CN110157899B - Method for strengthening removal and efficient recovery of harmful elements in sintering process - Google Patents
Method for strengthening removal and efficient recovery of harmful elements in sintering process Download PDFInfo
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- CN110157899B CN110157899B CN201910543190.4A CN201910543190A CN110157899B CN 110157899 B CN110157899 B CN 110157899B CN 201910543190 A CN201910543190 A CN 201910543190A CN 110157899 B CN110157899 B CN 110157899B
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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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
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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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
Abstract
The invention discloses a method for strengthening removal of harmful elements and efficiently recovering in a sintering process. The method divides the iron-containing raw materials into high K (Na or Zn or Sn) materials, high Pb (As) materials, high carbon materials and clean materials according to the contents of K, Na, Zn, Sn, Pb, As and fixed carbon; high-alkalinity spherulites are made from high-K (Na or Zn or Sn) material, high-carbon material, high-reactivity fuel and flux, low-alkalinity spherulites are made from high-Pb (As) material, low-reactivity fuel and flux, the two are mixed and distributed on the bottom layer, clean material is made into spherulites and distributed on the upper layer, ignition sintering is carried out, and dust particles in the flue gas in different sintering stages are collected and recovered respectively. The method provides conditions such as favorable chemical components, atmosphere, temperature and the like for the efficient removal of different harmful elements in the iron-containing raw material, greatly improves the removal rate of the harmful elements, and improves the recovery rate of dust particles containing valuable harmful elements to more than 99 percent through the shunting treatment of flue gas at different stages.
Description
Technical Field
The invention relates to a method for removing and recycling harmful elements in sintering flue gas, in particular to a method for classifying and pelletizing iron-containing raw materials according to chemical components, temperature and atmosphere differences required by high-efficiency removal of different types of harmful elements, creating conditions matched with the chemical components, temperature and atmosphere differences, and realizing synchronous high-efficiency removal of various types of harmful elements, belonging to the field of ferrous metallurgy.
Background
The annual output of crude steel in China exceeds 8 hundred million tons, and huge steel production capacity and iron ore consumption cause that high-quality iron ore resources are increasingly deficient. Iron ore resources such As non-mainstream imported ores, self-produced ores, iron-containing dust and mud and the like are increasingly used in steel production in China, and the large-scale application of the iron ore resources can increase the contents of harmful elements such As K, Na, Pb, Zn, Sn and As in steel production raw materials, further increase the difficulty of blast furnace smelting and high-quality steel production, and also increase the environmental pollution and the treatment difficulty in the steel production process.
Under the current sintering technical conditions, the removal proportion of K, Na, Pb, Zn, Sn, As and the like in the sintering process is low, so that the load of harmful elements entering a blast furnace is high, and particularly, the K, Na, Zn and Sn are circularly enriched in the blast furnace to generate adverse effects on the air permeability of the blast furnace and the smooth operation of the blast furnace; pb is deposited on the furnace bottom to influence the service life of the furnace hearth; in recent years, many iron and steel enterprises have frequent blast furnace accidents due to the problem of harmful elements, and even seriously affect iron-making production. Harmful elements enter molten iron, most of the harmful elements are difficult to remove or have the problems of complex treatment process, high cost and the like in the subsequent steelmaking process, and the residual harmful elements in the molten steel can finally cause the performance reduction of steel products.
Sintering not only takes on the function of powder agglomeration, but also takes on the task of removing harmful elements. Harmful elements are removed as much as possible in the sintering process, which is beneficial to reducing the difficulty of blast furnace smelting and reducing the task of impurity removal in the steelmaking process, thereby improving the purity of molten steel and the performance of steel products. Therefore, the atmosphere and temperature environment which are beneficial to removing different types of harmful elements are created in the sintering process, the removal of the harmful elements is strengthened, and the high-efficiency recovery of the valuable components entering the flue gas has important practical significance for the green manufacture of the steel industry.
Disclosure of Invention
Aiming at the problems of product quality reduction and environmental pollution caused by the large-scale use of iron-containing raw materials with high content of harmful elements in sintering in the prior art, the invention aims to provide a method for classifying and pelletizing iron-containing raw materials with different contents of harmful elements and carbon according to the difference of chemical components, temperature and atmosphere required by the high-efficiency removal of different types of harmful elements, creating conditions matched with the chemical components, temperature and atmosphere, and strengthening the removal and high-efficiency recovery of the harmful elements.
