Risk assessment methodology for fast breeder reactors /

"ANL/RAS 75-35."

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.

The development and optimisation of a fast pyrolysis process for bio-oil production

A two-tier study is presented in this thesis. The first involves the commissioning of an extant but at the time, unproven bubbling fluidised bed fast pyrolysis unit. The unit was designed for an intended nominal throughput of 300 g/h of biomass. The unit came complete with solids separation, pyrolysis vapour quenching and oil collection systems. Modifications were carried out on various sections of the system including the reactor heating, quenching and liquid collection systems. The modifications allowed for fast pyrolysis experiments to be carried out at the appropriate temperatures. Bio-oil was generated using conventional biomass feedstocks including Willow, beechwood, Pine and Miscanthus. Results from this phase of the research showed however, that although the rig was capable of processing biomass to bio-oil, it was characterised by low mass balance closures and recurrent operational problems. The problems included blockages, poor reactor hydrodynamics and reduced organic liquid yields. The less than optimal performance of individual sections, particularly the feed and reactor systems of the rig, culminated in a poor overall performance of the system. The second phase of this research involved the redesign of two key components of the unit. An alternative feeding system was commissioned for the unit. The feed system included an off the shelf gravimetric system for accurate metering and efficient delivery of biomass. Similarly, a new bubbling fluidised bed reactor with an intended nominal throughput of 500g/h of biomass was designed and constructed. The design leveraged on experience from the initial commissioning phase with proven kinetic and hydrodynamic studies. These units were commissioned as part of the optimisation phase of the study. Also as part of this study, two varieties each, of previously unreported feedstocks namely Jatropha curcas and Moringa olifiera oil seed press cakes were characterised to determine their suitability as feedstocks for liquid fuel production via fast pyrolysis. Consequently, the feedstocks were used for the production of pyrolysis liquids. The quality of the pyrolysis liquids from the feedstocks were then investigated via a number of analytical techniques. The oils from the press cakes showed high levels of stability and reduced pH values. The improvements to the design of the fast pyrolysis unit led to higher mass balance closures and increased organic liquid yields. The maximum liquid yield obtained from the press cakes was from African Jatropha press cake at 66 wt% on a dry basis.

Application of CFD to model fast pyrolysis of biomass

The article deals with the CFD modelling of fast pyrolysis of biomass in an Entrained Flow Reactor (EFR). The Lagrangian approach is adopted for the particle tracking, while the flow of the inert gas is treated with the standard Eulerian method for gases. The model includes the thermal degradation of biomass to char with simultaneous evolution of gases and tars from a discrete biomass particle. The chemical reactions are represented using a two-stage, semi-global model. The radial distribution of the pyrolysis products is predicted as well as their effect on the particle properties. The convective heat transfer to the surface of the particle is computed using the Ranz-Marshall correlation.

CFD modelling of the fast pyrolysis of an in-flight cellulosic particle subjected to convective heat transfer

The pyrolysis of a freely moving cellulosic particle inside a 41.7mgs -1 source continuously fed fluid bed reactor subjected to convective heat transfer is modelled. The Lagrangian approach is adopted for the particle tracking inside the reactor, while the flow of the inert gas is treated with the standard Eulerian method for gases. The model incorporates the thermal degradation of cellulose to char with simultaneous evolution of gases and vapours from discrete cellulosic particles. The reaction kinetics is represented according to the Broido–Shafizadeh scheme. The convective heat transfer to the surface of the particle is solved by two means, namely the Ranz–Marshall correlation and the limit case of infinitely fast external heat transfer rates. The results from both approaches are compared and discussed. The effect of the different heat transfer rates on the discrete phase trajectory is also considered.

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).

Numerical Comparison of the Drag Models of Granular Flows Applied to the Fast Pyrolysis of Biomass

The paper presents a comparison between the different drag models for granular flows developed in the literature and the effect of each one of them on the fast pyrolysis of wood. The process takes place on an 100 g/h lab scale bubbling fluidized bed reactor located at Aston University. FLUENT 6.3 is used as the modeling framework of the fluidized bed hydrodynamics, while the fast pyrolysis of the discrete wood particles is incorporated as an external user defined function (UDF) hooked to FLUENT’s main code structure. Three different drag models for granular flows are compared, namely the Gidaspow, Syamlal O’Brien, and Wen-Yu, already incorporated in FLUENT’s main code, and their impact on particle trajectory, heat transfer, degradation rate, product yields, and char residence time is quantified. The Eulerian approach is used to model the bubbling behavior of the sand, which is treated as a continuum. Biomass reaction kinetics is modeled according to the literature using a two-stage, semiglobal model that takes into account secondary reactions.

