Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUSRE32247 E
Publication typeGrant
Application numberUS 06/719,967
Publication dateSep 16, 1986
Filing dateApr 2, 1985
Priority dateOct 14, 1975
Also published asDE2700427A1, US4053301
Publication number06719967, 719967, US RE32247 E, US RE32247E, US-E-RE32247, USRE32247 E, USRE32247E
InventorsFrank M. Stephens, Jr.
Original AssigneeHazen Research, Inc.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for the direct production of steel
US RE32247 E
Abstract
A process for the direct production of steel from particulate iron oxides or concentrates including two major steps in which in Step (1) the iron oxides are converted to iron carbide and in Step (2) steel is produced directly from the carbide in the basic oxygen furnace or the electric furnace. In the production of the carbide the oxides are reduced and carburized in a single operation using a mixture of hydrogen as a reducing agent and carbon bearing substances such as propane primarily as carburizing agents. Iron carbide thus produced is introduced as all or part of the charge into a basic oxygen furnace to produce steel directly without the blast furnace step. In order to make the steel making process auto-thermal, heat is supplied either by using the hot iron carbide from Step (1) or preheating the iron carbide or by including sufficient fuel in the iron carbide to supply the required heat by combustion.
Images(1)
Previous page
Next page
Claims(53)
What is claimed is:
1. A process for the direct production of steel from iron oxides which comprises:
a converting the iron in the oxides to iron carbide .Iadd.by reducing the oxides and converting the iron to iron carbide in one step in a fluidized bed with a mixture of hydrogen-bearing gas and a carbon-containing material where the hydrogen serves only as a reducing material and the carbon-containing material serves only to provide carbon for the iron carbide.Iaddend.; and
b. converting the iron in the iron carbide directly to steel in .[.the basic oxygen.]. .Iadd.a steelmaking .Iaddend.furnace.
2. The process of claim 1 in which in step (b) the conversion is accomplished by oxidizing the carbon in the iron carbide to carbon monoxide with the heat released thereby providing heat for operation of .[.the.]. .Iadd.a .Iaddend.basic oxygen furnace.
3. A process for the direct production of steel from iron oxides which comprises:
a reducing the oxides and converting the iron to iron carbide in one step ion a fluidized bed with a mixture of hydrogen bearing gas and a carbon containing material which provides carbon for the iron carbide, the hydrogen being present in an amount exceeding 50% of the CO present; and
b. adding the iron carbide to a basic oxygen furnace and processing it to steel by the basic oxygen furance process without the addition of external heat .Iadd.to the furnace. .Iaddend. .[.4. The process of claim 3 in which steps (a) and (b) are performed in conjunction and the iron carbide of step (a) is added directly to the basic oxygen furnace without substantial
heat loss so that the process is auto-thermal..]. 5. The process of claim .[.4.]. .Iadd.3 .Iaddend.in which the iron carbide is at a temperature between about 900 F. to .Iadd.and .Iaddend.1300 F. when it
leaves step (a). 6. The process of .[.4.]. .Iadd.3 .Iaddend.in which
off-gas is cycled from step (b) to step (a). 7. The process of claim 6 in which the off-gas provides substantially all of the carbon for step (a).
The process of claim 3 in which in step (a) the ratio of hydrogen to formed water in the reaction medium of the fluidized bed is maintained from about 2.5 to 1 to about 8 to 1 and the CO/CO2 -hydrogen/H2
O ratios being essentially in equilibrium with methane. 9. The process of claim 3 in which the volume of hydrogen exceeds the volume of CO in said
fluidized bed. 10. The process of claim 3 in which the carbon containing
material is solid carbon. 11. The process of claim 3 in which the carbon
containing material is lower alkyl hydrocarbon gas. 12. The process of
claim 11 in which the gas is propane. 13. The process of claim 8 in which the temperature of the reaction gas mixture is between about 900
F. and 1300 F. 14. The process of claim 3 in which the iron carbide of step (a) has lost heat before step (b) is performed and sufficient heat in a preheat step is added to it for step (b) to render the reactions occurring in the conversion of the iron carbide to steel in
the basic oxygen .[.furance.]. .Iadd.furnace .Iaddend.auto-thermal. 15. The process of claim 14 in which the iron carbide charge is preheated to a temperature .[.between about 1300 F. and.]. about
2000 F. 16. The process of claim 14 in which at least part of the
heat for the preheat step is derived from off-gases from step (b). 17. The process of claim 14 in which at least some of the heat for the preheat
step is derived from sensible heat in the off-gases. 18. The process of claim 14 in which at least some of the heat for the preheat step is
derived from combustion of CO in the off-gases. 19. The process of claim 18 in which the CO/CO2 ratio in the gas combustion products is maintained from about 1:1 to about 2:1 when attaining preheat temperatures
of 900-1300 F. 20. The process of claim 14 in which the heat for the preheat step is provided by reacting at least part of the
off-gas to produce Fe2 C in the iron carbide from step (a). 21. The process of claim 20 in which the composition of the reactive medium of step (a) is adjusted to provide the required amount of Fe2 C in the
iron carbide charge. 22. The process of claim 3 in which the iron carbide of step (a) has lost heat before step (b) is performed and sufficient fuel is added to it to provide additional heat upon combustion in the process to render the reactions occurring in the conversion of the iron carbide to
steel in the basic oxygen furnace autothermal. 23. The process of claim 22
in which the fuel is carbon. 24. The process of claim 23 in which the carbon is added in an amount from about 3 to 5 weight percent of the iron
carbide charge. 25. The process of claim 23 in which the carbon is added
directly to the iron carbide charge. 26. The process of claim 3 in which molten pig iron is added to the iron carbide charge in step (b) and iron
carbide is used to control the temperature of the melt. 27. The process of claim 26 in which the temperature controlling iron carbide is added in an amount up to about 60 weight percent of the iron carbide-pig iron charge.
8. A process for conversion of iron oxides to iron carbide which comprises reducing the oxides and converting the iron to iron carbide in one step in a fluidized bed with a mixture of hydrogen and a carbon containing material which provides carbon for the iron carbide, the mixture containing hydrogen in an amount over 60 percent by volume of the
