CA2266301C - Method of producing reduced iron agglomerates - Google Patents
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- CA2266301C CA2266301C CA 2266301 CA2266301A CA2266301C CA 2266301 C CA2266301 C CA 2266301C CA 2266301 CA2266301 CA 2266301 CA 2266301 A CA2266301 A CA 2266301A CA 2266301 C CA2266301 C CA 2266301C
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Abstract
Iron oxide agglomerates incorporated with the carbonaceous material having a particle size within a range of about 10 to 30 mm are prepared upon production of reduced iron agglomerates. Then, the iron oxide agglomerates incorporated with the carbonaceous material were laid thinly at a laying density of less than 1.4 kg/m2/mm or lower on a hearth of a moving hearth furnace. Subsequently, the iron oxide agglomerates are heated rapidly such that the surface temperature of the iron oxide agglomerates reaches 1200°C or higher within one-thud of the retention period of time of the iron oxide agglomerates in the moving hearth furnace. Then, the iron oxide agglomerates are reduced till the metallization ratio thereof reaches 85% or higher to form reduced iron agglomerates and then the reduced iron agglomerates are discharged out of the moving hearth furnace. With the procedures, reduced iron agglomerates of a high average quality can be obtained at a high productivity.
Description
TITLE OF THE INVENTION
METHOD OF PRODUCING REDUCED IRON AGGLOMERATES
BACKGROZJND OF THE INVENTTON
(FIELD OF THE INVENTION) The present invention concerns a method of producing reduced iron agglomerates by reducing iron oxide agglomerates incorporated with a carbonaceous matexzal.
(DESCRIPTION OF THE RELATED ART) The MIDREX method is a well-known gas based direct reduction process of producing reduced iron. In the MIDREX. method, a reducing gas produced from natural gas is fed through a tuyere into a shaft furnace and allowed to rise therein for reduction of iron ores or iron oxide pellets charged therein, to thereby produce reduced iron. However, since the method required a supply, as a fuel, of a large amount of high-cost natural gas, the location of a plant utilizing the MIDREY
method is limited to a region producing natural gas.
In view of the above, a certain type of method for pre~ducing reduced iron has become of interest, in which relatively inexpensive coal can be used instead of natural gas as a reducing agent. A method of producing reduced iron is disclosed, for example, in US Patent Nos. 3,443,931 and 5,601,631, in which powdery ores and c~~rbonaceous matexzals are mixed and palletized and then reduced by heating iri a high-temperature atmosphere to thereby produce reduced. iron. This method has advantages in that coal can be used as a reducing agent, as well as powder of ores can be used directly, reduction can be performed at a high rate and the carbon content of products can be regulated.
In the method descxzbed in the US Patent applications, dried iron oxide agglomerates are charged in a traveling hearth heating .furnace such as a rotary hearth furnace, heated while movement in the furnace and the iron oxide agglomerate are reduced by a carbonaceous material.
Reduction of the iron oxide agglomerates by the carbonaceous material proceeds from the sux~ace of the agglomerates in view of the heat transfer.
Accordingly, in the latter half of the reduction process, while metallic iron is deposited on the upper surface layer of the agglomerates, the ~ceducing reaction has not yet proceeded su~ciently in the central portion or the lower surface where the temperature is low, and the quality of the reduced iron is not satisfactory. In addition, while the temperature for the rotary hearth furnace is controlled by a combustion burner or secondary combustion of a combustible gas released from the agglomerates, it is necessary to burn them combustible gas released from the fuel and the agglomerates substantially completely at the e:rdt of the furnace in order to decrease the fuel unit. However, unless an appropriate reducing atmosphere is maintained, the agglomerates are exposed to an oxidizing gas, particularly, in the latter half of the reducing zone and the metallic iron at the surface layer of the agglomerates is reoxidized to detexzor ate the quality of products.
Further, the iron oxide agglomerates should be of a size suitable to operation conditions. Those of a size suitable to the operation conditions attain a high quality after reduction, whereas those of a size smaller than the appropxzate size are reoxidized due to excess heating, while those of a size greater than the appropriate size are rec~~xced only insufficieni;ly due to ir~su~cient heating. In addition, if the particle size of the agglomerates is scattered, both of the reduction ratio and the strength are detE~riorated as a whole product SZJIVINIARY OF THE INVENTION
An object of the present invention is to provide a method of producing reduced iron capable of obtaining iron oxide agglomerates having high average quality at a high productivity.
In the method of producing the iron oxide agglomerates according to the present invention, iron oxide agglomerates incox~orated with a carbonaceous material having a particle size ranging about from 10 to 30 mm are produced at first. Then, the iron oxide agglomerates incorporated with the carbonaceous material are laid thinly at a laying density of 1.4 kg/m2/mm or less on a hearth of a moving hearth furnace. Subsequently, the iron oxide agglomerates are heated rapidly such that the surface temperature of the iron oadde agglomerates is raised to 1200°C or higher within one-tlxird of a retention t me of the iron oxide agglomerates in the moving hearth furnace. Then, after reducing the iron oxide agglomerates to a metallization ratio of 85% or higher to form reduced iron agglomerates and then, the reduced iron. agglomerates are discharged out of the moving hearth furnace.
In the step of producing the iron oxide agglomerates incorporated with the carbonaceous material, it is desirable to arrange such that more than 80%
of the iron oxide agglomerates are within a range for ~2 mm ~of the aimed particle size. It is also desirable that the maximum flowability of the carbonaceous material used is 0.8 or more upon softening and melting.
