Catalytic effect of iron on decomposition of carbon monoxide: II. Effect of additions of H2, H2O,CO2, SO2 and H2S

In this work the effect of additions of H₂, H₂O, CO₂, SO₂, and H₂S on the catalytic decomposition of CO by iron has been investigated at 400, 600, and 800°C and atmospheric pressure. The catalyst was porous iron formed by the reduction of hematite ore granules with hydrogen. The relative importance of carbon deposition by the reactions 2CO → C + CO₂ and H₂ + CO → C + H₂O was determined as a function of hydrogen concentration. It was found that even low concentrations of hydrogen greatly enhanced the rate of decomposition of CO, presumably by a catalytic action of adsorbed hydrogen on iron. The presence of water vapor had a dual effect. At low concentrations of hydrogen the rate of decomposition of CO increased with the addition of H₂O, apparently by a catalytic effect. At high concentrations of hydrogen, however, carbon deposition was retarded because of the effect of the reverse reaction H₂O + C → H₂ + CO. In CO-CO₂ mixtures the rate of carbon deposition decreased with increasing CO₂ content, because of the effect of the reverse reaction CO₂ + C → 2CO. The presence of traces of sulfur-bearing gaseous species, such as SO₂ and H₂S, retarded the decomposition of CO on iron and brought about the early cessation of carbon deposition. This strong effect may be due to the retardation of the decomposition of the intermediate product, cementite, and the formation of pyrrhotite on the surface of the iron catalyst.     

Deterioration of electromotive force of chromel-alumel thermocouples in reducing atmospheres at high temperatures

The deterioration of electromotive force (emf) of Chromel-Alumel (CA) thermocouples in 80 pct H₂ + 15 pct CO + 5 pct CO₂ has been analyzed in terms of the corrosion behavior of Chromel. Emf of the CA thermocouple deteriorated drastically in 80 pct H₂ + 15 pct CO + 5 pct CO₂. After exposure for about 1000 hours at 900 °C, the decrease of emf was about 16 mV. The deterioration process could be separated into three terms. The first term, which has the smallest time constant of about 20 hours, was attributed to carbon deposition on the Chromel surface in the temperature range of 600 to 700 °C. The second term, which has a time constant of about 100 hours, was attributed to the severe internal oxidation of chromium in the temperature range of 500 to 800 °C. The third term, having the largest time constant of several thousand hours, might be attributed to the moderate and gradual preferential oxidation of chromium in Chromel in the range 800 to 900 °C. Boron nitride (BN) coating on CA thermocouples could reduce this deterioration of emf; the decrease of emf was improved to about 3 °C during 700 hours test at 900 °C.     

Gaseous reduction of laterite ores

Lateritic nickel ores have been reduced under laboratory conditions. The reduction experiments were carried out at temperatures from 500 °C to 1100 °C in a horizontal tube furnace using various mixtures of H₂ and CO₂. The hydrogen evolution method was used to measure the degree of metallization of the reduced ore. It was found that the rate of reduction was very low at 500 °C but then increased rapidly upon heating the ore to 600 °C. The percent metallics increased with increasing H₂ to CO₂ ratios in the reducing gas. At temperatures between 600 °C and 1100 °C, a H₂ to CO₂ ratio of 3 leads to the formation of 5 to 6 pct metallics in the reduced calcine was shown. Heating the ore in air or nitrogen prior to reduction does not affect the degree of metallization. A H₂ to CO₂ ratio of at least 4 is required to obtain a ferronickel product analyzing 36 pct nickel if no further reduction is carried out during the subsequent smelting operation.     

