CN110669944A - Method for preparing pure ferromanganese alloy and active silicate particles from inferior alloy powder - Google Patents
Method for preparing pure ferromanganese alloy and active silicate particles from inferior alloy powder Download PDFInfo
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- CN110669944A CN110669944A CN201910943997.7A CN201910943997A CN110669944A CN 110669944 A CN110669944 A CN 110669944A CN 201910943997 A CN201910943997 A CN 201910943997A CN 110669944 A CN110669944 A CN 110669944A
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
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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
- C22B47/00—Obtaining manganese
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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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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- 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 method for preparing pure ferromanganese alloy and active silicate particles by using inferior alloy powder, which is characterized by comprising the following steps: firstly, adding inferior manganese-silicon alloy powder, silicon alloy powder and part of manganese-rich slag in a furnace into a reactor for electrifying and melting; secondly, adding a dephosphorizing agent, reacting for a certain time, and decanting all furnace slag, namely depleted slag; thirdly, pouring all the residual slag in the upper furnace into a hearth for depletion, and decanting all the depleted slag after the reaction is finished; fourthly, adding excessive manganese raw material with low phosphorus and low iron and a proper amount of lime for desiliconization and desulfurization to prepare pure ferromanganese alloy molten iron and divalent manganese slag; fifthly, discharging the pure ferromanganese alloy molten iron and the molten slag to a heat preservation bag at the same time, recycling the molten slag and casting the molten iron into a product; and sixthly, pouring all the depleted slag into a large water pool to be cooled to room temperature to obtain the active silicate particles. The invention finds another way for increasing the value of unqualified inferior alloy powder and can obviously improve the enterprise benefit.
Description
Technical Field
The invention relates to the technical field of metallurgical powder treatment and manganese-silicon alloy refining, in particular to a method for preparing pure manganese-iron alloy and active silicate particles by using inferior alloy powder.
Background
The manganese-silicon alloy is produced by about 1000 ten thousand tons every year in China, the unqualified powder produced in the processing process accounts for 5-10%, 50-100 ten thousand tons of unqualified powder produced every year can only be sold at a price lower than 18-30% of the market price or melted in an intermediate frequency furnace to be agglomerated and then processed into degraded alloy to be sold in the market or the powder is put into a submerged arc furnace again to be melted and recycled. Whichever way these powders were treated, the losses would reach 1500-. The unqualified powder is refined and purified to produce high-quality alloy, a value-added utilization way is found for the powder, and the method has great significance for the regular benefit and the initial benefit of an enterprise undoubtedly.
Disclosure of Invention
The invention aims to provide a method for preparing pure ferromanganese alloy and active silicate particles by using inferior alloy powder, so as to solve the defects of the prior art.
In order to achieve the above object, the present invention provides the following production method:
a method for preparing pure ferromanganese alloy and active silicate particles by using inferior alloy powder comprises the following steps:
firstly, melting and decarbonizing: adding part of the manganese-rich slag obtained by the last refining of the upper furnace, namely circulating slag, into a reactor, adding inferior manganese-silicon alloy powder and silicon powder with the height of C, P, S, which are generated when manganese-silicon alloys such as FeMn60Si14, FeMn65Si17 and the like are crushed into the reactor, powering on for melting, keeping the temperature at 1500-1600 ℃ for 8-12 minutes after cleaning, and carrying out decarburization and desilication reaction in the furnace:
[Mn3C]+ [Si]= [MnSi]+C↓
2(MnO）+[Si]= 2[Mn]+(SiO2)
the desired low carbon alloy and manganese depleted slag, can be obtained by controlling the concentration of [ Si ] in the alloy, typically to obtain an alloy composition of Si 24-30% by weight, Mn53-60% by weight, C0.05-0.1% by weight, P0.03-0.08% by weight and a slag composition of Mn2-3% by weight;
secondly, dephosphorization: directly add calcareous dephosphorization agent in reactor furnace to the intensive mixing makes dephosphorization agent and molten iron mix evenly, takes place following reaction in the molten iron inside:
3[Ca]+ 2[P]= Ca3P2↓
reaction equilibrium constant: [ Ca ]]3[P%]2= 1.6-4.1×10-5[Ca]
