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.

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.

Techno-economic assessment and uncertainty analysis of thermochemical processes for second generation biofuels

Biomass-To-Liquid (BTL) is one of the most promising low carbon processes available to support the expanding transportation sector. This multi-step process produces hydrocarbon fuels from biomass, the so-called “second generation biofuels” that, unlike first generation biofuels, have the ability to make use of a wider range of biomass feedstock than just plant oils and sugar/starch components. A BTL process based on gasification has yet to be commercialized. This work focuses on the techno-economic feasibility of nine BTL plants. The scope was limited to hydrocarbon products as these can be readily incorporated and integrated into conventional markets and supply chains. The evaluated BTL systems were based on pressurised oxygen gasification of wood biomass or bio-oil and they were characterised by different fuel synthesis processes including: Fischer-Tropsch synthesis, the Methanol to Gasoline (MTG) process and the Topsoe Integrated Gasoline (TIGAS) synthesis. This was the first time that these three fuel synthesis technologies were compared in a single, consistent evaluation. The selected process concepts were modelled using the process simulation software IPSEpro to determine mass balances, energy balances and product distributions. For each BTL concept, a cost model was developed in MS Excel to estimate capital, operating and production costs. An uncertainty analysis based on the Monte Carlo statistical method, was also carried out to examine how the uncertainty in the input parameters of the cost model could affect the output (i.e. production cost) of the model. This was the first time that an uncertainty analysis was included in a published techno-economic assessment study of BTL systems. It was found that bio-oil gasification cannot currently compete with solid biomass gasification due to the lower efficiencies and higher costs associated with the additional thermal conversion step of fast pyrolysis. Fischer-Tropsch synthesis was the most promising fuel synthesis technology for commercial production of liquid hydrocarbon fuels since it achieved higher efficiencies and lower costs than TIGAS and MTG. None of the BTL systems were competitive with conventional fossil fuel plants. However, if government tax take was reduced by approximately 33% or a subsidy of £55/t dry biomass was available, transport biofuels could be competitive with conventional fuels. Large scale biofuel production may be possible in the long term through subsidies, fuels price rises and legislation.

Heat and mass transfer in membrane distillation used for desalination with slip flow

A theoretical model for the transport phenomena in an air gap membrane distillation is presented. The model is based on the conservation equations for the mass, momentum, energy and species within the feed water solution as well as on the mass and energy balances on the membrane sides. The slip flow occurs due to the hydrophobic properties of the membrane. The slip boundary condition applied on the feed saline solution-membrane interface is taken into consideration showing its effects on process parameters particularly permeate flow, heat transfer coefficient and thermal efficiency. The theoretical model was validated with available experimental data and was found to be in good agreement especially when the slip condition is introduced. Increasing slip length from zero to 200 μm was found to increase the permeate flux and the thermal efficiency by 33% and 1.7% respectively.