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WO2022021466A1 - A method for treating a laterite-nickel ore surface ore by means of a three-stage reduction method - Google Patents

A method for treating a laterite-nickel ore surface ore by means of a three-stage reduction method Download PDF

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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
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王平
赵永璞
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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/14Multi-stage processes processes carried out in different vessels or furnaces
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00Hydraulic cements
    • C04B7/32Aluminous cements
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/0006Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/006Starting from ores containing non ferrous metallic oxides
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/0066Preliminary conditioning of the solid carbonaceous reductant
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/02Making spongy iron or liquid steel, by direct processes in shaft furnaces
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/04Making spongy iron or liquid steel, by direct processes in retorts
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/08Making spongy iron or liquid steel, by direct processes in rotary furnaces
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/12Making 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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Abstract

A method for treating a laterite-nickel ore surface ore by means of a three-stage reduction method, which belongs to the technical field of steel smelting, comprising the three steps of a fusing agent-free solid state reduction stage, a magma evolution reduction stage and a fractional reduction refining stage, wherein the method can finally produce a nickel chromium-containing base alloy steel or a low-nickel-iron and an aluminate cement clinker. By employing non-coke smelting, the high value recovery of alloying elements and resource utilization of waste Al 2O 3 in the laterite-nickel ore surface ore, which is difficult to treat using existing technology, are realized at a low cost, and the method has a high economic value.

Description

一种三段还原法处理红土镍矿表层矿的方法A method for treating surface ore of laterite nickel ore by three-stage reduction method 技术领域technical field

本发明属于钢铁冶炼技术领域,尤其涉及一种采用三段还原法处理红土镍矿表层矿的方法。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.

背景技术Background technique

据地质学家估计,地球上红土镍矿的远景储量达5000亿吨以上,红土镍矿表层矿资源量占红土镍矿资源量的三分之一左右。红土镍矿表层矿具有以下优点:①含铁量高,若去除红土镍矿表层矿中的结晶水,其含铁比可高达50以上;②含有优质合金钢生产所必须的镍铬合金元素,通过烘干去除结晶水的原矿中铁、铬、镍总量可高达60%以上;③铅、锡、砷、锑、铋含量低(200ppm以下,甚至可以达到100ppm以下),满足优质钢及高端钢生产的必须要求;④开采成本很低,一般采用露天挖掘机作业。According to estimates by geologists, 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.

然而,目前红土镍矿表层矿的利用量很低,绝大多数红土镍矿开采矿山只取深层矿,而将低镍含量的表层矿当成废弃土。这主要是由于当前处理红土镍矿表层矿存在以下技术问题:However, at present, the utilization of surface ore of laterite nickel ore is very low. Most of the laterite nickel ore mining mines only take deep ore, and the surface ore with low nickel content is regarded as waste soil. This is mainly due to the following technical problems in the current treatment of laterite nickel ore surface ore:

1)无法采用现有的干法冶炼(如RKEF)技术进行冶炼1) The existing dry smelting (such as RKEF) technology cannot be used for smelting

红土镍矿表层矿中Fe 2O 3含量较高,对于传统的干法冶炼技术,高含铁量会导致一旦出现还原,融态矿的电阻变小,电极起弧,阻断矿热炉电阻热冶炼;而高含氧量会致使达到反应温度时,发泡剧烈,炉况不稳定,不能进行正常冶炼。 The content of Fe 2 O 3 in the surface ore of laterite nickel ore is relatively high. For the traditional dry smelting technology, 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.

2)小高炉高焦比使红土镍矿表层矿成本优势尽失2) The high coke ratio of small blast furnace makes the cost advantage of laterite nickel ore surface ore lost

由于红土镍矿表层矿的烧结矿强度低,无法承受大型高炉料层压力,故一般只能采用450m 3以下的小高炉进行生产。尽管红土镍矿表层矿的开采成本每吨低于20元人民币,但经过小高炉冶炼,每吨含低镍生铁的生产一般消耗700kg以上的焦炭,其焦炭消耗量为普通矿冶炼生铁焦炭消耗量(350-400kg)的近两倍。高焦比的冶炼过程也导致所产低镍铁的高硫磷含量,生产的铁产品较为低品质化。 Due to the low strength of the sintered ore in the surface layer of laterite nickel ore, it cannot withstand the pressure of the large blast furnace charge layer, so generally only small blast furnaces below 450m 3 can be used for production. Although the mining cost of the surface ore of laterite nickel ore is less than 20 yuan per ton, after small blast furnace smelting, the production of low nickel pig iron per ton generally consumes more than 700kg of coke, and its coke consumption is the same as that of ordinary ore smelting pig iron coke. (350-400kg) nearly twice. The smelting process with high coke ratio also leads to the high content of sulfur and phosphorus in the produced low-nickel iron, and the produced iron products are of lower quality.

