Modelling of pyrolysis of large wood particles

A fully transient mathematical model has been developed to describe the pyrolysis of large biomass particles. The kinetic model consists of both primary and secondary reactions. The heat transfer model includes conductive and internal convection within the particle and convective and radiative heat transfer between the external surface and the bulk. An implicit Finite Volume Method (FVM) with Tridiagonal Matrix Algorithm (TDMA) is employed to solve the energy conservation equation. Experimental investigations are carried out for wood fines and large wood cylinder and sphere in an electrically heated furnace under inert atmosphere. The model predictions for temperature and mass loss histories are in excellent agreement with experimental results. The effect of internal convection and particle shrinkage on pyrolysis behaviour is investigated and found to be significant. Finally, simulation studies are carried out to analyze the effect of bulk temperature and particle size on total pyrolysis time and the final yield of char.     

Microwave induced pyrolysis of oil palm biomass

The purpose of this paper was to carry out microwave induced pyrolysis of oil palm biomass (shell and fibers) with the help of char as microwave absorber (MA). Rapid heating and yield of microwave pyrolysis products such as bio-oil, char, and gas was found to depend on the ratio of biomass to microwave absorber. Temperature profiles revealed the heating characteristics of the biomass materials which can rapidly heat-up to high temperature within seconds in presence of MA. Some characterization of pyrolysis products was also presented. The advantage of this technique includes substantial reduction in consumption of energy, time and cost in order to produce bio-oil from biomass materials. Large biomass particle size can be used directly in microwave heating, thus saving grinding as well as moisture removal cost. A synergistic effect was found in using MA with oil palm biomass.     

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.     

Non-isothermal thermogravimetric analysis of oil-palm solid wastes

Thermal decomposition of oil-palm solid wastes, including oil-palm shell, fibre and kernel, was studied by thermogravimetric analysis (TGA). Effect of heating rate and sample particle size on the behaviour of thermogram and kinetic parameters were investigated. The one-step global model, two-step consecutive model and two-parallel reactions model were used to simulate the pyrolysis process of the three materials studied. The one-step global model was able to describe the fractional weight loss upon pyrolysis of oil-palm kernel reasonably well but gave a large deviation for oil-palm shell and fibre. The two-step consecutive model could improve the fitting for oil-palm shell and fibre, but it cannot account for the inflection characteristic of the thermogram. Prediction by the two-parallel reactions model gave the best fitting with the experimental data of all oil-palm wastes under all pyrolysis conditions investigated. This proposed model was also tested with other biomass materials and proved to be satisfactory.     

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.     

熔盐热裂解生物质制生物油

为探讨热裂解条件对熔盐中生物质热裂解制生物油的影响,在自行设计的反应器中,以摩尔比为7∶6的ZnCl2-KCl混合熔盐作为热裂解的热载体、催化剂和分散剂,考察了500 ℃时添加的金属盐和生物质原料的影响,并采用气相色谱-质谱仪 (GC-MS) 对生物油的主要组成进行了分析。结果表明：添加的金属盐显著影响热裂解产物得率,稀土金属盐显著提高生物油得率,降低生物油的含水率,添加摩尔分数为5.0％ LaCl3时生物油得率为32.0％,含水率为61.5％;水稻秸秆热裂解的生物油和焦炭得率较高,稻壳热裂解的气体得率较高;金属添加盐对生物油组成有较强的选择性,LiCl和FeCl2对生物质向小分子裂解具有较强的催化作用,而CrCl3、CaCl2和LaCl3对生物油二次裂解具有抑制作用。研究结果为熔盐热裂解生物质制生物油提供了参考。     

Experimental study on air-stream gasification of biomass micron fuel (BMF) in a cyclone gasifier

