CN113862413B - Method for decarbonizing molten iron by using secondary dedusting ash of converter - Google Patents
Method for decarbonizing molten iron by using secondary dedusting ash of converter Download PDFInfo
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- CN113862413B CN113862413B CN202010612692.0A CN202010612692A CN113862413B CN 113862413 B CN113862413 B CN 113862413B CN 202010612692 A CN202010612692 A CN 202010612692A CN 113862413 B CN113862413 B CN 113862413B
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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
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/04—Removing impurities other than carbon, phosphorus or sulfur
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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
- C21C7/068—Decarburising
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
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- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
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Abstract
The invention relates to a method for decarbonizing molten iron by using secondary fly ash of a converter, which sequentially comprises the following steps: preparing a decarbonizing agent base stock, wherein the decarbonizing agent base stock comprises converter secondary dedusting ash as a raw material; mixing a decarbonizing agent base material with an inorganic binder to obtain a mixture, fully mixing the mixture with water, pressing the mixture into small blocks, and drying the small blocks to obtain a blocky decarbonizing agent, wherein the inorganic binder accounts for 5 to 10 percent of the weight of the mixture; filling a blocky decarbonizing agent to the bottom of an evacuated torpedo ladle car, wherein the using amount of the blocky decarbonizing agent is 4 to 8 percent of the weight of molten iron filled into the torpedo ladle car, and preheating the blocky decarbonizing agent by using the waste heat of the torpedo ladle car; and pouring the molten iron into a torpedo ladle car, wherein the temperature of the molten iron is 1330-1500 ℃, and the molten iron is in contact with the massive decarbonizer and is subjected to oxidation reaction for decarbonization treatment. The method has simple and convenient operation and easy realization, radically solves the problem of graphite dust pollution, can effectively utilize waste resources while ensuring the decarburization effect, and has less investment and low cost.
Description
Technical Field
The invention relates to a molten iron pretreatment technology in a steelmaking process, in particular to a method for decarbonizing molten iron by using secondary dedusting ash of a converter.
Background
On the basis that the current steel production process is basically mature and stable, the continuous improvement of the interface technology between equipment is an effective measure for optimizing production indexes, wherein the iron-steel interface between a blast furnace and a converter (a mixer furnace) is particularly important, namely molten iron (the temperature is about 1500 ℃) discharged from the blast furnace of a steel plant is filled into a torpedo tank car and then is transported into the mixer furnace or a converter ladle of the steel plant through the torpedo tank car, in the process, the temperature of the molten iron is sharply reduced to about 1320 ℃ due to heat dissipation loss, the solubility of carbon in the molten iron is greatly reduced due to the temperature reduction of more than 100 ℃, a large amount of precipitation is caused, a large amount of high-temperature carbon powder is generated, and even a large amount of flake graphite is seen, and the smoke dust is mainly detected and analyzedThe components are carbon and iron, and the content of the carbon and iron exceeds 70-80%. It has been found that the saturated solubility of carbon decreases by 0.24% on average for every 100 ℃ drop in the temperature of the molten iron, i.e. about 2.4kg of carbon is precipitated from 1 ton of molten iron, whereby several tens of tons of carbon-containing dust are generated at the iron-steel interface for a thousand tons of molten iron per day. Not only does this waste a large amount of carbon, iron resources, but also has influenced atmospheric quality, has caused great injury to equipment and human body, for example the flake graphite dust falls and is easy to take place to skid when driving rail surface, again like partial carbon forms Fe with iron 3 When C is separated out, the influence on the electrical equipment with the magnetic field in the production field is great, and the heat dissipation and insulation performance and the service life of the electrical equipment are seriously influenced. In addition, the graphite dust is smooth and easy to adhere, and skin itch, red swelling and other symptoms are easy to cause when the graphite dust contacts the skin of a human body.
There are several current approaches to solving this problem: firstly, an air draft dust removal method is adopted to purify air; secondly, the external heat insulation structure of the torpedo tank car is improved to reduce the heat loss of the molten iron in the tank, so that the temperature drop of the molten iron in the transportation process is reduced; thirdly, the torpedo tank car adopts a capping mode, so that the heat loss of molten iron is reduced. The first method is restricted by process operation, the dust removal smoke hood conflicts with the operation of other equipment, the equipment is difficult to arrange, the maintenance and operation cost is high, the smoke and dust complementary effect is not good, and the treatment of symptoms and root causes is not good. The latter two methods have certain effect, but still cannot avoid the generation of a large amount of graphite dust because the carbon-saturated molten iron from the blast furnace inevitably generates carbon precipitation in the temperature reduction process.
Therefore, there is a need to solve the problem of reducing graphite dust contamination by reducing the carbon content in the molten iron based on the prior art. Therefore, when a certain iron and steel enterprise carries out a carbon reduction test on a molten iron sample, iron concentrate powder such as Yunnan beach ore, brazil powder, premixed powder, sintered return ore and the like is used as a decarbonizer, the decarbonizer is filled into a 25kg woven bag, and when molten iron is discharged from a blast furnace, the mineral powder is manually added into an iron runner behind a small dam in front of the blast furnace. Although the test method can realize the carbon reduction of the molten iron, the following problems still exist: firstly, the iron ore concentrate powder is used as a decarbonizer, so the cost is higher; secondly, after the Yunnan beach mineral powder at room temperature is directly added into the molten iron, the temperature of the molten iron is reduced by about 20 ℃, the heat loss is large, and the generation of carbon-containing dust is aggravated; thirdly, when the iron concentrate powder is used on site, the Yunnan beach mineral powder packaged by the woven bag is directly added into the iron runner manually when the molten iron is discharged from the blast furnace, so that the molten iron is easy to splash and the material is lost, and potential safety hazards exist.
