CN114058788A - Method for preparing micro-nitrogen deoxidizing alloy by using aluminum ash - Google Patents
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 128
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 97
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 34
- 239000000956 alloy Substances 0.000 title claims abstract description 34
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000292 calcium oxide Substances 0.000 claims abstract description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 56
- 239000010959 steel Substances 0.000 claims description 56
- 239000000463 material Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 238000005121 nitriding Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 abstract description 29
- 239000002893 slag Substances 0.000 abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 12
- 238000009628 steelmaking Methods 0.000 abstract description 11
- 238000007670 refining Methods 0.000 abstract description 9
- 238000003723 Smelting Methods 0.000 abstract description 7
- 238000003825 pressing Methods 0.000 abstract description 7
- 238000002844 melting Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 6
- 238000010079 rubber tapping Methods 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 229910001199 N alloy Inorganic materials 0.000 description 10
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 10
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011775 sodium fluoride Substances 0.000 description 5
- 235000013024 sodium fluoride Nutrition 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 3
- 229910000720 Silicomanganese Inorganic materials 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910000616 Ferromanganese Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000009615 deamination Effects 0.000 description 2
- 238000006481 deamination reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000002221 fluorine Chemical class 0.000 description 2
- 239000010436 fluorite Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C21C7/06—Deoxidising, e.g. killing
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Abstract
The invention discloses a method for preparing micro-nitrogen deoxidized alloy by using aluminum ash, belonging to the technical field of metal smelting. According to the invention, the aluminum ash is treated by a dry method, the aluminum ash and calcium oxide are uniformly mixed at a high temperature, volatile components in the aluminum ash are fully treated and absorbed, most of aluminum in the aluminum ash is converted into aluminum nitride, the aluminum nitride and fluoride are added in the steel-making and tapping process after being pressed into balls by high-strength ball pressing equipment, the harmful aluminum nitride and fluoride in the aluminum ash are subjected to high temperature in the steel-making link, nitrogen in the aluminum nitride is converted into nitrogen, and the resource utilization of the nitrogen is realized; meanwhile, fluoride is solidified for slag melting in the processes of slag washing and refining of steel making, and aluminum ash is prepared into the micro-nitrogen deoxidized alloy, so that the resource utilization of solid waste is realized, and the method has good economic and social benefits.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a method for preparing micro-nitrogen deoxidized alloy by using aluminum ash.
Background
The vanadium-nitrogen alloy is mainly used as an additive of the deformed steel bar alloy, the vanadium is added into the steel to improve the performance of the steel and reduce the cost, and the carbonization reduction and nitridation processes of the vanadium-nitrogen alloy are the key for determining the quality of the vanadium-nitrogen alloy additive in the production process of the vanadium-nitrogen alloy additive. Generally, after the vanadium-nitrogen alloy is added into steel, a part of the vanadium-nitrogen alloy is dissolved in a matrix to generate solid solution strengthening; the other part is combined with C, N to form V (C, N) which is precipitated on the matrix and grain boundary to generate precipitation strengthening and prevent ferrite grain growth. Meanwhile, V (C, N) precipitated among the phases can be used as a nucleation point of ferrite, so that the formation of intragranular ferrite is promoted, and ferrite grains are refined. Long-term production practices prove that the nitrogen content in the molten steel can promote the generation of VN, so in the steelmaking production process, technicians increase the nitrogen content in the steel through various channels.
The nitrogen is blown in a simple production process, when the nitrogen content in the molten steel reaches about 70ppm, the nitrogen is not basically increased, the optimum nitrogen content for nitrogen reinforcement is about 110ppm, nitrogen is dissolved in the molten steel by the technologies of micro nitrogen alloy and the like in the industry, and the content of the liquid nitrogen in the molten steel is increased by adding the product. The nitriding process of the product is complex, and the effect is not obvious.
The aluminum ash is a product in the production of electrolytic aluminum, aluminum processing, cast aluminum, or the like, and mainly comes from infusible inclusions, oxides, additives, and reaction products produced by physical and chemical reactions with the additives, which float on the surface of an aluminum melt when aluminum and an aluminum alloy are melted, and is generated in all production processes in which aluminum is melted. The aluminum ash contains aluminum and a plurality of valuable elements, and mainly comprises metal aluminum (5-70%), aluminum nitride (10-50%), aluminum oxide (20-40%), other metal oxides (2-10%) and salt flux (2-30%). According to the different content of metallic aluminium, the aluminium ash can be divided into primary aluminium ash and secondary aluminium ash, the aluminium content of the primary aluminium ash is 15-70%, the secondary aluminium ash is black, and the aluminium content is generally 5-15%.
