Abstract:
A process for the reduction of iron oxides to produce molten iron in which olivine is introduced into a blast furnace in addition to iron oxide bearing materials and in which there is high content of alkali metal oxides in the materials charged into the furnace, resulting in minimizing or preventing &#34;scaffolding&#34; and improving the operation of the blast furnace. The disclosure also includes sinters and briquettes which contain olivine and processes of preparing them, and processes for furnace operation including the charging of such sinters or briquettes.

Description:
This invention relates to a process for producing molten iron in a blast furnace, and more particularly to such a process in which olivine is charged into the blast furnace in addition to the iron ore or other iron oxide bearing materials. 
     BACKGROUND OF THE INVENTION 
     The operation of the blast furnace in the production of iron involves processes of chemical reduction in which oxides of iron and other metals are reduced and oxygen removed. The furnace is charged with four basic ingredients; (1) iron oxides, in the form of raw ore, beneficiated pellets, briquettes, nodules, sinters, or other agglomerates. (2) calcium carbonate, (I use the term calcium carbonate to include either limestone or dolomite). (3) a fuel usually in the form of coke. (4) air which provides oxygen to support the combustion. The raw iron ore as it comes from the Lake Superior region contains approximately 50% iron in the form of iron oxide Fe 2  O 3  and manganese oxide (MnO), with the remainder being silica (SiO 2 ), aluminum (Al 2  O 3 ), magnesia (MgO), lime (CaO), sulfur (S), and phosphorus (P). The sulfur and phosphorus are commonly considered impurities. 
     The iron oxides, or other metallic charge materials, coke and calcium carbonate are charged into the blast furnace, one at a time, in measured amounts to form layers of iron ore, limestone or dolomite, and coke; and air (wind) is passed through these layers and the coke burned. Burning of the coke produces heat and carbon monoxide which has a part in the chemical reduction of the iron oxides. As the coke burns the iron oxides are reduced and come into the form of molten iron. The limestone, or dolomite, along with quantities of impurities such as sulfur and phosphorus, form a slag. The hearth, which is at a lower part of the furnace, is the hottest part of the furnace and the layers of ore, coke and calcium carbonate keep moving downwardly within the furnace to the hearth. At some point in this movement downwardly in the furnace slag is formed, and after its full passage downwardly in the furnace it is withdrawn from the furnace in the form of liquid slag. The slag is important to the operation of the furnace because it carries with it many unwanted impurities and so separates these from the iron and removes them from the furnace. 
     When the downward movement of the iron bearing charge materials, the coke and the calcium carbonate proceeds in a uniform way with the movement taking place constantly and evenly on all sides of the furnace, this is evidence of good operation. Unfortunately, this is not always the case. 
     As is well known to blast furnace operators there are times when the downward movement of the ingredients charged into the furnace is not regular and uniform or when the movement on one side of the furnace is greater than on the other side making the furnace unbalanced or &#34;lopsided&#34;. There are even times when the downward movement becomes severely restricted, and then after operation for a time under such conditions the whole mass may let loose descending at once into the hot part of the furnace with the result that the hearth temperature is reduced to below an operable temperature, sometimes almost extinguishing the fire. When this happens the furnace may have to be shut down, cleaned and then restarted, which is a time-consuming and expensive operation. 
     It is our belief that the faulty operation above referred to is due in large part to the presence in the charge materials of a greater than usual content of alkali metal oxides such as Na 2  O, K 2  O, Li 2  O. These oxides appear to pass downwardly to hotter parts of the furnace and there become volatilized after which they pass up the furnace inwalls with the wind and then condense above the mantle of the furnace forming stable alkali-alumino-silicates. Such alkali-alumino-silicates are believed to lead to a scaffolding effect which prevents the layered column of burden material from descending in a regular uniform manner. A continuation of this action develops a situation where the mass will collapse of its own weight, chilling the furnace hearth where the most important smelting reactions take place. 
     SUMMARY OF THE INVENTION 
     We have discovered that when processing charge material loads containing alkali metal oxides in excess of about one pound of alkali metal oxides per net ton of molten iron produced, it is possible to improve the operation of the blast furnace, remove a substantial part of the alkali metal oxides in the slag, and prevent the occurrence of falling burden as above described, by charging into the furnace in addition to the regular charge materials having a high alkali metal oxide content a special mineral known as olivine. 
    
