PROCESS FOR THE PRODUCTION OF CARBURIZED SPONGE IRON

Abstract

A process for the production of carburized sponge iron, including charging iron ore into a direct reduction shaft, and/or discharging carburized sponge iron from the direct reduction shaft, whereby a seal gas is introduced into the direct reduction shaft; removing a top gas from the direct reduction shaft; recycling a proportion of the top gas and mixing with a make-up gas to form a reducing gas; and introducing the reducing gas into the direct reduction shaft in countercurrent flow to the iron ore in order to reduce the iron ore and produce carburized sponge iron. The seal gas consists essentially of carbon dioxide, and the make-up gas comprises greater than 80 vol % hydrogen gas. Also provided is a system for the production of carburized sponge iron, as well as a carburized sponge iron produced by the aforementioned process.

Claims

1. A process for the production of carburized sponge iron from iron ore, the process comprising: charging iron ore into a direct reduction shaft, and/or discharging carburized sponge iron from the direct reduction shaft, whereby a seal gas is introduced into the direct reduction shaft in conjunction with charging the iron ore and/or discharging the carburized sponge iron; removing a top gas from the direct reduction shaft; recycling a proportion of the top gas and mixing with a make-up gas to form a reducing gas; and introducing the reducing gas into the direct reduction shaft in countercurrent flow to the iron ore in order to reduce the iron ore and produce carburized sponge iron; wherein the seal gas consists essentially of carbon dioxide, and the make-up gas comprises greater than 80 vol % hydrogen gas.

2. A process according to claim 1, wherein the make-up gas consists essentially of hydrogen and optionally carbon dioxide.

3. A process according to claim 2, wherein the make-up gas consists essentially of hydrogen, and wherein the hydrogen is optionally produced by electrolysis of water.

4. A process according to claim 1, wherein the recycled top gas is not passed through an external reformer.

5. A process according to claim 1, wherein no top gas is flared.

6. A process according to claim 1, wherein the carbon dioxide is obtained as a by-product of biofuel production.

7. A process according to claim 1, wherein recycling a proportion of the top gas comprises steps of removing water and dust from the top gas.

8. A process according to claim 1, wherein the direct reduction shaft operates at a pressure of greater than 2 Bar, and wherein the seal gas and the iron ore are introduced into the direct reduction shaft via a pressurizable charge hopper arranged at an inlet of the direct reduction shaft.

9. A process according to claim 1, wherein the direct reduction shaft operates at a pressure of 2 Bar or less, and wherein the seal gas and the iron ore are introduced into the direct reduction shaft via a seal leg arranged at an inlet of the direct reduction shaft.

10. A system for the production of carburized sponge iron, the system comprising: an electrolyser arranged to produce hydrogen from the electrolysis of water; a direct reduction shaft; an iron ore charging arrangement; a carburized sponge iron discharging arrangement; and a source of carbon dioxide, wherein the source of carbon dioxide is arranged in fluid connection with the iron ore charging arrangement and/or the carburized sponge iron discharging arrangement.

11. A system according to claim 10, wherein the system does not comprise a reformer.

12. A system according to claim 10, wherein the system does not comprise a device for CO2 capture.

13. A system according to claim 10, wherein the iron ore charging arrangement comprises a pressurizable charge hopper, wherein the pressurizable charge hopper comprises a seal gas inlet, and wherein the seal gas inlet is arranged in fluid connection with the source of carbon dioxide.

14. A system according to claim 10, wherein the iron ore charging arrangement comprises an ore bin and a seal leg, wherein the seal leg comprises a seal gas inlet, and wherein the seal gas inlet is arranged in fluid connection with the source of carbon dioxide.

15. A carburized sponge iron wherein the carburized sponge iron has a degree of reduction greater than 90% and comprises from 0.1 to 5 percent carbon by weight, and wherein the carburized sponge iron has a radiocarbon age of less than 10 000 years before present.