The interaction of fast neutrons with shielding and fusion blanket materials

In the present work the neutron emission spectra from a graphite cube, and from natural uranium, lithium fluoride, graphite, lead and steel slabs bombarded with 14.1 MeV neutrons were measured to test nuclear data and calculational methods for D - T fusion reactor neutronics. The neutron spectra measured were performed by an organic scintillator using a pulse shape discrimination technique based on a charge comparison method to reject the gamma rays counts. A computer programme was used to analyse the experimental data by the differentiation unfolding method. The 14.1 MeV neutron source was obtained from T(d,n)4He reaction by the bombardment of T - Ti target with a deuteron beam of energy 130 KeV. The total neutron yield was monitored by the associated particle method using a silicon surface barrier detector. The numerical calculations were performed using the one-dimensional discrete-ordinate neutron transport code ANISN with the ZZ-FEWG 1/ 31-1F cross section library. A computer programme based on Gaussian smoothing function was used to smooth the calculated data and to match the experimental data. There was general agreement between measured and calculated spectra for the range of materials studied. The ANISN calculations carried out with P3 - S8 calculations together with representation of the slab assemblies by a hollow sphere with no reflection at the internal boundary were adequate to model the experimental data and hence it appears that the cross section set is satisfactory and for the materials tested needs no modification in the range 14.1 MeV to 2 MeV. Also it would be possible to carry out a study on fusion reactor blankets, using cylindrical geometry and including a series of concentric cylindrical shells to represent the torus wall, possible neutron converter and breeder regions, and reflector and shielding regions.

A study of the scattering of fast neutrons in large samples

In the present work, the elastic scattering of fast neutrons from iron and concrete samples were studied at incident neutron energies of 14.0 and 14.4 Mev, using a neutron spectrometer based on the associated particle time-of-flight technique. These samples were chosen because of their importance in the design of fusion reactor shielding and construction. Using the S.A.M.E.S. accelerator and the 3 M v Dynamitron accelerator at the Radiation Centre, 14.0 and 14.4 Mev neutrons were produced by the T(d, n)4He reaction at incident deuteron energies of 140 keV and 900 keV mass III ions respectively. The time of origin of the neutron was determined by detecting the associated alpha particles. The samples used were extended flat plates of thicknesses up to 1.73 mean free paths for iron and 2.3 mean free paths for concrete. The associated alpha particles and fast neutrons were detected by means of a plastic scintillator mounted on a fast focused photomultiplier tube. The differential neutron elastic scattering cross-sections were measured for 14 Mev neutrons in various thicknesses of iron and concrete in the angular range from zero to 90°. In addition, the angular distributions of 14.4 Mev neutrons after passing through extended samples of iron were measured at several scattering angles in the same angular range. The measurements obtained for the thin sample of iron were compared with the results of Coon et al. The differential cross-sections for the thin iron sample were also analyzed on the optical model using the computer code RAROMP. For the concrete sample, the angular distribution of the thin sample was compared with the cross-sections calculated from the major constituent elements of concrete, and with the predicted values of the optical model for those elements. No published data could be found to compare with the results of the concrete differential cross-sections. In the case of thick samples of iron and concrete, the number of scattered neutrons were compared with a phenomological calculation based on the continuous slowing down model. The variation of measured cross-sections with sample thickness were found to follow the empirical relation σ = σ0 eαx. By using the universal constant "K", good fits were obtained to the experimental data. In parallel with the work at 14.0 and 14.4 Mev, an associated particle time-of-flight spectrometer was investigated which used the 2H(d,n)3He reaction for 3.02 Mev neutron energy at the incident deuteron energy of 1 Mev.

Upgrading of fast pyrolysis oils by hot filtration

A hot filtration unit downstream of a 1kg/h fluidised bed fast pyrolysis reactor was designed and built. The filter unit operates at 450oC and consists of 1 exchangeable filter candle with reverse pulse cleaning system. Hot filtration experiments up to 7 hours were performed with beech wood as feedstock. It was possible to produce fast pyrolysis oils with a solid content below 0.01 wt%. The additional residence time of the pyrolysis vapours and secondary vapour cracking on the filter cake caused an increase of non-condensable gases at the expense of organic liquid yield. The oils produced with hot filtration showed superior quality properties regarding viscosity than standard pyrolysis oils. The oils were analysed by rotational viscosimetry and gel permeation chromatography before and after accelerated aging. During filtration the separated particulates accumulate on the candle surface and build up the filter cake. The filter cake leads to an increase in pressure drop between the raw gas and the clean gas side of the filter candle. At a certain pressure drop the filter cake has to be removed by reverse pulse cleaning to regenerate the pressure drop. The experiments showed that successful pressure drop recovery was possible during the initial filtration cycles, thereafter further cycles showed minor pressure drop recovery and therefore a steady increase in differential pressure. Filtration with pre-coating the candle to form an additional layer between the filter candle and cake resulted in total removal of the dust cake.

