Pyrolytic characteristics of biomass acid hydrolysis residue rich in lignin

Pyrolytic characteristics of acid hydrolysis residue (AHR) of corncob and pinewood (CAHR, WAHR) were investigated using a thermo-gravimetric analyzer (TGA) and a self-designed pyrolysis apparatus. Gasification reactivity of CAHR char was then examined using TGA and X-ray diffractometer. Result of TGA showed that thermal degradation curves of AHR descended smoothly along with temperature increasing from 150 °C to 850 °C, while a “sharp mass loss stage” for original biomass feedstock (OBF) was observed. Char yield from AHR (42.64-30.35 wt.%) was found to be much greater than that from OBF (26.4-19.15 wt.%). In addition, gasification reactivity of CAHR char was lower than that of corncob char, and there was big difference in micro-crystallite structure. It was also found that CAHR char reactivity decreased with pyrolysis temperature, but increased with pyrolysis heating rate and gasification temperature at 850-950 °C. Furthermore, CAHR char reactivity performed better under steam atmosphere than under CO₂ atmosphere.     

Effects of the reforming reagents and fuel species on tar reforming reaction

In this study, using wood chips and polyethylene (PE) as fuels, the effects of air and/or steam as reagents on the tar reforming were clarified quantitatively with a simulated gasifier/reformer apparatus of a two-staged gasification process. The results show that when only steam or air was supplied into the reformer, the tar residual rate (defined as the ratio of the tar amount in the reformed gas to the tar amount in the pyrolysis gas) and the carbon particulate concentration in both reformed gases produced from pyrolysis gases of wood chips and PE decreased with the increase of the steam ratio (H₂O/C, 0–1.0) or the air ratio (ER, 0–0.30). Supplying steam into the reformer to suppress carbon particulate formation for PE pyrolysis gas is more effective than for wood chips pyrolysis gas. Comparing with the results of steam only reforming, the effect of air supply on reduction of the tar residual rate was more significant, while that on suppression of carbon particulate formation was smaller.     

Comparison of the pyrolysis behavior of lignins from different tree species

Despite the increasing importance of biomass pyrolysis, little is known about the pyrolysis behavior of lignin—one of the main components of biomass—due to its structural complexity and the difficulty in its isolation. In the present study, we extracted lignins from Manchurian ash (Fraxinus mandschurica) and Mongolian Scots pine (Pinus sylvestris var. mongolica) using the Bjorkman procedure, which has little effect on the structure of lignin. Fourier transform infrared (FTIR) spectrometry was used to characterize the microstructure of the Bjorkman lignins, i.e., milled wood lignins (MWLs), from the different tree species. The pyrolysis characteristics of MWLs were investigated using a thermogravimetric analyzer, and the release of the main volatile and gaseous products of pyrolysis were detected by FTIR spectroscopy. During the pyrolysis process, MWLs underwent thermo-degradation over a wide temperature range. Manchurian ash MWL showed a much higher thermal degradation rate than Mongolian Scots pine MWL in the temperature range from 290–430 °C. High residue yields were achieved at 37 wt.% for Mongolian Scots pine MWL and 26 wt.% for Manchurian ash MWL. In order to further investigate the mechanisms of lignin pyrolysis, we also analyzed the FTIR profiles for the main pyrolysis products (CO₂, CO, methane, methanol, phenols and formaldehyde) and investigated the variation in pyrolysis products between the different MWLs.     

Pyrolysis characteristics and kinetics of Arundo donax using thermogravimetric analysis

The increase of the price of fossil means, as well as their programmed disappearing, contributed to increase among appliances based on biomass and energy crops. The thermal behavior of Arundo donax by thermogravimetric analysis was studied under inert atmosphere at heating rates ranging from 5 to 20 °C min⁻¹ from room temperature to 750 °C. Gaseous emissions as CO₂, CO and volatile organic compounds (VOC) were measured and global kinetic parameters were determined during pyrolysis with the study of the influence of the heating rate. The thermal process describes two main phases. The first phase named active zone, characterizes the degradation of hemicellulose and cellulose polymers. It started at low temperature (200 °C) comparatively to wood samples and was finished at 350 °C. The pyrolysis of the lignin polymer occurred during the second phase from 350 to 750 °C, named passive zone. Carbon oxides are emitted during the active zone whereas VOC are mainly formed during the passive zone. Mass losses, mass loss rates and emission factors were strongly affected by the variation of the heating rate in the active zone. It was found that the global pyrolysis of A. donax can be satisfactorily described using global independent reactions model for hemicellulose and cellulose in the active zone. The activation energy for hemicellulose was not affected by a variation of the heating rate with a value close to 110 kJ mol⁻¹ and presented a reaction order close to 0.5. An increase of the heating rate decreased the activation energy of the cellulose. However, a first reaction order was observed for cellulose decomposition. The experimental results and kinetic parameters may provide useful data for the design of pyrolytic processing system using A. donax as feedstock.     