carbon monoxide present. 29. The process of claim 28 in which the ratio of hydrogen to formed water in the reaction medium of the fluidized bed is maintained from about 2.5 to 1 to about 8 to 1 and the ratio of CO/CO2 is maintained from about 1 to 1 to about 4 to 1, the prescribed CO/CO2 --hydrogen/H2 O ratios being essentially in
equilibrium with methane. 30. The process of claim 28 in which the carbon
containing material is solid carbon. 31. The process of claim 28 in which
the carbon containing material is a lower alkyl hydrocarbon gas. 32. The
process of claim 31 in which the gas is propane. 33. The process of claim 28 in which the temperature of the mixture is between about 1100
F. and about 1300 F. 34. A process for converting iron carbide to steel ion the basic oxygen furnace by the basic oxygen furnace process, said process comprising the step of augmenting the heat produced in the conversion process which is produced by oxidizing the carbon in the iron carbide, with additional .Iadd.in a preheat step, .Iaddend.to make the process in the basic oxygen furnace autothermal. .[.35. The process of
claim 34 in which the heat is added in a preheat step..]. 36. The process of claim .[.35.]. .Iadd.34 .Iaddend.in which the temperature of the iron carbide charge is .[.between about 1300 F. and.].about
2000 F. before it is added to the basic oxygen furnace. 37. The process of claim .[.35.]. .Iadd.34 .Iaddend.in which the preheat step is
performed by directly heating the iron carbide charge. 38. The process of claim .[.35.]. .Iadd.34 .Iaddend.in which at least some of the heat for
the preheat step is derived from sensible heat in the off-gases. 39. The process of claim .[.35.]. .Iadd.34 .Iaddend.in which at least some of the heat for the preheat step is derived from combustion to CO in the
off-gases. 40. The process of claim 39 in which the CO/CO2 ratio in the gas combustion products is maintained from about 1:1 to about 2:1 when
attaining preheat temperatures of 900-1300 F. 41. The process of claim .[.35.]. .Iadd.34 .Iaddend.in which the heat for the preheat step is provided by reacting at least part of the off-gas with the
iron carbide from step (a) to produce Fe2 C. 42. The process of claim 34 in which said heat is agmented by adding a fuel to the iron carbide charge for combustion during the conversion step. .[.43. The process of claim 42 in which sufficient fuel is added to the charge to provide additional heat upon combustion in the process to raise the temperature of
the charge to at least about 1100 F..]. 44. The process of claim
42 in which the fuel is carbon. 45. The process of claim 44 in which the carbon is added in an amount from about 3 to 5 weight percent of the iron
carbide charge. 46. A process of making steel from iron carbide in the basic oxygen furnace which comprises adding pig iron to the iron carbide charge and controlling the temperature of the charge by the addition of
iron carbide. 47. The process of claim 46 in which the pig iron is added in an amount up to about 40 weight percent of the charge and the temperature controlling iron carbide is added in an amount up to about 60
percent of the iron carbide-pig iron charge. 48. A process for concentrating non-magnetic low grade iron ores which comprises converting the iron oxide in the ores to iron carbide and separating the iron carbide
and gangue by subjecting the treated ores to magnetic separation. 49. The process of claim 48 in which the iron oxides are converted to iron carbide in one step in a fluidized bed with a mixture of hydrogen bearing gas and a carbon containing material which provides carbon for the iron carbide.
. The process of claim 49 in which hydrogen is present in an amount of over 60 percent by volume of carbon monoxide in the fluidized bed. .[.51. A process for the direct production of steel from iron oxides which comprises:
a. converting the iron in the oxides to iron carbide; and
b. converting an iron in the iron carbide directly to steel in an electric
furnace..]. 52. .[.A.]. .Iadd.The .Iaddend.process .[.for the direct production of steel from iron oxides which comprises:
a. reducing the oxides and converting the iron to iron carbide in one step in a fluidized bed with a mixture of a hydrogen bearing gas and a carbon containing material which provides carbon for the iron carbide,.]. .Iadd.of claim 1 or claim 54 wherein .Iaddend.the hydrogen .[.being.]. .Iadd.is .Iaddend.present in an amount exceeding 50% of the CO present.[.; and.]. .Iadd.. .Iaddend.
.[.b. adding the iron carbide to the electric furnace and processing it to steel in an electric furnace..]. .[.53. The process of claim 52 in which steps (a) and (b) are performed in conjunction and the iron carbide produced in step (a) is added directly to the electric furnace without
substantial heat loss..]. .Iadd.54. In a process for the production of steel in which iron oxide is first converted to iron carbide in a fluidized bed utilizing carbon monoxide as a reducing agent, and the formed iron carbide is then converted to steel in a steelmaking furnace, the improvement comprising:
utilizing hydrogen as the reducing agent and restricting the carbon monoxide to a carburizing function. .Iaddend. .Iadd.55. The process of claim 1 or claim 54 in which hydrogen- and carbon-containing gases are in equilibrium with methane in the fluidized bed. .Iaddend. .Iadd.56. The process of claim 1 in which water is withdrawn from the fluidized bed and carbon-containing gases are reused therein. .Iaddend. .Iadd.57. The process of claim 1 or claim 54 in which the volume of hydrogen in the fluidized bed exceeds the volume of carbon monoxide. .Iaddend. .Iadd.58. The process of claim 1 or claim 54 in which the reducing reaction in the fluidized bed is conducted at a temperature below that at which transient metallic iron would cause sticking. .Iaddend. .Iadd.59. The process of claim 1 or claim 54 in which the reducing reaction in the fluidized bed is conducted at a temperature below about 1300 F. .Iaddend. .Iadd.60. The process of claim 1 or claim 54 in which the reducing reaction in the fluidized bed is conducted at a temperature of at least about 900 F. .Iaddend. .Iadd.61. The process of claim 1 or claim 54 in which off-gas is cycled from the steelmaking furnace to the fluidized bed. .Iaddend. .Iadd.62. The process of claim 61 in which said off-gas contains about 90%carbon monoxide. .Iaddend. .Iadd.63. The process of claim 62 in which substantially all the carbon necessary for providing carbon for the formation of iron carbide in the fluidized bed is supplied by the carbon
