Characterization of oxide layers grown on D9 austenitic stainless steel in lead bismuth eutectic

Lead bismuth eutectic (LBE) is a possible coolant for fast reactors and targets in spallation neutron sources. Its low melting point, high evaporation point, good thermal conductivity, low reactivity, and good neutron yield make it a safe and high performance coolant in radiation environments. The disadvantage is that it is a corrosive medium for most steels and container materials. This study was performed to evaluate the corrosion behavior of the austenitic stainless steel D9 in oxygen controlled LBE. In order to predict the corrosion behavior of steel in this environment detailed analyses have to be performed on the oxide layers formed on these materials and various other relevant materials upon exposure to LBE. In this study the corrosion/oxidation of D9 stainless steel in LBE was investigated in great detail. The oxide layers formed were characterized using atomic force microscopy, magnetic force microscopy, nanoindentation, and scanning electron microscopy with wavelength-dispersive spectroscopy (WDS) to understand the corrosion and oxidation mechanisms of D9 stainless steel in contact with the LBE. What was previously believed to be a simple double oxide layer was identified here to consist of at least 4 different oxide layers. It was found that the inner most oxide layer takes over the grain structure of what used to be the bulk steel material while the outer oxide layer consists of freshly grown oxides with a columnar structure. These results lead to a descriptive model of how these oxide layers grow on this steel under the harsh environments encountered in these applications.

CFD modelling of the fast pyrolysis of biomass in fluidised bed reactors. Part B: Heat, momentum and mass transport in bubbling fluidised beds

The fluid–particle interaction inside a 150 g/h fluidised bed reactor is modelled. The biomass particle is injected into the fluidised bed and the heat, momentum and mass transport from the fluidising gas and fluidised sand is modelled. The Eulerian approach is used to model the bubbling behaviour of the sand, which is treated as a continuum. Heat transfer from the bubbling bed to the discrete biomass particle, as well as biomass reaction kinetics are modelled according to the literature. The particle motion inside the reactor is computed using drag laws, dependent on the local volume fraction of each phase. FLUENT 6.2 has been used as the modelling framework of the simulations with the whole pyrolysis model incorporated in the form of user-defined function (UDF). The study completes the fast pyrolysis modelling in bubbling fluidised bed reactors.

CFD modelling of the fast pyrolysis of biomass in fluidised bed reactors, Part A: Eulerian computation of momentum transport in bubbling fluidised beds

The fluid–particle interaction inside a 150 g/h fluidised bed reactor is modelled. The biomass particle is injected into the fluidised bed and the momentum transport from the fluidising gas and fluidised sand is modelled. The Eulerian approach is used to model the bubbling behaviour of the sand, which is treated as a continuum. The particle motion inside the reactor is computed using drag laws, dependent on the local volume fraction of each phase, according to the literature. FLUENT 6.2 has been used as the modelling framework of the simulations with a completely revised drag model, in the form of user defined function (UDF), to calculate the forces exerted on the particle as well as its velocity components. 2-D and 3-D simulations are tested and compared. The study is the first part of a complete pyrolysis model in fluidised bed reactors.

CFD modelling of the fast pyrolysis of biomass in fluidised bed reactors: modelling the impact of biomass shrinkage

The fluid–particle interaction and the impact of shrinkage on pyrolysis of biomass inside a 150 g/h fluidised bed reactor is modelled. Two 500 View the MathML sourcem in diameter biomass particles are injected into the fluidised bed with different shrinkage conditions. The two different conditions consist of (1) shrinkage equal to the volume left by the solid devolatilization, and (2) shrinkage parameters equal to approximately half of particle volume. The effect of shrinkage is analysed in terms of heat and momentum transfer as well as product yields, pyrolysis time and particle size considering spherical geometries. The Eulerian approach is used to model the bubbling behaviour of the sand, which is treated as a continuum. Heat transfer from the bubbling bed to the discrete biomass particle, as well as biomass reaction kinetics are modelled according to the literature. The particle motion inside the reactor is computed using drag laws, dependent on the local volume fraction of each phase. FLUENT 6.2 has been used as the modelling framework of the simulations with the whole pyrolysis model incorporated in the form of user defined function (UDF).

Comparison of the effect of pre-treatment and catalysts on liquid quality from fast pyrolysis of biomass

The overall objective of this work was to compare the effect of pre-treatment and catalysts on the quality of liquid products from fast pyrolysis of biomass. This study investigated the upgrading of bio-oil in terms of its quality as a bio-fuel and/or source of chemicals. Bio-oil used directly as a biofuel for heat or power needs to be improved particularly in terms of temperature sensitivity, oxygen content, chemical instability, solid content, and heating values. Chemicals produced from bio-oil need to be able to meet product specifications for market acceptability. There were two main objectives in this research. The first was to examine the influence of pre-treatment of biomass on the fast pyrolysis process and liquid quality. The relationship between the method of pre-treatment of biomass feedstock to fast pyrolysis oil quality was studied. The thermal decomposition behaviour of untreated and pretreated feedstocks was studied by using a TGA (thermogravimetric analysis) and a Py-GC/MS (pyroprobe-gas chromatography/mass spectrometry). Laboratory scale reactors (100g/h, 300g/h, 1kg/h) were used to process untreated and pretreated feedstocks by fast pyrolysis. The second objective was to study the influence of numerous catalysts on fast pyrolysis liquids from wheat straw. The first step applied analytical pyrolysis (Py-GC/MS) to determine which catalysts had an effect on fast pyrolysis liquid, in order to select catalysts for further laboratory fast pyrolysis. The effect of activation, temperature, and biomass pre-treatment on catalysts were also investigated. Laboratory experiments were also conducted using the existing 300g/h fluidised bed reactor system with a secondary catalytic fixed bed reactor. The screening of catalysts showed that CoMo was a highly active catalyst, which particularly reduced the higher molecular weight products of fast pyrolysis. From these screening tests, CoMo catalyst was selected for larger scale laboratory experiments. With reference to the effect of pre-treatment work on fast pyrolysis process, a significant effect occurred on the thermal decomposition of biomass, as well as the pyrolysis products composition, and the proportion of key components in bio-oil. Torrefaction proved to have a mild influence on pyrolysis products, when compared to aquathermolysis and steam pre-treatment.