It is desirable that the apparent density of the iron oxide agglomerates produced in the step of producing the iron oxide agglomerates incorporated with the carbonaceous matexzal is 2.3 g/cm3 or more.
Further, in the step of reducing the iron oxide agglomerates incorporated with the carbonaceous material, it is desirable to control the reduction ratio of a waste gas from a burner for heating the icon oxide agglomerates for Fe or Fe0 equilibxxum before the amount of CO gas released from the iron oxide agglomerates during reduction is reduced. to less than one-f:oux~th of that at peak of generation. Further, it is desirable that the apparent density of the iron oxide agglomerates after reduction is 2 g/c:m3 or higher.
BRIEF DESCRIPTION OF THE DRAWINGrS
Fig. 1 is a view showing a relation between the laying density of agglomerates and a metallization ratio;
r, Fig. 2 is a view illustrating a different of the metallization ratio of the reduced iron agglomerates between Example 2 and a campara.tive example;
Fig. 3 is a view showing a relation between the particle size and the rnetallization r atio of the reduced it on agglomerates;
Fig. 4 is a view showing a relation between the reduction ratio of a combustion gas and the metallization ratio in the latter half of reduction in E'~xample 3;
Fig. 5 is a view showing a relation between the temperature at the center of the agglomerates and the gas oxidation ratio ~CO/(C(J + CO~] in Example 4;
Fig. 6 is a view showing a relation between the heating time and the temperature at the center of the agglomerates when agglomerates using five kinds of carbonaceous mateizals of different ffowability are heated in an atmospheric temperature at 1300°C;
Fig. 7 is a view illustrating comparison the apparent density between h.ot-molded agglomerates (hot-pressed briquettes) of the present invention and green agglomerates after drying (pellets) of comparative examples;
Fig. 8 is a view showing results of a reducing test conducted to a reducing furnace maintained at 1300°C for hot pressed agglomerates and pelleted agglomerates with the apparent density being varied;
Fig. 9 is a view illustrating a relationship between the apparent density of agglomerates before reduction and the apparent density of reduced iron agglomerates; and Fit. 10 is a view showing a result of an experiment in which reduced ia~on agglomerates having apparent density of 1.6 g/cml and 2.4 g/cm2 are melted in a crucible.
DESCRIPTION OF T:HE PREFERRED EMBODI1VIENTS
Heat is transmitted predominantly by radiation of heat in a furnace.
Therefore, it is important to lay the iron oxide agglomerates incorporated with the carbonaceous material with no overlapping, in view of uniform heating, vnprovement of the productivity and improvement of the quality. For this purpose, it is desirable to make the laying density on the hearth to 1.4 kg/m2/mm or lower. In this text, "kg/m2" in the unit for the laying density means mass of the iron oxide agglomerates per unit area of the hearth, and ":mm" in the unit for the laying density means the average particle size of the iron oxide agglomerates.
Further, as shown in Fig. 5, since the reduction ratio [CO/(CO + CO~]
(shown by sampled data) rises abruptly if the temperature exceeds 1200°C, it is important to rapidly heat the iron oxide agglomerates charged in the furnace to 1200°C thereby promoting the reduction of the agglomerates. For this purpose, a heating time up to 1200°C is desirably as short as possible.
However, considering restriction in the actual operation, the surface temperature of the agglomerates may be raised to 1200°C within ane-third pex~od of the retention time in the furnace after charging.
At the instance the amount of CO gas released from the iron oxide agglomerates is lowered to t/4 compared with that at the peal; of generation during reduction, the central portion of the oxide agglomerates is reduced, while metallic iron is deposited on the surface layer. Accordingly, reoxidation of the metallic iron at the surface layer can be prevented and the reduction at the surface layer can be promoted by controlling the reduction ratio of the waste gas from the burner for Fe or Fe0 equilibrium.
By conducting molding upon softening and melting thereby filling the carbonaceous material in a space between each of iron oxide inn the agglomerates, the heat conductivity in the agglomerates can be improved. It is desirable to use a carbonaceous material having a maximum flowability upon softening and melting of 0.$ or greater. In this case, the surface of the agglomerates is not melted in the furnace even when the gas temperature in 1~he furnace is raised in order to enhance the productivity. Further, since the iron oxide agglomerates incorporated with the carbonaceous material is put to pressure molding, the gap at the inside is decreased also by thus process, to improve the heat conductivity. The reducing reaction is promoted by the improvement of the heat conductivity of the iron oxide agglomerates and, as a result, the productivity in the reduced iron production can be improved.
Further, when the apparent density of the iron oxide agglomerates incorporated with the carbonaceous material is increased, mass of the iron oxide agglomerates per unit area of the hearth is increased to improve the productivity. Accordingly, it is desirable that the apparent density of the iron ode agglomerates is 2.3 g/cm2 or more.
Upon melting the reduced iron agglomerates, if the apparent density of the iron oxide agglomerates is higher than that of stags in the melting fixrnace, since the reduced iron agglomerates do not float on the stags, the dissolution rate of the reduced iron agglomerates is increased. Accordingly, it is desirable that the apparent dcansity of the reduced iron agglomerates after the reduction is 2 g/cm3 or more which is greater than the usual apparent density of the stags.
