Mallee wood fast pyrolysis: Effects of alkali and alkaline earth metallic species on the yield and composition of bio-oil

The purpose of this study was to investigate the effects of inorganic species in biomass, especially the alkali and alkaline earth metallic (AAEM) species (K, Na, Mg and Ca), on the yield and properties of bio-oil from the pyrolysis of biomass. A mallee wood sample from Western Australia was washed with water and a dilute acid solution to remove its AAEM species. The water-washed and acid-washed mallee wood samples were then pyrolysed in a fluidised-bed reactor at 500 °C under fast heating rate conditions. The removal of AAEM species did not result in significant changes in the yields of bio-oil and bio-char. However, the bio-oil properties, e.g. viscosity, were drastically affected by the removal of AAEM species. Our results indicate that the water-soluble AAEM species were not as important as the water-insoluble but acid-soluble AAEM species in influencing the bio-oil composition and properties. It is believed that the acid-soluble AAEM species (especially Ca) were more closely linked with the organic matter in biomass and thus were closely involved in the reactions during pyrolysis. The removal of AAEM species, especially the acid-soluble AAEM species, led to very significant increases in the yields of sugars and lignin-derived oligomers, accompanied by decreases in the yields of water and light organic compounds in the bio-oil.     

Simultaneous catalytic esterification of carboxylic acids and acetalisation of aldehydes in a fast pyrolysis bio-oil from mallee biomass

This paper reports the simultaneous catalytic esterification and acetalisation of a bio-oil with methanol using a commercial Amberlyst-70 catalyst at temperatures between 70 and 170 °C. The bio-oil was prepared from the pyrolysis of mallee woody biomass in a fluidised-bed pyrolysis reactor under the fast heating rate conditions. Our results show that the conversion of light organic acids and aldehydes to esters and acetals rises significantly with increasing temperature, reaction time and catalysts loading. However, some acetals (e.g. dimethoxymethane) could decompose at higher operating temperatures (>110 °C) and catalyst loadings (>6 wt.%). The medium and heavy fractions of bio-oil also reacted with methanol to result in increases in their volatility (or decreases in boiling points) when their reactive O-containing functional groups were stabilised. The acid-catalysed reactions between bio-oil and methanol also decreased the coking propensity of the bio-oil reaction products.     

Effects of particle shape and size on devolatilization of biomass particle

Experimental and theoretical investigations indicate particle shape and size influence biomass particle dynamics, including drying, heating rate, and reaction rate. Experimental samples include disc/flake-like, cylindrical/cylinder-like, and equant (nearly spherical) shapes of wood particles with similar particle masses and volumes but different surface areas. Small samples (320 μm) passed through a laboratory entrained-flow reactor in a nitrogen atmosphere and a maximum reactor wall temperature of 1600 K. Large samples were suspended in the center of a single-particle reactor. Experimental data indicate that equant particles react more slowly than the other shapes, with the difference becoming more significant as particle mass or aspect ratio increases and reaching a factor of two or more for particles with sizes over 10 mm. A one-dimensional, time-dependent particle model simulates the rapid pyrolysis process of particles with different shapes. The model characterizes particles in three basic shapes (sphere, cylinder, and flat plate). With the particle geometric information (particle aspect ratio, volume, and surface area) included, this model simulates the devolatilization process of biomass particles of any shape. Model simulations of the three shapes show satisfactory agreement with the experimental data. Model predictions show that both particle shape and size affect the product yield distribution. Near-spherical particles exhibit lower volatile and higher tar yields relative to aspherical particles with the same mass under similar conditions. Volatile yields decrease with increasing particle size for particles of all shapes. Assuming spherical or isothermal conditions for biomass particles leads to large errors at most biomass particle sizes of practical interest.     

