CN113249540A - Production method for smelting nickel-based stainless steel by using AOD furnace and using nickel hydroxide as raw material - Google Patents
Production method for smelting nickel-based stainless steel by using AOD furnace and using nickel hydroxide as raw material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/005—Manufacture of stainless steel
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0006—Adding metallic additives
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/072—Treatment with gases
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with 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
- 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
- Y02P10/20—Recycling
Abstract
The invention discloses a production method for smelting nickel-based stainless steel by using nickel hydroxide as a raw material in an AOD furnace, which comprises the following steps: (1) baking the nickel hydroxide to convert the nickel hydroxide into nickel oxide; (2) mixing nickel oxide with a binder to prepare a nickel oxide press ball; (3) feeding the nickel oxide pressing balls into an AOD furnace, adding the pre-melted liquid into the AOD furnace, and performing AOD refining to obtain molten steel; (4) and LF refining and continuous casting are carried out on the molten steel. The production method of the invention not only can greatly reduce the production cost, but also can realize high nickel yield.
Description
Technical Field
The invention relates to the technical field of nickel-based stainless steel smelting, in particular to a production method for smelting nickel-based stainless steel by using nickel hydroxide as a raw material in an AOD furnace.
Background
Nickel is an important element of stainless steel, the cost of nickel alloy occupies a large proportion in the cost of stainless steel, and in order to further reduce the smelting cost of stainless steel, stainless steel factories at home and abroad use cheap nickel resources to reduce the cost. At present, cheap nickel raw materials used in stainless steel smelting comprise raw materials such as nickel pig iron, nickel iron and the like, the raw materials adopt pyrometallurgy, a large amount of resources such as coal, electricity and the like are consumed in the smelting process, the energy consumption is high, the cost is higher, and the environmental pollution is serious.
The nickel hydroxide is a product produced by adopting hydrometallurgy, wherein the content of nickel is 40-70 percent, and the nickel hydroxide is generally used as a raw material in large-scale nickel production enterprises to produce nickel plates after deep processing treatment due to high oxidizability. At present, the nickel hydroxide produced by adopting a wet process is not used in stainless steel production enterprises for precedent.
The Chinese patent application with application number of 201510345428.4 discloses a process for producing a nickel raw material for stainless steel by using nickel hydroxide, which comprises the following steps: 1) uniformly distributing the dried nickel hydroxide on a steel belt of a steel belt furnace; 2) introduction of N2Evacuating the air in the steel belt furnace, then heating and raising the temperature, and continuously introducing N while raising the temperature2(ii) a 3) When the temperature is raised to 200 ℃, H begins to be introduced into the steel strip furnace2And N2And continuously heating the mixed gas; 4) when the temperature is raised to 500 ℃, the constant temperature reduction is maintained in the steel belt furnace with the mixed gas introduced, and the constant temperature reduction time is 90-120 min; 5) obtaining nickel powder after the constant-temperature reduction is finished; the nickel powder is melted by an intermediate frequency furnace and then directly used for stainless steel smelting. However, this method employs H at high temperatures2Reduction of NiO by passing N continuously2Gas, H2Gas, H2High gas price, resulting in increased production cost of stainless steel, and H2Is inflammable gas, and has poor control and capacity in the production processIs easy to appear H2And safety accidents such as combustion and explosion. Meanwhile, the nickel powder reduced by the method has high H content, which can cause the increase of the hydrogen content in the steel in the rear stainless steel smelting process.
Disclosure of Invention
In view of the above problems, the present invention provides a method for producing a nickel-based stainless steel by using nickel hydroxide as a raw material. The production method not only can greatly reduce the production cost, but also can realize high nickel yield.
Specifically, the invention is realized by the following technical scheme:
a production method for smelting nickel-based stainless steel by using nickel hydroxide as a raw material comprises the following steps:
(1) baking the nickel hydroxide to convert the nickel hydroxide into nickel oxide;
(2) mixing nickel oxide with a binder to prepare a nickel oxide press ball;
(3) feeding the nickel oxide pressing balls into an AOD furnace, adding the pre-melted liquid into the AOD furnace, and performing AOD refining to obtain molten steel;
(4) and LF refining and continuous casting are carried out on the molten steel.