monoxide in said off-i gas. .Iaddend. .Iadd.64. The process of claim 1 or claim 54 in which the iron carbide produced in the fluidized bed comprises a mixture of Fe2 C and Fe3 C. .Iaddend. .Iadd.65. The process of claim 64 in which Fe3 C is predominant. .Iaddend. .Iadd.66. The process of claim 1 or claim 54 conducted in a basic oxygen furnace. .Iaddend. .Iadd.67. The process of claim 66 wherein the iron carbide charge added to the furnace contains a sufficiently high Fe2 C. to Fe3 C ratio and is at a temperature sufficient to make the process in the furnace autothermal. .Iaddend. .Iadd.68. The process of claim 1 or claim 54 conducted in an electric furnace. .Iaddend. .Iadd.69. The process of claim 1 or claim 54 in which carbon for the formation of iron carbide is added to the fluidized bed in the form of solid carbon. .Iaddend. .Iadd.70. The process of claim 1 or claim 54 in which carbon for the formation of iron carbide is added to the fluidized bed inthe form of carbon monoxide. .Iaddend. .Iadd.71. The process of claim 1 or claim 54 in which carbon for the formation of iron carbide is added to the fluidized bed in the form of a lower alkyl hydrocarbon gas. .Iaddend. .Iadd.72. The process of claim 1 or claim 54 in which carbon for the formation of iron carbide is added to the fluidized bed in the form of propane. .Iaddend. .Iadd.73. The process of claim 1 or claim 54 in which the hydrogen to water vapor ratio in the fluidized bed is maintained from about 5 to 1 to about 8 to 1. .Iaddend. .Iadd.74. The process of claim 1 or claim 54 in which the hydrogen to water vapor ratio in the fluidized bed is maintained from about 2.5 to 1 to about 8 to 1. .Iaddend. .Iadd.75. The process of claim 1 or claim 54 in which the CO to CO2 ratio in the fluidized bed
is maintained from about 1 to 1 to about 5 to 1. .Iaddend. .Iadd.76. The process of claim 1 or claim 54 in which the CO to CO2 ratio in the fluidized bed is maintained from about 1 to 1 to about 4 to 1. .Iaddend. .Iadd.77. The process of claim or claim 54 in which in the fluidized bed the ratio of hydrogen to formed water in the fluidized bed is maintained from about 2.5 to 1 to about 8 to 1 and the CO to CO2 ratio is maintained from about 1 to 1 to about 4 to 1, the prescribed CO to CO2 and hydrogen to H2 ratios being essentially in equilibrium with methane. .Iaddend. .Iadd.78. The process of claim 55 in which the concentration of methane in the fluidized bed is maintained between about 1 and about 70 volume percent. .Iaddend. .Iadd.79. The process for the direct production of steel from iron oxides which comprises:
(a( contacting the iron oxides in a fluidized bed at a temperature between about 900 F. and about 1300 F. with hydrogen gas and carbon-containing materials present in sufficient relative quantities to ensure that the hydrogen reduces the iron oxides to carbon carbides with concomitant formation of water, and the carbon of the carbon-containing materials is used only to provide carbon to the iron carbide and not to extract oxygen from the iron oxide; wherein water is withdrawn from the system and the balance of the gases are reused; and wherein the hydrogen- and carbon-containing gases in the fluidized bed are in equilibrium with methane; and
(b) converting the iron carbide directly to steel in a steel making furnace. .Iaddend. .Iadd.80. The process of claim 79 in which in step (a) the volume of hydrogen exceeds 50% of the volume of carbon monoxide in the fluidized bed. .Iaddend. .Iadd.81. The process of claim 79 in which in step (a) the volume of hydrogen exceeds the volume of carbon monozide in
the fluidized bed. .Iaddend. .Iadd.82. The process of claim 79 in which off-gas is cycled from step (b) to step (a). .Iaddend. .Iadd.83. The process of claim 79 in which the steel making furnace is a basic oxygen furnace contains sufficient Fe2 C. and is at a temperature sufficient to make the process in the basic oxygen furnace autothermal. .Iaddend. .Iadd.84. The process of claim 79 in which in the fluidized bed the hydrogen to water vapor ratio is maintained from about 5 to 1 to about 8 to 1 and the CO to CO2 ratio is maintained from about 1 to 1 to about 5 to 1. .Iaddend. .Iadd.85. A steel making process utilizing an iron oxide feed comprising:
(a) reducing the iron oxide to be converted to steel to iron carbide in a fluidized bed, at a temperature below that which would cause transiently-formed metallic iron to be sticky, with a reducing agent consisting essentially of hydrogen, in the presence of a carbon-containing material which supplies carbon for the formation of the iron carbide; wherein the hydrogen is present in an amount in excess of 50% of the CO present, the ratio of hydrogen to formed water in the reaction medium of the fluidized bed is maintained from about 2.5 to 1 to about 8 to 1 and the CO to CO2 ratio is maintained from about 1 to 1 to about 4 to 1, the prescribed CO to CO2 and H2 to H2 O ratios being essentially in equilibrium with methane;
(b) withdrawing H2 O from step (a);
(c) feeding the formed iron carbide to a steelmaking furnace to produce steel; and
(d) recycling carbon monoxide off-gases from step (c) to step (a) to supply carbon necessary for the formation of the iron carbide. .Iaddend.
.Iadd. The process of claim 85 in which the steelmaking furnace is a basic oxygen furnace or an electric furnace. .Iaddend. .Iadd.87. The process of claim 85 or claim 86 in which the temperature in the fluidized bed is maintained between about 1020 F. and about 1170 F. .Iaddend. .Iadd.88. The process of claim 85 or 86 in which carbon for the formation of iron carbide is supplied to the fluidized bed in the form of propane. .Iaddend. .Iadd.89. The process of claim 28 in which water and iron carbide are the only products withdrawn from the system. .Iaddend. .Iadd.90. The process of claim 28 in which the temperature of the fluidized bed is maintained at a temperature below that at which transient metallic iron would cause sticking. .Iaddend. .Iadd.91. The process of claim 90 in which the temperature in the fluidized bed is maintained at at least about 900 F. .Iaddend. .Iadd.92. The process of claim 28 in which the iron carbide produced comprises a mixture of Fe2 C and Fe3 C. .Iaddend. .Iadd.93. The process of claim 92 in which the major proportion of the iron carbide is Fe3 C. .Iaddend. .Iadd.94. The process of claim 28 or claim 49 in which the carbon of the carbon-containing is restricted to the function of supplying carbon to the iron carbide and does not act to reduce the iron oxides. .Iaddend.
Description
BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention lies in the field of the pyrometallurgy of ferrous metals.

