CN111424167A - Method for treating laterite-nickel ore - Google Patents
Method for treating laterite-nickel ore Download PDFInfo
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- CN111424167A CN111424167A CN202010301665.1A CN202010301665A CN111424167A CN 111424167 A CN111424167 A CN 111424167A CN 202010301665 A CN202010301665 A CN 202010301665A CN 111424167 A CN111424167 A CN 111424167A
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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
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/021—Obtaining nickel or cobalt by dry processes by reduction in solid state, e.g. by segregation processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
Abstract
The invention discloses a method for treating laterite-nickel ore, which comprises the following steps: (1) pretreating the laterite-nickel ore so as to obtain laterite-nickel ore particles; (2) mixing the laterite-nickel ore particles with a reducing agent to obtain a mixed material; (3) carrying out pre-reduction treatment on the mixed material so as to obtain calcine; (4) smelting the calcine, the sulfide ore, a smelting solvent, combustible fuel and oxygen-enriched air to obtain first low-nickel matte and smelting slag; (5) and carrying out converting and slagging treatment on the first low-nickel matte and the converting solvent so as to obtain high-nickel matte and converting slag. The method is high in efficiency, low in energy consumption and high in metal recovery rate when used for treating the laterite-nickel ore.
Description
Technical Field
The invention belongs to the technical field of laterite-nickel ore treatment, and particularly relates to a method for treating laterite-nickel ore.
Background
The reserves of global nickel resources are abundant, and the statistical data of 2017 by the U.S. geological survey shows that the reserved reserves of the global ascertained land-based nickel are about 7900 kilotons (calculated by metallic nickel), the total amount of nickel resources is about 1.4 hundred million tons, and the nickel resources are intensively distributed in countries such as Australia, Brazil, New Carlidonia, Russia, Cuba, Indonesia, south Africa, Philippines, China, Canada and the like. Of these nickel ore resources, nickel sulphide ore accounts for about 40% of the total nickel content, and the remaining 60% is laterite-nickel ore, however, at present 70% of the world's nickel production is from nickel sulphide ore and only 30% of the world's nickel production is from laterite-nickel ore. Along with the continuous consumption of the explored nickel sulfide ore and the continuous reduction of the reserves of the newly explored nickel sulfide ore, the resource of the nickel sulfide ore which can be exploited in the global scope is gradually exhausted, and the requirement of the continuously increased nickel production amount on the raw materials is difficult to meet. In recent years, the demand problem of nickel product raw materials is highlighted by the rapid increase of the stainless steel yield in China and the development trend of high nickel content of the ternary power battery for the new energy automobile, and how to develop laterite-nickel ore resources in an efficient, low-cost and green way has important significance for the development of nickel metallurgical industry.
At present, the process for industrially treating the laterite-nickel ore can be divided into pyrometallurgy and hydrometallurgy. Although the hydrometallurgy can efficiently extract nickel and cobalt, and the process energy consumption and the production cost are obviously lower than those of the pyrometallurgy, the hydrometallurgy is limited by factors of smaller production scale, longer production flow and the like, and the proportion of the hydrometallurgy in the nickel production of the laterite-nickel ore is smaller. The pyrometallurgy can meet the requirements of various industries on nickel products under the current situation through large-mold industrial production, and can recover iron to improve comprehensive economic benefits. According to incomplete statistics, more than 80% of the global nickel production is provided by pyrometallurgy at present, and the classification of products produced by the process specifically comprises a matte smelting process for producing nickel matte, a rotary kiln grain iron process for producing ferronickel, a blast furnace smelting process, a rotary kiln prereduction-electric furnace smelting process (RKEF) and the like.
(1) Matte smelting process
The production of nickel matte by matte making and smelting is the first pyrometallurgical process for laterite-nickel ore used in industrial production. The low grade nickel matte is prepared by adding vulcanizing agents such as sulfur, pyrite or gypsum and the like into the laterite-nickel ore, smelting at the temperature of 1600 ℃ in a blast furnace or an electric furnace, and then blowing by a converter to produce the high grade nickel matte with the nickel grade of more than 40%. Currently, the amount of nickel matte produced globally from laterite nickel ores is around 12 million tons (in terms of metallic nickel) per year.
The high nickel matte product has great flexibility, can be used for direct reduction and general nickel for stainless steel production after roasting and desulfurization, can also be used as a raw material for refining nickel by an atmospheric pressure carbonyl method to produce nickel pellets and nickel powder, and can also be made into an anode plate to produce cathode nickel through electrolytic refining.