3)红土镍矿表层矿生产的直接还原铁无法通过磁选去除Al 2O 3 3) The direct reduced iron produced by the surface layer of laterite nickel ore cannot remove Al 2 O 3 by magnetic separation

红土镍矿表层矿通过固态还原生产的铁产品含20%以上的Al 2O 3脉石,如果配入熔剂,渣量可达40%以上。采用直接还原法时,后续工序无法承受海绵状直接还原铁入炉所带来的渣量,同时固态还原时,矿中极其细小的Al 2O 3颗粒不能聚集,无法通过磁选去除,也导致无法入炉,由此所生产的高渣量的产品,即直接还原铁,几乎没有用途。 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%. When 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. At the same time, during solid-state reduction, 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.

4)高炉添加用量太小4) The amount added to the blast furnace is too small

少量硫磷含量低、铁含量高的低镍表层矿被少数钢厂限量(5%)加入高炉代替普通铁矿,但由于很多现行的钢铁标准限制铬镍的使用,其使用量极其有限,并且造成合金元素的浪费。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.

因此,开发一种适合工业生产的高效、低成本又经济环保的红土镍矿表层矿冶炼方法,科学合理地发挥红土镍矿表层矿的价值,对我国扩大资源来源、提高高端品种原料来源,研发出镍铬高价值元素含量高、有害金属杂质含量低的高端高品质钢具有重要意义。Therefore, to develop an efficient, low-cost, economical and environmentally friendly surface ore smelting method for laterite nickel ore that is suitable for industrial production, scientifically and rationally exert the value of laterite nickel ore surface ore, expand the source of resources for my country, improve the source of high-end varieties of raw materials, research and development It is of great significance to produce high-end high-quality steel with high content of high-value elements of nickel and chromium and low content of harmful metal impurities.

发明内容SUMMARY OF THE INVENTION

针对现有技术中存在的不足,本发明的目的在于,提供一种三段还原法处理红土镍矿表层矿的方法,包括无熔剂固态还原段、岩浆化还原段及熔分还原精炼段三个步骤。该方法通过采用非焦冶炼,以较低的成本实现了现有工艺所难处理的红土镍矿表层矿中合金元素的高价值回收和废弃物Al 2O 3的资源化利用,具有极高的经济价值。 In view of the deficiencies in the prior art, 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. By adopting non-coking smelting, 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.

为了实现上述目的,本发明采用以下技术方案:In order to achieve the above object, the present invention adopts the following technical solutions:

一种三段还原法处理红土镍矿表层矿的方法,包括以下步骤:A method for treating surface layer ore of laterite nickel ore by a three-stage reduction method, comprising the following steps:

(1)无熔剂固态还原段:将红土镍矿表层矿与还原煤粉碎后混匀,进行碳还原,将碳还原后的原料送入岩浆化反应釜;(1) solid-state reduction section without flux: the surface layer ore of laterite nickel ore and the reduced coal are pulverized and mixed, carbon reduction is carried out, and the raw material after carbon reduction is sent to the magmaization reactor;

(2)岩浆化还原段:对进入岩浆化反应釜的炉料进行加热,使炉料软熔,排出气体,控制并防止Al 2O 3析出阻塞炉口,将炉料以岩浆化状态送入电弧炉; (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;

(3)熔分还原精炼段:岩浆化熔融炉料进入电弧炉,按照炉料中Al 2O 3重量的50-80%加入钙/硅氧化物造渣,加入调渣剂进行调渣,促使Al 2O 3熔化,形成铝酸钙/硅铝酸钙;按照最终合金钢产品对基础合金钢的要求进行还原精炼,使硫、磷含量达到工艺要求,最终产出含镍铬的基础合金钢或低镍铁及铝酸盐/硅铝酸盐水泥熟料。 (3) smelting reduction and refining section: the magma melted charge enters the electric arc furnace, calcium/silicon oxide is added to make slag according to 50-80% of the weight of Al 2 O 3 in the charge, and a slag adjusting agent is added to adjust the slag to promote Al 2 O 2 O 3 is melted to form calcium aluminate/calcium aluminosilicate; reduction and refining are carried out according to the requirements of the final alloy steel product for the basic alloy steel, so that the content of sulfur and phosphorus meets the process requirements, and finally the basic alloy steel containing nickel and chromium or low Nickel-iron and aluminate/aluminosilicate cement clinker.

