CN110735012B - Method for preparing electric furnace smelting ferronickel raw material by using laterite-nickel ore - Google Patents

Method for preparing electric furnace smelting ferronickel raw material by using laterite-nickel ore Download PDF

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CN110735012B
CN110735012B CN201911010765.2A CN201911010765A CN110735012B CN 110735012 B CN110735012 B CN 110735012B CN 201911010765 A CN201911010765 A CN 201911010765A CN 110735012 B CN110735012 B CN 110735012B
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nickel ore
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吕亚男
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Suzhou Vocational Institute of Industrial Technology
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00Obtaining noble metals
    • C22B11/10Obtaining noble metals by amalgamating
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/02Roasting processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/12Dry methods smelting of sulfides or formation of mattes by gases
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/10Reduction of greenhouse gas [GHG] emissions
    • Y02P10/143Reduction of greenhouse gas [GHG] emissions of methane [CH4]

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Abstract

The invention discloses a method for preparing a ferronickel alloy raw material by an electric furnace from laterite-nickel ore. The method comprises the following steps: (1) evenly mixing laterite-nickel ore and alkaline flux to prepare pellets; (2) roasting the pellets in an oxidizing atmosphere; (3) the roasted pellets are placed in a reactor, and mixed gas of carbon dioxide and water vapor is introduced for reaction. Compared with the existing method for preparing the ferronickel alloy raw material by the electric furnace through the coal-based rotary kiln and the gas-based shaft furnace, the method has the advantages of lower roasting temperature, relatively low energy consumption, and stable raw material of the prepared electric furnace, and is not easy to oxidize and spontaneously combust.