The smelting process for preparing the low-nickel matte by reducing and vulcanizing the laterite-nickel ore mainly comprises the processes of treating the laterite-nickel ore by an ambo smelting plant of new karlidonia, a Clorodae smelting plant of Sulavivixi Indonesian and a blast furnace except for being gradually eliminated. The production process for preparing nickel matte by processing laterite-nickel ore in a new karlidonian plant comprises the steps of spraying molten sulfur liquid into a ferronickel alloy molten liquid melted in a converter for vulcanization, and simultaneously carrying out slagging blowing to finally prepare a high nickel matte product; the production process for preparing nickel matte by processing laterite-nickel ore in Indonesia factories comprises the steps of spraying molten sulfur liquid onto roasted sand with a certain temperature which is roasted in a rotary kiln, carrying out vulcanization by utilizing the waste heat of the roasted sand, converting pre-reduced nickel and iron particles into sulfide, then transferring the roasted sand into an electric furnace for smelting to produce low-nickel matte, and then carrying out converter blowing to finally obtain a high-nickel matte product; the process for preparing nickel matte by smelting laterite-nickel ore in a blast furnace is gradually eliminated along with the enlargement of production scale, the improvement of smelting technology, the improvement of requirements of steel plants on nickel raw materials and the improvement of environmental protection requirements due to the fact that the process is not environment-friendly, poor in ore adaptability, strict in requirement on magnesium content, incapable of processing fine ore and strict in limitation on furnace charging materials.
(2) Rotary kiln iron granulating method
The process is developed from a German Krupp-Renn direct reduction iron-making process, is developed into a 'Dajiang mountain' process by a smelting plant of the Japan Dajiang mountain and continuously operates to the present. Drying, crushing and screening laterite-nickel ore raw ore, mixing the laterite-nickel ore raw ore with a solvent and a reducing agent according to a certain proportion to prepare lumps, drying and reducing and roasting the lumps in a rotary kiln at a high temperature to generate ferronickel, and carrying out water quenching cooling, crushing, screening, magnetic separation or gravity separation on the roasted product to separate ferronickel and slag to obtain beaded ferronickel particles or ferronickel powder. Laterite-nickel ore lumps enter from the tail of a rotary kiln, and the high-temperature roasting process in the kiln can be divided into three stages, namely a drying stage, a reduction stage and a ferronickel particle growth stage. The temperature of the drying section is generally lower than 800 ℃, and crystal water in the laterite-nickel ore is removed; the temperature of the reduction section is about 800-; the temperature required by the ferronickel particle growth section should reach 1400-1450 ℃ so as to keep the molten or semi-molten state of the materials to ensure that the ferronickel particles generated in the reduction section are fully aggregated.
For the rotary kiln grain iron process, in order to realize effective separation of ferronickel and slag in the physical separation process, in the rotary kiln reduction process, the material needs to be in a molten or semi-molten state so as to improve the mass transfer condition inside the material and promote aggregation and growth of ferronickel particles. The melting point of phases such as pyroxene and olivine generated in the reduction roasting process of the laterite-nickel ore is high, in order to meet the generation condition of a liquid phase, the required reduction roasting temperature in the rotary kiln is high, and the operation condition is harsh. For example, the reduction temperature of the rotary kiln head ferronickel particle growth section is required to be increased to 1400 ℃ and 1450 ℃ in Japan Dajiang mountain ferronickel factory. On the other hand, the liquid phase amount is difficult to control in the production process, so that ring-forming substances are easy to generate in the reduction area and the ferronickel growing area of the rotary kiln, and the smooth production is seriously influenced. It is understood that, except for the realization of the real ferronickel production in the Nippon Dajiang mountain ferronickel factory, other direct reduction production lines can not realize the direct production of ferronickel, but carry out physical separation treatment on the reduced laterite-nickel ore by the technologies of ore grinding, magnetic separation and the like.
(3) Sintering-blast furnace process
The process flow for preparing the nickel-containing pig iron by smelting the laterite-nickel ore in the blast furnace is basically consistent with the current blast furnace iron-making process flow. Crushing the laterite-nickel ore, mixing the crushed laterite-nickel ore with solvent and fuel ingredients, performing air draft sintering on a sintering machine, and smelting finished sintered ore in a blast furnace to produce nickel-containing pig iron. The process generally uses high-iron low-magnesium type laterite-nickel ore as a raw material, the nickel grade in the product is kept between 3 wt.% and 6 wt.%, and the process is usually used for producing 200 series stainless steel.
