利用微藻热化学液化制备生物油的研究进展

微藻是制备生物质液体燃料的良好材料,利用微藻热化学液化制备生物油在环保和能源供应方向都具有非常重要的意义。目前国内外研究者主要采用快速热解液化和直接液化两种热化学转化技术进行以微藻为原料制备生物油的研究。快速热解生产过程在常压下进行,工艺简单、成本低、反应迅速、燃料油收率高、装置容易大型化,是目前最具开发潜力的生物质液化技术之一。但快速热解需要对原料进行干燥和粉碎等预处理,微藻含水率极高,会消耗大量的能量,使快速热解技术在以微藻为原料制备生物油方面受到限制。直接液化技术反应温度较快速热解低,原料无需烘干和粉碎等高耗能预处理过程,且能产生更优质的生物油,将会是微藻热化学液化制备生物油发展的主流方向,极具工业化前景。国内外研究者还尝试利用超临界液化、共液化、热化学催化液化、微波裂解液化等多种新型液化工艺进行微藻热化学液化制备生物油的实验研究。今后的主要研究方向应是将热化学液化原理研究、生产工艺开发、反应器研发、反应条件优化、产品精制等有机地结合起来,进行深入研究。同时应努力节约成本、降低能耗。     

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.     

Liquefaction of palm kernel shell in sub- and supercritical water for bio-oil production

The heavy palm oil industry in Malaysia has generated various oil palm biomass residues. These residues can be converted into liquids (bio-oil) for replacing fossil-based fuels and chemicals. Studies on the conversion of these residues to bio-oil via pyrolysis technology are widely available in the literature. However, thermochemical liquefaction of oil palm biomass for bio-oil production is rarely studied and reported. In this study, palm kernel shell (PKS) was hydrothermally liquefied under subcritical and supercritical conditions to produce bio-oil. Effects of reaction temperature, pressure and biomass-to-water ratio on the characteristics of bio-oil were investigated. The bio-oils were analyzed for their chemical compositions (by GC–MS and FT-IR) and higher heating values (HHV). It was found that phenolic compounds were the main constituents of bio-oils derived from PKS for all reaction conditions investigated. Based on the chemical composition of the bio-oil, a general reaction pathway of hydrothermal liquefaction of PKS was postulated. The HHV of the bio-oils ranged from 10.5 to 16.1 MJ/kg, which were comparable to the findings reported in the literature.     

生物质液化技术面临的挑战与技术选择

生物质液化技术可将低品位的固体生物质完全转化成高品位的液体燃料或化学品,是生物质能高效利用的主要方式之一。按照机理,液化技术可以分为热化学法、生化法、酯化法和化学合成法(间接液化),热化学法液化又分为快速热解技术和高压液化(直接液化)技术。生物质热化学法液化已成为国内外生物质液化的研究开发重点和热点,快速热解液化技术和高压液化技术是最具产业化前景的生物质能技术,生化法液化技术也是生物质能的研究热点。化学合成法液化技术并不适用于生物质液化,而利用生物柴油进一步生产生物航空煤油是得不偿失的,不仅成本高、资源利用率低,而且全生命周期碳排放增加,还不符合未来生物航煤的发展趋势。生物质含水量的高低是影响生物质液化过程中能耗、效率、污染指数和经济性指标等的关键因素,应根据含水量合理选择生物质液化技术。快速热解液化技术适用于低含水农林废弃物,高压液化和生化法液化技术适用于高含水生物质,酯化法液化技术适用于不可食用油脂,而各种液化技术均不适用于城市生活垃圾的处理,建议将其用作燃气型气化原料。     

Strategies for selection of thermo-chemical processes for the valorisation of biomass

Research on biomass conversion has been gaining a lot of interest as biomass is renewable and sustainable in nature. Products from biomass can be obtained by different methods amongst which thermo-chemical route has a very high potential. Biomass is generally available in a localised manner in varying quantities and qualities throughout the year and hence, region specific technologies have to be developed considering the end user requirement. Pyrolysis is a very versatile technique with the above considerations. The process parameters can be tweaked to necessity to produce more bio-oil or bio-char. Thermogravimetric analysis is essential for understanding the decomposition behaviour of the feedstock before the lab scale pyrolysis is carried out. Pyrolysis using several regional feedstocks has been carried out under nitrogen and hydrogen atmosphere and different biomass feedstocks were also liquefied using sub/supercritical solvents. This review aims to provide a comparison of the results obtained using various processes. This helps in the decentralised processing of biomass (dry biomass using pyrolysis and wet biomass by hydrothermal liquefaction) to produce bio-crude which can be upgraded to produce fuels/chemicals/petrochemical feedstocks in an environmental friendly manner.     