In order to achieve the technical purpose, the invention provides a method for strengthening removal and efficient recovery of harmful elements in a sintering process, which comprises the following steps:
1) raw material classification:
classifying the iron-containing raw materials into iron-containing raw materials I-IV according to the contents of K, Na, Pb, Zn, Sn, As and fixed carbon in the iron-containing raw materials;
the iron-containing raw material I contains any one of K, Na, Zn and Sn with the mass percent higher than 0.05 percent, or the total mass percent of more than two of the K, Na, Zn and Sn with the mass percent higher than 0.10 percent;
the mass percentage of any one of Pb and As in the iron-containing raw material II is higher than 0.04%, or the total mass percentage of the Pb and the As is higher than 0.06%;
the mass percentage content of fixed carbon in the iron-containing raw material III is higher than 5%;
the iron-containing raw material IV is an iron-containing raw material except the iron-containing raw materials I to III;
if the contents of K, Na, Pb, Zn, Sn, As and fixed carbon in the iron-containing raw material simultaneously meet two or three of the iron-containing raw material I, the iron-containing raw material II and the iron-containing raw material III, the iron-containing raw material II, the iron-containing raw material I and the iron-containing raw material III are sequentially classified in priority;
2) and (3) granulating:
mixing and granulating iron-containing raw materials I and III, a fusing agent and a high-reactivity fuel to obtain high-alkalinity spherulites ①, mixing and granulating iron-containing raw materials II, the fusing agent and a low-reactivity fuel to obtain low-alkalinity spherulites ②, mixing and granulating iron-containing raw materials IV, the fusing agent, fossil fuel and return fines to obtain spherulites ③;
3) material distribution:
after mixing pellets ① and ②, the mixture was fed first on a sintering bench and then pellets ③ were fed on top of the mixed pellets of pellets ① and ②;
4) and (3) sintering:
igniting and sintering, and respectively collecting and recovering dust particles in the flue gas at different sintering stages in the sintering process.
Preferably, the flux is a flux commonly used in the art, such as quicklime, dolomite, limestone, and the like.
Preferably, the high-reactivity fuel has the porosity of 50-80% and the specific surface area of 40-70 m2The average granularity is 1-2 mm, and the mass percentage content of the fraction smaller than 0.5mm is not less than 20%.
Preferably, the mass of the high-reactivity fuel accounts for 3.5-6.5% of the total mass of the pellets ①.
More preferably, the highly reactive fuel comprises at least one of biomass semi-coke, semi-coke and activated carbon.
The iron-containing raw material I is high in content of volatile metals such as K, Na, Zn, Sn and the like, and provides a required reducing atmosphere for efficient reduction and volatilization of harmful elements by adding fuel with high chemical reaction activity.
Preferably, the porosity of the low reactivity fuel is 20-40%, the proportion of the total number of pores with the diameter less than 1 μm is less than 40%, and the specific surface area is 5-20 m2The average particle size is 1-3 mm, and the mass percentage content of the particle fraction smaller than 0.5mm is not more than 15%.
Preferably, the mass of the low reactivity fuel accounts for 1.5-3% of the total mass of the pellets ②.
In a preferred embodiment, the low reactivity fuel includes at least one of coke powder, anthracite, briquette and formed coke.
The iron-containing raw material II has high Pb and As contents, and the reducing atmosphere formed by the adopted low-reaction active fuel is relatively weak, so that favorable atmosphere conditions are provided for the high-efficiency removal of As and Pb, and the high-efficiency removal of As and Pb is enhanced.
The iron-containing raw material III contains fine-grained carbon fuel, and the fine-grained carbon fuel is mixed with the iron-containing raw material I for granulation, so that the fine-grained carbon in the iron-containing raw material III is fully utilized, and the reduction atmosphere which is favorable for removing K, Na, Zn and Sn is formed.
In a preferable scheme, the binary alkalinity of the high-alkalinity spherulite ① is 2.0-2.4. the binary alkalinity in the spherulite ① is adjusted to be at a higher level, so that the rich CaO around the iron-containing material can accelerate the reduction and volatilization reaction of K, Na, Zn and Sn, and the high-efficiency removal of the CaO is realized.
In a preferable scheme, the binary alkalinity of the low-alkalinity spherical particle ② is 1.2-1.6. the binary alkalinity of the interior of the spherical particle ② is controlled at a lower level, so that the blocking effect of overhigh CaO content on Pb and As removal is weakened.
