Thermo-chemical behaviour and chemical product formation from Polar seaweeds during intermediate pyrolysis

Fundamental analytical pyrolysis studies of biomass from Polar seaweeds, which exhibit a different biomass composition than terrestrial and micro-algae biomass were performed via thermogravimetric analysis (TGA) and pyrolysis-gas chromatography/mass-spectrometry (Py-GC/MS). The main reason for this study is the adaptation of these species to very harsh environments making them an interesting source for thermo-chemical processing for bioenergy generation and production of biochemicals via intermediate pyrolysis. Several macroalgal species from the Arctic region Kongsfjorden, Spitsbergen/Norway (Prasiola crispa, Monostroma arcticum, Polysiphonia arctica, Devaleraea ramentacea, Odonthalia dentata, Phycodrys rubens, Sphacelaria plumosa) and from the Antarctic peninsula, Potter Cove King George Island (Gigartina skottsbergii, Plocamium cartilagineum, Myriogramme manginii, Hymencladiopsis crustigena, Kallymenia antarctica) were investigated under intermediate pyrolysis conditions. TGA of the Polar seaweeds revealed three stages of degradation representing dehydration, devolatilization and decomposition of carbonaceous solids. The maximum degradation temperatures Prasiola crispa were observed within the range of 220-320 C and are lower than typically obtained by terrestrial biomass, due to divergent polysaccharide compositions. Biochar residues accounted for 33-46% and ash contents of 27-45% were obtained. Identification of volatile products by Py-GC/MS revealed a complexity of generated chemical compounds and significant differences between the species. A widespread occurrence of aromatics (toluene, styrene, phenol and 4-methylphenol), acids (acetic acid, benzoic acid alkyl ester derivatives, 2-propenoic acid esters and octadecanoic acid octyl esters) in pyrolysates was detected. Ubiquitous furan-derived products included furfural and 5-methyl-2-furaldehyde. As a pyran-derived compound maltol was obtained by one red algal species (P. rubens) and the monosaccharide d-allose was detected in pyrolysates in one green algal (P. crispa). Further unique chemicals detected were dianhydromannitol from brown algae and isosorbide from green algae biomass. In contrast, the anhydrosugar levoglucosan and the triterpene squalene was detected in a large number of pyrolysates analysed. © 2013 Elsevier B.V. All rights reserved.

Investigation into the performance and emissions of a stationary diesel engine fuelled by sewage sludge intermediate pyrolysis oil and biodiesel blends

This paper studies the characteristics of blends of biodiesel and a new type of SSPO (sewage sludge derived intermediate pyrolysis oil) in various ratios, and evaluates the application of such blends in an unmodified Lister diesel engine. The engine performance and exhaust emissions were investigated and compared to those of diesel and biodiesel. The engine injectors were inspected and tested after the experiment. The SSPO-biodiesel blends were found to have comparable heating values to biodiesel, but relatively high acidity and carbon residue. The diesel engine has operated with a 30/70 SSPO-biodiesel blend and a 50/50 blend for up to 10h and there was no apparent deterioration in operation observed. It is concluded that with 30% SSPO, the engine gives better overall performance and fuel consumption than with 50% SSPO. The exhaust temperatures of 30% SSPO and 50% SSPO are similar, but 30% SSPO gives relatively lower NO emission than 50% SSPO. The CO and smoke emissions are lower with 50% SSPO than with 30% SSPO. The injectors of the engine operated with SSPO blends were found to have heavy carbon deposition and noticeably reduced opening pressure, which may lead to deteriorated engine performance and exhaust emissions in extended operation. © 2013 Elsevier Ltd.

Upgrading biomass fast pyrolysis liquids

A comprehensive examination is made of the characteristics and quality requirements of bio-oil from fast pyrolysis of biomass. 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. © 2012 American Institute of Chemical Engineers (AIChE).

Results of the IEA round robin on viscosity and stability of fast pyrolysis bio-oils

An international round robin study of the stability of fast pyrolysis bio-oil was undertaken. Fifteen laboratories in five different countries contributed. Two bio-oil samples were distributed to the laboratories for stability testing and further analysis. The stability test was defined in a method provided with the bio-oil samples. Viscosity measurement was a key input. The change in viscosity of a sealed sample of bio-oil held for 24 h at 80 °C was the defining element of stability. Subsequent analyses included ultimate analysis, density, moisture, ash, filterable solids, and TAN/pH determination, and gel permeation chromatography. The results showed that kinematic viscosity measurement was more generally conducted and more reproducibly performed versus dynamic viscosity measurement. The variation in the results of the stability test was great and a number of reasons for the variation were identified. The subsequent analyses proved to be at the level of reproducibility, as found in earlier round robins on bio-oil analysis. Clearly, the analyses were more straightforward and reproducible with a bio-oil sample low in filterable solids (0.2%), compared to one with a higher (2%) solids loading. These results can be helpful in setting standards for use of bio-oil, which is just coming into the marketplace. © 2012 American Chemical Society.