The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part II. The reduction of iron oxide/carbon composites

The reduction of iron oxide/carbon composite pellets with hydrogen at 900 °C to 1000 °C was studied. Compared to hydrogen, the reduction by carbon was negligible at 900 °C and below. However, significant carbon oxidation of the iron oxide/graphite pellets by H₂O generated from the reduction of Fe₂O₃ by H₂ was observed. At higher temperatures, reduction by carbon complicates the overall reduction mechanism, with the iron oxide/graphite composite pellet found to be more reactive than the iron oxide/char composite pellet. From the scanning electron micrographs, partially reduced composite pellets showed a typical topochemical interface with an intermediate region between an oxygen-rich unreacted core and an iron-rich outer shell. To determine the possibility of reduction by volatiles, a layer of iron oxide powders was spread on top of a high volatile containing bituminous coal and heated inside a reactor using infra-red radiation. By separating the individual reactions involved for an iron oxide/coal mixture where a complex set of reactions occur simultaneously, it was possible to determine the sole effect of volatile reduction. It was found that the light reducing gases evolve initially and react with the iron oxide, with complex hydrocarbons evolving at the later stages. The volatiles caused about 20 to 50 pct reduction of the iron oxide.     

Effect of Firing Temperature and Reducing Gas Composition during Low-Temperature Reduction of Nanocrystalline Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

Pure nanocrystalline hematite (40 to 100 nm) compacts were prepared and sintered at various temperatures (300 °C to 600 °C) and then reduced with 100 pct H₂ at 500 °C. On the other hand, fired compacts at 500 °C were reduced with a H₂-Ar gas mixture containing different concentration of hydrogen (100, 75, 50, and 25 pct) at 500 °C using thermogravimetric techniques. Nanocrystalline Fe₂O₃ compacts were characterized before and after reduction with X-ray diffraction, scanning electron microscopy (SEM), vibrating sample magnetometer (VSM), and reflected light microscope. It was found that the fired compacts at 400 °C to 600 °C have relatively faster reaction behaviors compared to that at lower firing temperature 300 °C. By decreasing the firing temperature to 300 °C, partial sintering with grain growth was observed clearly during reduction. Also, it was found that the reduction rate increased with increasing hydrogen content in the reducing gas. Comparatively, grain growth and partial coalescence took place during reduction with 25 pct H₂ due to long reaction time.

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Concept and present state of a coal-based smelting reduction process for iron ore fines

The concept of a two-stage smelting reduction process is presented. In the first stage highly metallized iron ore fines are produced in a circulating fluidized bed. In the second stage a hot metal is produced in a melter-gasifier where – together with metallized ore – coal and oxygen are injected to generate the required heat and the CO-rich reducing gas. The process was tested stepwise in pilot scale installations. Although only a reduction temperature of 830 °C instead of the required 880–900 °C could be realized in the pilot unit, test results make it very probable that a metallization of 90% can be reached with any fine ore without sticking problems, if the ore is covered with a carbon layer by CO decomposition in a pretreatment stage with the reduction offgas at 500–600 °C. The CO decomposition on the fresh ore leads to a high gas utilization which renders a CO₂ washing stage and gas recycling unnecessary. To prove the technical and economic feasibility of the combined process, the next development step should be the design and operation of a larger pilot plant with a capacity of at least 5 t hot metal/h for continuous and joint operation of both the melter/gasifier and the reduction stage.     

Study of the Reduction of Industrial Grade MoO<Subscript>3</Subscript> Powders with CO or CO-CO<Subscript>2</Subscript> Gases to Prepare MoO<Subscript>2</Subscript>

Industrial grade MoO₂ powders have a plenty of advantages relative to MoO₃ in the direct alloying steelmaking processes. In this work, the reduction of industrial grade MoO₃ powder with CO gas or the mixed gases of CO and CO₂ has been investigated in detail in order to prepare industrial grade MoO₂ powder. It is found that reaction temperature has a significant effect on the product composition. Using pure CO as the reducing gas, for temperatures below 868 K (595 °C), the main product is MoO₂ with some whisker carbon; for temperatures above 868 K (595 °C) the main reaction products are MoC and amorphous carbon; as the reaction temperature further increased, the final reaction product is Mo₂C. In addition, Mo₄O₁₁ is always formed as an intermediate product during the reaction processes both at lower and higher temperatures, which is similar to that observed on reduction of MoO₃ by H₂. It is found that adding CO₂ to the reducing gases eliminated carbon formation but still allows the formation of MoO₂ during the reaction process. This method may be applied to produce industrial grade MoO₂.     

