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WO2022021466A1 - Procédé de traitement d'un minerai à surface de minerai latérite-nickel à l'aide d'un procédé de réduction en trois étapes - Google Patents

Procédé de traitement d'un minerai à surface de minerai latérite-nickel à l'aide d'un procédé de réduction en trois étapes Download PDF

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Publication number
WO2022021466A1
WO2022021466A1 PCT/CN2020/107175 CN2020107175W WO2022021466A1 WO 2022021466 A1 WO2022021466 A1 WO 2022021466A1 CN 2020107175 W CN2020107175 W CN 2020107175W WO 2022021466 A1 WO2022021466 A1 WO 2022021466A1
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ore
reduction
surface layer
laterite
charge
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Chinese (zh)
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王平
赵永璞
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/14—Multi-stage processes processes carried out in different vessels or furnaces
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/32—Aluminous cements
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0006—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/006—Starting from ores containing non ferrous metallic oxides
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0066—Preliminary conditioning of the solid carbonaceous reductant
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/02—Making spongy iron or liquid steel, by direct processes in shaft furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/04—Making spongy iron or liquid steel, by direct processes in retorts
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/08—Making spongy iron or liquid steel, by direct processes in rotary furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/12—Making spongy iron or liquid steel, by direct processes in electric furnaces