    
     DETAILED DESCRIPTION 
     The olivine above referred to is a special mineral which may be obtained in the form of crushed, sized rock having the following typical analysis: 
     
         MgO        40 to 52 weight percentSiO.sub.2  35 to 45 weight percentFeO        6.5 to 10 weight percent 
    
     The main component of olivine is forsterite (2MgO.SiO 2 ) which may be contained in an amount of 80 to 95%, usually about 88-90%. Another component is iron silicate (2FeO.SiO 2 ) which may be contained in from about 5 to 12%, usually averaging about 8 to 9%. 
     The olivine may be charged into the furnace along with the iron ore or other iron oxide bearing charge materials and may be in an amount of from 0.25 to 5.0% by weight of the iron bearing charge materials which are charged into the furnace. Preferably the olivine may be charged into the furnace in an amount within the range of 1.0 to 2.0% by weight of the iron oxide bearing charge materials. We have found that charge materials having a high alkali metal oxide content, in excess of 1 pound per net ton molten metal produced, may be treated to produce molten iron in a blast furnace with much less difficulty when the olivine charge is included. 
     We do not know with certainty the exact reason for such improvement, but a possible theory explaining the improved results is that the olivine provides a source of useful oxides (MgO, FeO and SiO 2 ) without the evolution of carbon dioxide which is associated with dolomite, for example, and results in raising the point in the geometry of the furnace at which the slag becomes fused, or in other words causes the slag to be formed higher in the furnace, which means that the slag is formed earlier in the total reduction process. This allows more time for the slag reactions to take place and for the impurities to be converted to stable compounds, thus making the process more effective for the removal of sulfur and alkali metal compounds. The tendency for previously fused slag to resolidify is reduced by the relatively earlier slag formation. Further, we believe the earlier slag formation resulting from the introduction of olivine causes the slag to react with more iron oxide surfaces and more Fe 2  O 3  to be reduced to FeO. Also the olivine itself contains up to 10% FeO which also is reduced in the course of the reduction processes. 
     The olivine has a tough durable grain with a hardness of about 6.5 to 7.0 on the Mohs Scale and is mechanically strong as compared to limestone or dolomite, and has an advantage in burden permeability and gas-solid contact. Another benefit from the introduction of olivine is in the area of iron chemistry control. Less dust loss and increased carbon monoxide evolution means that control of silicon and manganese reduction are more precise. Heat losses due to calcination are lessened and slag mineralogy improved along with the better control obtained in this improved operation. The earlier formation of liquid slag further permits a more acid slag compostion thus lowering the requirement for basic oxides such as limestone or dolomite. 
     To demonstrate more specifically how to practice the improved process in which olivine and charge materials having a high alkali metal oxide content are introduced to a blast furnace, we set forth tests which may serve as specific illustrations of how the invention may be practiced and the results which are to be expected. 
     The following Table I describes a program to be followed over a 30 day period in which the amounts of the materials for one round of charges are listed in the left-hand column. It should be understood that the same amounts and relative proportions of charge materials are continued during the day listed in the Table until the time a different amount of the various charges is prescribed and carried out. The test is begun by accumulating data during a base period. After this the change in the charge is made and continued long enough to provide an evaluation of the operation. 
     