进一步地,上述步骤(1)中所述无熔剂固态还原段的反应温度为1100-1200℃;该工序结束时,碳还原后的原料中铁与全铁之比为0.7以上。Further, the 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.

进一步地,上述步骤(1)中通过回转窑或竖炉对红土镍矿表层矿进行碳还原;所述回转窑带有电阻加热除粘结的窑头段/出料段,其还原温度可以达到1200℃,喷吹用煤采用高热值烟煤。Further, in the above-mentioned 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 ℃, high calorific value bituminous coal is used for injection coal.

进一步地,上述步骤(1)中按照红土镍矿表层矿去掉表层水与结晶水后的干矿重量的30-35%过饱和配碳;所述干矿中铁以Fe 2O 3赋存,氧铁比为0.42,全铁含量按照55-60%计算,优选为60%。 Further, in above-mentioned 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%.

进一步地,上述步骤(1)中所述还原煤采用高固定碳、低灰分的无烟煤;红土镍矿表层矿与还原煤粉碎至尺寸小于10mm;使用球团粘结剂粘结造球,球团尺寸为30-50mm。Further, 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.

进一步地,上述步骤(1)中碳还原后的原料处于不完全还原的海绵态,比重为2-3。Further, in the above-mentioned step (1), the raw material after carbon reduction is in an incompletely reduced sponge state, and the specific gravity is 2-3.

进一步地,上述步骤(2)中所述岩浆化还原段的反应温度为1200-1300℃;该工序还原结束时,炉料中铁与全铁之比为0.9以上。Further, the 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.

进一步地,上述步骤(2)中通过岩浆化反应提升炉料比重,使比重大于6。Further, in the above step (2), the specific gravity of the charge is increased by the magma reaction, so that the specific gravity is greater than 6.

具体地,上述步骤(2)中按照还原料堆比重2-3t/m 3,料层厚度控制在1米以内,边岩浆化边送入电弧炉,绞龙推送料量速度等于岩浆化料量速度,等速推送;岩浆化的时间为电弧炉冶炼处理时间的一半。 Specifically, in the above-mentioned 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.

进一步地,上述步骤(3)所述熔分还原精炼段中出渣温度大于1550℃,出钢/铁水温度大于1500℃;该工序结束时,炉料中铁还原至0.97以上。Further, in the above-mentioned step (3), 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.

进一步地,上述步骤(3)中所述钙/硅氧化物优选为冶金石灰进行造渣,实现熔分及脱硫脱磷;所述调渣剂优选为CaF 2Further, in the above step (3), 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 .

进一步地,上述步骤(3)中所述基础合金钢成分如下,其中,硫、磷含量根据工艺要求进行严格控制:Further, 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:

元素element CC NiNi CrCr As+Sn+Pb+Sb+BiAs+Sn+Pb+Sb+Bi SS PP 含量content <2%<2% 0.8-2.0%0.8-2.0% 1-4%1-4% <200ppm<200ppm <0.04%<0.04% <0.05%<0.05%

需要说明的是,上述步骤(3)中所述基础合金钢不是具有某种性能的钢,而是供用户生产高端镍铬合金钢及不锈钢的原料;所述基础合金钢含有价值极高的镍铬元素,同时对高端钢品质有害的低熔点元素包括铅、锡、砷、锑、铋含量极低,总含量低于200ppm,是其它高端钢原料难以提供的,可以满足国内外一些重要舰船用钢、飞机起落架、高端轴承、高端军工用钢的原料需求。It should be noted that 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.

需要说明的是,上述步骤(3)中所述低镍铁可以作为低端不锈钢或镍铬合金钢原料。It should be noted that 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.

需要说明的是,上述步骤(3)中所述铝酸盐水泥熟料符合国家铝酸盐水泥标准GB/T 201-2015。It should be noted that the aluminate cement clinker described in the above step (3) complies with the national aluminate cement standard GB/T 201-2015.

本发明的另一方面为提供一种应用于上述方法的岩浆化反应釜装置,其包括供热热源、反应釜腔体、推送绞龙及出料口;所述推送绞龙用于将步骤(1)中碳还原后的炉料送入反应釜腔体,进行岩浆化;所述反应釜腔体从推送绞龙端到出料口端呈倾斜设置;所述出料口与步骤(3)中电弧炉连接,岩浆化炉料经出料口进入电弧炉。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.