Description

Method for preparing electric furnace smelting ferronickel raw material by using laterite-nickel ore
Technical Field
The invention relates to a method for preparing a ferronickel alloy raw material by an electric furnace from laterite-nickel ore, belonging to the technical field of metallurgy.
Background
Nickel is an important strategic metal material, has the characteristics of corrosion resistance, oxidation resistance, high temperature resistance, high strength, good ductility and the like, and has wide application in modern industry. The nickel is mainly used for stainless steel production, and the requirement of the nickel for the stainless steel accounts for more than 60 percent of the total consumption amount of the global nickel. The mineral resources of nickel are mainly nickel sulphide ores and laterite-nickel ores, and about 70% of nickel exists in the laterite-nickel ores. Currently, the main method for preparing ferronickel alloy from laterite-nickel ore is the pre-reduction-smelting ferronickel process (RKFF). The method firstly needs coal or reducing gas and the like as reducing agents, reduces nickel and iron in the laterite-nickel ore into metallic iron and metallic nickel in a rotary kiln or a shaft furnace under the condition of high temperature, and then prepares the ferronickel alloy by smelting in an electric furnace.
At present, the method for preparing the ferronickel raw material by electric furnace smelting at home and abroad mainly comprises the following steps:
(1) the preparation method comprises the following steps of (1) preparing by adopting a coal-based rotary kiln: the method takes coal as a reducing agent, and reduces nickel and iron in the laterite-nickel ore into metallic iron and metallic nickel at high temperature (above 1000 ℃), thereby preparing the ferronickel raw material smelted by an electric furnace.
(2) Preparing by using a gas-based shaft furnace: the method takes natural gas, oil and the like as reducing agents, and nickel and iron in the laterite-nickel ore are reduced into metallic iron and metallic nickel at high temperature (800-.
However, the prior art also has the following problems:
(1) according to the traditional method for smelting the ferronickel raw material by the electric furnace prepared by the coal-based rotary kiln, nickel and iron in the prepared raw material mainly exist in the forms of metallic nickel and metallic iron, and because the embedded particle size of the iron in the raw material is fine, the part of the raw material is easy to oxidize and even spontaneously combust in the storage or transportation process, for example, by adopting the traditional method of briquetting after high-temperature passivation, the passivation treatment cost is greatly increased because most of components in the raw material are gangue. And coal is used as a reducing agent, the reduction temperature is high, and a large amount of nitrogen oxides, sulfides and other pollution gases are discharged in the smelting process.
(2) The method for preparing the ferronickel alloy raw material by the electric furnace smelting by the gas-based shaft furnace can greatly reduce the amount of nitrogen oxides, sulfides and other polluted gases by using a gas reducing agent, but the roasting temperature is higher, so that the energy consumption is higher, and the prepared raw material containing metallic iron and metallic nickel is easily oxidized or spontaneously combusted and is not easily treated by a high-temperature passivation briquetting.
Based on the analysis, the method adopting the traditional coal-based rotary kiln or gas-based shaft furnace has obvious defects in the aspect of processing the laterite-nickel ore. Therefore, it is very important to deeply research and develop a method which can reduce the pollutant emission and smelting energy consumption, and can prepare raw materials which are not easy to oxidize and spontaneously combust and convenient to store and transport.
Disclosure of Invention
The method aims to solve the problems that the method for preparing the ferronickel alloy by the electric furnace in the prior art has high energy consumption, and the prepared furnace burden is easy to oxidize and spontaneously combust and is not beneficial to transportation and storage. The invention provides a method for preparing a ferronickel alloy raw material by an electric furnace from laterite-nickel ore.
The invention is realized by the following technical scheme:
a method for preparing a ferronickel alloy raw material for smelting an electric furnace by using laterite-nickel ore comprises the following steps:
(1) evenly mixing laterite-nickel ore and alkaline flux to prepare pellets;
(2) roasting the pellets in an oxidizing atmosphere with the oxygen content of more than 4 percent;
(3) the roasted pellets are placed in a reactor, and mixed gas of carbon dioxide and water vapor is introduced for reaction.
The method for preparing the ferronickel raw material for smelting the electric furnace by using the laterite-nickel ore comprises the following steps of (3) arranging three reactors: placing the roasted pellets into a first reactor, introducing mixed gas of carburizing gas, water vapor and gas discharged by a third reactor into the first reactor, wherein the pressure in the reactor is 1-3MPa, the roasting temperature is 900-1000 ℃, and the roasting time is 20-60 min; after the reaction is finished, putting the obtained product into a second reactor, simultaneously discharging the gas in the first reactor into the second reactor, wherein the roasting temperature in the second reactor is 850-; and after the reaction is finished, putting the obtained product into a third reactor, and simultaneously discharging the gas in the second reactor into the third reactor, wherein the roasting temperature in the third reactor is 650-850 ℃, and the roasting time is 20-60 min.
In the method for preparing the ferronickel raw material for smelting the electric furnace by using the laterite-nickel ore, the proportion of the water vapor introduced into the first reactor to the total of the natural gas and the water vapor is not more than 30 percent.
In the method for preparing the ferronickel raw material for smelting the electric furnace by using the laterite-nickel ore, the ratio of the tail gas discharged from the third reactor in the gas introduced into the first reactor is not less than 20%.
In the method for preparing the ferronickel raw material for smelting the electric furnace by using the laterite-nickel ore, the carburizing gas is natural gas or methane.
The method for preparing the ferronickel alloy raw material for smelting the electric furnace by using the laterite-nickel ore is characterized in that the grain size of the laterite-nickel ore is less than 200 meshes, and the proportion of the grain size is more than 50%.
The method for preparing the ferronickel alloy raw material by the electric furnace from the laterite-nickel ore is characterized in that the alkaline fusing agent is limestone, and the dosage of the alkaline fusing agent is to adjust the alkalinity of the pellets to be 0.8-2.0.
The method for preparing the ferronickel raw material by the electric furnace from the laterite-nickel ore comprises the step (2), wherein the roasting temperature is 800-1100 ℃, and the roasting time is 10-30 min.
The invention achieves the following beneficial effects:
(1) compared with the prior method for preparing the ferronickel alloy raw material by the electric furnace by the coal-based rotary kiln and the gas-based shaft furnace method, the method has the advantages of lower roasting temperature and relatively low energy consumption.
