生物质成型燃料热解特性及动力学研究

利用NETZSCH STA409PC型热重-差热分析仪对生物质成型燃料在以10℃/min、20℃/min及30℃/min升温速率下的热解过程进行了热重分析。对TG-T、DTG-T曲线分析,结果表明生物质成型燃料热解过程分为干燥、热解预热、热解与炭化4个阶段,热解过程随着升温速率升高出现热滞后现象。对剧烈失重区间建立了反应动力学模型,求解出此温度区间的表观活化能、频率因子等动力学参数。     

Techniques for studying and modeling coal pyrolysis and their relevance to biomass and wastes

Pyrolysis is the first step in the thermochemical conversion of any organic material. It plays a key role in coal conversion, where processes like combustion, gasification and hydrogenation include pyrolytic reactions as a starting step, and is the basic process in cokemaking. In the long history of industrial use of thermochemical coal conversion, various methods have been developed for feedstock characterization and for the main chemical reactions. Furthermore, approaches have been established to describe pyrolysis behavior quantitatively and to provide tools for reactor modeling. The main experimental techniques are reviewed and their relevance for the treatment of other solid feedstocks like biomass and wastes is discussed.     

木质类生物质的热重分析研究

在常压热重分析仪和加压热重分析仪上对木屑进行了热解实验，利用热重分析法对其热解行为特性和动力学规律进行了分析．得到了升温速率、压力等因素对木屑热解过程的影响规律。实验表明：常压下，随着升温速率的增加，反应激烈程度增加；与常压相比，加压状态下，活化能明显减小；随着热解压力的提高，挥发分初析温度和DTG峰值温度升高，最大失重速率减小；活化能E与频率因子A之间存在动力学补偿效应，升温速率不变，改变压力或者压力不变，改变升温速率，得到的利、偿效应表达式不同。     

Non-catalytic and catalytic pyrolysis of Ulva prolifera macroalgae for production of quality bio-oil

Pyrolysis of Ulva prolifera macroalgae (UM), an aquatic biomass, was carried out in a fixed-bed reactor in the presence of three zeolites based catalysts (ZSM-5, Y-Zeolite and Mordenite) with the different catalyst to biomass ratio. A comparison between non-catalytic and catalytic behavior of ZSM-5, Y-Zeolite and Mordenite catalyst in the conversion of UM showed that is affected by properties of zeolites. Bio-oil yield was increased in the presence of Y-Zeolite while decreased with ZSM-5 and Mordenite catalyst. Maximum bio-oil yield for non-catalytic pyrolysis was (38.5 wt%) and with Y-Zeolite catalyst (41.3 wt%) was obtained at 400 °C respectively. All catalyst showed a higher gas yield. The higher gas yield might be attributed to that catalytic pyrolysis did the secondary cracking of pyrolytic volatiles and promoted the larger small molecules. The chemical components and functional groups present in the pyrolytic bio-oils are identified by GC–MS, FT-IR, ¹H-NMR and elemental analysis techniques. Phenol observed very less percentage in the case of non-catalytic pyrolysis bio-oil (9.9%), whereas catalytic pyrolysis bio-oil showed a higher percentage (16.1%). The higher amount of oxygen present in raw biomass reduced significantly when used catalyst due to the oxygen reacts with carbon and produce (CO and CO₂) and water.     

生物质闪速热解挥发特性的研究

以等离子体为热源，利用层流炉热解试验台对稻壳等生物质进行了闪速热解挥发试验，得到了不同加热温度和挥发时间下的热解挥发百分比数据；根据试验数据，计算出了Arrhenius一级反应动力学模型的表观频率因子和表观活化能参数的值。研究发现，在闪速加热条件下，同一种生物质的热解动力学参数不随工况发生变化；不同生物质的表观频率因子和表观活化能的值不同；试验数据与模型具有很好的吻合性，该模型可以作为生物质闪速热解的计算模型之一。     

生物质热解液化技术经济分析

我国生物质资源十分丰富，但主要以各类农业残余废弃物为主，其特点是能量密度低、分布不集中，如果采用热解液化技术在产地将其先分散转化成生物油，然后再对生物油进行应用或再加工，则就避免了大规模收集和长距离运输生物质所带来的巨大困难。研究分析表明：热解液化设备的规模以每小时可处理2t农业残余废弃物较为适宜，且这种技术在我国具有良好的市场应用前景。     

Pyrolysis kinetics behaviour and thermal pyrolysis of Samanea saman seeds towards the production of renewable fuel