The aluminum ash has high content of metallic aluminum and aluminum oxide, and is a precious renewable resource. The deliquescence of aluminum nitride in the aluminum ash can release ammonia gas, which is a foul gas and is flammable and explosive. The salt flux in the aluminum ash is mainly chlorine salt and fluorine salt, wherein the content of soluble fluoride is very high, so that the aluminum ash can cause serious pollution to ecological environments such as land, water, air and the like if the aluminum ash is not treated properly. According to the national records of dangerous wastes of 2106, the aluminum ash is primary smelting slag generated in the aluminum pyrometallurgy process and belongs to dangerous wastes.
The harmfulness of the aluminum ash is mainly that soluble fluoride and aluminum nitride are hydrolyzed to generate ammonia gas, wherein the fluoride can be solidified by adding a fluorine-fixing agent, and the leaching toxicity of the fluoride can reach the standard of general solid wastes, so the key of the harmless treatment of the aluminum ash is the treatment of the aluminum nitride.
Patent No. 201510808471.X discloses a comprehensive utilization and treatment method for aluminum ash, wherein a catalytic hydrolysis technology for aluminum nitride is disclosed, namely, ammonia gas can be rapidly decomposed and generated by adding a catalyst to perform catalytic deamination, and the problem of continuous influence on the environment caused by long deamination treatment process of aluminum ash can be effectively solved. However, in the actual production process, the rapid decomposition of ammonia gas is found to possibly cause risks such as explosion, the traditional reaction device has potential safety hazards, and due to the fact that hydrolysis is an exothermic reaction, ammonia gas can bring a large amount of moisture during the reaction of aluminum ash slurry, the ammonia gas concentration is too low, the moisture content in the gas is high, and the concentration of recovered ammonia water is low. If ammonia gas is concentrated by evaporation, the evaporation cost is too high.
The patent document with the application number of 201710634163.9 discloses a high-efficiency AlN hydrolysis recycling process in aluminum ash and a device thereof, the patent document with the application number of 201810373362.3 discloses an aluminum ash ammonia resource recycling device, and the patent document with the application number of 201710893673.8 discloses a method for strengthening aluminum ash denitrification by a pressure-regulating hydrothermal cyclone process.
For the reasons, it is necessary to provide a method for preparing a micro-nitrogen deoxidation alloy by using aluminum ash in combination with the process characteristics of steel making, the method is used as a nitrogen increasing agent for producing nitrogen-containing steel by steel making through aluminum ash nitrogen increasing treatment, and simultaneously the problems of harmless treatment of aluminum ash, low-cost manufacture of steel making deoxidation and nitrogen increasing and the like are solved, so that the resource utilization of the aluminum ash is really realized.
Disclosure of Invention
The invention provides a method for preparing micro-nitrogen deoxidation alloy by using aluminum ash, aiming at solving the problems of high nitrogen increasing and deoxidation costs, high aluminum ash treatment cost, long environmental influence period and the like in the conventional deformed steel bar production.
Therefore, the invention adopts the following technical scheme:
the invention relates to a method for preparing micro-nitrogen deoxidation alloy by utilizing aluminum ash, which comprises the following raw materials of electrolytic aluminum secondary aluminum ash, active lime and calcium chloride solution, and mainly comprises a rotary furnace capable of heating to 1000 ℃, a high-strength ball press, a waste gas absorption tower and a moving machine.
1) Uniformly mixing aluminum ash and calcium oxide according to the mass ratio of 4:1, feeding the mixture into a rotary furnace through a feeding end, heating the mixture to over 980 ℃ in a nitrogen atmosphere, keeping the constant temperature for over 60 minutes, and fully reacting simple substance aluminum in the aluminum ash with nitrogen to produce aluminum nitride, wherein the uniform distribution of the aluminum nitride in materials is ensured along with the operation of the rotary furnace; continuously heating simultaneously makes sodium fluoride, aluminium fluoride fully react and volatilize, and volatile sodium fluoride, aluminium fluoride along with nitrogen gas entering absorption tower react with saturated calcium chloride solution and generate calcium fluoride and deposit, and the stage is carried out the calcium fluoride deposit, presses into artifical fluorite product through drying crushing back, supplies with the market demand according to the standard.
