Source: http://www.allindianpatents.com/patents/203381-a-method-of-producing-reduced-iron-in-a-tracvelling-hearth-furnace-and-apparatus-thereof
Timestamp: 2018-09-25 11:19:09
Document Index: 741063505

Matched Legal Cases: ['arth 1', 'arth 1', 'arth 1', 'arth 4', 'arth 5', 'arth 1', 'arth 1', 'arth 1']

Indian Patents. 203381:"A METHOD OF PRODUCING REDUCED IRON IN A TRACVELLING HEARTH FURNACE AND APPARATUS THEREOF"
"A METHOD OF PRODUCING REDUCED IRON IN A TRACVELLING HEARTH FURNACE AND APPARATUS THEREOF"
A method of producing reduced iron in a travelling hearth furnace and apparatus thereof, wherein the method comprises of stacking a layer consisting of a mixture of oxides such as fine iron ore and a fine solid reducing material onto a horizontally travelling hearth and reducing the oxides through radiant heat transfer from above the hearth, is based on melting the reduction product in the course of up to a discharge port, and causing aggregation and separation of slag in from the reduction product, followed by solidifying the reduced iron and discharging said reduced iron from the furnace.
apparatus for operating a traveling hearth furnace suitable for the manufacture of reduced iron from iron ore.
Production processes of crude steel are broadly classified into the blast furnace-converter process and the electric furnace proce.ss. An electric furnace is to manufacture steel, with scrap or reduced iron as an iron raw material, by heating and melting the raw material by electric energy, and refining the same as required. Scrap is a main raw material at present. Because of the recent supply shortage of scrap and the tendency toward manufacturing high-grade products by the electric furnace process, however, there is an increasing consumption of reduced iron.
As one of processes for manufacturing reduced iron, for example, Japanese Onexamined Patent Publication No. S63-108,188 discloses a method comprising the steps of
stacking a layer of an iron ore and a solid reducing material onto a hearth rotating in the horizontal direction, and heating the layer from above by radiant heat transfer to reduce the iron ore, thereby manufacturing reduced iron. This method provides advantages of a relatively low construction cost of facilities and a relatively low risk of operational troubles. In many cases, a form of rotary hearth as shown in Fig. 1 and Fig. 2 illustrating an A-A sectional view of Fig. 1 is adopted as the hearth traveling horizontally. A layer (t) of a mixed powder comprising an iron ore (oxide powder mainly comprising a fine iron ore) and a solid reducing material transported via a charger (a) is stacked onto the rotary hearth 1. The hearth 1 is covered with a furnace body 2 lined with refractory, and a burner 3 serving as a heat source is provided on the upper portion of the inside thereof so as to reduce the iron ore on the traveling hearth 1. A furnace temperature of about l,300°C is usually used. To prevent oxidation after discharge of the product to outside the furnace upon completion of reduction, and to achieve a high handling convenience, it is the usual practice to cool the reduced iron by a cooler on the rotary hearth, and then discharge the same from a discharge apparatus for recovery.
In this conventional manufacturing method, gangue and
ash contained in the raw material ore and the carbonaceous materials remain as they are in the reduced iron, the product, and are melted and reduced in an electric furnace (melting furnace) forming the next step. Gangue and ash contained in the feed stock ore or coal entrapped into the electric furnace, have caused the following problems.
(1)	In order to reduce sulfur contained in hot metal,
it is necessary to raise the CaO/SiO2 ratio in the produced
slag. It is thus necessary to supply a CaO source in a
large quantity in the form of limestone and dolomite
according as the SiO2 content resulting from gangue and ash
(2)	Addition of much limestone and dolomite requires
compensation of decomposition heat and sensible heat. For
this purpose, an increase in the electric power
consumption of the electric furnace is inevitable, hence
requiring use of an extra-fine powdery ore having a low
gangue content and concentrated and a low-ash coal so as
to minimize the quantity of slag entering the electric
Iron and steel-making via an electric furnace, as described above, it is necessary to provide high-grade ore and coal suitable for a traveling hearth furnace, and the cost thereof tends to increase, and in addition, the amount of deposits of resources and the production
capacity thereof have already reached the limits. Under these circumstances, therefore, the demand is increasing for supplying iron sources suitable for an electric furnace on the basis of ordinary ore and ordinary coal existing in large quantities .
It is easily conceivable that it is possible to maintain a reduced iron containing gangue and ash at high temperatures, bring the same in a molten state, and remove slag therefrom, but these cannot be achieved by the conventional method because of the following restrictions:
(1) Separation of slag and metal is achievable by keeping metal and slag at high temperatures until complete melting in a both-type melting furnace such as a melting reducing furnace, but this is difficult in a traveling hearth furnace because of restrictions in facilities. The lowest temperature, the holding time and other operating conditions for separating slag and metal in a radiant heating furnace such as a traveling hearth furnace and melting behavior for determining these conditions have not as yet been clarified.
(2) In order to increase the temperature of a radiant furnace, it is necessary to generate of high-temperature combustion flame. Increasing the temperature of the combustion flame requires preheating combustion air and accomplish combustion near the theoretical air ratio. For
the prevention of reoxidation of the reduced iron, on the other hand, it is necessary to maintain a very strong reducing gas atmosphere. Under this gas condition, however, it is difficult to obtain a high-temperature combustion flame.
(3) When melting the burden raw material in a traveling hearth furnace, a thin molten iron layer and a slag layer separated from each other are present on the traveling hearth, and problems of erosion of the traveling hearth caused by molten slag containing FeO and adhesion of slag to the hearth are encountered.
In this respect, the US Patent No. 3,442,931 discloses a technique of achieving a semi-molten state by adjusting an atmosphere to have a maximum temperature within a range of from 1,260 to 1,426°C, and to contain at least 10% combustible gas on a traveling hearth. While the disclosed technique permits maintenance of satisfactory contraction and oxidation resistance, separation of gangue is difficult.
Removal of gangue and ash by melting outside the furnace is naturally conceivable, but it is needless to mention that this requires facilities such as a new cupola.
The present invention Is to solve the problems in the conventional technique through disclosure of the following method.
The invention provides an operating method of a traveling hearth furnace, comprising, when stacking a layer comprising a mixture of oxides such as a fine iron ore and a fine solid reducing material onto a hearth traveling horizontally, and subjecting the layer to reduction of oxides via radiant heat transfer from the upper portion of the hearth, the steps of melting the reduction product in the course to a discharge port at a temperature over l,450°C, and separating slag In the reduction product through aggregation. In the present invention, the oxygen partial pressure of a gaseous phase In contact with the reduction product Is adjusted into a reducing atmosphere, and a layer different from the mixture layer may stacked.