The present study addresses pyrolysis behaviour and potential of Samanea saman seeds (SS) towards its bioenergy potential using thermogravimetric analyzer and in a cylindrical pyrolyzer (semi-batch reactor). Pyrolysis kinetic behaviour of biomass was carried out using Kissinger, Distributed Activation Energy Model (DAEM) and Miura-Maki-Integral method (MMI) while thermal pyrolysis was carried out in a cylindrical shaped semi-batch reactor. Kinetic results confirmed that the average activation energy was found 118.24 kJ mol⁻¹, 168.70 kJ mol⁻¹, and 97.87 kJ mol⁻¹ for Kissinger, DAEM, and MMI model respectively. Further, thermal pyrolysis of SS biomass yielded 44.20 wt% yield of pyrolytic liquid (31.20 wt% pyrolytic oil/organic oil and 13 wt% aqueous fraction). Characterization results of pyrolytic oil showed the presence of higher viscosity (86.01 cSt), higher oxygen content (33.11%), and lower ash content (0.46 wt%) and gross heating value. FTIR analysis confirmed mainly the presence of aromatics, acid, alkene, water, and protein impurities. Gas Chromatography (GC) results declared, an increase in hydrocarbon and hydrogen gas with an increase in temperature while reduced the generation of CO and CO₂. Further, GC-MS analysis of pyrolytic oil revealed the presence of higher acids (19.46%), phenols (11.01%) ethers (11.12%) and ester (7.33%) which is a potent source of oxygenated compounds. Characterization results of biochar showed the presence of higher gross heating value (23.14 MJ kg), carbon content (62.66%), volatile matter (34.15%) and lower moisture (5.14%) and BET surface area (8.20 m² g⁻¹). Combining these results, it can be suggested that SS biomass has the potential to produce renewable fuel and chemicals, while biochar can be used for various applications.     

Developments in the scale-up of the vortex-pyrolysis system

Fundamental and applied research and engineering development over the past 13 years has demonstrated that continuous reactors could be used with very fast heating rates and short residence times to produce high yields of liquids from biomass. The National Renewable Energy Laboratory developed the ablative pyrolysis system and Interchem Environmental is commercializing this technology. Interchem designed and built a first generation, 32.7 tonnes (36 tons) per day, prototype ablative pyrolysis system in Missouri. The system was operated for 15 months with varying degrees of success. A second generation plant was designed based on the operating data collected from the first plant and on NREL's design for the vortex reactor. This facility is currently being built in Kansas City, KS. This paper discusses the design and operation of the first generation prototype facility and the design of the second generation system. The second plant is designed to produce 70% oil, 15% char and 15% non-condensible gases from the incoming wood. The oil will be sold as boiler fuel, the char sold as a feedstock to charcoal briquette manufacturers and the gases burned to provide process heat. Upon successful commercialization of this process, agricultural and forest residues can be converted into valuable products. In addition, the process offers a mechanism to use biomass as a feedstock for chemical production rather than relying on petroleum feedstocks.     

我国生物质能源现代化应用前景展望(三)——生物质能源转化技术经济评估

秸秆、动植物油脂、微藻等生物质原料可以生产液体运输燃料,生物燃料的化学成分包括醇、酯、烃三类。燃料乙醇主要替代汽油,受到各国重视,其中纤维素乙醇技术发展较快。脂肪酸甲酯是第一代生物柴油的主要成分,价格主要受油脂原料价格的影响,由于和柴油相容性差,低温流动性不好,将逐渐被加氢生产的第二代生物柴油取代。相比醇、酯等含氧燃料,烃类生物燃料在使用性能上有很多优势。有多条技术路线可以生产烃类燃料,其中油脂加氢制喷气燃料已接近商业应用,热解油加氢可将木质生物质原料中的"木质素"组分转化为生物油,大型快速热解工厂可以和热电联产装置组成联合系统,从而提高工厂综合热效率,降低生物燃料生产成本。因此,快速热解生产汽柴油将成为主要的生物燃料生产路线。生物质与煤共气化技术通过提高气化温度,不仅可以提高生物质气化效率,减少焦油的生成,还可以解决生物质供给的季节性问题,为生物质的高效利用提供了一条新的技术途径。微藻高压液化生产柴油是最具发展潜力的第三代生物燃料技术,我国需要加强微藻养殖及加工技术攻关。     