For the sintering-blast furnace process, because the laterite-nickel ore has large difference with the modern blast furnace ironmaking raw materials, the operating conditions in the sintering and blast furnace smelting stages are not consistent. The problems of high sintering solid fuel consumption, large ore return quantity, low finished product sinter drum strength, unsatisfactory fraction and the like generally exist in the sintering production of the laterite-nickel ore. Because the laterite-nickel ore has low grade of iron and nickel, the amount of slag is large during blast furnace smelting, the temperature of molten iron on a furnace bar is low, the fluidity of the molten iron is poor, and the slag and the iron are difficult to separate. Particularly, when smelting low-iron high-magnesium type laterite-nickel ore, the amount of blast furnace slag and the viscosity of the slag are too large, so that the production is difficult to be smooth.
(4) Rotary kiln prereduction-electric furnace smelting method
The rotary kiln prereduction-electric furnace smelting process (RKEF) has been developed into a mainstream process for producing ferronickel by utilizing laterite nickel ore worldwide, and the capacity proportion of the process exceeds 2/3 of the global total ferronickel production capacity. The main process flow is that the laterite nickel ore is dried, then is reduced and roasted in a rotary kiln, and the roasted product is put into an electric furnace for further reduction smelting to produce crude ferronickel. The RKEF process has strong raw material adaptability, and various laterite-nickel ore resources can be used for production.
The biggest defect of the rotary kiln prereduction-electric furnace smelting process is that the electric furnace smelting process has high electricity consumption, so that the total energy consumption and the production cost of the process are high. The main reasons are that the amount of slag is large during smelting of the laterite-nickel ore, the smelting temperature required by the slag is high, and in order to ensure the separation of molten iron and slag, the temperature of the slag is generally required to be maintained above 1550 ℃ and even exceeds 1600 ℃, which causes huge electric energy consumption of the electric furnace. Therefore, the RKEF is utilized to smelt the ferronickel product, the requirement on the power supply of the site of the smelting plant is strict, and particularly in the power-deficient area, the production work of utilizing the laterite-nickel ore resource is difficult to develop.
In conclusion, the existing laterite-nickel ore pyrometallurgical process is developed rapidly, but the problems of large raw material fluctuation, poor process applicability, long production flow, large energy consumption, heavy environmental pollution, high dependence on electric power facilities in areas with abundant mineral resources and the like are exposed, so that the process becomes a hidden danger for restricting the development of the nickel metallurgical industry, and the development of a low-cost, high-efficiency and green laterite-nickel ore resource with high processing reserves is urgently needed to meet the requirements of various industries on nickel products.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to propose a method for treating lateritic nickel ores. The method has the advantages of high efficiency, low energy consumption and high metal recovery rate in laterite-nickel ore treatment.
In one aspect of the invention, the invention proposes a method of treating lateritic nickel ores, the method comprising, according to an embodiment of the invention:
(1) pretreating the laterite-nickel ore so as to obtain laterite-nickel ore particles;
(2) mixing the laterite-nickel ore particles with a reducing agent to obtain a mixed material;
(3) carrying out pre-reduction treatment on the mixed material so as to obtain calcine;
(4) smelting the calcine, the sulfide ore, a smelting solvent, combustible fuel and oxygen-enriched air to obtain first low-nickel matte and smelting slag;
(5) and carrying out converting and slagging treatment on the first low-nickel matte and the converting solvent so as to obtain high-nickel matte and converting slag.
According to the method for treating the laterite-nickel ore, the laterite-nickel ore is pretreated, so that laterite-nickel ore particles meeting the requirements of subsequent procedures can be obtained; by mixing the obtained laterite-nickel ore particles with a reducing agent, the surface contact area of the laterite-nickel ore particles and the reducing agent can be obviously increased, and the nickel laterite-nickel ore particles and the reducing agent are convenient to useA continuous pre-reduction process; the mixed material is pre-reduced, so that the metal oxide embedded in the gangue can be effectively reduced, the vulcanization rate of subsequent metal can be improved, and the recovery rate of valuable metal can be improved; in the smelting process, oxygen-enriched air is adopted to combust combustible materials to heat and melt the materials, so that the energy consumption of smelting is favorably reduced, minerals can be quickly melted due to the strong stirring action of the melts, the reaction efficiency is improved, furthermore, sulfide ores are used as metal particles in a sulfide reduction calcine of a vulcanizing agent in the smelting process, the use of the sulfide ores is favorable for reducing the use amount of a smelting solvent, the smelting temperature is reduced, meanwhile, the transportation cost and the production period can be greatly reduced by directly using the sulfide ores, the purposes of low cost, high efficiency, low energy consumption and green development of laterite-nickel ore resources are achieved, further, the smelting solvent can enhance the efficiency of sulfide ores for vulcanizing metal oxides, the metal recovery rate is improved, and the Ni-enriched nickel alloy is obtainedxFe1-xS、Ni3S2And a nickel matte of a mixture of NiFe alloys; the first low-nickel matte obtained by smelting is blown and slagged, so that the enrichment of nickel can be further realized, and high-nickel matte with the Ni content of 50-75 wt%, the Fe content of less than 3 wt% and the S content of 15-25% is obtained.