In addition, flue gas generated by the converter in the stages of molten iron charging, scrap steel adding, steel tapping, slag discharging and the like, and flue gas overflowing during bulk material adding and oxygen blowing smelting are collectively called secondary flue gas of the converter. The flue gas has the characteristics of high temperature, small dust particle size, large instantaneous flue gas amount and the like, is a main pollution source of a converter steelmaking plant at present, so that a converter secondary flue gas dust removal system is commonly used by steel enterprises, and the ash collected by the converter secondary flue gas dust removal system is converter secondary dedusting ash. The primary dedusting equipment is a cooler and is used for dedusting and cooling, and the primary dedusting ash has a thicker granularity and is recycled as a sintering raw material. The secondary dust removal equipment is an electrostatic dust remover and is used for removing dust and reducing temperature, the secondary dust removal ash has fine granularity, one part of the secondary dust removal ash is recycled as a sintering raw material, and the other part of the secondary dust removal ash is recycled as a shaft furnace pelletizing raw material. Generally, the total iron content of TFe in the secondary converter fly ash is 23.88 to 27.53 percent, the weight percentage of FeO is 10.00 to 12.00 percent, and Fe 2 O 3 The weight percentage is 23.00 to 26.00 percent.
Disclosure of Invention
The invention aims to provide a method for decarbonizing molten iron by utilizing converter secondary fly ash, which is characterized in that the converter secondary fly ash is used as a main raw material of a decarbonizer base material to prepare a decarbonizer, and the decarbonizer is applied to the molten iron in the process that blast furnace molten iron enters a torpedo car, so that iron oxide in the decarbonizer and carbon in the blast furnace molten iron are subjected to oxidation reaction, and the molten iron is decarbonized.
The invention is realized by the following steps:
a method for decarbonizing molten iron by using secondary fly ash of a converter comprises the following steps:
preparing a decarbonizing agent base stock, wherein the decarbonizing agent base stock comprises converter secondary dedusting ash as a raw material;
step two, mixing the base material of the decarbonizing agent with an inorganic binder to obtain a mixture, fully mixing the mixture with water, pressing the mixture into small blocks, and drying the small blocks to obtain a blocky decarbonizing agent, wherein the inorganic binder accounts for 5 to 10 percent of the weight of the mixture;
step three, filling the block-shaped decarbonizing agent to the bottom in the emptied torpedo ladle car, wherein the using amount of the block-shaped decarbonizing agent is 4-8% of the weight of the molten iron filled in the torpedo ladle car, and preheating the block-shaped decarbonizing agent by the waste heat of the torpedo ladle car;
and step four, pouring the molten iron into the torpedo ladle car, wherein the temperature of the molten iron is 1330 to 1500 ℃, and the molten iron is contacted with the massive decarbonizing agent and is subjected to oxidation reaction for decarbonization treatment.
In the first step, the converter secondary dedusting ash is roasted to be used as a decarbonizer base material, and the roasting conditions are as follows: baking in air at 800-1000 ℃ for 3-5 hours.
In the first step, the raw material of the base material of the decarbonizer also comprises iron ore concentrate powder, the converter secondary fly ash and the iron ore concentrate powder are blended to be used as the base material of the decarbonizer, the weight percentage of the converter secondary fly ash is 30-70%, and the rest is the iron ore concentrate powder.
In the first step, the raw materials of the base material of the decarbonizer also comprise rolled steel scales, the converter secondary dedusting ash and the rolled steel scales are blended to be used as the base material of the decarbonizer, the weight percentage of the converter secondary dedusting ash is 30-70%, and the balance is the rolled steel scales.
In the first step, the raw materials of the base material of the decarbonizer also comprise iron concentrate powder and steel rolling iron scale, and the converter secondary dedusting ash, the iron concentrate powder and the steel rolling iron scale are blended to be used as the base material of the decarbonizer, and the corresponding weight percentage is 20 to 50 percent, 10 to 30 percent and 30 to 60 percent.
Roasting treatment is carried out before blending of the secondary fly ash of the converter, and the roasting conditions are as follows: baking in air at 800-1000 deg.C for 3-5 hr.
And in the second step, the mixture is mixed with water and then is pressed and formed by a ball press machine or a briquetting machine, and the mixture is dried at the temperature of 110 to 120 ℃ for 3 to 5 hours.
In the second step, the block size of the block-shaped decarbonizer is 0.3 to 5cm.
In the fourth step, when the massive decarbonizer is mixed with molten iron for decarbonization, the temperature of the molten iron is 1400 to 1500 ℃.
In the second step, part of the base material of the decarbonizer is roasted to prepare a powdery decarbonizer; in the third step, a powdery decarbonizing agent is paved in advance in an iron runner connecting a blast furnace iron nozzle and a torpedo tank car; in the fourth step, the molten iron contacts with the powdery decarbonizer when flowing through the molten iron runner and is subjected to oxidation reaction for pre-decarbonization treatment.
The invention relates to a method for decarbonizing molten iron by utilizing converter secondary dedusting ash, which comprises the steps of firstly, adding a decarbonizer taking the converter secondary dedusting ash as a main raw material into the molten iron discharged from a blast furnace, and carrying out oxidation reduction reaction between the decarbonizer and carbon in the molten iron at a high temperature of 1330-1500 ℃ to effectively oxidize and remove the carbon in the molten iron, thereby realizing pretreatment decarbonization of the blast furnace discharged iron, and radically solving the pollution problem of graphite dust in the molten iron inversion link of iron and steel enterprises. In particular, fe of converter secondary fly ash before roasting 2 O 3 The content is only about 24.56 percent, the FeO content is about 11.44 percent, and after air roasting, the components such as S, C and the like can be oxidized into SO 2 、CO 2 While removing and converting FeO into Fe 2 O 3 So that the roasted converter secondary fly ash contains Fe 2 O 3 The content of the Fe can reach 36 to 40 percent, because of the Fe 2 O 3 Has strong oxidizability at high temperature, and can oxidize C contained in molten iron into CO or CO 2 And (3) removing the iron element in the secondary dust of the converter, and efficiently recovering the iron element. Moreover, the converter secondary dedusting ash after aerobic roasting is blended with iron concentrate powder and/or steel rolling iron scale to be used as the base material of the decarbonizer, so that the proportion of iron oxides in the base material of the decarbonizer can be comprehensively increased, and the oxidation decarbonization efficiency of the decarbonizer is further improved.
