流化床中单颗粒纤维素热解模型研究

为了研究生物质热解过程，该文对纤维素这种生物质中主要组份的流化床热解过程进行了数值模拟。模型在合理选取动力学模型的基础上考虑了单颗粒纤维素在流化床热解过程中由扩散和对流所引起的热量传递，包括了各种重要的气、液相热解产物的质量传递以及颗粒内部压力对过程的影响。计算结果显示，即使是对非常小的颗粒，热解反应热对热解过程的影响也至关重要；而无论是在大颗粒还是小颗粒中，热解液相中间产物流动对能量、质量传递的影响以及挥发份参加颗粒内二次反应的份额则可以忽略。计算还得到不同粒径颗粒热解的产物分布。总体来说，该模型为我们提供了一个探究纤维素热解细节的机会。计算结果可以为实际热解反应器的设计和运行提供依据。     

Reduction of primary tar vapor from biomass by hot char particles in fixed bed gasification

This study investigated the reduction of primary tar vapor from biomass pyrolysis over a bed of hot char particles, focusing on the effect of different operating conditions and char properties. The char samples were prepared from wood, paddy straw, palm kernel shell, and activated carbon. The primary tar was produced from fir wood by pyrolysis at 500 °C and passed through a reactor filled with char particles with different lengths and temperatures.The tar cracking reactions became active above 700 °C, and the presence of hot char particles promoted more tar reduction compared with thermal cracking alone. The mass yield of the primary tar was reduced from 24.8% by pyrolysis to 13.7% by thermal cracking at 800 °C, and further to 7.7% by hot char particles in a reactor volume of 1.48 cm³/g_wood. In terms of carbon yield, these values correspond to 32.1%, 19.9% and 11.8%, respectively. The tar with smaller molecular weights was quickly decomposed to gases, whereas the heavy tar was resistant to cracking, even when the reactor volume was increased to 6.90 cm³/g_wood. The tar cracking behaviors were similar for four char types despite differences in microscopic surface areas, pore-size distributions, and inorganic contents. The results suggest that creating a tar-cracking zone using char particles situated between the pyrolysis and gasification zones could be helpful in converting the primary tar vapor in a downdraft fixed-bed gasifier, but the degree of conversion is not high enough to eliminate tar issues completely.     

Evaluating the effect of potassium on cellulose pyrolysis reaction kinetics

This paper proposes modifications to an existing cellulose pyrolysis mechanism in order to include the effect of potassium on product yields and composition. The changes in activation energies and pre-exponential factors due to potassium were evaluated based on the experimental data collected from pyrolysis of cellulose samples treated with different levels of potassium (0–1% mass fraction). The experiments were performed in a pyrolysis reactor coupled to a molecular beam mass spectrometer (MBMS). Principal component analysis (PCA) performed on the collected data revealed that cellulose pyrolysis products could be divided into two groups: anhydrosugars and other fragmentation products (hydroxyacetaldehyde, 5-hydroxymethylfurfural, acetyl compounds). Multivariate curve resolution (MCR) was used to extract the time resolved concentration score profiles of principal components. Kinetic tests revealed that potassium apparently inhibits the formation of anhydrosugars and catalyzes char formation. Therefore, the oil yield predicted at 500 ^°C decreased from 87.9% from cellulose to 54.0% from cellulose with 0.5% mass fraction potassium treatment. The decrease in oil yield was accompanied by increased yield of char and gases produced via a catalyzed dehydration reaction. The predicted char and gas yield from cellulose were 3.7% and 8.4%, respectively. Introducing 0.5% mass fraction potassium treatment resulted in an increase of char yield to 12.1% and gas yield to 33.9%. The validation of the cellulose pyrolysis mechanism with experimental data from a fluidized-bed reactor, after this correction for potassium, showed good agreement with our results, with differences in product yields of up to 5%.     

Thermochemical conversion of biomass: Gasification by flash pyrolysis study

Thermal decomposition of the basic components of dried biomass (cellulose, lignin, wood) is studied in inert atmosphere. Glucose is studied for comparison. The experiments are performed in an alumina porous bed reactor heated at temperatures between 600 and 1000°C. Flash pyrolysis (heating rate 250°C/s) allows the production of a medium heating value synthetic gas with gas phase conversion thermal efficiency of up to 95 percent. The weight percent of carbon gasified during the pyrolysis reaches 90 percent for cellulose and 70 percent for wood. Light hydrocarbons (CH₄, C₂H₄, C₂H₂, C₂H₆) provide about 50 percent of the energy recovered in the gas. Ethylene represents 5 percent (vol) of the pyrolysis gas. The overall ethylene and acetylene yield is markedly increased at high temperatures for short gas residence times. The pyrolysis reactions are endothermic. The total amount of energy required for pyrolysing wood at 850°C roughly corresponds to 20 percent of its heating value.     

