CN111705225A - Method and device for preparing nickel matte - Google Patents
Method and device for preparing nickel matte Download PDFInfo
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- CN111705225A CN111705225A CN202010725996.8A CN202010725996A CN111705225A CN 111705225 A CN111705225 A CN 111705225A CN 202010725996 A CN202010725996 A CN 202010725996A CN 111705225 A CN111705225 A CN 111705225A
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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
- C22B23/025—Obtaining nickel or cobalt by dry processes with formation of a matte or by matte refining or converting into nickel or cobalt, e.g. by the Oxford process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/16—Evaporating by spraying
- B01D1/18—Evaporating by spraying to obtain dry solids
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/504—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific device
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
- F27D17/004—Systems for reclaiming waste heat
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
- F27D17/008—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases cleaning gases
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- B01D2258/02—Other waste gases
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention discloses a method and a device for preparing nickel matte. Wherein, the method comprises the following steps: s1, melting and pre-reducing the nickel-containing material, fuel, compressed air, reducing agent and vulcanizing agent in a smelting furnace to obtain liquid matte slag; s2, sending the liquid matte slag into an electrothermal reduction furnace for reduction and slag matte separation to obtain a nickel comb; and desulfurizing the flue gas generated in the steps S1 and S2 by adopting an active lime spray drying method, wherein all the desulfurized solid products are used as slagging raw materials for nickel matte smelting, and the desulfurized liquid products are circularly used for desulfurizing the flue gas by adopting the spray drying method. By applying the technical scheme of the invention, the desulfurized solid product is completely used as a slagging raw material for nickel matte smelting; the desulfurization liquid product is continuously recycled for the desulfurization of the flue gas by a spray drying method, so that zero emission of sulfur dioxide is realized; this approach creates a closed loop system for product production, waste utilization, and environmental control issues.
Description
Technical Field
The invention relates to the technical field of metal smelting, in particular to a method and a device for preparing nickel matte.
Background
Nickel has the characteristics of oxidation resistance, corrosion resistance, high temperature resistance, high strength, good ductility and the like, has wide application, particularly has the largest specific gravity in the smelting industry of steel and nonferrous metals, is applied to the industries of light industry, mechanical manufacturing, chemical industry, petroleum, electric power and the like, and has vigorous demand on nickel in the high and new technical field.
The world's land-based nickel reserves are about 417 million tons, 39.14% existing in the form of sulphide ores, while about 70% of the world's nickel is extracted from sulphide ores, giving nickel present in oxidic deposits up to 60.16% of the nickel reserves. Along with the depletion of the economically-usable nickel sulfide ore and high-grade laterite-nickel ore resources, the economic development of a great deal of existing low-grade laterite-nickel ore becomes a research hotspot of the current nickel metallurgy.
At present, the method for preparing nickel matte by using laterite nickel ore mainly comprises sintering furnace, blast furnace and rotary kiln processes, and the main sources of sulfur elements are sulfur, pyrite, gypsum and the like, but the method does not relate to how to harmlessly treat sulfur-containing slag after low-nickel matte is formed and completely recover the sulfur-containing slag. For example, CN 109680164 a discloses a method for preparing nickel matte, comprising: feeding the laterite-nickel ore and/or the nickel-containing waste slag into a melting furnace to obtain liquid molten high-nickel slag; and feeding the liquid molten high nickel slag and a vulcanizing agent into a matte making furnace for matte making and smelting to obtain nickel matte and slag.
Disclosure of Invention
The invention aims to provide a method and a device for preparing nickel matte, which aim to solve the technical problem that the sulfur slag in the nickel matte preparation process is not subjected to harmless treatment in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing nickel matte. The method comprises the following steps: s1, melting and pre-reducing the nickel-containing material, fuel, compressed air, reducing agent and vulcanizing agent in a smelting furnace to obtain liquid matte slag; s2, sending the liquid matte slag into an electrothermal reduction furnace for reduction and slag matte separation to obtain a nickel comb; and desulfurizing the flue gas generated in the steps S1 and S2 by adopting an active lime spray drying method, wherein all the desulfurized solid products are used as slagging raw materials for nickel matte smelting, and the desulfurized liquid products are circularly used for desulfurizing the flue gas by adopting the spray drying method.
Further, the nickel-containing material is laterite-nickel ore, and before the nickel-containing material, the reducing agent and the vulcanizing agent are introduced into the smelting furnace, the method further comprises the following steps: the nickel-containing material, the reducing agent, the fusing agent and the vulcanizing agent are granulated and then are sent into a smelting furnace by a belt conveyor.
Further, the smelting furnace is a top-blown furnace, a side-blown furnace, a bottom-blown furnace or an ore-smelting electric furnace; the smelting temperature in the smelting furnace is 1150-1450 ℃.
Further, the flue gas generated in the steps S1 and S2 is firstly subjected to secondary combustion and waste heat recovery by a waste heat boiler, and then is subjected to dust collection by an electric dust collector and desulfurization by adopting an active lime spray drying method.
Further, the smelting temperature in the electric heating reduction furnace is 1500-1650 ℃.
Further, slag is obtained in the reduction and slag matte separation processes, and the method further comprises the step of water quenching the slag.