In the invention, when stacking a mixture layer comprising a fine iron ore and a fine solid reducing material onto a hearth traveling horizontally, and reducing the fine ore by radiant heat transfer from above the hearth, first a fine coal char is stacked prior to stacking the mixture layer onto the hearth, then melting the product resulting from reduction of the mixture on the hearth at least once, and a carbonized gas produced upon
manufacturing a fine coal char by a preliminary carbonization of coal as a heating fuel of the traveling hearth furnace.
In the operating method of a traveling hearth furnace of the invention for stacking feed stock mainly consisting of a fine iron ore and a fine solid reducing material on a hearth traveling horizontally, the method comprises the steps of dividing a mixed powder of a fine iron ore and a fine solid reducing material or a mixed powder of fine iron ore, a fine additive and a fine solid reducing material into small blocks, dotting the hearth surface with these block via the fine solid reduction material so as to avoid direct contact of the blocks with the hearth, and melting the reduced iron on the hearth at least once.
The invention is described in details with reference to the accompanying drawings:
Fig. 1 illustrates a configuration of a rotary hearth furnace;
Fig. 2 is a sectional view of Fig. 1 cut along the line A-A;
Fig. 3 is a graph illustrating the relationship between the mixed slag concentration contained in the resultant metallic iron and the atmosphere temperature of the heating furnace;
Fig. 4 illustrates a configuration of an electric
furnace used in the experiment;
Fig. 5 illustrates a configuration of a furnace according to the invention;
Fig. 6 is a sectional view of a layer of a mixture and a single kind of carbonaceous material stacked on a hearth;
Fig. 7 illustrates the relationship between the reduced iron yield and the heating furnace atmosphere temperature;
Fig. 8 illustrates a mixed powder of iron ore and a solid reducing material directly stacked on a traveling hearth;
Fig. 9 illustrates reduced iron melted on a traveling hearth;
Fig. 10 is a descriptive view of the operating procedure according to the invention;
Fig. 11 illustrates a case using a material other than a coal char for stowing tacking under the mixture;
Fig. 12 illustrates the mixture and a coal char stacked on the hearth according to the invention; Fig. 13 is a sectional view of Fig. 12; Fig. 14 is a sectional view of a case melting of Fig. 13;
Fig. 15 is a descriptive view of a partial configuration of Fig. 20;
Fig. 16 illustrates a coal char manufacturing apparatus;
Fig. 17 (a) is a sectional view illustrating a mixed layer and a coal char layer used in an embodiment; and Fig. 17 (b) is a perspective view of Fig. 17 (a);
Fig. 18(a) is a descriptive view illustrating a case where a mixed powder of an iron ore and a solid reducing material is stacked directly on a traveling hearth; and Fig. 18(b) is a vertical sectional view of a molten state after reduction;
Fig.19 (a) is a perspective view illustrating the state of feed stocks stacking onto the hearth according to the invention; Fig. 19{b) is a vertical sectional view of Fig. 19(a); and Fig. 19(c) is a descriptive view of melting of a reduced iron;
Fig. 20 is a descriptive view of a rotary hearth furnace used in an embodiment;
Fig. 21 (a) is a vertical sectional view illustrating the state of feed stock stacking adopted in an embodiment of the invention; and Fig. 21(b) is a perspective view of Fig. 21(a), {condition 1: example of the invention);
Fig. 22(a) is a vertical sectional view illustrating the state of feed stock stacking adopted in an embodiment of the invention; and Fig. 22(b) is a perspective view of Fig. 22 (a), (condition 2: example of the invention) ;
Fig. 23 (a) is a vertical sectional view illustrating the state of feed stock stacking adopted in an embodiment of the invention; and Fig. 23 (b) is a perspective view of Fig. 23(a), (condition 3: comparative example);
Fig. 24(a) is a vertical sectional view illustrating the state of feed stock stacking adopted in an embodiment of the invention; and Fig. 24 (b) is a perspective view of Fig. 24 (a), (condition 4: comparative example);
Fig. 25 (a) is a vertical sectional view of the state of stacking in an embodiment of the invention; and' Fig. 25(b) is a perspective view of Fig. 25(a); and
Fig. 26 is a descriptive view of a discharge apparatus used when stowing in an embodiment according to the invention.
In the drawings, the reference numerals are as follows:
1: Hearth; 2: Furnace body; 3: Heating burner; 4: Partition; 5: Furnace body; 6: Carbonaceous material layer; 7: Mixture layer of iron ore (oxide) and solid reducing material; 8: Combustion burner; 9: Heater; 9a: Burner; 9b: Heat exchanger; 10: Discharge apparatus; 11: Gas supply nozzle; 12: Slag; 13: Cooler; 14: Discharge apparatus used when stowing in Fig. 25; 15: Discharge port; 16: Hot metal; 17: Fine coal char layer; 18:
Crusher; 19: Fine coal charging port; 20: Coal char discharging port; 21: Screw feeder; 22: Gas recovery port; 23: Reduced iron separated from gangue and ash; t: Mixture layer (feed stock); tl: Carbonaceous material layer; a: Charges (stacking apparatus); b: Discharging apparatus; c: Cutter; C1: Arm; f: Molten layer; g1: Waste gas; g2: Combustion air; h: Heater; i: Pyrometer; n: Nozzle; n1: Nozzle for waste gas; s: Bed;
When a mixture of an oxide powder such as a fine iron ore and a fine solid reducing material is heated from outside, reactions expressed by the following formulae (1) and (2) continuously take place and reducing reactions proceed:
CO + FeO - Fe + CO2 (near oxide particles)
CO2 + C - 2CO (carbonaceous material surface)
While the reducing reaction of the above formula (1) generally proceeds at a temperature of over 600°C, the reaction of the formula (2) proceeds only at a temperature higher than the reaction of the formula (1). In order to ensure continuous progress of the reaction, it is
necessary to achieve smooth diffusion of CO2 produced in the formula {1) to the solid reducing material particles and diffusion of CO produced in the formula (2) to the oxide particles.
In the case of ordinary iron ore and fine solid reducing material, the reactions can proceed by keeping the furnace temperature within a range of from 1,100 to 1,300°C. The reducing reactions of the formulae (1) and {2} basically proceed through reaction of solid iron oxides and the gas, and the resultant reduced iron is a porous solid metallic iron. The solid reducing material and the ash and the gangue contained In the fine Iron ore are in a solidus phase and are mixed finely in the reduced iron. It is therefore difficult to separate ash and gangue through physical means such as crushing or screening.