Catalytic intermediate pyrolysis of Brunei rice husk for bio-oil production

Rice husks from Brunei were subjected via intermediate pyrolysis for bio-oil production. Two main objectives were set out for this study. The application of intermediate pyrolysis on Brunei rice husk for the production of bio-oil is the main objective of this experiment. Characterisation of the rice husks was inclusive as a pre-requisite step to assess the suitability as feedstock for production of liquid fuels. Following on from the characterisation results, a temperature of 450°C was established as the optimum temperature for the production of bio-oil. A homogenous bio-oil was obtained from the pyrolysis of dry rice husk, and the physicochemical properties and chemical compositions were analysed. The second objective is the introduction of catalysts into the pyrolysis process which aims to improve the bio-oil quality, and maximise the desired liquid bio-oil properties. The incorporation of the catalysts was done via a fixed tube reactor into the pyrolysis system. Ceramic monoliths were used as the catalyst support, with montmorillonite clay as a binder to attach the catalysts onto the catalyst support. ZSM-5, Al-MCM-41, Al-MSU-F and Brunei rice husk ash (BRHA) together with its combination were adopted as catalysts. Proposed criterions dictated the selection of the best catalysts, subsequently leading to the optimisation process for bio-oil production. ZSM-5/Al-MCM-41 proved the most desirable catalyst, which increases the production of aromatics and phenols, decreased the organic acids and improved the physicochemical properties such as the pH, viscosity, density and H:C molar ratios. Variation in the ratio and positioning of both catalysts were the significant key factor for the catalyst optimisation study.

The pyrolysis of plastics in molten salts

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Flash pyrolysis of biomass for liquid fuels

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Combustion of fuel blends containing digestate pyrolysis oil in a multi-cylinder compression ignition engine

Digestate from the anaerobic digestion conversion process is widely used as a farm land fertiliser. This study proposes an alternative use as a source of energy. Dried digestate was pyrolysed and the resulting oil was blended with waste cooking oil and butanol (10, 20 and 30 vol.%). The physical and chemical properties of the pyrolysis oil blends were measured and compared with pure fossil diesel and waste cooking oil. The blends were tested in a multi-cylinder indirect injection compression ignition engine.Engine combustion, exhaust gas emissions and performance parameters were measured and compared with pure fossil diesel operation. The ASTM copper corrosion values for 20% and 30% pyrolysis blends were 2c, compared to 1b for fossil diesel. The kinematic viscosities of the blends at 40 C were 5–7 times higher than that of fossil diesel. Digested pyrolysis oil blends produced lower in-cylinder peak pressures than fossil diesel and waste cooking oil operation. The maximum heat release rates of the blends were approximately 8% higher than with fossil diesel. The ignition delay periods of the blends were higher; pyrolysis oil blends started to combust late and once combustion started burnt quicker than fossil diesel. The total burning duration of the 20% and 30% blends were decreased by 12% and 3% compared to fossil diesel. At full engine load, the brake thermal efficiencies of the blends were decreased by about 3–7% when compared to fossil diesel. The pyrolysis blends gave lower smoke levels; at full engine load, smoke level of the 20% blend was 44% lower than fossil diesel. In comparison to fossil diesel and at full load, the brake specific fuel consumption (wt.) of the 30% and 20% blends were approximately 32% and 15% higher. At full engine load, the CO emission of the 20% and 30% blends were decreased by 39% and 66% with respect to the fossil diesel. Blends CO2 emissions were similar to that of fossil diesel; at full engine load, 30% blend produced approximately 5% higher CO2 emission than fossil diesel. The study concludes that on the basis of short term engine experiment up to 30% blend of pyrolysis oil from digestate of arable crops can be used in a compression ignition engine.

