An investigation of the grindability of two torrefied energy crops

The process of torrefaction alters the physical properties of biomass, reducing its fibrous tenacious nature. This could allow increased rates of co-milling and therefore co-firing in coal fired power stations, which in turn would enable a reduction in the amount of coal used and an increase in the use of sustainable fuels, without the need for additional plant. This paper presents an experimental investigation of the pulverisation behaviour of two torrefied energy crops, namely: willow and Miscanthus. A multifactorial method approach was adopted to investigate the three process parameters of temperature, residence time and particle size, producing fuels treated using four different torrefaction conditions. The untreated and torrefied fuels were subjected to standard fuel analysis techniques including ultimate analysis, proximate analysis and calorific value determination. The grindability of these fuels was then determined using a laboratory ball mill and by adapting the Hardgrove Grindability Index (HGI) test for hard coals. After grinding, two sets of results were obtained. Firstly a determination similar to the HGI test was made, measuring the proportion of sample passing through a 75 μm sieve and plotting this on a calibrated HGI chart determined using four standard reference coals of known HGI values. Secondly the particle size distributions of the entire ground sample were measured and compared with the four standard reference coals. The standard fuel tests revealed that temperature was the most significant parameter in terms of mass loss, changes in elemental composition and energy content increase. The first grindability test results found that the untreated fuels and fuels treated at low temperatures showed very poor grindability behaviour. However, more severe torrefaction conditions caused the fuels to exhibit similar pulverisation properties as coals with low HGI values. Miscanthus was found to have a higher HGI value than willow. On examining the particle size distributions it was found that the particle size distributions of torrefied Miscanthus differed significantly from the untreated biomass and had comparable profiles to those of the standard reference coals with which they had similar HGI values. However, only the torrefied willow produced at the most severe conditions investigated exhibited this behaviour, and the HGI of torrefied willow was not generally a reliable indicator of grindability performance for this energy crop. Overall it was concluded that torrefied biomass can be successfully pulverised and that torrefied Miscanthus was easier to grind than torrefied willow.     

Isothermal and Morphological Studies of the Torrefaction of Spruce Wood

The replacement of fossil fuels by biofuel for decreasing the action of greenhouse gases on the global climate is encouraged in industrially developed countries. A promising trend in the refining of waste biomass is torrefaction—a mild pyrolysis process in which biomass is heated to 250–350°C without the access of oxygen at low heating rates; as a result, biocoal with improved chemical and physical properties is formed. The torrefaction (mild pyrolysis at 250–300°C) of spruce stem wood was studied in a fixed-bed reactor at different temperatures. The mass and energy yields of biocoal, its specific heat of combustion, and morphological changes in the biomass structure in the course of spruce wood torrefaction were determined. It was established that the torrefied samples began to decompose at higher temperatures, as compared with the nontorrefied biomass. The torrefied fuel had a higher heat of combustion, which increased with the temperature of torrefaction. Conclusions on the restructuring of test samples and the formation of a porous structure at different temperatures depending on exposure time were made.     

烘焙生物质燃烧过程中钾的赋存形态及析出迁移特性

选取稻秆和棉秆为原料,在烘焙预处理后,通过固定床燃烧实验结合HSC Chemistry热力学平衡计算,获得了烘焙生物质燃烧过程中碱金属K的析出和迁移规律。结果表明：烘焙过程中存在着少量水溶性K的释放及其向醋酸铵溶态K的转化,而其转化和释放能力与Cl/K呈正相关。烘焙生物质的成灰率随着燃烧温度的升高而下降,而K的释放率随温度的变化则相反,其主要释放形式为K的氯化物和KOH;此外,600℃时,水溶性K和醋酸铵溶态K主要转化为char-K,700~900℃时其主要转化为K的硅酸盐,随着温度的上升,其转化量不断增加。相比于原生生物质,烘焙生物质有更高的成灰率;此外,烘焙促进了生物质燃烧过程中醋酸铵溶态K向酸溶态或残渣态K转化,同时抑制了水溶性K的释放,这些使得烘焙生物质燃烧过程中K的释放率更低,而烘焙对生物质燃烧过程中K释放的抑制与烘焙过程中Cl的释放率呈正相关。     