Definitions

  • the invention belongs to the technical field of iron and steel smelting, and in particular relates to a method for treating surface ore of laterite nickel ore by adopting a three-stage reduction method.
  • the prospective reserves of laterite nickel ore on the earth are more than 500 billion tons, and the surface ore resources of laterite nickel ore account for about one-third of the laterite nickel ore resources.
  • the surface ore of laterite nickel ore has the following advantages: 1 It has high iron content. If the crystal water in the surface ore of laterite nickel ore is removed, the iron content ratio can be as high as 50 or more; 2 It contains nickel-chromium alloy elements necessary for the production of high-quality alloy steel.
  • the total amount of iron, chromium and nickel in the raw ore from which crystal water is removed by drying can be as high as more than 60%; 3 the content of lead, tin, arsenic, antimony and bismuth is low (below 200ppm, even below 100ppm), which meets the requirements of high-quality steel and high-end steel Production must be required; 4 The cost of mining is very low, and surface excavators are generally used for operation.
  • the content of Fe 2 O 3 in the surface ore of laterite nickel ore is relatively high.
  • the high iron content will cause the resistance of the molten ore to decrease once reduction occurs, the electrode arc starts, and the resistance of the submerged arc furnace is blocked. Hot smelting; and high oxygen content will cause violent foaming and unstable furnace conditions when the reaction temperature is reached, and normal smelting cannot be carried out.
  • the iron product produced by the surface layer of laterite nickel ore by solid-state reduction contains more than 20% Al 2 O 3 gangue, and if a flux is added, the slag content can reach more than 40%.
  • the direct reduction method is used, the subsequent process cannot bear the amount of slag brought by the spongy direct reduced iron entering the furnace.
  • the extremely fine Al 2 O 3 particles in the ore cannot be aggregated and cannot be removed by magnetic separation, which also leads to The high slag product produced therefrom, namely direct reduced iron, is of little use.
  • a small amount of low-nickel surface ore with low sulfur and phosphorus content and high iron content is added to the blast furnace in a limited amount (5%) by a few steel mills to replace ordinary iron ore. Causes waste of alloying elements.
  • the purpose of the present invention is to provide a three-stage reduction method for treating surface ore of laterite nickel ore, including three solid-state reduction sections without flux, magmatic reduction sections and melting reduction and refining sections step.
  • the method realizes the high-value recovery of alloying elements in the surface layer ore of laterite nickel ore, which is difficult to handle by the existing technology, and the resource utilization of waste Al 2 O 3 at low cost, and has extremely high performance. Economic Value.
  • a method for treating surface layer ore of laterite nickel ore by a three-stage reduction method comprising the following steps:
  • (2) Magmatization reduction section heating the charge entering the magma reaction kettle, remelting the charge, discharging gas, controlling and preventing Al 2 O 3 from precipitation and blocking the furnace mouth, and feeding the charge into the electric arc furnace in a magmatic state;
  • reaction temperature of the flux-free solid-state reduction section in the above step (1) is 1100-1200°C; when the process ends, the ratio of iron to total iron in the carbon-reduced raw material is more than 0.7.
  • step (1) carbon reduction is carried out to the surface layer ore of laterite nickel ore by a rotary kiln or a shaft furnace; the rotary kiln has a kiln head section/discharge section that is debonded by resistance heating, and its reduction temperature can reach 1200 °C, high calorific value bituminous coal is used for injection coal.
  • step ( 1 ) according to laterite nickel ore surface layer ore, remove 30-35% supersaturated carbon of the dry ore weight after surface water and crystal water ;
  • the iron ratio is 0.42, and the total iron content is calculated at 55-60%, preferably 60%.
  • the reduced coal described in the above step (1) adopts anthracite with high fixed carbon and low ash content; laterite nickel ore surface layer ore and reduced coal are pulverized to a size of less than 10 mm; the pelletized Size is 30-50mm.
  • the raw material after carbon reduction is in an incompletely reduced sponge state, and the specific gravity is 2-3.
  • reaction temperature of the magmatic reduction section in the above step (2) is 1200-1300°C; at the end of the reduction process, the ratio of iron to total iron in the charge is above 0.9.
  • the specific gravity of the charge is increased by the magma reaction, so that the specific gravity is greater than 6.
  • step (2) according to the specific gravity of the returned material pile of 2-3t/m 3 , the thickness of the material layer is controlled within 1 meter, and the magma is sent into the electric arc furnace, and the speed of the auger to push the material is equal to the amount of the magma material.
  • Speed constant velocity push; magmaization time is half the processing time of electric arc furnace smelting.
  • the slag tapping temperature in the melting reduction and refining section is greater than 1550°C, and the tapping/hot metal temperature is greater than 1500°C; when the process ends, the iron in the charge is reduced to more than 0.97.
  • the calcium/silicon oxide is preferably metallurgical lime for slagging, so as to achieve melting, desulfurization and dephosphorization;
  • the slag adjusting agent is preferably CaF 2 .
  • the basic alloy steel composition described in the above-mentioned step (3) is as follows, wherein, the content of sulfur and phosphorus is strictly controlled according to the process requirements:
  • the basic alloy steel described in the above step (3) is not a steel with certain properties, but a raw material for users to produce high-end nickel-chromium alloy steel and stainless steel; the basic alloy steel contains extremely valuable nickel Chromium and low-melting elements that are harmful to the quality of high-end steel include lead, tin, arsenic, antimony, and bismuth. Raw material requirements for steel, aircraft landing gear, high-end bearings, and high-end military steel.
  • the low-nickel iron in the above step (3) can be used as the raw material of low-end stainless steel or nickel-chromium alloy steel.
  • aluminate cement clinker described in the above step (3) complies with the national aluminate cement standard GB/T 201-2015.
  • Another aspect of the present invention is to provide a magma reaction kettle device applied to the above method, which comprises a heating source, a reaction kettle cavity, a push auger and a discharge port; the push auger is used for step ( 1) The charge after the carbon reduction is sent into the reaction kettle cavity for magmaization; the reaction kettle cavity is inclined from the push auger end to the discharge port end; the discharge port is the same as that in step (3) The electric arc furnace is connected, and the magmaized charge enters the electric arc furnace through the discharge port.
  • the heat supply heat source includes a coal-oxygen lance, an AC and DC heat source and other heat sources that meet the requirements.
  • magma reaction kettle device has a large reduction reaction surface area, which is conducive to gas release; has a certain inclination angle, which is conducive to the feeding of magma-state reducing materials into the electric arc furnace; has a large energy supply requirement, Adapt to the requirements of the final reduction speed of the electric arc furnace.
  • the reduction temperature rise range of the magmatization reactor device is 1000-1300°C.
  • the invention can also be used for reducing non-magnetic iron ore or magnetic iron ore resources with iron content greater than 50% for iron production.
  • the surface ore composition of laterite-nickel ore more than 97% of the surface ore of laterite-nickel ore is composed of iron oxides and Al 2 O 3 .
  • the phase diagram of Al 2 O 3 -Fe 2 O 3 shows that the lowest liquidus temperature (about 1600°C) of the two is on the iron oxide side, so the solid reduction method without flux is used in the rotary kiln or shaft furnace, and the charge is not easy to melt. , to avoid the occurrence of kiln wall or furnace wall adhesion problem, and high temperature reduction can be carried out.
  • the kiln head/discharge section of the rotary kiln is equipped with a resistance heating debonding device. If the discharge port or the kiln head is caking, the caking block can be quickly removed to ensure large-scale continuous production.