16. A carburized sponge iron according to claim 15, wherein the radiocarbon age is less than 1000 years before present.

17. A carburized sponge iron according to claim 16, wherein the radiocarbon age is less than 100 years before present.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0060] For a fuller understanding of the present invention and further objects and advantages of it, the detailed description set out below should be read together with the accompanying drawings, in which the same reference notations denote similar items in the various diagrams, and in which:

[0061] FIG. 1 schematically illustrates an ore-based steelmaking value chain according to the Hybrit concept;

[0062] FIG. 2a schematically illustrates an exemplifying embodiment of a system suitable for performing a process as disclosed herein;

[0063] FIG. 2b schematically illustrates another exemplifying embodiment of a system suitable for performing a process as disclosed herein;

[0064] FIG. 3 is a flow chart schematically illustrating an exemplifying embodiment of a process as disclosed herein;

[0065] FIG. 4a schematically illustrates a calculated equilibrium established from an input gas mixture;

[0066] FIG. 4b schematically illustrates an enlargement of a proportion of the calculated equilibrium of FIG. 4a.

DETAILED DESCRIPTION

[0067] The present invention is based upon a number of insights by the inventors. The inventors have recognised that in a process that utilizes hydrogen as the main component of the reducing gas, carbon dioxide will be removed from the process gas by carburization of the sponge iron. This stands in contrast to typical (fossil) carbon-based reducing systems where CO2 is accumulated in the process gas and must be removed and/or reformed. The inventors have further recognised that the relative inertness of CO2 means that it can be introduced to the process as seal gas, thus replacing the inert gases typically used as seal gas. In doing so, a wide range of advantages are obtained, as is described herein.

[0068] The term process gas is used herein to denote the gas mixture in the direct reduction process, regardless of stage in the process. That is to say that process gas refers to gas that is introduced to, passes through, leaves, and is recycled back to the direct reduction shaft. More specific terms are used to denote the process gas at various points in the process, or to denote component gases added to the process gas to form part of the process gas. Reducing gas is a gas introduced at a point lower than the inlet of the shaft, and which flows upwards counter to the moving bed of ore in order to reduce and/or carburize the ore. Top gas is partially spent process gas that is removed from an upper end of the shaft, in proximity to the ore inlet. After treatment, the top gas is recycled back to the direct reduction shaft as a component of the reducing gas. Make-up gas is fresh gas added to the reducing gas in order to maintain reducing ability. Thus, the reducing gas comprises make-up gas together with recycled top gas. The make-up gas and recycled top gas may be mixed together prior to introduction into the direct reduction shaft, or may be introduced separately and mixed in the shaft. Seal gas is gas entering the direct reduction shaft from the ore charging arrangement at the inlet of the direct reduction shaft. The outlet end of the direct reduction shaft is also sealed using a seal gas, and seal gas therefore may enter the DR shaft from the discharging arrangement at the outlet of the direct reduction shaft, albeit typically in lesser amounts. The present invention is therefore equally applicable using seal gas introduced during discharge of sponge iron from the direct reduction shaft.

SEAL GAS

[0069] In a direct reduction shaft, a charge of iron ore must be safely introduced to the shaft. Since the process gases passing through the shaft are highly combustible (typically comprising hydrogen, carbon monoxide and hydrocarbons), it is essential that the formation of explosive air/process gas mixtures are avoided when introducing ore to the shaft. This is typically achieved by ensuring that only an inert seal gas, and not air, is introduced to the shaft when charging ore, and that no process gas escapes the shaft from the charging arrangement. Exactly how this is achieved depends on the operating pressure of the direct reduction shaft.

[0070] Typically in DR shafts operating at low pressure (e.g. 2 Bar), such as the Midrex process, a dynamic gas seal is arranged at a seal leg connecting an ore charge hopper to the direct reduction shaft. Seal gas is introduced at a pressure exceeding the operating pressure of the DR shaft at one or more points in the seal leg. This higher-pressure seal gas prevents air from being introduced into the DR shaft with the iron ore charge, as well as preventing process gas from escaping the DR shaft through the seal leg.

[0071] Typically in DR shafts operating at higher pressures (e.g. >2 Bar), such as the Hyl ZR process, a pressurizable charge hopper is arranged at the inlet to the direct reduction shaft. Ore is charged to the pressurizable hopper, which is then first flushed with the inert seal gas to exclude air, then pressurized to approximately the operating pressure of the DR shaft using the seal gas. Once pressurized, the valve separating the charge hopper and DR shaft is opened to allow the iron ore charge to be introduced to the shaft, together with seal gas. Once the charge hopper is emptied of ore, the charge hopper is resealed and flushed again with seal gas to evacuate process gases from the hopper. Finally, the charge hopper can be opened to the atmosphere and refilled with ore. Typically, several pressurizable charge hoppers, such as 4 charge hoppers, are arranged in parallel to supply ore to the DR shaft.