In the preferred scheme, the flue gas in the pre-heating stage in the sintering process is purified and dedusted by an electrostatic precipitator, and the flue gas in the sintering heating stage is collected by a bag-type dust collector.
The method for strengthening the removal of harmful elements and efficiently recovering in the sintering process comprises the following specific steps:
(1) according to the content of harmful elements (K, Na, Pb, Zn, Sn and As) and the content of fixed carbon in the sintered iron-containing raw material, the sintered iron-containing raw material is divided into an iron-containing raw material (marked As a material I) with high K (Na or Zn or Sn) content, an iron-containing raw material (marked As a material II) with high Pb (As) content, an iron-containing raw material (marked As a material III) with high carbon content and a clean iron-containing raw material (marked As a material IV);
(2) mixing the material I and the material III with a fusing agent and a high-reactivity fuel for granulation to obtain high-alkalinity spherulites ①;
(3) mixing the material II with a fusing agent and a low-reactivity fuel for granulation to obtain low-alkalinity spherulites ②;
(4) mixing the material IV with the residual flux, conventional fossil fuel and return fines, and granulating to obtain pellets ③
(5) The pellets ① and ② are mixed and firstly distributed on a sintering machine trolley, then the pellets ③ are distributed, layered distribution of different types of pellets is achieved, then ignition and sintering are carried out, and dust particles in smoke at different stages in the sintering process are respectively collected.
The sintering process of the iron-containing raw material is conventional in the field, and the specific sintering conditions comprise that firstly, fuel in a surface layer mixture is ignited under the conditions that the ignition temperature is 1050 ℃, the ignition time is 1.5min and the ignition negative pressure is 5kPa, then the sintering negative pressure is adjusted to 10kPa for air draft sintering, the fuel combustion front edge in a material layer moves downwards layer by layer under the action of the air draft negative pressure, and K, Na, Pb, Zn, Sn and As are efficiently removed when the fuel is moved to the material layer where the spherical particles ① and ② are located, a thermocouple is adopted in the sintering process to detect the change of the temperature of flue gas, an electrostatic dust collector is adopted to collect dust particles in the flue gas before temperature rise, and a bag-type dust collector is adopted to collect dust particles in the flue gas of the temperature rise section after waste heat.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the invention synchronously granulates the materials with high carbon content and the materials with high K, Na, Zn and Sn content, provides a required reducing atmosphere for the efficient reduction and volatilization of harmful elements by adding fuels with high chemical reaction activity, synchronously regulates and controls the binary alkalinity in the granulated pellets to be at a higher level, and the rich CaO around the materials can accelerate the reduction and volatilization reaction of K, Na, Zn and Sn to realize the efficient removal.
(2) The invention separately granulates the materials with high Pb and As content, controls the alkalinity of the spherulites at a lower level, weakens the barrier effect of overhigh CaO content on Pb and As removal when not separately pelletized, creates favorable chemical component conditions for the high-efficiency removal of Pb and As, and provides favorable atmosphere conditions for the high-efficiency removal of As and Pb because the reducing atmosphere formed by the adopted low-reaction active fuel is relatively weaker.
(3) The invention distributes the material with high content of harmful elements at the lower part of the sinter bed, and further promotes the removal of K, Na, Zn and Pb by fully utilizing the characteristics of high heat storage temperature and long high-temperature duration of the lower part of the sinter bed; meanwhile, under the comprehensive action of the various reinforced removal methods, the high-efficiency removed heavy (alkali) metals are intensively discharged to the flue gas at the temperature-rising stage by taking the dust particles As carriers, and the flue gas is subjected to waste heat recovery by a heat exchanger and then is collected by a bag-type dust collector to collect the dust particles rich in K, Na, Pb, Zn, As, Sn and other valuable components, so that the subsequent resource recycling is facilitated.
By adopting the method, the removal rates of K, Na, Pb, Zn, As and Sn are greatly increased to 50-70%, 40-60%, 60-80%, 30-50%, 60-80% and 25-50% from 15-25%, 7-13%, 40-55%, 2-6%, 35-45% and 2-6% respectively according to a conventional sintering method, the content of harmful elements in the sintering ore is obviously reduced, and the recovery efficiency of dust particles rich in valuable components reaches more than 99% by adopting a bag-type dust remover.