Valorisation of lignocellulosic biomass investigating different pyrolysis temperatures

Presently, sugarcane bagasse (SB) and oat hulls (OH) have a distinctive potential as a renewable source of biomass, due to its global availability, which is advantageous for producing liquid and gaseous fuels by thermochemical processes. Thermo-Catalytic Reforming (TCR) is a pyrolysis based technology for generating energy vectors (char, bio-oil and syngas) from biomass wastes. This work aims to study the conversion of SB and OH into fuels, using TCR in a 2 kg/h continuous pilot-scale reactor at different pyrolysis temperatures. The pyrolysis temperatures were studied at 400, 450 and 500 °C, while the subsequent reforming temperature remained constant at 500 °C. The bio-oil contained the highest calorific value of 33.4 and 33.5 MJ/kg for SB and OH, respectively at 500 °C pyrolysis temperature, which represented a notable increase compared to the raw material calorific value of SB and OH (16.4 and 16.0 MJ/kg, respectively), this was the result of deoxygenation reactions occurring. Furthermore, the increment of the pyrolysis temperature improved the water content, total acid number (TAN), viscosity and density of the bio-oil. The syngas and the biochar properties did not change significantly with the increase of the pyrolysis temperature. In order to use TCR bio-oil as an engine fuel, it is necessary to carry out some upgrading treatments; or blend it with fossil fuels if it is to be used as a transportation fuel. Overall, TCR is a promising future route for the valorisation of lignocellulosic residues to produce energy vectors.     

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.     

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.     

Main routes for the thermo-conversion of biomass into fuels and chemicals. Part 1: Pyrolysis systems

Since the energy crises of the 1970s, many countries have become interest in biomass as a fuel source to expand the development of domestic and renewable energy sources and reduce the environmental impacts of energy production. Biomass is used to meet a variety of energy needs, including generating electricity, heating homes, fueling vehicles and providing process heat for industrial facilities. The methods available for energy production from biomass can be divided into two main categories: thermo-chemical and biological conversion routes. There are several thermo-chemical routes for biomass-based energy production, such as direct combustion, liquefaction, pyrolysis, supercritical water extraction, gasification, air–steam gasification and so on. The pyrolysis is thermal degradation of biomass by heat in the absence of oxygen, which results in the production of charcoal (solid), bio-oil (liquid), and fuel gas products. Pyrolysis liquid is referred to in the literature by terms such as pyrolysis oil, bio-oil, bio-crude oil, bio-fuel oil, wood liquid, wood oil, liquid smoke, wood distillates, pyroligneous tar, and pyroligneous acid. Bio-oil can be used as a fuel in boilers, diesel engines or gas turbines for heat and electricity generation.     

The current status and perspectives of biofuel production via catalytic cracking of edible and non-edible oils

Biofuel development has gained the attention of researchers in recent years owing to the rate of depletion of fossil fuels. Several processes are currently employed in the conventional production of different biofuels: the production of biodiesel is catalytically performed either through the transesterification of triglycerides using alcohol or the deoxygenative ecofining of triglycerides in a non-alcohol environment; bio-oil is produced by the pyrolysis of biomass; bio-ethanol is produced by the fermentation of sugars obtained from starch or cellulosic based biomass, while bio-gasoline is produced from the catalytic cracking of triglycerides. Owing to the enormous dependency of transport vehicles running on gasoline engines, the development of bio-gasoline may well reduced the dependence of the fuel market on fossil fuels. The present article summarizes recent progresses and future prospects of biofuel production via catalytic cracking technology. This technology can be implemented in current petroleum refineries with minor modifications. However, reactor design and catalyst choice are important issues and have to be addressed before successful implementation of this technology in commercial ventures.     

Bio-fuels from Agricutural Residues

Abstract

Bio-fuels, such as bio-oil, bio-char, and bio-gas, can be obtained from agricultural residues. Agricultural residues are potential renewable energy resources such as biogas from anaerobic digestion, bio-oil from pyrolysis, and bio-char from carbonization and slow pyrolysis processes. Pyrolysis process of agricultural residues are the most common and convenient methods for conversion into bio-oil and bio-char. When the pyrolysis temperature increased, the bio-char yield decreased. The bio-char yield increased with increasing particle size of the sample. The yield of bio-oil from pyrolysis of the samples increased with temperature. Anaerobic biogas 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.     