烟气烘焙对玉米秆可磨性的影响规律研究

可磨性是生物质在现有燃煤机组规模化燃烧利用中必须考虑的问题之一。本文基于固定床反应器对玉米秆进行烘焙预处理,针对生物质单烧和与煤混烧两种技术路线,利用臼式研磨仪、全自动粒径筛分仪、纤维素分析仪和傅里叶红外光谱,研究了不同烘焙气氛、温度对燃料可磨性的影响。结果表明,相比于氮气,烟气能够在更低的烘焙温度下使玉米秆可磨性提升至接近于典型动力用煤,主要是由于烟气中的氧化性组分促进了纤维素、半纤维素的分解。当共磨时,煤颗粒表现出助磨的作用提升了玉米秆的可磨性,在较高温度或烟气烘焙条件下,混样的可磨性近似甚至优于煤。     

生物质烘焙处理的能量平衡分析

基于烘焙过程分析,建立了生物质烘焙处理的能量平衡计算方法,结合固定床烘焙实验结果,研究了烘焙温度和保温时间对杨树枝烘焙特性、烘焙所需热及3种烘焙产物能量分布的影响,探讨了杨树枝烘焙处理的能量平衡. 结果表明,烘焙温度是影响生物炭得率、热值和能量分布的主要因素,随烘焙温度提高,杨树枝炭得率显著降低,液体产物和气体产物逐渐增加,杨树枝炭和不凝气体产物的热值显著增加,而液体产物热值变化不大. 烘焙产物中,杨树枝炭的能量显著高于液体和气体的能量. 随烘焙温度升高,杨树枝烘焙的能量平衡率先快速升高后趋于平稳,在温度225℃、保温时间30 min的条件下,烘焙可获得64.0%的杨树枝炭,能量平衡率约为2.5,烘焙所得液体和气体产物的燃烧热完全能满足杨树枝烘焙能量自给的需要.     

Influence of torrefaction on the grindability and reactivity of woody biomass

The use of biomass to produce energy is becoming more and more frequent as it helps to achieve a sustainable environmental scenario. However the exploitation of this fuel source does have drawbacks that need to be solved. In this work, the torrefaction of woody biomass (eucalyptus) was studied in order to improve its properties for pulverised systems. The process consisted in a heating treatment at moderate temperature (240, 260, 280 °C) under an inert atmosphere. The grindability of raw biomass and the treated samples was compared and an improvement in the grindability characteristics was observed after the torrefaction process. Thermogravimetric analysis of the samples was carried out in order to study their reactivity in air. The DTG curves of the torrefied biomass showed a double peak nature. The kinetic parameters were calculated for each reaction stage. The torrefaction process was found to influence the parameters of the first stage, whereas those corresponding to the second remained unaffected.     

烘焙对生物质理化性质及气化特性的影响

生物质资源丰富廉价,因清洁可再生、碳中和等优点备受研究者的关注,但是其能量密度低、水分和氧含量高等缺点也限制了其规模化应用;另外,生物质直接气化产生的合成气热值较低,且会产生大量焦油。本文阐述了烘焙预处理对生物质燃料品质的提升以及对气化过程积极的调控作用。文章指出,生物质烘焙后,氧元素含量、H/C和O/C下降,固定碳含量和高位热值增加;可磨性和疏水性得以提高,在一定程度上弥补了烘焙过程的耗能。文中从微观角度对生物质燃料品质的提升进行了解释,并简述了微波烘焙的特点与优势。使用烘焙生物质气化,产生的合成气可燃成分高,且焦油产量有所下降。文章总结后续工作可以考虑从以下三个方面展开,即对“烘焙-利用”过程进行全生命周期评价、利用微波技术更准确地探索温度对烘焙效果的的影响机制、结合烘焙与焦油催化重整技术进一步降低焦油产量。     