The concentration of [ Ca% ] in the molten iron is controlled to obtain the expected low-phosphorus molten iron, and after 5-10 minutes of dephosphorization reaction, all furnace slag is decanted into a heat-preservation slag ladle;
thirdly, diluting residual circulating slag: the residual circulating slag of the upper furnace is completely poured into a hearth of the reactor to carry out oxidation-reduction reaction with the high-silicon molten iron in the hearth, and the main reaction formula is as follows: 2 (MnO) + [ Si]= 2[Mn]+(SiO2) The alloy obtained after the reaction contains 12-18% of Si, 64-73% of Mn and slag, namely depleted slag, and the alloy contains 3-5% of Mn;
fourthly, deep desiliconization and desulfurization refining: adding a proper amount of lime particles and excessive manganese ore or low-valence state manganese oxide with low phosphorus and low iron, carrying out deep desiliconization and desulfurization, and keeping the temperature at 1500-1600 ℃ for 8-12 minutes after each time of cleaning to obtain pure ferromanganese molten iron and circulating slag; impurity elements Si, C, P and S in the pure ferromanganese alloy molten iron are fully removed, the content of each impurity element is 0.2-1.2% by weight of Si, 0.03-0.1% by weight of C, 0.025-0.08% by weight of P, and the content of S is less than or equal to 0.03%; the weight percentage content of the components of the circulating slag is Mn18-29 percent and (CaO + MgO)/SiO2=1.10-1.55；
Fifthly, tapping molten iron and slag: discharging all the pure ferromanganese alloy molten iron and the circulating slag in the furnace to a heat-preserving bag at the same time, and returning the circulating slag to the first step and the third step for recycling; casting molten iron into a product;
and sixthly, pouring the slag and the depleted slag in the heat-preservation slag ladle into a large water pool with the water temperature of 5-80 ℃ and the slag-water weight ratio =1 (5-10) to be cooled to the room temperature to obtain the active silicate particles.
The weight percentage content of the silicon alloy powder is 50-99% of the Si content.
Preferably, the silicon alloy powder contains not less than 70.5% of Si by weight.
More preferably, the Si content of the silicon alloy powder is not less than 90% by weight.
The silicate particles contain Mn3-5 wt% and (CaO + MgO)/SiO2=0.65-0.95。
The inferior manganese-silicon alloy powder comprises 55-75% of Mn, 12-30% of Si, not less than 0.15% of P, 1.5-3.0% of C and unqualified alloy powder with the granularity of 0-10mm in percentage by weight.
Preferably, the dephosphorizing agent is metallic calcium or silicon calcium barium alloy.
Preferably, the amount of the circulating slag added in the first step accounts for 5-40% of the total circulating slag by weight.
Preferably, the manganese ore or the low-valence manganese oxide contains 0.02 to 0.07 weight percent of phosphorus.
Preferably, the water temperature of the large water pool is 5-40 ℃, and the weight ratio of slag to water is =1 (8-10).
The reactor in the first step is a refining electric furnace or an induction furnace.
Compared with the prior art, the method for preparing pure manganese and active silicate particles by using inferior alloy powder has the following technical effects:
firstly, turning waste into wealth, manufacturing unqualified powder produced in the metallurgical industry into high-quality pure ferromanganese, realizing value-added utilization of inferior raw materials, and providing an urgently needed alloy material for manufacturing high-performance clean materials in the steel industry, the mechanical equipment industry and the national defense industry; secondly, the method is environment-friendly and low in investment, and multiple tasks of decarburization, dephosphorization, desulfurization, desilicication and slag depletion are completed in one station, so that the investment of pollution sources, equipment and dust removal equipment is reduced; thirdly, the manganese content in the waste slag is only 3-4% by weight, the manganese recovery rate is improved by 3-5%, the resource utilization rate is improved, and the product cost is reduced; fourthly, the waste slag becomes calcium aluminum silicate active colloid particles after water quenching, which is an ideal raw material for producing the high-performance concrete admixture; and fifthly, zero emission of solid wastes is realized.
Drawings
FIG. 1 is a flow chart of the process of example 1 for producing pure manganese and active silicate particles from poor quality alloy powders;
FIG. 2 is a flow chart of the preparation of pure manganese and active silicate particles from inferior alloy powders in examples 2 and 3.
Detailed Description
In order to illustrate the embodiments of the present invention more clearly, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings can be obtained by those skilled in the art without inventive effort.
The present invention will be further described with reference to the following examples.
Example 1
The present invention will be further explained with reference to fig. 1 and example 1.
