CN114672604A - Method for preparing direct reduced iron from carbon-containing waste - Google Patents

Method for preparing direct reduced iron from carbon-containing waste Download PDF

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CN114672604A
CN114672604A CN202210364087.5A CN202210364087A CN114672604A CN 114672604 A CN114672604 A CN 114672604A CN 202210364087 A CN202210364087 A CN 202210364087A CN 114672604 A CN114672604 A CN 114672604A
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coke
dry quenching
pellets
iron
carbon
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CN114672604B (en
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武吉
谢明辉
赵东明
李建军
车玉满
刘福军
李晓春
赵华
陈立哲
张�杰
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Angang Steel Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/14—Multi-stage processes processes carried out in different vessels or furnaces
    • C21B13/146—Multi-step reduction without melting
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/008—Use of special additives or fluxing agents
    • 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
    • C22B1/216—Sintering; Agglomerating in rotary furnaces
    • 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
    • C22B1/2406—Binding; Briquetting ; Granulating pelletizing
    • 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
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • C22B1/244—Binding; Briquetting ; Granulating with binders organic
    • C22B1/245—Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

The invention relates to a method for preparing direct reduced iron from carbon-containing waste, which comprises the following steps: 1) uniformly mixing iron ore powder, coking dedusting ash and a fusing agent, spraying a binding agent in the uniformly mixing process, performing heat exchange by using the waste heat of a coke oven ascending pipe, pressurizing, pelletizing and roasting to obtain primary reduction pellets; 2) respectively loading coke and the primary reduced pellets into a dry quenching furnace in batches, and carrying out secondary reduction on the primary reduced pellets by using coke waste heat in the dry quenching furnace to obtain sponge iron balls; 3) the sponge iron balls and the coke are cooled in the dry quenching furnace together, and are discharged from a coke discharge port of the dry quenching furnace together with the coke and enter the blast furnace together. The invention has the advantages that: the carbon-containing pellets are prepared by utilizing the coking and dedusting ash carbon-containing waste, the iron ore powder, the binder and the like, the carbon-containing pellets are directly utilized to exchange heat with red coke, the carbon-containing pellets undergo a pre-reduction reaction, and then the iron-containing pellets with high metallization rate are prepared.

Description

Method for preparing direct reduced iron from carbon-containing waste
Technical Field
The invention belongs to the field of ironmaking raw materials, and particularly relates to a method for preparing direct reduced iron from carbon-containing wastes.
Background
The coke is used as a main raw fuel for blast furnace ironmaking and plays an irreplaceable role in the blast furnace. On the one hand, in the coke production process, a large amount of fly ash can be generated, including coal-charging fly ash, coke-pushing fly ash, dry quenching fly ash, sieve transfer coke fly ash and the like. The property difference of the fly ash in each process is larger, but the fixed carbon content is higher. In the past, the fly ash is generally used as a common fuel in power generation or sintering processes, and the particle size of the fly ash is required to be not too fine in order to ensure sufficient combustion, so that the coking and dust removal with small particle size cannot be used with high added value. On the other hand, after the coke is pushed out from the coke oven, the temperature of the red coke generally reaches 800-1000 ℃, at present, the red coke is mainly conveyed to a dry quenching coke oven, and is subjected to heat exchange with nitrogen, and then the heat is recovered by a steam boiler. In order to realize high value-added utilization of carbon-containing solid waste and fully utilize the waste heat of red coke, the method provides the method for preparing carbon-containing pellets by utilizing the coking dust-removal carbon-containing waste, and utilizes the heat exchange between the carbon-containing pellets and the red coke to cause the carbon-containing pellets to generate pre-reduction reaction so as to prepare the iron-containing pellets with higher metallization rate.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing direct reduced iron from carbon-containing waste, so that high value-added utilization of the carbon-containing waste such as coking dust removal ash and the like is realized, and iron-containing pellets with high metallization rate are prepared by using the waste heat of red coke.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for preparing direct reduced iron from carbonaceous waste, comprising the steps of:
1) uniformly mixing iron ore powder, coking dedusting ash and a fusing agent, spraying a binding agent in the uniformly mixing process, performing heat exchange for 10-30 min by using the waste heat of an ascending pipe of a coke oven, pressurizing and pelletizing, and then roasting at 1000-1300 ℃ for 10-40 mm to obtain primary reduction pellets;
2) respectively loading coke and the primary reduced pellets in the step 1) into a dry quenching furnace in batches, and carrying out secondary reduction on the primary reduced pellets by using coke waste heat in the dry quenching furnace to obtain sponge iron balls;
or uniformly distributing the primary reduced pellets in the step 1) on the outer surface layer of red coke stored in the dry quenching tank, and feeding the red coke and the red coke in the dry quenching tank into a dry quenching furnace together to obtain secondary reduced sponge iron balls; the mass ratio of the primary reduction pellets to the red coke is controlled to be 1: 50-1: 10;
3) the sponge iron balls and the coke are cooled in the dry quenching furnace together, and are discharged from a coke discharging port of the dry quenching furnace together with the coke, and then enter the blast furnace together;
or magnetic separation devices are respectively arranged at the coke discharging port of the dry quenching furnace and the transfer belt, and when the sponge iron balls are discharged and transferred together with the coke from the coke discharging port of the dry quenching furnace, the sponge iron balls are separated from the coke.