2. Description of the Prior Art

The increasing necessity of using low grade iron ores for making steel because of the depletion of high grade ores, and economic factors, have created a demand for reduction of the costs in producing steel from iron ore. Efforts to reduce costs have been directed to the elimination of the use of the highly fuel-consuming blast furnace. The present invention is directed to elimination of the use of the blast furnace by converting the iron oxide to the carbide followed by producing steel directly from the carbide in the basic oxygen furnace. The conversion of iron oxides to carbides for various purposes has received some attention in the past but there has been no known activity toward producing steel directly from the carbide in a basic oxygen furnace.

U.S. Pat. No. 2,780,537, the closest prior art known, discloses a process for converting iron oxides to carbides in a fluidized bed process in which carbon monoxide is used as the chief reducing and carburizing gas. The patent teaches that the reducing gas cannot contain hydrogen in an amount more than 50 percent by volume of the carbon monoxide content. It also refers to the prior art disclosing the use of hydrogen in a fluidized bed as a reducing gas for iron oxides having a low iron content. The reference alludes to use of the iron carbide product for making "metallic iron" and in an "iron production furnace" operating below the melting point of iron or steel, however, there is no teaching of use of the product for introduction into a fully molten steel system such as the basic oxygen furnace or electric furnace. Other somewhat remote prior art discloses processes for converting metallic iron to iron carbide rather than conversion of iron oxide to the carbide.

Still other prior art discloses fluid bed processes for the direct reduction of iron oxides to metallic iron which in turn could be further converted to carbide. However, these other direct reduction processes have the disadvantages that the product may be pyrophoric in some cases requiring briquetting, and stickiness is not completely eliminated in some processes so that difficulties arise with the fluid bed process.

It is an object of this invention to provide a process for making steel from iron oxide without the use of a blast furnace.

it is another object of this invention to provide a successful process for making steel from iron oxide by first converting the oxide to the carbide, followed by introducing the carbide directly into the basic oxygen furnace to produce steel.

SUMMARY OF THE INVENTION

A process for the direct production of steel from particulate iron oxides or concentrates which comprises (1) converting the oxides to iron carbide in a single step in a fluidized bed at low temperatures with a mixture of reducing and carburizing gases followed by (2) direct conversion of the carbide to steel in a basic oxygen or electric furnace.

The reducing and carburizing temperature of Step (1) cannot exceed about 1300 F. with a preferred temperature range being about 900-1200 F. The carburizing of the reduced iron to carbide may be conducted so that enough carbon is left in the iron carbide product to supply sufficient heat upon combustion in the basic oxygen furnace to make the process auto-thermal. The CO/CO2 and hydrogen to water vapor ratios of the gases in the reaction of Step (1) are maintained at a point below which oxidation of iron carbide occurs.

Off-gases from the steel making step, about 90 percent carbon monoxide, may be circulated for use as part of the reducing gas for the reduction and carburizig step in the fluidized bed. Material balance calculations show that the carbon content of the off-gas is sufficient to supply all of the carbon necessary for the reduction and carburization step. Accordingly, when Steps 1 and 2 are performed in conjunction with each other as one continuous operation, all of the carbon necessary for Step 1, subject to slight operating losses, may be provided by continuous cycling of the off-gas from Step 2 to Step 1. This eliminates the necessity for adding carbon to Step 1 with the exception of small losses occurring in normal operations. The result is that the carbon originally added to Step 1 to make iron carbide may be used over and over by recovering it in Step 2 in the off-gas as steel is produced and reusing it in Step 1 to make more carbide. When the steps are performed in conjunction with each other added heat is not required to make the process auto-thermal, as the product going directly from Step 1 to Step 2 is at a temperature which eliminates the necessity for adding heat. When Steps 1 and 2 are performed separately then the hot off-gas from Step 2 may be used for preheating iron carbide or heat added by other means as necessary to make the steel making process auto-thermal.

The iron carbide produced in Step 1 is added directly as the charge to the basic oxygen or electric furnace along with fluxing agents, alloying material and other conventional additives to produce steel directly with elimination of the conventional blast furnace step. Heat is supplied to the charge when necessary in various ways to make the process auto-thermal. These ways may include direct heating, addition of fuel such as carbon, or producing sufficient free or combined carbon in the carbide as it is produced, or others. Sensible heat from the off-gas of the BOF may be used and the off-gas may be partially burned to provide heat to the charge. If the latter is done the CO/CO2 ratio in the combustion gases must be maintained below that at which iron carbide will decompose at the required preheat temperature.