Effect of crystallization temperature on the in situ valorization of physic nut (Jatropha curcus L.) wastes using synthetic HZSM-5 catalyst

Physic nut waste is selected as the biomass feedstock for fast pyrolysis as it is available in large amounts from biodiesel production in Thailand. The volatile matter and fixed carbon contents are 73.8% and 13.6% while ash contents are 5.8%. Carbon is the main element with 49.03 wt%. The oxygen content of 39.0 wt% is considerably high which could directly convert to the oxygenated pyrolysis liquid products. To decrease oxygenated compounds, HZSM-5 was used as a catalyst to upgrade pyrolytic products from fast pyrolysis using analytical pyrolysis–GC/MS method. The HZSM-5 catalyst was successfully synthesized by hydrothermal method at 160–180 °C for 24 h. The particle size, surface area, and pore diameter were 11.25–15.52 μm, 567–582 m²/g, and 21.78–26.11 Å, respectively. The pyrolysis was performed at 500 °C with the Jatropha wastes to catalyst ratio of 1:1–1:10. The presence of HZSM-5 contributed to eliminate the undesirable oxygenated compounds such as acids and ketones which could alleviate problem regarding acidity and instability in bio-oil. In addition, it enhanced significantly the yields of desirable hydrocarbon compounds. The increase in catalyst contents had an effect on the enhancement of hydrocarbons yields, and tended to promote deoxygenation and denitrogenation. At moderate biomass to catalyst ratio (1:5), HZSM-5 synthesized at 170 °C contributed to improve the hydrocarbon yields of 95%, including mainly toluene and xylene, which are valuable products because of their high heating value properties.     

The effect of coal particle size on pyrolysis and steam gasification

For future power generation from coal, one preferred option in the UK is the air-blown gasification cycle (ABGC). In this system coal particles sized up to 3 mm, perhaps up to 6 mm in a commercial plant, are pyrolysed and then gasified in air/steam in a spouted bed reactor. As this range of coal particle sizes is large it is of interest to investigate the importance of particle size for those two processes. In particular the relation between the coal and the char particle size distribution was investigated to assess the error involved in assuming the coal size distribution at the on-set of gasification. Different coal size fractions underwent different changes on pyrolysis. Smaller coal particles were more likely to produce char particles larger than themselves, larger coal particles had a greater tendency to fragment. However, for the sizes investigated in this study ranging from 0.5 to 2.8 mm, the pyrolysis and gasification behaviour was found not to vary significantly with particle size. The coal size fractions showed similar char yields, irrespective of the different char size distributions resulting from pyrolysis. Testing the reactivity of the chars in air and CO₂ did not reveal significant differences between size fractions of the char, nor did partial gasification in steam in the spouted bed reactor. From the work undertaken, it can be concluded that pyrolysis and gasification within the range of particle sizes investigated are relatively insensitive to particle size.     

Pyrolysis characteristics of Oriental white oak: Kinetic study and fast pyrolysis in a fluidized bed with an improved reaction system

The kinetic parameters for the pyrolysis of Oriental white oak were evaluated by thermogravimetric analysis (TGA). The white oak was pyrolyzed in a fluidized bed reactor with a two-staged char separation system under a variety of operating conditions. The influence of the pyrolysis conditions on the chemical and physical characteristics of the bio-oil was also examined. TGA showed that the Oriental white oak decomposed at temperatures ranging from 250 to 400 °C. The apparent activation energy ranged from 160 to 777 kJ mol^− 1. The optimal pyrolysis temperature for the production of bio-oil in the fluidized bed unit was between 400 and 450 °C. A much smaller and larger feed size adversely affected the production of bio-oil. A higher fluidizing gas flow and higher biomass feeding rate were more effective in the production of bio-oil but the above flow rates did not affect the bio-oil yields significantly. Recycling a part of the product gas as a fluidizing medium resulted the highest bio-oil yield of 60 wt.%. In addition, high-quality bio-oil with a low solid content was produced using a hot filter as well as a cyclone. With exception of the pyrolysis temperature, the other pyrolysis conditions did not significantly affect the chemical and physical characteristics of the resulting bio-oil.     