A method for preparing pure ferromanganese alloy and active silicate particles by using inferior alloy powder comprises the following steps:
1) melting and decarbonizing: about 10000kg of circulating slag which is obtained by the last refining of the furnace and contains 28.6 percent of Mn28 is added into a refining furnace, 20000kg of alloy powder which contains 51.5 percent of Mn, 30.3 percent of Si, 2.3 percent of C, 0.21 percent of P and 0.04 percent of S in percentage by weight of the comprehensive components is added into a hearth to be electrically transmitted and melted, and the temperature is kept at 1580 ℃ for 10 minutes;
2) dephosphorization: then 600kg of silicon-calcium-barium alloy is added into the furnace, power supply is continued for 5 minutes, then power is cut off, all furnace slag in the furnace is decanted into a heat-preservation slag ladle and is sent to water quenching, and the weight percentage content of the obtained alloy components is sampled and analyzed: mn58.5%, Si 24.2%, C0.08%, P0.07% and Mn 2.8% in slag;
3) depletion of residual circulating slag: pouring about 25000kg of residual circulating slag from the upper furnace into the hearth for 2 times to perform oxidation-reduction reaction with molten iron in the hearth, pouring depleted slag into a heat-preserving slag ladle after 10 minutes, and sending the depleted slag to water quenching; the molten iron is continuously kept in the furnace for further desiliconization and desulfurization, and the molten iron in the furnace comprises 72.2 percent of Mn, 12.4 percent of Si, 0.075 percent of C and 0.058 percent of P by weight percent; the depleted slag contains Mn4.8%;
4) deep desiliconization and desulfurization refining: 53520kg of raw material of bivalent manganese oxide with the weight percentage of Mn53.7%, 3.5% of Fe and 0.07% of P and 15600kg of lime with the granularity of 0-10mm are added, heat preservation is carried out for 10 minutes after each clearing, and the final molten iron comprises the components with the weight percentage of Mn85.2%, Si 0.9% and P0.073 percent and S0.02 percent; the weight percentage of the components of the circulating slag is Mn24.6 percent and SiO227.1%、（CaO+MgO）/SiO2=1.15；
5) Tapping molten iron and slag: discharging all molten iron and circulating slag in the furnace to a heat-insulating bag at the same time, and recycling the circulating slag; casting molten iron into a product;
6) and pouring the slag and the depleted slag in the heat-preservation slag ladle into a large water pool, namely a water quenching pool, with the water temperature of 40 ℃ and the slag-water weight ratio =1:5, and cooling to room temperature to obtain the active silicate particles.
Example 2
The present invention will be further explained with reference to fig. 2 and example 2.
A method for preparing pure ferromanganese alloy and active silicate particles by using inferior alloy powder comprises the following steps:
(1) melting and decarbonizing: 6000kg of alloy powder with the comprehensive components of 53.9 percent of Mn, 30.8 percent of Si, 1.6 percent of C, 0.2 percent of P and 0.07 percent of S by weight percent is added into an induction furnace and is electrified and melted; when the melting degree is 70-80%, adding about 1000kg of circulating slag which is obtained by the final smelting in the furnace and contains Mn22.9 percent by weight into the furnace, heating the furnace charge to 1550 ℃ by the melting degree, preserving the heat for 10 minutes, and decanting most of the decarbonized slag into a heat preservation slag ladle for remaining;
(2) dephosphorization: then 300kg of silicon-calcium alloy is added into the furnace, the furnace is continuously powered on and stirred for 5 minutes, and then the power is cut off to flush all furnace slag into the heat-preservation slag ladle so as to uniformly mix the furnace slag with the decarburization slag which is previously remained in the ladle and send the mixture to water quenching; sampling and analyzing the obtained alloy components in percentage by weight: 55.9 percent of Mn55, 29.0 percent of Si, 0.04 percent of C, 0.045 percent of P and 1.5 percent of Mn in slag;
(3) depletion of residual circulating slag: pouring about 9800kg of residual circulating slag from the upper furnace into the hearth for 2 times to perform oxidation-reduction reaction with molten iron in the hearth, pouring depleted slag into a heat-preserving slag ladle after 8 minutes, and sending the slag ladle to water quenching to prepare active silicate particles; the molten iron is continuously kept in the furnace for further deep desiliconization and desulfurization, the molten iron in the furnace comprises 70.9 percent of Mn, 15.8 percent of Si, 0.04 percent of C and 0.030 percent of P by weight, and lean slag contains 3.8 percent of Mn3;
(4) deep desiliconization and desulfurizationRefining: adding 12240kg of divalent manganese oxide raw material with the weight percentage content of Mn55.1%, Fe 1.5% and P0.025% and 4890kg of lime with the particle size of 0-10mm in batches, and preserving heat for 10 minutes after each cleaning, wherein the final molten iron comprises 88.2% of Mn88.2%, 0.7% of Si, 0.035% of P and 0.02% of S; the circulating slag comprises Mn22.9 wt% and SiO226.8%、(CaO+MgO)/SiO2=1.33；
(5) Tapping molten iron and slag: discharging all molten iron and circulating slag in the furnace to a heat-insulating bag at the same time, and recycling the circulating slag; casting molten iron into a product;
(6) and pouring the decarbonized slag, the dephosphorized slag and the depleted slag in the heat-preservation slag ladle into a large water pool, namely a water quenching pool, with the water temperature of 60 ℃ and the slag-water weight ratio =1:8, and cooling to room temperature to obtain the active silicate particles.