Drawings
FIG. 1 is a schematic diagram of the distribution and recovery of a high harmful element material layer.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
Example 1
The method comprises the steps of obtaining harmful elements of an iron-containing raw material used in the attached table 1, wherein the iron-containing raw material-1 is a high-K-content material accounting for 10% of the iron-containing raw material by mass, the iron-containing raw material-2 is a high-Sn-content material accounting for 5% of the iron-containing raw material by mass, the iron-containing raw material-3 is a high-Pb-content material accounting for 5% of the iron-containing raw material by mass, the iron-containing raw material-4 is a high-carbon-content material accounting for 5% of the iron-containing raw material by mass, the iron-containing raw material-5 is a clean material accounting for 75% of the iron-containing raw material by mass, the attached table 2 shows that the fuel-1 used in the test is a high-reactivity fuel, the fuel-2 is a low-reactivity fuel, the iron-1, the iron-containing raw material-2 and the iron-containing raw material-4 are mixed and granulated with quicklime and the fuel-1, the pellet-1 for 4min after the iron-containing raw material-4, the pellet-4.0% of alkalinity is obtained, the pellet- ① is mixed and granulated with the sintering particles with the flux and the fuel-2, the sintering particles, the dust-powder-dust is obtained after the sintering process of the mixture-dust-sintering particles, the mixture of the mixture-powder-dust-containing raw material-dust.
Example 2
The method comprises the steps of obtaining harmful elements of an iron-containing raw material used in the attached table 1, wherein the iron-containing raw material-1 is a high-K-content material accounting for 10% of the iron-containing raw material by mass, the iron-containing raw material-2 is a high-Sn-content material accounting for 5% of the iron-containing raw material by mass, the iron-containing raw material-3 is a high-Pb-content material accounting for 5% of the iron-containing raw material by mass, the iron-containing raw material-4 is a high-carbon-content material accounting for 5% of the iron-containing raw material by mass, the iron-containing raw material-5 is a clean material accounting for 75% of the iron-containing raw material by mass, the attached table 2 shows that the fuel-1 used in the test is a high-reactivity fuel, the fuel-2 is a low-reactivity fuel, the iron-1, the iron-containing raw material-2 and the iron-containing raw material-4 are mixed and granulated with quicklime and the fuel-1, the pellet-1 for 4min, the pellet-2, the pellet-fuel proportion is 5.0%, the pellet ① is obtained after the mixed and granulated with the flux and the pellet-2, the mixture of the sintered pellets and the fuel-2 is obtained after the granulation, the granulation is carried out, the granulation with the granulation time of the granulation with the dust removal of the.
Example 3
The method comprises the steps of obtaining harmful elements of an iron-containing raw material, namely a high-K-content material accounting for 10% of the weight of the iron-containing raw material, obtaining a high-Sn-content material accounting for 5% of the weight of the iron-containing raw material, obtaining a high-Pb-content material accounting for 5% of the weight of the iron-containing raw material, obtaining a high-carbon-content material accounting for 5% of the weight of the iron-containing raw material, obtaining a clean material accounting for 75% of the weight of the iron-containing raw material, obtaining a high-reactivity fuel as fuel-1 and a low-reactivity fuel as fuel-2, mixing and granulating the iron-containing raw material-1, the iron-containing raw material-2 and the iron-containing raw material-4 with quicklime and the fuel-1 for 4min to obtain pellets with a basicity of 2.3 and a fuel proportion of 5.5%, obtaining pellets ① with a basicity of 2.3 and a fuel proportion of 5.5%, obtaining pellets after mixing and granulating the iron-containing raw material-3 with a flux and the fuel-2, obtaining a mixture with a sintering pellet, obtaining a dust-sintering powder mixture with a dust-collecting powder, and a dust-removing powder-dust-.
Example 4
The method comprises the steps of obtaining harmful elements of an iron-containing raw material, namely a high-K-content material accounting for 10% of the weight of the iron-containing raw material, obtaining a high-Sn-content material accounting for 5% of the weight of the iron-containing raw material, obtaining an iron-containing raw material, namely a high-K-content material accounting for 10% of the weight of the iron-containing raw material, obtaining an iron-containing raw material, namely a high-Sn-content material accounting for 5% of the weight of the iron-containing raw material, obtaining an iron-containing raw material, namely a high-carbon-content material accounting for 5% of the weight of the iron-containing raw material, obtaining a clean material accounting for 75% of the weight of the iron-containing raw material, obtaining a high-reactivity fuel accounting for 1 of the iron-containing raw material, namely a high-reactivity fuel accounting for 75% of the weight of the iron-containing raw material, obtaining a low-reactivity fuel for 2 of the iron-containing raw material, namely a low-reactivity fuel for 5% of the iron-containing raw material, obtaining a pellet, namely a clean material accounting for 75% of the iron-containing raw material, obtaining a pellet by the high-reactivity fuel for 75% of the weight of the iron-containing raw material, obtaining the pellet-1 of the high-reactivity fuel for the high-reactivity fuel, obtaining a pellet-reactivity fuel, namely a pellet-reactivity fuel, obtaining pellet-reactivity fuel-pellet, obtaining pellet-.