The invention proposes aggregation and separation of slag and metal by melting the reduced product on the traveling hearth, and removal of slag crushing and magnetic concentration after cooling. According to this method, therefore, it is possible to relatively efficiently obtain a. reduced product even in an operation using an ore containing much gangue of an ordinary coal.
Fig. 3 illustrates the result of an experiment carried out in a small-capacity electric furnace having a
structure as shown in Fig. 4 using an ore and a coal
having compositions as shown in Table 1 (sample sectional area: 50 x 50 mm) to examine conditions necessary for aggregation and removal of slag and metal. In this experiment, a heating time of six minutes was adopted and the following three types of conditions were used: in the first case, a layer consisting of only carbonaceous materials was not provided under the mixture, and the gas ' atmosphere near the surface of the layer with an air ratio close to the theoretical air ratio; in the second case, a layer consisting of only carbonaceous materials was provided under the mixture, and the gas atmosphere near the surface of the layer with an air ratio colse to the theoretical air ratio; and in the third case, a layer consisting of only a single kind of carbonaceous material was provided under the mixture, and the gas atmosphere near the surface of the layer was a reducing atmosphere. The quantity of carbonaceous materials added to the mixture was sufficient even to cope with the reduction and the subsequent carbonization reaction. The surface gas atmosphere was defined to have a ratio of the total reactive gas concentration relative to the reducing components in the gas:
= (CO + H2)/(CO + H2 + H2O + CO2) x 100 [%] The composition near the theoretical air a ratio was defined as a reducing gas concentration of about 3%, and the reducing atmosphere, a reducing gas concentration of 90%.
An electric heater h was provided on the upper surface of the electric furnace used in the experiment, and a mixture t of carbonaceous materials and a fine ore provided on the bed was heated by radiant heat. A nozzle n was provided at a position of 10 mm above the sample surface to adjust the gas atmosphere on the sample surface, and an atmosphere adjusting gas was blown through this nozzle and discharged from n1. The produced reduced iron and slag were crushed to -10 mm and magnetically concentrated. The slag removal temperature was evaluated from the mixed slag concentration contained in the resultant metallic iron.
Irrespective of the experimental conditions, as shown in Fig. 3, the mixed slag concentration can be rearranged as a function of temperature. The mixed slag concentration suddenly decreased upon passing the level of heating furnace atmosphere temperature of 1,450°C, and the separation of metal and slag was thus clarified. A l,400°C sample was subjected to a microscopic observation to investigate the cause of such rapid metal-slag
separation, and the following features were observed:
(1)	Carburization is in progress into the metal.
This results in a decreased melting point, and the ore
fines do not keep the initial shape thereof since the
metal is in a molten state. Because of a very large
surface tension of the metal, many of the particles take a
(2)	The carbonaceous materials scatter over the
observed surface, but are not considered to disturb
aggregation of the metal.
(3)	Slag coming from the carbonaceous materials is
partly melted, and a non-melted portion still exists.
(4)	Disturbance of aggregation among the molten metal
particles is attributable to high-viscosity slag partly in
a molten state derived from the ash of carbonaceous
materials. At 1,500°C observed for comparison purposes,
melting, displacement and aggregation are in progress not
only of the metal but also of the slag.
These results reveal that, while separation of iron slag should start by selecting a temperature higher by 100°C than the melting point of carburized iron, 1,150°C if only melting of the metal is in question, melting and displacement of slag form restricting conditions, and it is necessary to keep a heating furnace atmosphere temperature above l,450°C. At this temperature of l,450°C,
Al2O3-SiO2-CaO slag which is the main component of coal ash melts with a decreased viscosity, and begins aggregating and displacing.
The configuration of the traveling hearth furnace of the invention permitting separation of slag and metal invented on the basis of the foregoing fundamental experiment is illustrated in Fig. 5. In Fig. 5, 1 is a hearth; 5 i.s a furnace body; 6 is a carbonaceous material layer stacked on the hearth 4; 7 is a mixture layer stacked on the carbonaceous material layer 6; 8 is a combustion burner arranged above the hearth 5; and 9 is a heater for melting the product resulting from reduction, this heater 9 comprises a burner 9a and a heat exchanger 9b for heating combustion air g2 by means of the burner 9a and a waste gas g1.
The traveling hearth furnace having the configuration described above comprises a preheating zone covering an area ranging from a charging port not shown to Ll, a reduction zone covering an area L2' following the above, a melting zone covering an area L3, and a cooling zone covering an area L4. In the first two zone, heating is performed by burning the combustion burner with the reducing gas generated from the layer of the mixture of the fine ore and the carbonaceous materials as a main heat source. The mixture layer having reached a reduction rate
of over 80% in the reduction zone L2 is heated at a temperature over l,450°C in the melting zone L3, and slag is removed from the produced reduced iron layer. Then,
after cooling and heat recovery in the cooling zone L4, the reduced product are crushed in a collector 10 and discharged from the discharge port 15. Since the high-temperature melting zone of over l,4 50°C is formed in the present invention, the heating method for the melting zone L3 is different from that for the other zones.. Waste gas from the melting zone L3 is heat-exchanged with combustion air through the high-temperature heat exchanger 9b.
By causing combustion of air preheated to about 900°C and a separately supplied fuel at substantially the theoretical air ratio, a high-temperature melting zone of over l,450°C can be formed. For the purpose of independently controlling the gas atmosphere of the melting zone L3 and the gas atmosphere of the reduced iron surface, a gas supply nozzle 11 should preferably be provided to supply an atmosphere adjusting gas. By using a traveling hearth furnace having the configuration as described above, it is possible to manufacture a reduced iron resulting from reduction of the mixed layer of the fine ore and the carbonaceous materials and removal of slag. In terms of production cost, a mixed layer of fine
ore and carbonaceous materials formed by simply mixing these materials would bad to the lowest cost. However, a layer of previously granulated or otherwise treated materials may be stacked and subjected to reduction and melting.
Apart from the mixed layer, in the invention, a layer of carbonaceous materials may be stacked under the mixed layer. Provision of such a carbonaceous material layer brings about an advantage of preventing contact of the molten materials melting in the melting zone with the hearth. The size of the fine iron ore and the fine solid reducing agent should under 10 mm, or preferably, under 8 mm, or more preferably, under 3 mm as screen mesh from the point of view of reducibility and reactivity with CO2.