Further, the method comprises the step of converter blowing the nickel matte.
Further, converter slag and flue gas are also obtained in the converter blowing process, and the method further comprises the following steps: returning the converter slag to the melting and pre-reduction step; and desulfurizing the obtained flue gas by adopting an active lime spray drying method.
Further, the vulcanizing agent is one or more of pyrite, sulfur and gypsum.
Further, during the melting and pre-reduction process, the slag form is controlled to comprise FeO, MgO and SiO2And CaO.
According to another aspect of the present invention, there is provided an apparatus for producing nickel matte. The device includes: the top of the side-blown smelting furnace is provided with a first inlet and a first flue gas outlet, the side part of the side-blown smelting furnace is provided with an immersed side-blown spray gun, the lower part of the side-blown smelting furnace is provided with a liquid-state fused matte slag-containing outlet, the first inlet is used for introducing a nickel-containing material and a reducing agent, and the immersed side-blown spray gun is used for injecting fuel and oxygen-enriched air into the side-blown smelting furnace; the electric heating reduction furnace is provided with a liquid-state molten matte slag inlet and a second flue gas outlet, and the liquid-state molten matte slag inlet is connected with the liquid-state molten matte slag outlet through a hot slag chute; the active lime spray drying desulfurization unit is provided with a flue gas inlet, a liquid inlet, a desulfurized solid product outlet and a desulfurized liquid product outlet, wherein the flue gas inlet is communicated with a first flue gas outlet of the side-blown smelting furnace and a second flue gas outlet of the electrothermal reduction furnace, the desulfurized solid product outlet is communicated with a first inlet of the side-blown smelting furnace, and the desulfurized liquid product outlet is communicated with a liquid inlet of the active lime spray drying desulfurization unit.
Further, the device also comprises a disc granulator, wherein the disc granulator is used for granulating the nickel-containing material, the reducing agent, the fusing agent and the vulcanizing agent, and an outlet of the disc granulator is connected with the first inlet.
Further, the apparatus further comprises: the bin is provided with a second inlet and a bin outlet, and the second inlet is connected with the outlet of the disc granulator; the quantitative feeder is provided with a third inlet and a feeding outlet, the third inlet is connected with the outlet of the storage bin, and the feeding outlet is connected with the first inlet.
Further, the apparatus further comprises: the first combustion unit is connected with the first flue gas outlet and is used for carrying out secondary combustion on the first flue gas discharged from the first flue gas outlet; the first waste heat recovery unit is provided with a first air inlet and a first exhaust port, and the first air inlet is connected with an outlet of the first combustion unit; and the first dust collecting unit is provided with a second air inlet, a second exhaust port and a first smoke outlet, and the second air inlet is connected with the first exhaust port.
Further, the first dust collection unit is an electric dust collector.
Further, the apparatus further comprises: the second combustion unit is connected with the second flue gas outlet and is used for carrying out secondary combustion on the second flue gas discharged from the second flue gas outlet; the second waste heat recovery unit is provided with a third air inlet and a third air outlet, and the third air inlet is connected with the outlet of the second combustion unit; and the second dust collecting unit is provided with a fourth air inlet, a fourth air outlet and a second smoke outlet, and the fourth air inlet is connected with the third air outlet.
Further, the second dust collection unit comprises a surface cooler and a bag dust collector which are sequentially connected in series.
Furthermore, the electric heating reduction furnace is also provided with a nickel matte outlet, and the device also comprises a converting converter, wherein the converting converter is connected with the nickel matte outlet.
Further, the converting converter is provided with a converter slag outlet, and the converter slag outlet is connected with the first inlet of the side-blown smelting furnace.
Furthermore, the converting converter is provided with a third flue gas outlet which is communicated with a flue gas inlet of the active lime spray drying desulfurization unit.
Furthermore, the electric heating reduction furnace is provided with a reduced slag outlet, and the device also comprises a water quenching unit which is connected with the reduced slag outlet.
By applying the technical scheme of the invention, the flue gas is desulfurized by adopting an active lime spray drying method in the nickel matte preparation process, and all desulfurized solid products are used as slagging raw materials for nickel matte smelting; the desulfurization liquid product is continuously recycled for the desulfurization of the flue gas by a spray drying method, so that zero emission of sulfur dioxide is realized; wherein, the desulfurized solid product is decomposed into calcium oxide and sulfur dioxide at high temperature, calcium oxide slag type smelting is adopted, and the calcium oxide formed by desulfurization can be completely used for slag batching; the slag has low melting point and good fluidity, is beneficial to the smooth smelting process, and has low content of valuable metals in the smelting waste slag; and sulfur dioxide decomposed at high temperature is continuously desulfurized and absorbed by adopting an active lime spray drying method to form circular disposal, so that the complete zero emission of sulfur-containing substances is achieved. This approach creates a closed loop system for product production, waste utilization, and environmental control issues.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a schematic flow diagram for the preparation of nickel matte according to an embodiment of the invention;
FIG. 2 is a block diagram showing an apparatus for preparing a nickel comb according to an embodiment of the present invention;
fig. 3 shows a schematic structural view of a side-blown smelting furnace, an electrothermal reduction furnace and an activated lime spray drying desulfurization unit according to an embodiment of the present invention.