Optionally, in step (1), the thickness of the nickel hydroxide layer is no more than 50 mm.
Optionally, in the step (1), the baking temperature is 400-600 ℃, and the baking time is 4-5 hours.
Optionally, in the step (2), the binder consists of starch and magnesium chloride in a weight ratio of (70-85): 15-30.
Optionally, in the step (2), the weight ratio of the nickel oxide to the binder is 1 (0.08-0.13).
Optionally, in the step (2), the nickel oxide is mixed with the binder and then is made into the nickel oxide press ball by an extrusion forming method, wherein the pressure is 15-20 Mpa.
Optionally, in the step (3), the content of C, Si and Cr in the pre-melt solution is 2.0-4.0%, 1.0-3.0% and 12-18% by weight.
Optionally, in the step (3), during AOD refining, inert gas is introduced for stirring.
Compared with the prior art, the production method for smelting the nickel-based stainless steel by using the nickel hydroxide as the raw material has at least the following beneficial effects:
1. the annealing kiln or the heating furnace is used for baking the nickel hydroxide, so that the moisture and the crystal water in the nickel hydroxide can be removed, the nickel hydroxide is converted into nickel oxide, the separation of the crystal water in the smelting process is reduced, and the increase of the hydrogen content in the steel is avoided.
2. The AOD is added with nickel oxide in batches, and under the condition of high temperature, Si and C elements in the pre-melting liquid are utilized to fully reduce the nickel in the nickel oxide, so that the nickel yield is improved, the Si and C elements in the pre-melting liquid are removed, and the oxygen blowing amount is reduced.
3. The nickel-based stainless steel is produced by taking nickel hydroxide as a raw material, can replace expensive raw materials such as metal nickel, imported ferronickel and the like, and can obviously reduce the smelting cost of the stainless steel.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. In the drawings:
FIG. 1 is a process flow diagram of the production method of the present invention for smelting nickel-based stainless steel using nickel hydroxide as a raw material.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention. The process of the present invention employs conventional methods or apparatus in the art, except as described below. The following noun terms have meanings commonly understood by those skilled in the art unless otherwise specified.
Aiming at the problems of raw materials, cost, nickel yield and the like in the production process of the nickel-based stainless steel at present, the inventor of the invention creatively provides a production method for smelting the nickel-based stainless steel by using nickel hydroxide as a raw material through intensive research.
The production method of the present invention for smelting nickel-based stainless steel using nickel hydroxide as a raw material will be described in detail with reference to FIG. 1.
A production method for smelting nickel stainless steel by using nickel hydroxide as a raw material comprises the following steps:
(1) the nickel hydroxide is baked to convert it to nickel oxide.
In this step, baking may be performed using a baking oven or an annealing kiln.
As a preferred embodiment, the powdery nickel hydroxide can be firstly put into a metal disc, the thickness of the nickel hydroxide material is less than or equal to 50mm, the metal disc is put into a baking furnace or an annealing kiln to be heated and heated, the temperature is controlled at 400-600 ℃, and the nickel hydroxide is baked for 4-5 hours to be converted into nickel oxide.
In this step, the chemical reaction mainly taking place is Ni (OH)2＝NiO+H2O↑。
In the step, the thickness of the nickel hydroxide material is controlled to be not more than 50mm, and the nickel hydroxide can be completely converted into nickel oxide by combining the baking temperature of 400-600 ℃ and the baking time of 4-5 hours.
In the step, the nickel hydroxide is roasted by using an annealing kiln or a heating furnace, so that the moisture and the crystal water in the nickel hydroxide can be removed, the nickel hydroxide is converted into nickel oxide, the separation of the crystal water in the smelting process is reduced, and the increase of the hydrogen content in the steel is avoided.