Bio-oil derived from empty fruit bunches

The fast pyrolysis of washed and unwashed empty fruit bunches (EFB), a waste of the palm oil industry, is investigated in this study. Firstly, the composition and particle size distribution of the washed and unwashed feedstock were determined and the thermal degradation behaviour was analysed by TGA. Then a 150 g/h fluidised bed bench scale fast pyrolysis unit was used to study the impact of key variables: reactor temperature in the range 425-550 °C and feedstock ash content in the range 1.03-5.43 mf wt%. The properties of the liquid product were analysed and compared with wood derived bio-oil and petroleum fuels. It was found that the maximum ash content of washed feedstock that still yields homogenous liquids is less than about 3 mf wt%. The experiments also indicated that the fast pyrolysis of washed EFB with a low ash content gave similar yields as commonly obtained for wood.     

Is it possible to predict gas yields of any biomass after rapid pyrolysis at high temperature from its composition in cellulose, hemicellulose and lignin?

Ligno-cellulosic biomass from different sources presents very variable compositions. Consequently, there is a wide variation in the nature and quantities of gaseous products obtained after thermal treatment of biomasses.The objective of this work is to establish a link between the composition of a biomass and its pyrolysis gas yields and composition. Experimental flash pyrolysis of several biomasses at a temperature of 950 °C and a gas residence time of about 2 s was carried out. An attempt was then made to predict gas yields of any biomass according to its composition. We show that an additivity law does not allow the gas yields of a biomass to be correlated with its fractions of cellulose, hemicellulose and lignin. Several potential explanations are then offered and quantitatively demonstrated: it is shown that interactions occur between compounds and that mineral matter influences the pyrolysis process.     

Mechanisms and kinetics of homogeneous secondary reactions of tar from continuous pyrolysis of wood chips

The change of mass and composition of biomass tar due to homogeneous secondary reactions was experimentally studied by means of a lab reactor system that allows the spatially separated production and conversion of biomass tar. A tarry pyrolysis gas was continuously produced by pyrolysis of wood chips (fir and spruce, 10-40 mm diameter) under fixed-bed biomass gasification conditions. Homogeneous secondary tar reactions without the external supply of oxidising agents were studied in a tubular flow reactor operated at temperatures from 500 to 1000 °C and with space times below 0.2 s. Extensive chemical analysis of wet chemical tar samples provided quantitative data about the mass and composition of biomass tar during homogeneous conversion. These data were used to study the kinetics of the conversion of gravimetric tar and the formation of PAH compounds, like naphthalene.It is shown that, under the reaction conditions chosen for the experiments, homogeneous secondary tar reactions become important at temperatures higher than 650 °C, which is indicated by the increasing concentrations of the gases CO, CH₄, and H₂ in the pyrolysis gas. The gravimetric tar yield decreases with increasing reactor temperatures during homogeneous tar conversion. The highest conversion reached in the experiments was 88% at a reference temperature of 990 °C and isothermal space time of 0.12 s. Hydrogen is a good indicator for reactions that convert the primary tar into aromatics, especially PAH. Soot appears to be a major product from homogeneous secondary tar reactions.     

Steam pyrolysis of an industrial waste for bio-oil production

Potato skin, a food industry waste, was pyrolysed under three different atmospheres namely static, nitrogen, and steam to produce bio-oil and its derivatives. The oil yield obtained at 550 °C was 24.77% in static atmosphere, whereas it reached to 27.11% in nitrogen atmosphere. Moreover, the use of steam caused a sharp increase of oil yields up to 41.09% with a steam velocity of 1.3 cm s^− 1. TG-DTA analyses were applied on the raw material to investigate the thermal degradation. Liquid products obtained under the most suitable conditions were characterized by elemental analyses, FT-IR and ¹H NMR. In addition, column chromatography was employed to separate the bio-oil into its derivatives. Asphaltene fraction of bio-oil is decreased under steam atmosphere. Gas chromatography was also used to investigate the C distributions. The characterization has shown that the bio-oil obtained under steam atmosphere was more beneficial than those obtained under both static and inert atmospheres. Further comparison of H/C ratios of pyrolysis oils with conventional fuels indicates that the H/C ratios of the oils obtained in this study lie between those of light and heavy petroleum products. It can be concluded that potato skin could be evaluated as a promising biomass candidate of bio-oil production.     