Wherein the figures include the following reference numerals:
10. a side-blown smelting furnace; 20. an electrothermal reduction furnace; 30. a disc granulator; 40. a storage bin; 50. a constant feeder; 60. a first combustion unit; 70. a first waste heat recovery unit; 80. a first dust collecting unit; 90. a second combustion unit; 100. a second waste heat recovery unit; 110. a second dust collecting unit; 120. blowing a converter; 130. an acid making system; 140. a water quenching unit; 150. a dosing unit; 160. and an active lime spray drying desulfurization unit.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
The existing technology for preparing nickel matte from laterite only considers how to prepare nickel matte, but does not consider how to solve the problems of waste utilization and environmental protection caused by nickel matte preparation in the system, and the technical schemes usually transfer waste utilization to other disposal systems to complete, thereby causing unnecessary cost investment.
In view of the above, the present invention proposes the following technical solutions. According to an exemplary embodiment of the present invention, a method for producing nickel matte is provided. Referring to fig. 1, the method includes the steps of: s1, melting and pre-reducing the nickel-containing material, fuel, compressed air, reducing agent and vulcanizing agent in a smelting furnace to obtain liquid matte slag; s2, sending the liquid matte slag into an electrothermal reduction furnace for reduction and slag matte separation to obtain a nickel comb; and desulfurizing the flue gas generated in the steps S1 and S2 by adopting an active lime spray drying method, wherein all the desulfurized solid products are used as slagging raw materials for nickel matte smelting, and the desulfurized liquid products are circularly used for desulfurizing the flue gas by adopting the spray drying method.
By applying the technical scheme of the invention, the flue gas is desulfurized by adopting an active lime spray drying method in the nickel matte preparation process, and all desulfurized solid products are used as slagging raw materials for nickel matte smelting; the desulfurization liquid product is continuously recycled for the desulfurization of the flue gas by a spray drying method, so that zero emission of sulfur dioxide is realized; wherein, the desulfurized solid product is decomposed into calcium oxide and sulfur dioxide at high temperature, calcium oxide slag type smelting is adopted, and the calcium oxide formed by desulfurization can be completely used for slag batching; the slag has low melting point and good fluidity, is beneficial to the smooth smelting process, and has low content of valuable metals in the smelting waste slag; and sulfur dioxide decomposed at high temperature is continuously desulfurized and absorbed by adopting an active lime spray drying method to form circular disposal, so that the complete zero emission of sulfur-containing substances is achieved. This approach creates a closed loop system for product production, waste utilization, and environmental control issues.
In order to further improve the pre-reduction effect of the nickel-containing material, improve the selective reduction degree of nickel, and simultaneously reduce the feeding difficulty and improve the slagging effect, in a preferred embodiment, the nickel-containing material is laterite-nickel ore, and before the step of introducing the nickel-containing material, a vulcanizing agent and a reducing agent into the side-blown reduction furnace, the method further comprises the following steps: the nickel-containing material, the reducing agent, the fusing agent and the vulcanizing agent are granulated and then are sent into a smelting furnace by a belt conveyor. The reducing agent is a solid reducing agent, such as granular coal, coke and the like, the fluxing agent can be a type commonly used in the field, such as a calcium fluxing agent, a siliceous fluxing agent and the like, the fuel can be a powdery fuel, such as pulverized coal, or a gaseous fuel, such as coal gas, natural gas and the like, and the vulcanizing agent can be selected from a type commonly used in the field, such as pyrite, gypsum and the like. In the actual operation process, the weight ratio of the laterite-nickel ore, the reducing coal, the vulcanizing agent and the flux can be adjusted by a person skilled in the art according to the actual situation.
Taking the laterite-nickel ore as an example, the laterite-nickel ore is aired to volatilize part of free water, and is preferably loosened properly. After the laterite-nickel ore, the reducing coal, the vulcanizing agent and the flux with proper water content are granulated by a disc granulator, the granules are conveyed into a front bin of a smelting furnace by a rubber belt conveyor and are continuously conveyed into the smelting furnace by a quantitative feeder and a movable rubber belt conveyor. The melting furnace of the present invention may be a top-blown furnace, a side-blown furnace, a bottom-blown furnace, an ore-smelting electric furnace, or the like.
In a typical embodiment of the invention, the smelting temperature in the smelting furnace is 1150-1450 ℃, and in this temperature range, on one hand, the smelting furnace is favorable for saving energy consumption, on the other hand, the lower reduction temperature is favorable for improving the selective reduction of nickel, so that the preparation for higher nickel matte grade is made, and the selective reduction of nickel is improved, so that the preparation for higher nickel comb grade is made. And then, introducing the liquid molten matte slag obtained by pre-reduction into an electrothermal reduction furnace through a hot slag chute, and completing deep reduction at a higher temperature (preferably 1500-1650 ℃) (only the liquid matte slag in the electrothermal reduction furnace is not added with other reagents, the required reagents are completely added in the ingredients; and the temperature in the electrothermal reduction furnace is high, and the reducing agent plays a deep reduction role). The electric heating reduction furnace can control the reduction temperature more flexibly, the temperature is increased or decreased according to the property of the furnace charge, and the foam slag phenomenon can be avoided in the operation process, thereby further improving the nickel matte grade.
