Abstract:The aim of this research was to investigate the effects of charcoal and Kraft-lignin additions on the structure, cold compression strength, and reactivity of bio-cokes produced at the laboratory scale. Bio-cokes were prepared by adding charcoal and Kraft-lignin (2.5, 5.0, 7.5, and 10.0 wt %) to medium-volatile coal and coking the mixture with controlled heating rate (3.5 • C/min) up to 1200 • C. In addition, four particle sizes of charcoal were added with a 5 wt % addition rate to investigate the effect of particle size on the compression strength and reactivity. Thermogravimetric analysis was used to evaluate the pyrolysis behavior of coal and biomasses. Optical microscopy was used to investigate the interaction of coal and biomass components. It was found that by controlling the amount of charcoal and Kraft-lignin in the coal blend, the compression strength of the bio-cokes remains at an acceptable level compared to the reference coke without biomass addition. The cold compression strength of the charcoal bio-cokes was higher compared to Kraft-lignin bio-cokes. The reactivity of the bio-cokes with charcoal addition was markedly higher compared to reference coke and Kraft-lignin bio-cokes, mainly due to the differences in the physical properties of the parental biomass. By increasing the bulk density of the coal/biomass charge, the cold compression strength of the bio-cokes can be improved substantially.

Most of world steel in 2018 has been produced from virgin iron ore via the blast furnace (BF)—basic oxygen furnace route. Therewith the BF is one of the most important unit processes in worldwide steel making. Among others, energy efficiency of the BF is dependent on coke reactivity. Coke gasification occurs via solution‐loss reactions either with CO2 or H2O. Herein, the gasification of coke is studied in CO–CO2–H2–H2O–N2 atmosphere simulating the BF conditions. The simulated atmospheres are based on the measurements from an actual BF. This research studies the effect of the composition of the BF atmosphere representing conditions near the wall as well as at the center and influence of the H2O content on coke gasification under simulated BF conditions. It is found that the location plays a role in coke gasification: wall atmosphere yields higher coke gasification compared with center. Dynamic tests show that introduction of H2 and H2O in gas atmosphere fastens coke gasification by +119% at temperature range between 800 and 1200 °C in wall conditions. When H2O is present in gas atmosphere, the mass loss of coke is also greater in both wall and center conditions.

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Replacement of part of the coal in the coking blend with lignin would be an attractive solution to reduce greenhouse gas emissions from blast furnace (BF) iron making and for obtaining additional value for lignin utilization. In this research, both non-pyrolyzed and pyrolyzed lignin was used in a powdered form in a coking blend for replacing 5-, 10- and 15 m-% of coal in the raw material bulk. Graphite powder was used as a comparative replacement material for lignin with corresponding replacement ratios. Thermogravimetric analysis was performed for all the raw materials to obtaining valuable data about the raw material behavior in the coking process. In addition, chemical analysis was performed for dried lignin, pyrolyzed lignin and coal that were used in the experiments. Produced bio cokes were tested in a compression strength experiment, in reactivity tests in a simulating blast furnace shaft gas profile and temperature. Also, an image analysis of the porosity and pore shapes was performed with a custom made MatLab-based image analysis software. The tests revealed that the pyrolysis of lignin before the coking process has an increasing impact on the bio coke strength, while the reactivity of the bio-cokes did not significantly change. However, after certain level of lignin addition the effect of lignin pyrolysis before the coking lost its significance. According to results of this research, the structure of bio cokes changes significantly when replacement of coal with lignin in the raw material bulk is at a level of 10 m-% or more, causing less uniform structure thus leading to a less strong structure for bio cokes.

Carbonaceous reductants for pyrometallurgical applications are usually obtained from fossil-based sources. The most important properties of the reductants greatly depend on the application and the feeding of the reductant into the process. However, the mechanical strength, calorific value, fixed carbon content, and reactivity of the reductant are the properties that usually define the applicability of the reductant for different processes. The reactivity of the biochars is usually high in comparison to metallurgical coke, which may restrict the applicability of the biochar in reduction processes. One cause of the higher reactivity is the higher surface area of the biochars, which can be suppressed with agglomeration treatment, e.g., briquetting. In this work, hydrolysis lignin was used for slow pyrolysis experiments to produce biochars. The biochars were pyrolyzed in briquetted form and in as-received form at various temperatures. The reactivity values of the biochars were tested in dynamic reactivity tests in a CO-CO2-N2 gas atmosphere at temperatures of up to 1350 °C. It was found that the yield of the hydrolysis lignin char only decreased by 3.36 wt% when the pyrolysis temperature was elevated from 600 to 1200 °C, while a decrease in yield of 4.88 wt% occurred when the pyrolysis temperature was elevated from 450 to 600 °C. The mass loss of hydrolysis lignin biochar in the reactivity experiment in CO-CO2-N2 atmosphere was significantly decreased from 79.41 wt% to 56.80 wt% when the hydrolysis lignin was briquetted before the slow pyrolysis process and the temperature of the pyrolysis process was elevated from 600 to 1200 °C. This means that the mass loss of the material was suppressed by 22.61 wt% due to the higher pyrolysis temperature and briquetting process.