Effects of extraction temperature, extraction pressure and nozzle diameter on micronization of cholesterol by RESS process

Micronized cholesterol particles were produced via the Rapid Expansion of Supercritical CO₂ Solutions (RESS) process. Taguchi design was used for designing the experimental plan to investigate the effects of three parameters including extraction temperature (40-60 °C), extraction pressure (100-160 bar) and nozzle diameter (0.15-0.24 mm) on the size and morphology of the cholesterol particles produced by the RESS process. The characterization of the particles was carried out using scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements to evaluate the performance of RESS process. The average particle size of the original material was 55 μm ± (2.84) while the average particle size of cholesterol after size reduction via the RESS process was between the minimum of 0.62 μm ± (0.03) and the maximum of 4.83 μm ± (0.18) depending upon the experimental conditions used. It was observed that both increasing the temperature from 40 to 60 °C and increasing the nozzle diameter from 0.15 to 0.24 mm result a reducing effect on the average particle size, whereas extraction pressure (100-160 bar) change has slight effect on the average particle size.     

Biofuels from waste fish oil pyrolysis: Continuous production in a pilot plant

Fast pyrolysis of waste fish oil was performed in a continuous pyrolysis pilot plant. The experiment was carried out under steady-state conditions in which 10 kg of biomass was added at a feed rate of 3.2 kg h⁻¹. A bio-oil yield of 72-73% was obtained with a controlled reaction temperature of 525 °C. The bio-oil was distilled to obtain purified products with boiling ranges corresponding to light bio-oil and heavy bio-oil. These biofuels were characterized according to their physico-chemical properties, and compared with the Brazilian-fuel specifications for conventional gasoline and diesel fuels. The results show that the fast pyrolysis process represents an alternative technique for the production of biofuels from waste fish oil with characteristics similar to petroleum fuels.     

Birch wood particle shrinkage during rapid pyrolysis

A study of the shrinkage of cubic (∼5 mm) birch wood particles during pyrolysis is presented. The particles were rapidly injected into a preheated furnace with a constant temperature in the range 350-900°C. The size of the particles in longitudinal, tangential and radial directions was measured until no further mass loss occurs. The volume shrinkage was found to be 45-70% and the shrinkage in the different directions 5-25, 25-40 and 15-40% for longitudinal, tangential and radial directions, respectively. Longitudinal shrinkage commenced after about 60% mass loss and is not strongly dependent on heating rate or on cellulose chain scission. A maximum shrinkage was found for tangential and radial directions at 400 and 500-700°C, respectively, and above these temperatures the shrinkage decreases. The char yield decreases and the char structure becomes more deranged with increasing temperature. Empirical models of shrinkage as a function of conversion are presented.     

In situ TEM investigations of reactions of Ni, Fe and Fe-Ni alloy particles and their oxides with amorphous carbon

Ni, Fe and Ni-Fe alloy particles were vapour deposited on thin films of amorphous carbon (a-C) inside a specially equipped transmission electron microscope, and reactions with the substrate were observed at elevated temperatures. The influence of oxidation of the particles was also investigated. In contrast to Ni, which was found in earlier work to graphitise the carbon at above 600 °C without bulk carbide being involved, pure Fe reacted with the a-C support at about 500 °C to Fe₃C, which graphitised the carbon similar to Ni, starting at about 600 °C. No carbide was formed from oxidised Fe particles. FeO decomposes above 500 °C, higher oxides (Fe₃O₄, Fe₂O₃) only above 750 °C. The remaining Fe particles graphitised the carbon support directly. Alloy particles with composition Ni80:Fe20 (permalloy) graphitised a-C in the same way as pure Ni, without any phase separation. Annealing of a mixed phase of finely dispersed Ni-Fe-oxide or deposition of Ni-Fe under oxygen at above 300 °C resulted in nucleation of three-dimensional crystallites of virtually pure Ni, which graphitised the carbon, while the remaining phase of small particles was converted to inactive Ni-ferrite, NiFe₂O₄.     