Preferably, the controlled slag form comprises FeO, MgO, SiO during melting and pre-reduction2And CaO, more preferably the slag form is controlled to be FeO 28-32%, MgO < 12%, SiO2In order to provide a weak reducing atmosphere in the side-blown smelting furnace to improve the pre-reduction effect, in a preferred embodiment, the air excess coefficient α in the side-blown smelting furnace is controlled to be 0.75-0.95 during the melting and pre-reduction process, namely the combustion coefficient, the air excess coefficient- (actual combustion air amount-theoretical combustion air amount)/theoretical combustion air amount, the excess air ensures sufficient combustion, and a reasonable coefficient ensures low cost (less heat is taken away by flue gas).
In the process of melting and pre-reducing the nickel-containing material in the smelting furnace and in the process of reducing in the electrothermal reduction furnace, smoke is generated, and in a preferred embodiment, the method further comprises the steps of sequentially carrying out secondary combustion, waste heat recovery and dust collection on the smoke. The secondary combustion can be used for carrying out secondary combustion on combustible components in the flue gas, the obtained flue gas is higher in temperature, and after waste heat is recovered through the waste heat recovery step, the dust in the flue gas is separated through the dust collection step. The heat in the pre-reduction flue gas is effectively recovered and the smoke dust in the pre-reduction flue gas is separated through the steps. It should be noted that, in addition to the dust collecting step, a part of the dust is also collected in the waste heat recovery step. The part of smoke dust can return to the granulating step, and is granulated after being mixed with nickel-containing materials, reducing agents and the like, and then enters the reduction process again. Because the temperature in the pre-reduction process is lower, the dust collection step of the first flue gas is preferably carried out in an electric precipitation mode directly.
In the actual operation process, the reduction process in the electrothermal reduction furnace is preferably carried out continuously, and the feeding, the slag discharging and the carding are carried out periodically. The electrothermal reduction furnace is provided with four discharging ports, wherein two reducing furnace slag outlets and two nickel matte outlets. In a preferred embodiment, slag is also obtained during the reduction and slag matte separation, and the method further comprises the step of water quenching the slag. The electric heating reduction furnace slag is stockpiled or sold as general solid waste after water quenching.
After obtaining the nickel matte, more preferably, as shown in fig. 1, the above method further includes a step of converter blowing the nickel matte. High-nickel matte with higher grade can be prepared by converter blowing. Specific blowing processes are well known to those skilled in the art and will not be described in detail herein.
In order to make more full use of resources, in a preferred embodiment, converter slag and flue gas are also obtained during converter blowing, and the method further comprises: returning the converter slag to the melting and pre-reduction step; the flue gas is desulfurized by adopting an active lime spray drying method.
According to another aspect of the present invention, there is also provided an apparatus for preparing nickel matte, as shown in fig. 2 and 3, the apparatus comprising: the side-blown smelting furnace 10 is provided with a first inlet at the top, an immersed side-blown spray gun is arranged at the side, a liquid-state fused matte slag outlet is arranged at the lower part, the first inlet is used for introducing nickel-containing materials and reducing agents, the immersed side-blown spray gun is used for spraying fuel and oxygen-enriched air (oxygen and compressed air can be used) into the side-blown smelting furnace 10, and the side-blown smelting furnace 10 is used for melting and pre-reducing the nickel-containing materials in the presence of the fuel, the oxygen-enriched air and the reducing agents to obtain the liquid-state fused matte slag; the electric heating reduction furnace 20 is provided with a liquid-state molten matte slag inlet, the liquid-state molten matte slag inlet is connected with a liquid-state molten matte slag outlet through a hot slag chute, and the electric heating reduction furnace 20 is used for reducing the liquid-state molten matte slag and separating slag matte to obtain nickel matte; the active lime spray drying desulfurization unit 160 is provided with a flue gas inlet, a liquid inlet, a desulfurized solid product outlet and a desulfurized liquid product outlet, the flue gas inlet is communicated with a first flue gas outlet of a side-blown smelting furnace and a second flue gas outlet of an electrothermal reduction furnace, the desulfurized solid product outlet is communicated with a first inlet of the side-blown smelting furnace, a desulfurized liquid product outlet is communicated with a liquid inlet of the active lime spray drying desulfurization unit, the active lime spray drying desulfurization unit 160 carries out desulfurization purification treatment on flue gas, all desulfurized solid products are used as slagging raw materials for nickel matte smelting, and desulfurized liquid products are circularly used for spray drying desulfurization of the flue gas.