Impact of torrefaction on syngas production from wood

Torrefaction is a way to treat biomass before transportation or thermochemical conversion. It can be used to increase the energy content of wood or to facilitate grinding. The purpose of this paper was to quantify the impact of such a treatment on the behaviour of wood during gasification by steam at high temperature to produce syngas. The aspects of both gas yields and reaction kinetics were considered.Beechwood was submitted both to light torrefaction and severe torrefaction, using a specially designed crossed fixed bed reactor. The initial wood and the torrefied woods were first characterised, then gasified in a new laboratory high-temperature entrained flow reactor (HT-EFR) at 1400 °C for 2 s in an atmosphere containing 20 vol% steam in N₂. The syngas produced was then analysed. The experiments were modelled using a thermo-dynamical equilibrium approach.It was confirmed that torrefaction decreased the O/C ratio. The quantity of syngas produced increased with the severity of the torrefaction. The equilibrium approach describes the results satisfactorily.Gasification experiments carried out at a lower temperature - 1200 °C - indicated that the chars from torrefied woods are less reactive towards steam than the char from wood.     

Effects of torrefaction process parameters on biomass feedstock upgrading

Biomass is a primary source of renewable carbon that can be utilized as a feedstock for biofuels or biochemicals production in order to achieve energy independence. The low bulk density, high moisture content, degradation during storage and low energy density of raw lignocellulosic biomass are all significant challenges in supplying agricultural residues as a cellulosic feedstock. Torrefaction is a thermochemical process conducted in the temperature range between 200 and 300 °C under an inert atmosphere which is currently being considered as a biomass pretreatment. Competitiveness and quality of biofuels and biochemicals may be significantly increased by incorporating torrefaction early in the production chain while further optimization of the process might enable its autothermal operation. In this study, torrefaction process parameters were investigated in order to improve biomass energy density and reduce its moisture content. The biomass of choice (corn stover) was torrefied at three moisture content levels (30%, 45% and 50%), three different temperatures (200, 250 and 300 °C), and three unique reaction times (10, 20 and 30 min). Solid, gaseous, and liquid products were analyzed, and the mass and energy balance of the reaction was quantified. An overall increase in energy density (2–19%) and decrease in mass and energy yield (3–45% and 1–35% respectively) was observed with the increase in process temperature. Mass and energy losses also increased with an increase in the initial biomass moisture content.     

生物质三组分在O2/CO2气氛下的着火行为研究

生物质的富氧燃烧技术结合了生物质燃烧与富氧燃烧的优点,既能减少化石燃料的使用,又易实现CO₂捕集。富氧燃烧的最显著特点是气氛中的氧气体积分数大于21%,其对生物质着火行为的影响至关重要。纤维素、半纤维素和木质素是生物质的3种主要组分,研究其在富氧条件下的着火及燃烧行为,可为生物质的着火及燃烧行为研究提供重要依据。利用滴管炉结合高速摄像机,研究了粒径74~154μm的纤维素、半纤维素和木质素在温度1273 K,氧气体积分数21%、30%、50%、70%和100%的O₂/CO₂气氛中的着火行为,并利用辐射能测温技术计算着火图片中的颗粒温度。结果表明,随着O₂体积分数增加,纤维素、半纤维素由联合着火以及木质素由均相着火均转为非均相着火,纤维素、半纤维素、木质素着火机理发生转化的O₂体积分数分别为30%、70%和50%。纤维素着火对O₂体积分数变化敏感,氧气体积分数超过30%时,纤维素焦率先发生着火。半纤维素和木质素的升温速率随氧气体积分数的升高而提高,半纤维素是由于挥发分在燃烧过程中随着氧气体积分数的增加,其燃烧比例减弱,焦燃烧比例增加,而木质素因为氧气体积分数的升高强化了木质素焦燃烧。半纤维素和木质素燃烧时间均随氧气体积分数的升高而缩短,两者都是由于氧气体积分数升高强化了焦的燃烧。另外,在较高氧气体积分数下木质素焦会发生熔融并膨胀,形成明显的膨胀火焰。     

Influence of fuel ash composition on high temperature aerosol formation in fixed bed combustion of woody biomass pellets