Further, as the particle size of the reduced iron oxide agglomerates incorporated with the carbonaceous material is made more uniform, the agglomerates can be laid with no overlapping on the hearth. Further, deterioration of the quality due to excess heataing or insufficient heating can be avoided to obtain products of uniform quality. Accordingly, it is desirable to control the particle size such that more than 80% of the iron oxide agglomerates incorporated with the carbonaceous material is within a range t2 mm of the aimed particle size.
In the pelletization of the iron oxide agglomerates incorporated with t:he carbonaceous material, a fuel unit can be decreased by recovering gases released in the heat-mixing step, pressure molding step and degasing step of t:he raw material and utilizing the recovered gas as a fuel for a reducing burner.
Further, reoxidation of the reduced iron agglomerates can be ;prevented by blowing the recovered gas at the final stage of reduction in the reducing furnace.
Further, a fuel supplied to the moving hearth heating furnace can be decreased by efficiently burning a combustible gas such as CO and H2 released from the iron oxide agglomerates incorporated with the carbonaceous matexial in the vicinity of the iron oxide agglomerates as a matter to be heated in the reducing, thereby using the same as a heat source to be supplied to the matter to be heated. For this purpose.. it is preferred to supply a secondary combustion air to burn the burnable gas.
Iron oxide agglomerates comprising iron ore (7$.3%) and coal (20.0%) of the ingredients shown in Table 1 in admixture with 1.7% of a binder were laid on a hearth at a laying density of 1.0 kg/m2/mm, and reduced by using a x°otaxy hearth furnace at a productivity of 100 kg/m2/hr. The results are shown in Fig. 1. In a comparative example shown in the figure, the laying density was changed to 1.5 kg/m2/mm. As apparent from Fig. 1, if the laying density of the agglomerates exceeds 1.4 kg/m2/mm, lowering of the metallization ratio is observed. In order to improve the quality of the reduced iron agglomerates, it i.s preferred to make the layer thickness to less than 1, specifically, to make the laying density to less than 1.4 kg/m2/rnm.
(Table 1) Dry mass Iron ore T.Fe Si02 A1203 Particle size(-75 ,ca~a) 67.9 1.0 0.5 _71 Fixed Volatile Ash Particle size(-75 Goal carbon matter ,um) 72.6 18.8 I 8.6 I 50 - 70 The same iron oxide agglomerates incoi~orated with the carbonaceous material as those in Example 1 were laid at a laying density of 1.1 kg/m2/mm on the hearth so as not to overlap and reduced by using a rotary hearth furnace a.t a productivity of 80 kg/m2/hr. The size of the agglomerates was controlled such that 80% of them had a size within a range of ~2 mm of the aimed particle size. As a result, reduced iron agglomerates of the quality shown in Fig. 2 were obtained. The laying density of the comparative example was 1.5 to 1.75 kg/m2/mm. As apparent from ~'ig. 2, since the laying density is high in the comparative example, the metallization ratio of the reduced iron agglomerates a.t a portion in which the agglomerates are overlapped is reduced by about 30%
compared with the example of the present invention. On the other hand, in t:he example of the present invention, reduced iron agglomerates of stable quality at the metallization ratio of 96% are obtained.
Further, Fig. 3 shows a relation between the particle size and the metallization degree of the reduced iron agglomerates. AS shown in Fig. 3, peak of the metallization ratio is present at 13 - 16 mm of the particle size of the reduced iron agglomerates, and the metallization ratio is lowered as the particle size is out of the above-mentioned range. From the result, it is optimum that all of the agglomerates are within a range of -~-1.5 anm of the aimed particle size, but it is not easy to attain the range of ~ 1.5 mm of the aimed particle size if the agglomerates are pelletized by a pan pelletizer and sieved by a roller screen.
Then, 80% of the agglomerates can be put into the range of ~2 mm of the aimed particle size by applying press molding to the iron oxide agglomerates. The particle size of the agglomerates is usually from 10 to 30 mm although different depending on the operation conditions.
The same iron oxide agglomerates incorporated with the carbonaceous material as those in Example 1 were charged into a rotary hearth furnace and reduced at an atmospheric temperature of 1300°C for 9 min. The laying density was 1.15 kg/m2/mm. The oxidation ratio of the combustion gas [(C02 +
F120)/(CO + HZ + COz + H20)] was changed within a range fio:m :1.0 in the former half and to 0 - 1.0 in the latter half. Further, the switching time between the fozmer half and the latter half was also changed within a range tom 0 to 8 min. Fig. 4 shows a relation between the axidation ratio of the combustion gas and the metallization ratio in the latter hal~
As shown in Fig. 4, the metallization ratio increases Gong with decrease of the reduction ratio of the combustion gas and by switching to low oxidation ratio more early. Metallization ratio of 85% or higher is obtained if the oxidation ratio of the combustion gas in the latter half is switched to 0.53 v~rithin 6 min, and the metallization ratio of 90% or higher can. be obtained by switching the oxidation ratio within 4 min, but if the switching time is late as 8 min, the metallization ratio is 8 5% or lower. Further, If the oxidation ratio of the combustion gas after switching is 0, the metallization ratio of 90% or higher can be ensured even if the switching tine is late as 6 min. 8;y the way, the amount of CO generated from the agglomerates is 80% for the peak generation at 4 min of the switching time, 47% for the peak generation at; 6 min, and 13%
for the peak generation at 8 min. Accordingly, improvement of the metallization ratio can not be expected even if the oxidation ratio of the combustion gas is switched to a low reduction ratio after the amount of CO
generated from the agglomerates has been lowered to less than l./4 for the peak generation.
