CN115341106A - Method and device for producing high nickel matte from low nickel matte - Google Patents
Method and device for producing high nickel matte from low nickel matte Download PDFInfo
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- CN115341106A CN115341106A CN202211059047.6A CN202211059047A CN115341106A CN 115341106 A CN115341106 A CN 115341106A CN 202211059047 A CN202211059047 A CN 202211059047A CN 115341106 A CN115341106 A CN 115341106A
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- 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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- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ
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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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
- C22B9/106—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents the refining being obtained by intimately mixing the molten metal with a molten salt or slag
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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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/14—Refining in the solid state
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Abstract
The invention relates to the technical field of nickel smelting, and discloses a method and a device for producing high nickel matte by using low nickel matte, wherein the method comprises the following steps: continuously introducing solid low nickel matte and silicon dioxide into an oxygen-enriched converting furnace for converting to produce high nickel matte, converting slag and converting flue gas; and spraying a reducing agent, a vulcanizing agent and oxygen-enriched air II into the slag oxygen-enriched dilution bath reaction zone to carry out reduction and vulcanization reaction with the converting slag so as to produce high-cobalt low-nickel matte and dilution slag. The process for producing high nickel matte by using low nickel matte provided by the invention has the advantages of high nickel and cobalt recovery rate, stable smoke components and smoke amount and environmental friendliness.
Description
Technical Field
The invention relates to the technical field of nickel smelting, in particular to a method and a device for producing high nickel matte by using low nickel matte.
Background
The nickel ore mainly comprises nickel sulfide ore and nickel oxide ore.
The smelting process of nickel mainly comprises a pyrogenic process and a wet process.
The method is characterized in that the nickel sulfide ore is generally processed by a pyrogenic process, the nickel sulfide ore is oxidized and smelted to produce low nickel matte, and the low nickel matte is further processed by blowing to produce high nickel matte.
For nickel oxide ore, a wet leaching process and a pyrometallurgy process are mainly adopted, and the intermediate products in the pyrometallurgy process are nickel-iron alloy and low grade nickel matte.
The low grade nickel matte intermediate products produced from the sulphide ores and the oxide ores need to be further blown to produce high grade nickel matte.
At present, the blowing of low grade nickel matte adopts the traditional converter blowing process. The converter blowing process mainly has the following defects: the field operation environment is severe, the operation is interrupted, the fluctuation of the concentration of sulfur dioxide in the flue gas is large, the subsequent acid making process is not facilitated, the hot material to be smelted is blown, the cold material is difficult to be blown separately, the service cycle of a furnace lining of a blowing furnace, particularly a tuyere brick, is short, and the recovery rate of nickel and cobalt is low.
Disclosure of Invention
The invention aims to overcome the defects existing in the air refining process of low grade nickel matte in the prior art, and provides a process for producing high grade nickel matte from low grade nickel matte with high nickel cobalt recovery rate.
In order to achieve the above object, a first aspect of the present invention provides a method for producing high nickel matte from low nickel matte, the method comprising:
(1) Low nickel matte converting
Continuously introducing solid low nickel matte and a flux I into an oxygen-enriched air refining furnace for air refining to produce high nickel matte, air refining slag and air refining flue gas;
(2) Oxygen-enriched dilution of blowing slag
Spraying a reducing agent, a vulcanizing agent and oxygen-enriched air II into a slag depletion furnace of a slag oxygen-enriched depletion bath reaction zone, and intermittently leading out blown slag from the oxygen-enriched blowing furnace to flow into the slag depletion furnace of the slag oxygen-enriched depletion bath reaction zone through a slag chute to perform a reduction vulcanization reaction to produce high-cobalt low-nickel matte and depleted slag; controlling the oxygen surplus coefficient alpha of the oxygen-enriched air II to the reducing agent to be 0.4-0.5; controlling the temperature in the slag dilution furnace to 1250-1400 ℃; and returning the high-cobalt low-nickel matte to the oxygen-enriched converting furnace for converting.
The second aspect of the present invention provides an apparatus for producing high nickel matte from low nickel matte, comprising:
an oxygen-enriched converting furnace;
a slag depletion furnace;
the slag chute is connected with the oxygen-enriched converting furnace and the slag depleting furnace;
the oxygen-enriched converting furnace and the slag dilution furnace both comprise vertical fixed furnace bodies;
the vertical fixed furnace body comprises a gas phase zone furnace body, a furnace top cover, a molten pool reaction zone furnace body formed by adopting a water cooling structure and a furnace hearth built by refractory materials;
the furnace hearth is provided with a slag tap and a siphon channel, the shell of the furnace hearth consists of a steel frame, a pull rod and a spring component, the spring component is positioned between the steel frame and the pull rod, and the shell of the furnace hearth is of an elastic structure.
The process for producing high nickel matte by using low nickel matte provided by the invention has the advantages of high nickel and cobalt recovery rate, stable smoke components and smoke amount and environmental friendliness.
In addition, SO in flue gas obtained by the process for producing high nickel matte from low nickel matte 2 The concentration is high, which is beneficial to acid preparation; furthermore, the acid making process can be separated from a smelting system to independently operate cold materials, so that the furnace body of the device for producing high nickel matte by low nickel matte has a long operation period.