A techno-economic assessment of the use of fast pyrolysis bio-oil from UK energy crops in the production of electricity and combined heat and power

This thesis investigates the cost of electricity generation using bio-oil produced by the fast pyrolysis of UK energy crops. The study covers cost from the farm to the generator’s terminals. The use of short rotation coppice willow and miscanthus as feedstocks was investigated. All costs and performance data have been taken from published papers, reports or web sites. Generation technologies are compared at scales where they have proved economic burning other fuels, rather than at a given size. A pyrolysis yield model was developed for a bubbling fluidised bed fast pyrolysis reactor from published data to predict bio-oil yields and pyrolysis plant energy demands. Generation using diesel engines, gas turbines in open and combined cycle (CCGT) operation and steam cycle plants was considered. The use of bio-oil storage to allow the pyrolysis and generation plants to operate independently of each other was investigated. The option of using diesel generators and open cycle gas turbines for combined heat and power was examined. The possible cost reductions that could be expected through learning if the technology is widely implemented were considered. It was found that none of the systems analysed would be viable without subsidy, but with the current Renewable Obligation Scheme CCGT plants in the 200 to 350 MWe range, super-critical coal fired boilers co-fired with bio-oil, and groups of diesel engine based CHP schemes supplied by a central pyrolysis plant would be viable. It was found that the cost would reduce with implementation and the planting of more energy crops but some subsidy would still be needed to make the plants viable.

Fast pyrolysis and nitrogenolysis of biomass and biogenic residues:production of a sustainable slow release fertiliser

The production of agricultural and horticultural products requires the use of nitrogenous fertiliser that can cause pollution of surface and ground water and has a large carbon footprint as it is mainly produced from fossil fuels. The overall objective of this research project was to investigate fast pyrolysis and in-situ nitrogenolysis of biomass and biogenic residues as an alternative route to produce a sustainable solid slow release fertiliser mitigating the above stated problems. A variety of biomasses and biogenic residues were characterized by proximate analysis, ultimate analysis, thermogravimetric analysis (TGA) and Pyrolysis – Gas chromatography – Mass Spectroscopy (Py–GC–MS) for their potential use as feedstocks using beech wood as a reference material. Beech wood was virtually nitrogen free and therefore suitable as a reference material as added nitrogen can be identified as such while Dried Distillers Grains with Solubles (DDGS) and rape meal had a nitrogen content between 5.5wt.% and 6.1wt.% qualifying them as high nitrogen feedstocks. Fast pyrolysis and in-situ nitrogenolysis experiments were carried out in a continuously fed 1kg/h bubbling fluidized bed reactor at around 500°C quenching the pyrolysis vapours with isoparaffin. In-situ nitrogenolysis experiments were performed by adding ammonia gas to the fast pyrolysis reactor at nominal nitrogen addition rates between 5wt.%C and 20wt.%C based on the dry feedstock’s carbon content basis. Mass balances were established for the processing experiments. The fast pyrolysis and in-situ nitrogenolysis products were characterized by proximate analysis, ultimate analysis and GC– MS. High liquid yields and good mass balance closures of over 92% were obtained. The most suitable nitrogen addition rate for the in-situ nitrogenolysis experiments was determined to be 12wt.%C on dry feedstock carbon content basis. However, only a few nitrogen compounds that were formed during in-situ nitrogenolysis could be identified by GC–MS. A batch reactor process was developed to thermally solidify the fast pyrolysis and in-situ nitrogenolysis liquids of beech wood and Barley DDGS producing a brittle solid product. This was obtained at 150°C with an addition of 2.5wt% char (as catalyst) after a processing time of 1h. The batch reactor was also used for modifying and solidifying fast pyrolysis liquids derived from beech wood by adding urea or ammonium phosphate as post processing nitrogenolysis. The results showed that this type of combined approach was not suitable to produce a slow release fertiliser, because the solid product contained up to 65wt.% of highly water soluble nitrogen compounds that would be released instantly by rain. To complement the processing experiments a comparative study via Py–GC–MS with inert and reactive gas was performed with cellulose, hemicellulose, lignin and beech wood. This revealed that the presence of ammonia gas during analytical pyrolysis did not appear to have any direct impact on the decomposition products of the tested materials. The chromatograms obtained showed almost no differences between inert and ammonia gas experiments indicating that the reaction between ammonia and pyrolysis vapours does not occur instantly. A comparative study via Fourier Transformed Infrared Spectroscopy of solidified fast pyrolysis and in-situ nitrogenolysis products showed that there were some alterations in the spectra obtained. A shift in frequencies indicating C=O stretches typically related to the presence of carboxylic acids to C=O stretches related to amides was observed and no double or triple bonded nitrogen was detected. This indicates that organic acids reacted with ammonia and that no potentially harmful or non-biodegradable triple bonded nitrogen compounds were formed. The impact of solid slow release fertiliser (SRF) derived from pyrolysis and in-situ nitrogenolysis products from beech wood and Barley DDGS on microbial life in soils and plant growth was tested in cooperation with Rothamsted Research. The microbial incubation tests indicated that microbes can thrive on the SRFs produced, although some microbial species seem to have a reduced activity at very high concentrations of beech wood and Barley DDGS derived SRF. The plant tests (pot trials) showed that the application of SRF derived from beech wood and barley DDGS had no negative impact on germination or plant growth of rye grass. The fertilizing effect was proven by the dry matter yields in three harvests after 47 days, 89 days and 131 days. The findings of this research indicate that in general a slow release fertiliser can be produced from biomass and biogenic residues by in-situ nitrogenolysis. Nevertheless the findings also show that additional research is necessary to identify which compounds are formed during this process.

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.