This application is being filed on 19 April 2012, as a PCT International Patent application in the name of Forest Vue Research, LLC, a U.S. national corporation, applicant for the designation of all countries except the US, and Michael P. Barkdoll, a citizen of the U.S., applicant for the designation of the US only, and claims priority to U.S. Application No. 13/225,900, filed September 6, 2011.

This application is a continuation-in-part of U.S. Application No. 13/225,900, filed September 6, 201 1, which is a continuation of International Application No. PCT/US2011/032201, filed April 13, 2011, which claims the benefit of U.S. Provisional Application No. 61/380,062, filed September 3, 2010, and the benefit of Indian Application No. 342/KOL/2011, filed March 15, 2011.

BACKGROUND

[0001] The fundamentals of reducing iron oxides into metallic iron are well established. An iron oxide in the presence of a reducing gas is heated to create the reducing reaction. In a laboratory setting, a workable process for reducing small quantities of most any iron oxide is achievable if the practicalities necessary for economic sustainability in a commercial setting are ignored. In other words, a process developed and tested in a laboratory on small quantities of raw materials may prove the concept, yet fail to provide a solution to the real world problems faced by the iron and steel industry. Many proposed industrial technology development projects have historically failed due to scale up problems. Scale up problems occur in processes that have been proven at the bench scale level

(laboratory scale), and even at the pilot plant level (nominally about 1% to 5% of full scale), but have failed at the full scale production level. In the very broadest of terms, a vast majority of these failures have occurred because the small scale process is a continuous process that cannot be sustained at an industrial level, the reactions occur in spherical or cylindrical reactors that are not reproducible at an industrial level, or the reduced scale reaction kinetics cannot be achieved in a full scale production facility. [0002] A fundamental challenge is the production of sufficient quantities of quality raw materials to meet the demands of the iron and steel industry. In this context, sufficient quantities are measured in metric tons. In evaluating the solution, efficiency and cost are significant factors, including the costs associated with obtaining and processing the raw material. A "successful" but energy inefficient laboratory reduction process is not a solution when scaled up to a commercial setting. In other words, if the operating costs of the scaled process offset the advantages of using a low cost raw material or if the scaled process cannot produce sufficient quantities of the iron/steel product in a timely fashion, it amounts to little more than theory with no practical application.

BRIEF DESCRIPTION OF THE DRAWINGS

[0003] Further features, aspects, and advantages of the invention represented by the embodiments described present disclosure will become better understood by reference to the following detailed description, appended claims, and accompanying figures, wherein elements are not to scale so as to more clearly show the details, wherein like reference numbers indicate like elements throughout the several views, and wherein:

Figure 1 depicts the setup of the first round of tests conducted in a full scale low temperature coke oven with a test box containing iron rich material placed on top of a coal bed;

Figure 2 depicts the setup of the second round of tests a full scale low temperature coke oven with a test box containing iron rich material placed under a coal bed;

Figure 3 depicts a pilot oven for testing iron reduction and coke production at the operating temperatures used in a low temperature coke oven;

Figure 4 depicts a full scale low temperature coke oven configured to implement the low temperature simultaneous process on a self-reducing arrangement of a layer of iron rich material placed under the coal charge and above a layer of reductant producing material; Figure 5 depicts a full scale low temperature coke oven configured to implement the low temperature simultaneous process on internal iron rich material layers interspersed between layers of the coal charge;

Figure 6 depicts reduced iron product forms produced using the self-reducing implementation shown in Figure 4;

Figure 7 depicts reduced iron product forms produced using the internal iron rich material layer implementation shown in Figure 5; and

Figure 8 depicts various embodiments of the reduced iron product recovery action following the coking and reduction action.

DETAILED DESCRIPTION

[0004] An alternative ironmaking process for simultaneously producing a highly metalized reduced iron product from an iron rich material and coke from coal during low temperature coking operations (the "Low Temperature Simultaneous Process") is described herein and illustrated in the accompanying figures. The Low Temperature Simultaneous Process is performed in the environment of a low temperature coke oven. One or more layers of the iron rich material is placed within or under the coal charge. The iron rich material and coal charge are heated in the presence of a reducing gas to reduce the iron oxides of the iron rich material into a reduced iron product and to devolatilize the coal charge. After quenching, the reduced iron product is magnetically separated from the coke.