In addition, the method for processing lateritic nickel ore according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the present invention, in step (1), the pretreatment includes a drying treatment, a crushing treatment, and a sieving treatment in this order.
In some embodiments of the invention, in step (2), the maximum particle size of the lateritic nickel ore particles and the reductant, respectively, is independently in the range of 2-10 mm.
In some embodiments of the invention, in step (2), the mass ratio of the lateritic nickel ore particles to the reductant is 100: 2.5-10.
In some embodiments of the invention, in step (2), the reductant is selected from at least one of anthracite and bituminous coal, coke.
In some embodiments of the present invention, in step (3), the temperature of the pre-reduction treatment is 700 ℃ to 800 ℃ for 1 to 3 hours.
In some embodiments of the invention, in step (4), the sulphide ore is selected from at least one of nickel concentrate, low-copper high-iron high-sulphur copper concentrate, pyrite.
In some embodiments of the present invention, in step (4), the temperature of the smelting process is 1300-1450 ℃ for 0.5-1 h.
In some embodiments of the invention, in step (4), the smelting solvent is selected from at least one of limestone and quartz.
In some embodiments of the invention, in the step (4), the mass ratio of the calcine to the sulfide ore is (0.5-1): 1, the mass ratio of the calcine to the smelting solvent is 1: (0.15-0.25).
In some embodiments of the invention, in step (4), the oxygen-enriched air has an oxygen concentration of 60-80% by volume.
In some embodiments of the invention, in step (4), the combustible fuel is natural gas and/or producer gas.
In some embodiments of the invention, in step (4), the FeO content of the smelting slag is 30-38 wt%, the MgO content is less than 10 wt%, and SiO2The content of (B) is 35-40 wt%, and the content of CaO is 5-15 wt%.
In some embodiments of the present invention, in step (5), the temperature of the blowing process is 1150- > 1350 ℃ and the time is 0.5-1 h.
In some embodiments of the invention, the blowing solvent is quartz.
In some embodiments of the present invention, the above method of treating lateritic nickel ores further comprises: and (4) returning the blowing slag to the step (4) for smelting treatment.
In some embodiments of the present invention, the above method of treating lateritic nickel ores further comprises: and (3) carrying out depletion treatment on the smelting slag so as to obtain second low-nickel matte and waste slag, and sending the second low-nickel matte to the step (5) for converting treatment.
In some embodiments of the present invention, the first matte and the second matte have Ni contents of 10 to 25 wt% respectively, Fe contents of 45 to 60 wt% respectively, and S contents of 10 to 25 wt% respectively.
In some embodiments of the invention, the temperature of the depletion treatment is 1350-.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic flow diagram of a method of treating lateritic nickel ores in accordance with one embodiment of the present invention;
fig. 2 is a schematic flow diagram of a method of treating lateritic nickel ores in accordance with yet another embodiment of the present invention;
fig. 3 is a schematic flow diagram of a method of treating lateritic nickel ores in accordance with yet another embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In one aspect of the invention, the invention proposes a method for treating lateritic nickel ores, according to an embodiment of the invention, with reference to fig. 1, the method comprising:
s100: pretreating laterite-nickel ore
In the step, the laterite-nickel ore is pretreated so as to obtain laterite-nickel ore particles. The inventors found that laterite-nickel ore particles meeting the requirements of the subsequent process can be obtained by pretreating laterite-nickel ore. It should be noted that the specific content of the pretreatment is not particularly limited, and those skilled in the art can select the pretreatment according to actual needs, such as the successive drying, crushing and screening treatments, and the successive drying, crushing and screening treatments can be included, and the laterite-nickel ore is suitable to be dried, crushed and screened in turn, so as to obtain laterite-nickel ore particles with the required particle size. Further, the maximum particle size of the lateritic nickel ore particles is also not particularly limited, such as may be 2-10 mm. The inventor finds that when the granularity of the laterite-nickel ore is too low, the smoke dust rate in the smelting operation process is high; after materials are put into the furnace, the materials are easy to be accumulated above the melt to form an interlayer, and the melting is influenced. When the granularity of the laterite-nickel ore is too high, the chemical reaction efficiency of valuable metal oxide and a reducing agent can be reduced, the effective utilization rate of subsequent sulphide ore is further reduced, and the recovery rate of valuable metal is reduced.
