Influence of pressure on pyrolysis of black liquor: 1. Swelling

This is the first of two papers concerning the behavior of black liquor during pyrolysis under pressurized conditions. Two industrial kraft liquors were pyrolyzed in a laboratory-scale pressurized single particle reactor and a pressurized grid heater at temperatures ranging from 650 to 1100 degrees C and at pressures between 1 and 20 bar. The dimensions of the chars produced were measured and the specific swollen volume was calculated. Swelling decreased roughly logarithmically over the pressure range 1-20 r. An expression is developed to predict the specific swollen volume at elevated pressure when the volume at 1 bar is known. The bulk density of the char increased with pressure, indicating that liquors will be entrained less easily at higher pressures.     

Compositional and Thermal Evaluation of Lignocellulosic and Poultry Litter Chars via High and Low Temperature Pyrolysis

Inorganic elements in biomass feedstocks can influence thermochemical reactions as well as the resultant char’s elemental, compositional, and thermal characteristics. Chars were produced using slow pyrolysis under low (≤400°C) and high (≥500°C) temperature regimes from sugarcane bagasse, peanut hulls, pecan shell, pine chips, poultry litter, and switchgrass. The chars and raw feedstocks were characterized for their elemental, structural, and thermal properties to ascertain the implications of feedstock selection and pyrolysis temperatures on these properties. Char mass yields from the six feedstocks ranged between 28% and 78% by weight while carbon yields ranged between 44% and 89%. In both instances, lower yields were obtained with increasing pyrolysis temperature. Higher pyrolysis temperatures (≥500°C) resulted in more neutral to alkaline chars possessing greater ash contents and increased aromatic character with narrow O/C and H/C ratios. A significant exponential curve response (r ²?=?0.87, P?<?0.001) was revealed between char mass yields vs. pyrolysis temperature. All raw feedstocks and chars contained mixed amounts of macro-, micro-, and trace element concentrations. The higher heating values (HHV) tended to increase with heightened pyrolysis temperature with some chars producing >30 MJ kg^?1. The chars’ HHV values inversely correlated to their total ash and Cl content. Lignocelluloses chars had better thermal characteristics and lower ash quality concerns implying suitable service in thermal energy production. In contrast, poultry litter char had greater ash contents, medium HHV values, and contained corrosive inorganic elements, which rendered it problematic as a feedstock for thermal energy generation.     

Fast Pyrolysis Behavior of Banagrass as a Function of Temperature and Volatiles Residence Time in a Fluidized Bed Reactor

A reactor was designed and commissioned to study the fast pyrolysis behavior of banagrass as a function of temperature and volatiles residence time. Four temperatures between 400 and 600°C were examined as well as four residence times between ~1.0 and 10 seconds. Pyrolysis product distributions of bio-oil, char and permanent gases were determined at each reaction condition. The elemental composition of the bio-oils and chars was also assessed. The greatest bio-oil yield was recorded when working at 450°C with a volatiles residence time of 1.4 s, ~37 wt% relative to the dry ash free feedstock (excluding pyrolysis water). The amounts of char (organic fraction) and permanent gases under these conditions are ~4 wt% and 8 wt% respectively. The bio-oil yield stated above is for ''dry'' bio-oil after rotary evaporation to remove solvent, which results in volatiles and pyrolysis water being removed from the bio-oil. The material removed during drying accounts for the remainder of the pyrolysis products. The ''dry'' bio-oil produced under these conditions contains ~56 wt% carbon which is ~40 wt% of the carbon present in the feedstock. The oxygen content of the 450°C, 1.4 s ''dry'' bio-oil is ~38 wt%, which accounts for ~33 wt% of the oxygen in the feedstock. At higher temperature or longer residence time less bio-oil and char is recovered and more gas and light volatiles are produced. Increasing the temperature has a more significant effect on product yields and composition than increasing the volatiles residence time. At 600°C and a volatiles residence time of 1.2 seconds the bio-oil yield is ~21 wt% of the daf feedstock, with a carbon content of 64 wt% of the bio-oil. The bio-oil yield from banagrass is significantly lower than from woody biomass or grasses such as switchgrass or miscanthus, but is similar to barley straw. The reason for the low bio-oil yield from banagrass is thought to be related to its high ash content (8.5 wt% dry basis) and high concentration of alkali and alkali earth metals (totaling ~2.8 wt% relative to the dry feedstock) which are catalytic and increase cracking reactions during pyrolysis.     

