Extended theoretical and experimental studies of the calcium looping process

Dissertation von Glykeria Duelli
Universität Stuttgart, 2017

The world is at a critical juncture in its efforts to combat climate change. Since the first Conference of the Parties (COP) in 1995, greenhouse-gas (GHG) emissions have risen by more than one-quarter and the atmospheric concentration of these gases has increased steadily to 435 parts per million carbon-dioxide equivalent (ppm CO2-eq) in 2012. The international commitment to keep the increase in long-term average temperatures below two degrees Centigrade, compared to pre-industrial levels, requires substantial and sustained reductions in global emissions. Given the dominant role that fossil fuels continue to play in primary energy consumption followed by the continuously increasing global energy demand, the deployment of carbon capture and storage technologies (CCS) is imperative. The individual component technologies required for CO2 capture, transport and storage are generally well-understood and, in some cases, technologically mature.

The largest challenge for CCS deployment is the integration of component technologies into large-scale (demonstration) projects. In this direction simulation and modeling works allow a cost effective investigation of the feasibility and the applicability of the prototype technology as well as its development and optimization. In addition, complete process approach allows determination of the impact that integration of the CO2 capture plant imposes on the power plant. However, a reliable assessment of the process performance requires the process models to be validated with experimental data.

In this work, one of the major CCS technologies, the calcium looping process is realized, investigated and evaluated at a 10 kWth dual fluidized bed (DFB) continuously operating facility at the University of Stuttgart. The performance of the process in terms of CO2 capture in the carbonator and sorbent calcination in the regenerator is studied. Natural limestones were used. The process was realised in presence of water vapor in both carbonator and regenerator reactor. The calcination took place in high CO2 concentration representative of the oxy-fuel combustion in the regenerator. Synthetic flue gas was used while both reactors were electrically heated with supplementary CH4 combustion in the regenerator when necessary. The Ca flow circulating between the reactors as well as the Ca mass in the reactors were varied. The regenerator and the carbonator temperatures were varied. The sorbent CO2 capture ability was studied through thermogravimetric analysis of the samples taken during experimentation. Attrition phenomena were studied by measuring the particle size distribution and weighting the material collected from the cyclones of the DFB facility.

The experimentation was successfully performed with reliable data and the trends observed are in good agreement with previous works. It was shown that CO2 capture efficiencies of more than 90% can be achieved at conditions closer to the industrial ones. The CO2 capture efficiency was improving by increasing bed inventory and looping ratio. The sorbent calcination degree is a decreasing function of the carbonate content of the incoming solid flow and an increasing function of the particle residence time and reactor temperature. In presence of water vapor, CO2 capture efficiencies of more than 90% and complete sorbent calcination were achieved for looping ratios of around 8. The temperatures were for the regenerator not more than 1193K and for the carbonator around 903K. The sorbent carbonation conversion was retained at about 0.2 molCaCO3/molCaO, constant for many hours of operation. The material loss was measured to be around 4.5%wt/h based on the total system inventory while the mean particle size of the sorbent decreased to around 400 µm and remained constant for many hours of operation.

Simplified semi-empirical models were successfully implemented in the experimental results. Kinetic and attrition constants were calculated and a good agreement between the predicted and the actual data is shown. Design parameter of active space time was found to be 30s for the carbonator and 0.11h for the regenerator with efficiencies of more than 90% in both reactors.

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