Synthesis of nanocrystalline Mn-Zn ferrite powders through thermolysis of mixed oxalates

Nanocrystalline Mn-Zn ferrite powders were synthesized by thermal decomposition of an oxalate precursor. Two polymorphs of a mixed Mn-Zn-Fe oxalate dihydrate were obtained by precipitation of metal ions with oxalic acid: monoclinic α-(Mn, Zn, Fe)₃(C₂O₄)₃·6H₂O is obtained after precipitation and ageing at 90 °C, whereas the orthorhombic β-type is formed after precipitation at room temperature. The morphology of the oxalate crystals can be controlled by the precipitation conditions. The α-polymorph of the mixed oxalate consists of prismatic and agglomerated particles. The β-oxalate forms non-agglomerated crystallites of submicron size. Thermal decomposition of the oxalate at 350 °C in air results in an amorphous product. Nanosize Mn-Zn ferrite powders are formed at 500 °C and a mixture of haematite and spinel is observed at 750 °C. The thermal decomposition of the mixed oxalate is monitored by thermal analysis, XRD and IR-spectroscopy. The morphology of the oxalate particles is preserved during thermal decomposition; the oxide particle aggregates display similar size and shape as the oxalates. The primary particles are much smaller; their size increases from 3 nm to 50 nm after decomposition of the oxalates at 350 and 500 °C, respectively. The powder synthesized by decomposition at 500 °C was sintered at 1150 °C to dense and fine-grained Mn-Zn ferrites.     

Pyrolysis of wood at high temperature: The influence of experimental parameters on gaseous products

The pyrolysis of wood was carried out in an Entrained Flow Reactor at high temperature (650 to 950 °C) and under rapid heating conditions (> 10³ K s^− 1). The influence of the diameter and initial moisture of the particle, reactor temperature, residence time and the nature of the gaseous atmosphere on the composition of the gaseous products has been characterised. Particle size, between 80-125 and 160-200 μm, did not show any impact. Pyrolysis and tar cracking essentially happen in very short time period: less than 0.6 s; the products yields are only slightly modified after 0.6 s in the short residence times (several seconds) of our experiments. Higher temperatures improve hydrogen yield in the gaseous product while CO yield decreases. Under nitrogen atmosphere, after 2 s at 950 °C, 76% (daf) of the mass of wood is recovered as gases: CO, CO₂, H₂, CH₄, C₂H₂, C₂H₄ and H₂O. Tests performed under steam partial pressure showed that hydrogen production is slightly enhanced.     

Formation of nanosize ZnO particles by thermal decomposition of zinc acetylacetonate monohydrate

Formation of ZnO particles by thermal decomposition of zinc acetylacetonate monohydrate in air atmosphere has been investigated using XRD, DTA, FT-IR, and FE-SEM as experimental techniques. ZnO as a single phase was produced by direct heating at ≥200 °C. DTA in air showed an endothermic peak at 195 °C assigned to the ZnO formation and exothermic peaks at 260, 315 and 365 °C, with a shoulder at 395 °C. Exothermic peaks can be assigned to combustion of an acetylacetonate ligand released at 195 °C. ZnO particles prepared at 200 °C have shown no presence of organic species, as found by FT-IR spectroscopy. Particles prepared for 0.5 h at 200 °C were in the nanosize range from ∼20 to ∼40 nm with a maximum at 30 nm approximately. The crystallite size of 30 nm was estimated in the direction of the a₁ and a₂ crystal axes, and in one direction of the c-axis it was 38 nm, as found with XRD. With prolonged heating of ZnO particles at 200 °C the particle/crystallite size changed little. However, with heating temperature increased up to 500 or 600 °C the ZnO particle size increased, as shown by FE-SEM observation. Nanosize ZnO particles were also prepared in two steps: (a) by heating of zinc acetylacetonate monohydrate up to 150 °C and distillation of water and organic phase, and (b) with further heating of so obtained precursor at 300 °C.     