进一步地,所述供热热源包括煤氧枪、交直流电热源及其它满足要求的热源。Further, the heat supply heat source includes a coal-oxygen lance, an AC and DC heat source and other heat sources that meet the requirements.

进一步地,所述岩浆化反应釜装置中具有较大的还原反应表面积,有利于气体释放;具有一定的倾斜角度,有利于岩浆状态的还原料送入电弧炉;具有较大的能量供应要求,适应电弧炉终还原速度的要求。Further, the 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.

进一步地,所述岩浆化反应釜装置的还原升温范围为1000-1300℃。Further, the reduction temperature rise range of the magmatization reactor device is 1000-1300°C.

本发明还可用于还原含铁量大于50%的非磁性铁矿或磁性铁矿资源,用于铁的生产。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.

以下对本发明的设计理念作进一步阐述:The design concept of the present invention is further elaborated below:

1)无熔剂固态还原段1) Flux-free solid-state reduction section

根据红土镍矿表层矿成分分析可知,红土镍矿表层矿97%以上的成分为铁的氧化物和Al 2O 3。Al 2O 3-Fe 2O 3相图表明,二者的最低液相温度(约1600℃)在氧化铁侧,故在回转窑或竖炉中采用不加熔剂的固态还原法,炉料不易熔化,避免窑壁或炉壁粘结问题的发生,可以进行高温还原。同时回转窑窑头段/出料段带有电阻加热除粘结装置,如果出料口或窑头出现粘结,可以快速清除粘结块,保证规模化连续生产。 According to the analysis of 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℃) 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. At the same time, 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.

2)岩浆化还原段2) Magmatization reduction section

从现有的经验来看,回转窑生产直接还原铁即使还原良好,在回转窑出窑后直接加入电炉也是不安全的,主要是由于:①来自回转窑的直接还原铁比重大约为2-3,这样比重的炉料加入电弧炉,导致炉容必须加倍;②来自回转窑的直接还原铁在还原过程中产生很多孔隙,形成海绵铁,直接加入电弧炉会加热产生爆炸性大沸腾。故此阶段先通过岩浆化反应釜将海绵状炉料高温软熔为岩浆化状态,完成还原反应,提升炉料比重并排出气体,从而可以避免红土镍矿表层矿中含氧量高而导致的在电炉中发泡剧烈,炉况不稳定等安全事故。From the existing experience, even if the direct reduction iron produced by the rotary kiln is well reduced, it is not safe to directly add it to the electric furnace after the rotary kiln is discharged, mainly because: ① the proportion of direct reduced iron from the rotary kiln is about 2-3 , the charge with such specific gravity is added to the electric arc furnace, so that the furnace capacity must be doubled; ② the direct reduced iron from the rotary kiln produces many pores during the reduction process to form sponge iron, and the direct addition of the electric arc furnace will cause explosive boiling. Therefore, at this stage, 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.

因此,该阶段工序为整个工艺流程的枢纽及关键控制环节,具有以下技术优势及作用:①将固态还原段未完全还原的原料进一步还原,避免由于欠还原而导致炉中氧化物过多,从而导致在后续熔分还原精炼段的电弧炉中出现剧烈碳氧反应,产生大沸腾生产安全事故;②去除还原料中的气体,去海绵化,提升还原料的比重,避免海绵化还原铁中的气体在电弧炉高温下爆炸性沸腾;③由于岩浆化反应釜具备保温功能,故可以调整工艺流程的节奏,实现作业缓冲,使工艺节奏平稳顺畅;④全流程连续化生产,热能损失小。Therefore, 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. The gas boils explosively at the high temperature of the electric arc furnace; ③Because the magma reaction kettle has the function of heat preservation, it can adjust the rhythm of the process flow, realize the operation buffer, and make the process rhythm smooth and smooth; ④The whole process is continuous in production, and the heat energy loss is small.