[0005] The Low Temperature Simultaneous Process converts a charge of coal and an iron rich material into a cake (or mass) of coke and a reduced iron product. For consistency in terminology, "charge" refers to the layers of coal and/or iron rich material, as applicable based on context, processed in a coke oven, and "cake" refers to the hot mass of carbonized coal (i.e., coke) and/or reduced iron, as applicable based on context, produced at the conclusion of the coking time. An iron rich material encompasses any form of unreduced iron oxides including, without limitation, FeO, Fe ₂ 0 ₃ , and Fe ₃ 0 ₄ , occurring in various products including, but not limited to, iron ore fines, mill scale, oily mill scale, blast furnace dust or sludge, basic oxygen furnace dust or sludge, and thermally treated electric arc furnace dust. In some embodiments, the iron rich material includes optional filler materials to increase the production and/or flow of an iron reducing gas.

[0006] Mill scale is a steel mill waste product that is a mixture of iron and iron oxides that is flaked off from hot iron being processed through rolling mills and is typically contaminated with oils and lubricants used in the rolling process. Mill scale is considered one of the most difficult of iron rich materials to reduce to metallic iron. Mill scale has a very high proportion of FeO so it is not easily reduced. Researchers have noted that while mill scale has a very high iron content and low contaminant level, it is very hard to reduce because it has no porosity. Iron ore fines is an iron bearing ore material including, but not limited to, Fe ₂ 0 ₃ hematite) or Fe ₃ 0 ₄ (magnetite) that is generally less than 1 mm (0.37 in) in size and that may contain non-iron elements (gangue) of silica, alumina, and/or other elements or compounds depending on the iron ore deposit characteristics.

[0007] The reduced iron product generally refers to reduced or pre-reduced iron and/or steel and any sub-products such as the iron/carbon amalgamation produced using the Low Temperature Simultaneous Process. The iron/carbon amalgamation is an amalgamation of a carbon substance and the reduced or pre- reduced iron and/or steel (i.e., the iron/steel bonded to or captured by the carbon substance). The reduction of the reduced iron product is quantified in terms of the metallization of the sample. Metallization is determined analytically by measuring the ratio of metallic iron (i.e., Fe) divided by the total amount of iron, including iron oxides, expressed as a percentage. The minimum metallization percentage considered suitable for commercial applications is approximately 90%.

[0008] Iron and steel are graded or categorized by the alloy contents, most notably the carbon content. In descending order of carbon content, the grades are pig iron (3.5% to 4.5%), cast iron (2.0% to 3.5%), ultra-high carbon steel (1.0% to 2.0%), high carbon steel (0.6% to 1.0%), medium carbon steel (0.3% to 0.6%), low carbon steel (0.05% to 0.3%), and ultra-low carbon steel (less than 0.05%). These grades and the specified carbon contents are not intended to limit the Low

Temperature Simultaneous Process described herein in any way.

[0009] In arriving at the present invention, the inventor designed and executed experiments with low temperature coke ovens at both the pilot plant and full scale levels. As used herein, a "low temperature coke oven" is a horizontal coke oven where the temperature above the bed is typically in the range of 800°C to 1250°C (1470°F to 2282°F). In contrast, a "high temperature coke oven" is a coke oven where the temperature above the bed is typically in the range of 1250°C to 1475°C (2282°F to 2687°F). Usage of the term "coke oven" should be considered as a reference to a low temperature coke oven unless the context indicates another meaning is more appropriate.

[0010] Figure 1 illustrates the test environment for the first round of tests using a full scale low temperature coke oven 100 with a text box 102 placed on top of a coal charge 104 ("Full Scale Top Charge Tests"). The Full Scale Top Charge Tests were conducted over two successive days of testing. The low temperature coke oven 100 had an inside width of 2.67 m (8.8 ft) wide and an inside length of 10.9 m (35.8 ft), and was charged with 24 tons of metallurgical grade coal. The coal charge 104 was leveled with a leveling bar.

[0011] Each test box 102 was constructed of plywood with a thickness of

19 mm (0.75 in) and inside dimensions of 220 mm x 470 mm x 50 mm (8.7 in x 18.5 in x 2 in). Each test box 102 was filled to a depth of approximately 50 mm (2 in) with an iron rich material 106. The iron rich materials tested included

Australian mill scale pulverized to 100% less than 1 mm (0.04 in) ("AUS Fine"), Australian mill scale used as received ("AUS Coarse"), and a mixture of 85% Australian mill scale used as received mixed with 15% coal at 85% less than 3 mm (0.12 in) ("AUS Coarse 85/15"). The filled test boxes 102 weighed between 9.0 kg (19.8 lb) and 12.6 kg (27.7 lb). The filled test boxes 102 were placed on top of the leveled coal charge 104 and the coking cycle was initiated. The coking time used during testing was approximately 72 hours.