Ni in the nickel hydroxide is more than 40 percent, impurity elements are as little as possible, and other qualities have no special requirements. The nickel hydroxide raw material is mainly obtained by market purchase.
(2) Preparing the nickel oxide pressed ball.
In this step, nickel oxide is mixed with a binder, and then formed into a nickel oxide press ball by extrusion molding.
As a preferable embodiment, the nickel oxide and the binder are uniformly stirred according to the weight ratio of 1 (0.08-0.13), and the uniformly mixed nickel oxide is extruded and formed by a double-roller ball press machine under the pressure of 15-20Mpa to obtain the finished product nickel oxide press ball. And drying the nickel oxide press balls, and then putting the dried nickel oxide press balls into an AOD high-level storage bin.
In this step, the binder comprises starch and magnesium chloride. Specifically, the adhesive is composed of starch and magnesium chloride according to a weight ratio of (70-85) to (15-30). The balling rate of the balling process reaches 95 percent, the balling strength reaches 2100N on average, the high strength is achieved, and the balling process is not easy to pulverize in the transportation and feeding processes.
(3) And refining in an AOD furnace.
In the step, the premelted liquid is added into an AOD furnace to refine the nickel oxide press balls.
In a preferred embodiment, the premelt is obtained by melting raw materials such as high carbon ferrochrome and stainless steel scrap in an intermediate frequency furnace or an electric furnace, and the C content in the molten premelt is 2.0-4.0 wt% and the Si content is 1.0-3.0 wt%. Adding 150-170 tons of high-temperature premelt liquid into the AOD furnace, and blowing oxygen for smelting at 1500-1550 ℃ by AOD, adding 10-20 tons of nickel oxide press balls into the AOD furnace in batches in the smelting process (the adding amount of the nickel oxide press balls is mainly determined according to the content of Ni in the premelt liquid), and strongly stirring by adopting inert gases such as nitrogen, argon and the like for 3-5 min. And reducing the nickel oxide by using Si and C elements in the pre-molten liquid. AOD oxygen blowing decarburization is carried out, and the top lance flow in the 2-stage decarburization is 190m3Permin, top lance flow 150m in decarburization 3 stage3Per minute, the oxygen blowing amount is reduced by 400-800 m3. And adding ferrosilicon and silicomanganese for reduction after the AOD decarburization is finished, wherein the adding amount of the ferrosilicon is 18-25 kg/t, the adding amount of the silicomanganese is 10-15 kg/t, adding lime for reduction and desulfurization, the adding amount of the lime is 5-10kg/t, the molten steel components meet the steel grade requirement after the reduction is finished, the sulfur content S in the steel is less than or equal to 0.005%, the temperature reaches 1630-.
In this step, the following chemical reactions mainly take place:
C+NiO＝Ni+CO↑
Si+2NiO＝2Ni+SiO2
in the step, under the high temperature condition (for example, 1500-.
(4) LF refining and continuous casting.
And feeding molten steel obtained by refining in the AOD furnace into an LF furnace for LF refining, and then carrying out continuous casting to obtain a casting blank.
This step can be carried out by methods conventional in the art. In the actual production process, a person skilled in the art can select a suitable operation mode as required, which is not described herein.
It should be noted here that, in addition to the unexpected effects that the process parameters of the above steps can bring to the present invention, the present invention also lies in the above process route, namely: the method comprises the steps of nickel hydroxide baking, nickel oxide ball pressing, melting of high-chromium and stainless steel scrap in an intermediate frequency furnace or an electric furnace, nickel oxide utilization in AOD, LF refining and continuous casting, and by means of the sequence and combination mode of the process steps, the production cost is greatly reduced, and high nickel yield is realized.