S200: mixing laterite nickel ore particles with a reducing agent
In the step, laterite-nickel ore particles and a reducing agent are mixed so as to obtain a mixed material. The inventor finds that the surface contact area of the laterite-nickel ore particles and the reducing agent can be remarkably increased by mixing the obtained laterite-nickel ore particles with the reducing agent, the subsequent pre-reduction process is facilitated, and the addition of the reducing agent is beneficial to extracting valuable metal elements in raw ores.
According to an embodiment of the present invention, the mass ratio of the lateritic nickel ore particles to the reducing agent is not particularly limited, and may be selected by those skilled in the art according to actual needs, such as 100: 2.5-10. The inventor finds that in the pre-reduction process, if a low-quality reducing agent is added into the laterite-nickel ore particles, the reducing agent required by the pre-reduction reaction is insufficient, the reduction condition is insufficient, and the formation of a subsequent low-nickel matte product is not facilitated; if the laterite nickel ore particles are added with a high-quality reducing agent, metallic iron oxide in the laterite nickel ore is greatly reduced, and a high-metallization low-nickel matte product is formed subsequently, so that the nickel grade of the nickel matte product is reduced. Further, the specific type and maximum particle size of the reducing agent are not particularly limited, and for example, the reducing agent may be selected from at least one of anthracite and bituminous coal, and coke, and the maximum particle size of the reducing agent may be 2 to 10 mm. The inventor finds that if the granularity of the reducing agent is too large, the reducing agent mainly participates in combustion heat compensation and has low reduction effect; if the reducing agent particles are too small, they are rapidly consumed during the melting process, and the reduction reaction does not proceed completely
S300: pre-reducing the mixed material
In the step, the mixed material is subjected to pre-reduction treatment so as to obtain calcine. The inventor finds that the mixed material is pre-reduced, so that the metal oxide embedded in the gangue can be effectively reduced, the vulcanization rate of subsequent metal can be improved, and the recovery rate of valuable metal can be improved.
According to an embodiment of the present invention, the specific conditions of the pre-reduction treatment are not particularly limited, and those skilled in the art can select the conditions according to actual needs, for example, the temperature of the pre-reduction treatment can be 700 ℃ to 800 ℃, and the time can be 1-3 h. The inventor finds that if the pre-reduction treatment temperature is too low, the time is too short, and the temperature condition for reducing valuable metals in the laterite-nickel ore and the time required for sufficient reduction cannot be met; if the temperature of the pre-reduction treatment is too high and the time is too long, the ring formation of the pre-reduction equipment is easily caused, and the smooth operation of the working procedure is influenced.
S400: the calcine, the sulphide ore, the smelting solvent, the combustible fuel and the oxygen-enriched air are smelted
In the step, the calcine, the sulphide ore, the smelting solvent, the combustible fuel and the oxygen-enriched air are smelted so as to obtain the first low-nickel matte and the smelting slag. The inventor finds that in the smelting process, oxygen-enriched air is adopted to combust combustible materials to heat and melt the materials, so that the smelting energy consumption is reduced, minerals can be rapidly melted due to the strong stirring action of the melt, the reaction efficiency is improved, furthermore, sulfide ores are used as metal particles in a sulfide reduction calcine of a vulcanizing agent in the smelting process, the use of the sulfide ores is favorable for reducing the use amount of a smelting solvent, the smelting temperature is reduced, meanwhile, the transportation cost and the production period can be greatly reduced by directly using the sulfide ores, the purposes of low cost, high efficiency, low energy consumption and green development of laterite nickel ore resources are achieved, further, the smelting solvent can enhance the efficiency of vulcanizing metal oxides in the sulfide ores, the metal recovery rate is improved, and the nickel-enriched laterite nickel ore withxFe1-xS、Ni3S2And a nickel matte of a mixture of NiFe alloys.