Effect of temperature on gas composition and char structural features of pyrolyzed agricultural residues

The gases and chars produced during fast pyrolysis of maize stalk, rice straw, cotton straw and rice husk at temperatures ranging from 600 to 1000 °C were studied by Fourier transform infrared spectroscopy, non-dispersive infrared technique, thermal conductivity detection method, ultimate analysis, X-ray diffraction, helium density measurement and N₂ adsorption method. The gas yield increased by more than 80% from 600 to 1000 °C, while the char and liquid yield decreased. The content of CO₂, CO and CH₄ accounted for more than 86%. The CO and CH₄ content increased with temperature, while the CO₂ content decreased. The hydroxyl, aliphatic CH, carbonyl, olefinic CC and ether groups were lost above 800 °C. Carbon skeleton shrinkage increased by more than 23% when the temperature increased from 600 to 1000 °C. Maximum porosity appeared at 900 °C. This study revealed the relationships between gas composition/char properties and pyrolysis temperature under high heating rate conditions.     

Evaluation of pyrolysis chars derived from marine macroalgae silage as soil amendments

Pyrolysis char residues from ensiled macroalgae were examined to determine their potential as growth promoters on germinating and transplanted seedlings. Macroalgae was harvested in May, July and August from beach collections, containing predominantly Laminaria digitata and Laminaria hyperborea; naturally seeded mussel lines dominated by Saccharina latissima; and lines seeded with cultivated L. digitata. Material was ensiled, pressed to pellets and underwent pyrolysis using a thermo‐catalytic reforming (TCR) process, with and without additional steam. The chars generated were then assessed through proximate and ultimate analysis. Seasonal changes had the prevalent impact on char composition, though using mixed beach‐harvested material gave a greater variability in elements than when using the offshore collections. Applying the char at 5% (v/v)/2% (w/w) into germination or seedling soils was universally negative for the plants, inhibiting or delaying all parameters assessed with no clear advantage in harvesting date, species or TCR processing methodology. In germinating lettuce seeds, soil containing the pyrolysis chars caused a longer germination time, poorer germination, fewer true leaves to be produced, a lower average plant health score and a lower final biomass yield. For transplanted ryegrass seedlings, there were lower plant survival rates, with surviving plants producing fewer leaves and tillers, lower biomass yields when cut and less regrowth after cutting. As water from the char‐contained plant pots inhibited the lettuce char control, one further observation was that run‐off water from the pyrolysis char released compounds which detrimentally affected cultivated plant growth. This study clearly shows that pyrolysed macroalgae char does not fit the standard assumption that chars can be used as soil amendments at 2% (w/w) addition levels. As the bioeconomy expands in the future, the end use of residues and wastes from bioprocessing will become a genuine global issue, requiring consideration and demonstration rather than hypothesized use.     

Fixed-bed catalytic pyrolysis of cotton-seed cake: effects of pyrolysis temperature, natural zeolite content and sweeping gas flow rate

Catalyzed pyrolysis of cotton-seed cake was studied under different experimental conditions. Variables investigated were pyrolysis temperature, zeolite content and sweeping gas flow rate. Experiments were carried out isothermally. Liquids, gases and char were obtained as products of pyrolysis. The distributions of these products were determined for various contents (1, 5, 10, 20 wt.% of raw material) of zeolite at four different pyrolysis temperatures. The maximum liquid yield obtained was 30.84% at a pyrolysis temperature of 550 degrees C with a sweeping gas flow rate of 100 cm(3) min(-1) in the presence of clinoptilolite (20% based on raw material) as catalyst. The pyrolytic and catalytic liquid products were analysed in detail to determine the predominant chemical classes and the identities of the major compounds present.     

The thermal decomposition studies of solid iron bamboo (Dendrocalamus strictus) - potential precursor for eco-materials

Block samples of carbonized solid iron bamboo (Dendrocalamus strictus) - unique genus among bamboos, were prepared by means of slow pyrolysis. They are expected to be promising monolithic supports for various composites. The purpose of this study is to describe the thermal decomposition of rectangular shapes cut from solid stems of Dendrocalamus strictus, raw and pre-charred in a wide range of temperatures: 300, 350, 400, 500 and 600 degrees C. The DTG thermograms of carbonized solid iron bamboo (char), determined at temperatures up to 900 degrees C, exhibited minima even for samples previously pyrolysed at temperatures over 400 degrees C, at which decomposition of plant material have to be completed. For pre-charred samples, the temperature of the DTG peaks increased, while the weight loss registered in the temperature range up to 900 degrees C decreased, with increasing temperature of carbonization. It was found that extension of time of holding at final temperature of carbonization decreased a height of the DTG peaks to full reduction of it after heating along the time of 8h. It was suggested that bamboo tar remaining in vessels after carbonization reacts with the bamboo char creating new compounds that decompose in distinctly higher temperatures.     