[0072] It should be noted that seal gas is also utilized when discharging a reduced sponge iron product from the outlet of the direct reduction shaft, and may typically also be introduced into the shaft at this point. However, the amount of seal gas introduced at the outlet is typically small compared to the amount introduced at the inlet.

[0073] Regardless of the technique used for charging of ore, seal gas is inevitably introduced into the process gas. As described above, the seal gases typically used, such as nitrogen, must be inert (i.e. not form explosive mixtures with process gas), and therefore are retained in the process gas. However, the other components of the process gas are typically either consumed by reaction (e.g. H2, CO, CH4) or removed from circulation (e.g. H2O, CO2). This means that seal gas would gradually accumulate in the process gas and comprise an ever-increasing proportion if no action was taken. The final result would be a process gas having diminished ability to reduce the ore. In order to avoid such a situation, a proportion of the process gas is typically removed from circulation (as top gas) and flared in order to maintain a suitable concentration of inert components in the process gas. This is at the very least economically deleterious, and depending on the source of the process gas (e.g. fossil fuels), may also be of negative environmental consequence.

[0074] In the present process however, carbon dioxide is used as the seal gas. As will be described below, under the conditions prevailing in a hydrogen-based direct reduction, the carbon-dioxide participates in carburizing the sponge iron produced in the direct reduction shaft, and is passively removed from the process gas. This has several advantages. A carburized sponge iron product is obtained with low concomitant CO2 emission. Depending on the source of carbon dioxide used, the overall CO2 emission may be near-zero, or even negative. Because the carbon dioxide seal gas is passively removed to a significant extent from the process gas, there is not necessarily any over-accumulation of the seal gas in the process gas. This means that there may be no need to dispose of top gas in order to control inert gas levels in the process gas. Nor may there be any need for any discrete apparatus to remove or convert the carbon dioxide, such as an external reformer or carbon capture apparatus. A further advantage is that the cost of producing seal gas may be lowered, as the nitrogen typically used in seal gas is typically produced by a costly air separation unit.

[0075] In order to ensure that sufficient carbon dioxide is introduced into the process, more seal gas than is strictly necessary for sealing purposes may be introduced into the process gas. For example, seal gas may be introduced at higher pressures in the seal leg or pressurizable charge hopper. The pressurizable charge hopper arrangement may also be constructed to allow a continuous (leakage) flow of carbon dioxide to the process gas, even between charging of iron ore burden to the shaft.

CARBURIZATION USING CO2

[0076] Adding carbon dioxide to a hydrogen-based direct-reduction process will, as stated above, result in ultimate removal of the carbon from the process gas by carburization of sponge iron. Without wishing to be bound by theory, it is thought that the carbon dioxide will initially be converted to carbon monoxide in the hydrogen-rich process gas by the reverse water-gas shift reaction.

[0077] The reverse water-gas shift reaction is as follows:

CO2+H2CO+H2O

[0078] In a prior art syngas-based process, significant quantities of both hydrogen and carbonaceous gases (CO, CO2) are already present. This means introduction of small additional quantities of carbon dioxide as seal gas would not significantly shift any equilibrium. However, in a hydrogen-based direct reduction process, any CO2 introduced to the process gas will be converted more-or-less quantitatively to CO at the elevated temperatures prevailing in the direct reduction shaft. A number of further factors also dictate that conversion of CO2 to CO will be favoured. Iron-based catalysts such as iron oxides (e.g. magnetite) are known to catalyse the water-gas shift reaction, meaning that the reaction will be catalysed by the iron-containing reactants and/or products of direct reduction, and no external reformer will be necessary. Water is continually removed from the top gas of the direct reduction process, thus enhancing production of CO by Le Chatelier's principle. The reverse WGS reaction is endothermic, meaning that, again by Le Chatelier's principle, the equilibrium is shifted towards CO by high temperatures. Finally, as described below, the carbon monoxide produced will be continuously removed from the process gas by carburization reactions, further enhancing the conversion of CO2 to CO.

[0079] Once formed, the carbon monoxide may partake in a range of further reactions, some of which are shown below.