Drawings
FIG. 1 is a process flow diagram for producing high nickel matte from low nickel matte according to the present invention;
FIG. 2 is a front view and a side view of an oxygen-rich converting furnace in the apparatus for producing high nickel matte from low nickel matte according to the present invention;
FIG. 3 is a schematic connection diagram of the apparatus for producing high nickel matte from low nickel matte according to the present invention.
Description of the reference numerals
a. An oxygen-enriched converting furnace; b. a slag chute; c. slag dilution furnace
1. A hearth; 2. a flat water jacket; 3. a layer of water-cooled pieces; 4. a second layer of water-cooling piece; 5. masonry of refractory material; 6. a water-cooling water jacket; 7. a smoke exhaust flue; 8. a flue water jacket; 9. a feed aperture; 10. a furnace roof; 11. a tertiary air port; 12. a secondary air port; 13. a slag tap; 14. a primary air port; 15. a nickel matte discharging port; 16. a steel frame; 17. pull rod
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously mentioned, a first aspect of the present invention provides a method for producing high nickel matte from low nickel matte, the method comprising:
(1) Low nickel matte converting
Continuously introducing the solid low nickel matte and the flux I into an oxygen-enriched converting furnace for converting to produce high nickel matte, converting slag and converting flue gas;
(2) Oxygen-enriched dilution of blowing slag
Spraying a reducing agent, a vulcanizing agent and oxygen-enriched air II into a slag depletion furnace of a slag oxygen-enriched depletion bath reaction zone, and intermittently leading out blown slag from the oxygen-enriched blowing furnace to flow into the slag depletion furnace of the slag oxygen-enriched depletion bath reaction zone through a slag chute to perform a reduction vulcanization reaction to produce high-cobalt low-nickel matte and depleted slag; controlling the oxygen surplus coefficient alpha of the oxygen-enriched air II to the reducing agent to be 0.4-0.5; controlling the temperature in the slag dilution furnace to 1250-1400 ℃; and returning the high-cobalt low-nickel matte to the oxygen-enriched converting furnace for converting.
In the present invention, the oxygen surplus coefficient α of the oxygen-enriched air II to the reducing agent = the actual supplied oxygen molar amount/the theoretical oxygen molar amount required for complete reaction of the system.
Preferably, in the step (1), the solid low grade nickel matte contains 20wt% to 25wt% of nickel element, 45wt% to 55wt% of iron element, 0.5wt% to 1.5wt% of cobalt element and 20wt% to 35wt% of sulfur element.
Preferably, in step (1), the blown slag flows through a slag chute into a slag-depletion furnace of the slag-oxygen-enrichment-depletion bath reaction zone; the flux I is silicon dioxide; controlling the conditions in the oxygen-enriched blowing furnace and controlling the dosage weight ratio of the solid low nickel matte to the flux I, so that the mass ratio of iron elements to silicon dioxide in the blowing slag is 1.5-2.5:1.
according to a preferred embodiment, in step (1), the method further comprises: and spraying oxygen-enriched air I into the oxygen-enriched converting furnace.
Preferably, in the step (1), the volume concentration of oxygen in the oxygen-enriched air I is 40-70%, and the pressure of the injected oxygen-enriched air I is 0.08-0.2 MPa.
Preferably, in step (1), the method further comprises: and spraying pulverized coal into a primary tuyere in the oxygen-enriched converting furnace, wherein the spraying amount of the pulverized coal is 1 to 3 weight percent of the amount of the material fed into the furnace, and the amount of the material fed into the furnace is the sum of the amounts of the solid low grade nickel matte and the flux I.
The present invention has no particular requirements on the particle size and source of the pulverized coal, and one skilled in the art can practice the present invention using pulverized coal known in the art.
Preferably, in the step (1), the converting temperature in the oxygen-rich converting furnace is 1250 to 1350 ℃.
Preferably, in step (1), the method further comprises: and the blown flue gas is sequentially passed through a waste heat boiler to recover waste heat, and an electric dust remover removes dust and then is introduced into a flue gas acid making system for post-treatment.
Preferably, in the step (2), the method further comprises: introducing a flux II into a slag dilution furnace in a slag oxygen-rich dilution molten pool reaction zone; the flux II is limestone.
Preferably, in the step (2), the method further comprises: introducing a flux II into a slag depletion furnace in a slag oxygen enrichment depletion molten pool reaction zone; the flux II is calcium oxide and/or calcium carbonate.
Preferably, in step (2), the method further comprises: introducing a flux II into a slag dilution furnace in a slag oxygen-rich dilution molten pool reaction zone; the flux II is calcium oxide and/or calcium carbonate; the introduction amount of the flux II is such that the slag in the slag-depleted furnace is CaO/SiO 2 In a weight ratio of 0.3-0.6:1.
preferably, in the step (2), the reducing agent is selected from at least one of coke powder, bituminous coal and anthracite coal; the amount of the reducing agent having a particle size of 200 mesh or more is 80wt% or more; the weight ratio of the blowing slag to the reducing agent is 100:5 to 15.