Iron ore reduction/cementation: experimental results and kinetic modelling

Abstract

Iron ore reduction and iron cementation by H₂-CH₄-Ar gas mixtures were investigated in a laboratory isothermal fixed bed reactor in the temperature range 600-925°C. Iron ore was first reduced to metallic iron by hydrogen, then metallic iron was carburised to cementite by methane. Increasing temperature and hydrogen content accelerated the reduction process. However, for >55 vol.-%, the effect of H₂ content was not significant. Methane had almost no effect on the reduction process. Increasing temperature increased the rate of iron cementation and also the rate of free carbon deposition. Optimum conditions for cementite formation were: temperature 750°C and reducing/carburising gas contents of 40-55 vol.-%H₂ and 35 vol.-%CH₄. Under these conditions, reduction of iron ore to cementite was completed in ~15 min. A two interface grain model and a volume reaction model were used to simulate the process of iron ore reduction and iron cementation. The simulated results for both reduction and cementation were consistent with the experimental data.     

The effect of hydrogen addition on the carbon-deposition behaviour during the reduction of pellets for the blast furnace process

With the application of large amount of pulverised coal injection into the blast furnace, the hydrogen content in the gas will increase, which accelerates the reduction of iron ore in lump zone of the blast furnace as well as carbon-deposition reaction. This study has investigated the effect of hydrogen addition on carbon-deposition reaction during the reduction of pellets through thermodynamic calculation and experiment. The results show that H₂ can promote the carbon-deposition reaction, while the increase of temperature and CO₂ can significantly inhibit it. The preference region of temperature for C formation is about 600°C. Moreover, the promotion effect of H₂ on the carbon-deposition reaction at 700°C is better than that at 600°C. The SEM observation results show that the generated carbon is mainly distributed on the surface of the pellet, and only a little carbon is located inside the pellet. The agglomerated carbon could be more easily formed due to the dramatic carbon-deposition reaction caused by the lower temperature or higher H₂ content. But, most of the carbon just exists as an individual particle at the lower carbon-deposition reaction rate. The results of SEM–EDS reveal that carbon deposited is primarily in the form of elemental carbon rather than in the form of cementite. The study also shows that with increasing reduction time, the rate of carbon-deposition increases, mainly due to the promotion effect of reduced iron during the reduction process of pellets.     

Reduction and carburization of iron-ore in a fluidized bed by CO,H2 and CH4

The reduction and carburization of fine iron-ore (100 - 200 μm, Fe₂O₃ mass content of 98%) by gas mixtures containing CO, H₂ and CH₄ was investigated in a fluidized bed at temperatures of 400 up to 700°C. In this temperature range carbon is formed from CO via the Boudouard reaction as well as by the decomposition of methane. Yet, both reactions only occur in the presence of metallic iron and therefore only at reduction degrees of the DRI (direct-reduced iron) of more than 33%. As a contribution to the development of a DRI process without a costly hot briquetting, the influence of the C- and O-content of the DRI on its tendency to reoxidize was also investigated by means of the ignition point method. It was found that reoxidation (at 20°C) of a totally reduced DRI can be suppressed by carbon mass contents of more than 7%. With decreasing reduction degrees, this value decreases, until for reduction degrees of less than 80% no carbon is needed to suppress reoxidation. With regard to the final reduction of the DRI in the electric arc furnace, the molar C to O ratio should be one. The maximal reduction degree is then about 86% to stabilize carbon rich DRI (C mass content of 4%) against reoxidation.     

Comparison of isothermal and nonisothermal reduction

Experimental investigation of the isothermal and nonisothermal reduction of low silica hematite pellets in H₂/CO mixture between 600 and 1234°C shows that the reduction rate in H₂ rich gas mixture for nonisothermal condition is lower than for isothermal case at comparable temperatures. On the basis of the two period reduction model, some of the physical and chemical characteristics of pellets and reducing gas is calculated. Because of the advantage shown for isothermal reduction, a new technique for direct reduction of pellets is suggested.     