Secondly, in the application mode of the decarbonizer, the decarbonizer base material is made into small blocks of blocky decarbonizer and placed in the torpedo car emptied of molten iron, in the process that the torpedo car returns from a steel plant to the iron plant, the blocky decarbonizer is preheated by the waste heat of the torpedo car, so that the blocky decarbonizer is raised to 800-1000 ℃ from normal temperature, the heat loss generated when the blocky decarbonizer is contacted with high-temperature molten iron (about 1480 ℃) is reduced, the phenomenon of carbon precipitation aggravated by over-large temperature drop is avoided, and the blast furnace molten iron is poured into the torpedo car to impact the blocky decarbonizer, so that the blocky decarbonizer and the molten iron are fully mixed and contacted, the carbon in the molten iron is removed, and stirring operation is not needed. Meanwhile, the secondary dedusting ash of the converter is briquetted to prepare the blocky decarbonizer, so that the molten iron splashing and the material loss are reduced, the dangerous accident caused by splashing is avoided, and the material utilization rate is effectively improved. In addition, a part of base materials of the decarbonizing agent can be made into powdery decarbonizing agent and is paved in an iron runner connected between a blast furnace and a torpedo tank car in advance to carry out pre-decarbonization on the flowing molten iron, the molten iron flows through the iron runner in sequence in a flowing state and can fully contact with the powdery decarbonizing agent to react for decarbonization, and the powdery decarbonizing agent does not need to be treated by an adhesive or a briquetting, so that the labor and the cost can be effectively reduced.
Compared with the prior art, the invention has the following beneficial effects: simple operation and easy realization, radically solves the problem of graphite dust pollution, can effectively utilize waste resources while ensuring the decarburization effect, and has less investment and low cost.
Detailed Description
The present invention will be further described with reference to the following specific examples.
The method for decarbonizing the molten iron by utilizing the secondary dedusting ash of the converter is to add a decarbonizer which takes the secondary dedusting ash of the converter as a main raw material into the molten iron discharged from a blast furnace for decarbonization treatment, thereby radically reducing the generation of carbon dust. The method comprises the following specific steps:
step one, preparing a base material of the decarbonizer, wherein the base material of the decarbonizer comprises secondary dedusting ash of a converter. Specifically, the converter secondary dedusting ash is roasted and then directly used as a decarbonizer base material, and can also be blended with iron concentrate powder and/or steel rolling iron scale to obtain the decarbonizer base material for use.
The TFe total iron content of the converter secondary fly ash is 23.88 to 27.53 percent, and the converter secondary fly ash comprises the following chemical components in percentage by weight: fe 2 O 3 ：23.00~26.00%、FeO：10.00~12.00%、S：0.180~0.200%、SiO 2 ：5.50~6.50%、Al 2 O 3 ：1.80~2.30%、CaO：24.00~27.00%、MgO：9.00~11.00%、MnO：0.60~0.80%、P 2 O 5 :0.130 to 0.190%, C:2.50-4.00%, znO:8.00 to 9.00 percent, and the balance of impurities: 6.00 to 7.00 percent. It can be seen that Fe in the untreated converter secondary fly ash 2 O 3 The content of (2) is small, and the carbon content is high, so that the decarburization efficiency of molten iron is poor. Therefore, before being used as a base material of the decarbonizer, the base material is decarbonized by roasting, or is used by being blended with iron concentrate powder and/or rolled iron scale as the base material of the decarbonizer, and preferably, the secondary dust of a converter can be roasted and decarbonized before being blended. The roasting conditions are as follows: baking in air at 800-1000 deg.c for 3-5 hr. After the secondary dedusting ash of the converter is roasted, the carbon content is close to 0, and basically all ferrous iron is converted into ferric iron, so that better oxidizing property can be provided.
Specifically, the preparation method of the base material of the decarbonizer includes but is not limited to the following methods: 1) Roasting the secondary fly ash of the converter to prepare a base material of the decarbonizer; 2) Directly blending the unfired converter secondary dedusting ash with iron concentrate powder to prepare a decarbonizer base material; 3) Directly blending the unfired converter secondary dedusting ash with steel rolling iron scale to prepare a decarbonizer base material; 4) Directly blending the unfired converter secondary dedusting ash with iron concentrate powder and steel rolling iron scale to prepare a decarbonizer base material; 5) Roasting the secondary fly ash of the converter, and then blending the roasted secondary fly ash with iron concentrate powder to prepare a decarbonizer base material; 6) Roasting the converter secondary dedusting ash, and blending the roasted converter secondary dedusting ash with steel rolling iron scale to prepare a decarbonizer base material; 7) Roasting the converter secondary dedusting ash, and then blending the converter secondary dedusting ash with iron concentrate powder and steel rolling iron scale to prepare a decarbonizer base material.