[0012] During the coking cycle, the coke oven 100 temperatures were continuously measured and recorded on a strip chart recorder. The plywood test boxes 102 readily burned away at the operating temperatures of the low temperature coke ovens 100 and the iron rich material 106 was deposited on top of the coal charge 104. At the end of the coking cycle, the cake was pushed out of the coke oven 100 and quenched to cool the coke and the reduced iron product. [0013] The resulting reduced iron products were recovered from the coke mass and preliminarily tested for metallization using a hand held magnet. Most of the recovered samples showed very low levels of magnetism, which indicated very low metallization. Various samples were taken from the top, middle, and/or bottom third of the reduced iron products as recovered. In other cases, the entire reduced iron product was homogenized before samples were taken (i.e., the sample location is not applicable). The samples were submitted to a laboratory for detailed content (iron, carbon, and sulfur) and property analysis, the results of which are presented in Table 1.

Table 1: Full Scale Top Charge Tests Sample Analysis Results

[0014] Five of the six samples showed metallization of less than 1.5%, which is less than the typical metallization of raw mill scale. Further study of the analytical results also shows that for those five samples, the reduced iron product was in fact oxidized to its highest oxidation potential (i.e., Fe ). The sixth sample, which was taken from the bottom third of the reduced iron product, showed moderate metallization of 66%. Given that reduced iron oxidizes in the presence of oxygen (air) at temperatures in excess of 700°C (1292°F), the inventor postulates that even if the mill scale was reduced during the first two to three hours of the coking time as expected, continued exposure to the oxygen in the combustion air at the operating temperatures of the low temperature coke oven for the remainder of the coking time resulted in re-oxidization.

[0015] The Full Scale Top Charge Tests established that (1) the results of the

Low Temperature Simultaneous Process in low temperature coke oven were not predictable based on previous experience with the simultaneous production of iron and coke in a high temperature coke oven and (2) top charging an iron rich material in a low temperature coke oven does not produce a highly metallized reduced iron product, much less a commercially viable reduced iron product. Following the failure of the top charge experiments, a second round of tests was conducted.

[0016] Figure 2 illustrates the test environment for the first round of tests using a full scale low temperature coke oven 100 with a text box 102 placed below a coal charge 104 ("Full Scale Bottom Charge Test"). In the Full Scale Bottom Charge Test, a test box 102 as described above was filled with an iron rich material 106 of fine Australian mill scale (AUS Fine) and placed onto the floor of the coke oven 100 and a 24-ton coal charge 104 was placed on top of it and leveled. After a coking time of approximately 72 hours, the cake was pushed out of the coke oven 100 and quenched to cool the coke and the reduced iron product.

[0017] The quenched coke mass was mined until the reduced iron product was located. In recovering the sample, an unexpected result was discovered. There was a layer of iron with a thickness of approximately 25 mm tightly bonded to the bottom of a coke finger immediately above where the iron rich material had been charged. A coke finger is a section of coke with typical dimensions in the range between approximately 75 mm to 100 mm x 30 mm (3.0 in to 3.9 in x 1.2 in) and 50 mm x 30 mm to 50 mm (2.0 in x 1.2 in to 2.0 in). Loose reduced iron fines were found below the iron/carbon amalgamation. A sample from the iron/ carbon amalgamation was freed from the attached coke and submitted for laboratory analysis. The analytical results are presented in Table 2.

Table 2: Full Scale Bottom Charge Tests Sample Analysis Results

[0018] The results of the recovered sample showed moderate metallization

(50.8%), showed no significant Fe ⁺³ , and indicated that partial reduction of the Fe ⁺³ to Fe ⁺² occurred. The inventor postulates that during the coking process, tar (bitumen) was expelled from the metallurgical coal and some of it flowed down into the test material. As the tarry mass further transitioned from semi-coke to coke, it released volatiles (mostly hydrogen) which reacted with and reduced the top portion of the iron rich material from Fe ⁺³ to Fe ⁺² or metallic iron; however, the remainder of the test material was not exposed to reducing gases (namely CO, ¾, and 4) from the coal volatiles because the path of least resistance for the coal volatiles was up through the coal bed rather than down through the densely packed fine mill scale. After these results were reviewed, additional full scale coke oven tests were suspended in favor of pilot oven tests. If nothing else, the second round of experiments confirmed that the results obtained using a low temperature coke oven are not predictable based on previous experience with a high temperature coke oven.

[0019] Figure 3 illustrates the pilot oven used in subsequent testing. The pilot oven 300 is lined with 1649°C (3000°F) insulating firebrick and refractory board material. A container 302 placed inside the pilot oven 300 holds the iron rich material 106 and the coal 304 acting as the coal charge during the test. In some embodiments, the container 302 is a test box as described above. In other embodiments, the container 302 is a saggar. A combustion source 308 heats the interior of the pilot oven 300 to the desired temperature. The heated air flow of the pilot oven 300 is designed such that the products of combustion flow through a lower heating channel 310 underneath the container 302, upward past a lower thermocouple 312, through an upper heating channel 314 above the container 312, and past an upper thermocouple 316 before exiting through the short firebrick stack 318. The stack 318 includes intake vents allowing additional air to be drawn into the stack. In one embodiment, the combustion source 308 is a propane fueled 147 kW (500 000 BTU/h) naturally aspirated burner. A sight port 320 is provided to visually monitor the iron rich material 106 on top of the coal in the container 302.