METHANATION

[0080]
CO+3H2CH4+H20 205.9 kJ/mol

2CO+2H2CH4+CO2 247.1 kJ/mol

REDUCTION

[0081]
3Fe2O3 (hematite)+CO 2Fe3O4+CO2 24.9 kJ/mol

2Fe3O4 (magnetite)+2CO6FeO+2CO2 +45.3 kJ/mol

6FeO (wstite)+6CO6Fe+6CO2 75.8 kJ/mol

CARBURIZATION (GRAPHITE PRODUCTION)

[0082]
2COCO2+C 173.7 kJ/mol

CO+H2C+H2O 131.8 kJ/mol

CH4C+2H2 +74.5 kJ/mol

CARBURIZATION (CEMENTITE PRODUCTION)

[0083]
3Fe+CH4Fe3C+2H2 +98.3 kJ/mol

3Fe+2COFe3C+CO2 148.8 kJ/mol

3Fe+CO+H2Fe3C+H2O 107.6 kJ/mol

[0084] Hydrogen also provides reduction of the iron ore by the following reactions:

6Fe2O3+2H2.fwdarw.4 Fe3O4+2H2O +32.7 kJ/mol

2Fe3O4+2H2.fwdarw.6FeO+2H2O +127.6 kJ/mol

6FeO+6H2.fwdarw.6Fe+6H2O +171.4 kJ/mol

2Fe3O4+8H2.fwdarw.6Fe+8H2O +299.0 kJ/mol

[0085] The reaction of hydrogen and carbon dioxide to produce methane is commonly termed the Sabatier reaction. The reaction of hydrogen and carbon dioxide to produce carbon and steam is commonly termed the Bosch reaction.

[0086] Hydrogen predominates in the process gas and will therefore be the primary reductant. However, since carbon monoxide is formed from the reaction of hydrogen with carbon dioxide, and since even if carbon monoxide acts as reductant this merely regenerates carbon dioxide, the primary reductant can in all cases be considered to be hydrogen. Carbon is only removed from the chemical system by carburization reactions, since a carburized sponge iron product is removed at the outlet of the direct reduction shaft. Thus, the overall chemical system can be conceptualised as hydrogen being consumed in converting ore and carbon dioxide to iron and carbon monoxide respectively, with the carbon monoxide subsequently being consumed by carburization, and the ultimate products being water and carburized sponge iron, both of which are removed from the system.

DIRECT REDUCTION

[0087] The direct reduction shaft may be of any kind commonly known in the art. By shaft, it is meant a solid-gas countercurrent moving bed reactor, whereby a burden of iron ore is charged at an inlet at the top of the reactor and descends by gravity towards an outlet arranged at the bottom of the reactor.

[0088] Reduction is typically performed at temperatures of from about 900 C. to about 1100 C. The temperatures required are typically maintained by pre-heating of the process gases introduced into the reactor, for example using a preheater such as an electric preheater. Further heating of the gases may be obtained after leaving the pre-heater and prior to introduction into the reactor by exothermic partial oxidation of the gases with oxygen or air. Reduction may be performed at a pressure of from about 1 Bar to about 10 Bar in the DR shaft, preferably from about 3 Bar to about 8 Bar.

[0089] The iron ore burden typically consists predominantly of iron ore pellets, although some lump iron ore may also be introduced. The iron ore pellets typically comprise mostly hematite, together with further additives or impurities such as gangue, fluxes and binders. However, the pellets may comprise some other metals and other ores such as magnetite. Iron ore pellets specified for direct reduction processes are commercially available, and such pellets may be used in the present process. Alternatively, the pellets may be specially adapted for a carbon-lean reduction step, as in the present process.

[0090] In contrast to present-day commercial direct reduction processes, the make-up gas used to replenish the reducing gas comprises little or essentially no carburizing gas. By carburizing gas it is meant carbon-containing gases that are capable of directly carburizing the sponge iron, e.g. all non-fully oxidised carbon compounds, such as hydrocarbons or carbon monoxide. The make-up gas may for example comprise, consist essentially of, or consist of, hydrogen. Instead, the main carburizing effect in the present process is achieved by the carbon dioxide introduced as seal gas, which is converted to carbon monoxide and subsequently carburizes the sponge iron. However, in order to achieve suitable levels of carburization of the sponge iron, small amounts of additional carbon may be contained in the make-up gas as carbon dioxide and/or an auxiliary carburizing gas. For example, the make-up gas may comprise, consist essentially of, or consist of at least 80 vol %, preferably greater than 90 vol %, even more preferably greater than 95 vol % hydrogen gas (vol % determined at normal conditions of 1 atm and 0 C.). The balance may comprise, consist essentially of, or consist of carbon dioxide and/or auxiliary carburizing gas. If carbon dioxide and/or auxiliary carburizing gas constitute part of the make-up gas these may be introduced to the direct reduction shaft together with the hydrogen make-up gas. Alternatively, a proportion or all of the carbon dioxide and/or auxiliary carburizing gas constituting part of the make-up gas may be added to the direct reduction shaft separately from the main volume of make-up gas. For example, an auxiliary carburizing gas may be added to a carburizing or cooling zone of the direct reduction shaft.