When the converter secondary fly ash and the iron concentrate powder are blended to prepare the base material of the decarbonizer, the weight percentage of the converter secondary fly ash is 30-70% (if the converter secondary fly ash is roasted, the weight percentage of the roasted converter secondary fly ash is the weight percentage), and the rest is the iron concentrate powder, wherein the iron concentrate powder is Yunnan beach ore, brazil powder or sintered return ore. When the converter secondary fly ash and the steel rolling iron scale are blended to prepare the decarbonizer base material, the weight percentage of the converter secondary fly ash is 30-70% (if the converter secondary fly ash is roasted, the weight percentage of the roasted converter secondary fly ash is the weight percentage), and the balance is the steel rolling iron scale, preferably, the mass ratio of the converter secondary fly ash to the steel rolling iron scale is 50:50. when the converter secondary dedusting ash, the iron concentrate powder and the steel rolling iron scale are blended to be used as the base material of the decarbonizer, the corresponding weight percentage is 20 to 50 percent, 10 to 30 percent and 30 to 60 percent.
And step two, mixing the base material of the decarbonizing agent with an inorganic binder to obtain a mixture, fully mixing the mixture with water, pressing the mixture into small blocks, and drying the small blocks to obtain the blocky decarbonizing agent, wherein the inorganic binder accounts for 5 to 10 percent of the weight of the mixture. The inorganic binder is preferably bentonite, the using amount of the inorganic binder is preferably 8-10% of the weight of the mixture, and carbon can be prevented from being introduced into molten iron by adopting the inorganic binder.
A base material of the decarbonizer is made into a small block-shaped decarbonizer, which aims to increase the particle size of the decarbonizer when the decarbonizer is added into blast furnace molten iron and prevent loss and safety problems caused by high-temperature splashing. Although the powdery decarbonizer can also be directly mixed with molten iron discharged from a blast furnace, if the adding mode is improper, splashing is easy to generate, and certain material loss is caused, and in comparison, the blocky decarbonizer can reduce the splashing. The specific shape of the block-shaped decarbonizer is not limited, and the block-shaped decarbonizer can be regular cylindrical, rectangular, ellipsoidal, spherical or irregular three-dimensional, and the block size is preferably 0.3-5 cm. The specific mode for preparing the blocky decarbonizer comprises the following steps: mixing the base material of the decarbonizer and an inorganic binder to obtain a mixture, fully mixing the mixture with a proper amount of water, then performing compression molding by a ball press or a briquetting machine, and drying at 110 to 120 ℃ for 3 to 5 hours.
In addition, part of the base material of the decarbonizer can be made into powdery decarbonizer which is paved in the molten iron ditch to carry out pre-decarbonization treatment on the molten iron. Wherein, the converter secondary dust removal ash and the iron ore concentrate powder are powder materials which can be directly used as a powdery decarbonizer, and the rolled steel scale is not easy to be made into powder materials, such as the rolled steel scale with small granularity or in a flake shape, and can also be directly laid in an iron runner.
And step three, filling the block-shaped decarbonizing agent to the bottom of the emptied torpedo ladle car, wherein the using amount of the block-shaped decarbonizing agent is 4-8% of the weight of the molten iron filled into the torpedo ladle car, and preheating the block-shaped decarbonizing agent by using the waste heat of the torpedo ladle car. In addition, powdery decarbonizing agent can be paved in the molten iron ditch connecting the blast furnace molten iron nozzle and the torpedo tank car in advance.
First, the most important way of applying the decarburizing agent is: the method comprises the steps of filling a blocky decarbonizer to the bottom in a torpedo tank car after molten iron is poured into a converter or a ladle of a steel plant from the torpedo tank car, preheating the blocky decarbonizer in the process that the torpedo tank car returns to the steel plant from the steel plant, and removing carbon in the molten iron after blast furnace molten iron is poured into the tank car without stirring operation when the torpedo tank car returns to the steel plant to carry the molten iron again, wherein the blocky decarbonizer in the tank car is heated to 800-1000 ℃. Secondly, still can carry out the decarbonization in advance before blast furnace molten iron flows through the iron runner and gets into the torpedo tank car, be about to make likepowder decarbonizer by partial decarbonizer base material, lay likepowder decarbonizer in advance in the iron runner of connecting blast furnace molten iron mouth and torpedo tank car, make the molten iron flow through likepowder decarbonizer and take place the reaction and realize the decarbonization, such application mode neither can appear a large amount of splash, has played partial decarbonization effect to the blast furnace molten iron that flows through, has also reduced the work load of carrying out briquetting stoving to whole decarbonizer base materials.
In addition, the converter secondary fly ash after roasting treatment is used as a base material of the decarbonizer, and Fe is used as the base material 2 O 3 The content of the iron ore is 36-40wt%, the amount of the decarbonizer is slightly increased, and the converter secondary dust is pre-roasted, blended with steel rolling iron scale or blended with iron concentrate powder to be used as the base material of the decarbonizer, and Fe 2 O 3 The content is relatively higher, and the amount of the decarbonizing agent can be properly adjusted downwards. If the amount of the decarbonizing agent is too small, sufficient decarbonization cannot be achieved, and if the amount of the decarbonizing agent is too high, the temperature drop may be too large, and the decarbonizing agent may be too largeThe method has the problems of residue, excessive impurities introduced into the molten iron, great influence on the original chemical composition of the molten iron and the like.
And step four, pouring the molten iron from a blast furnace molten iron port into the torpedo car through a molten iron ditch, and contacting the molten iron with a decarbonizing agent and carrying out an oxidation reaction to carry out decarbonization treatment. Specifically, molten iron can contact with a powdery decarbonizer laid in advance and carry out oxidation reaction when flowing through the molten iron ditch, and the molten iron can contact with a blocky decarbonizer and carry out oxidation reaction when entering the torpedo ladle car. When the massive decarbonizer is mixed with molten iron for decarbonization, the temperature of the molten iron ranges from 1330 ℃ to 1500 ℃, and particularly the temperature of the molten iron ranges from 1400 ℃ to 1500 ℃, so that a good decarbonization effect can be realized, because if the temperature of the molten iron is lower than 1400 ℃, the reaction speed is slow, the corresponding reaction time is prolonged, and partial decarbonizer is possibly left and incompletely reacted.
