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。     

Hydrothermal pretreatment of switchgrass and corn stover for production of ethanol and carbon microspheres

Pretreatment of biomass is viewed as a critical step to make the cellulose accessible to enzymes and for an adequate yield of fermentable sugars in ethanol production. Recently, hydrothermal pretreatment methods have attracted a great deal of attention because it uses water which is a inherently present in green biomass, non-toxic, environmentally benign, and inexpensive medium. Hydrothermal pretreatment of switchgrass and corn stover was conducted in a flow through reactor to enhance and optimize the enzymatic digestibility. More than 80% of glucan digestibility was achieved by pretreatment at 190 °C. Addition of a small amount of K₂CO₃ (0.45-0.9 wt.%) can enhance the pretreatment and allow use of lower temperatures. Switchgrass pretreated at 190 °C only with water had higher internal surface area than that pretreated in the presence of K₂CO₃, but both the substrates showed similar glucan digestibility. In comparison to switchgrass, corn stover required milder pretreatment conditions. The liquid hydrolyzate generated during pretreatment was converted into carbon microspheres by hydrothermal carbonization, providing a value-added byproduct. The carbonization process was further examined by GC-MS analysis to understand the mechanism of microsphere formation.     

Hydrothermal liquefaction of biomass: A review of subcritical water technologies

This article reviews the hydrothermal liquefaction of biomass with the aim of describing the current status of the technology. Hydrothermal liquefaction is a medium-temperature, high-pressure thermochemical process, which produces a liquid product, often called bio-oil or bi-crude. During the hydrothermal liquefaction process, the macromolecules of the biomass are first hydrolyzed and/or degraded into smaller molecules. Many of the produced molecules are unstable and reactive and can recombine into larger ones. During this process, a substantial part of the oxygen in the biomass is removed by dehydration or decarboxylation. The chemical properties of bio-oil are highly dependent of the biomass substrate composition. Biomass constitutes of various components such as protein; carbohydrates, lignin and fat, and each of them produce distinct spectra of compounds during hydrothermal liquefaction. In spite of the potential for hydrothermal production of renewable fuels, only a few hydrothermal technologies have so far gone beyond lab- or bench-scale.     

木质素及其模型化合物水热碳化过程研究现状

木质素作为世界上资源量仅次于纤维素的有机物,是一种尚未得到合理利用的可再生资源,具有较高的热值,是由三种醇单体形成的一种复杂酚类聚合物,这使得通过化学手段对其进行碳化成为可能。在现有的处理方法中,水热碳化（HTC）作为一种简单、高效的产碳方法,具有成本较低且不易造成污染等特点。本文综述了目前国内外以木质素及其模型化合物为原料进行水热碳化的研究现状,讨论了不同反应条件对碳化结果的影响,并对其未来发展方向进行了展望。     

成型炭化过程对磷酸-污泥-木屑成型炭性能的影响

以杉木屑和污泥为原料,磷酸为添加剂,探讨成型温度（70~100 ℃）、成型压力（80~110 MPa）和炭化温度（300~600 ℃）对磷酸-污泥-杉木屑成型炭物理性能和产率的影响,并对物理性能最佳的成型炭进行燃烧特性分析和重金属分析。结果表明,成型温度与成型压力对成型炭物理性能的影响相似,随着成型压力的增大和成型温度的升高成型炭物理性能均先升高后下降,炭化温度对成型炭物理性能影响较复杂。经80 ℃和100 MPa成型后再经500 ℃炭化制得的成型炭表观密度与抗压强度最大,分别为1279.0 kg/m³和18.7 MPa,均远高于商用烧烤炭。成型炭产率随炭化温度的升高而减小,由300 ℃的72.0%减至600 ℃的52.2%。较高的成型炭物理性能和产率可在一定程度上降低储存和运输成本,实现生物质废弃物的高效利用。     

Investigation on the physical properties of the charcoal briquettes prepared from wood sawdust and cotton stalk