Fast pyrolysis of biomass in a circulating fluidised bed reactor

The objective of this work was to design, construct, test and operate a novel circulating fluid bed fast pyrolysis reactor system for production of liquids from biomass. The novelty lies in incorporating an integral char combustor to provide autothermal operation. A reactor design methodology was devised which correlated input parameters to process variables, namely temperature, heat transfer and gas/vapour residence time, for both the char combustor and biomass pyrolyser. From this methodology a CFB reactor was designed with integral char combustion for 10 kg/h biomass throughput. A full-scale cold model of the CFB unit was constructed and tested to derive suitable hydrodynamic relationships and performance constraints. Early difficulties encountered with poor solids circulation and inefficient product recovery were overcome by a series of modifications. A total of 11 runs in a pyrolysis mode were carried out with a maximum total liquids yield of 61.50% wt on a maf biomass basis, obtained at 500°C and with 0.46 s gas/vapour residence time. This could be improved by improved vapour recovery by direct quenching up to an anticipated 75 % wt on a moisture-and-ash-free biomass basis. The reactor provides a very high specific throughput of 1.12 - 1.48 kg/hm2 and the lowest gas-to-feed ratio of 1.3 - 1.9 kg gas/kg feed compared to other fast pyrolysis processes based on pneumatic reactors and has a good scale-up potential. These features should provide significant capital cost reduction. Results to date suggest that the process is limited by the extent of char combustion. Future work will address resizing of the char combustor to increase overall system capacity, improvement in solid separation and substantially better liquid recovery. Extended testing will provide better evaluation of steady state operation and provide data for process simulation and reactor modeling.

Impact of Miscanthus x giganteus senescence times on fast pyrolysis bio-oil quality

In this study the impact of senescence and harvest time in Miscanthus on the quality of fast pyrolysis liquid (bio-oil) was investigated. Bio-oil was produced using a 1kgh fast pyrolysis reactor to obtain a quantity of bio-oil comparable with existing industrial reactors. Bio-oil stability was measured using viscosity, water content, pH and heating value changes under specific conditions. Plant developmental characteristics were significantly different (P=0.05) between all harvest points. The stage of crop senescence was correlated with nutrient remobilisation (N, P, K; r=0.9043, r=0.9920, r=0.9977 respectively) and affected bio-oil quality. Harvest time and senescence impacted bio-oil quality and stability. For fast pyrolysis processing of Miscanthus, the harvest time of Miscanthus can be extended to cover a wider harvest window whilst still maintaining bio-oil quality but this may impact mineral depletion in, and long term sustainability of, the crop unless these minerals can be recycled. © 2012 Elsevier Ltd.

Thermochemical characterisation of various biomass feedstock and bio-oil generated by fast pyrolysis

The projected decline in fossil fuel availability, environmental concerns, and security of supply attract increased interest in renewable energy derived from biomass. Fast pyrolysis is a possible thermochemical conversion route for the production of bio-oil, with promising advantages. The purpose of the experiments reported in this thesis was to extend our understanding of the fast pyrolysis process for straw, perennial grasses and hardwoods, and the implications of selective pyrolysis, crop harvest and storage on the thermal decomposition products. To this end, characterisation and laboratory-scale fast pyrolysis were conducted on the available feedstocks, and their products were compared. The variation in light and medium volatile decomposition products was investigated at different pyrolysis temperatures and heating rates, and a comparison of fast and slow pyrolysis products was conducted. Feedstocks from different harvests, storage durations and locations were characterised and compared in terms of their fuel and chemical properties. A range of analytical (e.g. Py-GC-MS and TGA) and processing equipment (0.3 kg/h and 1.0 kg/h fast pyrolysis reactors and 0.15 kg slow pyrolysis reactor) was used. Findings show that the high bio-oil and char heating value, and low water content of willow short rotation coppice (SRC) make this crop attractive for fast pyrolysis processing compared to the other investigated feedstocks in this project. From the analytical sequential investigation of willow SRC, it was found that the volatile product distribution can be tailored to achieve a better final product, by a variation of the heating rate and temperature. Time of harvest was most influential on the fuel properties of miscanthus; overall the late harvest produced the best fuel properties (high HHV, low moisture content, high volatile content, low ash content), and storage of the feedstock reduced the moisture and acid content.

Fast pyrolysis of biomass for energy and fuels

Bioenergy is now accepted as having the potential to provide the major part of the projected renewable energy provisions of the future as biofuels in the form of gas, liquid or solid fuels or electricity and heat. There are three main routes to providing these biofuels — thermal conversion, biological conversion and physical conversion — all of which employ a range of chemical reactor configurations and process designs. This paper focuses on fast pyrolysis from which the liquid, often referred to as bio-oil, can be used on-site or stored or transported to centralised and/or remote user facilities for utilisation for example as a fuel, or further processing to biofuels and/or chemicals. This offers the potential for system optimisation, much greater economies of scale and exploitation of the concepts of biorefineries. The technology of fast pyrolysis is described, particularly the reactors that have been developed to provide the necessary conditions to optimise performance. The primary liquid product is characterised, as well as the secondary products of electricity and/or heat, liquid fuels and a considerable number of chemicals. The main technical and non-technical barriers to the market deployment of the various technologies are identified and briefly discussed.