Swelling Behavior of Iron Ore Pellets during Reduction in H2 and N2/H2 Atmospheres at Different Temperatures

The need to develop green steelmaking techniques has led to the replacement of reducing agents such as CO with H₂. H₂ and N₂/H₂ mixtures can be used for the carbothermal reduction of iron ore. Herein, the reduction swelling index (RSI) of iron ore pellets in a forming gas (N₂/H₂) atmosphere at temperatures of 700–1000 °C is investigated and it is compared with that in pure H₂. It is showed in the experimental results that the RSI increases with increasing temperature for both the H₂ and N₂/H₂ atmospheres. The maximum swelling is reached approximately 5 min into the H₂ reduction process, while in the N₂/H₂ atmosphere, it is reached after 25–45 min of reduction, depending on the temperature. When the reduction temperature exceeds 900 °C, the RSI is greater than 20%. Scanning electron microscopy/energy-dispersive X-ray spectroscopy is performed to detect the changes in the microstructure and chemical composition of the samples. The nonreduced areas in the reduced pellets during the N₂/H₂ reduction process are analyzed using light optical microscopy.     

A study of chromite carbochlorination kinetics

The carbochlorination of a chromite concentrate was studied between 500 °C and 1000 °C using boat experiments. The reaction products were analyzed by scanning electron microscopy (SEM), x-ray diffraction (XRD), and chemical analysis. The carbochlorination of a chromite concentrate at about 600 °C led to the partial selective elimination of iron, thus increasing the Cr/Fe ratio in the treated concentrate. Total carbochlorination of the chromite concentrates and volatilization of the reaction products was achieved at temperatures higher than 800 °C. The kinetics of the chromite carbochlorination was studied between 750 °C and 1050 °C using thermogravimetric analysis (TGA). The results were discussed in terms of the effects of gas flow rate, temperature, partial pressure of Cl₂+CO, and Cl₂/CO ratio on the carbochlorination process. It was observed that the temperature effect changed significantly with the progress of the reaction. The initial stage of the carbochlorination was characterized by an apparent activation energy of about 135 and 74 kJ/mol below and above 925 °C, respectively, while a value of about of 195 kJ/mol was found for the remainder of the carbochlorination process.     

Reduction Behaviors of Pellets Under Different Reducing Potentials

Owing to the change of gas composition in top gas recycling-oxygen blast furnaces compared with traditional blast furnace, many attentions are attracted to the research on iron oxide reduction again. In order to study the influence of H₂ and CO on the reduction behavior of pellets, experiments were conducted with H₂-N₂, CO-N₂ or H₂-CO gas mixtures at 1173 K by measuring the mass loss, respectively. It was found that the reduction degree increased with increasing the ratio of H₂ or CO in the gas mixture, but the reduction with hydrogen was faster than that with carbon monoxide. The reduction degree could reach 96. 72% after 65 min for the reduction with 50% H₂ + 50% N₂, while it is only 53. 37% for the reduction with 50% CO+ 50% N₂. The addition of hydrogen to carbon monoxide will accelerate the reduction because the hydrogen molecules are more easily chemisorbed and reacted with iron oxide than carbon monoxide. A scanning electron microscope was used to characterize the structures of reduced samples. Dense structure of iron was obtained in the reduction with hydrogen while the structure of iron showed many small fragments for the reduction with carbon monoxide. At the later stage of reduction with the gas mixtures containing carbon monoxide, the reduction curves showed a descending trend because the rate of carbon deposition caused by the thermal decomposition of carbon monoxide was faster than the rate of oxygen loss. Compared with the reduction with CO-N₂ and H₂-CO gas mixtures, H₂ gas could enhance the carbon deposition while N₂ gas would reduce this phenomenon. The results of X-ray diffraction and chemical analysis demonstrated that the carbons are mainly in the form of cementite (Fc₃C) and graphite in reduced sample.     