3)熔分还原精炼段3) Melting reduction refining section

本阶段为产品生成阶段,关键是控制铁水的碳、硫、磷,分离红土镍矿表层矿中的铁和Al 2O 3,按照最终合金钢产品对基础合金钢的要求,进行还原精炼,产出优质基础合金钢,同时生产合格的铝酸钙水泥熟料。其中,控制碳和磷、硫属于电弧炉常规工艺方法,没有技术难点。电弧炉电弧的温度高达6000℃,可以将岩浆化的炉料迅速熔化,在炉料熔化时的大部分时间里,高温热源被炉料所包围。还原矿岩浆中未还原的铁氧化物中的氧与加入的碳反应及与炉渣相互作用,可使炉渣泡沫化,包围电弧,减少热量散失,热损失相对较少。此外,电加热容易精确地控制炉温,可以根据工艺要求在氧化气氛或还原气氛切换操作;也可以自由地造渣,对钢水/铁水脱硫脱磷;也可以通过吹氧脱碳等。 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. Among them, 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 ℃, 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. In addition, 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.

本阶段所产出的电弧炉炉渣的标准依据:①中华人民共和国铝酸盐水泥标准GB/T 201-2015;②Al 2O 3-CaO-SiO 2三元相图,依照该相图可找到以Al 2O 3与CaO为主,含有少量SiO 2三元渣系低温度成分配合,构成既满足冶炼基础合金钢精炼要求,也满足铝酸盐水泥要求渣系成分。 The standard basis of the electric arc furnace slag produced at this stage: ① The People's Republic of China Standard for Aluminate Cement GB/T 201-2015; ② Al 2 O 3 -CaO-SiO 2 ternary phase diagram, according to which you can find the following 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.

本发明的技术优势及积极效果至少包括:The technical advantages and positive effects of the present invention include at least:

本发明将红土镍矿表层矿难冶炼的特点转化为技术优势,产出主产品含镍铬基础合金钢的同时,又将难处理的Al 2O 3直接配制成铝酸盐水泥熟料,既为高端钢、高品质钢提供重要的有害金属元素含量极低的镍铬基础合金钢,从而获得较高的中间产品利润,又同时生产了品质高、附加值高的高铝水泥熟料,实现了废弃物资源化处理,极大地增加了工艺附加值和冶炼过程的环保意义。 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.

本发明生产的优质镍铬基础合金钢成本(不含铝酸盐水泥熟料的价值)比高炉焦炭法生产的低镍生铁成本低500元人民币以上,而作为高端镍铬合金钢及不锈钢的基础原料,又可获得较高的副产品利润。具体到生产工艺,本发明的红土镍矿表层矿的还原工艺为非焦还原工艺,避免了目前小高炉冶炼工艺的高焦比难题,不用担心焦煤资源短缺和焦炭价格走高,也避免了自建焦化厂带来的一系列环境问题。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. Specific to the production process, 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.

总而言之,从现有的研究成果来看,采用红土镍矿表层矿开发的含低镍不锈钢及含镍合金钢种性能极好,填补了很多本领域的技术空白。本发明申请人已经主导和参与了几十种含镍合金钢的开发,如:索氏体高强不锈结构钢(专利申请号201610504342.6)、电工钢(专利申请号:201710408062.X)、石油用钢等,其品质均优于一般原料冶炼的特殊钢。本发明申请人利用红土镍矿表层矿在一些重要的高端钢、高品质钢的开发方面已经取得成效,并提出了“天然合金矿;基础合金钢;目标合金化”的开发理念,该理念对重新认识红土镍矿表层矿的资源价值及目标使用方向具有重要意义,也可以为我国提供一个重要的高品质原料来源。All in all, judging from the existing research results, 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.

附图说明Description of drawings

图1为根据本发明一实施例的红土镍矿表层矿的工艺流程示意图;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;

图2为根据本发明一实施例的岩浆化反应釜布置示意图。FIG. 2 is a schematic diagram of the arrangement of a magmatization reactor according to an embodiment of the present invention.

具体实施方式detailed description

以下将结合具体实施例对本发明作进一步说明。The present invention will be further described below with reference to specific embodiments.

实施例1菲律宾红土镍矿表层矿的冶炼Embodiment 1 Smelting of Philippine laterite nickel ore surface ore

按照附图1所示工艺流程示意图,对菲律宾红土镍矿表层矿进行冶炼,其成分组成如表1所示,其中未去除结晶水,元素钴、铅、锡、砷、锑、铋未计;无熔剂固态还原段所使用的还原煤及喷吹煤的成分组成如表2所示。According to the schematic diagram of the process flow shown in accompanying drawing 1, 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.