Preferably, in the step (2), the vulcanizing agent is sulfur, and the amount of the vulcanizing agent with a particle size of 200 meshes or more is 80wt% or more; the weight ratio of the blowing slag to the vulcanizing agent is 100:3 to 5.
Preferably, in the step (2), the volume concentration of the oxygen in the oxygen-enriched air II is 60-80%, and the pressure of the injected oxygen-enriched air II is 0.2-0.4 MPa.
According to a preferred embodiment, in step (2), the reducing agent is injected into the oxygen-rich slag-depleted bath reaction zone by means of compressed air at a pressure of from 0.6MPa to 0.8MPa, and the sulfidizing agent is injected into the oxygen-rich slag-depleted bath reaction zone by means of nitrogen at a pressure of from 0.6MPa to 0.8 MPa.
Preferably, in the step (2), the conditions of the reduction and vulcanization reaction are controlled so that the metallization rate Me of the high-cobalt low-nickel matte is realized Form(s) of 0.20 to 0.4; wherein Me is Form(s) of ＝(S Theory of the invention -S In fact )/S Theory of the invention ，S Theory of the invention Is the theoretical mass content of sulfur element in high-cobalt low-nickel matte, S Practice of The theoretical mass content of the sulfur element in the high-cobalt low-nickel matte is the theoretical sulfur content when the iron element, the nickel element and the cobalt element in the high-cobalt low-nickel matte are completely vulcanized.
Preferably, in the step (2), the time of the blown slag participating in the reduction vulcanization reaction in the slag depletion furnace is 1.5-2.0h, the slag tapping time of the blown slag is 2-3h, and the slag tapping time interval of the depleted slag is 2-3h.
In the invention, the slag discharging interval of the high-cobalt low-nickel matte is determined according to the amount of slag materials.
The method for producing high nickel matte by low nickel matte according to the present invention is described in a preferred embodiment with reference to fig. 1, and comprises:
(1) Solid low nickel matte (namely 'low nickel matte' shown in figure 1) and a flux I (namely 'silicon dioxide' shown in figure 1) are mixed by a metering belt and then are continuously introduced into an oxygen-enriched converting furnace for converting, oxygen-enriched air I is sprayed into a molten pool of the oxygen-enriched converting furnace through a primary air port of a furnace body of a molten pool reaction area, pulverized coal (namely 'coal' shown in figure 1) is sprayed into a primary air port of the oxygen-enriched converting furnace, and secondary air is introduced into the oxygen-enriched converting furnace at the same time to produce high nickel matte, converting slag and converting smoke; water quenching the intermittently discharged high nickel matte; discharging the blown slag from the end slag tap every 2-3 hours, flowing into the slag depletion furnace in the step (2) through a slag chute, sequentially passing the blown flue gas through a waste heat boiler to recover waste heat, dedusting by an electric precipitator, and introducing into a flue gas acid making system for post-treatment;
controlling the conditions to ensure that the mass ratio of the iron element to the silicon dioxide in the blowing slag is 1.5-2.5:1; the volume concentration of oxygen in the oxygen-enriched air I is 40-70%, and the pressure of the injected oxygen-enriched air I is 0.08-0.2 MPa; the spraying amount of the pulverized coal is 1 to 3 weight percent of the amount of the materials fed into the furnace; the blowing temperature in the oxygen-enriched blowing furnace is 1250-1350 ℃;
(2) Spraying a flux II (specifically shown as 'limestone' in figure 1), a reducing agent, a vulcanizing agent, oxygen-enriched air II and blown slag into a slag depletion furnace in a slag oxygen enrichment depletion molten pool reaction zone to carry out reduction vulcanization reaction, simultaneously introducing secondary oxygen-enriched gas into the slag oxygen enrichment depletion molten pool reaction zone, and controlling the conditions of the reduction vulcanization reaction so as to ensure that the metallization rate Me of the high-cobalt low-nickel matte is Me Form(s) of 0.20-0.4, high-cobalt low-nickel matte, depleted slag and high-temperature flue gas are produced; spraying a reducing agent through compressed air, and spraying a vulcanizing agent through nitrogen;
controlling the oxygen excess coefficient alpha of the oxygen-enriched air II to the reducing agent to be 0.4-0.5; controlling the temperature of a slag dilution furnace in a slag oxygen enrichment dilution molten pool reaction zone to be 1250-1400 ℃; the pressure of the compressed air is 0.6Mpa to 0.8Mpa;the pressure of nitrogen is 0.6Mpa to 0.8Mpa; the introduction amount of the flux II is such that the slag in the slag-depleted furnace is CaO/SiO 2 In a weight ratio of 0.3:1 to 0.6:1; the weight ratio of the blowing slag to the reducing agent is 100:5 to 15 percent; the weight ratio of the blowing slag to the vulcanizing agent is 100:3 to 5; the volume concentration of oxygen in the oxygen-enriched air II is 60-80%, and the pressure of the oxygen-enriched air II is 0.2-0.4 MPa.