The physical properties of the charcoal briquettes prepared from biomass waste are usually poor. In the paper, an alternative approach to the charcoal briquette preparation from the densified biomass briquette by carbonization was addressed. The carbonization process of the biomass briquettes prepared from cotton stalk (CS), wood sawdust (WS) and their blends was performed in a fixed bed at 400~600°C. The variation in the mass and volume of the biomass briquettes before and after the carbonization process and the physical properties of the resulted charcoal briquettes were investigated. The results indicate that the physical properties of the charcoal briquettes including bulk density and compression strength decreased firstly and then increased as the temperature increased. CS charcoal briquettes with better physical properties showed more volume shrinkage than WS charcoal briquettes after the carbonization process. However, the physical properties of the charcoal briquettes from the blends were poorer than expected due to the co-pyrolysis characteristics of CS and WS.     

Sustainable hydrogen production options from food wastes

In this study, two thermochemical processes, namely steam gasification and supercritical water gasification (SCWG), were comparatively studied to produce hydrogen from food wastes containing about 90% water. The SCWG experiments were performed at 400 and 450 °C in presence of catalyst (Trona, K₂CO₃ and seaweed ash). The maximum hydrogen yield was obtained at 450 °C in presence of K₂CO₃ catalyst. In second process, hydrothermal carbonization was used to convert food wastes into a high-quality solid fuel (hydrochar) that was further gasified in a dual-bed reactor in presence of steam. The steam gasification of hydrochar was carried out with and without catalysts (iron?ceria catalyst and dolomite). The maximum hydrogen yield obtained from steam gasification process was 28.08 mmol/g dry waste, about 7.7 times of that from SCWG. This study proposed a new concept for hydrogen production from wet biomass, combination of hydrothermal carbonization following steam gasification.     

单釜间歇式生物质炭化热解设备的结构设计研究

针对当前生物炭生产设备仍以半机械化为主,生产连续性差、生产效率低、物料堆放松散不平、秸秆炭化不均匀等问题,提出一种生物质单釜间歇式炭化设备,通过选择热解参数以及热工计算,采用棉花秸秆原料进行炭化试验,获取现有技术条件下的炭化得率质量分数为45%,气体为CO₂（50.2%）、CO（28.1%）、H₂（7.2%）、CH₄（6.9%）和其他（7.6%）,其中CO、H₂、CH₄作为主要燃烧成分占气体总质量分数的42.2%,可实现设计目标、提高炭化得率。     

Bio-oil production and upgrading research: A review

Biomass can be utilized to produce bio-oil, a promising alternative energy source for the limited crude oil. There are mainly two processes involved in the conversion of biomass to bio-oil: flash pyrolysis and hydrothermal liquefaction. The cost of bio-oil production from biomass is relatively high based on current technologies, and the main challenges are the low yield and poor bio-oil quality. Considerable research efforts have been made to improve the bio-oil production from biomass. Scientific and technical developments towards improving bio-oil yield and quality to date are reviewed, with an emphasis on bio-oil upgrading research. Furthermore, the article covers some major issues that associated with bio-oil from biomass, which includes bio-oil basics (e.g., characteristics, chemistry), application, environmental and economic assessment. It also points out barriers to achieving improvements in the future.     

FeCl3对稻壳水热炭基本元素及燃烧特性影响

以稻壳为原料,FeCl₃为催化剂,利用元素分析仪和热重法研究稻壳水热炭元素结构和燃烧特性,考察水热温度、催化剂浓度对于水热炭元素结构和燃烧特性的影响。结果表明：1)随着水热温度升高,水热炭固定碳含量和热值增大,O/C和H/C原子比逐渐降低。FeCl₃的加入进一步加深了水热炭的碳化程度,但对于碳化程度影响效果,水热温度大于FeCl₃浓度;2)未添加FeCl₃时,水热炭燃烧呈双峰,且挥发分燃烧段峰值明显高于固定碳燃烧段。水热温度上升,挥发分燃烧峰值下降,固定碳燃烧峰值增加。加入FeCl₃后,固定碳燃烧范围扩大,双峰逐渐融为单峰,整体向高温区转移;3)水热温度一定时,随着催化剂浓度增大,水热炭燃烧DTG曲线由双峰变为单峰,整体向低温区转移;4)升温速率加快,导致样品着火温度、燃尽温度提高,水热炭燃烧整体向高温区转移;5)水热温度一定时,FeCl₃加入后,着火温度和燃尽温度均小幅度提前,综合燃烧特性指数S_N呈先增大后减小的趋势。FeCl     