(2) The iron in the furnace burden prepared by the invention mainly exists in the form of carbide, the iron can stably exist at normal temperature, spontaneous combustion and oxidation are avoided, and the carbon contained in the furnace burden can provide partial heat for the electric furnace smelting process, so that the energy consumption of the electric furnace smelting is reduced.
Drawings
FIG. 1 is a process flow diagram of the step (3) of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
The nickel grade of the laterite-nickel ore is 1.86 percent, and the iron grade is 21.30 percent. Firstly, grinding the laterite-nickel ore to a granularity of less than 200 meshes and accounting for 70 percent, then mixing quick lime and the laterite-nickel ore, adjusting the alkalinity to 1.2, preparing pellets, and roasting the pellets for 20min at 950 ℃ and under an oxidizing atmosphere with the oxygen content of 8 percent after drying. Placing the roasted pellets into a first reactor, and introducing mixed gas of natural gas, steam and tail gas of a third reactor into the first reactor, wherein the proportion of the steam is 5%, the proportion of the tail gas of the third reactor is 35%, the proportion of the natural gas is 60%, the pressure in the reactor is 1.5MPa, the roasting temperature is 950 ℃, and the roasting time is 30 min. The roasting temperature in the second reactor and the third reactor is 850 ℃ and 750 ℃, the roasting time is 20min and 30min, and the pressure of the second reactor is 1.5 MPa. The roasting gas in the second reactor is the gas discharged from the first reactor, and the roasting gas in the third reactor is the gas discharged from the second reactor. The pellets in the second reactor are the pellets roasted by the first reactor, and the pellets in the third reactor are the pellets roasted by the second reactor. The metallization rate of nickel in the finally obtained electric furnace charge is 98.2%, the metallization rate of iron is 11.2%, and the carbonization rate of iron is 87.0%.
The laterite nickel ore is prepared into pellets so that a material bed in a reactor has better air permeability, and gas in the reduction and carburization processes can be easily diffused to the surface of the material for reaction; the pellets are roasted in oxidizing atmosphere to convert nickel sulfide in the raw materials into nickel oxide, and the nickel oxide in the pellets is used for catalyzing methane to convert the methane into CO and H2Then CO and H2And (3) reducing the iron oxide.
Calcium oxide is added into the pellets to adjust the alkalinity, and no fluxing agent is needed to be added in the subsequent electric furnace smelting; the addition of flux in the pellets can also improve the strength of the pellets and increase the reduction rate of the pellets.
Introducing mixed gas of carbon dioxide and water vapor into the roasted pellets, wherein the nickel-containing pellets can be used as a catalyst for converting the mixed gas, the mixed gas can be converted into mixed gas of methane, carbon monoxide and hydrogen after passing through a first reactor, and the converted carbon monoxide and hydrogen in the first reactor can reduce iron minerals and nickel minerals in part of the pellets; the gas from the first reactor is continuously introduced into a second reactor, and methane is continuously converted into carbon monoxide and hydrogen in the second reactor, so that the second reactor contains carbon monoxide and hydrogen with higher concentration for reducing iron minerals and nickel minerals in the pellets, and the pellets in the second reactor are the pellets subjected to primary reduction in the first reactor; gas from the second reactor is continuously introduced into a third reactor for deep reduction and carburization, and metallic iron generated while iron minerals and nickel minerals are reduced by carbon monoxide and hydrogen in the third reactor continuously reacts with methane to generate iron carbide; ferronickel in the raw materials obtained after reaction in the three reactors mainly exists in the forms of metallic nickel, metallic iron and iron carbide, and can be directly used as a raw material for smelting ferronickel alloy in an electric furnace; one part of tail gas from the third reactor can be used for burning and heating the reactor, and the other part of tail gas is returned to the first reactor to react with methane, so that the content of carbon monoxide and hydrogen in the tail gas can be increased, and the tail gas is continuously used as a reducing agent and a carburizing agent for the pellets after the content of carbon dioxide and water vapor is reduced.
Example 2
The nickel grade of the laterite-nickel ore is 1.58 percent, and the iron grade is 18.10 percent. Firstly, grinding the laterite-nickel ore to a granularity of less than 200 meshes and accounting for 80%, then mixing quicklime and the laterite-nickel ore, adjusting the alkalinity to 1.0, preparing pellets, and roasting the pellets for 20min at 950 ℃ and under an oxidizing atmosphere with the oxygen content of 10% after drying. Placing the roasted pellets into a first reactor, and introducing mixed gas of biogas, steam and tail gas of a third reactor into the first reactor, wherein the proportion of the steam is 5%, the proportion of the tail gas of the third reactor is 20%, the proportion of the biogas is 75%, the pressure in the reactor is 1.8MPa, the roasting temperature is 1000 ℃, and the roasting time is 20 min. The roasting temperature in the second reactor and the third reactor is 900 ℃ and 700 ℃, the roasting time is 20min and 30min, and the pressure of the second reactor is 1.5 MPa. The roasting gas in the second reactor is the gas discharged from the first reactor, and the roasting gas in the third reactor is the gas discharged from the second reactor. The pellets in the second reactor are the pellets roasted by the first reactor, and the pellets in the third reactor are the pellets roasted by the second reactor. The proportion of the metal nickel in the finally obtained electric furnace charge is 99.2 percent, the proportion of the metal iron in the electric furnace charge is 13.2 percent, and the proportion of the iron carbide in the electric furnace charge is 85.0 percent.
Example 3
The nickel grade of the laterite-nickel ore is 1.25 percent, and the iron grade is 16.3 percent. Firstly, grinding the laterite-nickel ore to a granularity of less than 200 meshes and accounting for 80%, then mixing quicklime and the laterite-nickel ore, adjusting the alkalinity to 0.8, preparing pellets, and roasting the pellets for 20min at the temperature of 1000 ℃ and in an oxidizing atmosphere with the oxygen content of 12% after drying. Placing the roasted pellets into a first reactor, and introducing mixed gas of natural gas, steam and tail gas of a third reactor into the first reactor, wherein the proportion of the steam is 5%, the proportion of the tail gas of the third reactor is 30%, the proportion of the natural gas is 65%, the pressure in the reactor is 2.0MPa, the roasting temperature is 950 ℃, and the roasting time is 30 min. The roasting temperature in the second reactor and the third reactor is 900 ℃ and 650 ℃, the roasting time is 20min and 50min, and the pressure in the second reactor is 1.8 MPa. The roasting gas in the second reactor is the gas discharged from the first reactor, and the roasting gas in the third reactor is the gas discharged from the second reactor. The pellets in the second reactor are the pellets roasted by the first reactor, and the pellets in the third reactor are the pellets roasted by the second reactor. The proportion of the metal nickel in the finally obtained electric furnace charge is 99.2 percent, the proportion of the metal iron in the electric furnace charge is 16.3 percent, and the proportion of the iron carbide in the electric furnace charge is 81.0 percent.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (7)