An evaluation of pyrolytic techniques with regard to the Apollo 11, 12 and 14 lunar samples analyses

Two different pyrolysis techniques have been used in the analysis of lunar fines. The first technique involved pyrolysis at 700°C under an inert atmosphere in a flowing He system at normal pressure. The products were collected at liquid N₂ temperature and then allowed to pass instantaneously into a combined capillary gas chromatograph-mass spectrometer. The second technique consisted of a vacuum pyrolysis where the sample was first degassed at 150°C and then pyrolyzed at 500°C and 1000°C consecutively. The products were again collected at liquid N₂ temperature and then they were directly introduced to the ion source of the mass spectrometer through a modified gas inlet system.An evaluation of the two techniques based on control experiments has shown that the probability of secondary reactions is greater in the inert atmosphere pyrolysis method. Pyrolysis of benzene in He under atmospheric pressure at 600°C showed the presence of small quantities of biphenyl and trace amounts of naphthalene. Biphenyl pyrolyzed under vacuum at 600, 700, 800 and 900°C by passing through a hot zone containing a quartz wool plug showed the presence of a wide range of synthesis and breakdown products as the temperature increased.These experiments have shown the importance of taking into account the factors that influence pyrolytic degradation and/or the synthesis of products. These can be diffusion effects, involving sample size, sample form, pyrolysis pressure conditions; temperature, catalytic effects from the pyrolysis vessel, contamination, perhaps other factors. Pyrolysis is an effective method of analysis if used under carefully controlled conditions. Pyrolysis of Apollo 14 lunar fines and scrapings from an astronaut's glove gave different products by mass spectrometry and showed different looking flaky materials upon scanning electron microscopy.     

Effects of Feedstock and Pyrolysis Temperature on Biochar Adsorption of Ammonium and Nitrate

Biochar produced by pyrolysis of biomass can be used to counter nitrogen (N) pollution. The present study investigated the effects of feedstock and temperature on characteristics of biochars and their adsorption ability for ammonium N (NH₄ ⁺-N) and nitrate N (NO₃ ⁻-N). Twelve biochars were produced from wheat-straw (W-BC), corn-straw (C-BC) and peanut-shell (P-BC) at pyrolysis temperatures of 400, 500, 600 and 700°C. Biochar physical and chemical properties were determined and the biochars were used for N sorption experiments. The results showed that biochar yield and contents of N, hydrogen and oxygen decreased as pyrolysis temperature increased from 400°C to 700°C, whereas contents of ash, pH and carbon increased with greater pyrolysis temperature. All biochars could sorb substantial amounts of NH₄ ⁺-N, and the sorption characteristics were well fitted to the Freundlich isotherm model. The ability of biochars to adsorb NH₄ ⁺-N followed: C-BC>P-BC>W-BC, and the adsorption amount decreased with higher pyrolysis temperature. The ability of C-BC to sorb NH₄ ⁺-N was the highest because it had the largest cation exchange capacity (CEC) among all biochars (e.g., C-BC400 with a CEC of 38.3 cmol kg⁻¹ adsorbed 2.3 mg NH₄ ⁺-N g⁻¹ in solutions with 50 mg NH₄ ⁺ L⁻¹). Compared with NH₄ ⁺-N, none of NO₃ ⁻-N was adsorbed to biochars at different NO₃ ⁻ concentrations. Instead, some NO₃ ⁻-N was even released from the biochar materials. We conclude that biochars can be used under conditions where NH₄ ⁺-N (or NH₃) pollution is a concern, but further research is needed in terms of applying biochars to reduce NO₃ ⁻-N pollution.     

The mechanism for thermal decomposition of cellulose and its main products

Experiment is performed to investigate the mechanism of the cellulose pyrolysis and the formation of the main products. The evolution of the gaseous products is examined by the 3-D FTIR spectrogram at the heating rate of 5–60 K/min. A pyrolysis unit, composed of fluidized bed reactor, carbon filter, vapour condensing system and gas storage, is employed to investigate the products of the cellulose pyrolysis under different temperatures (430–730 °C) and residence time (0.44–1.32 s). The composition in the bio-oil is characterized by GC–MS while the gases sample is analyzed by GC. The effects of temperature and residence time on the main products in bio-oil (LG, 5-HMF, FF, HAA, HA and PA) are examined thoroughly. Furthermore the possible routes for the formation of the products are developed from the direct conversion of cellulose molecules and the secondary reactions of the fragments. It is found that the formation of CO is enhanced with elevated temperature and residence time, while slight change is observed for the yield of CO₂.     