Fig. 10 is a sectional view of a part of a traveling hearth furnace (the furnace having the same fundamental structure as present invention.) In Fig. 10, 17 is a layer of a fine coal char for mounting a layer of a mixture t; A is a partition forming a melting zone in which the reduced product in melted, and held by a furnace body 2; and f is a molten layer melted in the melting zone.
When the layer 17 consisting only a single kind of the fine coal char is stacked on a rotary hearth 1, and a mixture layer t is stacked on this layer 17 for reduction,
the layer t of the mixture charged from a charger a is
reduced in the course up to a discharge apparatus b. Subsequently, the product (reduced iron) is melted in the melting zone, and accordingly, gangue and ash contained in this product are separated in the form of slag. By preliminarily carbonizing the coal used as the fine solid reducing material, a fine coal char is available. Because this coal char has been preliminarily carbonized, almost no decomposition reaction takes place upon heating, and the amount of heat input is smaller than in a case using a coal. It is therefore possible to achieve a temperature permitting reduction of iron ore on the hearth having a relatively shot hearth length, and for the same hearth area, to improve productivity.
Fig. 11 illustrates a case using a fine solid reducing material as a coal containing much volatile matters in place of the coal char layer. In this case, there occurs melting of the fine solid reducing material or a change in volume along with volatilization from the fine solid reducing agent caused by the increase in temperature, resulting in occurrence of cracks in the layer 17. Upon melting, therefore, the- reduced iron 16 and slag 12 flow through these cracks onto the rotary hearth 1 and may erode the surface thereof. When forming the layer 17 with a fine coal char, in contrast, the
volatile matters have already been lost through carbonization. Because the ash content is about 10%, it keeps a solid state even at a high temperature of over l,000°C, and is never subject to melting or a change in volume, from the macroscopic point of view. No cracks therefore occur in the layer 17, and the molten iron 16 or slag 12 never erodes the rotary hearth 1 in contact therewith.
Fig. 12 illustrates a case where a mixture of a fine iron ore and a fine coal char or a mixture of a fine iron ore, a fine coal char and fine additives is stacked on a layer consisting of a single kind of the fine char, and Fig. 13 illustrates a sectional view of Fig. 12. When heated by radiant heat transfer from above the hearth, the fine iron ore is reduced into a reduced iron containing gangue. From the fine coal char used as the reducing agent, ash remains. The fine additives are added, when causing reduced iron and ash to melt, for facilitating melting, and include limestone, fluorspar, serpentine, and dolomite. Although evaporation of cyrstallized water and partial decomposition reaction (for example, CaCO3, the main component of limestone, is thermally decomposed into CaO) occur prior to melting, these additives keep solidus state. Upon heating further, these materials begin melting, together with gangue in the fine iron ore and ash
in the coal char, and ore separated into hot metal and slag- At this point, since the mixed powder of the fine iron ore and the fine coal char or the mixed powder of the fine iron ore, the fine coal char and the fine additives ' is present on the layer comprising the fine coal char only, hot metal 16 and slag 12 are formed on the layer 17 consisting only of the fine coal char as shown in Fig. 14, The hot metal 16 and the molten slag 12 usually have a specific gravity layer than that of the layer 17 composed only of the fine coal char. However because the layer 17 of the fine coal char alone is dense with the fine coal char, the hot metal 16 and the molten slag 12 are held on top of the fine coal char layer 17 and never cause a damage to the hearth refractory. To achieve a denser fine coal char layer, it suffices to adjust the screen mesh size to under 10 mm, or preferably to under 3 mm.
When obtaining a reduced iron by heating a mixture of a fine iron ore and a fine coal char or a mixture of a fine iron ore, a fine coal char and fine additives reduction of the iron ore takes place directly from the reducing reaction. It is therefore necessary to supply heat required for the reaction from outside. However, since combustible CO gas is produced by the active reducing reaction during the initial stage of reaction, heat can be supplied by burning this CO gas.
When the reducing reaction proceeds and the latter
period of reduction is reached, the quantity of produced CO gas decreases. It is necessary, therefore, to supply combustion or heat from outside. When causing the reduced iron to melt after reduction, there is a small quantity of produced CO gas because reduction has been almost completed. In order to cause further melting of the reduced iron, temperature should be higher than the reduction temperature,, and it is thus necessary to supply heat from outside. The combustible gas produced during the preliminary carbonization, having a large calorific value, can be used in the melting zone of the traveling hearth furnace in the present invention. By effectively utilizing this combustible gas produced upon preliminary carbonization, it is possible to reduce the energy consumption. As means for preliminarily carbonizing a fine coal, a preliminary carbonizing apparatus is applicable. The particle size of the fine iron ore and the fine solid reducing material should be adjusted a mesh size of under 10 mm, or preferably under 8 mm, or more preferably under 3 mm considering reducibility of ora and reactivity between the reducing agent and CO2.
According to the invention, furthermore, it is possible to facilitate discharge of the product by optimizing the charging method of raw materials onto the
traveling hearth. More specifically, small blocks formed
by driving the mixed powder of the fine iron ore and the fine solid reducing material or the mixed powder of the fine iron ore, the fine solid reducing material and the fine additives are scattered in the layer of the fine solid reducing material. Then, the resultant mixture is stacked on the horizontally traveling hearth so as not to be in direct contact with the hearth. After reduction, the reduced iron is melted.
As an example, Figs. 19(a), (b) and (c) are descriptive views illustrating feed stock stacked on a hearth according to the invention and changes occurring upon melting the reduced iron. In Fig. 19, 7 is a mixed powder of a fine iron ore and a fine solid reducing material (or a fine iron ore, fine additives an a fine solid reducing material); 6 is a layer of a fine solid reducing material; 1 is a traveling hearth; 23 is a reduced iron after separation of gangue and ash; and 12 is a slag. When stacking the raw materials as shown in Figs, 19(a) and 19(b), and heating the same from above by radiant heat transfer, the fine iron ore is reduced by the action of the fine solid reducing material into a reduced iron containing gangue. Ash remains from the fine solid reducing material having served as the reducing material. The additives are added to facilitate melting when causing
the reduced iron and ash to melt, including limestone,
fluosspar, serpentine and dolomite. Although evaporation of crystallized water and partial decomposition reaction (for example., CaCO3, the main component of limestone, is thermally decomposed into CaO) occur prior to melting, these additives keep solidus state. Upon heating further, these materials begin melting and are separated into hot metal and slag. At this point, since the mixed powder of the fine iron ore and the fine coal char or the mixed powder of the fine iron ore, the fine coal char and the fine additives scatters throughout the layer comprising the fine coal char only, and is present in the form not in direct contact with the horizontally traveling hearth, the hot metal and the molten slag aggregate every scattered block, and reduced iron lumps are formed on the layer of the fine solid reducing agent alone. Because hot metal and molten 'slag have usually a specific gravity layer than that of the layer of the fine solid reducing material alone, it is conceivable that hot metal and molten slag get under the layer of the fine solid reducing material alone. However, the layer of the fine solid reducing material alone is dotted with the mixed powder of the fine iron ore and the fine solid reducing material (or the mixed powder of the fine iron ore, the fine additives and the fine solid reducing material). Each block of hot
metal or molten slag is therefore small in size and is held on the layer of the fine solid reducing material alone by the action of surface tension.
