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Theses Doctoral

Sustainable Iron and Steel Making Systems Integrated with Carbon Sequestration

Zhou, Xiaozhou

As the world population has exceeded 7 billion in 2011, the global awareness of sustainability arises more than ever since we are facing unprecedented challenges in energy, water, material and climate change, in order to sustain our current and future generations on this planet. The Guardian has named the Iron Bridge opened in 1781 across the River Severn, Shropshire, UK as the cradle of the modern world, which is the world's first cast-iron bridge and remains as the enduring symbol of the Industrial Revolution (Guardian, 2009). Ever since, in the spanning of 250 years, iron and steel have been the cornerstone of modern industries from developed countries to developing ones especially for those which are still experiencing their major urbanization process. Nevertheless, iron and steel making are among the most raw material-dependent and energy intensive industries with large gaseous pollutants, CO2 and waste generations in the world. Therefore there is a pressing need to solve these resource and environmental problems associated with the iron and steel making. This work addresses a number of challenges stated above by focusing on the improvement of the overall sustainability of this highly energy-intensive industry via (1) utilizing inexpensive iron ore tailings to enhance the material sustainability, (2) CO2 reduction by mineral carbonation using its own solid waste stream, i.e., iron and steel slags, and (3) slag valorization through the use of carbonated slags as sustainable construction materials.

This work begins with the study of an ironmaking plant using the direct reduced iron (DRI) process, which is a molten iron production method utilizing fluidized bed and melter-gasifier technologies. This technology allows the direct production of the molten iron using the inexpensive iron ore tailings and the non-coking coal, during a gas-solid reaction in the fluidized bed. Practically, a higher percentage of the fine particles (i.e., iron ore tailings) is favored to mix in the feedstock because it is cheaper than the traditionally used coarse particles (i.e., bulk and fine iron ores). The challenge of this novel technology is attributed to the entrainment of the fine particles during the gas-solid fluidization. Since the electrostatic phenomenon was significant during the particulate fluidization systems which might affect the particle entrainment, the electrostatic charge generation and accumulation were investigated for binary and quaternary particulate systems. Specifically, the effect of the addition of two different iron ore tailings (i.e., hematite and magnetite) in the fluidized bed was studied in terms of particle-particle interactions, electrostatics, and entrainment rates. The behaviors of different particulate systems were found to be highly dependent on the chemical and physical properties of the particles. The results suggested that the enhanced electrostatic forces between the fine and coarse particles due to the electrostatic charging during the fluidized bed operation retained the fines to some extent and the sintering of the fine particles could happen on the surface of the coarse particles during the iron ore reduction. Therefore, for this fluidized bed based DRI process, iron ore tailings are proved to be able to replace the coarse iron ores to the extent that fine particles will sinter but not be entrained and thus the overall cost of raw materials could decrease.
In iron and steel making, limestone and dolomite are also mixed in the feedstock to remove the impurities of the iron ores, mostly silica, which forms slag as a silicate-based material in the downstream of this process. Slags of different types have been reused as cement clinker, aggregate, road base and fertilizer. Recently, iron and steel slags have also been deemed as alternatives for mineral sequestration because these slags are similar to natural Ca/Mg-bearing silicate minerals. The accelerated weathering of natural minerals or industrial wastes is an environmentally benign route to thermodynamically stabilize carbon. Thus, another study of this work is fixing the CO2, especially emitted from the iron and steel plant, into the slag, a solid waste generated from the same processing stream. In particular, the stainless steel slag has been a focus since its application in construction materials has been limited due to the high content of FeO and the environmental concern of heavy metals leaching (e.g., Cr).
Along with the iron and steel making, the cement industry is also among the largest industrial CO2 emitters. Mixing carbonated slags as a filler material in the cement mortar while guaranteeing the overall quality of the cementitious material could reduce the usage of limestone and the carbon emissions from limestone calcination and reduce energy input during the cement production. In this study, the production of environmentally benign cementitious material was coupled with the direct carbonation of stainless steel slag. Compressive strength, exothermic behavior and leaching behavior of the mixed cement mortar were investigated. Particularly, mixing 10 wt% of the direct carbonated stainless steel slag sample prepared at 30 °C in a Portland cement did enhance the compressive strength of the cement mortar. Also, the mixing retarded the hydration and overall setting time. Finally, the Cr leaching of the cement mortar with the addition of the direct carbonated stainless steel slag was minimized. Thus, the iron and steel industry and cement industry should collaborate, to minimize their overall material input, energy usage and carbon emission jointly.
During the direct carbonation, stainless steel slag and CO2 flows are introduced into the solvent simultaneously. Whereas for the two-step process, calcium ions are extracted from the solid matrix into an aqueous phase, and then the CO2 is bubbled through and reacts with the Ca. The two-step route allows optimizing the conditions for both the dissolution and the carbonation. Moreover, the precipitated end products (e.g., precipitated calcium carbonates, PCC) from the two-step process, normally with higher quality compared to direct carbonated slags, can be adapted for various industrial and construction applications.
However, the overall reaction is constrained by the kinetics of the stainless steel slag dissolution. Thus several organic and inorganic chelating agents were applied in order to accelerate the dissolution. Some of these agents were found to be desirable for the dissolution of stainless steel slag at different pH via the differential bed study. Ligand concentration and temperature affected the extent of the extraction in the batch reactor. For the carbonation step, PCC from the modeled chemical solution and the dissolved stainless steel slag solution were non-identical, which was also affected by the reaction pH and temperature. The properties of the PCC prepared in the batch reactor and the bubble column reactor were also found to be dissimilar. Thus, for an iron and steel plant that adopts the two-step carbonation of slags for CO2 reduction, the end products could be engineered by tuning the reaction conditions to meet different end-user requirements.
On the other hand, there have been significant efforts to reduce the cost of the two-step carbonation, including the utilization of value-added byproducts like iron oxide. In particular, silicate minerals or industrial waste often contain 5~20 wt% of Fe and by dissolving the iron into aqueous phase, a variety of Fe-based materials can be synthesized by precipitation. In this work, Fe-based catalysts were synthesized from serpentine and stainless steel slag (SSS) and applied to the biomass-to-hydrogen conversion via an alkaline thermal treatment pathway. The synthesized Fe-based materials were compared with the purchased hematite and magnetite and the reduced Fe-based catalyst derived from SSS was found to be catalytically active. This suggests an opportunity to produce inexpensive catalysts from the solid waste of the iron and steel making.
Finally, a novel iron making scheme based on a fluidized bed DRI system was proposed by this study. It combined all the studies above that inexpensive iron ore tailings were used as a feedstock for the iron production, slags were utilized for sequestering CO2 and ended as filler materials for cement mortar. Preliminary economical and life cycle assessment was investigated based on the current scale of an existing industrial plant. An economically, environmentally and ecologically favored iron, steel and cement production system could be potentially achieved with improved overall material sustainability and carbon footprint.

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More About This Work

Academic Units
Earth and Environmental Engineering
Thesis Advisors
Park, Ah-Hyung
Degree
Ph.D., Columbia University
Published Here
April 17, 2015
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