Supply chain optimisation of pyrolysis plant deployment using goal programming

This paper presents a goal programming model to optimise the deployment of pyrolysis plants in Punjab, India. Punjab has an abundance of waste straw and pyrolysis can convert this waste into alternative bio-fuels, which will facilitate the provision of valuable energy services and reduce open field burning. A goal programming model is outlined and demonstrated in two case study applications: small scale operations in villages and large scale deployment across Punjab's districts. To design the supply chain, optimal decisions for location, size and number of plants, downstream energy applications and feedstocks processed are simultaneously made based on stakeholder requirements for capital cost, payback period and production cost of bio-oil and electricity. The model comprises quantitative data obtained from primary research and qualitative data gathered from farmers and potential investors. The Punjab district of Fatehgarh Sahib is found to be the ideal location to initially utilise pyrolysis technology. We conclude that goal programming is an improved method over more conventional methods used in the literature for project planning in the field of bio-energy. The model and findings developed from this study will be particularly valuable to investors, plant developers and municipalities interested in waste to energy in India and elsewhere. © 2014 Elsevier Ltd. All rights reserved.

Potassium catalysis in the pyrolysis behaviour of short rotation willow coppice

Short rotation willow coppice (SRC) and a synthetic biomass, a mixture of the basic biomass components (cellulose, hemicellulose and lignin), have been investigated for the influence of potassium on their pyrolysis behaviours. The willow sample was pre-treated to remove salts and metals by hydrochloric acid, and this demineralised sample was impregnated with potassium. The same type of pre-treatment was applied to components of the synthetic biomass. Characterisation was performed using thermogravimetric analysis with measurement of products by means of Fourier transform infrared spectroscopy (TGA-FTIR) and pyrolysis-gas chromatography-mass spectrometry (PY-GC-MS). A comparison of product distributions and kinetics are reported. While the general features of decomposition of SRC are described well by an additive behaviour of the individual components, there are some differences in the magnitude of the influence of potassium, and on the products produced. For both SRC and the synthetic biomass, TGA traces indicate catalytic promotion of both of the two-stages of biomass decomposition, and potassium can lower the average apparent first-order activation energy for pyrolysis by up to 50 kJ/mol. For both SRC and synthetic biomass the yields and distribution of pyrolysis products have been influenced by the presence of the catalyst. Potassium catalysed pyrolysis increases the char yields markedly and this is more pronounced for synthetic biomass than SRC. Gas evolution profiles during pyrolysis show the same general features for both SRC and synthetic biomass. Relative methane yields increase during the char formation stage of pyrolysis of the potassium doped samples. The evolution profiles of acetic acid and formaldehyde change, and these products are seen in lower relative amounts for both the demineralised samples. A greater variation in pyrolysis products is observed from the treated SRC samples compared to the different synthetic biomass samples. Furthermore, substituted phenols from lignin pyrolysis are more dominant in the pyrolysis profiles of the synthetic biomass than of the SRC, implying that the extracted lignins used in the synthetic biomass yield a greater fraction of monomeric type species than the lignocellulosic cell wall material of SRC. For both types of samples, PY-GS-MS analyses show that potassium has a significant influence on cellulose decomposition markers, not just on the formation of levoglucosan, but also other species from the non-catalysed mechanism, such as 3,4-dihydroxy-3-cyclobutene-1,2-dione. © 2007 Elsevier Ltd. All rights reserved.

Ash control methods to limit biomass inorganic content and its effect on fast pyrolysis bio-oil stability

This research investigates specific ash control methods to limit inorganic content within biomass prior to fast pyrolysis and effect of specific ash components on fast pyrolysis processing, mass balance yields and bio-oil quality and stability. Inorganic content in miscanthus was naturally reduced over the winter period from June (7.36 wt. %) to February (2.80 wt. %) due to a combination of senescence and natural leaching from rain water. September harvest produced similar mass balance yields, bio-oil quality and stability compared to February harvest (conventional harvest), but nitrogen content in above ground crop was to high (208 kg ha.-1) to maintain sustainable crop production. Deionised water, 1.00% HCl and 0.10% Triton X-100 washes were used to reduce inorganic content of miscanthus. Miscanthus washed with 0.10% Triton X-100 resulted in the highest total liquid yield (76.21 wt. %) and lowest char and reaction water yields (9.77 wt. % and 8.25 wt. % respectively). Concentrations of Triton X-100 were varied to study further effects on mass balance yields and bio-oil stability. All concentrations of Triton X-100 increased total liquid yield and decreased char and reaction water yields compared to untreated miscanthus. In terms of bio-oil stability 1.00% Triton X-100 produced the most stable bio-oil with lowest viscosity index (2.43) and lowest water content index (1.01). Beech wood was impregnated with potassium and phosphorus resulting in lower liquid yields and increased char and gas yields due to their catalytic effect on fast pyrolysis product distribution. Increased potassium and phosphorus concentrations produced less stable bio-oils with viscosity and water content indexes increasing. Fast pyrolysis processing of phosphorus impregnated beech wood was problematic as the reactor bed material agglomerated into large clumps due to char formation within the reactor, affecting fluidisation and heat transfer.