[0091] The process gas is at least partially recycled, whereby top (spent) gas from the DR shaft may be cleaned and treated to remove by-products such as water and/or dust prior to re-introduction to the DR shaft. This recycled top gas may be mixed with fresh make-up gas prior to reintroduction into the reactor, or may be introduced separately from any fresh make-up gas supply.

[0092] Sponge iron is obtained as the product of reduction of the iron ore, and is discharged from the outlet at the bottom end of the direct reduction shaft. The shaft may have a cooling and discharge cone arranged at the bottom to allow the sponge iron to cool prior to discharge from the outlet.

SPONGE IRON

[0093] The term crude iron is used herein to denote all irons produced for further processing to steel, regardless of whether they are obtained from a blast furnace (i.e. pig iron), or a direct reduction shaft (i.e. sponge iron). The sponge iron obtained at the outlet of the DR shaft is typically predominantly in the form of pellets, due to the structural integrity of the direct reduction pellets, as well as the conditions prevailing in the DR shaft. Such sponge iron is typically referred to as direct reduced iron (DRI). Depending on the process parameters, it may be provided as hot (HDRI) or cold (CDRI). Cold DRI may also be known as Type (B) DRI. DRI may be prone to re-oxidation and in some cases is pyrophoric. However, there are a number of known means of passivating the DRI. One such passivating means commonly used to facilitate overseas transport of the product is to press the hot DRI into briquettes. Such briquettes are commonly termed hot briquetted iron (HBI), and may also be known as type (A) DRI.

[0094] The sponge iron product obtained by the process herein may be an essentially fully metallized sponge iron, i.e. a sponge iron having a degree of reduction (DoR) greater than about 90%, such as greater than about 94% or greater than about 96%. Degree of reduction is defined as the amount of oxygen removed from the iron oxide, expressed as a percentage of the initial amount of oxygen present in the iron oxide. It is often not commercially favourable to obtain sponge irons having a DoR greater than about 96% due to reaction kinetics, although such sponge irons may be produced if desired.

[0095] By carburized sponge iron it is meant carbon-containing sponge iron. The carbon present in the sponge iron product may typically be in the form of cementite (Fe3C) and/or graphite. Graphite tends to dust and to be lost from the sponge iron prior to reaching the melt of the EAF. For this reason, it may be preferable if carbon is present in the sponge iron as cementite.

[0096] The carburized sponge iron may comprises from 0.1 to 5 percent carbon by weight, such as from 0.5 to 3 percent carbon by weight such as about 1 to 2 percent carbon by weight. It is typically desirable for further processing that the sponge iron has a carbon content of from 0.5 to 5 percent carbon by weight, preferably from 1 to 4 percent by weight, such as about 3 percent by weight, although this may depend on the ratio of sponge iron to scrap used in a subsequent EAF processing step. If desired, the carburized sponge iron product of the present process may subsequently be further carburized by other means prior to further processing.

GASES

[0097] The hydrogen gas may preferably be obtained at least in part by electrolysis of water. If the water electrolysis is performed using renewable energy then this allows the provision of a reducing gas from renewable sources. The electrolytic hydrogen may be conveyed by a conduit directly from the electrolyser to the DR shaft, or the hydrogen may be stored upon production and conveyed to the DR shaft as required.

