The morphology of spray-dried particles

Samples of Various industrial or pilot plant spray-dried materials were obtained from manufacturers together with details of drying conditions and feed concentrations. The samples were subjected to qualitative and semi-quantitative examination to identify structural and morphological features. The results were related to measured bulk physical properties and to drying conditions. Single particles were produced in a convective drying process Analogous to spray drying, in which different solids or mixtures of solids were dried from solutions, slurries or pastes as single suspended droplets. The localized chemical and physical structures were analysed and in some cases the retention of volatiles monitored. The results were related to experimental conditions, viz.; air temperature, initial solids concentration and the degree of feed aeration. Three distinct categories of particle morphology were identified, i.e.; crystalline, skin-forming and agglomerate. Each category is evidence of a characteristic drying behaviour which is dependent on initial solids concentration. the degree of feed aeration, and drying temperature. Powder flow ability, particle and bulk density, particle-size, particle friability, and the retention of volatiles bear a direct relationship to morphological structure. Morphologies of multicomponent mixtures were complex, but the respective migration rates of the solutes were dependent on drying temperature. Gas-film heat and SDSS transfer coefficients of single pure liquid droplets were also measured over a temperature range of 50•C to 200•C under forced convection. Balanced transfer rates were obtained attributed to droplet instability or oscillation within the airflow, demonstrated in associated work with single free-flight droplets. The results are of relevance to drier optimisation and to the optimisation of product characteristics, e.g.; particle strength and essential volatiles-retention, in convective drying.

Ablative pyrolysis of biomass

The primary objectives of this work were to design, construct, test and operate a novel ablative pyrolysis reactor and product recovery system. Other key objectives included the development of an ablative pyrolysis reactor design methodology, mathematical modelling of the ablation process and measurement of empirical ablation rate data at 500°C. The constructed reactor utilised a rotating blade approach to achieve particle ablation in a 258mm internal diameter reactor. By fulfilling the key requirements of high relative motion and high contact pressure, pine wood particles of maximum size 6.35 mm were successfully ablated.Sixteen experiments were carried out: five initial commissioning experiments were used to test the rotating blade concept and to solve char separation problems. Mass balances were obtained for the other eleven experiments with good closures. Based on ablatively pyrolysed dry wood, a maximum organic liquid yield of 65.9 wt% was achieved with corresponding yields of 12.4 wt% char, 11.5 wt% water and 9.2 wt% non-condensable gas. Reactor throughputs of 2 kg/h dry ablated wood were achieved at 600°C. The theoretical ablative pyrolysis reactor design methodology was simplified and improved based upon empirical data derived from wood rod ablation experiments. Yields of chemicals were qualitatively similar to those of other fast pyrolysis processes.The product recovery system, comprising hot char removal, liquids collection in two ice-cooled condensers followed by gas filtration and drying, gave good mass balance closures. The most significant problem was char separation and removal from the reactor. This was solved by using a nitrogen blow line. In general, the reactor and product collection systems performed well.Future development of the reactor would involve modification of the reactor feed tube to allow the reactor residence time to be reduced and testing of the rotating blade approach with different blade angles, configurations and numbers of blades.

Technical and economic simulation of biomass pyrolysis processes for fuels and electricity

There is considerable concern over the increased effect of fossil fuel usage on the environment and this concern has resulted in an effort to find alternative, environmentally friendly energy sources. Biomass is an available alternative resource which may be converted by flash pyrolysis to produce a crude liquid product that can be used directly to substitute for conventional fossil fuels or upgraded to a higher quality fuel. Both the crude and upgraded products may be utilised for power generation. A computer program, BLUNT, has been developed to model the flash pyrolysis of biomass with subsequent upgrading, refining or power production. The program assesses and compares the economic and technical opportunities for biomass thermochemical conversion on the same basis. BLUNT works by building up a selected processing route from a number of process steps through which the material passes sequentially. Each process step has a step model that calculates the mass and energy balances, the utilities usage and the capital cost for that step of the process. The results of the step models are combined to determine the performance of the whole conversion route. Sample results from the modelling are presented in this thesis. Due to the large number of possible combinations of feeds, conversion processes, products and sensitivity analyses a complete set of results is impractical to present in a single publication. Variation of the production costs for the available products have been illustrated based on the cost of a wood feedstock. The effect of selected macroeconomic factors on the production costs of bio-diesel and gasoline are also given.