Hydrothermal pretreatment of fresh forest residues: Effects of feedstock pre-drying

Hydrothermal pretreatment has become an attractive method for upgrading biomass fuel because of its capacity to work effectively with various types of low cost wet feedstock. However, most of the past studies in the field dried the feedstock prior to the pretreatment without being aware of the effect of high temperature drying. In this study, fresh forest residues (Norway spruce and birch branches) were used as feedstocks to utilize the advantage of the hydrothermal pretreatment method. More importantly, the present work aims at investigating the effects of the pre-drying process on the solid product via a direct comparison on the fuel and physicochemical properties of hydrochars produced from fresh and dried forest residues. This assessment helps to identify differences when fresh and dried feedstocks are used for hydrothermal pretreatment study. The results showed that these differences were considerable with respect to solid and energy yields; and the use of dried feedstocks will be less representative for a commercially feasible hydrothermal process, using wet feedstock directly.     

Engineered pellets from dry torrefied and HTC biochar blends

Dry torrefaction and hydrothermal carbonization (HTC) are two thermal pretreatment processes for making homogenized, carbon rich, hydrophobic, and energy dense solid fuel from lignocellulosic biomass. Pellets made from torrefied biochar have poor durability compared to pellets of raw biomass. Durability, mass density, and energy density of torrefied biochar pellets decrease with increasing dry torrefaction temperature. Durable pellets of torrefied biochar may be engineered for high durability using HTC biochar as a binder. In this study, biomass dry torrefied for 1 h at 250, 275, 300, and 350 °C was pelletized with various proportions of biomass HTC treated at 260 °C for 5 min. During the pelletization of biochar blends, HTC biochar fills the void spaces and makes solid bridges between torrefied biochar particles, thus increasing the durability of the blended pellets. The engineered pellets' durability is increased with increasing HTC biochar fraction. For instance, engineered pellets of 90% Dry 300 and 10% HTC 260 are 82.5% durable, which is 33% more durable than 100% Dry 300 biochar pellets, and also have 7% higher energy density than 100% Dry 300 biochar pellets.     

Multi-scale complexities of solid acid catalysts in the catalytic fast pyrolysis of biomass for bio-oil production – A review

Despite remarkable progress in catalytic fast pyrolysis, bio-oil production is far from commercialization because of multi-scale challenges, and major constraints lie with catalysts. This review aims to introduce major constraints of acid catalysts and simultaneously to find out possible solutions for the production of fuel-grade bio-oil in biomass catalytic fast pyrolysis. The catalytic activities of several materials which act as acid catalysts and the impacts of Bronsted and Lewis acid site on the formation of aromatic hydrocarbons are discussed. Considering the complexity of catalytic fast pyrolysis of biomass with acid catalysts, in-depth understandings of cracking, deoxygenation, carbon-carbon coupling, and aromatization for both in-situ and ex-situ configurations are emphasized. The limitation of diffusion along with coke formation, active site poisoning, thermal/hydrothermal deactivation, sintering, and low aromatics in bio-oil are process complexities with solid acid catalysts. The economic viability of large-scale bio-oil production demands progress in catalyst modification or/and developing new catalysts. The potential of different catalyst modification strategies for an adequate amount of acid sites and pore size confinement is discussed. By critically evaluating the challenges and potential of catalyst modification techniques, multi-functional catalysts may be an effective approach for selective conversion of biomass to bio-oil and chemicals through catalytic fast pyrolysis. This review offers a scientific reference for the research and development of catalytic fast pyrolysis of biomass.     