表1 菲律宾红土镍矿表层矿的成分组成Table 1 Composition of surface ore of laterite nickel ore in the Philippines

元素element FeFe NiNi Cr 2O 3 Cr 2 O 3 SiO 2 SiO2 Al 2O 3 Al 2 O 3 MnOMnO PP SS 水分moisture 含量(wt%)Content (wt%) 49.0049.00 0.710.71 3.163.16 2.192.19 7.397.39 0.780.78 0.0040.004 0.200.20 31.5031.50

表2 还原煤及喷吹煤的成分组成Table 2 Composition of reduced coal and injection coal

Figure PCTCN2020107175-appb-000001
Figure PCTCN2020107175-appb-000001

1)无熔剂固态还原段1) Flux-free solid-state reduction section

将红土镍矿表层矿与还原煤进行烘干,结晶水量按照8%计量,按照每吨红土镍矿表层干矿添加还原煤0.30吨,粉碎后搅匀;加入粘结剂压球,球直径为30-40mm;将混合原料送入回转窑,喷枪点火;引入反应预热;出窑温度为1200℃,检验金属化率,每吨干矿脱除的氧量约250kg,增重灰分约30kg;之后转入岩浆化炉。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 ℃, 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.

2)岩浆化还原段2) Magmatization reduction section

送入一定量的初还原料后,点燃煤氧枪,对送入的初还原球进行加热,使之岩浆化,送料速度为每分钟2吨;升温至1350-1400℃,炉料岩浆化后,自动流入电弧炉专设加料口;经过岩浆化炉,金属氧化物的还原反应基本完成;岩浆化反应釜可按附图2进行布置。After feeding a certain amount of primary reduction raw materials, 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.

3)熔分还原精炼段3) Melting reduction refining section

岩浆料加入电弧炉的同时,加入还原前干矿所含Al 2O 3含量50-70%的石灰;半小时后,电弧炉加入岩浆料达到60吨左右,可产生50吨基础合金钢;边加入岩浆料和石灰,电弧炉边送电,形成连续加料、连续熔化;熔化完毕,立即检验钢中硫含量,如果钢中硫含量高于标准要求,向钢水中加入每吨钢1kg铝,用形成的渣料脱硫,脱硫完毕后,先出渣,留约100mm的薄渣层即可出钢。 When the rock slurry is added to the electric arc furnace, lime with an Al 2 O 3 content of 50-70% contained in the dry ore before reduction is added; half an hour later, the amount of rock slurry added to the electric arc furnace reaches about 60 tons, which can produce 50 tons of basic alloy steel; Add rock slurry and lime, and send electricity by the electric arc furnace to form continuous feeding and continuous melting; after melting, check the sulfur content in the steel immediately. The formed slag is desulfurized. After the desulfurization is completed, the slag is tapped first, and a thin slag layer of about 100mm can be tapped.

本实施例冶炼结束后主产产品成分如表3所示。The main product components after the smelting in this example is shown in Table 3.

表3 冶炼结束后所生产的主产产品成分组成Table 3 Composition of main products produced after smelting

元素element CC NiNi CrCr As+Sn+Pb+Sb+BiAs+Sn+Pb+Sb+Bi SS PP 含量(wt%)Content (wt%) 0.20.2 1.51.5 2.22.2 <0.012不分析<0.012 not analyzed 0.020.02 0.0070.007

实施例2印尼红土镍矿表层矿冶炼基础合金钢Example 2 Indonesian laterite nickel ore surface ore smelting basic alloy steel

本实施例中所处理的印尼红土镍矿表层矿的成分组成如表4所示。The composition of the surface ore of the Indonesian laterite nickel ore treated in this example is shown in Table 4.

表4 印尼红土镍矿表层矿的成分组成Table 4 Composition of surface ore of laterite nickel ore in Indonesia

组分component FeFe CoCo NiNi Al 2O 3 Al 2 O 3 Cr 2O 3 Cr 2 O 3 CaOCaO MgOMgO SiO 2 SiO2 MnMn PP SS 含量(wt%)Content (wt%) 48.5048.50 0.0220.022 0.660.66 7.987.98 3.363.36 0.0170.017 0.220.22 1.241.24 0.210.21 0.0550.055 0.180.18

无熔剂固态还原段与岩浆化还原段的工序流程操作同实施例1,不同处自出渣开始,炉渣出净,加入脱磷剂,送电造渣吹氧脱磷,每吨钢加入脱磷剂30kg,使钢中磷达到0.03-0.05%以下。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%.

本实施例冶炼结束后主产产品成分如表5所示。The components of the main products after the smelting of this example is completed are shown in Table 5.