A CFD study of biomass pyrolysis in a downer reactor equipped with a novel gas-solid separator - I:hydrodynamic performance

This study presents the first part of a CFD study on the performance of a downer reactor for biomass pyrolysis. The reactor was equipped with a novel gas-solid separation method, developed by the co-authors from the ICFAR (Canada). The separator, which was designed to allow for fast separation of clean pyrolysis gas, consisted of a cone deflector and a gas exit pipe installed inside the downer reactor. A multi-fluid model (Eulerian-Eulerian) with constitutive relations adopted from the kinetic theory of granular flow was used to simulate the multiphase flow. The effects of the various parameters including operation conditions, separator geometry and particle properties on the overall hydrodynamics and separation efficiency were investigated. The model prediction of the separator efficiency was compared with experimental measurements. The results revealed distinct hydrodynamic features around the cone separator, allowing for up to 100% separation efficiency. The developed model provided a platform for the second part of the study, where the biomass pyrolysis is simulated and the product quality as a function of operating conditions is analyzed. Crown Copyright © 2014 Published by Elsevier B.V. All rights reserved.

Thermo-chemical conversion of straw:Haloclean : a performance enhanced low temperature pyrolysis

Haloclean a performance enhanced low temperature pyrolysis for biomass developed by Forschungszentrum Karlsruhe and Sea Marconi Is closing the gap between classical and fast pyrolysis approaches. For pyrolysis of straw (chaffed-, finely ground and pellets) temperature ranges between 320 to 420°C and residence times of only 1 to 5 minutes can be realized. Liquid yields of up to 45 wt-% and 35 wt-% of solids are possible. Solid yields can be increased up to 73 wt-% while loosing 4.5 % of the feed energy by pyrolysis gases only. Toxicity tests of the fractions do not show relevant numbers.

Pyrolysis study of halogen-containing aromatics reflecting reactions with polypropylene in a posttreatment decontamination process

Halogen-containing aromatics, mainly bromine-containing phenols, are harmful compounds contaminating pyrolysis oil from electronic boards containing halogenated flame retardants. In addition, theirformation increases the potential for evolution of polybrominated dibenzo-p-dioxins (PBDDs) and dibenzofurans (PBDFs) at relatively low temperature (up to 500 °C). As a model compound, 2,4-dibromophenol (DBP) was pyrolyzed at 290-450 °C. While its pyrolysis in a nitrogen flow reactor or in encapsulated ampules yields bromine-containing phenols, phenoxyphenols, PBDDs, and PBDFs, pyrolysis of DBP in a hydrogen-donating medium of polypropylene (PP) at 290-350 °C mainly results in the formation of phenol and HBr, indicating the occurrence of a facile hydrodebromination of DBP. The hydrodebromination efficiency depends on temperature, pressure, and the ratio of the initial components. This thermal behavior of DBP is compared to that of 2,4-dichlorophenol and decabromodiphenyl ether. A treatment of halogen-containing aromatics with PP offers a new perspective on the development of low-environmental-impact disposal processes for electronic scrap. © 2005 American Chemical Society.

Fast pyrolysis processing of surfactant washed Miscanthus

Miscanthus × giganteus was subjected to pre-treatment with deionised water, hydrochloric acid or Triton X-100 surfactant, and subsequently fast pyrolysed in a fluidised bed reactor at 535 °C to obtain bio-oil. Triton X-100 surfactant was identified as a promising pre-treatment medium for removal of inorganic matter because its physicochemical nature was expected to mobilise inorganic matter in the biomass matrix. The influence of different concentrations of Triton X-100 pre-treatment solutions on the quality of bio-oil produced from fast pyrolysis was studied, as defined by a single phase bio-oil, viscosity index and water content index. The highest concentration of Triton X-100 surfactant produced the best quality bio-oil with high organic yield and low reaction water content. The calculated viscosity index from the accelerated ageing test showed that bio-oil stability improved as the concentration of Triton X-100 increased. © 2014 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license.