Catalytic pyrolysis of agricultural residues for bio-oil production

Agricultural residues from Thailand, namely stalk and rhizome of cassava plants, were employed as raw materials for bio-oil production via fast pyrolysis technology. There were two main objectives of this project. The first one was to determine the optimum pyrolysis temperature for maximising the organics yield and to investigate the properties of the bio-oils produced. To achieve this objective, pyrolysis experiments were conducted using a bench-scale (150 g/h) reactor system, followed by bio-oil analysis. It was found that the reactor bed temperature that could give the highest organics yield for both materials was 490±15ºC. At all temperatures studied, the rhizome gave about 2-4% higher organics yields than the stalk. The bio-oil derived from the rhizome had lower oxygen content, higher calorific value and better stability, thus indicating better quality than that produced from the stalk. The second objective was to improve the bio-oil properties in terms of heating value, viscosity and storage stability by the incorporation of catalyst into the pyrolysis process. Catalytic pyrolysis was initially performed in a micro-scale reactor to screen a large number of catalysts. Subsequently, seven catalysts were selected for experiments with larger-scale (150 g/h) pyrolysis unit. The catalysts were zeolite and related materials (ZSM-5, Al-MCM-41 and Al-MSU-F), commercial catalysts (Criterion-534 and MI-575), copper chromite and ash. Additionally, the combination of two catalysts in series was investigated. These were Criterion-534/ZSM-5 and Al-MSU-F/ZSM-5. The results showed that all catalysts could improve the bio-oils properties as they enhanced cracking and deoxygenation reactions and in some cases such as ZSM-5, Criterion-534 and Criterion-534/ZSM-5, valuable chemicals like hydrocarbons and light phenols were produced. The highest concentration of these compounds was obtained with Criterion-534/ZSM-5.

Upgrading biomass fast pyrolysis liquids

A comprehensive examination is made of the characteristics and quality requirements of bio-oil from fast pyrolysis of biomass. This considers all aspects of the special characteristics of bio-oil – how they are created and the solutions available to help meet requirements for utilisation. Particular attention is paid to chemical and catalytic upgrading including synthesis gas and hydrogen production which has seen a wide range of new research activities and also more limited attention to chemicals recovery. An appreciation of the potential for bio-oil to meet a broad spectrum of applications in renewable energy has led to a significantly increased R&D activity that has focused on addressing liquid quality issues both for direct use for heat and power and indirect use for biofuels and green chemicals. This increased activity is evident in North America, Europe and Asia with many new entrants as well as expansion of existing activities. The only disappointment is the more limited industrial development and also deployment of fast pyrolysis processes that are necessary to provide the basic bio-oil raw material.

Spray drier simulation and air flow pattern studies

The literature pertaining to the key stages of spray drying has been reviewed in the context of the mathematical modelling of drier performance. A critical review is also presented of previous spray drying models. A new mathematical model has been developed for prediction of spray drier performance. This is applicable to slurries of rigid, porous crust-forming materials to predict trajectories and drying profiles for droplets with a distribution of sizes sprayed from a centrifugal pressure nozzle. The model has been validated by comparing model predictions to experimental data from a pilot-scale counter-current drier and from a full-scale co-current drier. For the latter, the computed product moisture content was within 2%, and the computed air exit temperature within 10oC of experimental data. Air flow patterns have been investigated in a 1.2m diameter transparent countercurrent spray tower by flow visualisation. Smoke was introduced into various zones within the tower to trace the direction, and gauge the intensity, of the air flow. By means of a set of variable-angle air inlet nozzles, a variety of air entry configurations was investigated. The existence of a core of high rotational and axial velocity channelling up the axis of the tower was confirmed. The stability of flow within the core was found to be strongly dependent upon the air entry arrangement. A probe was developed for the measurement of air temperature and humidity profiles. This was employed for studying evaporation of pure water drops in a 1.2m diameter pilot-scale counter-current drier. A rapid approach to the exit air properties was detected within a 1m distance from the air entry ports. Measured radial profiles were found to be virtually flat but, from the axial profiles, the existence of plug-flow, well-mixed-flow and some degree of air short-circuiting can be inferred. The model and conclusions should assist in the improved design and optimum operation of industrial spray driers.

Development of multiphase and multiscale mathematical models for thermal spray process

High velocity oxyfuel (HVOF) thermal spraying is one of the most significant developments in the thermal spray industry since the development of the original plasma spray technique. The first investigation deals with the combustion and discrete particle models within the general purpose commercial CFD code FLUENT to solve the combustion of kerosene and couple the motion of fuel droplets with the gas flow dynamics in a Lagrangian fashion. The effects of liquid fuel droplets on the thermodynamics of the combusting gas flow are examined thoroughly showing that combustion process of kerosene is independent on the initial fuel droplet sizes. The second analysis copes with the full water cooling numerical model, which can assist on thermal performance optimisation or to determine the best method for heat removal without the cost of building physical prototypes. The numerical results indicate that the water flow rate and direction has noticeable influence on the cooling efficiency but no noticeable effect on the gas flow dynamics within the thermal spraying gun. The third investigation deals with the development and implementation of discrete phase particle models. The results indicate that most powder particles are not melted upon hitting the substrate to be coated. The oxidation model confirms that HVOF guns can produce metallic coating with low oxidation within the typical standing-off distance about 30cm. Physical properties such as porosity, microstructure, surface roughness and adhesion strength of coatings produced by droplet deposition in a thermal spray process are determined to a large extent by the dynamics of deformation and solidification of the particles impinging on the substrate. Therefore, is one of the objectives of this study to present a complete numerical model of droplet impact and solidification. The modelling results show that solidification of droplets is significantly affected by the thermal contact resistance/substrate surface roughness.