In this work, the influence of fuel ash composition on high temperature aerosol formation during fixed bed combustion of woody biomass (two wood pellets and one bark pellets) were investigated experimentally in a laboratory reactor and theoretically through chemical equilibrium model calculations. For all fuels, the particle mass size distribution in the PM_2.5 region was bimodal, with one fine mode and one coarse mode. Early in the flame, the fine mode was dominated by particles from incomplete combustion and these particles were rapidly oxidised in the post flame zone. After the hot flame, the fine mode concentration and the particle diameter increases gradually when the temperature decreases due to condensation of vaporised inorganic matter, K, Na, S, Cl, and Zn. For two of the fuels also P could be found in the fine particles. The coarse mode consisted of carbon, refractory metals and considerable amount of alkali. Further, the initial fuel alkali concentration and the alkali to silicon ratio (K + Na)/Si influenced the amount of vaporised aerosol forming alkali matter. Finally, the present study shows that, combustion temperature and fuel ash composition is of major importance for the formation of high temperature aerosols in fixed bed combustion of woody biomass pellets.     

Reaction kinetics and producer gas compositions of steam gasification of coal and biomass blend chars, part 1: Experimental investigation

Biomass and coal are important solid fuels for generation of hydrogen-rich syngas from steam gasification. In this work, experiments were performed in a bench-scale gasifier to investigate the effect of coal-to-biomass ratio and the reaction kinetics for gasification of chars of biomass, coal and coal–biomass blends. In the gasification of these chars, steam was used as the gasification agent, while nitrogen was used as a gas carrier. The gasification temperature was controlled at 850, 900 and 950 °C. Gas produced was analysed using a micro-GC from which carbon conversion rate was also determined. From the experiments, it is found that the coal and biomass chars have different gasification characteristics and the overall reaction rate decreases with an increase in the ratio of coal–to-biomass.The microstructure of the coal char and biomass char was examined using scanning electronic microscopy (SEM), and it was found that the biomass char is more amorphous, whereas the coal char has larger pore size. The former enhances the intrinsic reaction rate and the latter influences the intra particle mass transportation. The difference in mass transfer of the gasification agent into the char particles between the two fuels is dominant in the char gasification.     

Potassium catalysis in the pyrolysis behaviour of short rotation willow coppice

Short rotation willow coppice (SRC) and a synthetic biomass, a mixture of the basic biomass components (cellulose, hemicellulose and lignin), have been investigated for the influence of potassium on their pyrolysis behaviours. The willow sample was pre-treated to remove salts and metals by hydrochloric acid, and this demineralised sample was impregnated with potassium. The same type of pre-treatment was applied to components of the synthetic biomass. Characterisation was performed using thermogravimetric analysis with measurement of products by means of Fourier transform infrared spectroscopy (TGA-FTIR) and pyrolysis-gas chromatography-mass spectrometry (PY-GC-MS). A comparison of product distributions and kinetics are reported. While the general features of decomposition of SRC are described well by an additive behaviour of the individual components, there are some differences in the magnitude of the influence of potassium, and on the products produced. For both SRC and the synthetic biomass, TGA traces indicate catalytic promotion of both of the two-stages of biomass decomposition, and potassium can lower the average apparent first-order activation energy for pyrolysis by up to 50 kJ/mol. For both SRC and synthetic biomass the yields and distribution of pyrolysis products have been influenced by the presence of the catalyst. Potassium catalysed pyrolysis increases the char yields markedly and this is more pronounced for synthetic biomass than SRC. Gas evolution profiles during pyrolysis show the same general features for both SRC and synthetic biomass. Relative methane yields increase during the char formation stage of pyrolysis of the potassium doped samples. The evolution profiles of acetic acid and formaldehyde change, and these products are seen in lower relative amounts for both the demineralised samples. A greater variation in pyrolysis products is observed from the treated SRC samples compared to the different synthetic biomass samples. Furthermore, substituted phenols from lignin pyrolysis are more dominant in the pyrolysis profiles of the synthetic biomass than of the SRC, implying that the extracted lignins used in the synthetic biomass yield a greater fraction of monomeric type species than the lignocellulosic cell wall material of SRC. For both types of samples, PY-GS-MS analyses show that potassium has a significant influence on cellulose decomposition markers, not just on the formation of levoglucosan, but also other species from the non-catalysed mechanism, such as 3,4-dihydroxy-3-cyclobutene-1,2-dione.     