石油炼厂加工纤维素/木质纤维素生物质原料的前景

生物质热解与生物油改质、生物质气化与合成气费-托转化工艺是正在研究开发的第二代生物燃料技术,前者利用快速热解工艺对生物质进行热解或热加氢改质生成热解油;后者用生物质直接合成或先转化为生物油后再生成合成气,合成气经改质和转化生产费-托合成烃。许多石油公司都在以纤维素/木质纤维素为原料,研究开发在石油炼厂内对生物质原料进行后续加工和应用的相关技术。在石油炼厂中引入生物质原料,其挑战是要找到源自非食用生物质或生物质废弃物的原料,而且这些原料应易于运输并易于在炼厂中进行处理,同时应尽可能使用现有的工艺和装置。虽然石油炼厂加工生物质原料尚存在一些问题,但近来开发势头十分强劲。从长远角度来看,任何能为炼厂提供原料,生命周期分析证明能减少CO2排放,并在经济上可行的技术均会在生物燃料开发竞争中成为赢家。     

Potential evolution of Turkish agricultural residues as bio-gas,bio-char and bio-oil sources

A study has been conducted to evaluate the potential power production from the pyrolysis for bio-oil and bio-char, and anaerobic digestion (for bio-gas), of agricultural residues in Turkey. Agricultural residues are potential renewable energy resources such as bio-gas from anaerobic digestion, bio-oil from pyrolysis, and bio-char from carbonization and slow pyrolysis processes. Anaerobic bio-gas production is an effective process for conversion of a broad variety of agricultural biomass to methane to substitute natural gas and medium calorific value gases. When the pyrolysis temperature increased the bio-char yield decreased. The bio-char yield increased with increasing particle size of the sample. Thermochemical conversion processes of biomass are the most common and convenient methods for conversion into energy. Among the processes of energy production from biomass, pyrolysis is the most popular thermal conversion process.     

Hydrothermal carbonization of biomass as a route for the sequestration of CO2: Chemical and structural properties of the carbonized products

A highly functionalized carbonaceous material (hydrochar) was obtained by means of the hydrothermal carbonization (250 °C) of two representative types of biomass, i.e. eucalyptus sawdust and barley straw. This product has a brown colour; it contains around 50-60% of the carbon originally present in the biomass and it is composed of particles that retain the cellular appearance of the raw material. These particles are covered by microspheres (1-10 ??m) which were probably formed as a consequence of the transformation of the cellulose fraction. From a chemical point of view, the hydrochar products have a high degree of aromatization and they contain a large amount of oxygen-containing groups (i.e. carbonyl, carboxylic, hydroxyl, quinone, ester, etc) as was confirmed by Raman, IR and XPS spectroscopic techniques. The presence of these oxygen functionalities on the surface of the hydrochar particles explains their high water affinity (hydrophilic properties). On the basis of the highly condensed chemical nature of the hydrochar products, we postulated that this material has a recalcitrant nature that could lead to a significant increase in carbon turnover time in relation to the biomass. This suggests an important route for the sequestration of CO₂ present in the atmosphere.     

Supercritical water gasification of biomass for hydrogen production

Hydrogen from waste biomass is considered to be a clean gaseous fuel and efficient for heat and power generation due to its high energy content. Supercritical water gasification is found promising in hydrogen production by avoiding biomass drying and allowing maximum conversion. Waste biomass contains cellulose, hemicellulose and lignin; hence it is essential to understand their degradation mechanisms to engineer hydrogen production in high-pressure systems. Process conditions higher than 374 °C and 22.1 MPa are required for biomass conversion to gases. Reaction temperature, pressure, feed concentration, residence time and catalyst have prominent roles in gasification. This review focuses on the degradation routes of biomass model compounds such as cellulose and lignin at near and supercritical conditions. Some homogenous and heterogeneous catalysts leading to water–gas shift, methanation and other sub-reactions during supercritical water gasification are highlighted. The parametric impacts along with some reactor configurations for maximum hydrogen production and technical challenges encountered during hydrothermal gasification processes are also discussed.     