Based on biomass micron fuel (BMF) with particle size of less than 250 microm, a cyclone gasifier concept has been considered in our laboratory for biomass gasification. The concept combines and integrates partial oxidation, fast pyrolysis, gasification, and tar cracking, as well as a shift reaction, with the purpose of producing a high quality of gas. In this paper, experiments of BMF air-stream gasification were carried out by the gasifier, with energy for BMF gasification produced by partial combustion of BMF within the gasifier using a hypostoichiometric amount of air. The effects of ER (0.22-0.37) and S/B (0.15-0.59) and biomass particle size on the performances of BMF gasification and the gasification temperature were studied. Under the experimental conditions, the temperature, gas yields, LHV of the gas fuel, carbon conversion efficiency, stream decomposition and gasification efficiency varied in the range of 586-845 degrees C, 1.42-2.21 N m(3)/kg biomass, 3806-4921 kJ/m(3), 54.44%-85.45%, 37.98%-70.72%, and 36.35%-56.55%, respectively. The experimental results showed that the gasification performance was best with ER being 3.7 and S/B being 0.31 and smaller particle, as well as H(2)-content. And the BMF gasification by air and low temperature stream in the cyclone gasifier with the energy self-sufficiency is reliable.     

Biomass as an energy source: thermodynamic constraints on the performance of the conversion process

In the present work an equilibrium model (gas-solid), based on the minimization of the Gibbs energy, has been used in order to estimate the theoretical yield and the equilibrium composition of the reaction products (syngas and char) of biomass thermochemical conversion processes (pyrolysis and gasification). The data obtained from this model have also been used to calculate the heating value of the fuel gas, in order to evaluate the overall energy efficiency of the thermal conversion stage. The proposed model has been applied both to partial oxidation and steam gasification processes with varying air to biomass (ER) and steam to carbon (SC) ratio values and using different feedstocks; the obtained results have been compared with experimental data and with other model predictions obtaining a satisfactory agreement.     

Comparison of non-catalytic and catalytic fast pyrolysis of corncob in a fluidized bed reactor

Fast pyrolysis of corncob with and without catalyst was investigated in a fluidized bed to determine the effects of pyrolysis parameters (temperature, gas flow rate, static bed height and particle size) and a HZSM-5 zeolite catalyst on the product yields and the qualities of the liquid products. The result showed that the optimal conditions for liquid yield (56.8%) were a pyrolysis temperature of 550 degrees C, gas flow rate of 3.4 L/min, static bed height of 10 cm and particle size of 1.0-2.0mm. The presence of the catalyst increased the yields of non-condensable gas, water and coke, while decreased the liquid and char yields. The elemental analysis showed that more than 25% decrease in oxygen content of the collected liquid in the second condenser with HZSM-5 was observed compared with that without catalyst. The H/C, O/C molar ratios and the higher heating value of the oil fraction in the collected liquid with the catalyst were 1.511, 0.149 and 34.6 MJ/kg, respectively. It was indicated that the collected liquid in the second condenser had high qualities and might be used as transport oil.     

Kinetic studies of overlapping pyrolysis reactions in industrial waste activated sludge

A sludge pyrolytic kinetics model was established in this study. Two types of sewage sludge from different industrial wastewater treatment plant produced different DTG (Derivative Thermogravimetry) shapes with an overlapping pattern. The multi-heating rate method was conducted to evaluate the kinetics for obtaining reasonable pyrolysis mechanisms and DTG curves were divided into several peaks using the Lorentz fitting method based on the composition of the sludge and the desire for precision. The peaks formed corresponded to the pyrolysis reactions of volatile matter, microbe cells, proteins, inorganic substances and char respectively, which can be reasonably explained based on the results from the flue gas analyzer and the chemical analysis. Two types of sewage sludge were found to have similar pyrolysis mechanisms. Reasonable reasons were also given to explain the distortion and lag observed in the DTG curves and pyrolysis mechanism.     