When the hot metal and the molten slag are cooled by a cooler on the traveling hearth in this state, the reduced iron and slag after separation of gangue and ash float on the layer of the fine solid reducing material alone, and form lumps for the individual blocks scattered. The reduced iron and slag having solidified are thus apart from the traveling hearth as a result of presence of the layer of the fine solid reducing material alone, and the individual block are small lumps, thus permitting easy discharge outside the furnace. The fine iron ore should preferably have a size in screen mesh of under 8 mm, the fine additives under 8 mm, and the fine solid reducing material, under 8 mm.
It is also possible to use a pitch coke containing almost no ash as the fine solid reducing material in the mixed powder of the fine iron ore and the fine solid reducing material. In this case, there is no more the idea of removal of ash in the present invention, with however the same separating effect of gangue in the ore. When using a coking coal for the layer of the fine solid reducing material alone, the coal melts into coke at a temperature lower than the temperature at which hot metal
and molten slag are formed. At a temperature at which hot metal and molten slag are formed, the coal is already in a solid state, and can exert the above effect. A mixture of use or more of coal char, coke, general coal and anthracite usually contains about 10% ash. These fine solid reducing material can be favorably utilized in the present invention, and when using any of these materials as the fine solid reducing material, it may of the same kind as, or a different kind from, the fine solid reducing material from the point of view of removing ash. >
Operation was carried out by the following procedure using a traveling hearth furnace (having the same configuration in detail as that shown in Fig. 5) as shown in Figs. 1 and 2 provided with a rotary hearth lined with alumina refractory and having a diameter of 2.2 mm in which the refractory of the melting zone comprised a high-alumina high-refractory brick work, to investigate the effect of a change in temperature of the melting zone on the yield of the final product (reduced iron), A screw type discharging apparatus was arranged at the discharge port of the furnace, and a mixture t of a fine iron ore and a fine solid reducing material and a layer t1 of a carbonaceous material alone were stacked at the charging
port as shown in Fig. 6. The particle size of the fine iron ore and the fine solid reducing material was adjusted to a screen mesh of under 3 mm.
An iron ore and a carbonaceous material having compositions as shown in Table 1 were employed. The furnace temperature in the reducing zone was controlled to l,300°C through combustion control of the burner, with a standard staying time in the melting zone of six minutes. Three operational patterns were used: in a first pattern, a layer of a carbonaceous material alone was not provided under the mixture, with a surface gas atmosphere near the theoretical air ratio; in a second pattern, a layer of a carbonaceous material alone was provided under the mixture, with a surface gas atmosphere near the theoretical air ratio; and -in a third pattern, a layer of a carbonaceous material alone was provided under the mixture, with a surface gas atmosphere being a reducing atmosphere.
Fig. 7 illustrates the relationship between the melting zone temperature and the reduced iron yield under various conditions. At low temperatures under l,450°C at which melting did not occur, there was no change in the reduced iron yield irrespective of presence or absence of a lower carbonaceous material layer. In the absence of a carbonaceous material layer under the mixture, at a
temperature over 1,450oC at which melting occurs, the produced hot metal and slag melted and adhered to the traveling hearth surface, thus largely reducing the reduced iron yield. In a case where a carbonaceous material layer was provided under the mixture, on the other hand, pores of the porous reduced iron were clogged along with melting, thus inhibiting oxidation caused by the atmosphere gas, leading once to an increased reduced iron yield. With the increase in temperature, however, oxidation was caused by the combustion gas near the theoretical oxidative air ratio for iron, and the resultant FeO flows out into slag, and as a result, the reduced iron yield largely decreased. When a reducing gas of a concentration of 90% was supplied through blowing of an atmosphere adjusting gas on the exit side of the melting zone with a reducing gas atmosphere on the surface of the reduced iron, it was confirmed that the prevention from reoxidation by the atmosphere gas resulted in a stable reduced iron yield of over 97% at low temperatures, It was therefore possible to confirm, from this result, that slag can be removed from the reduced iron at a melting zone temperature of over l,450°C, that, for improving the reduced iron yield, it is necessary to provide a layer of carbonaceous material under the mixture, and that it is important to adjust the gas
atmosphere on the reduced iron surface into a reducing
The experiment Nos. 1 to 3 in Table 2 shown the
results of operation (comparative example) carried out with a low melting zone temperature without a carbonaceous material layer under the mixture. In this example, although the metal recovery ratio was high, separation of slag, the main object of the invention, was insufficient. The experiment Nos. 4 to 7 represent examples for examining the effect of the melting zone temperature (examples of the invention), showing that the slag concentration largely decreased at temperatures of over l,450°C. The experiment Nos. 8 and 9 are examples for examining the effect of the heating time (examples of the invention): a longer heating time leads to a progress of slag separation. In the experiment No. 10, the atmosphere on the layer surface was a reducing atmosphere and there is observed a remarkable improvement of" the reduced iron yield. The experiment Nos. 11 and 12 represent cases without carbonaceous material layer under the mixture: in spite of achievement of separation of slag, the main object of the invention, the reduced iron yield is slightly lower than that available under the optimum conditions. The experiment Nos, 13 to 16 show results obtained by changing the kind of the carbonaceous material
into char and coke: results similar to those with coal were obtained.
A mixture was reduced by the following procedure using a traveling hearth furnace provided with a traveling hearth lined with alumina refractory, of which the surface was further covered with granular alumina refractory, and having a diameter of 2.2 mm, as shown in Fig. 20, to investigate the presence or absence of a damage to the refractory and the iron recovery ratio.