  • the sponge-like charge is first remelted into a magmatic state at high temperature through the magmaization reactor, the reduction reaction is completed, the specific gravity of the charge is increased, and the gas is discharged, so as to avoid the occurrence of high oxygen content in the surface ore of laterite nickel ore in the electric furnace.
  • Safety accidents such as violent foaming and unstable furnace conditions.
  • this stage process is the pivot and key control link of the entire process flow, and has the following technical advantages and functions: 1 Further reduction of the raw materials that are not completely reduced in the solid-state reduction section to avoid excessive oxides in the furnace due to under-reduction, thereby This leads to a violent carbon-oxygen reaction in the electric arc furnace of the subsequent melting reduction and refining section, resulting in a high-boiling production safety accident; 2Remove the gas in the reduced raw material, de-sponge, increase the proportion of the reduced raw material, and avoid the sponge in the reduced iron.
  • This stage is the product generation stage.
  • the key is to control the carbon, sulfur and phosphorus of molten iron, to separate iron and Al 2 O 3 in the surface ore of laterite nickel ore, and to carry out reduction refining according to the requirements of the final alloy steel product for the basic alloy steel. It produces high-quality basic alloy steel and produces qualified calcium aluminate cement clinker.
  • the control of carbon, phosphorus and sulfur belongs to the conventional process method of electric arc furnace, and there is no technical difficulty.
  • the arc temperature of the electric arc furnace is as high as 6000 °C, which can quickly melt the magmaized charge. During most of the time when the charge is melted, the high temperature heat source is surrounded by the charge.
  • the oxygen in the unreduced iron oxides in the magma of the reduced ore reacts with the added carbon and interacts with the slag, which can make the slag foam, surround the arc, reduce heat loss, and the heat loss is relatively small.
  • electric heating can easily and accurately control the furnace temperature, and the operation can be switched between the oxidizing atmosphere or the reducing atmosphere according to the process requirements; it can also freely slag, desulfurize and dephosphorize molten steel/hot metal; it can also be decarburized by oxygen blowing, etc.
  • Al 2 O 3 is mainly composed of CaO and contains a small amount of SiO 2 ternary slag-based low-temperature components, which not only meet the refining requirements of smelting basic alloy steel, but also meet the slag-based components of aluminate cement.
  • the invention converts the characteristics of laterite-nickel ore surface ore difficulty smelting into technical advantages, and at the same time the main product is nickel-chromium-containing basic alloy steel, the refractory Al 2 O 3 is directly formulated into aluminate cement clinker, which is not only High-end steel and high-quality steel provide nickel-chromium basic alloy steel with extremely low content of important harmful metal elements, so as to obtain higher profits of intermediate products, and at the same time produce high-quality and high-value-added high-alumina cement clinker, which realizes the The recycling of waste has greatly increased the added value of the process and the environmental protection significance of the smelting process.
  • the cost of high-quality nickel-chromium basic alloy steel produced by the invention (excluding the value of aluminate cement clinker) is more than RMB 500 lower than that of low-nickel pig iron produced by blast furnace coke method, and it is used as the basis for high-end nickel-chromium alloy steel and stainless steel. raw materials, and can obtain higher by-product profits.
  • the reduction process of the surface layer ore of the laterite nickel ore of the present invention is a non-coke reduction process, which avoids the high coke ratio problem of the current small blast furnace smelting process, does not have to worry about the shortage of coking coal resources and the increase in coke prices, and avoids self-construction. A series of environmental problems brought about by coking plants.
  • the low-nickel stainless steel and nickel-containing alloy steel developed by using laterite-nickel surface ore have excellent performance, filling many technical gaps in this field.
  • the applicant of the present invention has led and participated in the development of dozens of nickel-containing alloy steels, such as: sorbite high-strength stainless structural steel (patent application number 201610504342.6), electrical steel (patent application number: 201710408062.X), petroleum Steel, etc., the quality of which is better than that of special steel smelted from general raw materials.
  • the applicant of the present invention has made achievements in the development of some important high-end steel and high-quality steel by using the surface layer of laterite nickel ore, and proposed the development concept of "natural alloy ore; basic alloy steel; target alloying". It is of great significance to re-understand the resource value and target use direction of laterite nickel ore surface ore, and it can also provide my country with an important source of high-quality raw materials.
  • Fig. 1 is the process flow schematic diagram of the surface layer ore of laterite nickel ore according to an embodiment of the present invention
  • FIG. 2 is a schematic diagram of the arrangement of a magmatization reactor according to an embodiment of the present invention.
  • Embodiment 1 Smelting of Philippine laterite nickel ore surface ore
  • the surface layer ore of the Philippine laterite nickel ore is smelted, and its composition is as shown in Table 1, wherein the crystal water is not removed, and the elements cobalt, lead, tin, arsenic, antimony and bismuth are not counted;
  • the composition of the reducing coal and the injection coal used in the solid-state reduction section without flux is shown in Table 2.
  • Dry the surface layer ore and reduced coal of laterite nickel ore measure the amount of crystallization water at 8%, add 0.30 tons of reduced coal per ton of dry surface layer ore of laterite nickel ore, pulverize and stir well; add binder to press balls, the diameter of the balls is 30-40mm; send the mixed raw material into the rotary kiln, ignite the spray gun; introduce the reaction preheating; the temperature of leaving the kiln is 1200 °C, check the metallization rate, the amount of oxygen removed per ton of dry ore is about 250kg, and the ash content is about 30kg; Then transfer to the magma furnace.
  • the coal oxygen lance is ignited, and the primary reduction balls are heated to make them magma, and the feeding speed is 2 tons per minute; , automatically flow into the special feeding port of the electric arc furnace; after the magmaization furnace, the reduction reaction of metal oxides is basically completed; the magmaization reactor can be arranged according to Figure 2.
  • composition of the surface ore of the Indonesian laterite nickel ore treated in this example is shown in Table 4.
  • the process flow operation of the flux-free solid-state reduction section and the magmatic reduction section is the same as that of Example 1.
  • the difference is that the slag is discharged from the slag, and the dephosphorization agent is added. 30kg of agent, so that the phosphorus in the steel reaches below 0.03-0.05%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un procédé de traitement d'un minerai à surface de minerai latérite-nickel à l'aide d'un procédé de réduction en trois étapes, qui appartient au domaine technique de la fusion de l'acier, comprenant les trois étapes d'un stade de réduction d'état solide sans agent de fusion, d'un stade de réduction par évolution de magma et d'un stade de raffinage à réduction fractionnée, le procédé pouvant produire à la fin un acier d'alliage à base de nickel chrome ou du fer à faible teneur en nickel et un clinker de ciment d'aluminate. À l'aide de la fusion non-coke, la récupération à haute valeur d'éléments d'alliage et l'utilisation des ressources de déchets d'Al2O3 dans le minerai à surface de minerai latérite-nickel, qui est difficile à traiter à l'aide de la technologie existante, sont réalisées à un faible coût, et le procédé présente une valeur économique supérieure.
PCT/CN2020/107175 2020-07-28 2020-08-05 Procédé de traitement d'un minerai à surface de minerai latérite-nickel à l'aide d'un procédé de réduction en trois étapes Ceased WO2022021466A1 (fr)