By utilizing the device provided by the invention, the nickel-containing material is treated by the side-blown smelting furnace 10 and the electrothermal reduction furnace 20 in sequence, so that the nickel-containing material is firstly melted and pre-reduced in the side-blown smelting furnace 10 and then is reduced and slag-matte separation is carried out in the electrothermal reduction furnace 20. In the side-blown smelting furnace 10, oxygen-enriched air and fuel can be directly sprayed into a molten pool through an immersed side-blown spray gun at the furnace side to provide heat for melting and pre-reduction of nickel-containing materials, the heat utilization rate can be improved, immersed combustion flame directly contacts with a melt, combustion flue gas stirs the molten pool, mass transfer of the molten pool is strengthened, reaction is accelerated, and the laterite-nickel ore granular materials are quickly melted, so that the melting and pre-reduction process can be carried out in an oxygen-enriched state and at a lower reduction temperature (1150-1450 ℃). This is advantageous on the one hand for saving energy consumption and on the other hand for increasing the selective reduction of nickel by lower reduction temperatures, thereby providing for a higher nickel matte grade. And then, the liquid molten matte slag obtained by pre-reduction is introduced into an electrothermal reduction furnace 20 through a hot slag chute, and deep reduction is completed at a high temperature (1500-1650 ℃). The reduction temperature can be more flexibly controlled by adopting the electrothermal reduction furnace 20, the temperature can be increased or decreased according to the property of the furnace charge, and the phenomenon of foaming slag can be avoided in the operation process, thereby further improving the nickel matte grade.
In a preferred embodiment, the apparatus further comprises a disk granulator 30, the disk granulator 30 being adapted to granulate the nickel containing material, the reducing agent, the flux and the vulcanizing agent, the outlet of the disk granulator 30 being connected to the first inlet. More preferably, the apparatus further comprises a batching unit 150, the batching unit 150 is used for batching the nickel-containing material, the reducing agent, the fusing agent and the vulcanizing agent, and the batched raw materials are sent to the disc granulator 30 through a belt conveyor for granulation.
More preferably, as shown in fig. 2, the apparatus further comprises: a bin 40 provided with a second inlet and a bin outlet, the second inlet being connected to the outlet of the disc granulator 30; the constant feeder 50 is provided with a third inlet and a feeding outlet, the third inlet is connected with the bin outlet, and the feeding outlet is connected with the first inlet. The arrangement can stably and quantitatively convey the raw materials into the side-blown smelting furnace 10, and is beneficial to maintaining the continuity and stability of the operation of the equipment.
The nickel-containing material generates flue gas during the melting and pre-reduction process in the side-blown smelting furnace 10, and in a preferred embodiment, as shown in fig. 2, the side-blown smelting furnace 10 is further provided with a first flue gas outlet, and the apparatus further comprises: the first combustion unit 60 is connected with the first flue gas outlet and is used for carrying out secondary combustion on the first flue gas discharged from the first flue gas outlet; a first waste heat recovery unit 70 having a first air inlet and a first air outlet, the first air inlet being connected to an outlet of the first combustion unit 60; the first dust collecting unit 80 has a second air inlet, a second air outlet and a first smoke outlet, and the second air inlet is connected to the first air outlet. The first combustion unit 60 can perform secondary combustion on combustible components in the first flue gas, the obtained flue gas has a higher temperature, and after the waste heat is recovered by the first waste heat recovery unit 70, the smoke and dust in the first flue gas are separated by the first dust collection unit 80. Through the device, the heat in the first flue gas is effectively recovered, and the smoke dust in the first flue gas is separated. It should be noted that, in addition to the dust collecting step, a part of the dust is also collected in the waste heat recovery step. Preferably, the smoke outlets of the first waste heat recovery unit 70 and the first dust collection unit 80 are connected to the dosing unit 150, and the mixture is returned to the dosing and granulating step, and is granulated after being dosed together with the nickel-containing material, the reducing agent and the like, and then enters the reduction process again. Preferably, the first dust collecting unit 80 is an electric dust collector due to the low temperature during the pre-reduction process.
Similarly, in order to treat the second flue gas discharged from the electrothermic reduction furnace 20, in a preferred embodiment, as shown in fig. 2, the electrothermic reduction furnace 20 is further provided with a second flue gas outlet, and the apparatus further comprises: the second combustion unit 90 is connected with the second flue gas outlet and is used for carrying out secondary combustion on the second flue gas discharged from the second flue gas outlet; a second waste heat recovery unit 100 having a third air inlet and a third air outlet, the third air inlet being connected to the outlet of the second combustion unit 70; and the second dust collecting unit 110 is provided with a fourth air inlet, a fourth air outlet and a second smoke outlet, and the fourth air inlet is connected with the third air outlet. Therefore, secondary combustion, waste heat recovery and dust collection treatment can be carried out on the second flue gas. Preferably, the smoke outlets of the second waste heat recovery unit 100 and the second dust collection unit 110 are connected with the dosing unit 150, and the mixture returns to the dosing and granulating step, and is granulated after being dosed together with the nickel-containing material, the reducing agent and the like, and enters the reduction process again.
Because the temperature during the reduction process is higher and the temperature of the second flue gas is higher, in a preferred embodiment, the second dust collecting unit 110 comprises a surface cooler and a bag dust collector which are sequentially connected in series. Preferably, the flue gas outlets of the first dust collecting unit 80 and the second dust collecting unit 110 are both connected with the active lime spray drying desulfurization unit 160 to perform desulfurization and purification treatment on the flue gas, the desulfurized solid product is all used as a slagging raw material for nickel matte smelting, and the desulfurized liquid product is recycled for flue gas desulfurization by a spray drying method.
Preferably, the side-blown smelting furnace 10 is provided with two first flue gas outlets at the top, two liquid-state molten matte slag outlets at the lower part and a bottom discharge outlet at the bottom. The bottom discharge port can be arranged to discharge nickel matte in the furnace cleanly in the furnace repairing or accident state.
