Oxygen-carrier particles consisting of 40 wt% NiO supported on 60 wt% Mg-stabilized ZrO₂ were produced by freeze granulation and examined as oxygen carrier for chemical-looping applications. Firstly, the particles were examined by oxidation and reduction experiments in a batch fluidized-bed reactor. These experiments indicated very high reactivity with CH₄ and low affinity for carbon formation. For highly oxidized particles the products were CO₂ and H₂O, while for reduced particles they were CO and H₂. Secondly, the particles were examined by 40 hours of operation in a small circulating fluidized-bed reactor, using natural gas as fuel. For chemical-looping combustion, there was complete conversion of fuel into products with high selectivity towards CO₂ and H₂O. At 950 °C, a combustion efficiency of 99.3% was achieved, which is only 0.1% point below the theoretical maximum, i.e. thermodynamic equilibrium. For chemical-looping reforming, the conversion of fuel was 99.9% or higher, with high selectivity towards CO and H₂. Operating at the desired process parameters, which was a fuel reactor temperature of 950 °C and an air ratio of 0.30, worked flawlessly. When only natural gas was used as fuel there was slight formation of solid carbon in the fuel reactor. Adding 30 vol% steam to the fuel removed the carbon formation. The particles retained their physical and chemical structure reasonably well during operation. Approximately 5% of the particles added to the reactor were lost as fines during the first hours of operation. Further, the porosity of the particles increased somewhat during operation. The density was 10% lower for used particles, compared to fresh.

Oxygen Carrier Aided Combustion (OCAC) is realized by using an active oxygen-carrying bed material in fluidized bed boilers. The active material is reduced in fuel rich parts of the boiler and oxidized in air rich parts. Advantages could be achieved such as new mechanisms for oxygen transport in space and time. Here calcined manganese ore has been used as active bed material in a 12 MW_th circulating fluidized bed boiler. The fuel was wood chips and the campaign lasted more than two weeks. From an operational point of view, manganese ore worked excellently. From the temperature profile of the boiler it can be concluded that fuel conversion was facilitated, especially in the dense bottom bed. The effect did not always translate to reduced emissions, which suggests that final combustion in the cyclone outlet was also influenced. Substituting 10% of the sand bed with manganese ore made it possible to reduce the air to fuel ratio without generating large amounts of CO. The use of 100% manganese ore resulted in higher emissions of CO than the sand reference, but, when combined sulphur feeding, dramatic reductions in CO emissions, up to 90% compared to sand reference, was achieved.

Biomass pyrolysis is considered as a thermochemical conversion system that is performed under oxygen-depleted conditions. A large body of literature exists in which thermodynamic equilibrium (TE) and kinetic approaches have been applied to predict pyrolysis products. However, the reliability, accuracy and predictive power of both modeling approaches is an area of concern. To address these concerns, in this paper, two new simulation models based on the TE and kinetic approaches are developed using Aspen Plus, to analyze the performance of each approach. Subsequently, the results of two models are compared with modeling and experimental results available in the literature. The comparison shows that, on the one hand, the performance of the TE approach is not satisfactory and cannot be used as an effective way for pyrolysis modeling. On the other hand, the results generated by the new model based on the kinetic approach suggests that this approach is suitable for modeling biomass pyrolysis processes. Calculation of the root mean square error (RMS), to quantify the deviation of the model results from the experiment results, confirms that this kinetic model presents superior agreement with experimental data in comparison with other kinetic models in the literature. The acquired RMS for the developed kinetic method in this paper varies within the span of 1.2 to 3.2 depending on temperature (400–600 °C) and various feedstocks (pine spruce sawdust, bagasse, wood bark, beech wood and paddy straw).

The novel combustion concept Oxygen Carrier Aided Combustion (OCAC) is realized by addition of an active oxygen-carrying bed material to conventional fluidized bed boilers. The active bed material is meant to become reduced in fuel-rich parts of the boiler and oxidized in oxygen-rich parts, thus potentially providing advantages such as new mechanisms for oxygen transport in space and time. In this study, oxygen-carrier particles prepared from so called Linz-Donawitz (LD)-slag are examined as active bed material in a 12 MW_th Circulating Fluidized Bed (CFB) boiler. LD-slag is the second largest by-product in steel making and is generated in the basic LD oxygen converter process. The experimental campaign lasted for two full weeks. The fuel was wood chips. LD-slag worked well from an operational point of view and no problems related to handling, agglomeration or sintering were experienced, albeit the production of fly ash increased. The boiler temperature profile suggested that fuel conversion in the main boiler body was facilitated, but the effect did not readily translate into reduced emissions from the stack. Spraying an aqueous solution of ammonium sulphate directly into the cyclone outlet with the aim of rejecting alkali metals as alkali suphates was found to solve the problems related to carbon monoxide emissions, suggesting that the problems could be due to the poor ability of LD-slag to absorb certain ash components. Use of a mixed bed consisting of 10–50 wt% LD-slag, with the remaining part being silica sand for ash absorption, also worked well. It is concluded that LD-slag could be a very cheap and readily available oxygen-carrying bed material for use in fluidized bed applications.