In the step 1), the mass percent of the iron ore powder is 50-80%, the mass percent of the coking dust removal ash is 5-45%, the mass percent of the binder is 0.5-3.0%, and the mass percent of the flux is 1-20%.
The pressure resistance of the primary reduction pellet obtained in the step 1) is more than or equal to 2000N, and the drum strength is more than or equal to 78%.
The coking fly ash is one or more of dry quenching fly ash, coal loading fly ash, coke pushing fly ash and belt transfer station fly ash, and the coking fly ash contains 80-90% of fixed carbon, 1.0-5.0% of volatile matter and 5.0-13.5% of ash.
The blending amount of the coking dust removal ash in the step 1) is more than the dust removal ash amount calculated by the reduction of all reducible oxides in the iron ore powder by fixed carbon.
The iron ore powder in the step 1) comprises one or more of magnetite, hematite, goethite and tailings after iron separation.
In the step 2), the coke and the primary reducing pellets are respectively loaded into the dry quenching furnace in batches, or the primary reducing pellets are uniformly distributed on the outer surface layer of the red coke stored in the dry quenching tank, the uniform distribution is carried out by utilizing a spiral distributor, the angle between the spiral distributor and a central shaft is adjustable, and the spiral distributing pellets are uniformly distributed on the red coke surface of the dry quenching furnace or the dry quenching tank.
The fusing agent in the step 1) comprises one or more of lime, limestone, marble powder and hydrated lime.
The binder in the step 1) comprises one or more of tar, asphalt and resin, and in the process of uniformly mixing the materials, the tar, the asphalt and the resin are sprayed in a mist form, wherein the temperature of the tar is controlled to be above 80 ℃, the temperature of the asphalt is controlled to be above 200 ℃, and the temperature of the resin is controlled to be above 100 ℃.
The total reducible oxide comprises FeO and Fe3O4、Fe2O3、FeO(OH)、SiO2。
Compared with the prior art, the invention has the beneficial effects that:
the invention utilizes coking dust-removing carbon-containing waste, iron ore powder, flux, binder and the like to prepare carbon-containing pellets, directly utilizes high-temperature roasting, the carbon-containing pellets and red coke to exchange heat, and the carbon-containing pellets undergo a pre-reduction reaction, so as to prepare iron-containing pellets with higher metallization rate, and has the following specific beneficial effects:
(1) because the solid waste coking and dedusting ash does not have cohesiveness, the iron ore powder, the coking and dedusting ash and the flux are mixed uniformly, and the binder is added in the mixing process, so that the balling rate and the green balling strength are improved, and the reduction sufficiency is ensured.
(2) And a flux is added in the material mixing process, so that the liquid phase generation amount of the pellet in the high-temperature direct reduction process is increased, the full contact of carbon and iron-containing minerals in the reduction process is improved, and the sponge pellet with high metallization rate is prepared.
(3) The method utilizes the carbon-containing solid waste dedusting ash with no bonding viscosity and high fixed carbon content as a reducing agent, utilizes a small amount of bonding agent and fusing agent to realize pressurized pelletizing and rotary kiln roasting primary reduction to prepare pressure-resistant and wear-resistant carbon-containing pellets, simultaneously fully utilizes red coke waste heat to realize secondary reduction of the carbon-containing pellets in a dry quenching furnace, and obviously reduces the CO content of the blast furnace2The discharge amount is reduced, and the high value-added utilization of the coking and dedusting wastes is realized.
Drawings
FIG. 1 is a schematic flow diagram of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, but it should be noted that the present invention is not limited to the following embodiments.