1. A method for preparing a ferronickel alloy raw material for smelting an electric furnace by using laterite-nickel ore is characterized by comprising the following steps: (1) evenly mixing laterite-nickel ore and alkaline flux to prepare pellets;
(2) roasting the pellets in an oxidizing atmosphere with the oxygen content of more than 4 percent;
(3) placing the roasted pellets in a reactor, and introducing a mixed gas of carbon dioxide and water vapor for reaction; the reactor is provided with three reactors, and the specific reaction steps are as follows: placing the roasted pellets into a first reactor, introducing mixed gas of carburizing gas, water vapor and gas discharged by a third reactor into the first reactor, wherein the pressure in the reactor is 1-3MPa, the roasting temperature is 900-1000 ℃, and the roasting time is 20-60 min; after the reaction is finished, putting the obtained product into a second reactor, simultaneously discharging the gas in the first reactor into the second reactor, wherein the roasting temperature in the second reactor is 850-; and after the reaction is finished, putting the obtained product into a third reactor, and simultaneously discharging the gas in the second reactor into the third reactor, wherein the roasting temperature in the third reactor is 650-850 ℃, and the roasting time is 20-60 min.
2. The method for preparing ferronickel raw material for electric furnace smelting from lateritic nickel ores according to claim 1, characterized in that the proportion of the steam introduced into the first reactor to the total of natural gas and steam is not more than 30%.
3. The method for preparing ferronickel raw material for electric furnace smelting from lateritic nickel ore according to claim 2, characterized in that the ratio of the tail gas discharged from the third reactor in the gas introduced into the first reactor is not less than 20%.
4. The method for preparing ferronickel raw material for electric furnace smelting from lateritic nickel ore according to claim 3, characterized in that the carburizing gas is natural gas or biogas.
5. The method for preparing ferronickel raw material for electric furnace smelting from lateritic nickel ore according to claim 1, characterized in that the grain fraction of the lateritic nickel ore with the grain size of less than 200 meshes accounts for more than 50 percent.
6. The method for preparing ferronickel raw material for electric furnace smelting from lateritic nickel ore according to claim 5, characterized in that the alkaline flux is limestone in an amount to adjust the basicity of the pellets to 0.8-2.0.
7. The method for preparing the ferronickel raw material for the electric furnace smelting from the lateritic nickel ore according to the claim 5, characterized in that in the step (2), the roasting temperature is 800-.
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