Crop Management Impacts Biofuel Quality: Influence of Switchgrass Harvest Time on Yield, Nitrogen and Ash of Fast Pyrolysis Products

Although upgrading bio-oil from fast pyrolysis of biomass is an attractive pathway for biofuel production, nitrogen (N) and mineral matter carried over from the feedstock to the bio-oil represents a serious contaminant in the process. Reducing the N and ash content of biomass feedstocks would improve process reliability and reduce production costs of pyrolytic biofuels. This study investigated: (1) How does switchgrass harvest date influence the yield, N concentration ([N]), and ash concentration of biomass and fast pyrolysis products? and (2) Is there a predictive relationship between [N] of switchgrass biomass and [N] of fast pyrolysis products? Switchgrass from five harvest dates and varying [N] from central Iowa were pyrolyzed using a free-fall reactor. Harvestable biomass peaked in August (8.6 Mg ha^?1), dropping significantly by November (6.7 Mg ha^?1, P?=?0.0027). Production of bio-oil per unit area mirrored that of harvested biomass at each harvest date; however, bio-oil yield per unit dry biomass increased from 46.6 % to 56.7 % during the season (P?=?0.0018). Allowing switchgrass to senesce lowered biomass [N] dramatically, by as much as 68 % from June to November (P?<?0.0001). Concurrently, bio-oil [N] declined from 0.51 % in June to 0.17 % by November (P?<?0.0001). Significant reductions in ash concentration were also observed in biomass and char. Finally, we show for the first time that the [N] of switchgrass biomass is a strong predictor of the [N] of bio-oil, char, and non-condensable gas with R ² values of 0.89, 0.94, and 0.88, respectively.     

Pyrolysis of ramie residue: kinetic study and fuel gas produced in a cyclone furnace

The thermal decomposition behavior of ramie residue (RR) and the characteristics of fuel gas produced in a cyclone furnace were studied. The pyrolysis kinetics was investigated using thermogravimetric analysis (TGA) at heating rates of 5-20°C/min. The results showed that RR mainly decomposed between 250 and 390°C, and the apparent activation energy ranged from 200 to 258 kJ/mol. In the cyclone furnace, fast pyrolysis, partial combustion and gasification occurred almost simultaneously, and the thermal energy was supplied by partial combustion of RR powder at the hypo stoichiometric amount of air. Higher effect of equivalence ratio (ER) led to higher reaction temperature and fewer contents of tar and char, but too high ER lowered fuel gas content and degraded fuel gas quality. Over the ranges of the experimental conditions, the gas yield varied between 1.07 and 2.08 N m(3)/kg and the LHV was between 3350 and 4798 kJ/Nm(3).     

Time‐dependent climate impact and energy efficiency of combined heat and power production from short‐rotation coppice willow using pyrolysis or direct combustion

A life cycle assessment of a Swedish short‐rotation coppice willow bioenergy system generating electricity and heat was performed to investigate how the energy efficiency and time‐dependent climate impact were affected when the feedstock was converted into bio‐oil and char before generating electricity and heat, compared with being combusted directly. The study also investigated how the climate impact was affected when part of the char was applied to soil as biochar to act as a carbon sequestration agent and potential soil improver. The energy efficiencies were calculated separately for electricity and heat as the energy ratios between the amount of energy service delivered by the system compared to the amount of external energy inputs used in each scenario after having allocated the primary energy related to the inputs between the two energy services. The energy in the feedstock was not included in the external energy inputs. Direct combustion had the highest energy efficiency. It had energy ratios of 10 and 36 for electricity and heat, respectively. The least energy‐efficient scenario was the pyrolysis scenario where biochar was applied to soils. It had energy ratios of 4 and 12 for electricity and heat, respectively. The results showed that pyrolysis with carbon sequestration might be an option to counteract the current trend in global warming. The pyrolysis system with soil application of the biochar removed the largest amount of from the atmosphere. However, compared with the direct combustion scenario, the climate change mitigation potential depended on the energy system to which the bioenergy system delivered its energy services. A system expansion showed that direct combustion had the highest climate change mitigation potential when coal or natural gas were used as external energy sources to compensate for the lower energy efficiency of the pyrolysis scenario.     