In order to further produce high nickel matte with higher nickel grade, in a preferred embodiment, the electrothermal reduction furnace 20 is further provided with a nickel matte outlet, and the apparatus further comprises an converting converter 120, and the converting converter 120 is connected with the nickel matte outlet. The converter 120 may be of a type commonly used in the art. More preferably, in order to effectively utilize resources, the converting converter 120 is provided with a converter slag outlet connected to the first inlet of the side-blown smelting furnace 10.
The flue gas produced by the converting furnace 120 has a relatively high sulfur content, and in a preferred embodiment, the converting furnace 120 is provided with a third flue gas outlet, and the device further comprises an acid making system 130, and the acid making system 130 is connected with the third flue gas outlet.
In a preferred embodiment, the electrothermic reduction furnace 20 is provided with a reduced slag outlet, and the apparatus further includes a water quenching unit 140, and the water quenching unit 140 is connected to the reduced slag outlet.
Preferably, the electrothermic reduction furnace 20 is provided with two nickel matte outlets and two reduced slag outlets.
The following examples are provided to further illustrate the advantageous effects of the present invention.
Example 1
Refer to FIG. 1
Top-blown prereduction stage
The laterite nickel ore is dried in the sun, and part of free water is volatilized, so that the laterite nickel ore is properly loosened. After the laterite-nickel ore, the reduced coal, the vulcanizing agent (pyrite) and the slagging flux (containing a desulfurization solid product) with proper water content (the water content is 16-25%) are granulated by a disc granulator, the granulated product is conveyed into a front storage bin of a smelting furnace by a rubber belt conveyor, and the granulated product is continuously conveyed into the smelting furnace by a quantitative feeder and a movable rubber belt conveyor.
Oxygen-enriched air (60%) and reducing gas are blown into a molten pool through a pulverized coal spray gun at the top of the furnace body, and the blowing pressure of the reducing gas and the oxygen-enriched air is 0.2-0.8 MPa. The combustion flame of the spray gun directly contacts with the melt, the combustion flue gas stirs the molten pool, the mass transfer of the molten pool is strengthened to accelerate the reaction, the laterite-nickel ore granular material is rapidly melted, the fluxes such as lime and the like are added from the top of the furnace, the slag type and the melting point of the molten pool in the furnace are adjusted, wherein the smelting temperature is controlled to be about 1300-1400 ℃, and the slag type is controlled: FeO 30%, MgO less than 12%, SiO 240％，CaO 15％。
And controlling the air excess coefficient alpha in the furnace to be 0.75-0.95, and melting and slagging the laterite-nickel ore to form liquid molten matte slag. After the slag layer in the furnace reaches a certain thickness, the slag is discharged from a slag port at one end of the top-blown furnace semi-continuously, and the slag discharging temperature is 1350 ℃. The liquid molten matte slag is added into an electrothermal reduction furnace through a hot slag chute.
The smelting flue gas temperature of the top-blown furnace is about 1350 ℃, air leaks from the upper part of the furnace body and the ascending flue, CO in the flue gas is combusted secondarily, the temperature of the flue gas is initially reduced to 350 ℃ by the waste heat boiler, waste heat is recovered, and the flue gas is further reduced in temperature by electric dust collection and then is sent to tail gas desulfurization treatment.
The tail gas desulfurization treatment is carried out by adopting a spray drying method desulfurization device, and SO in the tail gas is desulfurized2The content is less than 50mg/Nm3Can be directly discharged; the desulfurized solid product is aired and can be used as a calcareous raw material to be completely mixed into furnace burden; the desulfurized liquid product is continuously recycled for flue gas desulfurization by a spray drying method.
Deep reduction stage
The liquid molten matte slag is added from a hot material inlet of the electric heating reduction furnace. And after the charging is finished, power transmission heating is carried out, the smelting temperature in the furnace is 1550-1600 ℃, the electric heat reduction process is continuously carried out, and the charging, the slag discharging and the matte discharging are carried out periodically.
The electric heating reduction furnace is provided with four discharging ports, two slag discharging ports and two nickel matte discharging ports. The slag discharge temperature is 1550 ℃, the low nickel matte discharge temperature is 1500 ℃, wherein the low nickel matte grade: 15-35% of Ni, 55-75% of Fe and 10-15% of S, and feeding molten nickel matte into a converter for further blowing to obtain high-nickel sulfur. High nickel matte grade: 75-80% of Ni, 1% of Fe and 18-22% of S.
The electrothermal reduction slag (containing Ni < 0.15%) is water-quenched and stockpiled or sold as general solid waste. High-temperature flue gas generated by the electric heating reduction furnace leaks air at the upper part of the furnace body and an ascending flue, CO and S in the flue gas are combusted secondarily, the temperature is initially reduced to 350 ℃ through a waste heat boiler to recover waste heat, the flue gas is treated by a tail gas desulfurization system after being dedusted by a surface cooler and a bag dust collector, and the flue gas is transported back to smelting reduction ingredients.
The tail gas desulfurization treatment is still carried out by adopting a spray drying method desulfurization device, and SO in the desulfurized tail gas2The content is less than 50mg/Nm3Can be directly discharged; the desulfurized solid product is aired and can be used as a calcareous raw material to be completely mixed into furnace burden; the desulfurized liquid product is continuously recycled for flue gas desulfurization by a spray drying method.