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PH1/2021/551638A PH12021551638A1 (en) 2020-07-28 2020-08-05 Method for processing surface ore of lateritic nickel ore by three-stage reduction method

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CN202010740833.7A CN111910039B (zh) 2020-07-28 2020-07-28 一种三段还原法处理红土镍矿表层矿的方法
CN202010740833.7 2020-07-28

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WO2024165393A1 (fr) * 2023-02-08 2024-08-15 Thyssenkrupp Steel Europe Ag Procédé de production d'un bain de fer fondu et de laitier liquide dans un dispositif de fusion électrique

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CN101265572A (zh) * 2008-04-18 2008-09-17 刘科 一种可连续化生产的加热反应炉
WO2009146518A1 (fr) * 2008-06-02 2009-12-10 Vale S.A. Récupération de magnésium et de soufre dans la lixiviation de minerais de nickel latéritique
CN102094094A (zh) * 2011-01-17 2011-06-15 中国恩菲工程技术有限公司 红土镍矿冶炼镍铁的工艺
CN103276278A (zh) * 2013-06-04 2013-09-04 罕王实业集团有限公司 一种用于红土镍矿冶炼的熔融还原炉
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024165393A1 (fr) * 2023-02-08 2024-08-15 Thyssenkrupp Steel Europe Ag Procédé de production d'un bain de fer fondu et de laitier liquide dans un dispositif de fusion électrique

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