                       TABLE I______________________________________Base period -- quantities of charge ingredients for one roundPellets       29,550   lbs.Mn-Bearing ore         450      lbs.Scrap         2,000    lbs.Coke          14,000   lbs.Dolomite      3,000    lbs.Limestone     2,000    lbs.First day of olivine test -- quantities/roundPellets       (same as in base period)Mn-bearing ore         (same as in base period)Scrap         (same as in base period)Coke          (same as in base period)Olivine       125      lbs. of size -2+1/2Dolomite      2,650    lbs.Limestone     2,250    lbs.Third day of olivine test -- quantities/roundPellets       (same as in base period)Mn-bearing ore         (same as in base period)Scrap         (same as in base period)Coke          (same as in base period)Olivine       250      lbs.Dolomite      2,300    lbs.Calcite Stone 2,500    lbs.Fifth day of olivine test -- quantities/roundPellets       (same as in base period)Mn-bearing ore         (same as in base period)Scrap         (same as in base period)Coke          (same as in base period)Olivine       375      lbs.Dolomite      1,950    lbs.Limestone     2,750    lbs. Seventh day of olivine test -- quantities/roundPellets       (same as in base period)Mn-bearing ore         (same as in base period)Scrap         (same as in base period)Coke          (same as in base period)Olivine       500      lbs.Dolomite      1,600    lbs.Limestone     3,100    lbs.Fifth day of olivine test -- quantities/roundPellets       (same as in base period)Mn-bearing ore         (same as in base period)Scrap         (same as in base period)Coke          (same as in base period)Olivine       375      lbs.Dolomite      1,950    lbs.Limestone     2,750    lbs.Seventh day of test -- quantities/roundPellets       (same as in base period)Mn-bearing ore         (same as in base period)Scrap         (same as in base period)Coke          (same as in base period)Olivine       500      lbs.Dolomite      1,600    lbs.Limestone     3,100    lbs.Seventeenth day of test -- quantities/roundPellets       (same as in base period)Mn-bearing ore         (same as in base period)Scrap         (same as in base period)Coke          (same as in base period)Olivine       600      lbs.Dolomite      1,200    lbs.Limestone     3,400    lbs.Eighteenth day of test -- quantities/roundPellets       (same as in base period)Mn-bearing ore         (same as in base period)Scrap         (same as in base period)Coke          (same as in base period)Olivine       600      lbs.Dolomite      800      lbs.Limestone     3,800    lbs.Nineteenth day of test -- quantities/roundPellets       (same as in base period)Mn-bearing ore         (same as in base period)Scrap         (same as in base period)Coke          (same as in base period)Olivine       600      lbs.Dolomite      400      lbs.Limestone     4,200    lbs.Twentieth day of test -- quantities/roundPellets       (same as in base period)Mn-bearing ore         (same as in base period)Scrap         (same as in base period)Coke          (same as in base period)Olivine       600      lbs.Limestone     4,200    lbs.Twenty-fifth day of test -- quantities/roundPellets       (same as in base period)Mn-bearing ore         (same as in base period)Scrap         (same as in base period)Coke          (same as in base period)Olivine        600     lbs.Limestone     4,600    lbs.Thirtieth day of test -- quantities/roundTest terminated.______________________________________ 
    
     The purpose of the test set forth in Table I is to demonstrate the effect of the olivine on the operation of the blast furnace. As shown in this Table the olivine is increased during the first seven days of the test. The volume of slag may be expected to increase during the test but the basicity and V-ratio will decline. The NaO and K 2  O content of the slag may be expected to increase. Since the Al 2  O 3  content of the slag should be substantially constant the increase in the NaO and K 2  O content of the slag may be established by plotting the NaO/Al 2  O and the K 2  O/Al 2  O 3  ratios. Also the ratio of CO to CO 2  may be determined and plotted to measure furnace efficiency, and if it is determined that more Fe 2  O 3  is being reduced to FeO this is an indication that the olivine is promoting early slag formation, and an improvement in the coke rate will result. Further, if the furnace starts to peel early in the test, this is an indication the olivine is having a favorable effect. 
     