Example 3
The invention will be further explained with reference to fig. 2 and example 3.
A method for preparing pure ferromanganese alloy and active silicate particles by using inferior alloy powder comprises the following steps:
a. melting and decarbonizing: firstly, 1000kg of alloy powder with the comprehensive composition weight percentage content of Mn 48%, Si 31.4%, C1.5%, P0.16% and S0.05% is added into an induction furnace and is electrified and melted; when the melting degree is 70-80%, adding about 500kg of circulating slag with the weight percentage of Mn20.5% obtained by final smelting in the furnace into the furnace, heating the furnace charge to 1550 ℃ by full melting and cleaning, preserving the heat for 10 minutes, and decanting most of the decarbonized slag into a heat preservation slag ladle for remaining;
b. dephosphorization: then adding 30kg of silicon-calcium-barium-aluminum alloy into the furnace, continuously transmitting power and stirring for 5 minutes, then stopping power supply to quickly flush all furnace slag into the heat-preservation slag ladle to uniformly mix the furnace slag with the decarburization slag remained in the ladle, then cooling the furnace slag to room temperature by water, sampling and analyzing the obtained alloy components by weight percent: mn53.4%, Si 27.1%, C0.11%, P0.08% and Mn 2.0% in slag;
c. depletion of residual circulating slag: pouring about 1300kg of residual circulating slag from the upper furnace into a hearth to perform oxidation-reduction reaction with molten iron in the hearth, pouring depleted slag into a heat-preserving slag ladle after 10 minutes, and sending the slag ladle to water quenching to prepare active silicate particles; the molten iron is continuously kept in the furnace for further deep desiliconization and desulfurization, the molten iron in the furnace comprises the following components, by weight, Mn63.2%, Si 18.3%, C0.09%, P0.06% and lean slag containing Mn4.7%;
d. deep desiliconization and desulfurization refining: adding 1560kg of tetravalent manganese oxide with the weight percentage content of Mn57.1%, 1.5% of Fe and 0.05% of P and 600kg of lime with the granularity of 0-10mm, and preserving heat for 15 minutes after clearing, wherein the final molten iron comprises the components with the weight percentage content of Mn81.5%, Si 1.2%, P0.065% and S0.03%; the weight percentage of the components of the circulating slag is Mn21.2 percent and SiO225.7%、(CaO+MgO)/SiO2=1.55；
e. Tapping molten iron and slag: discharging all molten iron and circulating slag in the furnace to a heat-insulating bag at the same time, and recycling the circulating slag; casting molten iron into a product;
f. and pouring the decarbonized slag, the dephosphorized slag and the depleted slag in the heat-preservation slag ladle into a large water pool, namely a water quenching pool, with the water temperature of 80 ℃ and the slag-water weight ratio =1:10, and cooling to room temperature to obtain the active silicate particles.