Recent insights in synthesis and energy storage applications of porous carbon derived from biomass waste: A review

In the last few decades, global warming, environmental pollution, and an energy shortage of fossil fuel may cause a severe economic crisis and health threats. Storage, conversion, and application of regenerable and dispersive energy would be a promising solution to release this crisis. The development of porous carbon materials from regenerated biomass are competent methods to store energy with high performance and limited environmental damages. In this regard, bio-carbon with abundant surface functional groups and an easily tunable three-dimensional porous structure may be a potential candidate as a sustainable and green carbon material. Up to now, although some literature has screened the biomass source, reaction temperature, and activator dosage during thermochemical synthesis, a comprehensive evaluation and a detailed discussion of the relationship between raw materials, preparation methods, and the structural and chemical properties of carbon materials are still lacking. Hence, in this review, we first assess the recent advancements in carbonization and activation process of biomass with different compositions and the activity performance in various energy storage applications including supercapacitors, lithium-ion batteries, and hydrogen storage, highlighting the mechanisms and open questions in current energy society. After that, the connections between preparation methods and porous carbon properties including specific surface area, pore volume, and surface chemistry are reviewed in detail. Importantly, we discuss the relationship between the pore structure of prepared porous carbon with surface functional groups, and the energy storage performance in various energy storage fields for different biomass sources and thermal conversion methods. Finally, the conclusion and prospective are concluded to give an outlook for the development of biomass carbon materials, and energy storage applications technologies. This review demonstrates significant potentials for energy applications of biomass materials, and it is expected to inspire new discoveries to promote practical applications of biomass materials in more energy storage and conversion fields.     

Hydrothermal carbonization of microalgae II. Fatty acid,char, and algal nutrient products

A process for isolation of three products (fatty acids, chars and nutrient-rich aqueous phases) from the hydrothermal carbonization of microalgae is described. Fatty acid products derived from hydrolysis of fatty acid ester groups in the microalgae were obtained in high yield and were found to be principally adsorbed onto the char also created in the process. With the highest lipid-containing microalga investigated, 92% of the fatty acids isolated were obtained by solvent extraction of the char product, with the remaining 8% obtained by extraction of the acidified filtrate. Obtaining the fatty acids principally by a solid–liquid extraction eliminates potential emulsification and phase separation problems commonly encountered in liquid–liquid extractions. The aqueous phase was investigated as a nutrient amendment to algal growth media, and a 20-fold dilution of the concentrate supported algal growth to a level of about half that of the optimal nutrient growth medium. Uses for the extracted char other than as a solid fuel are also discussed. Results of these studies indicate that fatty acids derived from hydrothermal carbonization of microalgae hold great promise for the production of liquid biofuels.     

Sludge stabilization and energy recovery by hydrothermal carbonization process

Hydrothermal carbonization (HTC) is a thermal conversion process that converts high-moisture biomass into hydrochar. HTC was applied to stabilize and process sludge collected from septic tanks into hydrochar for practical energy recovery. Experiments were conducted with a 1-L high-pressure reactor operating at different temperatures and reaction times in which the sludge was mixed with catalysts and biomass at different ratios. The effects of catalysts (i.e., acetic acid, lithium chloride, borax, and zeolite) and biomass (i.e., cassava pulp, dried leaves, pig manure, and rice husks) mixing with sludge for hydrochar production were investigated. The experimental data showed acetic acid and cassava pulp to be the most effective catalyst and biomass, respectively, increasing energy contents to the maximum value of 28.5 MJ/kg. The optimum HTC conditions were as follows: sludge/acetic acid/cassava pulp mixing ratio of 1/0.4/1 (by weight), at a temperature of 220 °C, and reaction time of 0.5 h. The relatively high energy contents of the produced hydrochar suggest its applicability as a solid fuel.