Example 1
And carrying out aerobic roasting treatment on the secondary fly ash of the converter to obtain a decarbonizer base material, and mixing the base material with blast furnace molten iron to realize decarbonization. Table 1 lists the TFe total iron content, chemical composition and weight percent thereof for the unfired converter secondary fly ash sample of example 1 as follows:
and (2) carrying out aerobic roasting on 500g of the converter secondary fly ash which is not roasted, wherein the roasting conditions are as follows: roasting in air at 900 deg.c for 4 hr. Table 2 lists the TFe total iron content, chemical composition and weight percent of the calcined converter secondary fly ash of example 1 as follows:
as can be seen from Table 2, after aerobic roasting, most of FeO in the secondary fly ash in the converter is converted into Fe 2 O 3 And simultaneously realizes the decarbonization effect. Mixing a certain amount of roasted converter secondary fly ash and bentonite to obtain a mixtureAnd then the mixture is fully mixed with a proper amount of water to be uniformly pulped and pressed into blocks, and the blocks are dried at the temperature of 110 to 120 ℃ for 3 to 5 hours to obtain the cylindrical block-shaped decarbonizer, wherein the diameter of the cylindrical block-shaped decarbonizer is 1cm, the height of the cylindrical block-shaped decarbonizer is 1.5cm, and bentonite accounts for 8 percent of the weight of the mixture.
Sampling from a steel plant, slightly different components exist in each iron block sample (about 500g in weight), in order to enable the detection result to be more accurate, each sample is detected for three times, the average value of the three times is taken, and the carbon content in the iron block sample is repeatedly detected in each experiment, wherein the average content of Si and Mn in the iron block sample is 0.28 percent and 0.20 percent respectively.
In this example, the influence of different amounts of decarburizing agents on the decarburization effect of molten iron was studied, specifically, 4%, 5%, and 8% of converter secondary dedusting ash block-shaped decarburizing agents based on the weight of molten iron were respectively added to molten iron, and the temperature of molten iron was maintained at 1450 ℃. Table 3 lists the results of the carbon content testing of the iron nugget sample of example 1, as follows:
as can be seen from Table 3, as the amount of the secondary precipitator for removing dust from the converter increases, the amount of carbon reduction in the molten iron gradually increases, and the decarburization effect is remarkable.
Example 2
The converter secondary dust removal ash is made into a decarbonizer base material by aerobic roasting and steel rolling iron scale blending. The converter secondary fly ash and the calcination treatment process thereof in this example were the same as in example 1, to obtain the calcined converter secondary fly ash in table 2. The rolled scale, which is a metallic iron oxide attached to the surface formed when the steel slab is processed in a heated or hot rolled state, is shown in table 4 as the TFe total iron content, chemical composition and weight percentage of the rolled scale used in example 2, as follows:
and (3) mixing the roasted converter secondary fly ash and the steel rolling iron scale according to the mass ratio of 1:1, mixing to obtain a decarbonizer base material, then mixing with bentonite to obtain a mixture, fully and uniformly mixing with a proper amount of water to prepare slurry, directly pelletizing by a disk pelletizer, drying to obtain a spherical blocky decarbonizer with the diameter of 2cm, and drying at 110 to 120 ℃ for 3 to 5 hours, wherein the bentonite accounts for 8 percent of the weight of the mixture. Table 5 lists the TFe total iron content, chemical composition and weight percent of the base decarburizer of example 2 as follows:
in this example, the influence of different amounts of decarburizing agents on the decarburization effect of molten iron was studied, specifically, 4%, 5%, and 6% of spherical block-shaped decarburizing agents based on the weight of molten iron were respectively added to molten iron, and the temperature of molten iron was maintained at 1450 ℃. The specification and the detection method of the iron nugget sample were the same as those of example 1. Table 6 lists the results of the test for carbon content of the iron nugget sample of example 2, as follows:
as can be seen from comparison between example 1 and example 2, the decarburization effect of example 2 is better when the same amount of decarburization agent is used for the decarburization agent prepared by using the converter secondary fly ash as a decarburization agent base after calcination and the decarburization agent prepared by blending the converter secondary fly ash with the rolled steel scale as a decarburization agent base after calcination.
As can be seen from Table 6, the roasted converter secondary fly ash and the rolled steel scale are blended to prepare the decarbonizing agent, on one hand, the rolled steel scale contains 73.18 percent of TFe, and the iron in the rolled steel scale can be efficiently recovered; on the other hand, the use amount of secondary dust removal ash of the converter can be reduced, and the contents of impurity elements such as Ca, mg, si and the like in the steel rolling iron scale are very low, so that the introduction of excessive impurity elements into blast furnace molten iron is avoided.
Example 3
In this example, the spherical block decarbonizer obtained in example 2 was used to study the influence of the converter secondary dedusting ash decarbonizer on the decarbonization effect of molten iron under different molten iron temperature conditions, specifically, the molten iron temperatures for the decarbonization reaction were respectively maintained at 1330 ℃, 1390 ℃ and 1450 ℃, and in each set of temperature experiment, the amount of the decarbonizer was 4% of the molten iron weight. The specification and the detection method of the iron nugget sample were the same as in example 1. Table 7 lists the results of the carbon content testing of the iron nugget samples of example 3, as follows:
as can be seen from Table 7, in the case where the amount of the decarburization agent was constant, the relationship between the amount of carbon reduction and the temperature of molten iron during the decarburization reaction was small, the amount of carbon reduction at 1330 ℃ was close to that at 1450 ℃, and the amount of carbon reduction at 1390 ℃ was relatively high. Thus, the amount of carbon reduction depends mainly on the amount of the decarbonizing agent. The comprehensive consideration of the factors of complete reaction, cost saving and the like is that the dosage of the decarbonizer prepared by blending the secondary fly ash of the converter after roasting and the steel rolling iron scale as the base material of the decarbonizer is preferably 5 percent, the temperature of molten iron is preferably 1390-1400 ℃, and the carbon reduction amount of the molten iron of the blast furnace is more than 0.58 percent.