[0098] The present invention requires a source of carbon dioxide as seal gas. Some carbon dioxide may also be introduced as make-up gas in order to provide increased carburization of sponge iron. In order to avoid accumulation of inert gases in the process gas, the seal gas consists essentially of carbon dioxide, i.e. consists of carbon dioxide and impurities in the gas source. For example, it is preferable that the source of carbon dioxide is essentially pure carbon dioxide, e.g. 95 vol % carbon dioxide or greater, preferably 98 vol % or greater. The source of carbon dioxide may preferably be from a high-concentration source, preferably a high-concentration biogenic source. For example, concentrated green CO2 may be obtained as a by-product of bio-gas production by anaerobic digestion, or as a by-product of bioethanol production. If the carbon dioxide used in the process is from a renewable source then the process may be net negative with regard to CO2 emissions. However, even use of a source of carbon dioxide from a fossil source that otherwise would have been directly emitted means that the process may not result in any excess emission of CO2. An alternative means of providing carbon dioxide is to preheat the reducing gas prior to introduction into the direct reduction shaft using oxy-fuel combustion of biomass. The principle of oxy-fuel combustion is simple: the biomass is combusted using essentially pure oxygen as the oxidant. The resulting flue stream consists essentially of carbon dioxide and steam. The steam may be removed by simple condensation, providing an essentially pure source of carbon dioxide. Conventionally, the provision of essentially pure oxygen is an economic impediment to the utilization of oxy-fuel combustion. However, in the present case there may be a ready supply of oxygen available at low additional cost from water electrolysis, making oxy-fuel preheating of the reduction gas economically feasible.

[0099] The auxiliary carburizing gas may be any gas known or expected in the art to provide carburization. Gas in this respect refers to a substance that is gaseous at the high temperatures prevailing in the carburization reactor, although it may be liquid or solid at room temperature. Suitable carburizing gases include hydrocarbons such as methane, natural gas, LPG or petroleum, or other carbonaceous substances such as syngas, lower (C1-C6) alcohols, esters and ethers. The carburizing gas may be of fossil origin, but it is preferable that it is obtained partly or wholly from a renewable source in order to reduce net CO2 emissions. By renewable it is meant a resource that is naturally replenished on a human timescale. The high utilization of carbon present in the carburizing gas permits use of renewable carburizing gases, despite their relative scarcity and high cost as compared to fossil equivalents. Suitable renewable carburizing gases include biomethane, biogas, gas obtained from the pyrolysis or partial combustion of biomass, lower alcohols or ethers such as methanol, DME or ethanol derived from renewable feedstocks, or combinations thereof. Sulfur-containing carburizing gases may be used, as the sulfur is known to prevent nucleation of graphite and passivate the sponge iron product.

[0100] The composition of the carburizing gas may be chosen to suit the final carburized sponge iron to be obtained. The carburization reaction with hydrocarbons is relatively endothermic, leading to a relatively cool final product, whereas the reaction with CO-containing carburizing gases is more exothermic, leading to a hotter final product. This effect may be utilized to tailor the temperature of the final product obtained. For example, if a hot product is desired for briquetting (HBI), a gas comprising some partially oxidized carbon (e.g. in the form of CO, ketones, aldehydes) may be used, whereas if cold sponge iron (CDRI) is desired then biomethane may be used.

[0101] In considering the total quantities of carbon dioxide and/or auxiliary carburizing gas suitable to be added to the process gas, either as seal gas (carbon dioxide) or in the make-up gas (carbon dioxide and/or auxiliary carburizing gas), factors to consider are the degree of carburization desired, the effect on the added carbon on the water-gas shift equilibrium, and the effect the added carbon has on the reducing capacity of the reducing gas. For example, Excessive addition of carbon may result in significant accumulation of carbon dioxide in the process gas, potentially decreasing the reducing capacity of the reducing gas.

[0102] It is preferred that the carbon dioxide and any auxiliary carburizing gas used is derived from a renewable source, and in such case, the carbon in the sponge iron product will also derive from a renewable source. It can be determined whether the carbon in the sponge iron derives from a renewable source or a fossil source by radiocarbon dating of the sponge iron. Methods for sample preparation and radiocarbon dating of iron products are known in the art. For example, an appropriate method is disclosed in Cook, A., Wadsworth, J., & Southon, J. (2001). AMS Radiocarbon Dating of Ancient Iron Artifacts: A New Carbon Extraction Method in Use at LLNL. Radiocarbon, 43(2A), 221-227, the methods of which are incorporated by reference herein.

[0103] Carbon derived from fossil resources typically has a radiocarbon age of in excess of 35 000 years, whereas carbon derived from renewable sources is found to be modern. Depending on the proportion of renewable carbon to fossil carbon in the sponge iron, which in turn depends on the proportion of renewable carbon to fossil carbon in the carbon dioxide and carburizing gas, the radiocarbon age of the sponge iron may range from about 35 000 years (if the carbon is exclusively fossil-derived) to modern (if the carbon is exclusively renewable-derived). A list of radiocarbon dated iron objects is provided in Cook, A. C., Southon, J. R. & Wadsworth, J. Using radiocarbon dating to establish the age of iron-based artifacts. JOM 55, 15-22 (2003). The process described herein, due to its excellent utilization of carbon, is capable of being performed in a commercially viable manner using carbon dioxide and optionally carburizing gas derived predominantly or essentially from renewable sources. Thus the resulting sponge iron product may have a radiocarbon age of less than 10 000 years before present, preferably less than 1 000 years, such as less than 100 years before present.