[0020] Propane and induced air are used to quickly bring the pilot oven 300 near operating temperature. Oxygen enrichment is supplied as needed to produce the desired operating temperature. During heat up and operation, the coal off-gases volatile material, primarily H ₂ , CH , and CO. The coal volatiles provide a continuous stream of hot reducing gas, flowing up through the iron rich

material 106. After escaping from the iron rich material 106, the reducing gas reacts with remaining oxygen (induced air) in the flue gas and combusts thereby maintaining the temperature of the upper heating channel 314 at the desired level.

[0021] In the pilot test ("Pilot Scale Self Reducing Bottom Charge Test"), the iron rich material 106 was a mixture of small lump coal, mill scale, and sawdust. Lump coal generally has a largest dimension in the range of approximately 12 mm to 50 mm (0.5 in to 2.0 in), with small lump coal tending to fall in the lower half of that range. The bottom layer in the test box was 38 mm (1.5 in) of a mixture of 75% coarse American mill scale, 21% small lump non-metallurgical coal with a largest dimension in the range of approximately 9 mm to 19 mm (0.37 in to 0.75 in), and 4% dry coarse sawdust ("Mill Scale 75/21/4"). Placed on top of the iron rich material mixture was 89 mm (3.5 in) of metallurgical coal at 85% minus 3 mm (0.12 in). One objective of the Pilot Scale Self Reducing Bottom Charge Test was to determine if combining relatively small lump non-metallurgical coal with the mill scale would create a self-reducing mixture not dependent upon the gases released by the overlying metallurgical coal bed/layer due. Another objective of the Pilot Scale Self Reducing Bottom Charge Test was to determine if the larger piece size of the small lump coal would result in continued devolatilization and release of reducing gases into the coarse mill scale throughout a substantial portion of the coking time. Moreover, the smaller lump coal was intended to be small enough to fully devolatilize within the selected coking time. Further, adding sawdust to the mixture was intended to make the mixture more porous and allow the reducing gases to circulate around and through the iron rich material in the mixture.

[0022] The test box with the iron rich material prepared as described above was placed in the pilot oven. After the initial heat-up period of approximately 56 minutes, the temperature of the pilot oven was maintained at an average temperature of 1055°C (1931°F) for 85 minutes until all of the volatiles were driven out of the overlying metallurgical coal layer. This temperature is consistent with the typical floor brick temperature experienced in a low temperature non-recovery coke oven. After allowing the pilot scale test oven to cool, the test box was removed. The coke was removed from the test box which exposed approximately 25 mm (1 in) of highly magnetic iron fines. It is noteworthy that approximately 1.5 mm (0.06 in) of magnetic iron fines was loosely bonded to the bottom of the coke. It was observed that the char remaining from the devolatilization of the non-metallurgical coal appeared to weaken the interface between the coke and the highly magnetic iron fines. Reduced iron product samples recovered from the magnetic iron fines bonded to the coke ("Bond"), the loose reduced iron fines just below the coke ("Fines"), and the partially sintered iron fines at the bottom of the test box ("Sinter") were submitted for laboratory analysis. The results of the analysis are presented in Table 3.

Table 3: Pilot Scale Self Reducing Bottom Charge Tests Sample Analysis Results

[0023] Although these results showed improvement over the results of the full scale experiments, commercially viable metallization percentages were not reached despite a suitable temperature (i.e., 700+°C) and the presence of a suitable reducing gas for reducing iron. The inventor noted that the further metallization decreased as the distance from the interface between the charge coal and the test material increased. The inventor postulated that the iron rich material was not sufficiently exposed to the reducing gas. In other words, the reducing gas did not adequately flow through the iron rich material layer. Adequate information about the devolatilization rate of coal was not available. Accordingly, the inventor was led to determine the devolatilization rate of large lump metallurgical coal experimentally in order to continue development of the Low Temperature Simultaneous Process.

[0024] In a reference devolatilization test, four pieces of large lump metallurgical coal of varying size were placed onto a refractory board platform in the pilot oven and exposed to temperatures of in the range of approximately 550°C to 700°C (1022°F to 1292°F) for 35 minutes. Two of the coal pieces had a largest dimension of approximately 25 mm (1 in), and the other two had a largest dimension of approximately 38 mm (1.5 inches). During the test, visual observations of the four pieces of lump met coal were made through site port. With a hot, oxygen rich gas flowing over and around the four pieces of coal, the occurrence of devolatilization was indicated by the presence of flames emanating from the coal pieces. The smaller pieces devolatilized for approximately 18 minutes, while the larger pieces devolatilized for approximately 28 minutes.