Example 1:
referring to fig. 1, a method for preparing direct reduced iron from carbon-containing waste comprises the following steps:
1. hematite powder, coking fly ash and lime are mixed according to the mass percentage of 53.5%: 35%: mixing 10 percent of the raw materials, heating tar to 110 ℃ in the process of uniformly mixing, spraying tar accounting for 1.5 percent of the mass of the uniformly mixed materials in a mist form, carrying out heat exchange for 10min by using the waste heat of an ascending pipe of a coke oven, pressurizing to 10MPa for pelletizing after the tar is in a paste state, drying the pressurized pellets, and roasting at 1300 ℃ for 40mim to obtain the primary reduction pellet. The pressure resistance of the primary reduction pellets after roasting is 2200N, and the drum strength is 85%. The coking fly ash is screen coking fly ash, the fixed carbon content is 85%, the volatile matter content is 1.0%, and the ash content is 13.5%.
2. And (3) adding coke and the primary reduced pellets in the step (1) into a dry quenching furnace in batches, and uniformly distributing the materials by using a spiral material distributor, wherein the angle between the spiral material distributor and a central shaft is 30-85 degrees, and the spirally distributed pellets are uniformly distributed on the surface of red coke. And the carbon-containing pellets are subjected to secondary reduction at the prestore section of the dry quenching furnace by fully utilizing the coke waste heat in the dry quenching furnace to obtain the sponge iron balls. The mass ratio of the primary reduction pellets to the red coke is controlled to be 1: 50.
The reduction reaction that takes place comprises two parts:
firstly, reducing fixed carbon, iron-containing mineral and SiO in pellet ore at one time2Direct reduction reaction:
Figure BDA0003574588680000031
Figure BDA0003574588680000032
② CO generated by reduction or CO and H in dry quenching cycle gas2Reacting with iron-containing minerals or dry-quenching coke and coke containing iron
Iron mineral interface reduction reaction:
Figure BDA0003574588680000041
Figure BDA0003574588680000042
Figure BDA0003574588680000043
Figure BDA0003574588680000044
Figure BDA0003574588680000045
Figure BDA0003574588680000046
Figure BDA0003574588680000047
3. and (3) cooling the reduced sponge iron balls and coke in the dry quenching furnace, discharging the cooled sponge iron balls and the coke together from an outlet of the dry quenching furnace, and separating the sponge iron balls from the coke at the outlet of the dry quenching furnace and a transfer belt by using a magnetic separation device to obtain the sponge iron balls with the metallization rate of 88%.
Example 2:
referring to fig. 1, a method for preparing direct reduced iron from carbon-containing waste comprises the following steps:
1. and mixing magnetite powder, coking fly ash, limestone and marble powder according to the mass percentage of 57%: 22%: 10%: 10 percent of waste asphalt is mixed, in the process of uniformly mixing, the waste asphalt is heated to 215 ℃, the waste asphalt accounting for 1.0 percent of the mass of the uniformly mixed materials is sprayed in a mist form, heat exchange is carried out for 30min by utilizing the waste heat of a coke oven ascending pipe, the waste asphalt is pressed to 15MPa for pelletizing after being pasty, then the pressed pellets are dried and are roasted for 40mim at 1000 ℃, and the primary reduction pellets are obtained. The pressure resistance of the primary reduced pellet after roasting is 2100N, and the drum strength is 78%. The coking fly ash is a mixture of coal-charging fly ash and coke-pushing fly ash, the fixed carbon content is 80%, the volatile content is 3.5%, and the ash content is 11.5%.
2. Uniformly and directly distributing the primary reduction pellets in the step 1 on the outer surface layer of red coke stored in a dry quenching coke tank, feeding the red coke and the red coke in the dry quenching coke tank into a dry quenching furnace, fully utilizing coke waste heat in the dry quenching furnace, carrying out secondary reduction on carbon-containing pellets at a pre-storage section of the dry quenching furnace to obtain sponge iron pellets, and controlling the mass percentages of the primary reduction pellets and the red coke to be 1: 50.
the reduction reaction that takes place comprises two parts:
firstly, reducing fixed carbon, iron-containing mineral and SiO in pellet ore at one time2Direct reduction reaction:
Figure BDA0003574588680000048
Figure BDA0003574588680000049
② CO generated by reduction or CO and H in dry quenching cycle gas2Reacting with iron-containing minerals or dry quenching coke and coke containing iron
Iron mineral interface reduction reaction:
Figure BDA0003574588680000051
Figure BDA0003574588680000052
Figure BDA0003574588680000053
Figure BDA0003574588680000054
Figure BDA0003574588680000055
3. and (3) cooling the reduced sponge iron balls and coke in the dry quenching furnace, discharging the cooled sponge iron balls and the coke together from an outlet of the dry quenching furnace, and separating the sponge iron balls from the coke at the outlet of the dry quenching furnace and a transfer belt by using a magnetic separation device to obtain the sponge iron balls with the metallization rate of 85%.