The low nickel matte is blown and oxidized in the oxygen-enriched blowing furnace to produce high nickel matte and blowing slag, the blowing slag enters the slag depletion furnace to be reduced and vulcanized, and the obtained low nickel matte can return to the oxygen-enriched blowing furnace to be blown continuously. In the step (1), nickel sulfide and iron sulfide need to be converted into nickel oxide, iron oxide and sulfur dioxide in the oxygen-enriched converting furnace, impurities such as iron and sulfur are removed through oxidation, so more oxygen is needed, and meanwhile, a flux needs to be added to separate impurities such as iron oxide in the melt. In the step (2), the slag depletion furnace needs to reduce and sulfide nickel oxide in the blowing slag into nickel sulfide for enrichment, and if the oxygen content is too high, the reduction is insufficient, so that the nickel enrichment effect is poor. In order to obtain higher nickel yield, the invention controls the oxidation-reduction degree by respectively controlling different oxygen concentrations, different pressures, different temperatures, different proportions of other raw materials, different feeding methods and the like of oxygen-enriched air sprayed into the oxygen-enriched converting furnace and the slag-depletion furnace.
As previously described, a second aspect of the present invention provides an apparatus for producing high nickel matte from low nickel matte, the apparatus comprising:
an oxygen-enriched converting furnace;
a slag depletion furnace;
the slag chute is connected with the oxygen-enriched converting furnace and the slag depleting furnace;
the oxygen-enriched converting furnace and the slag dilution furnace both comprise vertical fixed furnace bodies;
the vertical fixed furnace body comprises a gas phase zone furnace body, a furnace top cover, a molten pool reaction zone furnace body formed by adopting a water cooling structure and a furnace hearth built by refractory materials;
the furnace hearth is provided with a slag tap and a siphon channel, a shell of the furnace hearth consists of a steel frame, a pull rod and a spring part, the spring part is positioned between the steel frame and the pull rod, and the shell of the furnace hearth is of an elastic structure.
Preferably, the vertical fixed furnace body also comprises a flue.
Preferably, in the furnace body of the reaction zone of the molten pool, the water cooling structure is formed by combining a plurality of layers of water cooling pieces, and the water cooling pieces are copper water jackets or molten steel jackets; the water cooling piece positioned at the lowest part of the furnace body is a layer of water cooling piece, the upper part of the layer of water cooling piece is a layer of water cooling piece, and the layer of water cooling piece is provided with at least two primary air ports; the angle of the tuyere is-5 to 5 degrees in the horizontal direction;
the primary tuyere of the oxygen-enriched converting furnace is used for spraying oxygen-enriched air I, and the primary tuyere of the slag-depleting furnace is used for spraying oxygen-enriched air II, a reducing agent and a vulcanizing agent; and a charging hole of the slag depletion furnace is used for adding a fusing agent II.
Preferably, the gas phase zone furnace body is formed by alternately adopting refractory brickworks and water-cooling water jacket structures, and the thickness of the refractory brickworks between the water-cooling water jacket structures is 200 mm-400 mm respectively and independently.
Preferably, the furnace top cover adopts a water cooling structure, the water cooling structure is formed by combining a plurality of layers of water cooling pieces, the water cooling pieces are copper water jackets or steel water jackets, and the furnace top cover is provided with at least 1 feeding hole.
Preferably, a slag tap is arranged at one end of the furnace body of the reaction zone of the molten pool, which is higher than the tuyere.
Preferably, the water jackets of the reaction zones of the molten pool of the oxygen-enriched converting furnace and the slag-depleted furnace are connected with the steel frame through pull rods.
The following describes a preferred embodiment of the apparatus for producing high nickel matte from low nickel matte according to the present invention with reference to fig. 2 and 3, the apparatus comprising:
an oxygen-enriched converting furnace a;
a slag dilution furnace c;
the slag chute b is connected with the oxygen-enriched converting furnace a and the slag dilution furnace c;
the oxygen-enriched converting furnace a and the slag depletion furnace c both comprise vertical fixed furnace bodies;
the vertical fixed furnace body comprises a gas phase zone furnace body, a furnace top cover 10, a molten pool reaction zone furnace body formed by adopting a water cooling structure, and a furnace hearth 1 built by refractory materials;
the slag tap 13 and the siphon channel are arranged on the hearth 1, the shell of the hearth 1 consists of a steel frame 16, a pull rod 17 and a spring component, the spring component is positioned between the steel frame and the pull rod, and the shell of the hearth is of an elastic structure.
Preferably, a nickel matte discharge port 15 is provided on the hearth 1 to discharge high-cobalt low-nickel matte.
Preferably, the upper surface of the hearth 1 is provided with a flat water jacket 2.
Preferably, in the furnace body of the reaction zone of the molten pool, the water cooling structure is formed by combining a plurality of layers of water cooling pieces, and the water cooling pieces are copper water jackets or molten steel jackets; the water cooling piece positioned at the lowest part of the furnace body is a layer of water cooling piece 3, the upper part of the layer of water cooling piece 3 is a layer of water cooling piece 4, wherein, the layer of water cooling piece 3 is provided with at least two primary air ports 14; the angle of the primary air port is-5 to 5 degrees in the horizontal direction.
Preferably, the two-layer water cooling member 4 is provided with not less than two secondary tuyeres 12.