Experimental study of pyrolysis for potential energy,hydrogen and carbon material production from lignocellulosic biomass

Experimental results of slow, fast and catalytic pyrolysis of five lignocellulosic residues (corncobs and corn stalks, sunflower residues, olive kernels and olive tree prunings) are reported in this paper. Pyrolysis took place in two different reactor configurations: a captive sample wire mesh reactor for fast pyrolysis and a fixed bed reactor for non-catalytic and catalytic pyrolysis. Comparison of the experimental results showed that pyrolysis in the captive sample reactor produced more H₂-rich gas than in the fixed bed reactor, while the fixed bed reactor configuration seemed to favor the production of liquid products. Analysis of gaseous, liquid and solid products was performed by GC and GC/MS. Pyrolysis results were assessed, and recommendations for the further use of their products were made.     

Fluidization analysis for catalytic decomposition of methane over carbon blacks for solar hydrogen production

A series of bed collapse tests were conducted for determining the dense fluidization flow rate of a gas-solid mixture in a micro-channel fluidized bed reactor, and a separate simulation was created for calculating the reactor conversion and temperature of the catalytic methane pyrolysis. The minimum fluidization and minimum bubbling flow rates were determined to be 3.04 and 8.07 sccm for a 2 × 4 mm² reactor channel with an average voidage of 0.57; 6.21 and 15.9 sccm for a 4 × 6 mm² channel with an average voidage of 0.42, respectively. By building a correlation between these critical velocities and the cross-sectional area of the fluidized bed reactor channel, the dense fluidization flow rate at the micro-/mini-channel level with an internal diameter range from 0.3 to 1 mm is predicted between 1.47 to 4.21 sccm. In the simulation, an internal diameter of 0.6 mm, a 10-kW solar input rate, and an initial gas flow rate from 0.08 to 0.23 sccm that expands to 1.5–4.3 ccm at the reaction temperature, are considered as the optimal conditions to maintain a reasonable conversion of methane pyrolysis and to keep the mixed fluid in the dense fluidization within the laminar flow range. The conversion of 79% under these conditions was calculated numerically and found to be promising compared to literature reports. An additional force analysis on a single carbon black particle is shown with different reactor orientations to validate the experimental data and simulation results.     

一种测定光催化反应器中紫外光辐射能的新方法

设计了一种利用光导纤维测定多相光催化反应器中紫外光辐射能的新方法，并系统地研究了影响光催化反应器中紫外光辐射能分布规律的各种因素。结果表明：光催化剂对紫外光辐射能的吸收和阻挡作用较大，其紫外光辐射能量与在反应器中的穿透距离之间的关系可用一指数方程表示，Y=8．98exp(-1．1408X)。紫外光辐射能在反应器中轴向上的分布是不均匀的，在反应器的中间处最强，而在反应器上、下两部分则较小。     

A model of wood flash pyrolysis in fluidized bed reactor

With a view of exploiting renewable biomass energy as a highly efficient and clean energy, liquid fuel from biomass pyrolysis, called bio-oil, is expected to play a major role in future energy supply. At present, fluidized bed technology appears to have maximum potential in producing high-quality bio-oil. A model of wood pyrolysis in a fluidized bed reactor has been developed. The effect of main operation parameters on wood pyrolysis product distribution was well simulated. The model shows that reaction temperature plays a major important role in wood pyrolysis. And a good agreement between experimental and theoretical results was obtained. It was shown that particles less than 500 μm could achieve a high heating-up rate to meet flash pyrolysis demand.     

Influence of reaction conditions on bio-oil production from pyrolysis of construction waste wood

The pyrolysis characteristics of construction waste wood were investigated for conversion into renewable liquid fuels. The activation energy of pyrolysis derived from thermogravimetric analysis increased gradually with temperature, from 149.41 kJ/mol to 590.22 kJ/mol, as the decomposition of cellulose and hemicellulose was completed and only lignin remained to be decomposed slowly. The yield and properties of pyrolysis oil were studied using two types of reactors, a batch reactor and a fluidized-bed reactor, for a temperature range of 400–550 °C. While both reactors revealed the maximum oil yield at 500 °C, the fluidized-bed reactor consistently gave larger and less temperature-dependent oil yields than the batch reactor. This type of reactor also reduced the moisture content of the oil and improved the oil quality by minimizing the secondary condensation and dehydration. The oil from the fluidized-bed reactor resulted in a larger phenolic content than from the batch reactor, indicating more effective decomposition of lignin. The catalytic pyrolysis over HZSM-5 in the batch reactor increased the proportion of light phenolics and aromatics, which was helpful in upgrading the oil quality.     