Examples
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1: production of 304 stainless steel by using nickel hydroxide in 180-ton AOD furnace
In the embodiment, a 180-ton AOD furnace is adopted to smelt 304 stainless steel (the main components of 304 stainless steel are less than or equal to 0.03 percent of C, less than or equal to 1.0 percent of Si, less than or equal to 2.0 percent of Mn, less than or equal to 0.040 percent of P, less than or equal to 0.005 percent of S, 17.5-18.5 percent of Cr and 7.8-8.5 percent of Ni). The process flow of the embodiment: baking nickel hydroxide, pressing nickel oxide balls, feeding the nickel oxide balls into an AOD bin, melting high chromium and scrap steel in an intermediate frequency furnace, adding the nickel oxide into a 180-ton AOD furnace, refining and continuously casting.
The embodiment is as follows:
(1) putting nickel hydroxide (the Ni content is 43 wt%) into a steel tray, putting the tray into a baking furnace, heating to 500 ℃, dehydrating to obtain nickel oxide, keeping the temperature for 5 hours, and cooling to obtain powdery nickel oxide, wherein the thickness of the nickel hydroxide is 50 mm.
(2) Uniformly stirring and mixing nickel oxide powder and a binder according to the proportion of 1:0.1, wherein the binder comprises starch and magnesium chloride (the proportion of the starch to the magnesium chloride is 75: 25). And (3) extruding and forming the uniformly mixed nickel oxide powder by using a pair-roller ball press machine under the pressure of 18Mpa to obtain a finished product nickel oxide pressed ball, and putting the dried nickel oxide into an AOD high-level bin.
(3) Adopting an intermediate frequency furnace to melt stainless steel raw materials such as high-carbon ferrochrome, stainless steel scrap and the like, and melting the raw materials into high-temperature pre-molten liquid, wherein C: 3.0%, Si: 2.0 percent of the mixture is added into an AOD furnace.
Adding AOD into 1510 ℃ high-temperature pre-melted liquid, adding 10 tons of nickel oxide press balls in batches, and strongly stirring by adopting inert gases such as nitrogen, argon and the like for 5 min. AOD oxygen blowing desiliconization and decarburization with top lance flow of 190m in 2-stage decarburization3Permin, top lance flow 150m in decarburization 3 stage3And/min. Compared with AOD adopting imported ferronickel alloying method, the oxygen blowing amount is reduced by 500m3。
And after the AOD blowing decarburization is finished, reducing by adopting ferrosilicon and silicomanganese, and simultaneously adding lime for deep desulfurization. Tapping after the temperature reaches 1650 ℃, wherein the tapping steel comprises the following elements in percentage by mass: c: 0.0213%, Si: 0.43%, Mn: 1.63%, P: 0.0341%, S: 0.0038%, Cr: 18.124%, Ni: 8.01%, N: 0.0553% and the balance of Fe and inevitable impurity elements.
(4) After AOD tapping, the molten steel is hoisted to an LF furnace for refining and temperature adjustment, and is hoisted to a continuous casting process for continuous casting.
In the embodiment, the nickel oxide is directly used for nickel alloying to smelt the 304 stainless steel, the nickel yield is 99 percent, and compared with the AOD which uses imported ferronickel for nickel alloying, the cost is reduced by 200 yuan/t.
Example 2: 160 ton AOD adopting nickel hydroxide to produce 316L stainless steel
In the embodiment, 160 tons of AOD are adopted to smelt 316L stainless steel (the main components of the 316L stainless steel comprise less than or equal to 0.03 percent of C, less than or equal to 1.0 percent of Si, less than or equal to 2.0 percent of Mn, less than or equal to 0.040 percent of P, less than or equal to 0.005 percent of S, 16.0-18.0 percent of Cr and 10.0-14.0 percent of Ni). The process flow of the embodiment: baking nickel hydroxide, pressing nickel oxide balls, feeding the nickel oxide balls into an AOD bin, melting high chromium and scrap steel in an intermediate frequency furnace, adding the nickel oxide into a 180-ton AOD furnace, refining and continuously casting.
The embodiment is as follows:
(1) putting nickel hydroxide (Ni content is 51 wt%) into a steel tray, wherein the thickness of the nickel hydroxide is 50mm, putting the tray into a baking furnace, heating to 500 ℃, dehydrating to obtain nickel oxide, keeping the temperature for 5 hours, and cooling to obtain powdery nickel oxide.