Example 3:
referring to fig. 1, a method for preparing direct reduced iron from carbon-containing waste comprises the following steps:
1. the method comprises the following steps of mixing goethite powder, coking fly ash and lime according to the mass percentage of 52%: 35%: mixing 10 percent of the raw materials, heating the waste resin to 200 ℃ in the process of uniformly mixing, spraying the waste resin accounting for 3.0 percent of the mass of the uniformly mixed materials in a mist form, performing heat exchange for 20min by using the waste heat of an ascending pipe of a coke oven, pressurizing to 12MPa for pelletizing after the waste resin is pasty, drying the pressurized pellets, and roasting at 1200 ℃ for 20mim to obtain the primary reduction pellet ore. The pressure resistance of the primary pellets after roasting is 2400N, and the drum strength is 88%. The coking fly ash is mainly coal-charging fly ash, the fixed carbon content is 88%, the volatile matter content is 5.0%, and the ash content is 9.5%.
2. Uniformly and directly distributing the primary reducing pellets in the step 1 on the outer surface layer of red coke stored in a dry quenching coke tank, feeding the red coke and the red coke in the dry quenching coke tank into a dry quenching furnace, fully utilizing coke waste heat in the dry quenching furnace, carrying out secondary reduction on the primary reducing pellets at a prestoring section of the dry quenching furnace to obtain sponge iron pellets, and controlling the mass percentages of the primary reducing pellets and the red coke to be 1: 20.
the reduction reaction that takes place comprises two parts:
firstly, reducing fixed carbon, iron-containing mineral and SiO in pellet ore at one time2Direct reduction reaction:
Figure BDA0003574588680000056
Figure BDA0003574588680000057
② CO generated by reduction or CO and H in dry quenching cycle gas2Reacting with iron-containing minerals or dry quenching coke and coke containing iron
Iron mineral interface reduction reaction:
Figure BDA0003574588680000061
Figure BDA0003574588680000062
Figure BDA0003574588680000063
Figure BDA0003574588680000064
Figure BDA0003574588680000065
3. and (3) cooling the reduced sponge iron balls and coke in the dry quenching furnace, discharging the cooled sponge iron balls and the coke together from an outlet of the dry quenching furnace, and separating the sponge iron balls from the coke at the outlet of the dry quenching furnace and a transfer belt by using a magnetic separation device to obtain the sponge iron balls with the metallization rate of 95%.
Example 4:
referring to fig. 1, a method for preparing direct reduced iron from carbon-containing waste comprises the following steps:
1. iron ore dressing tailing powder, coking fly ash and hydrated lime are mixed according to the mass percentage of 53%: 25%: mixing 20 percent of the mixture, heating the mixture of tar and asphalt to 205 ℃ in the process of uniformly mixing, spraying the mixture of tar and asphalt accounting for 2.0 percent of the mass of the uniformly mixed material in a mist form, performing heat exchange for 40min by using the waste heat of an ascending pipe of a coke oven, pressurizing and pelletizing the mixture of tar and asphalt until the mixture of tar and asphalt is pasty, drying the pressurized pellets, and roasting the dried pellets at 1300 ℃ for 40 mm to obtain the primary reduction pellets. The pressure resistance of the primary reduced pellet after roasting is 2600N, and the drum strength is 87%. The coking fly ash is a mixture of dry quenching fly ash, coal loading fly ash, coke pushing fly ash and belt transfer station fly ash, the fixed carbon content is 80%, the volatile matter is 2.0%, and the ash content is 13.0%.
2. And (3) uniformly distributing the primary reduced pellets in the step (1) on the surface of red coke by using a spiral distributor, wherein the angle between the spiral distributor and a central shaft is 30-85 degrees. The primary reduction pellets and red coke in a dry quenching coke tank enter a dry quenching coke oven together, the residual heat of the coke in the dry quenching coke oven is fully utilized, the carbon-containing pellets are subjected to secondary reduction at the prestoring stage of the dry quenching coke oven to obtain sponge iron pellets, and the mass percentages of the primary reduction pellets and the red coke are controlled to be 1: 30.
the reduction reaction occurred in the same manner as in example 1.