Example 4
The converter secondary dedusting ash is mixed with steel rolling iron scale to prepare a decarbonizer base material through aerobic roasting. The converter secondary fly ash and the calcination treatment process thereof in this example were the same as in example 1, to obtain the calcined converter secondary fly ash in table 2. The rolled scale in this example is the same as in example 2. And (3) mixing the roasted converter secondary fly ash and the steel rolling iron scale according to a mass ratio of 67:33, mixing to prepare a decarbonizer base material, then mixing with bentonite to obtain a mixture, fully and uniformly mixing with a proper amount of water to prepare slurry, directly pelletizing by a disk pelletizer, drying to obtain a spherical blocky decarbonizer with the diameter of 2cm, and drying at 110 to 120 ℃ for 3 to 5 hours, wherein the bentonite accounts for 8 percent of the weight of the mixture. Table 8 lists the TFe total iron content, chemical composition and weight percent of the decarboniser base in example 4, as follows:
in this example, the influence of different amounts of decarburizing agents on the decarburization effect of molten iron was studied, specifically, 4%, 5%, and 6% of spherical block-shaped decarburizing agents based on the weight of molten iron were respectively added to molten iron, and the temperature of molten iron was maintained at 1450 ℃. The specification and the detection method of the iron nugget sample were the same as those of example 1. Table 9 lists the results of the carbon content testing of the iron nugget sample of example 4, as follows:
as is clear from comparison between example 2 (Table 6) and example 4 (Table 9), the carbon reduction effect of example 2 is better than that of example 4 when the amount of the decarburization agent is the same and the temperature of the molten iron is the same, and it is demonstrated that the decarburization efficiency is not improved by increasing the proportion of secondary fly ash in the converter after calcination in the decarburization base. Therefore, preferably, the converter secondary fly ash after roasting is mixed with the rolled steel scale according to the ratio of 50.
Example 5
The converter secondary dedusting ash is mixed with iron concentrate powder to prepare the base material of the decarbonizer through aerobic roasting. The converter secondary fly ash and the calcination treatment process thereof in this example were the same as those in example 1, to obtain the calcined converter secondary fly ash in table 2. The iron ore concentrate powder in this example is brazilian iron ore concentrate powder, and table 10 lists the TFe total iron content, chemical components and weight percentages thereof of the iron ore concentrate powder of example 5, as follows:
| TFe total iron content% | Chemical composition | Fe 2 O 3 | FeO | SiO 2 | Al 2 O 3 | MnO | The rest impurities |
| 65.23 | Weight percent (wt%) | 92.61 | 0.52 | 3.66 | 1.50 | 0.69 | 1.02 |
Blending the roasted converter secondary dedusting ash and iron ore concentrate powder according to a mass ratio of 70 to obtain a decarbonizer base material, mixing the base material with bentonite to obtain a mixture, fully and uniformly mixing the mixture with a proper amount of water to prepare slurry, pressing the slurry into blocks, and drying the blocks at 110 to 120 ℃ for 3 to 5 hours to obtain a cylindrical blocky decarbonizer with the diameter of 1cm and the height of 1.5cm, wherein the bentonite accounts for 8 percent of the weight of the mixture. Table 11 lists the TFe total iron content, chemical composition and weight percent of the decarboniser base in example 5, as follows:
as can be seen from Table 11, the secondary fly ash of the roasted converter was mixed with the iron ore concentrate powder, in which Fe was contained 2 O 3 The content of the molten iron reaches 53.37 percent, and the method has very ideal molten iron decarburization effect.
In this example, the influence of different amounts of decarburizing agents on the decarburization effect of molten iron was studied, specifically, 4%, 5%, and 6% of cylindrical block-shaped decarburizing agents based on the weight of molten iron were respectively added to molten iron, and the temperature of molten iron was maintained at 1450 ℃. The specification and the detection method of the iron nugget sample were the same as those of example 1. Table 12 lists the results of the carbon content testing of the iron nugget samples of example 5, as follows:
as can be seen from Table 12, the decarbonizer prepared by blending the roasted converter secondary fly ash and the iron ore concentrate powder as the base materials of the decarbonizer has very remarkable carbon reduction effect of molten iron. Comparing the experimental results of example 5 with those of examples 1, 2 and 4, the decarburization effect of this example is much higher than that of example 1, and is not much different from that of example 4, but is slightly lower than that of example 2, which is also related to the ratio of converter secondary fly ash to decarburization base. Therefore, the carbon reduction efficiency of the decarbonizer can be greatly improved by a mode of blending a certain amount of iron concentrate powder and the secondary fly ash of the roasted converter. Because the cost of the parazium iron concentrate powder is higher, the dosage proportion of the parazium iron concentrate powder can be slightly lower, and the good carbon reduction effect can be achieved. In addition, in the embodiment, the decarbonization of the iron ore concentrate powder and the production of the molten iron are directly utilized, and the special pelletizing treatment of the iron ore concentrate powder is not needed.
Example 6
The unfired converter secondary dedusting ash and the iron ore concentrate powder are blended to prepare the base material of the decarbonizer. The converter secondary fly ash in this example is the same as that in example 1, and the specific chemical components and weight percentages thereof can be found in table 1. The iron ore concentrate powder in this example was brazilian iron ore concentrate powder, and the same as in example 5, the specific chemical components and weight percentages thereof are shown in table 10.