(2) Uniformly stirring and mixing nickel oxide powder and a binder according to the proportion of 1:0.1, wherein the binder comprises starch and magnesium chloride (the weight ratio of the starch to the magnesium chloride is 75: 25). And (3) extruding and forming the uniformly mixed nickel oxide powder by using a pair-roller ball press machine under the pressure of 18Mpa to obtain a finished product nickel oxide press ball, and putting the dried nickel oxide press ball into an AOD high-level bin.
(3) Adopting an intermediate frequency furnace to melt stainless steel raw materials such as high-carbon ferrochrome, stainless steel scrap and the like, and melting the raw materials into high-temperature pre-molten liquid, wherein C: 3.0%, Si: 2.0 percent of the mixture is added into an AOD furnace.
Adding AOD into 1520 deg.C high temperature pre-melted liquid, adding nickel oxide press balls 12 tons in batches, and stirring strongly with inert gas such as nitrogen gas/argon gas for 5 min. AOD oxygen blowing desiliconization and decarburization with top lance flow of 190m in 2-stage decarburization3Permin, top lance flow 150m in decarburization 3 stage3And/min. Compared with the method of nickel alloying by adopting imported ferronickel, the oxygen blowing amount is reduced by 500m3。
And after the AOD blowing decarburization is finished, reducing by adopting ferrosilicon and silicomanganese, and adding lime for deep desulfurization. Tapping after the temperature is 1650 ℃ and the components are proper. The steel after tapping comprises the following elements in percentage by mass: c: 0.0189%, Si: 0.41%, Mn: 1.21%, P: 0.0323%, S: 0.0018%, Cr: 16.67%, Ni: 10.03%, N: 0.0512% and the balance of Fe and inevitable impurity elements.
(4) After AOD tapping, the molten steel is sent to an LF furnace for refining and temperature adjustment, and is hoisted to a continuous casting process for continuous casting.
In the embodiment, the nickel oxide is directly adopted to carry out the nickel alloying smelting of 316L, the AOD nickel yield is 99 percent, and compared with the method adopting imported ferronickel to carry out the nickel alloying, the cost is reduced by 260 yuan/t.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other substitutions, modifications, combinations, changes, simplifications, etc., which are made without departing from the spirit and principle of the present invention, should be construed as equivalents and included in the protection scope of the present invention.
Claims (8)
1. A production method for smelting nickel stainless steel by using nickel hydroxide as a raw material is characterized by comprising the following steps:
(1) baking the nickel hydroxide to convert the nickel hydroxide into nickel oxide;
(2) mixing nickel oxide with a binder to prepare a nickel oxide press ball;
(3) feeding the nickel oxide pressing balls into an AOD furnace, adding the pre-melted liquid into the AOD furnace, and performing AOD refining to obtain molten steel;
(4) and LF refining and continuous casting are carried out on the molten steel.
2. The production method according to claim 1, wherein in step (1), the thickness of the nickel hydroxide layer is not more than 50 mm.
3. The production method according to claim 1, wherein in the step (1), the baking temperature is 400 to 600 ℃ and the baking time is 4 to 5 hours.
4. The production method according to claim 1, wherein in the step (2), the binder is composed of starch and magnesium chloride in a weight ratio of (70-85): 15-30).
5. The production method according to claim 1, wherein in the step (2), the weight ratio of the nickel oxide to the binder is 1 (0.08 to 0.13).
6. The production method according to claim 1, wherein in the step (2), the nickel oxide is mixed with the binder and then is made into the nickel oxide pressure ball by extrusion forming, and the pressure is 15-20 MPa.
7. The production method according to claim 1, wherein in the step (3), the C content in the pre-melt is 2.0 to 4.0% and the Si content is 1.0 to 3.0% in weight percentage.
8. The production method according to claim 1, wherein in the step (3), during the AOD refining, an inert gas is introduced for stirring.
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