The same iron oxide agglomerates incorporated with the carbonaceous material as in Example 1 were charged so as not to be overlapped at a laying density of 1.04 kg/m2/mm into a rotary hearth furnace and reduced. Table 2 shows a portion of reducing conditions and the quality of the reduced iron agglomerates. The reduction ratio of the waste gas from the burner shown in t:he table is for Fe203 equilibrium. This reduction shows the presence of operation conditions capable of attaining a high metallization ratio even if the reduction ratio of the waste gas from the burner is not controlled for Fe or Fe0 equilibrium. This is considered as below. That is, as shown in Fig. 5, the temperature of the agglomerates is raised along with increase of the temperature in the furnace, in which the solution loss reaction is activated and the CO/(CO + CO~ value is increased. CO/(CO + CO~ value shows the reduction ratio of the burner waste gas and as the value is away from the boundary between Fe and FeO, the reducing potential is improved. Therefore, an extremely high reducing atmosphere is formed at the periphery of the agglomerates by the high temperature operation, and it is assumed that the effect by the reduction ratio of the burner waste gas is lowered.
(Table 2) Gas tempe-Air/fue~l Gas Metalliza-Productivityrature ratio ire atmospher tion ratio near the later eequili-agglome- half of brium Example ~g/m2~~mm) rates reducing metal (%) step 90 - 94 80 1300-1360 10.;; Fe203 Fig. 6 shows a relation between the heating time and the temperature at the center of agglomerates when agglomerates using five l4inds of carbonaceous materials A, C, E, H and I of different fluidity were heated at an atmospheric temperature of 1300°C. As shown in Fig. G, the time that the carbonaceous matexzals of high fluidity (carbonaceous materials H, I) reach 1300°C is shorter compared with that of the carbonaceous materials of low fluidity (carbonaceous materials A, C). Further, since the reducing reaction starts at about 800°C, the temperature hysteresis in the course of the temperature elevation is also important, in which the temperature elevation rate at the inside of the agglomerates is high in a case of using carbonaceous materials of high fluidity. Based on the observation for the cross sectional tissue of the agglomerates in the reducing process, it was consumed that connected structure of the iron oxide particles with a solid carbon~iceous material was formed. In view of the above, it is preferred to use a carbonaceous material having a highest fluidity upon softening and melting of 0.8 or higher.
After mixing the iron ore and pulverized coal shown :in Table 1 at a ratio of 78% iron ore and 22% of'coal, they were heated to 450°C and agglomerates of 2 to 5 cm3 were hot molded at a pressure of 3!9 MPa (hot molded briquettes). As a comparative example, iron ore and pulverized coal were mixed at an identical mixing ratio to which bentonite w;xs added by about l.% as a binder and molded into agglomerates of 2 cm3 volume (pellets) by a pelletizer. Fig. 7 shows an apparent density for each of them. As shown in Fig. 7, the hot molded agglomerates have an apparent density higher by 40%.
Then, a reducing test was conducted in a reducing furnace in which h.ot molded agglomerates and pellet agglomerates were kept apt 1300°C.
The results are shown in Fig. 8. As apparent from the figure, the reduction time is shortened as the apparent density of the agglomerates is increased at an identical volume. Accordingly, the productivity is also improved by the increase in the apparent density of the agglomerates. Fig. 9 shows an apparent density of the agglomerates after reducing the hot molded agglomerates. As shown in the figure, as the apparent density of the agglomerates before reduction increases, the apparent density of the agglomerates after reduction also increases in propoWion therewith. Further F'ig. 9 shows that when the hot malded agglomerates are applied with a d.egasing treatment at 500°C for 30 min, swelling of the agglomerates is decreased in the reducing step, and the apparent density of the reduced iron reaches 2 g/cm3 or greater.
Fig. 10 shows the results of an experiment in which reduced iron agglomerates having an apparent density of 1.6 g/crn3 and 2.4 g/cm3 were melted in a crucible. The density of the molten slag is usually about 2 g/cm3 and, if the apparent density of the reduced iron agglomerates is lower than that, the agglomerates float on the slag surface as shown in the figure and melting is retarded. On the other hand, if the apparent density of the reduced iron agglomerates is high, the agglomerates sink into the slags to promote melting.
As a result of the test, if the apparent density of the agglomerates is 1.6 g/cm3, the melting rate is 0.5 kg/min, while if the apparent density is 2.4 g/cm3, the melting rate is 2 kg/min. As described above, the milting rage is improved to four tames by increasing the apparent density of the reduced iron agglomerates to greater than the apparent density of the slags in the melting furnace.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from tile spirit and scope thereof.
METHOD OF PRODUCING REDUCED IRON AGGLOMERATES
BACKGROZJND OF THE INVENTTON
(FIELD OF THE INVENTION) The present invention concerns a method of producing reduced iron agglomerates by reducing iron oxide agglomerates incorporated with a carbonaceous matexzal.
(DESCRIPTION OF THE RELATED ART) The MIDREX method is a well-known gas based direct reduction process of producing reduced iron. In the MIDREX. method, a reducing gas produced from natural gas is fed through a tuyere into a shaft furnace and allowed to rise therein for reduction of iron ores or iron oxide pellets charged therein, to thereby produce reduced iron. However, since the method required a supply, as a fuel, of a large amount of high-cost natural gas, the location of a plant utilizing the MIDREY
method is limited to a region producing natural gas.