Example 2
Pre-reduction stage of ore-smelting electric furnace
The laterite nickel ore is dried in the sun, and part of free water is volatilized, so that the laterite nickel ore is properly loosened. After the laterite-nickel ore, the reduced coal, the vulcanizing agent (sulfur) and the slagging flux (containing the desulfurization solid product) with proper water content are granulated by a disc granulator, the granules are conveyed into an electric furnace feeding bin by a rubber belt conveyor and are continuously conveyed into an electric furnace by a quantitative feeder and a movable rubber belt conveyor.
After the furnace burden is added, the furnace burden is electrified and melted, and after a molten pool is formed, the molten pool of the electric furnace is stirred to strengthen the mass transfer of the molten pool, so that the reaction is accelerated, and the laterite-nickel ore granular materials are quickly melted; adding lime and other fluxes from a feeding hole, and adjusting the slag form and the melting point of a molten pool in the furnace, wherein the smelting temperature is controlled to be about 1300-1400 ℃, and the slag form is controlled: FeO 30%, MgO less than 12%, SiO 240％，CaO15％。
The laterite-nickel ore is melted and slagged to form liquid molten matte slag, after the slag layer in the furnace reaches a certain thickness, the slag layer is discharged from a slag hole at one end of the electric furnace semi-continuously, and the slag discharging temperature is 1350 ℃. The liquid molten matte slag is added into an electrothermal reduction furnace through a hot slag chute.
The temperature of the smelting flue gas of the electric furnace is about 1350 ℃, air leaks from the upper part of the furnace body and the ascending flue, CO in the flue gas is combusted secondarily, the temperature of the flue gas is initially reduced to 350 ℃ by a waste heat boiler to recover waste heat, and the flue gas is further reduced by electric dust collection and then is sent to tail gas desulfurization treatment.
The tail gas desulfurization treatment is carried out by adopting a spray drying method desulfurization device, and SO in the desulfurized tail gas2The content is less than 50mg/Nm3Can be directly discharged; the desulfurized solid product is aired and can be used as a calcareous raw material to be completely mixed into furnace burden; the desulfurized liquid product is continuously recycled for flue gas desulfurization by a spray drying method.
Deep reduction stage
The liquid molten matte slag is added from a hot material inlet of the electric heating reduction furnace. And after the charging is finished, power transmission heating is carried out, the smelting temperature in the furnace is 1550-1600 ℃, the electric heat reduction process is continuously carried out, and the charging, the slag discharging and the matte discharging are carried out periodically.
The electric heating reduction furnace is provided with four discharging ports, two slag discharging ports and two nickel matte discharging ports. The slag discharge temperature is 1550 ℃, the low nickel matte discharge temperature is 1500 ℃, wherein the low nickel matte grade: 15-35% of Ni, 55-75% of Fe and 78-15% of S10, and feeding molten nickel matte into a converter for further blowing to obtain high nickel sulfur. High nickel matte grade: 75-80% of Ni, 1% of Fe and 18-22% of S.
The electrothermal reduction slag (containing Ni < 0.15%) is water-quenched and stockpiled or sold as general solid waste. High-temperature flue gas generated by the electric heating reduction furnace leaks air at the upper part of the furnace body and an ascending flue, CO and S in the flue gas are combusted secondarily, the temperature is initially reduced to 350 ℃ through a waste heat boiler to recover waste heat, the flue gas is treated by a tail gas desulfurization system after being dedusted by a surface cooler and a bag dust collector, and the flue gas is transported back to smelting reduction ingredients.
The tail gas desulfurization treatment is still carried out by adopting a spray drying method desulfurization device, and SO in the tail gas is desulfurized2The content is less than 50mg/Nm3Can be directly discharged; the desulfurized solid product is aired and can be used as a calcareous raw material to be completely mixed into furnace burden; the desulfurized liquid product is continuously recycled for flue gas desulfurization by a spray drying method.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the system solves the problems of waste utilization and environmental protection caused by preparing nickel matte from laterite, so that a closed circulation system is formed for product production and the problems of waste utilization and environmental protection control caused by the product production, and other systems are not required to solve the problems.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (21)
1. A method for producing nickel matte, characterized by the steps of:
s1, melting and pre-reducing the nickel-containing material, fuel, compressed air, reducing agent and vulcanizing agent in a smelting furnace to obtain liquid matte slag;
s2, sending the liquid matte slag into an electrothermal reduction furnace for reduction and slag matte separation to obtain a nickel comb;
and the flue gas generated in the S1 and S2 steps is desulfurized by adopting an active lime spray drying method, all desulfurized solid products are used as slagging raw materials for nickel matte smelting, and desulfurized liquid products are circularly used for desulfurization of the flue gas by adopting the spray drying method.
2. The method according to claim 1, characterised in that the nickel bearing material is a lateritic nickel ore, and before passing the nickel bearing material, the reducing agent and the sulphiding agent to the smelting furnace, the method further comprises: and granulating the nickel-containing material, the reducing agent, the fusing agent and the vulcanizing agent, and then feeding the mixture into the smelting furnace by a belt conveyor.
