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.

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.

A comparative study on the pyrolysis of metal- and ash-enriched wood and the combustion properties of the gained char

This study aims to investigate the pyrolysis behaviour of metal-contaminated wood and the combustion properties of char derived from wood pyrolysis. Seven metals (Na, Mg, Ca, Zn, Cd, Pb and Fe(III)) were introduced to willow in cation form by ion-exchange and the thermal behaviour of demineralised samples and samples with additional ash were also investigated. The results show that the char yield increased from 21% to 24-28% and levoglucosan yield in vapour phase decreased from 88% to 62-29% after the addition of inorganic compounds, even though the metal binding capacity of wood varied from one metal ion to another. While char yield seems to be effected mainly by the concentration of the metal ions, levoglucosan yield was more dependent on the ionic species especially when sodium ions were present. When combustion experiments were carried out with char made of the metal enriched wood, two consecutive steps were observed, both effected by the presence of inorganic compounds. The first step was identified as the release and combustion of volatiles, while the second peak of the burning profile is the actual combustion of the fixed carbon. The burnout temperatures, estimated ignition indices and the conversion indicate that the type and not the amount of metal ions were the determining factors during the second step of combustion. © 2012 Published by Elsevier B.V.

Characteristics of the upper phase of bio-oil obtained from co-pyrolysis of sewage sludge with wood, rapeseed and straw

Sewage sludge was pyrolysed with 40% mixed wood, 40% rapeseed and 40% straw. The reason for the mixture of different biomass is to investigate the impact of co-pyrolysis on the upper phase of bio-oil in terms of changes to composition, elemental analysis, viscosity, water content, pH, higher heating value and acid number that could impact on their applications. The biomass was pyrolysed in a laboratory at 450 °C and bio-oil was collected from two cooling traps. The bio-oil obtained from co-pyrolysis of sewage sludge with wood, rapeseed and straw was analysed for composition using the gas chromatography mass spectrometry. The upper phase from the co-pyrolysis process was also characterised for ultimate analysis, higher heating values, water content, viscosity, pH and acid number. There was an increase in the amount of upper phase produced with co-pyrolysis of 40% rapeseed. It was also found that the upper phase from sewage sludge with mixed wood has the highest viscosity, acid number and lowest pH. The bio-oil containing 40% straw was found to have a pH of 6.5 with a very low acid number while the 40% rapeseed was found to have no acid number. Sewage sludge with 40% rapeseed was found to have the highest energy content of 34.8 MJ/kg, 40% straw has 32.5 MJ/kg while the 40% mixed wood pyrolysis oil has the lowest energy content of 31.3 MJ/kg. The 40% rapeseed fraction was found to have the highest water content of 8.2% compared to other fractions.

Application of space-charge electrostatic precipitator for collection of oil mist from pyrolysis gases

A novel electrostatic precipitator CAROLA® is developed for collection of fine oil mists. It operates on the principle of unipolar particle charging in the corona discharge and particle precipitation under the field of space charge. The pilot precipitator was tested at different gas temperatures. It is shown that the increase of gas temperature changes the characteristics of the corona discharge and particle size distribution, especially for droplets sub-micron droplets. The CAROLA® precipitator was used for collection of oil mist from pyrolysis gases at the HALOCLEAN® plant. The flow rate of biomass in the HALOCLEAN® plant was 15-30 kg/h. The particle mass concentration in the raw gas was over 100 g/Nm. The operation voltage of the precipitator was 10-12 kV and corona current up to 0,1 mA. Single stage electrostatic precipitator ensured mass collection efficiency 97-99,5% for pyrolysis oil mist.