CN115927874A - Method for vulcanizing ferronickel - Google Patents
Method for vulcanizing ferronickel Download PDFInfo
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- CN115927874A CN115927874A CN202211597967.3A CN202211597967A CN115927874A CN 115927874 A CN115927874 A CN 115927874A CN 202211597967 A CN202211597967 A CN 202211597967A CN 115927874 A CN115927874 A CN 115927874A
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- ferronickel
- sulfur
- nickel
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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
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Abstract
The invention discloses a method for vulcanizing nickel-iron, which comprises the steps of smelting ferronickel in an ore-smelting electric furnace, enabling generated nickel-iron liquid to flow to a ladle automatically, entering a vulcanizing process, slowly inserting a rotary stirring device into the molten iron, adding a vulcanizing agent into the nickel-iron liquid through the stirring device after the rotary stirring device is inserted to a certain depth, and fully mixing sulfur and the nickel-iron liquid under the action of strong stirring to react with nickel, cobalt and iron in the nickel-iron liquid to generate nickel-sulfur and nickel-cobalt-iron alloy. The method provided by the invention strengthens the mixing reaction of molten ferronickel and sulfur, the solidification rate of nickel and cobalt reaches more than 95%, the utilization rate of sulfur is more than 90%, the content of sulfur dioxide in flue gas is reduced, and the method is environment-friendly, is suitable for two liquid-solid vulcanizing agents, and can also flexibly adjust the existing ferronickel production line.
Description
Technical Field
The invention belongs to the technical field of non-ferrous metal smelting, and particularly relates to a method for vulcanizing ferronickel.
Background
At present, the main vulcanization modes for producing high nickel matte from laterite ore comprise the following steps: (1) Spraying sulfur to the calcine tank and sulfurizing with calcium sulfate in an electric furnace to produce sulfur, nickel, iron and cobalt compound melt; (2) Producing sulfur, nickel, iron and cobalt compound melt by using the calcine tank spraying sulfur and the electric furnace molten iron chute steel ladle reinforcing body sulfur; and (4) carrying out combined vulcanization on the ferronickel and the air refining converter for vulcanization.
The problems of the sulfur addition of the calcine tank are as follows: because the calcine is in a semi-molten state (750-850 ℃), the added sulfur cannot be completely mixed with the calcine, so that the utilization rate of the sulfur is low, and a large amount of generated sulfur dioxide overflows to pollute the environment.
The problems of the solid sulfur reinforced by the molten iron chute ladle of the electric furnace are as follows: because the specific gravity of the molten iron is high, the specific gravity of the sulfur is low, and the added sulfur mainly floats on the surface of the molten iron, the utilization rate of the sulfur is low, a large amount of generated sulfur dioxide overflows to pollute the environment, and the occupied area of a chute and a ladle is large, so that the construction investment is large.
The problems existing in the vulcanization of the ferronickel composite vulcanization converting converter are that: because air and liquid sulfur are blown into the composite vulcanizing furnace simultaneously, a large amount of sulfur is oxidized to form sulfur dioxide, so that the utilization rate of the sulfur is low, and because the composite vulcanizing blowing converter is complex to operate, the composite vulcanizing blowing converter is only in a laboratory stage at present and has no industrial application case.
Therefore, the existing ferronickel vulcanization process has the defects of low nickel-cobalt reaction rate, low sulfur utilization rate, high sulfur dioxide concentration in flue gas, serious environmental pollution, poor regulation and control performance on the content of nickel sulfide in the ferronickel sulfide and low nickel-cobalt-sulfur curing rate, thereby further influencing the high nickel matte index produced by converter blowing, the nickel-cobalt-containing index of converter slag and the operation cost.
Disclosure of Invention
Aiming at the problems existing in the prior nickel-iron vulcanization process, the invention provides a nickel-iron vulcanization process, which aims to: the nickel-iron vulcanization reaction is strengthened, the utilization rate of sulfur and the solidification rate of nickel and cobalt are improved, and the content of sulfur dioxide in tail gas is reduced.
The invention designs a set of unique ferronickel vulcanization and vulcanization modes: the vulcanization mode is divided into two types: solid sulfur and liquid sulfur. Solid sulfur is added into a nitrogen conveyer through a rigid feeder, pressurized in the nitrogen conveyer and conveyed into the nickel-iron water through a stainless steel hose and a main shaft center hole.
Heating the liquid sulfur at 130-155 ℃, arranging a vertical stirrer on the top of the tank to ensure uniform sulfur melting, selecting a submerged pump as a sulfur adding pump, and regulating and controlling the flow rate by frequency conversion; the stainless steel pipe is subjected to heat tracing conveying and is connected with a stirring device through a straight-through type rotary sealing joint, liquid sulfur is injected into the molten iron through a main shaft center feeding hole or a stirring paddle blade, and meanwhile, a nitrogen pressurizing bypass joint is arranged to prevent the molten iron from overflowing from the center pipe when the molten iron is not sulfurized.