Blending converter secondary fly ash which is not roasted with iron ore concentrate powder according to the mass ratio of 70 to obtain a base material of the decarbonizer, mixing the base material with bentonite to obtain a mixture, fully and uniformly mixing the mixture with a proper amount of water to prepare pulp, pressing the pulp into a block, and drying the block at the temperature of 110 to 120 ℃ for 3 to 5 hours to obtain a cylindrical blocky decarbonizer, wherein the diameter of the cylindrical blocky decarbonizer is 1cm, the height of the cylindrical blocky decarbonizer is 1.5cm, and the bentonite accounts for 8 percent of the weight of the mixture. Table 13 lists the TFe total iron content, chemical composition and weight percent of the decarboniser base in example 6, as follows:
as can be seen from Table 13, the unfired secondary fly ash of the converter, in which Fe was contained, was mixed with the iron ore concentrate powder 2 O 3 The content of the molten iron reaches 44.98 percent, and the method has ideal molten iron decarburization effect.
In this example, the influence of different amounts of decarburizing agents on the decarburization effect of molten iron was studied, specifically, 4%, 5%, and 6% of cylindrical block-shaped decarburizing agents based on the weight of molten iron were respectively added to molten iron, and the temperature of molten iron was maintained at 1450 ℃. The specification and the detection method of the iron nugget sample were the same as those of example 1. Table 14 lists the results of the carbon content testing of the iron nugget samples of example 6, as follows:
as can be seen from Table 14, the decarburization efficiency of the decarburization agent prepared by blending unfired converter secondary fly ash and iron ore concentrate powder as the base material of the decarburization agent is lower than that of example 5 (Table 12), which shows that the decarburization efficiency of the converter secondary fly ash as the decarburization agent can be improved after the converter secondary fly ash is sufficiently roasted with oxygen. However, the roasting involves the problem of energy consumption, and corresponding roasting equipment is needed, so that the cost is increased, the converter secondary dedusting ash which is not roasted can be directly blended with iron concentrate powder in a proper proportion to be used as the decarbonizer prepared by the decarbonizer base material, the expected decarbonization effect can still be realized, and the iron concentrate powder accounts for 30-70% of the decarbonizer base material by weight.
Example 7
The converter secondary dedusting ash is mixed with steel rolling iron scale and iron concentrate powder to prepare the base material of the decarbonizer through aerobic roasting. The converter secondary fly ash and the calcination treatment process thereof in this example were the same as in example 1, to obtain the calcined converter secondary fly ash in table 2. The rolled scale in this example was the same as in example 2 (see table 4). The iron ore concentrate powder (brazilian iron ore concentrate powder) in this example was the same as that in example 5 (see table 10). And (3) mixing the roasted converter secondary fly ash and steel rolling iron scale according to the mass ratio of 2:2, blending the mixture with iron ore concentrate powder according to a mass ratio of 4:1, blending to obtain a decarbonizer base material, mixing with bentonite to obtain a mixture, fully mixing with a proper amount of water, directly pelletizing by a disc pelletizer, drying to obtain a spherical blocky decarbonizer with the diameter of 2cm, and drying at 110 to 120 ℃ for 3 to 5 hours, wherein the bentonite accounts for 8 percent of the weight of the mixture. Table 15 lists the TFe total iron content, chemical composition and weight percent thereof for the base decarboniser in example 7, as follows:
table 15 it can be seen that the converter secondary fly ash after roasting, the rolled scale and brazilian iron concentrate powder were mixed with a mixture of 40 2 O 3 The percentage content of the iron oxide scale reaches 47.44 percent, the ideal molten iron decarburization effect is achieved, the rolled steel iron oxide scale belongs to waste materials, the price is low, the impurity elements are few, the iron oxide scale serving as a raw material of a decarburization agent has incomparable advantages, and the use amount of Brazilian iron concentrate powder with high cost can be reduced.
In this example, the influence of different amounts of decarburizing agents on the decarburization effect of molten iron was studied, specifically, 4% and 5% of spherical block-shaped decarburizing agents based on the weight of molten iron were respectively added to molten iron, and the temperature of molten iron was maintained at 1450 ℃. The specification and the detection method of the iron nugget sample were the same as those of example 1. Table 16 lists the results of the carbon content testing of the iron nugget samples of example 7, as follows:
as can be seen from table 16, the ratio of the secondary fly ash of the roasted converter to the iron scale and iron concentrate powder of the rolled steel is 40:40:20 the mixture is used as the decarbonizer base material to prepare the decarbonizer, which can obtain the ideal carbon reduction effect, when the dosage of the decarbonizer is 4 percent, the carbon reduction amount of the molten iron reaches 0.47 percent, and the high-efficiency recycling of the secondary dedusting ash of the converter and the iron in the steel rolling iron scale is realized. The use of the steel rolling iron scale can reduce the use amount of secondary dust removal ash and iron concentrate powder of the converter, reduce the decarburization treatment cost, reduce the amount of impurity elements introduced into the molten iron, not only can reduce the pollution problem of graphite dust generated in the molten iron inversion link, but also can effectively recycle the iron elements in the steel rolling iron scale by the process.
In the above examples 1 to 7, the converter secondary fly ash is used as a main raw material of a decarbonizer base material, and is baked to be used as the decarbonizer base material, or is baked or not baked and then blended with at least one of iron concentrate powder and steel rolling iron scale to be used as the decarbonizer base material, and a block-shaped decarbonizer is obtained from the decarbonizer base material, from experimental results, the decarbonizer prepared by baking the converter secondary fly ash and then blending with the iron concentrate powder and/or the steel rolling iron scale has a good carbon reduction effect, and particularly, the decarbonizer obtained by blending the converter secondary fly ash after baking and the steel rolling iron scale as the decarbonizer base material in example 2 has a good decarbonization efficiency, and the decarbonizer has a low comprehensive cost, and can recycle iron elements in the steel rolling iron scale.