BRIEF DESCRIPTION OF THE DRAWING

The single drawing is a schematic flowsheet for the direct steel making process of the invention.

DESCRIPTION OF PREFERRED EMBODIMENTS

The invention will be described in detail in conjunction with the accompanying drawing.

The basic oxygen and electric furnace processes referred to herein for making steel are well known in the prior art. The basic oxygen process or basic oxygen furnace process differs chiefly from Bessemer converters and open hearth furnaces in that the reactant used to oxidize the carbon and certain impurities (sulfur, phosphorus, etc.) in the charge is not air, but oxygen. The oxygen is introduced by blowing it with a lance onto or below the surface of the molten iron.

The iron carbide produced by the process described herein is a mixture of carbides havig the molecular formulas Fe2 C and Fe3 C content being predominant.

The fluidized bed reactor referred to herein is of the conventional type in which finely divided feed material on a grate or other perforate support is fluidized by upwardly flowing gases which may include or entirely comprise the reactant gases. Auxiliary equipment includes heating and temperature control and monitoring equipment, heat exchangers, scrubbers, cyclones, gas cycling equipment, and other conventional equipment. Some of this auxiliary equipment is shown schematically in the flowsheet.

In this specification and the claims the reduction and carburization step is referred to as Step 1 and the steel making step as Step 2. The term "hydrogen bearing gas" includes hydrogen gas alone and the term "carbon containing material" includes carbon alone.

Step 1 of the overall process is the conversion of the oxides in the iron ore concentrate to iron carbide in the fluidized bed unit shown in the flowsheet. The conversion process must be carefully controlled to provide a product suitable for use in the basic oxygen or electric furnace. The iron carbide is desirable for use in these processes because it is non-pyrophoric and resistant to weathering which permits transport for long distances and storage for reasonable periods.

The oxides are reduced to iron and the iron converted to the carbide in a continuous process in the fluid bed reactor in which the reducing .[.the.]. .Iadd.and .Iaddend.carburizing gases are added together. In order to prevent any sticking caused by the transient presence of metallic iron the temperature is maintained below about 1300 F. at all times and preferably in the range of about 900-1200 F.

Hydrogen is preferably used as the reducing gas although carbon monoxide or hydrocarbon gases or mixtures of hydrogen with CO and hydrocarbon gases may be used. The flowsheet shows the use of hydrogen and carbon monoxide with water being given off. Hydrogen is preferred as the reducing gas because the oxidation product of hydrogen, which is water, may be easily removed form the furance off-gas thus permitting recycling of the balance of the gas without the need for extensive complicated and expensive chemical systems for removing the oxidation products of carbon which are carbon monoxide and carbon dioxide when carbon containing reducing gases are used.

The preferred carburizing gas which is mixed with the reducing gas is propane, although carbon monoxide or other hydrocarbon gases, or solid carbon, may be used with the lower alkyl hydrocarbon gases being preferred. A wide range of carbonaceous materials may be used so long as they supply carbon to form iron carbide.

By proper balancing of the ratios of the hydrogen and carbon bearing materials, it is possible to restrict the hydrogen to a reducing function and the carbon to a carburizing function. This can readily be done by maintaining quantities of hydrogen bearing gases which are in excess of the quantities of the carbon bearing gases.

Because of the equilibrium conditions involved in hydrogen-carbon-oxygen gas systems, the required hydrogen-carbon ratios will automatically require that methane be present in the gas system. The quantity of methane present will be a function of carbon to hydrogen ratios, as well as temperature and pressure conditions.

Representative tests and results from an extensive test program using the reduction and carburization procedure described above in a fluid bed reactor are presented in the following Table I.

                                  TABLE I__________________________________________________________________________EXAMPLES OF Fe3 C PRODUCTIONTest           Feed              Gas Additions   Off-gas Analysis*                                             Pro-No.   Type  Mesh  Rate              H2                  C3 H8                      N2                          Temp                              H2                                 N2                                    CH4                                       CO CO2                                             ductFB-   of Ore    Size Ore          g/min              l/min                  l/min                      l/min                          F.                              %  %  %  %  %  % C Remarks__________________________________________________________________________30 Hematite    -20 + 100          0   2.5 1.0 0.5 1168                              77.0                                 0.5                                    6.3                                       8.9                                          2.0                                             4.35                                                 Final red in                                                 reactor 5.02% C36 Hematite    -20 + 100          0   2.5 1.0 0.5 1170                              72.0                                 -- 5.2                                       13.2                                          2.9                                             5.02                                                 Good clean Fe3                                                 C                                                 produced37B   Hematite    -20 + 100          0   2.5 1.0 0.5 1018                              72.1                                 -- 6.5                                       7.8                                          3.4                                             8.96                                                 Good Fe3 C                                                 satur-                                                 ated with excess C38B   Hematite    -20 + 100          0   2.5 1.0 0.5 1081                              72.6                                 -- 6.4                                       10.6                                          4.0                                             4.94                                                 Good Fe3 C39B   Hematite    -20 + 100          0   2.5 1.0 0.5 1108                              69.3                                 -- 7.9                                       12.2                                          4.4                                             4.67                                                 Good Fe3 C40 Hematite    -20 + 100          2.7 2.5 1.0 0.5 1112                              62.5                                 -- 6.7                                       16.1                                          6.7                                             4.77                                                 Good Fe3 C41B   Magnetite    -20 + 100          0   2.5 1.0 0.5 1103                              67.5                                 -- 6.0                                       11.6                                          3.9                                             4.69                                                 Good Fe3 C41C   Magnetite    -325  3.8 2.5 1.0 0.5 1130                              58.3                                 -- 6.1                                       21.4                                          6.8                                             5.42                                                 Good Fe3__________________________________________________________________________                                                 C *The balance of gas in water vapor.