Thermal degradation mechanisms of wood under inert and oxidative environments using DAEM methods

The pyrolytic behavior of wood is investigated under inert and oxidative conditions. The TGA experiment is given a temperature variation from 323 to 1173 K by setting the heating rate between 5 and 40 K/min. The results of DTG curves show that the hemicellulose shoulder peak for birch is more visible under inert atmosphere due to the higher content of reactive xylan-based hemicellulose (mannan-based for pine). When oxygen presents, thermal reactivity of biomass (especially the cellulose) is greatly enhanced due to the acceleration of mass loss in the first stage, and complex reactions occur simultaneously in the second stage when char and lignin oxidize. A new kinetic model is employed for biomass pyrolysis, namely the distributed activation energy model (DAEM). Under inert atmosphere, the distributed activation energy for the two species is found to be increased from 180 to 220 kJ/mol at the solid conversion of 10-85% with the high correlation coefficient. Under oxidative atmosphere, the distributed activation energy is about 175-235 kJ/mol at the solid conversion of 10-65% and 300-770 kJ/mol at the solid conversion of 70-95% with the low correlation coefficient (below 0.90). Comparatively, the activation energy obtained from established global kinetic model is correspondingly lower than that from DAEM under both inert and oxidative environments, giving relatively higher correlation coefficient (more than 0.96). The results imply that the DAEM is not suitable for oxidative pyrolysis of biomass (especially for the second mass loss stage in air), but it could represent the intrinsic mechanism of thermal decomposition of wood under nitrogen better than global kinetic model when it is applicable.     

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.     

The Impact of Hydrothermal and Dilute Acid Pretreatments and Inorganic Metals on Thermal Decomposition of Agricultural Residues and Agricultural Residue Ash Properties

The impacts of hydrothermal and dilute acid pretreatments and alkali and alkaline earth metals (AAEMs) on the thermal degradation of biomass were studied. Besides, the influence of these pretreatments on the biomass ash properties was investigated. The influence of pretreatments on the biomass thermal degradation was manifested in the removal of potassium out of the biomass. The presence of potassium in the biomass catalyzed cellulose thermal degradation and increased the char percentage at temperatures higher than 380 °C. Pretreatments were effective at removing the potassium from biomass and dramatically reduced the char percentage at temperatures higher than 380 °C. It was found that the best burning temperature for biomass ash production was 500 °C because at this temperature the thermal degradation of biomass was completed under pure combustion. It was shown that when burning biomass in oxygen-limited environments, removing AAEMs, particularly potassium, will improve the quality of ash as a potential candidate for supplementary cementitious materials for concrete application.     

Classification of macroalgae as fuel and its thermochemical behaviour

A preliminary classification of five macroalgae from the British Isles; Fucus vesiculosus, Chorda filum, Laminaria digitata, Fucus serratus, Laminaria hyperborea, and Macrocystis pyrifera from South America, has been presented in terms of a Van Krevelen diagram. The macroalgae have been characterised for proximate and ultimate analysis, inorganic content, and calorific value. The different options for thermal conversion and behaviour under combustion and pyrolysis have been evaluated and compared to several types of terrestrial biomass including Miscanthus, short rotation Willow coppice and Oat straw. Thermal treatment of the macroalgae has been investigated using thermogravimetry (TGA) and pyrolysis-gc-ms. Combustion behaviour is investigated using TGA in an oxidising atmosphere. The suitability of macroalgae for the different thermal processing routes is discussed. Ash chemistry restricts the use of macroalgae for direct combustion and gasification. Pyrolysis produces a range of pentosans and a significant proportion of nitrogen containing compounds. High char yields are produced.     

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.     

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.     

Characteristics of rice husk gasification in an entrained flow reactor

Experiments were performed in an entrained flow reactor to better understand the characteristics of biomass gasification. Rice husk was used in this study. Effects of the gasification temperature (700, 800, 900 and 1000 °C) and the equivalence ratio in the range of 0.220.34 on the biomass gasification and the axial gas distribution in the reactor were studied. The results showed that reactions of CnHm were less important in the gasification process except cracking reactions which occurred at higher temperature. In the oxidization zone, reactions between char and oxygen had a more prevailing role. The optimal gasification temperature of the rice husk could be above 900 °C, and the optimal value of ER was 0.25. The gasification process was finished in 1.42 s when the gasification temperature was above 800 °C. A first order kinetic model was developed for describing rice husk air gasification characteristics and the relevant kinetic parameters were determined.