In view of the above, a certain type of method for pre~ducing reduced iron has become of interest, in which relatively inexpensive coal can be used instead of natural gas as a reducing agent. A method of producing reduced iron is disclosed, for example, in US Patent Nos. 3,443,931 and 5,601,631, in which powdery ores and c~~rbonaceous matexzals are mixed and palletized and then reduced by heating iri a high-temperature atmosphere to thereby produce reduced. iron. This method has advantages in that coal can be used as a reducing agent, as well as powder of ores can be used directly, reduction can be performed at a high rate and the carbon content of products can be regulated.
In the method descxzbed in the US Patent applications, dried iron oxide agglomerates are charged in a traveling hearth heating .furnace such as a rotary hearth furnace, heated while movement in the furnace and the iron oxide agglomerate are reduced by a carbonaceous material.
Reduction of the iron oxide agglomerates by the carbonaceous material proceeds from the sux~ace of the agglomerates in view of the heat transfer.
Accordingly, in the latter half of the reduction process, while metallic iron is deposited on the upper surface layer of the agglomerates, the ~ceducing reaction has not yet proceeded su~ciently in the central portion or the lower surface where the temperature is low, and the quality of the reduced iron is not satisfactory. In addition, while the temperature for the rotary hearth furnace is controlled by a combustion burner or secondary combustion of a combustible gas released from the agglomerates, it is necessary to burn them combustible gas released from the fuel and the agglomerates substantially completely at the e:rdt of the furnace in order to decrease the fuel unit. However, unless an appropriate reducing atmosphere is maintained, the agglomerates are exposed to an oxidizing gas, particularly, in the latter half of the reducing zone and the metallic iron at the surface layer of the agglomerates is reoxidized to detexzor ate the quality of products.
Further, the iron oxide agglomerates should be of a size suitable to operation conditions. Those of a size suitable to the operation conditions attain a high quality after reduction, whereas those of a size smaller than the appropxzate size are reoxidized due to excess heating, while those of a size greater than the appropriate size are rec~~xced only insufficieni;ly due to ir~su~cient heating. In addition, if the particle size of the agglomerates is scattered, both of the reduction ratio and the strength are detE~riorated as a whole product SZJIVINIARY OF THE INVENTION
An object of the present invention is to provide a method of producing reduced iron capable of obtaining iron oxide agglomerates having high average quality at a high productivity.
In the method of producing the iron oxide agglomerates according to the present invention, iron oxide agglomerates incox~orated with a carbonaceous material having a particle size ranging about from 10 to 30 mm are produced at first. Then, the iron oxide agglomerates incorporated with the carbonaceous material are laid thinly at a laying density of 1.4 kg/m2/mm or less on a hearth of a moving hearth furnace. Subsequently, the iron oxide agglomerates are heated rapidly such that the surface temperature of the iron oadde agglomerates is raised to 1200°C or higher within one-tlxird of a retention t me of the iron oxide agglomerates in the moving hearth furnace. Then, after reducing the iron oxide agglomerates to a metallization ratio of 85% or higher to form reduced iron agglomerates and then, the reduced iron. agglomerates are discharged out of the moving hearth furnace.
In the step of producing the iron oxide agglomerates incorporated with the carbonaceous material, it is desirable to arrange such that more than 80%
of the iron oxide agglomerates are within a range for ~2 mm ~of the aimed particle size. It is also desirable that the maximum flowability of the carbonaceous material used is 0.8 or more upon softening and melting.
It is desirable that the apparent density of the iron oxide agglomerates produced in the step of producing the iron oxide agglomerates incorporated with the carbonaceous matexzal is 2.3 g/cm3 or more.
Further, in the step of reducing the iron oxide agglomerates incorporated with the carbonaceous material, it is desirable to control the reduction ratio of a waste gas from a burner for heating the icon oxide agglomerates for Fe or Fe0 equilibxxum before the amount of CO gas released from the iron oxide agglomerates during reduction is reduced. to less than one-f:oux~th of that at peak of generation. Further, it is desirable that the apparent density of the iron oxide agglomerates after reduction is 2 g/c:m3 or higher.
BRIEF DESCRIPTION OF THE DRAWINGrS
Fig. 1 is a view showing a relation between the laying density of agglomerates and a metallization ratio;
r, Fig. 2 is a view illustrating a different of the metallization ratio of the reduced iron agglomerates between Example 2 and a campara.tive example;
Fig. 3 is a view showing a relation between the particle size and the rnetallization r atio of the reduced it on agglomerates;
Fig. 4 is a view showing a relation between the reduction ratio of a combustion gas and the metallization ratio in the latter half of reduction in E'~xample 3;
Fig. 5 is a view showing a relation between the temperature at the center of the agglomerates and the gas oxidation ratio ~CO/(C(J + CO~] in Example 4;
Fig. 6 is a view showing a relation between the heating time and the temperature at the center of the agglomerates when agglomerates using five kinds of carbonaceous mateizals of different ffowability are heated in an atmospheric temperature at 1300°C;
Fig. 7 is a view illustrating comparison the apparent density between h.ot-molded agglomerates (hot-pressed briquettes) of the present invention and green agglomerates after drying (pellets) of comparative examples;
Fig. 8 is a view showing results of a reducing test conducted to a reducing furnace maintained at 1300°C for hot pressed agglomerates and pelleted agglomerates with the apparent density being varied;
Fig. 9 is a view illustrating a relationship between the apparent density of agglomerates before reduction and the apparent density of reduced iron agglomerates; and Fit. 10 is a view showing a result of an experiment in which reduced ia~on agglomerates having apparent density of 1.6 g/cml and 2.4 g/cm2 are melted in a crucible.
