermenté, puis de la soude caustique solide et de l'eau sont ajoutées pour ajuster la bouillie, laquelle est chauffée et agitée pour produire le liant pour boulettes oxydées. La quantité de soude caustique solide ajoutée représente 20 % à 30 % de la masse du charbon de rang bas; la quantité d'eau ajoutée est de 2 à 5 fois la masse du charbon de rang bas. Le liant pour boulettes oxydées est ajouté dans de la poudre de minerai de fer pourla mise en boulettes afin d'obtenir des boulettes brutes de minerai de fer destinées à être utilisées en tant que boulettes oxydées. La présente invention utilise du charbon de rang bas en tant que matière première et produit le liant pour boulettes oxydées au moyen de simples opérations d'oxydation et de fermentation suivies de la réalisation simultanée d'extraction d'acide humique et d'ajustement de la bouillie. La matière première est bon marché et aisément disponible et est de mise en œuvre simple. Le liant permet une utilisation réduite, offre une grande performance de liaison et a une grande applicabilité. Non seulement il améliore les performances de mise en boulettes d'une ressource de minerai de fer difficile à mettre en boulettes, mais encore il n'a pas d'incidence sur la qualité de produit de fer des boulettes obtenues.
PCT/CN2021/083574 2020-03-30 2021-03-29 Liant pour boulettes oxydées formé à partir de charbon de rang bas, procédé de préparation de celui-ci et ses applications WO2021197258A1 (fr)

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CN202010235639.3A CN111254278B (zh) 2020-03-30 2020-03-30 一种由低阶煤制造的氧化球团粘结剂及其制备方法和应用

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CN114854984A (zh) * 2022-04-13 2022-08-05 昆明理工大学 一种生产氧化球团的复合粘结剂的制备方法及其应用方法
CN114959151A (zh) * 2022-06-16 2022-08-30 浙江工贸职业技术学院 钒钛矿与含铁粉尘耦合还原工艺
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CN114854984A (zh) * 2022-04-13 2022-08-05 昆明理工大学 一种生产氧化球团的复合粘结剂的制备方法及其应用方法
CN114854984B (zh) * 2022-04-13 2023-08-29 昆明理工大学 一种生产氧化球团的复合粘结剂的制备方法及其应用方法
CN114774678A (zh) * 2022-05-31 2022-07-22 本钢板材股份有限公司 一种高硅矿粉生产熔剂性球团的方法
CN115198088A (zh) * 2022-06-07 2022-10-18 首钢京唐钢铁联合有限责任公司 一种配加高炉环境除尘灰生产的球团矿及其制备方法
CN115198088B (zh) * 2022-06-07 2023-11-14 首钢京唐钢铁联合有限责任公司 一种配加高炉环境除尘灰生产的球团矿及其制备方法
CN114959151A (zh) * 2022-06-16 2022-08-30 浙江工贸职业技术学院 钒钛矿与含铁粉尘耦合还原工艺
CN114959151B (zh) * 2022-06-16 2023-06-23 浙江工贸职业技术学院 钒钛矿与含铁粉尘耦合还原工艺
CN115323169A (zh) * 2022-08-02 2022-11-11 首钢京唐钢铁联合有限责任公司 一种球团矿及其制备方法
CN115323169B (zh) * 2022-08-02 2023-11-14 首钢京唐钢铁联合有限责任公司 一种球团矿及其制备方法
CN116287680A (zh) * 2023-04-23 2023-06-23 中天钢铁集团(南通)有限公司 一种镜铁矿球团生产的方法

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