The reactions involved in the present invention:
sulfurizing nickel-cobalt-iron: ni & gtCo & gtFe
Chemical reaction of nickel cobalt iron with sulfur:
Ni+S=NiS(Ni 3 S 2 ；Ni 2 S 3 ；Ni 3 S 4 ；NiS 2 ；……)
Co+S=CoS(CoS 2 )
Fe+S=FeS(FeS 2 )
Ni+FeS(FeS 2 )= NiS(Ni 3 S 2 ；Ni 2 S 3 ；Ni 3 S 4 ；NiS 2 ；……)+Fe
Ni+CoS(CoS 2 )= NiS(Ni 3 S 2 ；Ni 2 S 3 ；Ni 3 S 4 ；NiS 2 ；……)+Co
Co+FeS(FeS 2 )= CoS(CoS 2 )+Fe
the technical solution of the invention is as follows:
a method for ferronickel sulfidation, comprising the steps of:
firstly, enabling a ferronickel melt to automatically flow into a specially-made steel ladle, starting a tail gas induced draft fan and a stirring device at the same time after the steel ladle enters a vulcanization process, slowly inserting a rotating stirring head into the ferronickel melt for 5-20 cm, starting a vulcanizing device at the same time when the stirring device contacts the melt, adding a vulcanizing agent, and keeping the temperature of the ferronickel melt within 1250-1500 ℃;
and step two, adjusting the rotating speed of the stirring device, adjusting the rotating speed of the sulfur valve, stopping vulcanizing after full vulcanization, automatically reducing the rotating speed of the stirring device until stirring is stopped, and lifting the stirring head of the stirring device to finish vulcanization operation.
Preferably, the vulcanizing agent in the first step is solid sulfur or liquid sulfur, and the vulcanizing agent is added in a mode of being conveyed into the ferronickel water through a central feeding port or a stirring blade of a stirring device.
Further preferably, the vulcanizing agent in the first step is liquid sulfur. The liquid sulfur has uniform temperature, stable flow and easy control of reaction.
Preferably, the weight ratio of the ferronickel melt to the added sulfur in the step one is 10-40.
Further preferably, the weight ratio of the ferronickel melt to the added sulfur in the first step is 20.
Preferably, the rotating speed of the stirring device in the first step is 10-30 rpm.
Preferably, the rotating speed of the stirring device in the second step is adjusted to 80-150 rpm. The more uniform the mixing degree of the sulfur and the nickel molten iron is, the higher the reaction strength is, and the better the reaction effect is.
Preferably, the adding amount of the vulcanizing agent in the second step can be dynamically adjusted according to the amount of the iron water, the stirring speed and the sulfur content in the flue gas.
Preferably, the time for vulcanizing in the second step is 10-30 min. Dynamically adjusting according to the amount of the iron water, the sulfur adding amount, the stirring speed and the sulfur content of the sulfide.
Further preferably, the vulcanization time in the second step is 20min.
The invention has the beneficial effects that: molten nickel-iron water is stirred by a stirring device in a semi-closed space, then liquid sulfur or solid sulfur is added to enable the nickel-iron water and the sulfur to be fully mixed and reacted to produce vulcanized mixtures such as nickel sulfide, cobalt sulfide, iron sulfide and the like, nickel and cobalt are fully vulcanized and reacted by controlling the adding amount of the sulfur, the vulcanizing speed, the stirring speed, the reaction time and the like according to the chemical components of the nickel-iron water, the solidification rate of nickel-cobalt-sulfur is improved, a nickel-iron-sulfur compound conforming to the subsequent converting grade is produced, and finally high nickel matte and high nickel-cobalt recovery rate are obtained by blowing.
Compared with the prior art, the invention has the advantages that:
(1) The mechanical stirring device is easy to operate, the rotating speed is automatically adjusted, the stirring is carried out while the vulcanization is carried out, the vulcanization reaction is strengthened, the vulcanization time is 30-50% of that of the traditional vulcanization mode under the same effect, and the sulfur utilization rate is up to more than 90%;
(2) Solid sulfur can be added, and liquid sulfur can also be added, so that the adaptability is strong, and the operation is flexible; when solid sulfur is added into the center of the stirring device, the number of solid sulfur liquefying devices is reduced, and the production cost is reduced;
(3) Solid sulfur and liquid sulfur are added below the liquid level, the reaction is sufficient, the amount of flue gas is reduced by more than 50% compared with the traditional vulcanization mode, the flue gas desulfurization cost can be reduced by 60%, and the operation cost is low;
(4) The environment-friendly effect is good, and no smoke overflow can be realized;
(5) The nickel-cobalt solidification rate is high and reaches more than 95 percent, and the nickel-cobalt recovery rate of converting high nickel matte can be effectively improved;
(6) Because the ferronickel is vulcanized at the outlet of the ferronickel molten iron of the submerged arc furnace, the ferronickel production is not influenced, and the free switching of high nickel matte and ferronickel products can be realized.