Modelling solid-convective flash pyrolysis of straw and wood in the Pyrolysis Centrifuge Reactor

Less than a handful of solid-convective pyrolysis reactors for the production of liquid fuel from biomass have been presented and for only a single reactor a detailed mathematical model has been presented. In this article we present a predictive mathematical model of the pyrolysis process in the Pyrolysis Centrifuge Reactor, a novel solid-convective flash pyrolysis reactor. The model relies on the original concept for ablative pyrolysis of particles being pyrolysed through the formation of an intermediate liquid compound which is further degraded to form liquid organics, char, and gas. To describe the kinetics of the pyrolysis reactions the Broido–Shafizadeh scheme is employed with cellulose parameters for wood and modified parameters for straw to include the catalytic effect of its alkali-containing ash content. The model describes the presented experimental results adequately for engineering purposes for both wood and straw feedstock even though conditions for ablative pyrolysis from a reaction engineering point of view are not satisfied. Accordingly, even though the concept of an ablatively melting particle may constitute a limiting case, it can still be used to model flash pyrolysis provided that the reacting particle continuously shed the formed char layer.     

Pyrolysis-catalytic steam reforming of agricultural biomass wastes and biomass components for production of hydrogen/syngas

The pyrolysis-catalytic steam reforming of six agricultural biomass waste samples as well as the three main components of biomass was investigated in a two stage fixed bed reactor. Pyrolysis of the biomass took place in the first stage followed by catalytic steam reforming of the evolved pyrolysis gases in the second stage catalytic reactor. The waste biomass samples were, rice husk, coconut shell, sugarcane bagasse, palm kernel shell, cotton stalk and wheat straw and the biomass components were, cellulose, hemicellulose (xylan) and lignin. The catalyst used for steam reforming was a 10 wt.% nickel-based alumina catalyst (NiAl₂O₃). In addition, the thermal decomposition characteristics of the biomass wastes and biomass components were also determined using thermogravimetric analysis (TGA). The TGA results showed distinct peaks for the individual biomass components, which were also evident in the biomass waste samples reflecting the existence of the main biomass components in the biomass wastes. The results for the two-stage pyrolysis-catalytic steam reforming showed that introduction of steam and catalyst into the pyrolysis-catalytic steam reforming process significantly increased gas yield and syngas production notably hydrogen. For instance, hydrogen composition increased from 6.62 to 25.35 mmol g^?1 by introducing steam and catalyst into the pyrolysis-catalytic steam reforming of palm kernel shell. Lignin produced the most hydrogen compared to cellulose and hemicellulose at 25.25 mmol g^?1. The highest residual char production was observed with lignin which produced about 45 wt.% char, more than twice that of cellulose and hemicellulose.     

The influence of temperature and heating rate on the slow pyrolysis of biomass

The slow pyrolysis of biomass in the form of pine wood was investigated in a static batch reactor at pyrolysis temperatures from 300 to 720°C and heating rates from 5 to 80 K min⁻¹. The compositions and properties of the derived gases, pyrolytic oils and solid char were determined in relation to pyrolysis temperatures and heating rates. In addition, the wood and the major components of the wood—cellulose, hemicellulose and lignin—were pyrolysed in a thermogravimetric analyser (TGA) under the same experimental conditions as in the static batch reactor. The static batch reactor results showed that as the pyrolysis temperature was increased, the percentage mass of solid char decreased, while gas and oil products increased. There was a small effect of heating rate on product yield. The lower temperature regime of decomposition of wood showed that mainly H₂O, CO₂ and CO were evolved and at the higher temperature regime, the main decomposition products were oil, H₂O, H₂, hydrocarbon gases and lower concentrations of CO and CO₂. Fourier transformation infra-red spectroscopy and elemental analysis of the oils showed they were highly oxygenated. The TGA results for wood showed two main regimes of weight loss, the lower temperature regime could be correlated with the decomposition of hemicellulose and the initial stages of cellulose decomposition whilst the upper temperature regime correlated mainly with the later stages of cellulose decomposition. Lignin thermal decomposition occurred throughout the temperature range of pyrolysis.     