The carbon content in the final product varies as the percent iron oxide in the feed materials varies. Lower grade ores with lower iron contents will automatically yield products with lower carbon contents.

The volume of hydrogen in the hydrogen-carbon monoxide reducing and carburizing mixture in the fluidized unit should exceed the volume of carbon monoxide, the preferred amount of hydrogen being over about 60 percent by volume of the carbon monoxide present.

The results show production by Step 1 of the process of clean iron carbide which is highly suitable for use in the basic oxygen or electric furnace. X-ray diffraction analysis showed the carbon to be present as iron carbide with no nonpyrophoric. Stimulated weathering tests showed that the product was stable in oxidizing atmospheres containing water vapor up to a temperature of 250 C.

The results also show that Step 1 of the process is highly successful in producing iron carbide directly from iron oxides when operated within temperature ranges of about 1020 F.`1170 F. using hydrogen to water vapor ratios between 5 to 1 and 8 to 1 and CO/CO2 ratios between about 1 to 1 and 5 to 1. As stated herein, Step 1 can be successfully operated within a temperature range of about 900-1300 F., a hydrogen to water vapor ratio of about 2.5 to 1 to about 8 to 1 and a CO/CO2 ratio of about 1 to 1, up to about 4 to 1. Under these conditions, methane will be present in quantities ranging from 1 to 70 percent by volume of the gas system containing the prescribed amounts of hydrogen, weater vapor, CO, and CO2. It was found that Step 1 would not operate outside these ranges to successfully produce iron carbide.

Step 2 of the overall process is the conversion of the iron carbide to steel in the basic oxygen furnace. Because of the nature of the basic oxygen furnace process, special conditions apply to the processing of iron carbide to steel by this process as compared to other steel making processes in furnaces.

If Steps 1 and 2 are close-coupled so that the iron carbide comes out of the fluid unit at an elevated temperature of about 1100-1300 F. and at that temperature is added directly to the basic oxygen furnace, then the heat calculations show that no added heat is required and the process is continuous and auto-thermal.

The modification shown in the flowsheet wherein the off-gases are being sent directly to the fluidized bed unit is used when Steps 1 and 2 are close-coupled in time. In this modification of the process substantially all of the carbon used in the fluidized bed unit to convert the oxides to iron carbide is recovered as CO ion the furnace and recycled to the fluidized bed unit to be reused in again making iron carbide.

If for purposes of transport or storage the Step 1 product becomes or is cooled before Step 2, then heat must be readded either in the form of reheating the product or adding extra fuel to Step 2.

Heat balance calculations show that at ambient temperature iron carbide does not contain sufficient fuel value so that the reaction taking place in the basic oxygen furnace is autothermal without adding heat to the charge.

The additional heat required to make the reaction self-sustaining may be supplied in a number of ways. The off-gas from the basic oxygen furnace produced by the processing of iron carbide contains about 90 percent carbon monoxide in addition to substantial sensible heat. The sensible heat may be used through heat exchangers or otherwise to heat the incoming iron carbide. By burning part of the off-gas, sufficient heat is achieved for augmenting the sensible heat to effect the required preheating of the incoming iron carbide charge to make the process auto-thermal. Under some conditions the sensible heat alone is sufficient. The heat for the preheating can be obtained entirely from combustion of the off-gas. The preferred preheat temperature range is from about 1300 F. to about 2000 F.

Tests conducted with iron carbide in a gaseous medium simulating that of the combustion products from partial combustion of the off-gas showed that the iron carbide is not only stable under these conditions but actually ioncreased in carbon content from 5.9 to 7.1 percent due to the formation of the Fe2 C carbide from the normally predominant Fe3 C. To achieve this result the CO/CO2 ratio ion the combustion gas must be between 1 to 1 and 2 to 1 when attaining preheat temperatures of 900-1300 .

Adding heat to make the process auto-thermal can be supplied wholly or in part by direct heating of the Fe3 C charge with an external heat source. Sufficient carbon may be added to the iron carbide to provide the required additional heat by combustion during the process. The amount of carbon added varies from about 3 to 5 weight percent of the iron carbide charge. The carbon may be added directly to the iron carbide by preheating the iron carbideoxide in carbon bearing gases having a CO/CO2 ratio greater than 1 to 1.

Heat may be supplied by reaction of the basic oxygen furnace off-gas with incoming iron carbide. The necessary carbon content of the iron carbide to furnish the required heat upon combustion can be supplied during Step 1 of the process described above by adjusting the content of the carbonaceous material in the reacting gas mixture of the fluidized bed to provide for the production of sufficient Fe2 C in the Fe3 C product. As shown in the flow sheet, hot scrap metal may be added to the basic oxygen furnace charge.

Step 2 of the process may also include the addition of pig iron .Iadd.to the .Iaddend.carbide charge in the basic oxygen and electric furnaces. A significant advantage of this feature is that iron carbide can then be added for cooling in an amount three times that of scrap iron which can be added to conventional basic oxygen furnace prcesses for cooling. Iron carbide for this purpose can be added in an amount up to about 60 percent by weight of the iron carbide-pig iron charge. One advantage of this is that present pig iron furnaces can be continued in operation in conjunction with the present process.

The invention includes all of the above procedures alone or combined for providing the necessary heat for the iron carbide charge to make the reaction in the basic oxygen furnace auto-thermal.

If Step 2 is conducted in the electric furnace, any extraneous heat required may be supplied by means of the electrical evergy normally used in this type of furnace.