3. And after reduction, the sponge iron balls with the metallization rate of 90 percent and coke are cooled in the dry quenching furnace together, and are discharged from an outlet of the dry quenching furnace along with the coke to enter the blast furnace.
In the above embodiment, the iron ore powder may be one or more of magnetite, hematite, goethite and tailings after iron separation, and may also be iron-containing minerals which are difficult to separate or are not applicable to the conventional method.

Claims (10)

1. A method for preparing direct reduced iron from carbon-containing wastes is characterized by comprising the following steps:
1) uniformly mixing iron ore powder, coking dedusting ash and a fusing agent, spraying a binding agent in the uniformly mixing process, performing heat exchange for 10-30 min by using the waste heat of an ascending pipe of a coke oven, pressurizing and pelletizing, and then roasting for 10-40 mim at 1000-1300 ℃ to obtain primary reduction pellets;
2) respectively loading coke and the primary reduced pellets in the step 1) into a dry quenching furnace in batches, and carrying out secondary reduction on the primary reduced pellets by using coke waste heat in the dry quenching furnace to obtain sponge iron balls;
or uniformly distributing the primary reduced pellets in the step 1) on the outer surface layer of red coke stored in the dry quenching tank, and feeding the red coke and the red coke in the dry quenching tank into a dry quenching furnace together to obtain secondary reduced sponge iron balls; the mass ratio of the primary reduction pellets to the red coke is controlled to be 1: 50-1: 10;
3) the sponge iron balls and the coke are cooled in the dry quenching furnace together, and are discharged from a coke discharge port of the dry quenching furnace together with the coke, and enter the blast furnace together;
or magnetic separation devices are respectively arranged at the coke discharging port of the dry quenching furnace and the transfer belt, and when the sponge iron balls are discharged and transferred together with the coke from the coke discharging port of the dry quenching furnace, the sponge iron balls are separated from the coke.
2. The method for preparing direct reduced iron from carbonaceous waste according to claim 1, wherein in the step 1), the mass percentage of the iron ore powder is 50-80%, the mass percentage of the coking and dedusting ash is 5-45%, the mass percentage of the binding agent is 0.5-3.0%, and the mass percentage of the flux is 1-20%.
3. The method for preparing direct reduced iron from carbon-containing waste according to claim 1, wherein the compression resistance of the primary reduced pellets obtained in step 1) is not less than 2000N, and the drum strength is not less than 78%.
4. The method for preparing direct reduced iron from carbon-containing wastes according to claim 1, wherein the coking fly ash is one or more of dry quenching fly ash, coal charging fly ash, coke pushing fly ash and belt transfer station fly ash, the coking fly ash has a fixed carbon content of 80-90%, a volatile matter content of 1.0-5.0% and an ash content of 5.0-13.5%.
5. The method for preparing direct reduced iron from carbonaceous waste according to claim 1, wherein the amount of the coking fly ash blended in the step 1) is larger than the amount of the fly ash calculated by the fixed carbon required for reducing all the reducible oxides in the iron ore powder.
6. The method for preparing direct reduced iron from carbonaceous waste according to claim 1, wherein the iron ore powder in step 1) comprises one or more of magnetite, hematite, goethite and tailings after iron separation.
7. The method for preparing direct reduced iron from carbon-containing wastes according to claim 1, wherein in the step 2), the coke and the primary reduced pellets are respectively loaded into the dry quenching furnace in batches, or the primary reduced pellets are uniformly distributed on the outer surface layer of the red coke stored in the dry quenching furnace, the uniform distribution is carried out by using a spiral distributor, the angle between the spiral distributor and the central shaft is adjustable, and the spiral distributed pellets are uniformly distributed on the red coke surface of the dry quenching furnace or the red coke surface of the dry quenching furnace.
8. The method for preparing direct reduced iron from carbonaceous waste according to claim 1, wherein the flux in step 1) comprises one or more of lime, limestone powder and hydrated lime.
9. The method for preparing direct reduced iron from carbon-containing wastes according to claim 1, wherein the binder in step 1) comprises one or more of tar, asphalt and resin, and the tar, the asphalt and the resin are sprayed in the form of mist during the process of uniformly mixing the materials, wherein the temperature of the tar is controlled to be above 80 ℃, the temperature of the asphalt is controlled to be above 200 ℃, and the temperature of the resin is controlled to be above 100 ℃.
10. The method of claim 5, wherein the total reducible oxides include FeO and Fe3O4、Fe2O3、FeO(OH)、SiO2。
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