Estimation of the production cost of fast pyrolysis bio-oil

A number of papers and reports covering the techno-economic analysis of bio-oil production has been published. These have had different scopes, use different feedstocks and reflected national cost structures. This paper reviews and compares their cost estimates and the experimental results that underpin them. A comprehensive cost and performance model was produced based on consensus data from the previous studies or stated scenarios where data is not available that reflected UK costs. The model takes account sales of bio-char that is a co-product of pyrolysis and the electricity consumption of the pyrolysis plant and biomass pre-processing plants. It was concluded that it should be able to produce bio-oil in the UK from energy crops for a similar cost as distillate fuel oil. It was also found that there was little difference in the processing cost for woodchips and baled miscanthus. © 2011 Elsevier Ltd.

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.

Effect of the temperature on the composition of lignin pyrolysis products

The temperature dependence of the pyrolysis products of two types of lignin (Alcell lignin and Asian lignin) was investigated using pyrolysis-gas chromatography-mass spectrometry (PyGC-MS). About 50 compounds were identified and quantified for each type of lignin over a temperature range of 400-800C. The maximum yield of phenolic compounds was obtained at 600C for both lignins, which was 17.2% for Alcell lignin and 15.5% for Asian lignin. Most of the phenolic compounds had an individual yield of less than 1%; however, for Alcell lignin, 5-hydroxyvanillin was the highest yield at 4.29 wt%on dry ash-free lignin, and for Asian lignin, 2-methoxy-4-vinylphenol was the highest yield at 4.15 wt % on dry ash-free lignin.

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.

Analysis of transport costs for energy crops for use in biomass pyrolysis plant networks

Fast pyrolysis of biomass produces a liquid bio-oil that can be used for electricity generation. Bio-oil can be stored and transported so it is possible to decouple the pyrolysis process from the generation process. This allows each process to be separately optimised. It is necessary to have an understanding of the transport costs involved in order to carry out techno-economic assessments of combinations of remote pyrolysis plants and generation plants. Published fixed and variable costs for freight haulage have been used to calculate the transport cost for trucks running between field stores and a pyrolysis plant. It was found that the key parameter for estimating these costs was the number of round trips a day a truck could make rather than the distance covered. This zone costing approach was used to estimate the transport costs for a range of pyrolysis plants size for willow woodchips and baled miscanthus. The possibility of saving transport costs by producing bio-oil near to the field stores and transporting the bio-oil to a central plant was investigated and it was found that this would only be cost effective for large generation plants.

Review of fast pyrolysis of biomass and product upgrading

This paper provides an updated review on fast pyrolysis of biomass for production of a liquid usually referred to as bio-oil. The technology of fast pyrolysis is described including the major reaction systems. The primary liquid product is characterised by reference to the many properties that impact on its use. These properties have caused increasingly extensive research to be undertaken to address properties that need modification and this area is reviewed in terms of physical, catalytic and chemical upgrading. Of particular note is the increasing diversity of methods and catalysts and particularly the complexity and sophistication of multi-functional catalyst systems. It is also important to see more companies involved in this technology area and increased take-up of evolving upgrading processes. © 2011 Elsevier Ltd.

Sequential pyrolysis and catalytic low temperature reforming of wheat straw

Aim of the work is the implementation of a low temperature reforming (LT reforming) unit downstream the Haloclean pyrolyser in order to enhance the heating value of the pyrolysis gas. Outside the focus of this work was to gain a synthesis gas quality for further use. Temperatures between 400 °C and 500 °C were applied. A commercial pre-reforming catalyst on a nickel basis from Südchemie was chosen for LT reforming. As biogenic feedstock wheat straw has been used. Pyrolysis of wheat straw at 450 °C by means of Haloclean pyrolysis leads to 28% of char, 50% of condensate and 22% of gas. The condensate separates in a water phase and an organic phase. The organic phase is liquid, but contains viscous compounds. These compounds could underlay aging and could lead to solid tars which can cause post processing problems. Therefore, the implementation of a catalytic reformer is not only of interest from an energetic point of view, it is generally interesting for tar conversion purposes after pyrolysis applications. By using a fixed bed reforming unit at 450–490 °C and space velocities about 3000 l/h the pyrolysis gas volume flow could be increased to about 58%. This corresponds to a decrease of the yields of condensates by means of catalysis up to 17%, the yield of char remains unchanged, since pyrolysis conditions are the same. The heating value in the pyrolysis gas could be increased by the factor of 1.64. Hydrogen concentrations up to 14% could be realised.