[0025] To determine the effect of an iron rich material on the devolatilization of the lump metallurgical coal, a second test was conducted in the pilot oven. In the second test, a single piece of lump coal having dimensions of 25 mm x 30 mm (1 in x 1.2 in) was placed in a silicon carbide (SiC) crucible and buried in mill scale. A thermocouple was buried within 10 mm (0.4 in) of the lump coal. The crucible was heated to 800°C (1472°F) and was visually monitored for the presence of flames on top the crucible indicating the devolatilization of the lump coal. In the second test, the time needed to devolatilize the lump coal mixed in with an iron rich material was approximately 41 minutes. Even at the higher temperature, the devolatilization period for the piece of large lump metallurgical coal increased when covered by the iron rich material. Based on these results and the results of other tests, the inventor determined that placing an iron rich material within or beneath a coal charge in a low temperature horizontal coke oven allows commercially meaningful reduction of iron rich material.

[0026] Another series of tests ("Pilot Scale Iron/Glass Tests") using mixtures of iron rich material and glass ("IRM/Glass") were conducted to explore the production of an iron/glass product. These tests were conducted in a silica carbide (SiC) crucible with a diameter of 115 mm (3.5 in) and height of 127 mm (4 in). The iron rich material/glass mixture was placed on top of a layer of metallurgical coal having volatile matter with weight fraction of 29%, and each crucible was placed in the pilot scale oven. The crucibles were heated (for approximately 34 minutes) to a typical low temperature coke oven average operating temperature of approximately 1145°C (2093 °F), and the operating temperature was maintained until evidence of coal devolatilization (i.e., flames from the coal) was no longer visible. After devolatilization ceased, the crucibles were covered and allowed to cool for sample recovery.

[0027] Differing ratios of iron rich material to glass were tested. The iron rich material used in the Iron/Glass tests was mill scale, and the glass matrix used in the Iron/Glass tests was a matrix of Si0 ₂ having a weight fraction of approximately 66%, CaMg(C0 ₃ ) ₂ having a weight fraction of approximately 24.3%, and NaHC0 ₃ having a weight fraction of approximately 9.7%. One iron rich material/glass mixture tested included mill scale having a weight fraction of approximately 20% combined with a glass matrix having a weight fraction of approximately 80%. A second iron rich material/glass mixture tested included mill scale having a weight fraction of approximately 60% combined with a second glass matrix having a weight fraction of approximately 40%. Table 4 presents the results from the laboratory analysis of selected recovered samples.

Table 4: Pilot Scale Iron/Glass Tests Sample Analysis Results

[0028] Restricted by the short heating time used in the Iron/Glass Tests, higher metallization is apparent when the quantity of the iron rich material is small relative to the quantity of glass. Accordingly, some embodiments, the ratio of the iron rich material to the glass material in the iron rich material/glass mixture is between approximately 1 :20 and 1 :4. In other embodiments, the ratio of the iron rich material to the glass material in the iron/glass mixture is between approximately 1:10 and 3:20. However, in a production coke oven with a coking time that is 30 to 150 times longer than the heating time used in the Iron/Glass Tests, the long reaction time allows high metallization to occur even where the ratio of iron rich material to glass is larger.

[0029] At the production level, high metallization is achieved in a low temperature horizontal coke oven when the iron rich material (e.g., mill scale, iron ore fines, or other suitable iron rich material) is mixed with glass and placed on top of a layer of coal. The glass material becomes molten at typical low temperature horizontal coke oven operating temperatures in the range of approximately 1000°C to 1200°C (1832°F to 2192°F). Factors such as buoyancy facilitate passage of the reducing gases (e.g., H2/CO/CH4) produced by the devolatilizing coal through the molten mixture. While passing through the molten mixture, the reducing gases have intimate contact with the iron rich material in the mixture resulting in reduction. As the coking process continues, the molten mixture flows into the natural fissures formed between the coke fingers, and the reduced iron and glass separate due to the extreme density differences.

[0030] Alternative glass recipes may be used provided that the glass has a glass transition temperature that is approximately equal to or less than the average operating temperature of the coke oven. Further, alternative glass recipes with higher silica and limestone proportions and lower sodium levels may be used. One such alternative glass recipe produces a matrix of Si0 ₂ having a weight fraction of approximately 81%, CaO having a weight fraction of approximately 9%, MgO having a weight fraction of approximately 8%, and Na20 having a weight fraction of approximately 2%.