The principle and the implementation mode of the invention are explained by applying a specific example, and the description of the embodiment is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (9)
1. A method for preparing pure ferromanganese alloy and active silicate particles by using inferior alloy powder is characterized by comprising the following steps:
firstly, melting and decarbonizing: adding a part of the manganese-rich slag obtained by the last refining of the upper furnace, namely the circulating slag, into a reactor, adding inferior manganese-silicon alloy powder and silicon powder into the reactor for melting, and preserving heat for 8-12 minutes at 1500-1600 ℃ after cleaning;
secondly, dephosphorization: adding a dephosphorizing agent into the reactor, uniformly mixing with molten iron, and decanting all furnace slag into a heat-preservation slag ladle after the reaction is finished;
thirdly, diluting residual circulating slag: completely pouring the residual circulating slag in the upper furnace into a hearth of a reactor for depletion to obtain depleted slag with low manganese content;
fourthly, deep desiliconization and desulfurization refining: adding excessive manganese raw material with low phosphorus and low iron and a proper amount of lime powder for deep desiliconization and desulfurization, and preserving the heat for 8-12 minutes at 1500-1600 ℃ after each time of cleaning to obtain pure ferromanganese alloy molten iron and slag with higher concentration of divalent manganese, namely circulating slag;
discharging molten iron and circulating slag, discharging the pure ferromanganese alloy molten iron and the circulating slag in the furnace to a heat-preserving bag simultaneously, and returning the circulating slag to the first step and the third step for recycling; casting molten iron into a product;
and sixthly, pouring the slag and the depleted slag in the heat-preservation slag ladle into a large water pool with the water temperature of 5-80 ℃ and the slag-water weight ratio =1 (5-10) to be cooled to the room temperature to obtain the active silicate particles.
2. The method of claim 1 for producing pure ferromanganese alloy and active silicate particles from poor quality alloy powders, wherein the method comprises the steps of: the weight percentage content of the silicon alloy powder is 50-99% of the Si content.
3. The method of claim 1 for producing pure ferromanganese alloy and active silicate particles from poor quality alloy powders, wherein the method comprises the steps of: the main elements of the pure ferromanganese alloy are Mn and Fe, the content of each impurity element is 0.2-1.2% by weight of Si, 0.03-0.1% by weight of C, 0.025-0.08% by weight of P, and the content of S is less than or equal to 0.03%.
4. The method of claim 1 for producing pure ferromanganese alloy and active silicate particles from poor quality alloy powders, wherein the method comprises the steps of: the dephosphorizing agent is metal calcium or silicon calcium barium alloy.
5. The method of claim 1 for producing pure ferromanganese alloy and active silicate particles from poor quality alloy powders, wherein the method comprises the steps of: the circulating slag comprises Mn18-29 percent by weight, (B) CCaO+MgO)/SiO2=1.10-1.55。
6. The method of claim 1 for producing pure ferromanganese alloy and active silicate particles from poor quality alloy powders, wherein the method comprises the steps of: the silicate particles contain Mn3-5 wt% and (CaO + MgO)/SiO2=0.65-0.95。
7. The method of claim 1 for producing pure ferromanganese alloy and active silicate particles from poor quality alloy powders, wherein the method comprises the steps of: the inferior manganese-silicon alloy powder comprises 55-75% of Mn, 12-30% of Si, not less than 0.15% of P, 1.5-3.0% of C and unqualified alloy powder with the granularity of 0-10mm in percentage by weight.
8. The method of claim 1 for producing pure ferromanganese alloy and active silicate particles from poor quality alloy powders, wherein the method comprises the steps of: the amount of the circulating slag added in the first step accounts for 5-40% of the total circulating slag by weight.
9. The method of claim 1 for producing pure ferromanganese alloy and active silicate particles from poor quality alloy powders, wherein the method comprises the steps of: in the sixth step, the water temperature of the large water tank is 5-40 ℃.
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| CN101705336A (en) * | 2009-11-25 | 2010-05-12 | 北京科技大学 | Method for producing medium and low carbon ferromanganese through furnace refining |
| CN104878213A (en) * | 2015-06-08 | 2015-09-02 | 湖南大学 | Method for producing low-carbon ferromanganese from washed iron through decarbonizing and dephosphorizing |
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| CN101705336A (en) * | 2009-11-25 | 2010-05-12 | 北京科技大学 | Method for producing medium and low carbon ferromanganese through furnace refining |
| CN104878213A (en) * | 2015-06-08 | 2015-09-02 | 湖南大学 | Method for producing low-carbon ferromanganese from washed iron through decarbonizing and dephosphorizing |
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Effective date of registration: 20210528 Address after: No. 705, building 2, Guantang R & D center, No. 10, Shuangren Road, Liudong New District, Liuzhou City, Guangxi Zhuang Autonomous Region Applicant after: Guangxi Xingye Technology Co.,Ltd. Address before: 530000 Room 101, building 10, No.5, Zhujin Road, Qingxiu District, Nanning City, Guangxi Zhuang Autonomous Region Applicant before: Zeng Shilin |
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