Tar reduction in pyrolysis vapours from biomass over a hot char bed

The behaviour of pyrolysis vapours over char was investigated in order to maximise tar conversion for the development of a new fixed bed gasifier. Wood samples were decomposed at a typical pyrolysis temperature (500 °C) and the pyrolysis vapours were then passed directly through a tar cracking zone in a tubular reactor. The product yields and properties of the condensable phases and non-condensable gases were studied for different bed lengths of char (0–450 mm), temperatures (500–800 °C), particle sizes (10 and 15 mm) and nitrogen purge rates (1.84–14.70 mm/s). The carbon in the condensable phases showed about 66% reduction by a 300 mm long char section at 800 °C, compared to that for pyrolysis at 500 °C. The amount of heavy condensable phase decreased with increasing temperature from about 18.4 wt% of the biomass input at 500 °C to 8.0 wt% at 800 °C, forming CO, H₂ and other light molecules. The main mode of tar conversion was found to be in the vapour phase when compared to the results without the presence of char. The composition of the heavy condensable phase was simplified into much fewer secondary and tertiary tar components at 800 °C. Additional measures were required to maximise the heterogeneous effect of char for tar reduction.     

Pyrolysis temperature and steam activation effects on sorption of phosphate on pine sawdust biochars in aqueous solutions

Biochar can be used as an adsorbent for phosphate removal in aquatic environments to treat eutrophication problems. Designing biochars that have large phosphate adsorption capacity through altering pyrolysis conditions and applying activation techniques will improve phosphate removal efficiency. In this study, four pine sawdust biochars were produced at 300 and 550 °C with and without steam activation. Batch sorption experiments including isotherm and kinetic studies were conducted to understand how phosphate removal capabilities and adsorption mechanisms of biochars were affected by pyrolysis temperature and steam activation. Our results showed that the steam activation and pyrolysis temperature did not affect phosphate adsorption by the biochars. The four biochars removed <4% of phosphate from the aqueous solution, which were not affected by the pH of the solution and biochar application rate. The repulsion forces between biochar surfaces and phosphate ions were likely the cause of the low adsorption.     

Numerical simulation of the pyrolysis zone in a downdraft gasification process

Models of the gasification process are mostly based on lumped analysis with distinct zones of the process treated as one entity. The study presented here was conducted to develop a more useful model specifically for the pyrolysis zone of the reactor of a downdraft gasifier based on finite computation method. Applying principles of energy and mass conservation, governing equations formed were solved by implicit finite difference method on the node of 100 throughout the length of the considered pyrolysis range (20 cm). Heat transfer considered convection, conduction, and the influence of solid radiation components. Chemical kinetics concept was also adopted to simultaneously solve the temperature profile and feedstock consumption rate on the pyrolysis zone. The convergence criteria were set at 10⁻⁶ and simulation used Fortran Power Station 4.0. Validation experiments were also conducted resulting in maximum deviation of 24 °C and 0.37 kg/h for temperature and feedstock feed rate, respectively.     

Pyrolysis of safflower (Charthamus tinctorius L.) seed press cake: part 1. The effects of pyrolysis parameters on the product yields

Safflower (Charthamus tinctorius L.) seed press cake was pyrolysed in a fixed-bed reactor. The effects of pyrolysis temperature, heating rate and sweep gas flow rates on the yields of the products were investigated. Pyrolysis runs were performed using pyrolysis temperatures between 400 and 600 °C with heating rates of 10, 30 and 50 °C min⁻¹. The obtained bio-char, gas and bio-oil yields ranged between 25 and 34 wt%, 19 and 25 wt%, and 28 and 36 wt%, respectively, at different pyrolysis conditions. The highest liquid yield was obtained at 500 °C pyrolysis temperature with a heating rate of 50 °C min⁻¹ under the sweep gas of N₂ with a flow rate of 100 cm³ min⁻¹. Employing the higher heating rate of 50 °C min⁻¹ results in maximum bio-oil yield, probably due to the decrease in mass transfer limitations. According to the results obtained under the conditions of this study, the effects of pyrolysis temperature and sweep gas flow rate are more significant than the effect of heating rate on the yields.     