DESCRIPTION OF T:HE PREFERRED EMBODI1VIENTS
Heat is transmitted predominantly by radiation of heat in a furnace.
Therefore, it is important to lay the iron oxide agglomerates incorporated with the carbonaceous material with no overlapping, in view of uniform heating, vnprovement of the productivity and improvement of the quality. For this purpose, it is desirable to make the laying density on the hearth to 1.4 kg/m2/mm or lower. In this text, "kg/m2" in the unit for the laying density means mass of the iron oxide agglomerates per unit area of the hearth, and ":mm" in the unit for the laying density means the average particle size of the iron oxide agglomerates.
Further, as shown in Fig. 5, since the reduction ratio [CO/(CO + CO~]
(shown by sampled data) rises abruptly if the temperature exceeds 1200°C, it is important to rapidly heat the iron oxide agglomerates charged in the furnace to 1200°C thereby promoting the reduction of the agglomerates. For this purpose, a heating time up to 1200°C is desirably as short as possible.
However, considering restriction in the actual operation, the surface temperature of the agglomerates may be raised to 1200°C within ane-third pex~od of the retention time in the furnace after charging.
At the instance the amount of CO gas released from the iron oxide agglomerates is lowered to t/4 compared with that at the peal; of generation during reduction, the central portion of the oxide agglomerates is reduced, while metallic iron is deposited on the surface layer. Accordingly, reoxidation of the metallic iron at the surface layer can be prevented and the reduction at the surface layer can be promoted by controlling the reduction ratio of the waste gas from the burner for Fe or Fe0 equilibrium.
By conducting molding upon softening and melting thereby filling the carbonaceous material in a space between each of iron oxide inn the agglomerates, the heat conductivity in the agglomerates can be improved. It is desirable to use a carbonaceous material having a maximum flowability upon softening and melting of 0.$ or greater. In this case, the surface of the agglomerates is not melted in the furnace even when the gas temperature in 1~he furnace is raised in order to enhance the productivity. Further, since the iron oxide agglomerates incorporated with the carbonaceous material is put to pressure molding, the gap at the inside is decreased also by thus process, to improve the heat conductivity. The reducing reaction is promoted by the improvement of the heat conductivity of the iron oxide agglomerates and, as a result, the productivity in the reduced iron production can be improved.
Further, when the apparent density of the iron oxide agglomerates incorporated with the carbonaceous material is increased, mass of the iron oxide agglomerates per unit area of the hearth is increased to improve the productivity. Accordingly, it is desirable that the apparent density of the iron ode agglomerates is 2.3 g/cm2 or more.
Upon melting the reduced iron agglomerates, if the apparent density of the iron oxide agglomerates is higher than that of stags in the melting fixrnace, since the reduced iron agglomerates do not float on the stags, the dissolution rate of the reduced iron agglomerates is increased. Accordingly, it is desirable that the apparent dcansity of the reduced iron agglomerates after the reduction is 2 g/cm3 or more which is greater than the usual apparent density of the stags.
Further, as the particle size of the reduced iron oxide agglomerates incorporated with the carbonaceous material is made more uniform, the agglomerates can be laid with no overlapping on the hearth. Further, deterioration of the quality due to excess heataing or insufficient heating can be avoided to obtain products of uniform quality. Accordingly, it is desirable to control the particle size such that more than 80% of the iron oxide agglomerates incorporated with the carbonaceous material is within a range t2 mm of the aimed particle size.
In the pelletization of the iron oxide agglomerates incorporated with t:he carbonaceous material, a fuel unit can be decreased by recovering gases released in the heat-mixing step, pressure molding step and degasing step of t:he raw material and utilizing the recovered gas as a fuel for a reducing burner.
Further, reoxidation of the reduced iron agglomerates can be ;prevented by blowing the recovered gas at the final stage of reduction in the reducing furnace.
Further, a fuel supplied to the moving hearth heating furnace can be decreased by efficiently burning a combustible gas such as CO and H2 released from the iron oxide agglomerates incorporated with the carbonaceous matexial in the vicinity of the iron oxide agglomerates as a matter to be heated in the reducing, thereby using the same as a heat source to be supplied to the matter to be heated. For this purpose.. it is preferred to supply a secondary combustion air to burn the burnable gas.
Iron oxide agglomerates comprising iron ore (7$.3%) and coal (20.0%) of the ingredients shown in Table 1 in admixture with 1.7% of a binder were laid on a hearth at a laying density of 1.0 kg/m2/mm, and reduced by using a x°otaxy hearth furnace at a productivity of 100 kg/m2/hr. The results are shown in Fig. 1. In a comparative example shown in the figure, the laying density was changed to 1.5 kg/m2/mm. As apparent from Fig. 1, if the laying density of the agglomerates exceeds 1.4 kg/m2/mm, lowering of the metallization ratio is observed. In order to improve the quality of the reduced iron agglomerates, it i.s preferred to make the layer thickness to less than 1, specifically, to make the laying density to less than 1.4 kg/m2/rnm.