EMBODIMENTS

[0104] The invention will now be described in more detail with reference to certain exemplifying embodiments and the drawings. However, the invention is not limited to the exemplifying embodiments discussed herein and/or shown in the drawings, but may be varied within the scope of the appended claims. Furthermore, the drawings shall not be considered drawn to scale as some features may be exaggerated in order to more clearly illustrate certain features.

[0105] FIG. 1 schematically illustrates a prior art embodiment of the ore-based steelmaking value chain according to the Hybrit concept. The ore-based steelmaking value chain starts at the iron ore mine 101. After mining, iron ore 103 is concentrated and processed in a pelletizing plant 105, and iron ore pellets 107 are produced. These pellets, together with any lump ore used in the process, are converted to sponge iron 109 by reduction in a direct reduction shaft 111 using hydrogen gas 115 as the main reductant and producing water 117 as the main by-product. The hydrogen gas 115 is produced by electrolysis of water 117 in an electrolyser 119 using electricity 121 that is preferably primarily derived from fossil-free or renewable sources 122. The hydrogen gas 115 may be stored in a hydrogen storage 120 prior to introduction into the direct reduction shaft 111. The sponge iron 109 is melted using an electric arc furnace 123, optionally together with a proportion of scrap iron 125 or other iron source, to provide a melt 127. The melt 127 is subjected to further downstream secondary metallurgical processes 129, and steel 131 is produced. It is intended that the entire value-chain, from ore to steel may be fossil-free and produce only low or zero carbon emissions.

[0106] FIG. 2a schematically illustrates an exemplifying embodiment of a system suitable for performing the process as disclosed herein. The system illustrated in FIG. 2a is particularly suitable for direct reduction processes operating at elevated pressures (e.g. >2 Bar).

[0107] A direct reduction shaft 211 is arranged with an inlet 211a for iron ore 207, an outlet 211b for discharging sponge iron 208, an inlet for reducing gas 211c and an outlet for top gas 211d. A pressurizable charge hopper 213 is arranged in communication with the inlet 211a to the direct reduction shaft 211. The pressurizable charge hopper 213 comprises an inlet 213a for iron ore 207, an outlet 213b for iron ore 207, a gas inlet 213c and a gas outlet 213d. The inlet 213a of the pressurizable charge hopper 213 is arranged in connection with an ore bin 227. The gas inlet 213c of the pressurizable charge hopper 213 is arranged in connection with a source of carbon dioxide 221.

[0108] In use, iron ore 207 from ore bin 227 is introduced into the pressurizable charge hopper 213. Once loaded with ore, the ore inlet 213a and outlet 213b are sealed and the hopper 213 is purged with a volume of carbon dioxide 223 from the source of carbon dioxide 221 in order to expel air from the hopper 213. Air mixed with carbon dioxide leaves the hopper 213 as purged gas 225. The purged gas mixture may be recycled to recuperate carbon dioxide if desired. Gas outlet 213d is then sealed and the hopper 213 is pressurized with carbon dioxide 223 to a pressure approximating the operating pressure of the direct reduction shaft 211. Once pressurized, the outlet 213b of the hopper 213 is opened to allow iron ore 207 to be charged to the inlet 211a of the direct reduction shaft 211. Carbon dioxide 223 is inevitably concomitantly introduced to the direct reduction shaft in the charging operation. The iron ore 207 charged to the direct reduction shaft 211 progressively passes through the shaft to be discharged at outlet 211b. During its passage through the shaft 211 the ore 207 is reduced by reducing gas 217 in a counter-current flow, such that sponge iron 208 is obtained at the discharge outlet 211b of the reactor 211.