                                           TABLE II__________________________________________________________________________CHARGE CALCULATIONS IN TEST OF BLAST FURNACE OPERATION                                   SLAG VOLUMECHARGE--LBS./ROUND           SLAG AIM CHEMISTRY      LBS./TON of IRON                                              LENGTH OF PERIOD                            Base/Acid           CaO MgO SiO.sub.2                       Al.sub.2 O.sub.3                            Ratio__________________________________________________________________________BASE PERIOD--LBS./ROUNDErie  69,500Sinter 13,900BOFS  6,500     42  12  35  8.9  1.23   665        IndefinitelyDolomite 6,800Coke  28,0001st TEST PERIOD--LBS./ ROUNDERIE  70,000Sinter 15,000BOFS  5,000     38.6               13.5                   36.5                       9.1  1.14   640        10 daysDolomite 6,000Olivine 1,000Coke  28,0002nd TEST PERIOD--LBS./ ROUNDErie  70,000Sinter 15,000BOFS  6,500     37.7               12.7                   38.2                       8.9  1.07   659        5 daysDolomite 4,000Olivine 1,500Coke  28,0003rd TEST PERIOD--LBS./  ROUNDErie  70,000Sinter 15,000BOFS  7,000     38.1               11.8                   39.0                        9.03                            1.04   651        5 daysDolomite 3,000Olivine 1,500Coke  28,0004th TEST PERIOD--LBS./ ROUNDErie  70,000Sinter 15,000BOFS  7,000     36.7               12.8                   39.1                       8.8  1.03   668        5 daysDolomite 3,000Olivine 2,000Coke  28,0005th TEST PERIOD--LBS./ ROUNDErie  70,000Sinter 15,000BOFS  8,000Dolomite 2,000Olivine 2,000Coke  28,000__________________________________________________________________________ In the above Table II the term: ERIE means Iron Ore Pellets; Sinter means Sinter Clinker; BOFS means Basic Oxygen Furnace Slag 
    
     Table II describes another series of tests of blast furnace operation in which the ingredients charge in one round are given for a base period in which no olivine is included, and then during subsequent periods in which the olivine is first included at 1,000 lbs./round and in subsequent periods increased up to 2,000 lbs./round. 
     As shown by the chemical calculations given in Table II the slag volume may increase with increased amounts of olivine, and the base-acid ratio decreases. An increase of the alkali metal compounds in the slag may be expected, and a noticeable improvement in the operation of the furnace. 
     It is an added feature of our invention that instead of charging a self-contained volume of olivine into the furnace the olivine may be premixed with another of the charging ingredients such as the coke. Also it may be incorporated into the iron oxide bearing sinters prior to being charged into the furnace. 
     We may prepare an olivine sinter charging material by mixing the olivine with the materials of the type heretofore used in the formation of sinters, such as ore fines, mill scale, blast furnace flue dust, limestone or dolomite, and then firing the mixture to produce the sinter material. The sinters thus produced may then be used as an ingredient in the charging of the blast furnace. 
     The olivine may also be used in a similar way to prepare briquettes to be used as a blast furnace charging ingredient. In this case, the mixture of materials are mixed with the olivine, fired, and pressed into the form of briquettes, and the briquettes charge as one of the charging ingredients into a blast furnace. 
     To demonstrate the preparation of sinters or briquettes for use as blast furnace charging materials we give in Table III the materials and proportions included in a typical mixture which may be formed into sinters or briquettes. 
     
                       TABLE III______________________________________Materials          Weight Percent______________________________________Ore Fines          30 to 50Mill Scale         10 to 25Blast Furnace Flue Dust              5 to 15Coke Breeze        1 to  5Limestone Fines    1 to 10Dolomite Fines     1 to 10Olivine Fines      0.25 to 10.0______________________________________ 
    
     Alternatively, the olivine may be mixed with coke and the mixture of coke and olivine may then be formed into coke briquettes in a manner similar to that heretofore used in making coke briquettes, and these coke briquettes containing olivine may be charged as one of the charging ingredients into a blast furnace. The olivine may be mixed with the coke in any proportion; for example, in an amount of from 0.25-10.0 weight percent of the mixture of preferably from 0.5 to 5.0. 
     We find that a substantial additional advantage is gained when the olivine is premixed with materials from which sinters or briquettes are made. We cannot say with certainty the exact reason for the improved results from such practice, but it is possible that the results may be at least partially explained by the fact that the olivine is found to come into better physical distribution in a blast furnace when this practice is followed. This results in the abatement of &#34;bridging&#34; or scaffolding throughout the layers formed by the different charging ingredients. 
     While in the foregoing detailed description only certain embodiments of the invention are set forth, it is understood that many embodiments may be practiced and many changes and variations may be made all within the spirit of the invention and the scope of the appended claims.