2) Adding anhydrous calcium chloride not more than 2% and manganese iron powder in a set proportion into the aluminum ash raw material subjected to the full mixing treatment, pressing the mixture into spherical materials with the diameter of about 30mm by using a high-strength ball press, and bagging the spherical materials according to the specification of 10 kg/bag; according to the mass fraction, 30-50% of manganese iron powder in the spherical material is manganese iron powder, 48-56% of reaction material and 2-4% of anhydrous calcium chloride;
3) when high-nitrogen steel is produced, tapping steel is added along with steel flow according to the proportion of 3-8 kg/ton, wherein aluminum rapidly reacts with oxides in the steel to generate aluminum oxide, and the oxygen content in the steel is reduced; the aluminum nitride reacts with iron oxide and manganese oxide in the steel to generate aluminum oxide, iron, manganese and nitrogen which are soluble, and the soluble nitrogen in the steel increases the absorption rate of vanadium effectively; meanwhile, fluorine is not volatilized and solidified in the aluminum ash and forms a new slag system with the molten slag, so that the melting point and viscosity of the molten slag are effectively reduced, and the subsequent refining effect is improved.
The method is added in the early stage of tapping of the smelted deformed steel bar, a pressed product is rapidly melted under the conditions of high temperature and strong stirring, and each element rapidly reacts with other elements in the steel. The specific reaction is as follows:
wherein, the aluminum reacts with the oxide in the steel rapidly to generate aluminum oxide, and the oxygen content in the steel is reduced; the aluminum nitride reacts with the iron oxide and manganese oxide in the steel to generate aluminum oxide, iron, manganese and nitrogen[ soluble in solution)]Soluble nitrogen in steel is increased, so that the absorption rate of vanadium is effectively improved; meanwhile, the unvolatilized and solidified fluorine in the aluminum ash and the molten slag form a new slag system, so that the melting point and viscosity of the molten slag are effectively reduced, and the subsequent refining effect is improved.
The invention has the beneficial effects that:
1. according to the invention, the aluminum nitride in the secondary aluminum ash is used as a nitrogen-increasing raw material for smelting the nitrogen-containing steel, so that the link of ammonia gas generated by hydrolyzing the aluminum nitride in the conventional process is avoided, and the efficient utilization of the aluminum nitride is realized;
2. according to the invention, low-melting-point fluorine salts such as sodium fluoride and aluminum fluoride in the secondary aluminum ash are calcified through the rotary furnace, and the volatilized fluorine is absorbed and converted into calcium fluoride through calcium chloride, so that the safe disposal of fluoride in the aluminum ash is realized;
3. pressing the treated materials into a micro-nitrogen deoxidation alloy according to requirements, wherein the micro-nitrogen deoxidation alloy is used for producing steel-making nitrogenous steel, aluminum nitride reacts with iron oxide and manganese oxide in the steel to generate aluminum oxide, iron, manganese and soluble nitrogen, and simple substance aluminum reacts with free oxygen in the steel to perform deoxidation; soluble fluorine in the micro-nitrogen deoxidized alloy reacts with calcium oxide to generate calcium fluoride, so that the melting point and slag system of pre-melted slag are effectively reduced, and the subsequent refining difficulty is reduced;
4. according to the invention, the aluminum ash is treated by a dry method, harmful aluminum nitride and fluoride in the aluminum ash are subjected to high temperature in a steel-making link, nitrogen in the aluminum nitride is converted into nitrogen, and resource utilization of the nitrogen is realized; meanwhile, fluoride is solidified and used for slag melting in the processes of slag washing and refining of steel making, and aluminum ash is prepared into the micro-nitrogen deoxidized alloy, so that the resource utilization of solid waste is realized, and the method has good economic and social benefits;
5. the method utilizes the fact that the aluminum nitride is decomposed at high temperature to generate N3 < - >, which is more beneficial to the generation of vanadium nitride under the ionic state, greatly improves the absorption rate of vanadium, thoroughly changes the situation that the high position cost and the high danger of the aluminum nitride are high in the previous secondary aluminum ash treatment process, replaces the nitrogen increasing substance with high cost in the steelmaking process, and realizes the high-value utilization of changing waste into valuable. In order to solve the harm caused by fluoride volatilization in the aluminum ash, the invention converts low-melting-point volatile components into high-melting-point calcium fluoride through material pretreatment, thoroughly solves the possible harm caused by fluoride volatilization through absorption treatment on the pretreated flue gas, and the pretreated material has the effects of reducing viscosity and melting point on ladle slag and can strengthen the subsequent refining effect. Therefore, the method of the invention is an effective method for resource utilization of the aluminum ash.