The ribonucleotide sequence of 5s rRNA from two strains of deep-sea barophilic bacteria

Deep-sea bacteria were isolated from the digestive tract of animals inhabiting depths of 5900 m in the Puerto Rico Trench and 4300 m near the Walvis Ridge. Growth of two bacterial strains was measured in marine broth and in solid media under a range of pressures and temperatures. Both strains were barophilic at 2 degrees C (+/- 1 degrees C) with an optimal growth rate of 0.22 h-1 at a pressure 30% lower than that encountered in situ. At 1 atm they grew at temperatures ranging from 1.2 to 18.2 degrees C (+/- 0.3 degrees C), while in situ pressures increased the upper temperature limit to 23.3 degrees C. Both strains were identified as members of the genus Vibrio, based on standard taxonomic tests and mol% G + C values (47.0 and 47.1). Ribonucleotide sequences determined for 5S ribosomal RNA from each strain confirmed relationship to the Vibrio-Photobacterium group, as represented by V. harveyi and P. phosphoreum, but the barophiles were clearly distinct from these species. Secondary structure conformed to the established model for eubacterial 5S rRNA.     

Reaction chemistry and phase behavior of lignin in high-temperature and supercritical water

Decomposition of organosolve lignin in water/phenol solutions was studied in a 50 nL micro-reactor coupled with optical, Raman and infrared microscopies at temperatures up to 600 degrees C and water densities up to 1165 kg/m3. It was found that when phenol was used with {lignin+water} mixtures that a homogenous phase was formed that seemed to promote the decomposition of lignin into phenolic fragments by hydrolysis and pyrolysis. Phenol, along with the homogenous reaction conditions also inhibited re-polymerization of the phenolics and promoted oil formation. On the other hand, in the absence of phenol, lignin remained as a heterogeneous phase with water over the range of conditions studied. The homogeneous conditions and conditions for inhibiting char formation by phenol were elucidated and it was found that mixtures of phenol and lignin become homogeneous at 400-600 degrees C and high water densities of 428-683 kg/m3, corresponding to maximum pressures of 93 MPa. These results were further used to propose reaction paths.     

High-pressure-temperature gradient instrument: use for determining the temperature and pressure limits of bacterial growth.

A pressurized temperature gradient instrument allowed a synoptic determination of the effects of temperature and pressure on the reproduction of bacteria. The instrument consisted of eight pressure vessels housed parallel to each other in an insulated aluminum block in which a linear temperature gradient was supported. For a given experiment, eight pressures between 1 and 1,100 bars were chosen; the linear temperature gradient was established over an interval within -20 to 100 degrees C. Pure cultures and natural populations were studied in liquid or solid medium either in short (ca. 2-cm) culture tubes or in long (76.2-cm) glass capillaries. In the case of a pure culture, experiments with the pressurized temperature gradient instrument determined values of temperature and pressure that bounded its growth. Feasibility experiments with mixed populations of bacteria from water samples from a shallow depth of the sea showed that the instrument may be useful in identifying the extent to which a natural population is adapted to the temperatures and pressures at the locale of origin of the sample. Additional conceived uses of the instrument included synoptic determinations of cell functions other than reproduction and of biochemical activities.     

Thermal analysis and devolatilization kinetics of cotton stalk, sugar cane bagasse and shea meal under nitrogen and air atmospheres

Thermal degradation, reactivity and kinetics for biomass materials cotton stalk (CS), sugarcane bagasse 1 (SB1), sugarcane bagasse 2 (SB2) and shea meal (SM) have been evaluated under pyrolysis (N(2)) and oxidising (dry air) conditions, using a non-isothermal thermogravimetric method (TGA). In the cases of CS and SB1 the peak temperatures were 51 degrees C higher for pyrolysis compared with oxidative degradation, whereas for SB2 and SM the difference was approximately 38 degrees C. However, the differences in the rates of weight loss were significantly higher under oxidising conditions for all the materials studied. Maximum rate of weight loss (%s(-1)) under pyrolysis conditions ranged from 0.10 to 0.18 whereas these values accelerated to the range of 0.19-0.28 under oxidising conditions, corresponding to respective peak temperatures. Samples ranked in order of reactivity (R(M)x10(3)) (%s(-1) degrees C(-1)) are CS=1.31 approximately SM=1.30>SB2=1.14>SB1=0.94 for air and CS=0.54>SB2=0.49>SB1=0.45>SM=0.31 for nitrogen. Shea meal exhibited a complex char combustion behaviour indicating that there may be two distinct types of char derived from fibrous and woody components in the original material. Activation energy calculations were based on the Arrhenius correlation.     