Size and structural characterization of lignin-cellulosic fuels after the rapid devolatilization

The aim of this work is to develop and test a method for assessing the size and the morphology of biomass fuels and their chars. Severe thermal conditions (high temperature and heating rate) are programmed during the pyrolysis, focusing on characteristics of chars in combustion or gasification. An image analysis program is used to quantitatively study several scanning electron microscopy images of fuel and char samples. Distributions of results are obtained for a significant number of particles from a statistical point of view. Average values and the standard deviations of the distributions quantify the heterogeneous nature of the fuel and char particles, providing useful parameters for advanced modeling. Size, shape factors (aspect and roundness) and superficial parameters are defined and measured (or calculated) developing a procedure for a low time-consuming analysis. The structural variations caused by the fast release of a high amount of volatile products are evaluated comparing the results obtained on fuel and char particles. The results are discussed to assessing the suitability of the selected parameters and the possibility to quantify softening, melting, shrinking and fragmentation phenomena. The method is applied to two biomass fuels of different origin and chemical composition: wood pellets and olive residue.     

Characterisation of biomass and coal co-firing on a 3 MWth Combustion Test Facility using flame imaging and gas/ash sampling techniques

Co-firing of biomass with pulverised coal at existing coal power stations remains a practical option available to power plant operators and is being widely adopted as one of the main technologies for reducing greenhouse gas emissions. However, there is a range of technological problems that are not well understood. This paper presents experimental investigations into the co-firing of pulverised coal directly co-milled with 5–20% biomass on a 3 MWth Combustion Test Facility. A number of combustion parameters, including flame temperature and oscillation frequency and particle size distribution, were measured under a range of co-firing conditions. The gas species within the flame and fly ash in flue gas were also sampled and analysed. The experimental data collected are used to study the impact of biomass additions to pulverised coal on the combustion characteristics of the co-firing process. The relationships between the flame characteristics, gas species and ash deposition of the furnace are investigated. The results suggest that, due to the varying physical and chemical properties of the biomass fuels, the biomass additions have impact on the combustion characteristics in a very complicated way. It has been found that the biomass addition to coal would improve the combustion efficiency because of the lower CO concentrations and higher char burnout level in co-firing. In addition, NO_x emission has been found closely linked to the flame stability, and SO_x emission reduced in general for all co-firing cases.     

磷酸二氢铵对玉米秆烘焙及固定床燃烧颗粒物排放特性的影响

使用立式管式炉反应器并结合低压撞击器颗粒物采集装置研究了玉米秆掺混磷酸二氢铵（NH₄H₂PO₄）烘焙对烘焙产物理化性质及固定床中燃烧颗粒物排放的影响。结果表明,玉米秆单独烘焙可有效提升生物质品质,但也提升了颗粒物排放。300℃烘焙时,PM₁、PM_1-2.5和PM_2.5-10分别增排76.5%、194.8%和170.2%。在烘焙过程掺混NH₄H₂PO₄可进一步提质,使得固体产物灰分有不同程度的增加,显著降低固体产物的O/C比,并提高样品的无灰基热值。此外,研究发现掺混NH₄H₂PO₄可显著提高烘焙过程Cl的释放率并降低固体产物中Cl的含量,有利于降低后续燃烧PM₁的排放。在掺混比例P/K摩尔比为1时减排效果最佳,此时PM₁相比无掺混时减排28.8%。结果表明在生物质烘焙过程引入NH₄H₂PO₄可以促进Cl的脱除并减少后续燃烧过程细颗粒物的排放,是一种有前景的生物质预处理手段。     

The effect of alkali metals on combustion and pyrolysis of Lolium and Festuca grasses,switchgrass and willow