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.     

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.     

Pyrolysis of grape bagasse: effect of pyrolysis conditions on the product yields and characterization of the liquid product

In this study, pyrolysis of grape bagasse was investigated with the aim to study the product distribution and their chemical compositions and to identify optimum process conditions for maximizing the bio-oil yield. Particular investigated process variables were temperature (350-600 °C), heating rate (10-50 °C/min) and nitrogen gas flow rate (50-200 cm³/min). The maximum oil yield of 27.60% was obtained at the final pyrolysis temperature of 550 °C, sweeping gas flow rate of 100 cm³/min and heating rate of 50 °C/min in a fixed-bed reactor. The elemental analysis and heating value of the bio-oils were determined, and then the chemical composition of the bio-oil was investigated using chromatographic and spectroscopic techniques such as column chromatography, ¹H NMR and FTIR. The fuel properties of the bio-oil such as flash point, viscosity and density were also determined. The bio-oils obtained from grape bagasse were presented as an environmentally friendly feedstock candidate for bio-fuels.     

A renewable energy source — hydrocarbon gases resulting from pyrolysis of the marine nanoplanktonic alga Emiliania huxleyi

The marine coccolithophore, Emiliania huxleyi, grown in the laboratory was subjected to vacuum pyrolysis at various temperatures from 100 to 500 °C. The highest yield of pyrolytic gases (183 mL g⁻¹ dry cells) was obtained at 400 °C. The amount of total hydrocarbon gas produced at 400 °C was 129 mL, about 10 times higher than at 300 °C. CH₄ was the major component at the high gas-production stage (400–500 °C). The great increase in hydrocarbon gases at 400 °C was accompanied by a marked decrease in liquid saturates and aromatics. The results indicate that the liquid hydrocarbons (oil) produced by pyrolysis at lower temperature is a direct source for the formation of the hydrocarbon gases. Due to its large potential for the production of biomass and hydrocarbons with low energy input, E. huxleyi is suggested as one of candidates for the production of renewable fuels. This revised version was published online in July 2006 with corrections to the Cover Date.     

Biomass fast pyrolysis in a fluidized bed reactor under N2, CO2, CO, CH4 and H2 atmospheres

Biomass fast pyrolysis is one of the most promising technologies for biomass utilization. In order to increase its economic potential, pyrolysis gas is usually recycled to serve as carrier gas. In this study, biomass fast pyrolysis was carried out in a fluidized bed reactor using various main pyrolysis gas components, namely N₂, CO₂, CO, CH₄ and H₂, as carrier gases. The atmosphere effects on product yields and oil fraction compositions were investigated. Results show that CO atmosphere gave the lowest liquid yield (49.6%) compared to highest 58.7% obtained with CH₄. CO and H₂ atmospheres converted more oxygen into CO₂ and H₂O, respectively. GC/MS analysis of the liquid products shows that CO and CO₂ atmospheres produced less methoxy-containing compounds and more monofunctional phenols. The higher heating value of the obtained bio-oil under N₂ atmosphere is only 17.8 MJ/kg, while that under CO and H₂ atmospheres increased to 23.7 and 24.4 MJ/kg, respectively.     

Relationships among Isoprene Emission Rate, Photosynthesis, and Isoprene Synthase Activity as Influenced by Temperature

Isoprene emissions from the leaves of velvet bean (Mucuna pruriens L. var utilis) plants exhibited temperature response patterns that were dependent on the plant's growth temperature. Plants grown in a warm regimen (34/28°C, day/night) exhibited a temperature optimum for emissions of 45°C, whereas those grown in a cooler regimen (26/20°C, day/night) exhibited an optimum of 40°C. Several previous studies have provided evidence of a linkage between isoprene emissions and photosynthesis, and more recent studies have demonstrated that isoprene emissions are linked to the activity of isoprene synthase in plant leaves. To further explore this linkage within the context of the temperature dependence of isoprene emissions, we determined the relative temperature dependencies of photosynthetic electron transport, CO₂ assimilation, and isoprene synthase activity. When measured over a broad range of temperatures, the temperature dependence of isoprene emission rate was not closely correlated with either the electron transport rate or the CO₂ assimilation rate. The temperature optima for electron transport rate and CO₂ assimilation rate were 5 to 10°C lower than that for the isoprene emission rate. The dependence of isoprene emissions on photon flux density was also affected by measurement temperature in a pattern independent of those exhibited for electron transport rate and CO₂ assimilation rate. Thus, despite no change in the electron transport rate or CO₂ assimilation rate at 26 and 34°C, the isoprene emission rate changed markedly. The quantum yield of isoprene emissions was stimulated by a temperature increase from 26 to 34°C, whereas the quantum yield for CO₂ assimilation was inhibited. In greenhouse-grown aspen leaves (Populus tremuloides Michaux.), the high temperature threshold for inhibition of isoprene emissions was closely correlated with the high temperature-induced decrease in the in vitro activity of isoprene synthase. When taken together, the results indicate that although there may be a linkage between isoprene emission rate and photosynthesis, the temperature dependence of isoprene emission is not determined solely by the rates of CO₂ assimilation or electron transport. Rather, we propose that regulation is accomplished primarily through the enzyme isoprene synthase.     