According to an embodiment of the present invention, the conditions of the smelting process are not particularly limited, for example, the temperature can be 1300-. The inventor finds that the side-blown converter adopts a mode of directly heating materials by combustion to melt the materials, and the heating efficiency is high. The smelting material is added into the furnace and directly enters a molten pool to react, and reduction and vulcanization reactions are carried out in the melting process to form a low-nickel matte product. If the temperature of the side blowing furnace is too high and the smelting time is too long, the oxygen potential in the slag is too high, so that foam slag is easily formed, and the smooth smelting is influenced; if the temperature of the side blowing furnace is too low and the smelting time is too short, the materials cannot be fully reflected, the nickel matte and the slag are not completely separated, so that the content of valuable metal elements in the slag is too high, and economic loss is caused. Further, the specific type of the sulfide ore is not particularly limited, and those skilled in the art can select the sulfide ore according to the local existing ore, such as at least one selected from nickel concentrate, low-copper high-iron high-sulfur copper concentrate, and pyrite. Further, the specific type of the smelting solvent is also not particularly limited, and may be at least one selected from the group consisting of limestone and quartz. Further, when the smelting solvent is a mixed material of quartz and limestone, the mass ratio of quartz to limestone can be 2-8: 1. further, the mass ratio of the calcine to the sulphide ore is (0.5-1): 1, the mass ratio of the calcine to the smelting solvent is 1: (0.15-0.25). The inventor finds that the adding amount of the smelting solvent is specifically determined according to the type components of the laterite nickel ore. If the content of a smelting solvent is too low, a low-nickel matte product is difficult to form in the smelting process due to the fact that the content of iron oxide in the mineral is too high; because the raw ore has high silicon and magnesium contents, in the smelting process, in order to reduce the smelting temperature and adjust the alkalinity and viscosity of the slag, limestone is properly added, if the proportion of the smelting solvent is too high, the melting point of the slag is easily increased, the viscosity is too high, the smelting temperature is too high, and the smelting cannot be carried out. If the mass ratio of the sulfide ore is too low, the equivalent of the effective sulfur brought in is insufficient, and valuable metals of nickel, cobalt and a small amount of iron in the mineral raw materials cannot be combined to form a nickel matte product. Therefore, the metal recovery rate can be improved while the energy consumption is reduced by adopting the mixing ratio.
Further, the oxygen concentration of the oxygen-enriched air may be 60-80% by volume. The inventor finds that if the concentration is too low, the heating is too slow, the heat supply efficiency is low, the melting and melting are difficult, and the smelting temperature of a furnace body is insufficient; if the concentration is too high, the oxygen potential in the slag is easy to be too large, so that the reduction reaction is reduced, the smelting time is too long, and foam slag can be formed to influence the smooth smelting. Further, the combustible material may be natural gas and/or producer gas.
Further, FeO, MgO and SiO in the smelting slag2And CaO content are also not particularly limited, and for example, FeO content may be 30 to 38 wt%, MgO content may be less than 10 wt%, SiO2May be present in an amount of 35-40 wt% and CaO in an amount of 5-15 wt%. The inventor finds that in the process of smelting low-nickel matte from laterite-nickel ore, the slag type components need to be controlled so as to obtain smelting slag with a proper melting point. Because the melting point temperature of the low nickel matte is lower and is between 1050 ℃ and 1200 ℃, the melting temperature of the smelting slag is adjusted by the component content in the slag and is generally controlled between 1250 ℃ and 1350 ℃. E.g. M in slagWhen the content of gO is too high, the melting point temperature of the slag is easy to rise; when the contents of FeO and CaO are too high or too low, the temperature of the smelting slag is easily increased relatively. Therefore, the component components in the slag are adjusted according to the contents of silicon and magnesium in the mineral raw materials so as to obtain the slag type components suitable for smelting low-nickel matte. Further, the contents of Ni, Fe and S in the first matte are also not particularly limited, and for example, the content of Ni may be 10 to 25 wt%, the content of Fe may be 45 to 60 wt%, and the content of S may be 10 to 25 wt%. The inventors have found that the level of nickel in the low nickel matte is mainly influenced by the metallic iron content. The low-nickel matte ensures that the slag has good smelting properties (melting point, viscosity, alkalinity and the like) while the grade of the nickel matte is improved as much as possible. If the sulfur content is too low, forming high-metallization low-nickel matte or forming ferronickel alloy; if the sulfur content is too high, the burden of the subsequent blowing sulfur removal process is increased.