[0109] Make-up gas 215 is supplied from a source of make-up gas 220, such as a hydrogen gas store or water electrolyser. The make-up gas 215 is mixed with treated top gas 218 to form reducing gas 217. The reducing gas 217 is passed through a pre-heater 241 prior to introduction into the direct reduction shaft 211. The top gas 216 exiting outlet 211d is passed through a plurality of treatment apparatuses 243 in order to prepare the gas for re-introduction to the DR shaft 211. The plurality of treatment apparatuses may include a cleaning step, such as passage through an electrostatic precipitator to remove solids from the gas, heat exchange with other process gases such as the reducing gas 217, and separation of water. The treated top gas 218 is mixed with the make-up gas 215 and passed through the pre-heater 241 prior to reintroduction into the direct reduction shaft 211 through inlet 211c. The temperature of the gases entering inlet 211c may be further increased by partial oxidation. In such a case, a supply of oxygen (not shown) will be arranged between the pre-heater 241 and inlet 211c.

[0110] The carbon dioxide 223 introduced to the direct reduction shaft with the ore 207 will circulate in the process gases where, without wishing to be bound by theory, it will first be converted by reaction with hydrogen to carbon monoxide and then be taken up as carbon (e.g. graphite or cementite) in the sponge iron. Thus, the carbon dioxide 223 will be passively removed from circulation and will not accumulate in the process.

[0111] FIG. 2b schematically illustrates a similar process system to that illustrated in FIG. 2a, with the difference that the system is particularly suitable for direct reduction processes operating at near-atmospheric pressures (e.g. 2 Bar). In this system, iron ore 207 is charged to the inlet 211a of the direct reduction shaft 211 via a seal leg 229. Carbon dioxide 223 is provided to the seal leg 229 at a seal gas inlet 229c at a pressure in excess of the operating pressure of the direct reduction shaft 211 and a mixture of carbon dioxide and air is expunged as purged gas 225. In this manner, iron ore 207 being charged to the inlet 211a of the direct reduction shaft 211 will be stripped of air, and process gases from the direct reduction shaft 211 will be prevented from exiting the shaft via the seal leg 229. However, such an arrangement also inevitably leads to the introduction of carbon dioxide 223 into the direct reduction shaft 211 together with ore 207. In other aspects, the operation of the system and process is similar to that described in FIG. 2a. Again, it may be possible to recycle the purged gas 225.

[0112] Although not illustrated, the process systems illustrated in FIGS. 2a and 2b also comprise a carburized sponge iron discharging arrangement, arranged at the discharge outlet 211b of the direct reduction shaft. Such discharging arrangements are known in the art and may comprise a pressurized discharge hopper, or a seal leg and discharge bin. Such discharging arrangements function in a similar manner to the ore charging arrangements described in conjunction with FIGS. 2a and 2b.

[0113] FIG. 3 is a flow chart schematically illustrating an exemplifying embodiment of the process disclosed herein. Step s301 denotes the start of the process. In step s303a iron ore is charged into a direct reduction shaft, whereby carbon dioxide as seal gas is inevitably introduced into the direct reduction shaft together with the iron ore. In step s305 a top gas is removed from the direct reduction shaft. In step s307 a proportion of the top gas is recycled and mixed with a make-up gas to form a reducing gas. In step s309 the reducing gas is introduced into the direct reduction shaft in countercurrent flow to the iron ore in order to reduce the iron ore and produce carburized sponge iron. Step s311 denotes the end of the process. Alternatively, or in addition, another step, step s303b may replace or complement step s303a. In step s303b carburized sponge iron is discharged from the direct reduction shaft, whereby carbon dioxide as seal gas is introduced into the direct reduction shaft in conjunction with discharge of the carburized sponge iron.

[0114] FIGS. 4a and 4b illustrate an equilibrium composition formed using an initial gas composition of: H2: 91%; CO2: 4%; and H2O: 5% (by volume) at a pressure of 4 Bar. The equilibrium is calculated using HSC Equilibrium software from Outotec. FIG. 4a illustrates all components, whereas FIG. 4b focusses on the carbonaceous components of the mixture. It can be seen that at relatively low temperatures (<approx. 600 C.) methane dominates, at intermediate temperature (approx. 600-900 C.) carbon (graphite formation) dominates, whereas at temperatures in excess of approx. 900 C. carbon monoxide dominates. Carbon dioxide is not favoured at any of the equilibrium conditions investigated, although at low temperature it can be assumed that it will be kinetically favoured since it is a component of the initial gas mixture. It should be noted that the prevailing temperature at the reducing gas inlet of a direct reduction shaft is typically in excess of 950 C., and therefore carbon monoxide will be favoured by equilibrium. Once formed, the carbon monoxide will participate in carburization and be removed from the process in the manner previously described.