Preparation and characterization of activated carbon derived from the thermo-chemical conversion of chicken manure

Physico-chemical properties of a bioorganic char were modified by pyrolysis in the presence of NaOH, and with subsequent physical activation of carbonaceous species with CO2 a value-added activated carbon was fabricated. Bioorganic char is produced as a co-product during the production of bio-fuel from the pyrolysis of chicken litter. Untreated char contains approximately 37 wt% of C and approximately 43-45 wt% of inorganic minerals containing K, Ca, Fe, P, Cu, Mg, and Si. Carbonization and chemical activation of the char at 600 degrees C in the presence of NaOH in forming gas (4% H2 balanced with Ar) produced mainly demineralized activated carbon having BET (Brunauer, Emmett, and Teller) surface area of 486 m2/g and average pore size of 2.8 nm. Further physical activation with CO2 at 800 degrees C for 30 min resulted in activated carbon with BET surface area of 788 m2/g and average pore size of 2.2 nm. The mineral content was 10 wt%. X-ray photoelectron spectroscopy (XPS) indicated that the latter activation process reduced the pyrrolic- and/or pyridonic-N, increased pyridinic-N and formed quaternary-N at the expense of pyrrolic- and/or pyridonic-N found in the untreated char.     

Bromide-free TEMPO-mediated oxidation of primary alcohol groups in starch and methyl alpha-D-glucopyranoside

TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl)-mediated oxidation of potato starch and methyl alpha-D-glucopyranoside (MGP) was performed in the absence of sodium bromide (NaBr) as co-catalyst, solely using sodium hypochlorite (NaOCl) as the primary oxidant. The low reaction rate associated with a bromide-free process was increased by performing the oxidation at increased temperatures. The reaction proceeded stoichiometrically and with high selectivity and with only minor depolymerisation, provided that temperature and pH were kept < or = 20 degrees C and < 9.0, respectively. At 20 degrees C and pH 8.5, the reaction rate was comparable to that of a corresponding oxidation catalysed by NaBr at 2 degrees C. Consequently, this is a simple approach to raise the TEMPO/NaOCl reaction rate under bromide-free conditions while still maintaining good product properties. At higher oxidation temperatures (> or = 25 degrees C) and under more alkaline conditions (pH > or = 9.0) degradation of the starch skeleton occurred. Simultaneously, side-reactions of the nitrosonium ion lowered the yield of the oxidation. Despite the absence of the NaBr catalyst, the reaction rate-controlling step was found to be the oxidation of the primary hydroxyl groups with the nitrosonium ion. The reaction was first-order in MGP and in TEMPO.     

Growth of the extreme thermophile Sulfolobus acidocaldarius in a hyperbaric helium bioreactor

The relationship between pressure and temperature as it affects microbial growth and metabolism has been examined only for a limited number of bacterial species. Because many newly-discovered, extremely thermophilic bacteria have been isolated from pressurized environments, this relationship merits closer scrutiny. In this study, the extremely thermophilic bacterium, Sulfolobus acidocaldarius, was cultured successfully in a hyperbaric chamber containing helium and air enriched with 5% carbon dioxide. Over a pressure range of approximately 1-120 bar and a temperature range of 67-80 degrees C, growth was achieved in a heterotrophic medium with the air mixture at partial pressures up to 3.5 bar. Helium was used to obtain the final, desired incubation pressure. No significant growth was noted above 80 degrees C over the same range of hyperbaric pressures, or at 70 degrees C when pressure was applied hydrostatically. Growth experiments conducted under hyperbaric conditions may provide a means to study these bacteria under simulated in situ conditions and simultaneously avoid the complications associated with hydrostatic experiments. Results indicate that hyperbaric helium bioreactors will be important in the study of extremely thermophilic bacteria that are isolated from pressurized environments.     