Detailed Description
The invention will be further illustrated with reference to specific examples:
the nitrogen-containing steel produced has special requirements for nitrogen increase in the process, the specific initial nitrogen content is high, about 60ppm can be achieved depending on process operation and materials, the subsequent nitrogen increasing agent needs to be continuous and stable, the reaction product does not cause molten steel pollution, and the provided nitrogen source can exist in the steel in an ion form and is beneficial to nitrogen absorption.
A method for preparing micro-nitrogen deoxidizing alloy by using aluminum ash comprises the following specific steps:
1) uniformly mixing aluminum ash and calcium oxide according to the mass ratio of 4:1, feeding the mixture into a rotary furnace through a feeding end, heating the mixture to 980 ℃ in a nitrogen atmosphere, keeping the constant temperature for more than 60 minutes, fully reacting simple substance aluminum in the aluminum ash with nitrogen to produce aluminum nitride, and ensuring the uniform distribution of the aluminum nitride in materials along with the operation of the rotary furnace; continuously heating simultaneously makes sodium fluoride, aluminium fluoride fully react and volatilize, and volatile sodium fluoride, aluminium fluoride along with nitrogen gas entering absorption tower react with saturated calcium chloride solution and generate calcium fluoride and deposit, and the stage is carried out the calcium fluoride deposit, presses into artifical fluorite product through drying crushing back, supplies with the market demand according to the standard.
2) Adding anhydrous calcium chloride not more than 2% and manganese iron powder in a set proportion into the aluminum ash raw material which is fully mixed, pressing the mixture into a spherical material with the diameter of about 30mm by a high-strength ball press, and bagging the spherical material according to the specification of 10 kg/bag.
3) When high-nitrogen steel is produced, tapping is added along with steel flow according to the proportion of 3-8 kg/ton, wherein the components of the micro-nitrogen deoxidation alloy comprise 30-50% of manganese iron powder, 48-56% of secondary aluminum ash and the balance of anhydrous calcium chloride in percentage by weight.
The weight percentage of ferromanganese in the component of the micro-nitrogen deoxidation alloy is mainly determined according to the manganese content in the component of a finished product of a smelting steel seed, and the lower the end manganese content is, the lower the ferromanganese selected in the micro-nitrogen deoxidation alloy is.
The adding amount of the micro-nitrogen deoxidation alloy is determined according to the content of the liquid nitrogen of the steel and a final target, the lower the end point nitrogen content is, the higher the nitrogen content of a finished product is, and the more the adding amount of the slag splashing material is selected by the upper limit.
Table 1 shows the composition and content of aluminum ash in a certain plant
TABLE 2 aluminum ash after nitriding and its content
Example 1
A method for preparing micro-nitrogen deoxidation alloy by using aluminum ash comprises the steps of fully and uniformly mixing aluminum nitride ash and calcium oxide according to a ratio of 4:1, pressing balls and bagging, smelting a steel seed HRB400 in a converter, controlling the end point temperature to 1650 ℃, starting to add when the converter taps to 1/3, controlling the end point nitrogen content of molten steel to be 75ppm, controlling the oxygen content to be 540ppm, adding according to 3kg/t, and ending when the tap taps to 2/3. The micro-nitrogen deoxidation alloy balls are quickly dissolved under the stirring of the steel flow, the aluminum nitride in the aluminum ash is quickly decomposed, and the decomposed nitrogen[ soluble in solution)]The nitrogen content in the molten steel is improved, and the oxygen content is reduced. When the nitrogen content of molten steel entering a refining station is increased to 93ppm and the oxygen content is reduced to 50ppm, the yield of ferrosilicon and silicomanganese alloy is respectively increased by 0.5 percent and 0.9 percent, and under the condition of adding the same amount of vanadium-nitrogen alloy, the vanadium content is 8ppm higher than that of the conventional method.