The effect of heating rate on yields and compositions of oil products from esparto pyrolysis

Recently, much research has been focused on liquid oil from biomass pyrolysis, which is considered as an alternative to conventional fossil fuels. This paper studies the effect of heating rate on both the yields and the chemical composition of the oil product obtained from pyrolysis of esparto which is the most important biomass in Morocco. The pyrolysis experiments of esparto was performed in a fixed bed reactor under argon atmosphere with different heating rate: 50, 150 and 250°C min^?1. The maximum conversion of esparto in oil of pyrolysis was obtained with fast pyrolysis 68.5% at 550°C. The FT‐IR and ¹H NMR analysis showed that the oil of pyrolysis formed principally by aliphatic compound. The analysis elemental showed that the H/C ratio increase and O/C decrease as the heating rate increase. The PCV improved slightly from 33.5 to 34.8 MJ kg^?1. The oil obtained with higher heating rate has chemical properties similar to diesel that can be used with an economic and environmental advantage. Copyright © 2006 John Wiley & Sons, Ltd.     

Low energy consumption and high quality bio-fuels production via in-situ fast pyrolysis of reed straw by adding metallic particles in an induction heating reactor

An in-situ fast pyrolysis of biomass by adding metallic particles in an induction heating reactor was proposed to produce high quality bio-fuels. After adding metallic particles into biomass, the times required to reach complete pyrolysis during reed straw pyrolysis process were significantly reduced up to 28.9%. The yields of combustible gas and bio-oil products were significantly increased. Furthermore, higher-quality combustible gas and bio-oil products were obtained with the LHV of gas products and HHV of bio-oil (dry basis) increased by 14.2%–19.1% and 4.16%–16.35%, respectively, under 400–600 °C. The lower oxygen content and higher yields of aromatics, alkenes and alkanes contents in bio-oil were obtained after metallic particles addition. More importantly, up to 26.5% of the total energy consumption during pyrolysis process was reduced after adding metallic particles into biomass in an induction heating reactor. The results indicate that adding metallic particles into biomass in an induction heating reactor can significantly enhance the heat transfer, decomposition reaction intensity and energy utilization efficiency of biomass pyrolysis process with lower energy consumption and higher-quality bio-fuel production.     

Thermal decomposition behavior,characterization and evaluation of pyrolysis products of agricultural wastes

Thermal decomposition behavior during pyrolysis, the composition and the physicochemical characteristics of the pyrolysis products were studied for four agricultural wastes from Southern Greece. These wastes are produced in abundance in the Mediterranean Region but still remain relatively unexploited, while there is also lack or little relevant scientific information. Pyrolysis process for the examined samples was studied using a TGA analyzer and a properly tested and calibrated TG/MS setup, at a heating rate of 10 °C/min up to 850 °C. Determination of important quantitative parameters of pyrolysis as a function of temperature, on an instantaneous or integral basis, and correlation of the evolved gas results with the degradation of pseudocomponents of raw biomass was made possible. The average higher heating value of the pyrolysis light gases was found to be in a satisfactory for energy purposes range of 11.2–14.4 MJ/Nm³. Furthermore, biochars produced at 450, 550 and 650 °C in a fixed bed reactor were found to exhibit calorific value ranging from 20.1 to 28.7 MJ/kg and structural stability. They were also found to have a high nutrients content and below limits or negligible heavy metals content for soils applications, regardless of production temperature.     

Flash pyrolysis of palmyra palm (Borassus flabellifer) using an electrically heated fluidized bed reactor

Agriculture residues such as palmyra fruit bunch are one of the biomass categories that can be utilized for conversion to bio-oil by using pyrolysis process. Flash pyrolysis experiments have been conducted in the electrically heated fluidized bed reactor to determine the effect of pyrolysis temperature, particle size, and sweep gas flow rate on the pyrolysis product yield. In this study the maximum oil yield of 48.2% was achieved at a temperature of 500°C, particle size of 1 mm, and at a sweep gas flow rate of 2 m³/h. The results show that the effects of pyrolysis temperature and particle size on pyrolysis yields are more significant than that of sweep gas flow rate. Bio-oil was identified as a biofuel candidate and it was further upgraded for better-quality biofuel. Various physical and elemental analyses were performed for bio-oil and the same characteristics study was also carried out for biofuel.     