Pressurised pyrolysis of Miscanthus using a fixed bed reactor

Miscanthus x giganteus was pyrolysed, in a fixed bed reactor in a constant flow of dinitrogen gas, at a rate of 13°C/min from ambient to 550°C, then held for 25 min at this temperature. The pressures employed ranged from atmospheric to 26 bar. The major compounds identified in the bio-oil were water, phenol, and phenol derivatives. The water contents impact on the usefulness of the bio-oil as a fuel. However, the phenols could provide useful platform chemicals and products. The properties of the char were determined using elemental analyses, surface area measurements using the Brunauer-Emmett-Teller equation, a calorimetric bomb, Scanning Electron Microscopy, and solid state (13)C NMR spectroscopy. The chars were highly carbonised, especially at the higher pressures, and provided thermally stable materials. Pressure impacted greatly on the surface area. Char formed at atmospheric pressure had a surface area of 162 m(2)/g, whereas that from the highest pressure applied was only 0.137 m(2)/g.     

Production Factors Controlling the Physical Characteristics of Biochar Derived from Phytoremediation Willow for Agricultural Applications

Willow, a leading bioenergy feedstock, may be planted for bioremediation and has been used, more recently, as the biomass feedstock in the manufacture of biochar for agricultural applications. Here, we present a detailed study of the physical and chemical factors affecting willow char properties, where the feedstock is a by-product of bioremediation, potentially transferring pollutants such as heavy metals to the wood feed. Biochar samples were produced via pyrolysis of short-rotation coppice willow, grown on contaminated land, using several treatment times at heat treatment temperatures (HTTs) in the range 350–650 °C, under a constant flow of argon, set at either 100 or 500 mL min^?1. The samples were analysed for yield, elemental analysis and structural characteristics, including surface area and pore size distribution, surface functionality and metal content. All chars obtained have high fixed carbon contents but vary in surface characteristics with a marked increase in basic character with increasing HTT, ascribed to the removal of surface oxygen moieties. Results indicate a minimum pyrolysis temperature of 450 °C is required to produce a defined mesoporous structure, as required to facilitate oxygen transport, HTT?≥?550 °C produces total surface area of >170 m² g^?1 and, more importantly, an appreciable external surface area suitable for microbial colonisation. The data show that selection and optimisation of char properties is possible; however, the interplay of factors may mean some compromise is required.     

Influence of manure types and pyrolysis conditions on the oxidation behavior of manure char

Livestock manure can be quickly converted into valuable products (H₂, syn-gas and char) by low temperature gasification. Manure char combustion offers energy for the gasification reactions. In the paper, the influence of manure type and pyrolysis conditions on manure char reactivity is addressed. The results show that the oxidation behaviors of manure char are dependent strongly on manure type and pyrolysis conditions employed. The large difference between the oxidation behaviors of pig and hen manure chars can be attributed to the difference in the organic materials and minerals of the samples. High final temperature, flash pyrolysis and water steam atmosphere used for char preparation promote the resultant char reactivity.     

Physical and thermochemical characterization of rice husk char as a potential biomass energy source

The fixed bed pyrolysis of rice husk was studied under conventional conditions with the aim of determining the characteristics of the charcoal formed for its applicability as a solid fuel. Thermoanalytic methods were used to determine the kinetic parameters of its combustion. Palletisation using different binders and techniques to improve the time of sustained combustion of the char pallets were investigated. The optimum temperature for carbonization to obtain a char having moderately high heating value was found as 400 degrees C. For the active char combustion zone, the order of reaction was nearly 1, the activation energy 73.403 kJ/mol and the pre-exponential factor 4.97 x 10(4)min(-1). Addition of starch as a binder and 10% ferrous sulphate heptahydrate or sodium hypophosphite as an additive enhanced the ignitibility of the char pallets.     

Escherichia coli inactivation mechanism by pressurized CO2

The effects of pressurized CO2 on the survival of Escherichia coli and the mechanism of cell inactivation were studied. Bacterial cultures were inoculated in nutrient broth and incubated at 30 degrees C for 18 h. Exposure of the cells to CO2 under pressures ranging from 2.5 to 25 MPa and at temperatures between 8 and 40 degrees C was performed in a double-walled reactor with a 1 L capacity. The effect of the treatment on the cells was evaluated by plating and by transmission and scanning electron microscopy observation. Vapour CO2 generated a bacteriostatic effect. In liquid or supercritical state, CO2 provided a bactericidal effect. The bactericidal effect increased with pressure and temperature. The mechanism of cell inactivation by liquid CO2 involved two stages. First, cell stress caused by the CO2 penetration provoked cell wall collapse and cellular content precipitation. Second, the cell death caused by supercritical extraction of intracellular substances and cell envelope perforation resulted in leaking of intracellular constituents. In supercritical conditions, the cell inactivation process had one single phase: cellular death.