TABLE 1 harmful element composition of iron-containing raw material used in the test
TABLE 2 physicochemical characteristics of fuels used in the tests
Claims (6)
1. A method for strengthening removal and efficient recovery of harmful elements in a sintering process is characterized by comprising the following steps: the method comprises the following steps:
1) raw material classification:
classifying the iron-containing raw materials into iron-containing raw materials I-IV according to the contents of K, Na, Pb, Zn, Sn, As and fixed carbon in the iron-containing raw materials;
the iron-containing raw material I contains any one of K, Na, Zn and Sn with the mass percent higher than 0.05 percent, or the total mass percent of more than two of the K, Na, Zn and Sn with the mass percent higher than 0.10 percent;
the mass percentage of any one of Pb and As in the iron-containing raw material II is higher than 0.04%, or the total mass percentage of the Pb and the As is higher than 0.06%;
the mass percentage content of fixed carbon in the iron-containing raw material III is higher than 5%;
the iron-containing raw material IV is an iron-containing raw material except the iron-containing raw materials I to III;
if the contents of K, Na, Pb, Zn, Sn, As and fixed carbon in the iron-containing raw material simultaneously meet two or three of the iron-containing raw material I, the iron-containing raw material II and the iron-containing raw material III, the iron-containing raw material II, the iron-containing raw material I and the iron-containing raw material III are sequentially classified according to the priority;
2) and (3) granulating:
mixing and granulating iron-containing raw materials I and III, a flux and a high-reactivity fuel to obtain high-alkalinity spherulites ①, mixing and granulating iron-containing raw materials II, the flux and a low-reactivity fuel to obtain low-alkalinity spherulites ②, mixing and granulating iron-containing raw materials IV, the flux, a fossil fuel and return ores to obtain spherulites ③, wherein the porosity of the high-reactivity fuel is 50-80%, and the specific surface area of the high-reactivity fuel is 40-70 m2The average granularity is 1-2 mm, and the mass percentage content of the fraction smaller than 0.5mm is not less than 20%; the low reactivity fuel has a porosity of 20 to 40%, a number of pores smaller than 1 μm is less than 40% of the total pore ratio, and a specific surface area of 5 to 20m2The average particle size is 1-3 mm, the mass percentage content of the particle fraction smaller than 0.5mm is not more than 15%, the binary alkalinity of the high alkalinity spherulites ① is 2.0-2.4, and the binary alkalinity of the low alkalinity spherulites ② is 1.2-1.6;
3) material distribution:
after mixing pellets ① and ②, the mixture was fed first on a sintering bench and then pellets ③ were fed on top of the mixed pellets of pellets ① and ②;
4) and (3) sintering:
igniting and sintering, and respectively collecting and recovering dust particles in the flue gas at different sintering stages in the sintering process.
2. The method for enhancing the removal of harmful elements and efficiently recovering the harmful elements in the sintering process as claimed in claim 1, wherein the mass of the high-reactivity fuel accounts for 3.5-6.5% of the total mass of the pellets ①.
3. The method for enhancing the removal and efficient recovery of harmful elements in the sintering process according to any one of claims 1 to 2, wherein the method comprises the following steps: the high-reactivity fuel comprises at least one of biomass semi-coke, semi-coke and activated carbon.
4. The method for enhanced removal and efficient recovery of harmful elements during sintering according to claim 1, wherein the mass of the low reactivity fuel is 1.5-3% of the total mass of the pellets ②.
5. The method for enhancing harmful element removal and high-efficiency recovery in the sintering process according to claim 1 or 4, wherein: the low reactivity fuel comprises at least one of coke powder, anthracite, briquette and formed coke.
6. The method for enhanced removal and efficient recovery of harmful elements in a sintering process according to claim 1, wherein: the flue gas in the pre-heating stage in the sintering process is purified and dedusted by an electrostatic precipitator, and the flue gas in the sintering heating stage is collected by a bag-type dust collector.
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