Preferably, the angle of each secondary tuyere is each independently 0 ° to 30 ° downward in the horizontal direction.
Preferably, the cross-sectional area ratio of the primary tuyere of the oxygen-enriched converting furnace a to the primary tuyere of the slag-depleted furnace c is 1.1 to 1.25:1.
preferably, the oxygen-rich converting furnace is located higher than the slag-depleted furnace.
Preferably, the gas phase zone furnace body is formed by adopting a structure of alternately arranging refractory brickworks 5 and water-cooling water jackets 6, and the thickness of the refractory brickworks between the water-cooling water jacket structures is 200 mm-400 mm respectively and independently.
Preferably, three air ports 11 are arranged on two sides of the furnace body of the gas phase zone and used for injecting air or oxygen-enriched air into the furnace, and the angle of each three air port is 0-30 degrees downwards along the horizontal direction independently.
Preferably, the furnace roof 10 is provided with a smoke exhaust flue 7, a flue water jacket 8.
Preferably, the furnace top cover 10 adopts a water cooling structure, the water cooling structure is formed by combining a plurality of layers of water cooling pieces, the water cooling pieces are copper water jackets or molten steel jackets, and the furnace top cover 10 is provided with at least 1 feeding hole 9.
Preferably, the water jackets of the reaction zones of the oxygen-enriched converting furnace and the slag-depleted furnace are connected with the steel frame 16 through a pull rod 17.
Preferably, a slag tap 13 is arranged at one end of the furnace body of the reaction zone of the molten pool, which is higher than the tuyere.
The scheme provided by the invention has the characteristics of short process flow, low energy consumption, good environmental protection effect, high automation degree and the like, and particularly has the following advantages:
(1) The invention adopts continuous feeding and continuous oxygen-enriched blowing, and the vulcanizing agent is slightly excessive, so that the concentration of the sulfur dioxide in the flue gas is high and stable, the acid preparation by the flue gas is facilitated, and the problems of large concentration fluctuation and low air pollution of the sulfur dioxide in the flue gas blown by the low nickel matte converter at present are solved;
(2) According to the invention, cold charge blowing is adopted, and a blowing system can be operated independently without smelting, so that the problems that hot charge blowing of the converter must be configured with smelting at present, and cold charge blowing is difficult to operate independently are solved;
(3) The special blowing and slag depletion device adopted by the invention reduces the temperature, and the tuyere area adopts a water cooling structure of a copper water jacket or a steel water jacket, so that the service life of the furnace body is longer, and the problem of short service cycle caused by overhigh temperature of the refractory material masonry of the blowing furnace body of the converter, especially the refractory material masonry of the tuyere area, is solved;
(4) According to the invention, the hot blowing slag flows into the slag depletion furnace through the slag chute, and reduction and vulcanization reaction is carried out in the slag depletion furnace, so that nickel and cobalt are fully recovered, high-cobalt low-nickel matte can be produced, the low-nickel matte obtained by reduction and enrichment is obtained, and the problem of low nickel and cobalt recovery rate is solved;
(5) The oxygen-enriched converting furnace is provided with the tertiary air ports, so that the introduction amount of the oxygen enrichment is increased, and the slag and the high nickel matte are better separated by controlling the proportion of the raw materials, so that the purity of the high nickel matte is improved.
The present invention will be described in detail below by way of examples. In the following examples, the raw materials used are all common commercial products unless otherwise specified.
The following examples were carried out using the process flow shown in FIG. 1, unless otherwise specified.
The solid low grade nickel matte has a composition of, calculated on element basis, 22.5wt% nickel, 49.09wt% Fe, 0.81wt% cobalt, 27.6wt% sulfur.
The following nickel recovery rate = [ (the sum of the mass of nickel elements in the high nickel matte product and the high cobalt low nickel matte product)/the mass of nickel elements in the solid low nickel matte raw material ] × 100%;
the following cobalt recovery = [ (the sum of the mass of cobalt elements in the high nickel matte product and the high cobalt low nickel matte product)/the mass of cobalt elements in the low nickel matte material ] × 100%.