Drawings
Fig. 1 is a flow chart of the ferronickel vulcanization process of the invention.
Detailed Description
In order to facilitate the understanding of the technical solutions of the present invention for those skilled in the art, the technical solutions of the present invention will now be further described by specific examples.
Example 1
The method for vulcanizing ferronickel in the embodiment comprises the following steps:
step one, ferronickel melt flows into a steel ladle automatically, after the steel ladle enters a vulcanization room, a tail gas induced draft fan is started, a stirring device is started simultaneously, the rotating speed is 30 revolutions per minute, a rotating stirring head is slowly inserted into the ferronickel melt for 20cm, when the stirring device contacts the melt, a vulcanizing device is started simultaneously, solid sulfur is added into the center of the stirring device, and the temperature of the ferronickel melt is kept at 1450 ℃.
And step two, adjusting the rotating speed of the stirring device to 150 revolutions per minute, simultaneously adjusting the frequency of a sulfur valve, slowly adding a vulcanizing agent, stopping vulcanizing after sufficient vulcanization for 30min, automatically reducing the rotating speed of the stirring device until stirring is stopped, and then lifting the stirring device to finish vulcanization operation.
Example 2
The method for vulcanizing ferronickel in the embodiment comprises the following steps:
step one, ferronickel melt flows into a steel ladle automatically, after the steel ladle enters a vulcanization room, a tail gas induced draft fan is started, a stirring device is started simultaneously, the rotating speed is 20 revolutions per minute, a rotating stirring head is slowly inserted into the ferronickel melt by 10cm, when the stirring device contacts the melt, a vulcanizing device is started simultaneously, solid sulfur is added into the center of the stirring device, and the temperature of the ferronickel melt is kept at 1500 ℃.
And step two, adjusting the rotating speed of the stirring device to 120 revolutions per minute, simultaneously adjusting the frequency of a sulfur valve, slowly adding a vulcanizing agent, stopping vulcanizing after sufficient vulcanization is carried out for 25min, automatically reducing the rotating speed of the stirring device until stirring is stopped, and then lifting the stirring device to finish vulcanization operation.
Example 3
The method for vulcanizing ferronickel in the embodiment comprises the following steps:
step one, the ferronickel melt flows into a steel ladle automatically, after the steel ladle enters a vulcanization room, a tail gas induced draft fan is started, a stirring device is started simultaneously, the rotating speed is 10 revolutions per minute, a rotating stirring head is slowly inserted into the ferronickel melt for 5cm, when the stirring device contacts the melt, a vulcanizing device is started simultaneously, liquid sulfur is added, and the temperature of the ferronickel melt is kept at 1450 ℃.
And step two, adjusting the rotating speed of the stirring device to 110 revolutions per minute, simultaneously adjusting the frequency of a sulfur valve, slowly adding a vulcanizing agent, stopping vulcanizing after sufficient vulcanization for 20min, automatically reducing the rotating speed of the stirring device until stirring is stopped, and then lifting the stirring device to finish vulcanization operation.
Comparative example
The method for vulcanizing ferronickel in the comparative example comprises the following steps:
step one, enabling a ferronickel melt to automatically flow into a steel ladle, starting a tail gas induced draft fan after the steel ladle enters a vulcanization room, not starting a stirring device, slowly inserting a stirring head into the ferronickel melt for 20cm, starting a vulcanizing device when the stirring device contacts the melt, adding solid sulfur into the center of the stirring device, and keeping the temperature of the ferronickel melt at 1450 ℃;
and step two, adjusting the frequency of a sulfur valve, stopping sulfur addition after sufficient vulcanization for 30min, and then lifting the stirring device to complete vulcanization operation.
