Experimental Investigation of Calcium Looping CO2 Capture for Application in Cement Plants

Thesis from Matthias Hornberger
University of Stuttgart, 2022

This thesis assesses the application of the calcium looping technology for CO2 capture from cement plants. The cement industry contributes significantly to the anthropogenic CO2 emissions. Due to process inherent CO2 emissions, the application of CCS technologies is inevitable to fully decarbonise the cement sector and mitigate climate change. Within this thesis, various integration options of the calcium looping technology into the cement clinker manufacturing process have been developed addressing different boundary conditions of the cement plants. The more mature options using fluidised bed reactors have been extensively studied at semi industrial scale for operation conditions anticipated for the respective integration option. Furthermore, a novel concept using entrained flow reactors has been assessed by investigating the sorbent properties of various raw meals in such a system. Besides, a comprehensive study regarding the suitability of various potential sorbents (i.e. limestone, raw meal and raw meal components) have been conducted using thermo-gravimetric analysis. The comprehensive sorbent screening showed that raw meal based sorbents suffer a severe deactivation during the first calcination that can be attributed to belite formation. The severity of the initial sorbent deactivation increased slightly with increasing SiO2 content of the sorbent. Short calcination times enhanced the sorbent activity as the formation of belite is limited. At oxy-fuel conditions, all raw meal based sorbents show very similar cyclic CO2 carrying capacities that can be described by a single deactivation model. For a calcination time of 10 min, the raw meals’ CO2 carrying capacity can be described using the deactivation model of Ortiz et al. with an initial CO2 carrying capacity of 0.30 mol mol−1, a deactivation constant of 0.44 and a residual activity of 0.075 mol mol−1. Whereas, a calcination time of 1 min yields an initial CO2 carrying capacity of 0.39 mol mol−1, a deactivation constant of 0.28 and a residual activity of 0.091 mol mol−1. Assessing various raw meal qualities at entrained flow conditions showed that the calcination degree increased with in- creasing calcination temperature and increasing residence time. The recarbonation showed no dependence of the calcination temperature in the investigated temperature range (i.e. 900 °C and 920 °C) but decreased slightly with increased residence time. Overall, the re-carbonation performances of entrained flow calcined raw meals are in agreement with the recarbonation behaviour of limestone based sorbents. The CO2 carrying capacity increased with increasing carbonation temperature, whereas the CO2 concentration did not affect the sorbent conversion but its carbonation reaction rate. For CO2 concentrations below 0.2 m³ m-3, a reaction order of 1 regarding the driving force was found. The investigation of the fluidised bed calcium looping CO2 capture options yielded CO2 capture efficiencies up to 98 % due to the significantly increased sorbent activity. For high integration levels CO2 capture in the carbonator was limited by the achievable equilibrium CO2 concentration. At lower integration levels CO2 capture was limited by the circulated amount of active CaO. The CO2 capture could be adjusted by altering the circulation rate. Overall, the CO2 capture efficiency in the fluidised bed carbonator can be described by the active space time model developed for power plant application. Based on the experiments a CO2 purity of 0.95  m³ m-3 can be anticipated for the oxy-fuel calciner’s flue gas before compression and purification (i.e. before the CPU) with excess oxygen being the main side component. Due to the large quantity of calcium in the calciner, sulphurous components were completely captured from the flue gas, whereas NOx formation increased significantly. NOx concentration increased with excess oxygen and ranged from 500 ∙ 10−6 m³ m-3 to 750 ∙ 10−6 m³ m-3 requiring a dedicated NOx removal step during compression and purification.

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