表5 冶炼结束后所生产的主产产品成分组成Table 5 Composition of main products produced after smelting

元素element CC NiNi CrCr As+Sn+Pb+Sb+BiAs+Sn+Pb+Sb+Bi SS PP 含量(wt%)Content (wt%) 0.20.2 1.21.2 2.52.5 <0.012不分析<0.012 not analyzed 0.020.02 0.040.04

以上所述仅为本申请的实施例而已,并不用于限制本申请。对于本领域技术人员来说,本申请可以有各种更改和变化。凡在本申请的精神和原理之内所作的任何修改、等同替换、改进等,均应包含在本申请的权利要求范围之内。The above descriptions are merely examples of the present application, and are not intended to limit the present application. Various modifications and variations of this application are possible for those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included within the scope of the claims of the present application.

Claims (10)

一种三段还原法处理红土镍矿表层矿的方法,其特征在于,包括以下步骤:A method for treating the surface layer ore of laterite nickel ore by a three-stage reduction method is characterized in that, comprising the following steps: (1)无熔剂固态还原段:将红土镍矿表层矿与还原煤粉碎后混匀,进行碳还原,将碳还原后的原料送入岩浆化反应釜;(1) solid-state reduction section without flux: the surface layer ore of laterite nickel ore and the reduced coal are pulverized and mixed, carbon reduction is carried out, and the raw material after carbon reduction is sent to the magmaization reactor; (2)岩浆化还原段:对进入岩浆化反应釜的炉料进行加热,使炉料软熔,排出气体,控制并防止Al 2O 3析出阻塞炉口,将炉料以岩浆化状态送入电弧炉; (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; (3)熔分还原精炼段:岩浆化熔融炉料进入电弧炉,按照炉料中Al 2O 3重量的50-80%加入钙/硅氧化物造渣,加入调渣剂进行调渣,促使Al 2O 3熔化,形成铝酸钙/硅铝酸钙;按照最终合金钢产品对基础合金钢的要求进行还原精炼,使硫、磷含量达到工艺要求,最终产出含镍铬的基础合金钢或低镍铁及铝酸盐/硅铝酸盐水泥熟料。 (3) smelting reduction and refining section: the magma melted charge enters the electric arc furnace, calcium/silicon oxide is added to make slag according to 50-80% of the weight of Al 2 O 3 in the charge, and a slag adjusting agent is added to adjust the slag to promote Al 2 O 2 O 3 is melted to form calcium aluminate/calcium aluminosilicate; reduction and refining are carried out according to the requirements of the final alloy steel product for the basic alloy steel, so that the content of sulfur and phosphorus meets the process requirements, and finally the basic alloy steel containing nickel and chromium or low Nickel-iron and aluminate/aluminosilicate cement clinker. 如权利要求1所述的三段还原法处理红土镍矿表层矿的方法,其特征在于,步骤(1)中所述无熔剂固态还原段的反应温度为1100-1200℃;所述无熔剂固态还原段结束时,炉料中铁与全铁之比为0.7以上,处于不完全还原的海绵态,比重为2-3。The method for treating the surface layer ore of laterite nickel ore by three-stage reduction method according to claim 1, wherein the reaction temperature of the solid-state reduction section without flux in step (1) is 1100-1200 °C; At the end of the reduction section, the ratio of iron to total iron in the charge is above 0.7, and it is in an incompletely reduced sponge state with a specific gravity of 2-3. 如权利要求1所述的三段还原法处理红土镍矿表层矿的方法,其特征在于,步骤(1)中通过回转窑或竖炉对红土镍矿表层矿进行碳还原;所述回转窑带有电阻加热除粘结的窑头段/出料段,喷吹用煤采用高热值烟煤。The method for treating the surface layer ore of laterite nickel ore by three-stage reduction method as claimed in claim 1, wherein in step (1), carbon reduction is carried out on the surface layer ore of laterite nickel ore by a rotary kiln or a shaft furnace; There is resistance heating in the kiln head section/discharge section for removing adhesion, and the coal for injection adopts bituminous coal with high calorific value. 如权利要求1所述的三段还原法处理红土镍矿表层矿的方法,其特征在于,步骤(1)中按照红土镍矿表层矿去掉表层水与结晶水后的干矿重量的30-35%过饱和配碳;所述干矿全铁含量按照55-60%计算。The method for treating the surface layer ore of laterite nickel ore by three-stage reduction method as claimed in claim 1, it is characterized in that, in step (1), remove 30-35% of the dry ore weight after surface layer water and crystal water according to the surface layer ore of laterite nickel ore. % supersaturated carbon; the total iron content of the dry ore is calculated according to 55-60%. 