Example 1
(1) Solid low nickel matte and silicon dioxide are proportioned by a metering belt and then are continuously introduced into an oxygen-enriched converting furnace through a charging hole for converting, oxygen-enriched air I is sprayed into a melting bath of the oxygen-enriched converting furnace through a primary air port of a melting bath reaction zone furnace body, pulverized coal is sprayed into a primary air port of the oxygen-enriched converting furnace, and high nickel matte, converting slag and converting smoke are produced; discharging the high nickel matte intermittently and quenching with water; blowing slag is discharged from an end slag tap every 2 hours and flows into the slag depletion furnace in the step (2) through a slag chute, and blowing flue gas is introduced into a flue gas acid making system for post-treatment after sequentially passing through a waste heat boiler to recover waste heat and an electric dust remover to remove dust;
controlling the conditions to ensure that the mass ratio of the iron element to the silicon dioxide in the blowing slag is 2.0:1; the volume concentration of oxygen in the oxygen-enriched air I is 50 percent, and the pressure of the oxygen-enriched air is 0.2Mpa; the spraying amount of the pulverized coal is 1wt% of the amount of the materials fed into the furnace; the blowing temperature in the oxygen-enriched blowing furnace is 1250 ℃;
(2) After the blowing slag flows into the slag dilution furnace through the slag chute, limestone is added through the charging hole, a reducing agent, a vulcanizing agent and oxygen-enriched air II are sprayed into the slag dilution furnace in the slag oxygen-enriched dilution bath reaction zone through the primary air port to carry out reduction vulcanization reaction, and the conditions of the reduction vulcanization reaction are controlled, so that the metallization rate Me of the high-cobalt low-nickel matte is realized Form(s) of The cobalt content is 0.20, and high-cobalt low-nickel matte and depleted slag are produced; the reducing agent is sprayed in through compressed air, and the vulcanizing agent is sprayed in through nitrogen;
controlling the oxygen surplus coefficient alpha of the oxygen-enriched air II to the reducing agent to be 0.4; control slag oxygen enrichment depletion molten poolThe temperature in the slag depletion furnace in the reaction zone is 1250 ℃; the pressure of the compressed air is 0.6Mpa; the pressure of nitrogen is 0.6Mpa; the quantity of flux II (calcium oxide) is such that the slag is depleted in CaO/SiO of the slag in the furnace 2 In a weight ratio of 0.3:1; the dosage weight ratio of the blowing slag to the reducing agent (anthracite) is 100:5; the weight ratio of the blowing slag to a vulcanizing agent (sulfur) is 100:3; the volume concentration of oxygen in the oxygen-enriched air II is 80 percent, and the pressure of the oxygen-enriched air II is 0.3Mpa.
And the blown flue gas is sequentially passed through a waste heat boiler to recover waste heat, and an electric dust remover removes dust and then is introduced into a flue gas acid making system for post-treatment.
As a result:
high nickel matte: based on the mass content of the elements, ni was 73.94%, co was 1.82%, fe was 1.8%, and S was 21.77%.
High cobalt low nickel matte: based on the mass content of the elements, ni was 20.50%, co was 4.60%, fe was 45.44%, and S was 28.20%.
The nickel recovery rate is 99.5%, and the cobalt recovery rate is 86.3%.
Example 2
This example was carried out using a similar process to that of example 1, except that in this example:
(1) The spraying amount of the pulverized coal is 2wt% of the amount of the materials fed into the furnace; the converting temperature in the oxygen-enriched converting furnace is 1300 ℃;
(2) Controlling the oxygen surplus coefficient alpha of the oxygen-enriched air II to the reducing agent to be 0.5; controlling the temperature in a slag dilution furnace in the slag oxygen enrichment dilution molten pool reaction area to be 1300 ℃; the weight ratio of the blowing slag to the reducing agent (pulverized coal) is 100:10; the weight ratio of the blowing slag to a vulcanizing agent (sulfur) is 100:4.
as a result:
high nickel matte: based on the element contents, ni was 74.52%, co was 1.92%, fe was 1.25%, and S was 21.86%.
High cobalt low nickel matte: based on the element contents, ni was 22.60%, co was 4.77%, fe was 50.35%, and S was 29.16%.
The nickel recovery rate was 99.41% and the cobalt recovery rate was 85.32%.
Example 3
This example was carried out using a similar process to example 1, except that in this example:
(1) The spraying amount of the pulverized coal is 3 percent of the amount of the materials fed into the furnace;
(2) Controlling the oxygen surplus coefficient alpha of the oxygen-enriched air II to the reducing agent to be 0.5; the weight ratio of the blowing slag to the reducing agent (pulverized coal) is 100:15; the weight ratio of the blowing slag to a vulcanizing agent (sulfur) is 100:5.
as a result:
high nickel matte: based on the mass content of the elements, ni was 75.52%, co was 1.72%, fe was 1.05%, and S was 22.13%.
High cobalt low nickel matte: based on the element contents by mass, ni was 25.10%, co was 5.32%, fe was 39.92%, and S was 29.20%.
The nickel recovery rate is 99.6 percent, and the cobalt recovery rate is 88.32 percent.
Example 4
This example was carried out using a similar process to example 1, except that in this example:
(1) Controlling the conditions to ensure that the mass ratio of the iron element to the silicon dioxide in the blowing slag is 1.8:1; the volume concentration of oxygen in the oxygen-enriched air I is 60 percent, and the pressure of the oxygen-enriched air is 0.2Mpa; the blowing temperature in the oxygen-enriched blowing furnace is 1350 ℃;
(2) The flux II (calcium oxide) is introduced in such an amount that the slag in the slag-depleted furnace is CaO/SiO 2 In a weight ratio of 0.4:1; the volume concentration of oxygen in the oxygen-enriched air II is 80 percent, and the pressure of the oxygen-enriched air II is 0.4Mpa; the temperature in the slag-depleted furnace in the slag-enriched oxygen-depleted bath reaction zone is controlled to 1350 ℃.
High nickel matte: based on the mass content of the elements, ni was 74.38%, co was 1.45%, fe was 1.65%, and S was 21.23%.