The effect of alkali metals on the thermal degradation of biomass during combustion and pyrolysis has been investigated for 19 Lolium and Festuca grass varieties. These samples have been grown under the same conditions, but has been genetically mutated to give varying lignin contents in the range 2–6% measured by Klason. These grasses also have a high alkali metal content resulting in a high ash content. In order to compare the Lolium and Festuca grasses willow chip and switchgrass were also studied to act as a reference fuels. All samples were subjected to different washing conditions to investigate the effect of decreasing the metal content. The resulting biomass samples were studied for pyrolysis characteristics using thermogravimetric analysis (TGA) and pyrolysis gas chromatography–mass spectrometry (pyroprobe-GC/MS) and for combustion characteristics by TGA. A strong catalytic effect of metals, particularly potassium, was observed in both pyrolysis and combustion. Also, it was found that as the lignin content increases, the metal content (especially potassium and sodium) decreases. Furthermore, the char yield from pyrolysis (measured at 773 K from TGA pyrolysis traces) increases as metals increase, and hence char yield increases as the lignin content decreases. Py-GCMS showed that peak intensities varied for untreated and treated samples; in particular the levoglucosan yield is higher and the hydroxyacetaldehyde yield is lower for treated (low metal content) samples. This supports previous work mechanisms by Liden et al. in which alkali metals promote an ionic route that favours ring-scission and hydroxyacetaldehyde formation.     

Model for biomass char combustion in the riser of a dual fluidized bed gasification unit: Part II — Model validation and parameter variation

The two-phase combustion model for biomass char combustion in a riser of a dual fluidized bed gasification unit that has been presented in part I is validated using the data obtained from the 8 MWth dual fluidized bed reactor at Guessing/Austria. The model is capable of calculating the average temperatures in all zones, the gas phase composition, solid hold up, char feed rates and air ratio. The model predictions for the temperature profile along the riser and for the exiting gas composition are in good agreement with the measured values. The simulation results show that the residual char from the gasifier is only partly converted in the riser for char particles larger than 0.6 mm. Un-combusted char is circulated back into the gasification reactor. Parameter variations show that the exact location where additional liquid fuels are introduced in the middle zone of the riser does not affect the global behaviour of the combustion reactor. Based on the simulation results it is proposed that external supply of char (additional) may be a very effective method for reducing producer gas recycling to the riser, which is currently necessary to obtain the desired gasification temperatures.     

Optimization of pre-treatment selection for the use of woody waste in co-combustion plants

This work is focused on the use of biomass waste to feed already existing coal combustion plants as a part of paving the way toward the reduction of the environmental impact. The biomass waste supply chain optimization is critical to conceive long-term viable projects and deal with the biomass heterogeneous nature and drawbacks to be used with coal, i.e. principally high moisture content and low bulk density. This paper studies biomass transportation, storage and change of properties (moisture content and hence dry matter, energy density and bulk density) through the use of different pre-treatments: (i) torrefaction, (ii) torrefaction combined with pelletization, (iii) pelletization, (iv) fast pyrolysis and (v) fast pyrolysis combined with char grinding, which produce a range of very different pre-treated biomass. The optimization problem is formulated as a mixed integer linear program (MILP) that evaluates the net present value and the environmental impact through a life cycle assessment (LCA). The results propose location–allocation decision together with the selection/capacity of pre-treatment technologies for each scenario. The scenarios contemplate different biomass characteristics, availability and distribution for a supply chain case study located in Spain: forest and agricultural woody residues used to replace at least 10% of the total thermal inlet power provided by coal in the existing network of thermal plants.     

Effect of fuel properties on biomass combustion: Part I. Experiments—fuel type,equivalence ratio and particle size

Moving bed combustion is commonly used for energy conversion of biomass. Conditions on the moving bed can be conveniently represented by a time dependent fixed bed. The present work experimentally investigates the combustion of four biomass materials having different fuel properties in a fixed bed under fuel-rich conditions. Temperature, gas composition and mass loss curves identified two distinct periods as the combustion progresses in the bed: the ignition propagation and char oxidation. The effects of bulk density, particle size and air flow rate on the combustion characteristics during the two periods are interpreted by using the ignition front speed, burning rate, percentage of mass loss, equivalence ratio and temperature gradient. Different channelling of air was observed for small miscanthus pellets and large wood particles due to the fast propagation of the ignition front around a channel. The elemental ash composition was also analysed, which explained the sintered agglomerates of miscanthus ashes in terms of alkali index.