In the furnace shown in Fig. 20, a cooler 13 was arranged in the middle between a heating zone (see Fig. 10) and the discharge apparatus to cool the product. As shown in Fig. 15 illustrating a portion of Fig. 20/ a crusher 18 comprising a cutter c vertically moving to crush the reduced iron and slag and an arm cl pulling out the crushed reduced iron and slag was arranged in the discharge apparatus b. Coal char stacked under the mixture was manufactured by the use of a screen feeder type preliminary carbonizing furnace as shown in Fig. 16, provided with a screen feeder 21 between the feed stock charging port 19 and the discharge port 20 and a gas recovery port 22. Waste gas from a traveling hearth furnace has usually a temperature of about 1,150°C. In this example, the preliminary carbonization furnace was
heated by the use of waste gas from the traveling hearth furnace.
As shown In the sectional view and the perspective view illustrated in Figs, 17(a) and 17(b), the mixture and the coal char to be subjected to reduction were stacked with D = 800 mm, D1 = 25 mm and D2 = 40 mm. The fine iron ore and the fine solid reducing material used for the mixture were adjusted to a screen mesh of under 3 mm. The coal char stacked on the hearth was adjusted to under 3mm. The furnace temperature in the reduction zone was controlled to l,300°C through combustion control of the burner. The fuel was mainly composed of CO gas produced from the fine solid reducing material, and natural gas was employed as an auxiliary fuel. The staying time In the furnace was controlled to 27 minutes as a target by means of the rotation speed of the hearth.
Composition of the ore used in the experiment (containing more than 7% gangue such as SiO2 and A12O3) is shown in Table 3, and composition of the fine solid reducing agent (ash: about 6 to 11%), in Table 4. In this example, limestone was used as an additive. Experimental conditions are shown in Table 5, and the result of experiment, in Table 6. In the column of mixed powder in Table 5, the fine solid reducing material, the ore, and the additives total 100%, The term "gangue + ash" is
expressed by the weight percentage relative to the mixed powder, and include gangue in the ore, ash in the solid reducing agent, and CaO in the additive (limestone). The run Nos. 17 to 19 represent examples of the invention in which a fine coal char made from a fine coal through preliminary carbonization was used as the fine solid reducing material. In the run Nos. 17 to 19, there was no damage to the refractory of any hearth, and the reduced iron after removal of gangue and ash could be collected. The run Nos. 20 and 21 represent cases
¦ according to the invention in which the combustible gas produced in the preliminary carbonization furnace was further collected and used for heating the
high-temperature portion of the rotary hearth furnace. In the run Nos. 20 and 21, these was no damage to the
refractory of any hearth, and the reduced iron after removal of gangue and ash could be collected. In this example, waste gas from the rotary hearth furnace was used for heating the coal in the preliminary carbonization furnace, and combustible gas produced in the preliminary carbonization furnace was used for heating the high-temperature of the rotary hearth furnace. The combustible gas from the preliminary carbonization furnace has a high calorific value, and could be used for heating the high-temperature portion of the rotary hearth furnace.
Particularly in the run Nos. 20 and 21, as compared with the run Nos. 17 to 19, the consumption of natural gas used as an auxiliary fuel could be reduced, and the possibility to further reduce the heat input per ton reduced iron was confirmed.
Run Nos. 22 and 23 represent cases where a fine coal not subjected to preliminary carbonization was employed as the fine solid reducing agent. In these cases, the reduced iron and ash were melted for removing gangue and ash. Cracks occurred in the layer upon carbonization of a portion of fine coal on the rotary hearth. Molten slag and hot metal leaking from this portion were partially mixed directly with granular alumina refractory on the rotary hearth. Slag and reduced iron could be collected by taking out slag, reduced iron and granular alumina refractory mixed therewith to outside the furnace. Separation of granular alumina refractory from slag and reduced iron required operations outside the furnace. In Table 6, as compared with cases using preliminary carbonization of coal, the run Nos. 22 and 23 required a larger consumption of the auxiliary fuel with a view to keeping a constant temperature in the furnace because a decomposition of coal occurs upon reduction. When using the fine coal as the layer of fine solid reducing material alone, a longer period of time is required until reaching
the temperature at which the iron ore is reduced than in the case of preliminary carbonization of coal. In order to obtain a iron recovery ratio of the same order as in the case with preliminary carbonization of coal, therefore, it is necessary to use a longer staying time of iron ore in the furnace, resulting in a disadvantage in terms of productivity.
The following test operation was carried out by using a rotary hearth furnace shown in Fig. 20 having a rotary hearth having a diameter of 2.2 m and a burner provided above the hearth, these components as a whole being covered with a furnace body. In Fig. 20, 1 is a rotary hearth lined with alumina refractory on the upper surface; b is a screw type discharge apparatus; a is a charger (feed stock stacking position onto the hearth);2 is a furnace body; 3.is a burner; and 13 is a cooler provided in front of the discharge port for cooling and removing the reduced iron. The feed stock at the supply port were stacked on the rotary hearth under any of the four kinds of conditions as shown in the descriptive view of the feed stock stacking method in Figs. 21 to 24 by means of the charger a: feed stock included a fine iron ore, a fine additive and a fine solid reducing material. In Figs. 21 to 24, 7 is a mixed powder of the fine iron ore, the fine
additives and the fine solid reducing material; 6 is the fine solid reducing material; and 1 is the rotary hearth.
The fine iron ore containing more than 7% gangue (such as SiO2 and A12O3) having the composition shown in Table 3 was used, with limestone as the fine additive. Fine solid reducing materials containing ash within a range of from 6 to 13% and having four kinds of composition shown in Table 7, respectively, were used. These materials were used after adjustment to a mesh size of under 3 mm. The experimental conditions and operating results are comprehensively shown in Table 8. In the line of mixed powder in Table 8, the term "gangue + ash" means the content thereof in the mixed powder, and includes gangue in the fine iron ore, ash in the fine solid reducing material, and CaO in the fine additive (limestone).
In Table 8, experiment Nos. 24 to 33 are examples of the invention. Under any of the conditions, there was no damage to the refractory of the hearth, with no trouble in product discharge. A reduced iron after removal of gangue and ash could be collected with an iron recovery ratio of higher than 97.4%.
The comparative examples of the experiment Nos. 34 and 35 (condition 3) show, on the other hand, the stacking method: the mixture is stacked so that the mixed powder is
in direct contact with the hearth refractory. Reduced iron and ash were melted in this stowing condition for the removing operation of gangue and ash. Slag and hot metal deposited in molten state to the hearth refractory and oeroded the refractory. In addition, in the subsequent cooling operation, slag and hot metal adhered as deposited to the hearth refractory, thus making it impossible to discharge the product by the discharge apparatus.