(Table 1) Dry mass Iron ore T.Fe Si02 A1203 Particle size(-75 ,ca~a) 67.9 1.0 0.5 _71 Fixed Volatile Ash Particle size(-75 Goal carbon matter ,um) 72.6 18.8 I 8.6 I 50 - 70 The same iron oxide agglomerates incoi~orated with the carbonaceous material as those in Example 1 were laid at a laying density of 1.1 kg/m2/mm on the hearth so as not to overlap and reduced by using a rotary hearth furnace a.t a productivity of 80 kg/m2/hr. The size of the agglomerates was controlled such that 80% of them had a size within a range of ~2 mm of the aimed particle size. As a result, reduced iron agglomerates of the quality shown in Fig. 2 were obtained. The laying density of the comparative example was 1.5 to 1.75 kg/m2/mm. As apparent from ~'ig. 2, since the laying density is high in the comparative example, the metallization ratio of the reduced iron agglomerates a.t a portion in which the agglomerates are overlapped is reduced by about 30%
compared with the example of the present invention. On the other hand, in t:he example of the present invention, reduced iron agglomerates of stable quality at the metallization ratio of 96% are obtained.
Further, Fig. 3 shows a relation between the particle size and the metallization degree of the reduced iron agglomerates. AS shown in Fig. 3, peak of the metallization ratio is present at 13 - 16 mm of the particle size of the reduced iron agglomerates, and the metallization ratio is lowered as the particle size is out of the above-mentioned range. From the result, it is optimum that all of the agglomerates are within a range of -~-1.5 anm of the aimed particle size, but it is not easy to attain the range of ~ 1.5 mm of the aimed particle size if the agglomerates are pelletized by a pan pelletizer and sieved by a roller screen.
Then, 80% of the agglomerates can be put into the range of ~2 mm of the aimed particle size by applying press molding to the iron oxide agglomerates. The particle size of the agglomerates is usually from 10 to 30 mm although different depending on the operation conditions.
The same iron oxide agglomerates incorporated with the carbonaceous material as those in Example 1 were charged into a rotary hearth furnace and reduced at an atmospheric temperature of 1300°C for 9 min. The laying density was 1.15 kg/m2/mm. The oxidation ratio of the combustion gas [(C02 +
F120)/(CO + HZ + COz + H20)] was changed within a range fio:m :1.0 in the former half and to 0 - 1.0 in the latter half. Further, the switching time between the fozmer half and the latter half was also changed within a range tom 0 to 8 min. Fig. 4 shows a relation between the axidation ratio of the combustion gas and the metallization ratio in the latter hal~
As shown in Fig. 4, the metallization ratio increases Gong with decrease of the reduction ratio of the combustion gas and by switching to low oxidation ratio more early. Metallization ratio of 85% or higher is obtained if the oxidation ratio of the combustion gas in the latter half is switched to 0.53 v~rithin 6 min, and the metallization ratio of 90% or higher can. be obtained by switching the oxidation ratio within 4 min, but if the switching time is late as 8 min, the metallization ratio is 8 5% or lower. Further, If the oxidation ratio of the combustion gas after switching is 0, the metallization ratio of 90% or higher can be ensured even if the switching tine is late as 6 min. 8;y the way, the amount of CO generated from the agglomerates is 80% for the peak generation at 4 min of the switching time, 47% for the peak generation at; 6 min, and 13%
for the peak generation at 8 min. Accordingly, improvement of the metallization ratio can not be expected even if the oxidation ratio of the combustion gas is switched to a low reduction ratio after the amount of CO
generated from the agglomerates has been lowered to less than l./4 for the peak generation.
The same iron oxide agglomerates incorporated with the carbonaceous material as in Example 1 were charged so as not to be overlapped at a laying density of 1.04 kg/m2/mm into a rotary hearth furnace and reduced. Table 2 shows a portion of reducing conditions and the quality of the reduced iron agglomerates. The reduction ratio of the waste gas from the burner shown in t:he table is for Fe203 equilibrium. This reduction shows the presence of operation conditions capable of attaining a high metallization ratio even if the reduction ratio of the waste gas from the burner is not controlled for Fe or Fe0 equilibrium. This is considered as below. That is, as shown in Fig. 5, the temperature of the agglomerates is raised along with increase of the temperature in the furnace, in which the solution loss reaction is activated and the CO/(CO + CO~ value is increased. CO/(CO + CO~ value shows the reduction ratio of the burner waste gas and as the value is away from the boundary between Fe and FeO, the reducing potential is improved. Therefore, an extremely high reducing atmosphere is formed at the periphery of the agglomerates by the high temperature operation, and it is assumed that the effect by the reduction ratio of the burner waste gas is lowered.
(Table 2) Gas tempe-Air/fue~l Gas Metalliza-Productivityrature ratio ire atmospher tion ratio near the later eequili-agglome- half of brium Example ~g/m2~~mm) rates reducing metal (%) step 90 - 94 80 1300-1360 10.;; Fe203 Fig. 6 shows a relation between the heating time and the temperature at the center of agglomerates when agglomerates using five l4inds of carbonaceous materials A, C, E, H and I of different fluidity were heated at an atmospheric temperature of 1300°C. As shown in Fig. G, the time that the carbonaceous matexzals of high fluidity (carbonaceous materials H, I) reach 1300°C is shorter compared with that of the carbonaceous materials of low fluidity (carbonaceous materials A, C). Further, since the reducing reaction starts at about 800°C, the temperature hysteresis in the course of the temperature elevation is also important, in which the temperature elevation rate at the inside of the agglomerates is high in a case of using carbonaceous materials of high fluidity. Based on the observation for the cross sectional tissue of the agglomerates in the reducing process, it was consumed that connected structure of the iron oxide particles with a solid carbon~iceous material was formed. In view of the above, it is preferred to use a carbonaceous material having a highest fluidity upon softening and melting of 0.8 or higher.