S500: the first low-nickel matte and the converting solvent are subjected to converting and slagging treatment
In the step, the first low nickel matte and the converting solvent are subjected to converting and slagging treatment so as to obtain high nickel matte and converting slag. The inventor finds that the nickel enrichment can be further realized by blowing and slagging the first low-nickel matte obtained by smelting, and high-nickel matte with the Ni content of 50-75 wt%, the Fe content of less than 3 wt% and the S content of 15-25% is obtained. In the blowing process, because the binding capacities of metal nickel and iron and oxygen and sulfur are different, Fe and FeS in the low-nickel matte and oxygen-enriched O are enabled to be different2Combining to form FeO, and then the FeO and SiO in the slag2Slag is formed, so that the aim of removing iron and part of over-high sulfur in the low-nickel matte is fulfilled.
According to an embodiment of the present invention, the temperature of the blowing process may be 1150-. The inventor finds that the blowing temperature is too high, the blowing time is too long, the iron in the low-nickel matte is easy to enter the slag completely, and part of valuable metals form oxides and enter the slag to cause loss; the temperature is too low, the time is too short, and the aim of removing iron from low-nickel matte cannot be fulfilled. Further, the blowing solvent may be quartz.
According to still another embodiment of the present invention, referring to fig. 2, in order to further improve the recovery rate of nickel, the blown slag may be returned to step S400 to be subjected to a smelting process.
According to the method for treating the laterite-nickel ore, the laterite-nickel ore is pretreated, so that laterite-nickel ore particles meeting the requirements of subsequent procedures can be obtained; by mixing the obtained laterite-nickel ore particles with a reducing agent, the surface contact area of the laterite-nickel ore particles and the reducing agent can be remarkably increased, and the subsequent pre-reduction process is facilitated; the mixed material is pre-reduced, so that the metal oxide embedded in the gangue can be effectively reduced, the vulcanization rate of subsequent metal can be improved, and the recovery rate of valuable metal can be improved; in the smelting process, oxygen-enriched air is adopted to combust combustible materials to heat and melt the materials, so that the energy consumption of smelting is favorably reduced, minerals can be quickly melted due to the strong stirring action of the melts, the reaction efficiency is improved, furthermore, sulfide ores are used as metal particles in a sulfide reduction calcine of a vulcanizing agent in the smelting process, the use of the sulfide ores is favorable for reducing the use amount of a smelting solvent, the smelting temperature is reduced, meanwhile, the transportation cost and the production period can be greatly reduced by directly using the sulfide ores, the purposes of low cost, high efficiency, low energy consumption and green development of laterite-nickel ore resources are achieved, further, the smelting solvent can enhance the efficiency of sulfide ores for vulcanizing metal oxides, the metal recovery rate is improved, and the Ni-enriched nickel alloy is obtainedxFe1-xS、Ni3S2And a nickel matte of a mixture of NiFe alloys; the first low-nickel matte obtained by smelting is blown and slagged, so that the enrichment of nickel can be further realized, and high-nickel matte with the Ni content of 50-75 wt%, the Fe content of less than 3 wt% and the S content of 15-25% is obtained.
According to an embodiment of the invention, referring to fig. 3, the method for treating the red nickel ore further comprises:
s600: carrying out dilution treatment on the smelting slag
In this step, the smelting slag is subjected to depletion treatment to obtain second low nickel matte and waste slag, and the second low nickel matte is sent to step S500 to be subjected to converting treatment. The inventors have found that the second matte and the reject in the molten slag can be further separated by subjecting the molten slag obtained by the melting to a dilution treatmentThe slag and the valuable metal oxide or the valuable metal in the smelting slag are subjected to reduction and vulcanization reaction, the purposes of selective reduction and vulcanization are finally completed according to the strong and weak binding capacity of the metal nickel, cobalt and iron with oxygen and sulfur, the further separation of nickel and slag is realized, the recovery rate of nickel is further improved, and the Ni which is mainly Ni is finally obtainedxFe1-xS、Ni3S2And a second nickel matte of a mixture of NiFe alloys. Namely a melting slag depletion process, and mainly finishes low nickel matte which is not obtained by sedimentation separation in the melting process. And the obtained second low-nickel matte is subjected to converting treatment like the first low-nickel matte, so that high-nickel matte and converting slag can be obtained, and the recovery and enrichment rate of nickel is further improved.