Mass Loss and Direct Reduction Characteristics of Iron Ore-coal Composite Pellets

Mass loss and direct reduction characteristics of iron ore-coal composite pellets under different technological parameters were investigated. Meanwhile, changes of iron phase at different temperatures were analyzed by using X-ray diffraction （XRD）, and characteristics of crushed products were studied by using a scanning electron microscope （SEM）. The results showed that heating rate had little influence on the reduction, but the temperature played an important role in the reduction process. The mass loss rate increased rapidly from 800 to 1 100 ℃. The reduction process can be divided into three steps which correspond to different temperature ranges. Fe2 03 began to transform into Fe304 below 500 ℃, and FeO was reduced into Fe from 900 ℃. At 900 ℃, the reduction product showed a clear porous structure, which promoted the reduction progress. At 1000 ℃, the metallic Fe dominated the sample, and the reduction reached a very high degree.     

Carbon deposition on iron surfaces in CO–CO2 atmosphere

Thermodynamic calculations and thermogravimetric (TG) analysis were performed in order to understand the mechanism of carbon deposition on the surfaces of iron particles during the reduction of iron ore in a CO–CO₂ atmosphere. The results of the thermodynamic equilibrium phase analysis indicate that the phases of the carbon deposition process can be predicted on the basis of the carbon potential, reaction temperature and gas pressure. The optimal thermodynamic conditions for carburisation are a low temperature (T?<?T_m) and a high carbon potential (α_c>1). TG analysis is performed in a gas mixture of 65 vol.-% CO and 35 vol.-% CO₂ at 650, 706 and 750°C. Cementite (Fe₃C) is generated as an intermediate product, which acts as a catalyst for carbon deposition. Carbon deposition is inhibited at high temperatures (T>791°C) owing to the high stability of Fe₃C. When the reaction temperature is higher than the thermodynamic limit for the formation of Fe₃C, carbon deposition cannot occur. A mechanism for carbon deposition is proposed based on the experimental results.     

Rate of the reduction of the iron oxides in red mud by hydrogen and converted gas

The drying and gas reduction of the iron oxides in the red mud of bauxite processing are studied. It is shown that at most 25% of aluminum oxide are fixed by iron oxides in this red mud, and the other 75% are fixed by sodium aluminosilicates. A software package is developed to calculate the gas reduction of iron oxides, including those in mud. Small hematite samples fully transform into magnetite in hydrogen at a temperature below 300°C and a heating rate of 500 K/h, and complete reduction of magnetite to metallic iron takes place below 420°C. The densification of a thin red mud layer weakly affects the character and temperature range of magnetizing calcination, and the rate of reduction to iron decreases approximately twofold and reduction covers a high-temperature range (above 900°C). The substitution of a converted natural gas for hydrogen results in a certain delay in magnetite formation and an increase in the temperature of the end of reaction to 375°C. In the temperature range 450–550°C, the transformation of hematite into magnetite in red mud pellets 1 cm in diameter in a converted natural gas is 30–90 faster than the reduction of hematite to iron in hydrogen. The hematite-magnetite transformation rate in pellets is almost constant in the temperature range under study, and reduction occurs in a diffusion mode. At a temperature of ～500°C, the reaction layer thickness of pellets in a shaft process is calculated to be ～1 m at a converted-gas flow rate of 0.1 m³/(m² s) and ～2.5 m at a flow rate of 0.25 m³/(m² s). The specific capacity of 1 m² of the shaft cross section under these conditions is 240 and 600 t/day, respectively. The use of low-temperature gas reduction processes is promising for the development of an in situ optimum red mud utilization technology.     