Example 2
A method for preparing micro-nitrogen deoxidation alloy by using aluminum ash comprises the steps of fully and uniformly mixing aluminum nitride ash and calcium oxide according to a ratio of 4:1, pressing balls and bagging, smelting a steel seed HRB500 in a converter, wherein the end point temperature is 1670 ℃, adding is started when the converter taps 1/3, the end point nitrogen content of molten steel is 70ppm, the oxygen content is 580ppm, adding is carried out according to 5kg/t, and adding is finished when the tap taps 2/3. The micro-nitrogen deoxidation alloy balls are quickly dissolved under the stirring of the steel flow, the aluminum nitride in the aluminum ash is quickly decomposed, and the decomposed nitrogen[ soluble in solution)]The nitrogen content in the molten steel is improved, and the oxygen content is reduced. When the nitrogen content of molten steel entering a refining station is increased to 103ppm, the oxygen content is reduced to 55ppm, the yield of ferrosilicon and silicomanganese alloy is respectively increased by 0.55 percent and 0.93 percent, and under the condition of adding the same amount of vanadium-nitrogen alloy, the vanadium content is 13ppm higher than that of the conventional method.
Example 3
A method for preparing micro-nitrogen deoxidation alloy by using aluminum ash comprises the steps of fully and uniformly mixing aluminum nitride ash and calcium oxide according to a ratio of 4:1, pressing balls and bagging, smelting a steel seed HRB400 in a converter, wherein the final temperature is 1690 ℃, the converter is added when steel is tapped to 1/3, the nitrogen content of the steel liquid at the final point is 60ppm, the oxygen content is 650ppm, the amount is added according to 8kg/t, and the adding is finished when the steel is tapped to 2/3. The micro-nitrogen deoxidation alloy balls are quickly dissolved under the stirring of the steel flow, the aluminum nitride in the aluminum ash is quickly decomposed, and the decomposed nitrogen[ soluble in solution)]The nitrogen content in the molten steel is improved, and the oxygen content is reduced. And when the nitrogen content of the molten steel entering the refining station is increased to 115ppm, the oxygen content is reduced to 48ppm, the yield of the ferrosilicon and the yield of the silicomanganese alloy are respectively increased by 0.58 percent and 0.96 percent, and under the condition of adding the same amount of the vanadium-nitrogen alloy, the vanadium content is 16ppm higher than that of the conventional method.
Claims (7)
1. A method for preparing micro-nitrogen deoxidation alloy by using aluminum ash is characterized by comprising the following steps:
1) uniformly mixing aluminum ash and calcium oxide according to the mass ratio of 4:1, heating to over 980 ℃, preserving the temperature in a nitrogen atmosphere for at least 60min to enable soluble fluorine in the aluminum ash to react with the calcium oxide to generate calcium fluoride, discharging other parts along with flue gas, then feeding the other parts into an absorption tower, and discharging reaction materials after the reaction is finished;
2) adding anhydrous calcium chloride and manganese iron powder into the reaction material prepared in the step 1) to prepare a sphere, and transferring the sphere to a high-nitrogen steel production process; according to the mass fraction, 30-50% of manganese iron powder in the spherical material is manganese iron powder, 48-56% of reaction material and 2-4% of anhydrous calcium chloride;
3) when producing high nitrogen steel, the ball is added with molten steel according to 3-8 kg/t.
2. The method for preparing denitrified deoxidized alloy by utilizing aluminum ash as claimed in claim 1, wherein the diameter of the sphere in the step 2) is 25-30 mm.
3. The method for preparing denitrified deoxidized alloy from aluminum ash as claimed in claim 2, wherein in the step 2), the spheres are bagged according to the specification of 10 kg/bag and then transported to a high-nitrogen steel production process.
4. The method for preparing denitrified deoxidization alloy by utilizing aluminum ash as claimed in claim 1, wherein in the step 3), the nitrogen is continuously introduced into the nitriding rotary furnace while adding the spheres.
5. The method for preparing the denitrified deoxidizing alloy with aluminum ash as claimed in claim 1, wherein the aluminum content of the aluminum ash in step 1) is not less than 12%.
6. The method for preparing the denitrified deoxidized alloy by utilizing the aluminum ash as claimed in claim 1, wherein a rotary furnace is used for heating the aluminum ash and the calcium oxide in the step 1).
7. The method for preparing the denitrified deoxidizing alloy of aluminum ash as recited in claim 1, wherein in said step 2), high-strength ball press is used for ball making.
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