According to an embodiment of the present invention, the conditions of the depletion treatment are not particularly limited, for example, the temperature of the depletion treatment may be 1350-. The inventor finds that the smelting temperature is too high, the time is too long, and the energy consumption is large; the smelting temperature is too low, the time is too short, and the sedimentation separation of the nickel matte is not facilitated. Further, the contents of Ni, Fe and S in the second matte are also not particularly limited, and for example, the content of Ni may be 10 to 25 wt%, the content of Fe may be 45 to 60 wt%, and the content of S may be 10 to 25 wt%.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for treating laterite-nickel ore is characterized by comprising the following steps:
(1) pretreating the laterite-nickel ore so as to obtain laterite-nickel ore particles;
(2) mixing the laterite-nickel ore particles with a reducing agent to obtain a mixed material;
(3) carrying out pre-reduction treatment on the mixed material so as to obtain calcine;
(4) smelting the calcine, the sulfide ore, a smelting solvent, combustible fuel and oxygen-enriched air to obtain first low-nickel matte and smelting slag;
(5) and carrying out converting and slagging treatment on the first low-nickel matte and the converting solvent so as to obtain high-nickel matte and converting slag.
2. The method according to claim 1, wherein in step (1), the pretreatment comprises a drying treatment, a crushing treatment and a sieving treatment in this order.
3. The method according to claim 1 or 2, characterized in that, in step (2), the maximum particle size of the lateritic nickel ore particles and the reductant, respectively, is independently 2-10 mm;
optionally, in step (2), the mass ratio of the lateritic nickel ore particles to the reducing agent is 100: 2.5-10;
optionally, in step (2), the reductant is selected from at least one of anthracite and bituminous coal, coke.
4. The method as claimed in claim 1, wherein in step (3), the temperature of the pre-reduction treatment is 700 ℃ and 800 ℃ for 1-3 h.
5. The method according to claim 1 or 4, wherein in step (4), the sulphide ore is selected from at least one of nickel concentrate, low copper high iron high sulphur copper concentrate, pyrite;
optionally, in the step (4), the temperature of the smelting treatment is 1300-1450 ℃, and the time is 0.5-1 h;
optionally, in step (4), the smelting solvent is selected from at least one of limestone and quartz;
optionally, in the step (4), the mass ratio of the calcine to the sulphide ore is (0.5-1): 1, the mass ratio of the calcine to the smelting solvent is 1: (0.15 to 0.25);
optionally, in the step (4), the volume concentration of oxygen in the oxygen-enriched air is 60-80%;
optionally, in step (4), the combustible fuel is natural gas and/or producer gas;
optionally, in the step (4), the content of FeO in the smelting slag is 30-38 wt%, the content of MgO is less than 10 wt%, and SiO is2The content of (B) is 35-40 wt%, and the content of CaO is 5-15 wt%.
6. The method as claimed in claim 1, wherein, in the step (5), the temperature of the blowing treatment is 1150- > 1350 ℃ and the time is 0.5-1 h;
optionally, the blowing solvent is quartz.
7. The method of claim 1, further comprising: and (4) returning the blowing slag to the step (4) for smelting treatment.
8. The method of claim 1, further comprising: and (3) carrying out depletion treatment on the smelting slag so as to obtain second low-nickel matte and waste slag, and sending the second low-nickel matte to the step (5) for converting treatment.
9. The method according to claim 8, characterized in that the first matte and the second matte have a Ni content of 10-25 wt% respectively, a Fe content of 45-60 wt% respectively, and a S content of 10-25 wt% respectively.
10. The method as claimed in claim 8, wherein the temperature of the depletion treatment is 1350-.
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| CN111811262A (en) * | 2020-07-21 | 2020-10-23 | 湖北大江环保科技股份有限公司 | Side-blowing type oxygen-enriched immersion smelting system |
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| CN113528858A (en) * | 2021-06-30 | 2021-10-22 | 广东邦普循环科技有限公司 | Method for preparing high-nickel ternary precursor through nickel-iron conversion and application thereof |
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| CN114438342A (en) * | 2022-04-11 | 2022-05-06 | 矿冶科技集团有限公司 | Method for producing high nickel matte from nickel-cobalt concentrate and high nickel matte |
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| CN111811262A (en) * | 2020-07-21 | 2020-10-23 | 湖北大江环保科技股份有限公司 | Side-blowing type oxygen-enriched immersion smelting system |
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| CN114854997A (en) * | 2022-03-31 | 2022-08-05 | 中南大学 | Injection type sulfur supplement and strengthening vulcanization method for laterite-nickel ore vulcanization smelting |
| CN114438342B (en) * | 2022-04-11 | 2022-06-17 | 矿冶科技集团有限公司 | Method for producing high nickel matte from nickel-cobalt concentrate and high nickel matte |
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| RU2817629C1 (en) * | 2023-08-15 | 2024-04-17 | Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) | Charge for reducing-sulphiding melting of oxidised nickel ores |
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