High cobalt low nickel matte: based on the mass content of the elements, ni was 25.20%, co was 6.37%, fe was 39.62%, and S was 27.50%.
The nickel recovery was 99.52% and the cobalt recovery was 89.32%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (19)
1. A method for producing high nickel matte from low nickel matte is characterized by comprising the following steps:
(1) Low nickel matte converting
Continuously introducing solid low nickel matte and a flux I into an oxygen-enriched air refining furnace for air refining to produce high nickel matte, air refining slag and air refining flue gas;
(2) Oxygen-enriched dilution of blowing slag
Spraying a reducing agent, a vulcanizing agent and oxygen-enriched air II into a slag depletion furnace of a slag oxygen-enriched depletion molten pool reaction area, and intermittently introducing the converting slag into the slag depletion furnace of the slag oxygen-enriched depletion molten pool reaction area from the oxygen-enriched converting furnace to carry out reduction vulcanization reaction so as to produce high-cobalt low-nickel matte and depletion slag; controlling the oxygen surplus coefficient alpha of the oxygen-enriched air II to the reducing agent to be 0.4-0.5; controlling the temperature in the slag dilution furnace to be 1250-1400 ℃; and returning the high-cobalt low-nickel matte to the oxygen-enriched converting furnace for converting.
2. The process defined in claim 1 wherein, in step (1), the blown slag flows through a slag chute into a slag-depleted furnace of the oxygen-rich slag-depleted bath reaction zone; the flux I is silicon dioxide; controlling the conditions in the oxygen-enriched converting furnace to ensure that the mass ratio of the iron element in the converting slag to the silicon dioxide is 1.5-2.5:1.
3. the method of claim 1, wherein in step (1), the method further comprises: and spraying oxygen-enriched air I into the oxygen-enriched converting furnace.
4. The method as claimed in claim 3, wherein, in the step (1), the oxygen concentration of the oxygen-enriched air I is 40-70% by volume, and the pressure of the injected oxygen-enriched air I is 0.08-0.2 MPa.
5. The method of claim 1, wherein in step (1), the method further comprises: and spraying pulverized coal into a primary air port in the oxygen-enriched air converting furnace, wherein the spraying amount of the pulverized coal is 1-3 wt% of the amount of the material entering the furnace, and the amount of the material entering the furnace is the sum of the amounts of the solid low nickel matte and the flux I.
6. The method as claimed in claim 1, wherein, in the step (1), the blowing temperature in the oxygen-rich blowing furnace is 1250 to 1350 ℃.
7. The method of claim 1, wherein in step (1), the method further comprises: and the converting flue gas is introduced into a flue gas acid making system for post-treatment after sequentially passing through a waste heat boiler for waste heat recovery and an electric dust remover for dust removal.
8. The method of any one of claims 1-7, wherein in step (2), the method further comprises: adding a flux II to the slag-depleted furnace; the flux II is limestone.
9. The method according to any one of claims 1 to 7, wherein, in step (2), the reductant is selected from at least one of coke powder, bituminous coal and anthracite coal; the amount of the reducing agent with the particle size of more than 200 meshes is more than 80 wt%; the dosage weight ratio of the blowing slag to the reducing agent is 100:5 to 15.
10. The process according to any one of claims 1 to 7, wherein in step (2), the vulcanizing agent is sulfur, and the amount of the vulcanizing agent having a particle size of 200 mesh or more is 80wt% or more; the dosage weight ratio of the blowing slag to the vulcanizing agent is 100:3 to 5.
11. The method as claimed in any one of claims 1 to 7, wherein, in the step (2), the oxygen concentration of the oxygen-enriched air II is 60% to 80% by volume, and the pressure of the injected oxygen-enriched air II is 0.2MPa to 0.4MPa.
12. The process defined in any one of claims 1 to 7 wherein, in step (2), the reducing agent is injected into the oxygen-rich slag-depleted bath reaction zone by compressed air at a pressure of from 0.6 to 0.8MPa and the sulfidizing agent is injected into the oxygen-rich slag-depleted bath reaction zone by nitrogen at a pressure of from 0.6 to 0.8 MPa.
13. The method according to any one of claims 1 to 7, wherein in step (2), the conditions of the reduction sulfurization reaction are controlled so that the metallization ratio Me of the high-cobalt low-nickel matte is such that Form(s) of 0.20 to 0.4; wherein Me is Form(s) of ＝(S Theory of the invention -S Practice of )/S Theory of the invention ，S Theory of the invention Is the theoretical mass content of sulfur element in the high-cobalt low-nickel matte, S In fact The theoretical mass content of the sulfur element in the high-cobalt low-nickel matte is the theoretical sulfur content when the iron element, the nickel element and the cobalt element in the high-cobalt low-nickel matte are completely vulcanized.
14. The method as claimed in any one of claims 1 to 7, wherein in the step (2), the time for the blown slag to participate in the reduction and vulcanization reaction in the slag-depleted furnace is 1.5 to 2.0h, the slag tapping time of the blown slag is 2 to 3h, and the slag tapping time interval of the depleted slag is 2 to 3h.