Step 1 of the process provides a convenient and effective means for concentrating low grade non-magnetic ores to separate the iron ore from the gangue. As the iron carbide produced from non-magnetic ores is magnetic it is only necessary to process non-magnetic ore, such as, oxidized taconites, in accordance with Step 1 to convert the iron oxide therein to iron carbide and subject the treated ore to magnetic separation to separate the magnetic iron carbide from the gangue. The iron carbide recovered may then be used in Step 2 of the process of the invention.

A number of advantages of the invention are apparent from the above description. Its principal advantage is that it eliminates the expensive intermediate blast furnace step in converting iron ore to steel. When the two steps are performed in conjunction no added heat is necessary for the second step and carbon monoxide from the second step provides the necessary carbon for carbonization of reduced continuously in both steps. Step 1 includes the production of water as a by-product, thus simplifying the recovery of by-product carbon containing gases. This step can be performed to give a product having a high enough ratio of Fe2 C to Fe3 C to provide a high enough carbon content in the charge for the basic oxygen furnace to make the steel making process auto-thermal.

Advantages of Step 2 are that it provides sources of heat for making this step auto-thermal without the use of extra materials, i.e., sensible heat from the off-gases can be used or the CO in the off-gases can be burned to provide the necessary heat, or the CO can be reacted with the iron carbide from Step 1 to raise the ratio of Fe2 C to Fe3 C in the charge so that sufficient carbon will be available for combustion to supply the augmenting heat to make Step 2 auto-thermal. When pig iron is added to the charge, large amounts of iron carbide can be added for cooling. The overall process is practically pollution-free and provides for maximum conservation and reuse of non-product reactants. A further advantage of the overall process is that it results in a saving in transportation costs when the carbide is made near the mine before transport to the steel making furnace as iron carbide represents a higher percentage of usable material than the oxide.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US88939 *Apr 13, 1869 Improved mode op roasting iron-ores
US228329 *Apr 7, 1880Jun 1, 1880 Thomas a
US1786386 *May 4, 1928Dec 23, 1930Ashcroft Edgar ArthurExtraction of tin from ores or materials containing tin
US2598393 *Oct 24, 1949May 27, 1952Lennart Lindskog OskarMethod in carrying out treatment of melted pig iron or other alloyed iron
US2653088 *Aug 9, 1951Sep 22, 1953Pike Robert DDirect production of steel from oxides of iron
US2780537 *Oct 30, 1953Feb 5, 1957StellingProcess of treating pulverulent iron oxides
US2806779 *Sep 29, 1953Sep 17, 1957Mcwane Cast Iron Pipe CoMethod of producing iron
US2894831 *Nov 28, 1956Jul 14, 1959Scott Old BruceProcess of fluidized bed reduction of iron ore followed by electric furnace melting
US2978318 *Jun 30, 1958Apr 4, 1961Stora Kopparbergs Bergslags AbMethod of producing steel from pulverulent iron products rich in carbon
US3140168 *May 31, 1961Jul 7, 1964Inland Steel CoReduction of iron ore with hydrogen
US3160498 *Jun 29, 1960Dec 8, 1964Armco Steel CorpFluidized iron ore reduction process and apparatus
US3288590 *Jul 22, 1963Nov 29, 1966Hydrocarbon Research IncContinuous oxide reduction process
US3364009 *Mar 12, 1964Jan 16, 1968Kemmetmuller RolandMethod for the production of iron and steel
US3499755 *Jan 3, 1967Mar 10, 1970Morris David OMethod for the production of pig iron and steel
US3502461 *Dec 10, 1965Mar 24, 1970Elektrometallurgie GmbhMethod of reducing oxidic raw materials
US3637368 *Oct 16, 1968Jan 25, 1972Exxon Research Engineering CoIncreased metallizations of iron ore from fluidized bed processes
US3765872 *Dec 16, 1970Oct 16, 1973Fierro EsponjaMethod and apparatus for the gaseous reduction of iron ore to sponge iron
US3788835 *Dec 30, 1970Jan 29, 1974Exxon Research Engineering CoIron ore reduction process(nu-9)
US3997333 *Feb 26, 1975Dec 14, 1976Westinghouse Electric CorporationProcess for the reduction of complex metallic ores
DE2401909A1 *Jan 16, 1974Jul 17, 1975Krupp GmbhVerfahren zur herstellung von stahl
GB747584A * Title not available
GB759224A * Title not available
GB1269842A * Title not available
GB1284309A * Title not available
Non-Patent Citations
Reference
1 *Blast Furnace and Steel Plant, by Kalling et al., Feb. 1957, pp. 200 203.
2Blast Furnace and Steel Plant, by Kalling et al., Feb. 1957, pp. 200-203.
3 *Carbon Monoxide Reduction of Iron Ore, by O. Stelling, Journal of Metals, Apr. 1958, pp. 290 295.
4Carbon Monoxide Reduction of Iron Ore, by O. Stelling, Journal of Metals, Apr. 1958, pp. 290-295.
5 *The Making, Shaping and Treating of Steel, 8th ed., 1964, pp. 378 379.
6The Making, Shaping and Treating of Steel, 8th ed., 1964, pp. 378-379.
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5064467 *Dec 22, 1989Nov 12, 1991C.V.G. Siderurgica Del Orinoco, C.A.Method and apparatus for the direct reduction of iron
US5069716 *Apr 20, 1990Dec 3, 1991C.V.G. Siderurgica Del Orinoco, C.A.Process for the production of liquid steel from iron containing metal oxides