Bio‐oil,solid and gaseous biofuels from biomass pyrolysis processes—An overview

As the global demand for energy rapidly increases and fossil fuels will be soon exhausted, bio‐energy has become one of the key options for shorter and medium term substitution for fossil fuels and the mitigation of greenhouse gas emissions. Biomass currently supplies 14% of the world's energy needs. Biomass pyrolysis has a long history and substantial future potential—driven by increased interest in renewable energy. This article presents the state‐of‐the‐art of biomass pyrolysis systems, which have been—or are expected to be—commercialized. Performance levels, technological status, market penetration of new technologies and the costs of modern forms of biomass energy are discussed. Advanced methods have been developed in the last two decades for the direct thermal conversion of biomass to liquid fuels, charcoals and various chemicals in higher yields than those obtained by traditional pyrolysis processes. The most important reactor configurations are fluidized beds, rotating cones, vacuum and ablative pyrolysis reactors. Fluidized beds and rotating cones are easier for scaling and possibly more cost effective. Slow pyrolysis is being used for the production of charcoal, which can also be gasified to obtain hydrogen‐rich gas. The short residence time pyrolysis of biomass (flash pyrolysis), at moderate temperatures, is being used to obtain a high yield of liquid products (up to 70% wt), particularly interesting as energetic vectors. Bio‐oil can substitute for fuel oil—or diesel fuel—in many static applications including boilers, furnaces, engines and turbines for electricity generation. While commercial biocrudes can easily substitute for heavy fuel oils, it is necessary to improve the quality in order to consider biocrudes as a replacement for light fuel oils. For transportation fuels, high severity chemical/catalytic processes are needed. An attractive future transportation fuel can be hydrogen, produced by steam reforming of the whole oil, or its carbohydrate‐derived fraction. Pyrolysis gas—containing significant amount of carbon dioxide, along with methane—might be used as a fuel for industrial combustion. Presently, heat applications are most economically competitive, followed by combined heat and power applications; electric applications are generally not competitive. Copyright © 2011 John Wiley & Sons, Ltd.     

A review on operating parameters for optimum liquid oil yield in biomass pyrolysis

Pyrolysis is one of the potential routes to harness energy and useful chemicals from biomass. The major objective of biomass pyrolysis is to produce liquid fuel, which is easier to transport, store and can be an alternative to energy source. The yield and composition of pyrolysis oil depend upon biomass feedstock and operating parameters. It is often necessary to explore about the effect of variables on response yield and instinct about their optimization. This study reviews operating variables from existing literature on biomass pyrolysis. The major operating variables include final pyrolysis temperature, inert gas sweeping, residence times, rate of biomass heating, mineral matter, size of biomass particle and moisture contents of biomass. The scope of this paper is to review the influence of operating parameters on production of pyrolysis oil.     

Comparison of catalytic and noncatalytic pyrolysis and product yields of some waste biomass species

The products obtained by fast pyrolysis of biomass can be used as an energy source or chemical raw material. In this study, samples of hazelnut shells, tea bush, and hazelnut knot selected as waste biomass were from the cities of Trabzon and Rize in the Eastern Black Sea Region. Firstly, the waste biomass samples were granulated into four different particle sizes by milling and sieving operations. Fast pyrolysis of the samples with specific mixing rates was carried out in a fixed bed reactor. Additionally, 2 wt% vanadium (V) oxide (V₂O₅) was used as catalyst to maximize the yield of pyrolysis liquid products. The influence of temperature, heating rate, and particle size on fast pyrolysis yields under both catalytic and noncatalytic conditions were investigated and compared. While the amount of liquid product increased with the addition of catalyst, the amount of solid products decreased. It has been found that the temperature and heating rate parameters are very effective in liquid product yield. In all experiments, the maximum liquid yield was acquired at the same heating rate of 450°C min^?1 and the temperature of 450°C with particle size of 0.5 to 1.0 mm. The maximum pyrolysis liquid (bio‐oil) was obtained with catalytic pyrolysis, and this value was 60.58 wt%.     

常压及加压条件下生物质热解特性的热重研究

在常压热重分析仪和自行研制的加压热重分析仪上进行了生物质热解特性的系统研究 ,得到了升温速率、压力等因素对生物质热解过程的影响规律。对不同试验条件下的反应动力学参数进行了求解和比较 ,并作了机理分析。试验表明 :与常压热解相比 ,在加压条件下 ,生物质的反应速率有明显提高 ;随着升温速率的增加 ,热解反应趋于更加激烈。上述研究结果为生物质的合理利用提供了一定的理论基础。     

Syngas from sugarcane pyrolysis: An experimental study for fuel cell applications

The use of biomass for the production of electrical energy is a promising technological solution for those countries where there are problems with the disposal of agricultural waste and/or the production of low-cost energy. The gasification and/or pyrolysis of the biomass produces a gas rich in hydrogen that can be used in a fuel cell system to produce electrical energy with reduced environmental impact and significant energy recovery.In this work, a study of the pyrolysis of Brazilian sugarcane bagasse was carried out. The experimental process consisted of the pyrolysis of the biomass material in a batch pyrolysis reactor. In some runs the biomass was dry, while in others it was pre-treated by the addition of water. It was noted that the water added to the biomass before the pyrolysis process resulted in a decrease in the quantity of steam added to the fuel cell feeding gas, necessary to avoid carbon deposition, and in an increase in cell power, but, at the same time, caused a decrease in the quantity of syngas produced.Then, the composition of the gas obtained from the experimental pyrolysis of the sugarcane was inserted in a simulation tool of a molten carbonate fuel cell system in order to estimate the feasibility of the entire process in terms of operating conditions and electrical performance.The present study indicates that the syngas obtained from the sugarcane biomass (about 40%) can be converted into electricity using a fuel cell system with a high efficiency.     