[0031] Following the Iron/Glass Tests, another test was conducted using a mixture of iron rich material and coal ("IRM/Coal") to explore the production of the iron/carbon amalgamation ("Pilot Scale Iron/Carbon Test") first observed during the Full Scale Bottom Charge Tests. In the Iron/Carbon Tests a mixture of mill scale with weight fraction of 75% and metallurgical coal with a weight fraction of 25% was placed into a silica carbide (SiC) crucible with a diameter of 115 mm (4.5 in) and height of 127 mm (5 in), and the crucible was placed in the pilot scale oven. The crucible was heated (for approximately 34 minutes) to typical a low temperature coke oven average operating temperature of approximately 1145°C (2093 °F), and the operating temperature was maintained until evidence of coal devolatilization (i.e., flames from the coal) was no longer visible. After devolatilization ceased, the crucible was covered and allowed to cool for sample recovery. Table 5 presents the results from the laboratory analysis of the recovered sample. Table 5: Pilot Scale Iron/Coke Tests Sample Analysis Results

[0032] The results from the Pilot Scale Iron/Carbon Test was both exiting and unexpected. The material produced (i.e., the iron/carbon amalgamation) was cohesive, porous, consolidated, and had a high degree of metallization. These attributes are very attractive for full scale operations because a porous mass that is both cohesive and consolidated is well suited for product recovery and subsequent material handling processes. As previously discussed in relation to the results of the Pilot Scale Iron/Glass Tests, the long coking time, which is 30 to 150 times longer than the heating time in the Pilot Scale Iron/Coke Test, results in high metallization values (exceeding the 60% metallization reported in Table 5).

[0033] The iron/carbon amalgamation has great utility. First, the iron/carbon amalgamation is suitable as a feedstock for iron furnaces typically requiring specific feedstock qualities and shapes for proper operation (e.g., electric arc furnaces, induction furnaces, blast furnaces and mini-blast furnaces). Most importantly, the high porosity of the iron/coke product making it suitable for use as an iron rich material in coking processes using top, middle, or bottom charging. Unlike other iron rich materials previously discussed, the iron/carbon amalgamation is suitable for use in vertical (slot) coke ovens. In other words, the iron/carbon amalgamation extends the simultaneous process into coking plants utilizing vertical coke ovens. Considering that the majority of coke ovens are vertical coke ovens and vertical coke ovens produce approximately 94% of the world's metallurgical coke supply, the value of the iron/carbon amalgamation is significant.

[0034] Figure 4 illustrates an exemplary low temperature horizontal coke oven 100 implementing the Low Temperature Simultaneous Process with an iron rich material layer 106 on top of a reductant producing layer 402 below the coal charge 104. The reductant producing layer 402 is a layer of lump coal. The piece size of the lump coal is selected to avoid completing devolatilization of the reductant producing layer 402 until approximately the end of the coking time. In other words, the piece size of the lump coal is selected so the reductant producing layer 404 continues to produce a reducing gas during all or substantially all of the coking time. In some embodiments, the thickness (i.e., height) of the reductant producing layer 402 is in the range of approximately 25 mm to 75 mm (1 in to 3 in). In other embodiments, the thickness of the reductant producing layer 402 is in the range of approximately 35 mm to 50 mm (1.4 in to 2 in). In some embodiments, the thickness of the iron rich material layer 106 is in the range of approximately 12 mm to 50 mm (0.5 in to 2 in). In other embodiments, the thickness of the iron rich material layer 106 is in the range of approximately 25 mm to 38 mm (1 in to 1.5 in). In another embodiment, the thickness of the iron rich material layer 106 is

approximately 31 mm (1.2 in).

[0035] Figure 5 illustrates an exemplary low temperature horizontal coke oven 100 implementing the Low Temperature Simultaneous Process utilizing dual internal iron rich material layers 502 made up of an iron rich material and porosity enhancers. Each internal iron rich material layer 502 is sandwiched between two layers of coal 504. The porosity enhancers increase the permeability of the iron rich material layer 502. The increased permeability allows the reducing gas generated by the coal layer 504 below the iron rich material layer 502 to flow up through the iron rich material layer 502 rather than traveling along a path through the coal/coke near the layer transition that offers less resistance and bypassing the iron rich material layer 502. Because the reduced iron is below a layer of coal/coke, there is little to no chance of re-oxidation. As a result, the Low Temperature Simultaneous Process results in complete or nearly complete reduction of the iron rich material.