The comparative example of the experiment No. 36 uses the stacking method shown in Fig. 24 {condition 4) : the mixed powder was stacked In lamination on the entire upper surface of the layer of the fine solid reducing material alone. In this form of stacking, the reduced iron and ash were melted for removal of gangue and ash. Both slag and hot metal took a shape of a large plate, and the effect of surface tension decreased relative to the weight. At some portions, hot metal and slag penetrated under the layer of the fine solid reducing material, and came into direct contact with the refractory of the hearth. The hot metal and slag thus eroded the refractory at these portions, and as a result of the subsequent operation, the hot metal adhered as it was to the hearth refractory, thus making it impossible to discharge the product by means of the discharge apparatus.
The comparative example of the experiment No. 37
covers the same stacking method as that in the experiment No. 36. In this form of stacking, the reduced iron and ash was melted. The hot metal and slag never penetrated fortunately under the layer of the fine solid reducing material alone as in the experiment No. 35. Apart from partial cracks caused by contraction during the cooling process, slag and reduced iron after cooling formed a large slab, and it was difficult to discharge them.
As a variant of the invention, there is conceivable a stacking method as shown in Fig. 25. In this case, slag and reduced iron after cooling coming to the discharge port take the form of a bar extending in the radial direction of the rotary hearth. Use of a discharge apparatus having the construction as shown in Fig. 26 is therefore considered appropriate. In Fig. 26, 1 is a rotary hearth; 2 is a furnace body; and 14 is a discharge apparatus used when stacking in the case of the variant.
t-Fe	SiO2	Al2	o3	CaO	MgO	TiO2	S	P
Iron	ore	62.3	4.31	2.	6	0.04	0.05	0.1	0.	014	0	.075
FC	VM	Ash
Coal	56.8	32.8	10.2
Char	82.08	2	15.46
Coke	87.7	0.9	11.2
Experiment No.	Kind of carbonaceous
material	Quantity of carbonaceous material (kg/t)	Presence of lower carbonaceous
material layer	Melting zone temp. (°C)	Heating time (nun.)	Layer surface reducing gas concentration (%)	Slag concentration (kg-slag /kg-metal)	Slag separating ratio (%)	Reduced iron yield	Remarks
1	Coal	600	None	1300	6	3	160.3	10	92	Comparative ex.
2	Coal	600	None	1400	6	3	160.3	10	94	Comparative ex.
3	Coal	600	None	1450	6	3	133.6	25	95	Comparative ex.
4	Coal	600	Present	1480	6	3	71.3	60	96	Ex. of invention
5	Coal	600	Present	1500	6	3	44.5	75	95	Ex. of invention
6	Coal	600	Present	1550	6	3	26.7	85	94	Ex. of invention
7	Coal	600	Present	1600	6	3	14.3	92	92	Ex. of invention
8	Coal	600	Present	1480	-3	3	74.8	58	97	Ex. of invention
9	Coal	600	Present	1480 .	8	3	64.1	64	92	Ex. of invention
10	Coal	600	Present	1480	6	90	42.8	76	98	Ex. of invention
11	Coal	600	None	1480	6	3	65.9	63	82	Ex. of invention
12	Cosl	600	None	1480	6	90	57.0	68	83	Ex. of invention
13	Coke	515	Present	1480	6	90	32.9	80	96	Ex. of invention
14	Coke	415	Present	1480	6	3	37.9	77	94	Ex. of invention
15	Char	389	Present	1480	6	90	33.1	81	98	Ex. of invention
16	Char	389	Present	1480	6	3	41.8	76	92	Ex. of invention
Layer surface reducing gas concentration = (CO + H2) / (CO + H2 + H2O + CO2)
water %	T. Fe
%	FeO
%	SiO, %	A12O3
%	CaO %	MgO %	P %	S %
3.25	62.30	0.11	4.31	2.60	0.04	0.05	0.075	0.014
Volatile matters %	Ash
B	Coal char General coal	3.0
44.5	10.4 6.6
Run No.	Mixed powder
Solid reducing agent	Ore	Additive (limestone)	Gangue + ash
mass %	mass %	mass %	mass %	mass %
17	17.7	75.3	7.0	10.9
18	17.4	75.6	7.0	11.3
19	18.8	81.2	7.6
20	17.5	75.5	7.0	10.9
21	18.6	81 .4	7.6
22	27	66	7.0	10.2
i	29 .1	70.9 6.9
Layer of powdery solid reducing agent alone
mass %	mass %
Run No.	Damage to hearth refractory	Product reduced iron	Heat input	Staying period in rotary hearth furnace
Iron recovery yield	Gangue	Production	Gcal/t-DRI	min
mass %	mass %	kg-DRI/hour
17 18 19	Ex. of invention Ex. of invention Ex. of invention	None None None	98.5 98.1 97.8	0.1 0.1 0.2	127 125 130	5.57 5.54 5.60	27 27 27
20 21	Ex. of invention Ex. of invention	None None	98.8 97.4	0.1 0.2	123
129	5.10 5.08	27 27
22 23	Comparative ex. Comparative ex.	Present Present	96.6 95.9	0.2 0.2	107 104	6.55 6.62	32 32
Table 7{%)
Symbol	Material	Volatile matters	Ash
A	Coke	1.0	12.0
B	General coal	44.5	6.6
C	Coal char	3.0	10.4
D	Anthracite	3.6	7.5
Experiment No.	Mixed powder	Layer of powdery solid reducing agent alone	Stacking condition	Damage to hearth re- ¦ frac-	Trouble in product dis-	Product reduced iron	Remarks
Soli	d reducing agent	Ore	Additive	Gangue + ash
Iron re-	Gangue
A	B	C	D	(limestone)
A ¦	B	C	D
tory	charge	covery yield
%	mass	mass
%	mass
%	Mass %	mass %	mass
%	mass %	mass %
24	17.4	75.6	7.0	11.3	100	1	None	None	98.0	0.1	Example *
25	27.1	65.9	7.0	10.3	100	1	None	None	97.8	0.2	Example *
26	17.5	75.5	7.0	11.0	100	2	None	None	98.8	0.1	Example *
27	17.1	75.9	7.0	10.5	50	50	2	None	None	98.5	0.1	Example *
28	11.1	9.8	72.1	7.0	10.9	100	2	None	None	97.7	0.2	Example *
29	12.0	9.7	71.3	7.0	10.7	50	50	2	None	None	98.2	30	9.0	9.6	81.4	7.4	25	25	50	1	None	None	97.6	31	5.0	5.0	10.6	79.4	7.7	25	25	50	1	None	None	98.7	0.2	Example *
32	5.0	5.0	9.1	73.9	7.0	10.6	25	25	25	25	1	None	None	97.4	0.3	Example *
33	5.0	5.0	5.0	4.2	73.8	7.0	10.8	100	1	None	None	99.0	0.1	Example *
34	17.4	75.6	7.0	. 11.3	3	Present	Present	-	-	Comparative ex.