When the decarburization agent is used on site in the molten iron inversion link of a steel plant, on the aspect of the application mode of the decarburization agent, firstly, after molten iron is poured into a converter or a ladle of the steel plant from a torpedo car, the blocky decarburization agent is filled to the bottom in the torpedo car, so that in the process that the torpedo car returns to the steel plant from the steel plant, the blocky decarburization agent is preheated by the waste heat of the torpedo car, and the heat loss of the molten iron caused by directly mixing the blocky decarburization agent with molten iron of a blast furnace is reduced; secondly, before the blast furnace tapping, a powdery decarbonizing agent is paved in a molten iron groove connecting a molten iron hole from the blast furnace and a torpedo car, so that the molten iron flows through the powdery decarbonizing agent and reacts with each other to realize pre-decarbonization, and the powdery decarbonizing agent can quickly react with the molten iron in the molten iron groove without splashing. Therefore, the decarbonizer taking the secondary dedusting ash of the converter as the main raw material is added into the molten iron which is discharged from the blast furnace and is in the inverted link, so that the content of C in the molten iron can be effectively reduced, a large amount of graphite dust generated by the molten iron of the blast furnace due to temperature drop is radically reduced, the dust pollution problem of a steel mill is relieved, and the load of dedusting equipment of the steel mill is reduced.
The present invention is not limited to the above embodiments, and any modifications, equivalent replacements, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for carrying out molten iron decarburization by using secondary fly ash of a converter is characterized by comprising the following steps: the method comprises the following steps:
preparing a decarbonizing agent base stock, wherein the decarbonizing agent base stock comprises converter secondary dedusting ash as a raw material;
step two, mixing the base material of the decarbonizing agent with an inorganic binder to obtain a mixture, fully mixing the mixture with water, pressing the mixture into small blocks, and drying the small blocks to obtain a blocky decarbonizing agent, wherein the inorganic binder accounts for 5 to 10 percent of the weight of the mixture;
step three, filling the block-shaped decarbonizing agent to the bottom in the emptied torpedo ladle car, wherein the using amount of the block-shaped decarbonizing agent is 4-8% of the weight of the molten iron filled in the torpedo ladle car, and preheating the block-shaped decarbonizing agent by the waste heat of the torpedo ladle car;
pouring the molten iron into a torpedo ladle car, wherein the temperature of the molten iron is 1330 to 1500 ℃, and the molten iron is in contact with a massive decarbonizing agent and is subjected to oxidation reaction for decarbonization treatment;
in the first step, the converter secondary dedusting ash is roasted to be used as a decarbonizer base material, and the roasting conditions are as follows: baking in air at 800-1000 ℃ for 3-5 hours;
the converter secondary dedusting ash comprises the following chemical components in percentage by weight: fe 2 O 3 ：23.00~26.00%、FeO：10.00~12.00%、S：0.180~0.200%、SiO 2 ：5.50~6.50%、Al 2 O 3 ：1.80~2.30%、CaO：24.00~27.00%、MgO：9.00~11.00%、MnO：0.60~0.80%、P 2 O 5 :0.130 to 0.190%, C:2.50-4.00%, znO:8.00 to 9.00%, and the balance of impurities: 6.00 to 7.00 percent.
2. The method for decarbonizing molten iron by using the secondary precipitator dust of the converter according to claim 1, wherein the method comprises the following steps: in the first step, the base material of the decarbonizer also comprises iron ore concentrate, the converter secondary fly ash and the iron ore concentrate are blended to be used as the base material of the decarbonizer, the weight percentage of the converter secondary fly ash is 30-70%, and the balance is the iron ore concentrate.
3. The method for decarbonizing molten iron by using the secondary dedusting ash of the converter according to claim 1, is characterized in that: in the first step, the raw materials of the base material of the decarbonizer also comprise rolled steel scales, the converter secondary dedusting ash and the rolled steel scales are blended to be used as the base material of the decarbonizer, the weight percentage of the converter secondary dedusting ash is 30-70%, and the balance is the rolled steel scales.
4. The method for decarbonizing molten iron by using the secondary precipitator dust of the converter according to claim 1, wherein the method comprises the following steps: in the first step, the raw materials of the base material of the decarbonizer also comprise iron concentrate powder and steel rolling iron scale, and the converter secondary dedusting ash, the iron concentrate powder and the steel rolling iron scale are blended to be used as the base material of the decarbonizer, and the corresponding weight percentage is 20 to 50 percent, 10 to 30 percent and 30 to 60 percent.
5. The method for decarbonizing molten iron by using the secondary dedusting ash of the converter according to claim 1, is characterized in that: and in the second step, the mixture is mixed with water and then is pressed and formed by a ball press machine or a briquetting machine, and the mixture is dried at the temperature of 110 to 120 ℃ for 3 to 5 hours.
6. The method for decarbonizing molten iron using secondary fly ash of a converter according to claim 1 or 5, wherein: in the second step, the block size of the block-shaped decarbonizer is 0.3 to 5cm.
7. The method for decarbonizing molten iron by using the secondary dedusting ash of the converter according to claim 1, is characterized in that: in the fourth step, when the massive decarbonizer is mixed with molten iron for decarbonization, the temperature of the molten iron is 1400 to 1500 ℃.
8. The method for decarbonizing molten iron by using the secondary dedusting ash of the converter according to claim 1, is characterized in that: in the second step, part of the base material of the decarbonizer is roasted to prepare a powdery decarbonizer; in the third step, a powdery decarbonizing agent is paved in advance in an iron runner connecting a blast furnace iron nozzle and a torpedo tank car; in the fourth step, the molten iron contacts with the powdery decarbonizer when flowing through the molten iron runner and is subjected to oxidation reaction for pre-decarbonization treatment.
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