Pyrolytic oil from fixed bed pyrolysis of municipal solid waste and its characterization

Municipal solid waste, in the form of paper waste, has been converted into liquid oil by a fixed bed pyrolysis process. Favorable properties for pyrolysis conversion such as high volatile content, elemental composition, and thermochemical behavior of the waste were investigated by characterization study. The waste paper feedstock was pyrolyzed in an externally heated 7 cm diameter, 38 cm high fixed bed reactor with nitrogen as a carrier gas. The pyrolysis oil was collected in a series of condenser and ice-cooled collectors. The char was separately collected while the gas was flared. The effect of process conditions, like fixed bed reactor temperature, feedstock size and effect of running time on the product yields, was studied. The composition of the oil was determined at a bed temperature of 450 °C, at which the liquid yield was maximum. The liquid product was analyzed for physical, elemental and chemical composition using Fourier transform infra-red (FTIR) spectroscopy.     

Autoignition of solid combustibles subjected to a uniform incident heat flux: The effect of distance from the radiation source

The ignitability of solid combustibles by a radiation source has been investigated experimentally as a function of distance between the solid and the source, for heating with a uniform incident heat flux. Unlike piloted ignition, the critical incident heat flux for autoignition increases with the increase of radiant distance, which is a result that has not been reported before. It is found that the generation rate of combustible pyrolysis volatiles is a necessary but not sufficient condition for autoignition. By two dimensionless parameters, it is clearly indicated that the occurrence of autoignition needs both sufficient gas-phase temperature and sufficient concentration of combustible pyrolysis volatiles simultaneously, especially for the larger radiant heating distance condition which is also closer to realistic fire conditions.     

Radiation attenuation characteristics of pyrolysis volatiles of solid fuels and their effect for radiant ignition model

Radiation attenuation characteristics of pyrolysis volatiles from heated solid fuels, a neglected physical effect in radiant ignition process, are studied by simulated experiment and mathematical models. Firstly, it is experimentally found the radiation attenuation of an incident heat flux when pine or Polymethyl Methacrylate (PMMA) is heated occurs before flaming ignition (6–14%), especially for the one in the experiment of the Cone Calorimeter style apparatus with a shorter test radiation distance (D < 100 mm). Then, a more reasonable parameter using Beer’s law for determining the radiation absorptivity of pyrolysis volatiles of different fuels is presented. It is found the radiation absorptivity of pyrolysis volatiles of PMMA is actually larger than the one of pine and the ignition of PMMA more depends on the gas-phase heating by radiation absorption. Finally, the calculated results with the experimental radiation attenuation data illustrates that consideration of the radiation attenuation by pyrolysis volatiles in radiant ignition models is necessary. A constant radiation attenuation coefficient G = 0.1 is approximately accepted for the general calculation of radiant ignition model.     

Bench-scale bubbling fluidized bed systems around the world - Bed agglomeration and collapse: A comprehensive review

Thermochemical conversion by gasification process is one of the most relevant technologies for energy recovery from solid fuel, with an energy conversion efficiency better than other alternatives like combustion and pyrolysis. Nevertheless, the most common technology used in the last decades for thermochemical conversion of solid fuel through gasification process, such as coal, agriculture residues or biomass residues are the fluidized bed or bubbling fluidized bed system. For these gasification technologies, an inert bed material is fed into reactor to improve the homogenization of the particles mixture and increase the heat transfer between solid fuel particles and the bed material. The fluidized bed reactors usually operate at isothermal bed temperatures in the range of 700–1000 °C, providing a suitable contact between solid and gas phases. In this way, chemical reactions with high conversion yield, as well as an intense circulation and mixing of the solid particles are encouraged. Moreover, a high gasification temperature favours carbon conversion efficiency, increasing the syngas production and energy performance of the gasifier. However, the risk of eutectic mixtures formation and its subsequent melting process are increased, and hence the probability of bed agglomeration and the system collapse could be increased, mainly when alkali and alkaline earth metals-rich biomasses are considered. Generally, bed agglomeration occurs when biomass-derived ash reacts with bed material, and the lower melting temperature of ash components promotes the formation of highly viscous layers, which encourages the progressive agglomerates creation, and consequently, the bed collapse and system de-fluidization. Taking into account the relevance of this topic to ensure the normal gasification process operating, this paper provides several aspects about bed agglomeration, mostly for biomass gasification systems. In this way, chemistry and mechanism of bed agglomeration, as well as, some methods for in-situ detection and prediction of the bed agglomeration phenomenon are reviewed and discussed.