35	29.1	70.9	6.9	3	Present	Present	-	-	Comparative ex.
36	17.5	75.5	7.0 ¦	11.0	50	50	4	None	Present	-	-	Comparative ex.
37	18.4	81.6	7.2	100	4	None	Present	-	-	Comparative ex.
Examination * means Examination of the invention
efficiently separate slag from reduced iron in a traveling hearth furnace. It is therefore possible to reduce the lime consumption and electric power consumption in the 5 subsequent electric furnace. At the same time, there is available an advantage of using inexpensive ore and coal with high contents of gangue and ash, which are most abundantly available.
In the present invention, furthermore, use of a coal
10 char as a carbonaceous material permits further
improvement of productivity, and use of carbonized gas generated upon manufacturing a char as a fuel permits saving energy consumption.
Further, the present invention proposes a process
15 comprising the steps of dividing a mixed powder containing a fine iron ore and a fine solid reducing material into small blocks, dotting the hearth surface with these blocks and melting the reduced iron on the hearth so as not to be in direct contact with the hearth via the fine solid
20 reducing material, in the reduction of iron ore in a traveling hearth furnace. According to the invention, therefore, it is possible to obtain a reduced iron free from gangue or 'ash without causing a damage to the
facilities while using a simple equipment and while ensuring a smooth operation.
1.	A method of producing reduced iron in a travelling hearth
furnace, comprising:
stacking a layer comprising a mixture of fine iron ore and a fine
solid reducing material onto a hearth travelling horizontally
therewith while transferring said layer along a course in said
subjecting said layer to a reduction reaction via radiant heat
transfer from the upper portion of the hearth,
melting reduced iron from said reduction reaction,
subjecting said reduced iron to separation of slag from said
reduced iron by melting said reduced iron to reduce viscosity of
said slag, causing separation of said slag from said reduced iron
by aggregation and displacement, thus converting said reduced
iron into separate bodies comprising said reduced iron and said
solidifying said reduced iron, and
discharging said reduced iron from the furnace.
2.	A travelling hearth furnace according to claim l, wnerexn
said travelling hearth is a rotary hearth.
3.	A method according to claim 1, wherein said method comprises
generating an oxygen partial pressure of a gaseous phase over
said reduction product into a reducing atmosphere.
4.	A method according to claim 1, wherein a layer different from
the mixture layer is layered on between said hearth and said
5.	A method according to claim 4, wherein said layer different
from said mixture layer is a layer of a carbonaceous material.
6.	A method according to claim 5, wherein, prior to positioning
said mixture layer onto said hearth, fine coal char is first
placed on said hearth, wherein the said mixture layer is layered
upon said layer consisting of the said fine coal char, and
wherein the product resulting from reduction of the resulting
mixture is melted on said hearth at least once.
7.	A method according to claim 6, wherein a carbonized gas is
produced upon manufacturing the fine coal char by preliminary
carbonization of coal, and wherein said carbonized gas is used as
a heating fuel.
8.	A method according to claim 5, wherein said method comprises
the steps of dividing a mixed powder of a fine iron ore and a
f ine solid reducing material or a mixed powder of a f ine ore,
fine additives and a fine solid reducing material into small
blocks, dotting the hearth surface with said small blocks on said
fine solid reduction material so as to avoid direct contact of
said blocks with said hearth, and melting the reduced iron on
said hearth at least once.
9.	A method according to claim 8, wherein	said fine solid
reducing material is one or a mixed powder	of two or more
materials selected from the group consisting of	coal char, coke,
general coal and anthracite.
10.	The method defined in claim l, wherein said continuous layer
of finely divided carbonaceous material has a particle size below 10 mm.
11.	The method define in claim l, wherein said layer of iron
oxide has a particle size of under 8 mm.
12.	A travelling hearth furnace as claimed in claim 1, comprising:
a hearth(1) for conducting preheating and reduction of a layer
comprising a mixture of fine iron ore and a fine solid reducing
material stacked thereon while transferring said layer along a
course in said furnace, and a furnace body(5) surrounding said
hearth and provided with one or more burners(8) at the top of the
inside thereof;
wherein said hearth furnace has a distinct melting zone comprising physical partitioning(4) to create a melting chamber separate from a preheating zone and a reduction zone, wherein said physical partitioning allows free movement of said hearth, and wherein a reduced iron is melted in said melting chamber to provide means to separate therefrom slag contained therein by reducing viscosity of said slag, and means for causing separation of said slag from said reduced iron by aggregation and displacement, and the product is led to a discharge port(15) for
discharging said product.
13. A travelling hearth furnace according to claim 12, wherein said travelling hearth is a rotary hearth.
00545-cal-1998 abstract.pdf
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545/CAL/1998
1-28,KITAHONMACHIDORI 1-CHOME, CHOU-KU, KOBE-SHI, HYOGO 651-0075,
1 KANJI TAKEDA C/O TECHNICAL RESEARCH LABORATIES, KAWASAKI STEEL CORPORATION.1 KAWASAKICHO, CHOU-KU,CHIBA-SHI CHIBA 260-0835
2 YOSHITAKA SAWA C/O TECHNICAL RESEARCH LABORATIES, KAWASAKI STEEL CORPORATION.1 KAWASAKICHO, CHOU-KU,CHIBA-SHI CHIBA 260-0835
3 TETSUYA YAMAMOTO C/O TECHNICAL RESEARCH LABORATIES, KAWASAKI STEEL CORPORATION.1 KAWASAKICHO, CHOU-KU,CHIBA-SHI CHIBA 260-0835
4 TETSUYA KIKUI C/O TECHNICAL RESEARCH LABORATIES, KAWASAKI STEEL CORPORATION.1 KAWASAKICHO, CHOU-KU,CHIBA-SHI CHIBA 260-0835
1 9-265410 1997-09-30 Japan
2 9-265406 1997-09-30 Japan
3 9-265411 1997-09-30 Japan