Liquefactions of peat in supercritical water with a novel iron catalyst

Raw iron ore has been investigated for use as a catalyst in direct liquefaction of peat into bio-crude by supercritical water treatment. The liquefaction treatments were conducted at temperatures from 350 °C to 500 °C for a residence time from 10 min to 4 h. The supercritical water treatment of peat with the iron ore generally resulted in 19-40 wt% yield of heavy oil (HO) that has a higher heating value (HHV) of 30-37 MJ/kg. An increase in the operating temperature generally increased gas yield and decreased oil and char yields, while a maximum HO formation was observed at around 400 °C. At 400 °C for a residence time of 2 h, the addition of the raw iron ore in the operation produced HO at a very high yield of about 40 wt%, nearly doubling that of the treatment without catalyst. An increase of water-to-peat ratio led to enhanced formation of HO products, accompanied by a decrease in gas or char yield. The optimal reaction time appeared to be 2 h for the maximum HO production, and a longer residence time than 2 h generally led to a decrease in HO yield but an increase in gas yield. Compared with the raw iron ore, its H₂-reduced form and two synthesized iron-based catalysts (FeOOH and Fe₂O₃) all showed a lower activity for HO production. Some conventional biomass liquefaction catalysts (i.e., KOH, FeCl₃ and FeSO₄) showed negligible or even negative effects on the HO yield, while these catalysts were found very active for promoting the gas yields and hydrogen formation.     

Particle size design of digitoxin in supercritical fluids

Bioavailability of the pharmaceutical substances is very important for their activity. In case of necessity, bioavailability can be improved by reducing the particle size of the drugs. In this study, particle size of digitoxin was reduced by the Rapid Expansion of Supercritical Solutions (RESS). The effects of pre-expansion temperature (90-110 °C), flow rate (2.5-7.5 ml/min), spray distance (3-7 cm) on the size and size distribution of the precipitated digitoxin particles were carried out. The particles were characterized by dynamic light scattering (DLS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and LC-MS analysis.While the particle size range of the original digitoxin was 0.2-8 μm, it was decreased to 68-458 nm and determined that 97% of the particles were below 200 nm depending on the different experimental conditions.Response surface method (RSM) was used to optimize the process parameters. The flow rate, 7 ml/min; spray distance, 7 cm; pre-expansion temperature, 95 °C were found to be the optimum conditions to achieve the minimum particle size of digitoxin.     

Investigation of turbulence modulation in solid–liquid suspensions using parallel competing reactions as probes for micro-mixing efficiency

The Bourne and the Villermaux competitive reaction chemistries were applied to study the effects of suspended particles on the yield of an undesired product and hence to infer their effects on local dissipation rates. Two-phase micro-mixing experiments were carried out in a 1 l stirred vessel, agitated by a pitched-blade turbine, using four particle size ranges: 70–100, 250–300, 700–750 and 1000 μm. Experiments were carried out with up to 1.75 vol% particles in the Bourne scheme and 3 vol% in the Villermaux scheme. Both reaction schemes gave qualitatively similar results, although stronger effects of added particles were obtained with the Bourne chemistry. The effect of 700–750 μm particles could not be distinguished from experimental error, but the other size ranges gave increased by-product yields and suppressed the dissipation rates. These results confirmed earlier two-phase PIV observations: smaller particles (70–100 and 250–300 μm) gave maximum suppression at ∼1 vol%. Above this volume fraction, the level of suppression decreased and in some cases turbulence augmentation occurred, indicating that particle concentration, as well as size, is an important factor.