3. The method according to claim 1, characterized in that the smelting furnace is a top-blown furnace, a side-blown furnace, a bottom-blown furnace or an ore-smelting electric furnace; the smelting temperature in the smelting furnace is 1150-1450 ℃.
4. The method as claimed in claim 1, wherein the flue gas generated in the steps S1 and S2 is firstly subjected to secondary combustion, waste heat recovery by a waste heat boiler, dust collection by an electric dust collector and desulfurization by an active lime spray drying method.
5. The method according to claim 1, wherein the in-furnace smelting temperature of the electrothermic reduction furnace is 1500 to 1650 ℃.
6. A method according to any one of claims 1-5, characterized in that slag is also obtained in the reduction and matte separation process, and that the method further comprises the step of water quenching the slag.
7. A method according to any one of claims 1-5, characterized in that the method further comprises the step of converter blowing the nickel matte.
8. The method of claim 7, wherein converter slag and flue gas are also obtained during the converter blowing, the method further comprising: returning the converter slag to the melting and pre-reduction step; and desulfurizing the obtained flue gas by adopting an active lime spray drying method.
9. The method of claim 1, wherein the sulfiding agent is one or more of pyrite, sulfur, and gypsum.
10. The method of claim 1, wherein during the melting and pre-reducing, the controlled slag form comprises FeO, MgO, SiO2And CaO.
11. An apparatus for producing nickel matte, comprising:
the side-blown smelting furnace is characterized by comprising a side-blown smelting furnace, wherein the top of the side-blown smelting furnace is provided with a first inlet and a first flue gas outlet, the side part of the side-blown smelting furnace is provided with an immersed side-blown spray gun, the lower part of the side-blown smelting furnace is provided with a liquid-state molten matte slag outlet, the first inlet is used for introducing a nickel-containing material and a reducing agent, and the immersed side-blown spray gun is used for spraying fuel and oxygen;
the electric heating reduction furnace is provided with a liquid-state molten matte slag inlet and a second flue gas outlet, and the liquid-state molten matte slag inlet is connected with the liquid-state molten matte slag outlet through a hot slag chute;
the active lime spray drying desulfurization unit is provided with a flue gas inlet, a liquid inlet, a desulfurized solid product outlet and a desulfurized liquid product outlet, wherein the flue gas inlet is communicated with a first flue gas outlet of the side-blown smelting furnace and a second flue gas outlet of the electrothermal reduction furnace, the desulfurized solid product outlet is communicated with a first inlet of the side-blown smelting furnace, and the desulfurized liquid product outlet is communicated with a liquid inlet of the active lime spray drying desulfurization unit.
12. The apparatus of claim 11, further comprising a disk granulator for granulating the nickel containing material, the reducing agent, the fusing agent and the vulcanizing agent, the outlet of the disk granulator being connected to the first inlet.
13. The apparatus of claim 12, further comprising:
the bin is provided with a second inlet and a bin outlet, and the second inlet is connected with the outlet of the disc granulator;
the quantitative feeder is provided with a third inlet and a feeding outlet, the third inlet is connected with the bin outlet, and the feeding outlet is connected with the first inlet.
14. The apparatus of claim 11, further comprising:
the first combustion unit is connected with the first flue gas outlet and is used for carrying out secondary combustion on the first flue gas discharged from the first flue gas outlet;
the first waste heat recovery unit is provided with a first air inlet and a first exhaust port, and the first air inlet is connected with an outlet of the first combustion unit;
the first dust collecting unit is provided with a second air inlet, a second air outlet and a first smoke outlet, and the second air inlet is connected with the first air outlet.
15. The apparatus of claim 14, wherein the first dust collection unit is an electric dust collector.
16. The apparatus of any one of claims 11 to 13, further comprising:
the second combustion unit is connected with the second flue gas outlet and is used for carrying out secondary combustion on the second flue gas discharged from the second flue gas outlet;
a second waste heat recovery unit having a third air inlet and a third air outlet, the third air inlet being connected to the outlet of the second combustion unit;
and the second dust collecting unit is provided with a fourth air inlet, a fourth air outlet and a second smoke outlet, and the fourth air inlet is connected with the third air outlet.
17. The apparatus of claim 16, wherein the second dust collection unit comprises a surface cooler and a bag collector arranged in series in that order.
18. An apparatus according to any one of claims 11 to 15, characterized in that the electrothermic reduction furnace is further provided with a nickel matte outlet, and the apparatus further comprises an converting furnace connected to the nickel matte outlet.
19. The arrangement according to claim 18, characterized by the converting converter being provided with a converter slag outlet, which is connected to the first inlet of the side blown smelting furnace.
20. The apparatus according to claim 18, wherein the converting converter is provided with a third flue gas outlet communicating with the flue gas inlet of the active lime spray drying desulfurization unit.
21. The apparatus according to any one of claims 11 to 15, wherein the electrothermic reduction furnace is provided with a reduced slag outlet, the apparatus further comprising a water quenching unit connected to the reduced slag outlet.
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| CN114350977A (en) * | 2021-12-13 | 2022-04-15 | 中南大学 | Method for extracting nickel and cobalt from laterite-nickel ore through circulating vulcanization |
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