[0036] Internal iron rich material layers are well suited for, but not limited to, low temperature horizontal coke ovens that utilize stamp charging. Stamp charging refers to practice of forming a coal charge of two to three layers of coal, each with a thickness of approximately 300 mm (11.8 in) and mechanically compacted to a density of greater than approximately 1000 kg/m (62.4 lb/ft ) before use in a coke oven. When preparing the coal charge via stamp charging for use with the Low Temperature Simultaneous Process, an iron rich material layer is placed on top of the current coal layer before stacking another coal layer on top of the coal charge.

[0037] Adding a suitable porosity enhancer allows the improved permeation of the reducing gas through the iron rich material layer without degrading the reduced iron product. Generally, a porosity enhancer does not degrade the reduced iron product if it is non-reactive with the reduced iron product or burns away at low temperature coke oven operating temperatures. Because the porosity enhancer is a filler material consumed during the Low Temperature Simultaneous Process, it is desirable, although not necessary, that the porosity enhancer has little economic value (i.e., is low cost). Examples of suitable porosity enhancers include, but are not limited to, pea coke, steam coal, metallurgical coal, and sawdust. Pea coke refers to small coke having a largest dimension that is typically less than approximately 6 mm (0.24 in). It is readily available at most operating coke plants and has little commercial value due to its small size.

[0038] The number of internal iron rich material layers may vary without departing from the scope and spirit of the present invention. For example, a single internal iron rich material layer may be used with a corresponding reduction in quantity of the reduced iron product generated. Alternatively, additional internal iron rich material layers may be used to increase the quantity of the reduced iron product generated, provided that coal surrounding each internal iron rich material layer produces sufficient reducing gases and minimizes or prevents re-oxidation of the reduced iron product. In particular, the thickness of the top layer of coal should be sufficient to prevent the re-oxidation of the reduced iron product from the oxygen in the combustion air. Further, the layer of coal beneath each internal iron rich material layer should have sufficient thickness to output reducing gases throughout at least the reduction period of iron rich material. In some embodiments, the layer of coal beneath each internal iron rich material layer should have sufficient thickness to output reducing gases throughout all or substantially all of the coking time. Each additional layer of iron rich material increases the output of the reduced iron product with a corresponding positive, significant economic value to the coke plant.

[0039] In some embodiments, the thickness of the iron rich material layer is in the range of approximately 25 mm to 75 mm (1 in to 3 in). In other embodiments, the thickness of the iron rich material layer is approximately 35 mm (1.4 in). When porosity enhancers are utilized, the thickness of the iron rich material layer is in the range of 25 mm to 100 mm (1 in to 4 in). In other embodiments, the thickness of the iron rich material layer with porosity enhancers is in the range of approximately 50 mm to 75 mm (2 in to 3 in). In still further embodiments, the thickness of the iron rich material layer with porosity enhancers is approximately 60 mm (2.4 in).

[0040] The coking time and the thickness of the coal charge are directly related. A thicker coal charge requires a longer coking time, and a longer coking time allows use of a thicker coal charge. In some embodiments, the coking time ranges between approximately 15 h and 96 h. In other embodiments, the coking time ranges between approximately 20 h and 96 h. In alternate embodiments, the coking time ranges between approximately 30 h and 96 h. In still further embodiments, the coking time ranges between approximately 56 h and 72 h. In some embodiments, the thickness of the charge coal layer is in the range of approximately 750 mm to 1500 mm (30 in to 60 in).

[0041] Figures 6 and 7 illustrate the forms of the reduced iron product obtainable using the Low Temperature Simultaneous Process based on the position of the iron rich material layer. The full scale and pilot scale tests show that the resultant reduced iron product occurs in distinctly different forms, namely the iron/carbon amalgamation, loose iron fines, and partially sintered iron fines, depending upon the local temperature surrounding the iron rich material layer. The basic reduced iron product created by the Low Temperature Simultaneous Process is iron fines. If the local temperature is high enough, some sintering of the iron fines occurs to create aggregations of the iron fines (i.e., partially sintered iron fines). The iron/carbon amalgamation is formed when the tar (i.e., bitumen) driven out of the metallurgical coal during heating flows down into the iron rich material and co- mingles with the fine iron rich material. As the temperature increases, the tar devolatizes and forms a coke structure that encompasses the fine iron product to form the iron/carbon amalgamation. All three forms are desirable both from a separation perspective and from a marketability perspective.

[0042] Figure 6 shows the types of reduced iron products obtained from the

Low Temperature Simultaneous Process when the iron rich material is placed below the coal charge. At the end of the coking time, the coal charge has devolatilized into a mass of coke 600. The topmost layer of the reduced iron products where the tar mixed with and devolatilized around the iron rich material forms the iron/carbon amalgamation 602. Below the iron/coke product is a layer of reduced iron fines 604. In addition to the iron/carbon amalgamation 602 and the reduced iron fines 604, partially sintered iron fines 606 are created because the floor brick temperature in the coke oven, which is typically in the range of approximately 1100°C to 1200°C (2000°F to 2200°F), is hot enough to partial sinter the proximate reduced iron fines.