Structural changes and kinetics in the gaseous reduction of hematite

The mechanism of the gaseous reduction of hematite grains to magnetite was studied. Grav-imetric measurements were carried out for the reduction of Carol Lake hematite pellets and grains in CO-CO₂ atmospheres over the temperature range 500 to 1100°C. The pore size distribution in the reduced magnetite was measured by mercury porosimetry. Partially reduced grains were examined by optical microscopy. At temperatures below 800°C, the reduction of a hematite grain to magnetite occurred at a well-defined shrinking-core inter-face. The average pore size in magnetite formed at 600°C was found to be 0.03 μm. An es-timate of the rate of CO diffusion through pores of this size indicated that the reaction rate at 600°C was controlled by a step near the hematite-magnetite interface. At temperatures above 800°C, the reaction mechanism became altered due to the preferential growth of magnetite along a single direction in each hematite grain. The reduction rate decreased with an increase in temperature, and no microporosity was present in magnetite formed at 1000°C and above. It was postulated that the reaction rate was controlled by the rate of formation of fresh nuclei and by their rate of subsequent growth. Formerly Professor of Applied Metallurgy, Imperial College     

Corrosion behaviors of inconel 617 in hydrogen base gas mixture

The corrosion behavior of Inconel 617, a candidate for the structural material of heat exchanger in the high temperature gas-cooled reactor (HTGR), has been investigated at elevated temperatures in the hydrogen base gas mixture (80 pct H₂ + 15 pct CO + 5 pct CO₂). This gas mixture simulates the reducing gas in the direct steel making system that uses heat from HTGR in Japan. This gas has relatively high oxidizing and carburizing potentials. In the temperature range of 650 to 1000 °C Inconel 617 oxidized to form a Cr₂O₃ scale containing titanium oxide. The activation energy for this process is estimated to be 50 to 60 kcal/mol. The time dependence of the growth of the surface oxide scale was parabolic. The aluminum in Inconel 617 was internally oxidized. The time dependence of the internal oxidation was noticed to obey a 0.4 power rate law. Carburization was noticed at 650 and 900 °C. At 900 °C, carbides containing Si, Ti, and Mo precipitated beneath the oxide scale for gas exposure times up to 200 h. After 200 h, the formation and growth of the surface scale suppresses carburization. The thermodynamic analysis of gas atmosphere proposed by Gurry could be applied successfully to the experimental results. Some inconsistency existed mainly because of the scale formation and direct gas-metal interactions.     

High-Temperature Oxidation of Alloy 617 in Helium Containing Part-Per-Million Levels of CO and CO<Subscript>2</Subscript> as Impurities

The objective of this study was to determine the mechanisms of carburization and decarburization of alloy 617 in impure helium. To avoid the coupling of multiple gas/metal reactions that occurs in impure helium, oxidation studies were conducted in binary He + CO + CO₂ gas mixtures with CO/CO₂ ratios of 9 and 1272 in the temperature range 1123 K to 1273 K (850 °C to 1000 °C). The mechanisms were corroborated through measurements of oxidation kinetics, gas-phase analysis, and surface/bulk microstructure examination. A critical temperature corresponding to the equilibrium of the reaction 27Cr + 6CO ↔ 2Cr₂O₃ + Cr₂₃C₆ was identified to lie between 1173 K and 1223 K (900 °C and 950 °C) at CO/CO₂ ratio 9, above which decarburization of the alloy occurred via a kinetic competition between two simultaneous surface reactions: chromia formation and chromia reduction. The reduction rate exceeded the formation rate, preventing the growth of a stable chromia film until carbon in the sample was depleted. Surface and bulk carburization of the samples occurred for a CO/CO₂ ratio of 1272 at all temperatures. The surface carbide, Cr₇C₃, was metastable and nucleated due to preferential adsorption of carbon on the chromia surface. The Cr₇C₃ precipitates grew at the gas/scale interface via outward diffusion of Cr cations through the chromia scale until the activity of Cr at the reaction site fell below a critical value. The decrease in activity of chromium triggered a reaction between chromia and carbide: Cr₂O₃ + Cr₇C₃ → 9Cr+3CO, which resulted in a porous surface scale. The results show that the industrial application of the alloy 617 at T > 1173 K (900 °C) in impure helium will be limited by oxidation.