Entrained flow gasification of straw- and wood-derived pyrolysis oil in a pressurized oxygen blown gasifier

Fast pyrolysis oil can be used as a feedstock for syngas production. This approach can have certain advantages over direct biomass gasification. Pilot scale tests were performed to investigate the route from biomass via fast pyrolysis and entrained flow gasification to syngas. Wheat straw and clean pine wood were used as feedstocks; both were converted into homogeneous pyrolysis oils with very similar properties using in-situ water removal. These pyrolysis oils were subsequently gasified in a pressurized, oxygen blown entrained flow gasifier using a thermal load of 0.4 MW. At a pressure of 0.4 MPa and a lambda value of 0.4, temperatures around 1250 °C were obtained. Syngas volume fractions of 46% CO, 30% H₂ and 23% CO₂ were obtained for both pyrolysis oils. 2% of CH₄ remained in the product gas, along with 0.1% of both C₂H₂ and C₂H₄. Minor quantities of H₂S (3 vs. 23) cm³ m⁻³, COS (22 vs. 94) cm³ m⁻³ and benzene (310 vs. 532) cm³ m⁻³ were measured for wood- and straw derived pyrolysis oils respectively. A continuous 2-day gasification run with wood derived pyrolysis oil demonstrated full steady state operation. The experimental results show that pyrolysis oils from different biomass feedstocks can be processed in the same gasifier, and issues with ash composition and melting behaviour of the feedstocks are avoided by applying fast pyrolysis pre-treatment.     

生物质快速热解制取生物质油

根据浅床层鼓泡流化床的特点以及生物质的热解特性,研制出生物质快速热解的流化床热解反应器,并进行生物质快速热解制取生物质油的试验研究。通过定量给料研究不同温度、不同流化气流量对热解产物的影响规律。试验得出生物质油的产率达65%(kg/kg),并对产出的生物质油用色质联机进行成分分析得出生物质油的主要成分,通过热重分析得到了生物质油的热解特性。     

Biocrude from biomass: pyrolysis of cottonseed cake

Fixed-bed pyrolysis experiments have been conducted on a sample of cottonseed cake to determine the possibility of being a potential source of renewable fuels and chemicals feedstocks, in two different reactors, namely a tubular and a Heinze retort. Pyrolysis atmosphere and pyrolysis temperature effects on the pyrolysis product yields and chemical composition have been investigated. The maximumm oil yield of 29.68% was obtained in N₂ atmosphere at a pyrolysis temperature of 550°C with a heating rate of 7°C min⁻¹ in a tubular reactor.     

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.     

Investigating pellet charring and temperature in ultrasonic vibration-assisted pelleting of wheat straw for cellulosic biofuel manufacturing

Biofuels are only alternative solution for liquid transportation fuels among different kinds of renewable energy. To avoid the competition with the food, cellulosic biomass has been proposed as feedstock for manufacturing of cellulosic biofuels. Costs associated with collection, transportation, and storage of cellulosic biomass account for more than 80% cost of the feedstock. By processing cellulosic biomass into high density pellets, handling efficiency of cellulosic feedstocks can be improved, leading to costs reduction in transportation and storage. Ultrasonic vibration-assisted (UV-A) pelleting is a recently developed pelleting method, which can not only produce higher density but also break the lignin shell, to some extent, to increase cellulose accessibility and then increase sugar and biofuel yield. The reported investigations on UV-A pelleting provided little information about the relationship between charring and pelleting temperature under different input variables of pelleting. In this paper, effects of different input variables of pelleting on both charring ratio and pelleting temperature were studied. This paper, for the first time, reported the relationship between charring ratio and pelleting temperature. The obtained results will be helpful in understanding the mechanism of UV-A pelleting and providing guide to control pellet charring for a higher biofuel yield.     

生物质连续热解炭化设备研究

针对现有生物质热解炭化设备需要引用外部热源加热导致的能源损耗、炭化装置复杂等问题,提出采用热解气回用燃烧的生物质热解炭化方案,设计一种新型回转连续式炭化设备。通过仿真分析与试验研究的方法,得到所设计炭化炉的最佳转速范围,并以生物质玉米秸秆为原料进行炭化试验。试验结果表明,设备纯小时处理生物质2.13 t,生物炭得率为30.2%,各项性能皆达到预期指标,可实现生物质的连续高效炭化。