After mixing the iron ore and pulverized coal shown :in Table 1 at a ratio of 78% iron ore and 22% of'coal, they were heated to 450°C and agglomerates of 2 to 5 cm3 were hot molded at a pressure of 3!9 MPa (hot molded briquettes). As a comparative example, iron ore and pulverized coal were mixed at an identical mixing ratio to which bentonite w;xs added by about l.% as a binder and molded into agglomerates of 2 cm3 volume (pellets) by a pelletizer. Fig. 7 shows an apparent density for each of them. As shown in Fig. 7, the hot molded agglomerates have an apparent density higher by 40%.
Then, a reducing test was conducted in a reducing furnace in which h.ot molded agglomerates and pellet agglomerates were kept apt 1300°C.
The results are shown in Fig. 8. As apparent from the figure, the reduction time is shortened as the apparent density of the agglomerates is increased at an identical volume. Accordingly, the productivity is also improved by the increase in the apparent density of the agglomerates. Fig. 9 shows an apparent density of the agglomerates after reducing the hot molded agglomerates. As shown in the figure, as the apparent density of the agglomerates before reduction increases, the apparent density of the agglomerates after reduction also increases in propoWion therewith. Further F'ig. 9 shows that when the hot malded agglomerates are applied with a d.egasing treatment at 500°C for 30 min, swelling of the agglomerates is decreased in the reducing step, and the apparent density of the reduced iron reaches 2 g/cm3 or greater.
Fig. 10 shows the results of an experiment in which reduced iron agglomerates having an apparent density of 1.6 g/crn3 and 2.4 g/cm3 were melted in a crucible. The density of the molten slag is usually about 2 g/cm3 and, if the apparent density of the reduced iron agglomerates is lower than that, the agglomerates float on the slag surface as shown in the figure and melting is retarded. On the other hand, if the apparent density of the reduced iron agglomerates is high, the agglomerates sink into the slags to promote melting.
As a result of the test, if the apparent density of the agglomerates is 1.6 g/cm3, the melting rate is 0.5 kg/min, while if the apparent density is 2.4 g/cm3, the melting rate is 2 kg/min. As described above, the milting rage is improved to four tames by increasing the apparent density of the reduced iron agglomerates to greater than the apparent density of the slags in the melting furnace.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from tile spirit and scope thereof.
Claims (6)
1. A method of producing reduced iron agglomerates comprising the following steps of:
preparing iron oxide agglomerates incorporated with a carbonaceous material having a particle size within a range about from 10 to 30 nm, thinly laying the iron oxide agglomerates incorporated with the carbonaceous material at a laying density of 1.4 kg/m2/mm or lower on a hearth of a moving hearth furnace; and rapidly heatsrrg the reduced iron agglomerates such that the surface temperature of the reduced iron agglomerates reaches 1200°C or higher within one-third of the retention period of time of the iron oxide agglomerates in the moving hearth furnace;
reducing the iron oxide agglomerates to a metallization ratio of 85% or higher to prepare reduced iron agglomerates and then discharging the reduced iron agglomerates out of the moving hearth furnace.
preparing iron oxide agglomerates incorporated with a carbonaceous material having a particle size within a range about from 10 to 30 nm, thinly laying the iron oxide agglomerates incorporated with the carbonaceous material at a laying density of 1.4 kg/m2/mm or lower on a hearth of a moving hearth furnace; and rapidly heatsrrg the reduced iron agglomerates such that the surface temperature of the reduced iron agglomerates reaches 1200°C or higher within one-third of the retention period of time of the iron oxide agglomerates in the moving hearth furnace;
reducing the iron oxide agglomerates to a metallization ratio of 85% or higher to prepare reduced iron agglomerates and then discharging the reduced iron agglomerates out of the moving hearth furnace.
2. A method of producing reduced iron agglomerates as defined in claim 1, wherein the particle size of more than 80% of the iron oxide agglomerates is arranged within a range of t2 mm of an aimed particle size in the step of preparing the iron oxide agglomerates incorporated with the carbonaceous material.
3. A method of producing reduced iron agglomerates as defined in claim 1, wherein the highest fluidity of the carbonaceous material upon softening and melting is 0.8 or higher in the step of preparing the iron oxide agglomerates incorporated with the carbonaceous material.
4. A method of producing reduced iron agglomerates as defined in claim 1, wherein the reduction ratio of a waste gas from a burner for heating the iron oxide agglomerates is controlled to Fe or FeO equilibrium before the amount of CO gas released from the iron oxide agglomerates during reduction is lowered to less than one-fourth of the amount upon peak generation in the step of reducing the iron oxide agglomerates incorporated with the carbonaceous material.
5. A method of producing reduced iron agglomerates as defined in claim 1, wherein the apparent density of the iron oxide agglomerates produced in the step of preparing the iron oxide agglomerates incorporated with the carbonaceous material is 2.3 g/cm3 or more.
6. A method of producing reduced iron agglomerates as defined in claim 1, wherein the apparent density of the reduced iron agglomerates after reduction is 2 g/cm3 or higher in the step of reducing the iron oxide agglomerates incorporated with the carbonaceous material.
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