TABLE 1 test results in examples 1 to 3 and comparative example
| Sulfur utilization (%) | With or without smoke overflow | Nickel cobalt Cure (%) | |
| Example 1 | 91.82 | Is free of | 96.52 |
| Example 2 | 90.53 | Is free of | 95.63 |
| Example 3 | 92.14 | Is free of | 96.15 |
| Comparative example | 30.25 | Is provided with | 60.23 |
The invention adopts a mechanical stirring device, is easy to operate, automatically adjusts the rotating speed, adds sulfur and stirs simultaneously, strengthens the vulcanization reaction, and has 30-50% of the vulcanization time of the traditional vulcanization mode under the same effect; solid sulfur can be added, and liquid sulfur can also be added, so that the adaptability is strong, and the operation is flexible; when solid sulfur is added into the center of the stirring device, the number of solid sulfur liquefying devices is reduced, and the production cost is reduced; solid sulfur and liquid sulfur are added below the liquid level, the reaction is sufficient, the amount of flue gas is reduced by more than 50% compared with the traditional vulcanization mode, the flue gas desulfurization cost can be reduced by 60%, and the operation cost is low; because the ferronickel is vulcanized at the outlet of the ferronickel molten iron of the submerged arc furnace, the ferronickel production is not influenced, and the free switching of high nickel matte and ferronickel products can be realized. As can be seen from Table 1, the sulfur utilization rate is more than 90% and the nickel-cobalt solidification rate is more than 95% in the embodiment of the invention, which are far higher than the sulfur utilization rate and the nickel-cobalt solidification rate in the comparative example.
The above description is only an embodiment of the present invention, but the design concept of the present invention is not limited thereto, and any insubstantial modification of the present invention using this concept shall fall within the scope of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. A ferronickel vulcanization method is characterized by comprising the following steps: the method comprises the following steps:
firstly, enabling a ferronickel melt to automatically flow into a specially-made steel ladle, starting a tail gas induced draft fan and a stirring device at the same time after the steel ladle enters a vulcanization process, slowly inserting a rotating stirring head into the ferronickel melt for 5-20 cm, starting a vulcanizing device at the same time when the stirring device contacts the melt, adding a vulcanizing agent, and keeping the temperature of the ferronickel melt within 1250-1500 ℃;
and step two, adjusting the rotating speed of the stirring device, adjusting the rotating speed of the sulfur valve, stopping vulcanizing after full vulcanization, automatically reducing the rotating speed of the stirring device until stirring is stopped, and lifting the stirring head of the stirring device to finish vulcanization operation.
2. A method of ferronickel sulfidation as claimed in claim 1, wherein: and in the step I, the vulcanizing agent is solid sulfur or liquid sulfur, and the vulcanizing agent is added in a mode of being conveyed into the ferronickel water through a central feeding port of a stirring device or a stirring blade.
3. A method of ferronickel sulfidation as claimed in claim 1, wherein: and the vulcanizing agent in the step one is liquid sulfur.
4. A method of ferronickel sulfidation as claimed in claim 1, wherein: the weight ratio of the ferronickel melt to the added sulfur in the step one is 10-40.
5. A method of ferronickel sulfidation as claimed in claim 1, wherein: the weight ratio of the ferronickel melt to the added sulfur in the step one is 20.
6. A method of ferronickel sulfidation as claimed in claim 1, wherein: the rotating speed of the stirring device in the first step is 10-30 r/min.
7. A method for ferronickel sulphidation according to claim 1 characterized by the steps of: and in the second step, the rotating speed of the stirring device is adjusted to 80-150 rpm.
8. A method of ferronickel sulfidation as claimed in claim 1, wherein: and the vulcanization time in the second step is 10-30 min.
9. A method for ferronickel sulphidation according to claim 1 characterized by the steps of: and the vulcanization time in the second step is 20min.
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| JP2015017290A (en) * | 2013-07-09 | 2015-01-29 | 株式会社日向製錬所 | Method for desulfurizing ferronickel |
| CN112501446A (en) * | 2020-11-30 | 2021-03-16 | 贵州航天风华精密设备有限公司 | Mechanical rotary stirring and blowing treatment device and treatment method for magnesium alloy melt |
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| CN113943863A (en) * | 2021-09-27 | 2022-01-18 | 中国恩菲工程技术有限公司 | Device and method for producing high nickel matte by using nickel-iron liquid |
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| CN114854997A (en) * | 2022-03-31 | 2022-08-05 | 中南大学 | Injection type sulfur supplement and strengthening vulcanization method for laterite-nickel ore vulcanization smelting |
-
2022
- 2022-12-12 CN CN202211597967.3A patent/CN115927874A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703730A (en) * | 2012-06-18 | 2012-10-03 | 中国恩菲工程技术有限公司 | Method for smelting nickel matte by using lateritic nickel ore |
| JP2015017290A (en) * | 2013-07-09 | 2015-01-29 | 株式会社日向製錬所 | Method for desulfurizing ferronickel |
| CN112501446A (en) * | 2020-11-30 | 2021-03-16 | 贵州航天风华精密设备有限公司 | Mechanical rotary stirring and blowing treatment device and treatment method for magnesium alloy melt |
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