15. An apparatus for producing high nickel matte from low nickel matte is characterized in that the apparatus comprises:
an oxygen-enriched converting furnace;
a slag depletion furnace;
the slag chute is connected with the oxygen-enriched converting furnace and the slag-depleting furnace;
the oxygen-enriched converting furnace and the slag depletion furnace both comprise vertical fixed furnace bodies;
the vertical fixed furnace body comprises a gas phase zone furnace body, a furnace top cover, a molten pool reaction zone furnace body formed by adopting a water cooling structure, and a furnace hearth built by refractory materials;
the furnace hearth is provided with a slag tap and a siphon, the shell of the furnace hearth consists of a steel frame, a pull rod and a spring part, the spring part is positioned between the steel frame and the pull rod, and the shell of the furnace hearth is of an elastic structure.
16. The apparatus of claim 15, wherein in the molten bath reaction zone shaft, the water-cooling structure is combined by multiple layers of water-cooling pieces, and the water-cooling pieces are copper water jackets or molten steel jackets; the water cooling piece positioned at the lowest part of the furnace body is a layer of water cooling piece, the upper part of the layer of water cooling piece is a layer of water cooling piece, and the layer of water cooling piece is provided with at least two primary air ports; the angle of the primary air port is-5 to 5 degrees in the horizontal direction;
the primary air port of the oxygen-enriched converting furnace is used for spraying oxygen-enriched air I, and the primary air port of the slag-depleting furnace is used for spraying oxygen-enriched air II, a reducing agent and a vulcanizing agent; and a feeding hole of the slag depletion furnace is used for adding a fusing agent II.
17. The apparatus defined in claim 15 wherein the gas phase zone shaft is formed by alternating refractory bricks and water-cooled jacket structures, the thickness of the refractory bricks between the water-cooled jacket structures being 200mm to 400mm each independently.
18. The device of claim 15, wherein the furnace top cover adopts a water cooling structure, the water cooling structure is formed by combining a plurality of layers of water cooling pieces, and the water cooling pieces are copper water jackets or molten steel jackets; the furnace top cover is provided with at least 1 feeding hole.
19. The apparatus defined in claim 15 wherein the molten bath reaction zone shaft is provided with a tap hole at an end thereof above the tuyeres.
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| CN202211059047.6A CN115341106A (en) | 2022-08-30 | 2022-08-30 | Method and device for producing high nickel matte from low nickel matte |
| PCT/CN2023/115145 WO2024046244A1 (en) | 2022-08-30 | 2023-08-28 | Method and apparatus for producing high-nickel matte from low-nickel matte |
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| CN202211059047.6A CN115341106A (en) | 2022-08-30 | 2022-08-30 | Method and device for producing high nickel matte from low nickel matte |
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| CN116162804A (en) * | 2023-02-22 | 2023-05-26 | 浙江华友钴业股份有限公司 | Method for producing high nickel matte and molten iron from ferronickel |
| WO2024046244A1 (en) * | 2022-08-30 | 2024-03-07 | 中伟新材料股份有限公司 | Method and apparatus for producing high-nickel matte from low-nickel matte |
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| JP5125543B2 (en) * | 2008-01-23 | 2013-01-23 | 住友金属鉱山株式会社 | Method for producing sulfide containing nickel and cobalt |
| CN101358297B (en) * | 2008-07-15 | 2011-01-12 | 朝阳昊天有色金属有限公司 | Method for preparing high nickel matte |
| CN101358294A (en) * | 2008-07-16 | 2009-02-04 | 朝阳昊天有色金属有限公司 | Method for preparing high nickel matte |
| CN101705367B (en) * | 2009-11-23 | 2012-09-05 | 长沙有色冶金设计研究院有限公司 | Copper nickel smelting process with oxygen-enriched side-blowing bath smelting method |
| CN102851518B (en) * | 2012-08-24 | 2014-04-02 | 赤峰富邦铜业有限责任公司 | Fubang oxygen-enriched side-blown bath copper smelting furnace and operation method thereof |
| CN115386738B (en) * | 2022-08-10 | 2023-12-12 | 广东邦普循环科技有限公司 | Method for producing high nickel matte by reducing, vulcanizing and smelting laterite-nickel ore |
| CN218059144U (en) * | 2022-08-30 | 2022-12-16 | 中伟新材料股份有限公司 | Device for producing high nickel matte from low nickel matte |
| CN115341106A (en) * | 2022-08-30 | 2022-11-15 | 中伟新材料股份有限公司 | Method and device for producing high nickel matte from low nickel matte |
| CN116162804B (en) * | 2023-02-22 | 2023-12-12 | 浙江华友钴业股份有限公司 | Method for producing high nickel matte and molten iron from ferronickel |
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| WO2024046244A1 (en) * | 2022-08-30 | 2024-03-07 | 中伟新材料股份有限公司 | Method and apparatus for producing high-nickel matte from low-nickel matte |
| CN116162804A (en) * | 2023-02-22 | 2023-05-26 | 浙江华友钴业股份有限公司 | Method for producing high nickel matte and molten iron from ferronickel |
| CN116162804B (en) * | 2023-02-22 | 2023-12-12 | 浙江华友钴业股份有限公司 | Method for producing high nickel matte and molten iron from ferronickel |
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