Production and characterization of pyrolysis liquids from sunflower-pressed bagasse

Pyrolysis experiments on sunflower (Helianthus annus L.)-pressed bagasse were performed in a fixed-bed tubular reactor. The effects of nitrogen flow rate and final pyrolysis temperature on the pyrolysis product yields and chemical compositions were investigated. The maximum bio-oil yield of 52.10 wt.% was obtained in a nitrogen atmosphere with flow rate of 50 ml min(-1) and at a pyrolysis temperature of 550 degrees C with a heating rate of 5 degrees C s(-1). The chemical characterization results showed that the oil obtained from sunflower-pressed bagasse may be a potentially valuable source as fuel or chemical feedstocks.     

Liquid hydrocarbon fuels obtained by the pyrolysis of soybean oils

The pyrolysis reactions of soybean oils have been studied. The pyrolytic products were analyzed by GC–MS and FTIR and show the formation of olefins, paraffins, carboxylic acids and aldehydes. Several kinds of catalysts were compared. It was found that the amounts of carboxylic acids and aldehydes were significantly decreased by using base catalysts such as Na₂CO₃ and K₂CO₃. The low acid value pyrolytic products showed good cold flow properties and good solubility in diesel oil at low temperature. The results presented in this work have shown that the pyrolysis of soybean oils generates fuels that have chemical composition similar to petroleum based fuels.     

Reduction of metabolic rate and thermoregulation during daily torpor

Physiological mechanisms causing reduction of metabolic rate during torpor in heterothermic endotherms are controversial. The original view that metabolic rate is reduced below the basal metabolic rate because the lowered body temperature reduces tissue metabolism has been challenged by a recent hypothesis which claims that metabolic rate during torpor is actively downregulated and is a function of the differential between body temperature and ambient temperature, rather than body temperature per se. In the present study, both the steady-state metabolic rate and body temperature of torpid stripe-faced dunnarts, Sminthopsis macroura (Dasyuridae: Marsupialia), showed two clearly different phases in response to change of air temperature. At air temperatures between 14 and 30°C, metabolic rate and body temperature decreased with air temperature, and metabolic rate showed an exponential relationship with body temperature (r ²=0.74). The Q ₁₀ for metabolic rate was between 2 and 3 over the body temperature range of 16 to 32°C. The difference between body temperature and air temperature over this temperature range did not change significantly, and the metabolic rate was not related to the difference between body temperature and air temperature (P=0.35). However, the apparent conductance decreased with air temperature. At air temperatures below 14°C, metabolic rate increased linearly with the decrease of air temperature (r ²=0.58) and body temperature was maintained above 16°C, largely independent of air temperature. Over this air temperature range, metabolic rate was positively correlated with the difference between body temperature and air temperature (r ²=0.61). Nevertheless, the Q ₁₀ for metabolic rate between normothermic and torpid thermoregulating animals at the same air temperature was also in the range of 2–3. These results suggest that over the air temperature range in which body temperature of S. macroura was not metabolically defended, metabolic rate during daily torpor was largely a function of body temperature. At air temperatures below 14°C, at which the torpid animals showed an increase of metabolic rate to regulate body temperature, the negative relationship between metabolic rate and air temperature was a function of the differential between body temperature and air temperature as during normothermia. However, even in thermoregulating animals, the reduction of metabolic rate from normothermia to torpor at a given air temperature can also be explained by temperature effects.Abbreviations BM body mass - BMR basal metabolic rate - C apparent conductance - MR metabolic rate - RMR resting metabolic rate - RQ respiratory quotient - T _a air temperature - T _b body temperature - T _lc lower critical temperature - T _tc critical air temperature during torpor - TMR metabolic rate during torpor - TNZ thermoneutral zone - T difference between body temperature and air temperature - VO₂ rate of oxygen consumption