US5073194 *Aug 1, 1990Dec 17, 1991Iron Carbide Holdings, LimitedProcess for controlling the product quality in the conversion of reactor feed into iron carbide
US5078788 *Oct 12, 1990Jan 7, 1992C.V.G. Siderurgica Del Orinoco, C.A.Using heavy hydrocarbon oil as natural gas source in a simultaneous reforming-reduction process
US5118479 *Aug 1, 1990Jun 2, 1992Iron Carbide Holdings, LimitedConverting reactor feed to iron carbide for steel making
US5137566 *Aug 1, 1990Aug 11, 1992Iron Carbide Holdings, LimitedProcess for preheating iron-containing reactor feed prior to being treated in a fluidized bed reactor
US5139568 *Oct 3, 1991Aug 18, 1992Cargill, IncorporatedContinuous production of iron-carbon alloy using iron carbide
US5316565 *Apr 26, 1993May 31, 1994Kibby Robert MLess CO2 emitted during the reduction of metal oxides, reacting carbon monoxide with hydrogen to produce carbon and water
US5431711 *Aug 12, 1994Jul 11, 1995Midrex International B.V. Rotterdam, Zurich BranchIron oxide to iron
US5435831 *Aug 12, 1994Jul 25, 1995Midrex International B.V. Rotterdam, Zurich BranchSeparating and reducing fines with lumps and pellets
US5437708 *May 4, 1994Aug 1, 1995Midrex International B.V. Rotterdam, Zurich BranchCarburizing the metal oxide particle with a mixture reducing gas containing carbon monooxide, carbon dioxide, methane, hydrogen and water
US5474280 *Aug 20, 1993Dec 12, 1995Martin; Charles A.Apparatus for preheating a reactor feed
US5500034 *May 5, 1995Mar 19, 1996Martin; Charles A.Method for preheating a reactor feed
US5516358 *Nov 17, 1994May 14, 1996Pro-Tech Reclamation, Inc.Method for the production of iron carbide
US5527379 *Jun 17, 1994Jun 18, 1996Metallgesellschaft AktiengesellschaftTwo stage reduction, carburization using fluidized bed system
US5529291 *Mar 7, 1995Jun 25, 1996Midrex International B.V. Rotterdam, Zurich BranchCirculating fluidized bed direct reduction system
US5618032 *May 5, 1995Apr 8, 1997Midrex International B.V. Rotterdam, Zurich BranchApparatus using carbon-containing reducing gas; efficiency, high speed process
US5647887 *Apr 13, 1995Jul 15, 1997Midrex International B.V. Rotterdam, Zurich BranchFluidizable bed co-processing fines in a direct reduction system
US5665140 *Dec 4, 1995Sep 9, 1997Allmet Technologies, Inc.Method for the production of iron carbide
US5674308 *Sep 13, 1995Oct 7, 1997Midrex International B.V. Rotterdam, Zurich BranchReaction of strong reducing gas mixture through series of beds allows intimate contact to facilitate direct reduction of iron oxide fines to metallized iron
US5690717 *Mar 29, 1995Nov 25, 1997Iron Carbide Holdings, Ltd.Iron carbide process
US5733357 *Feb 5, 1996Mar 31, 1998Iron Carbide Holdings, Ltd.Process for converting iron oxide to iron carbide employing internally generated carbon oxide as the carbiding agent
US5733358 *Sep 11, 1995Mar 31, 1998Usx Corporation And Praxair Technology, Inc.Process and apparatus for the manufacture of steel from iron carbide
US5804156 *Jul 19, 1996Sep 8, 1998Iron Carbide Holdings, Ltd.Large scale production in a fluid bed reactor; controlling temperature, pressure so that hydrogen concentration is above equilibrium concentration.
US5810906 *Aug 28, 1996Sep 22, 1998Iron Carbide Holdings, Ltd.Method for preheating feed materials for the production of iron carbide
US5824134 *Jan 29, 1997Oct 20, 1998Powers; JimDirect reduction of iron ore utilizing organic hazardous materials
US5869018 *Jan 14, 1994Feb 9, 1999Iron Carbide Holdings, Ltd.Two step process for the production of iron carbide from iron oxide
US6197087Oct 10, 1998Mar 6, 2001James M. PowersPyrolysis of halogenated organic hazardous wastes with direct reduction of iron oxides
US6328946Feb 8, 1999Dec 11, 2001Iron Carbide Holdings, Ltd.Two step process for the conversion of iron oxide into iron carbide using gas recycle
US6428763Mar 22, 2000Aug 6, 2002Iron Carbide Holdings, Ltd.Multistage reduction of magnetite or hematite using hydrogen to form iron, then carbiding
DE4320359C1 *Jun 19, 1993Oct 20, 1994Metallgesellschaft AgProcess for the direct reduction of substances containing iron oxide to sponge iron and carburising to Fe3C
DE4410093C1 *Mar 24, 1994Mar 9, 1995Metallgesellschaft AgProcess for the direct reduction of materials containing iron oxides
WO1992002646A1 *Jul 23, 1991Feb 2, 1992Iron Carbide Holdings LtdProcess for preheating iron-containing reactor feed prior to being treated in a fluidized bed reactor
WO1996019591A1 *Dec 5, 1995Jun 27, 1996Uss Eng & ConsultProcess and apparatus for the manufacture of steel from iron carbide
Classifications
U.S. Classification75/10.38, 75/446, 423/148, 75/10.43, 75/10.36
International ClassificationC21B13/02, C21B13/14, C21C5/32, C21B15/02, C21C5/28, C21B13/00, C21C5/56, C01B31/30, C21B15/00, C22B, B01J8/18, C21B, C22B1/00, C22B5/10, B03C1/00, C21B13/12, C22B5/14, B03B1/00, C22B5/20
Cooperative ClassificationC21B13/0033, C21B13/006, C21B13/0073, C21B13/14, C21C5/28, C21C5/32, C21C5/56, C21B13/00
European ClassificationC21B13/14, C21B13/00, C21B13/00B, C21C5/28, C21C5/56, C21B13/00F, C21C5/32, C21B13/00K
Legal Events
DateCodeEventDescription
Sep 17, 1990ASAssignment
Owner name: IRON CARBIDE HOLDINGS, LTD., COLORADO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:HAZEN RESEARCH, INC., A CORP. OF CO;REEL/FRAME:005463/0073
Effective date: 19871204