[0043] Figure 7 shows the types of reduced iron products obtained from the

Low Temperature Simultaneous Process when the iron rich material layer is placed between two layers of coal in the coal charge. The coal charge devolatilizes into a mass of coke 600 surrounding the reduced iron products. The illustrated

embodiment shows the top and the bottom of the iron rich material formed the iron/carbon amalgamation 602. Near the top of the iron rich material, the molten tar flows down into the iron rich material to produce the iron/carbon amalgamation 602. Near the bottom of the iron rich material, the molten tar bubbles up into the iron rich material and/or the iron rich material sinks down into the molten tar to produce the iron/carbon amalgamation 602. Depending upon the positioning of the iron rich material layer and the local temperature achieved around the iron rich material layer during coking, the iron/carbon amalgamation product may form only near the top, only near the bottom, or, in some cases, at neither the top nor bottom of the iron rich material layer. The middle portion of the iron rich material isolated from the tar produces the reduced iron fines 604. Partially sintered iron fines are not produced because the temperature at the middle of the coke bed is not high enough to cause partial sintering.

[0044] Figure 8 illustrates an exemplary reduced iron product recovery system 800 in a post-production coke material handling system. The reduced iron product and iron/carbon amalgamation is efficiently separated from the coke by magnetic separation. During post production, the hot coke is pushed out of the coke oven 802 onto a hot car 804. The hot coke is transported to a quench tower 806 where water is sprayed onto the coke to cool it for downstream handling. After quenching, the coke is dumped on to an inclined surface called the coke wharf 808. The coke is then metered onto belt conveyors 810 and across a screen 812 where the smaller coke is filtered out into the breeze pile 814. The larger coke that is not filtered by the screen 812 large coke reports to the blast furnace pile 816. To recover the reduced iron product and the iron/coke product, the reduced iron product recovery system 800 employs one or more magnets 818a-818e at selected locations in the post production coke material handling system. The illustrated embodiment of the post production coke material handling system shows a number of suitable optional locations for the reduced iron product recovery magnets 818a-818e.

[0045] Some iron fines will be washed out during the quenching operation and will be recovered magnetically by the quench tower magnet 818a. Iron fines, sintered iron and iron/coke are recovered by the wharf magnet 818b and/or the conveyor magnet 818c. A substantial portion of the iron fines will be filtered out at the screen 812 and will be recovered via the breeze pile magnet 818d. Any remaining iron/coke will be recovered by the blast furnace pile magnet 818e. In some embodiments, only the quench tower magnet 818a and the breeze pile magnet 818d are used. It should be appreciated that the number and location of magnetic reduced iron product recovery points may vary without departing from the scope and spirit of the present invention.

[0046] The reduced iron products produced by the Low Temperature

Simultaneous Process are suitable, if not superior, raw materials for use by the iron foundry and steel industry. The reduced iron fines, sintered iron fines, and iron/carbon amalgamation are raw materials ready for use in steel mills employing a variety of steel production technologies, such as, electric arc furnaces (EAF), blast furnaces (BF), mini-blast furnaces (MBF), induction furnaces (IF), and basic oxygen furnaces (BOF). In particular, using the iron/carbon amalgamation as the feedstock increases productivity in a mini-blast furnace. The reduced iron fines have low contaminant levels making them an attractive alternative when compared to scrap metal, which is the standard primary feedstock for electric arc furnaces. On an annual tonnage basis, the foundry industry is quite small compared to the steel industry; however its products can command substantially higher prices. While the foundry industry has not be described in detail, it must be recognized that the reduced iron product obtained using the Low Temperature Simultaneous Process can be readily used as a raw material in the iron foundry industry.

[0047] The terms defined in this application are to be interpreted without regard to meanings attributed to these terms in prior related applications and without restriction of the meanings attributed to these terms in future related applications.

[0048] The description and illustration of one or more embodiments provided in this application are not intended to limit or restrict the scope of the invention as claimed in any way. The embodiments, examples, and details provided in this application are considered sufficient to convey possession and enable others to make and use the best mode of claimed invention. The claimed invention should not be construed as being limited to any embodiment, example, or detail provided in this application. Regardless of whether shown and described in combination or separately, the various features (both structural and methodological) are intended to be selectively included or omitted to produce an embodiment with a particular set of features. Having been provided with the description and illustration of the present application, one skilled in the art may envision variations, modifications, and alternate embodiments falling within the spirit of the broader aspects of the general inventive concept embodied in this application that do not depart from the broader scope of the claimed invention.