如权利要求1所述的三段还原法处理红土镍矿表层矿的方法,其特征在于,步骤(1)中所述还原煤采用高固定碳、低灰分的无烟煤;红土镍矿表层矿与还原煤粉碎至尺寸小于10mm;使用球团粘结剂粘结造球,球团尺寸为30-50mm。The method for treating the surface layer ore of laterite-nickel ore by three-stage reduction method as claimed in claim 1, wherein the reduction coal in step (1) adopts anthracite with high fixed carbon and low ash content; The raw coal is pulverized to a size of less than 10mm; the pellets are formed by bonding with a pellet binder, and the pellet size is 30-50mm. 如权利要求1所述的三段还原法处理红土镍矿表层矿的方法,其特征在于,步骤(2)中所述岩浆化还原段的反应温度为1200-1300℃;所述岩浆化还原段结束时,炉料中铁与全铁之比为0.9以上,比重大于6。The method for treating surface ore of laterite nickel ore by three-stage reduction method according to claim 1, wherein the reaction temperature of the magmatic reduction section in step (2) is 1200-1300°C; At the end, the ratio of iron to total iron in the charge is more than 0.9, and the specific gravity is greater than 6. 如权利要求1所述的三段还原法处理红土镍矿表层矿的方法,其特征在于,步骤(2)中按照还原料堆比重2-3t/m 3,边岩浆化边送入电弧炉,绞龙推送料量速度等于岩浆化料量速度,等速推送。 The method for treating the surface layer ore of laterite nickel ore by three-stage reduction method as claimed in claim 1, characterized in that, in step (2), according to the specific gravity of 2-3t/m 3 of the reduced material pile, the magma is sent into the electric arc furnace, The speed of the auger to push the material is equal to the speed of the magma material, and it is pushed at a constant speed. 如权利要求1所述的三段还原法处理红土镍矿表层矿的方法,其特征在于,步骤(3)中所述熔分还原精炼段中出渣温度大于1550℃,出钢/铁水温度大于1500℃;所述熔分还原精炼段结束时,炉料中铁还原至0.97以上。The method for treating surface layer ore of laterite nickel ore by three-stage reduction method as claimed in claim 1, characterized in that, in step (3), 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 1550° C. 1500°C; at the end of the melting reduction refining section, the iron in the charge is reduced to more than 0.97. 如权利要求1所述的三段还原法处理红土镍矿表层矿的方法,其特征在于,步骤(3)中所述基础合金钢成分如下,其中,硫、磷含量根据工艺要求进行严格控制:The three-stage reduction method as claimed in claim 1 is characterized in that, the basic alloy steel composition described in step (3) is as follows, wherein, sulfur and phosphorus content are strictly controlled according to process requirements: 元素 C Ni Cr As+Sn+Pb+Sb+Bi S P 含量 <2% 0.8-2.0% 1-4% <200ppm <0.04% <0.05%
element C Ni Cr As+Sn+Pb+Sb+Bi S P content <2% 0.8-2.0% 1-4% <200ppm <0.04% <0.05%
.
一种应用于权利要求1-9任一所述方法的岩浆化反应釜装置,包括供热热源、反应釜腔体、推送绞龙及出料口,其特征在于:所述推送绞龙用于将步骤(1)中碳还原后的炉料送入反应釜腔体,进行岩浆化;所述供热热源包括煤氧枪、交直流电热源及其它满足要求的热源;所述反应釜腔体从推送绞龙端到出料口端呈倾斜设置;所述出料口与步骤(3)中电弧炉连接,岩浆化炉料经出料口进入电弧炉;所述岩浆化反应釜装置的还原升温范围为1000-1300℃。A magma reaction kettle device applied to any one of the methods of claims 1-9, comprising a heating source, a reactor cavity, a push auger and a discharge port, wherein the push auger is used for The charge after carbon reduction in step (1) is sent into the reaction kettle cavity for magmaization; the heat supply heat source includes coal oxygen lances, AC and DC heat sources and other heat sources that meet the requirements; the reaction kettle cavity is pushed from the push The end of the auger is inclined to the end of the discharge port; the discharge port is connected to the electric arc furnace in step (3), and the magmaized charge enters the electric arc furnace through the discharge port; the reduction temperature rise range of the magmaization reactor device is: 1000-1300℃.
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