生物质高压液化制生物油研究进展

以生物质为原料进行高压液化制备生物油是目前生物质能领域研究的一个热点。纤维素在水中的降解是复杂的竞争和连串反应机理;在180℃以上,半纤维素就很容易水解,而且不管是酸还是碱都能催化半纤维素的水解反应;在水热条件下木质素会发生分解,生成多种苯酚、甲氧基苯酚等,这些产物可进一步被水解成甲氧基化合物。影响生物质液化产率及生物油组成的主要因素是温度、生物质类型和溶剂种类;次要因素包括停留时间、催化剂、还原性气体和供氢溶剂、加热速率、生物质颗粒大小、反应压力等。纤维素类生物质通过高压液化可以生产生物油,生物油经物理精制及化学加工可以制取车用燃料、生物气及化工产品等。生物油有轻油和重油之分,都是通过对生物质液化产物的分离精制而得到的。目前用来分析生物油的主要方法包括GC-MS(色-质联用)、EA(元素分析)、FTIR(傅里叶变换红外光谱)、HPLC(高效液相色谱)、NMR(核磁共振)、TOC(总有机碳测定)等。人们对生物质高压液化研究已经进行多年,并建立了几套工业试验示范装置。不过因为操作条件太苛刻,到目前为止还没有建立商业化装置。     

Recent progress in the direct liquefaction of typical biomass

Energy from biomass, bioenergy, is a promising source to replace fossil fuels in the future, as it is abundant, clean, and carbon dioxide neutral. Thermochemical liquefaction of biomass is widely investigated as a promising method to produce one kind of liquid biofuel, namely bio-oil. This review presents the recent research progress in the liquefaction of typical biomass from a new perspective. Particularly, this article summarizes five aspects of related work: first, the effect of solvent type on the liquefaction behaviors of biomass; second, the effect of biomass type on the liquefaction behaviors of biomass; third, the liquefaction of biomass in sub-/super-critical ethanol; fourth, the liquefaction of biomass in organic solvent–water mixed solvents; fifth, the liquefaction of sewage sludge. Meanwhile, the research advance in the migration and transformation behavior of heavy metals during the liquefaction of sewage sludge was also summarized in this review. This review can offer an important reference for the study of biomass liquefaction.     

Economic tradeoff between biochar and bio-oil production via pyrolysis

This paper examines some of the economic tradeoffs in the joint production of biochar and bio-oil from cellulosic biomass. The pyrolysis process can be performed at different final temperatures, and with different heating rates. While most carbonization technologies operating at low heating rates (large biomass particles) result in higher yields of charcoal, fast pyrolysis (which processes small biomass particles) is the preferred technology to produce bio-oils. Varying operational and design parameters can change the relative quantity and quality of biochar and bio-oil produced for a given feedstock. These changes in quantity and quality of both products affect the potential revenue from their production and sale. We estimate quadratic production functions for biochar and bio-oil. The results are then used to calculate a product transformation curve that characterizes the yields of bio-oil and biochar that can be produced for a given amount of feedstock, movement along the curve corresponds to changes in temperatures, and it can be used to infer optimal pyrolysis temperature settings for a given ratio of biochar and bio-oil prices.     

Life cycle assessment of electricity generation using fast pyrolysis bio-oil

Biomass is expected to become an important energy source in U.S. electricity generation under state-lead renewable portfolio standards. This paper investigated the greenhouse gas (GHG) emissions for energy generated from forest resources through pyrolysis-based processing. The GHG emissions of producing pyrolysis bio-oil (pyrolysis oil) from different forest resources were first investigated; logging residues collected from natural regeneration mixed hardwood stands, hybrid poplar cultivated and harvested from abandoned agricultural lands, short rotation forestry (SRF) willow plantations and waste wood available at the site of the pyrolysis plant. Effects of biomass transportation were investigated through a range of distances to a central pyrolysis facility through road transport by semi-truck. Pyrolysis oil is assumed to be converted to electrical power through co-combustion in conventional fossil fuels power plants, gas turbine combined cycle (GTCC) and diesel generators. Life cycle GHG emissions were compared with power generated using fossil fuels and power generated using biomass direct combustion in a conventional Rankine power plant. Life cycle GHG savings of 77%–99% were estimated for power generation from pyrolysis oil combustion relative to fossil fuels combustion, depending on the biomass feedstock and combustion technologies used. Several scenario analyses were conducted to determine effects of pyrolysis oil transportation distance, N-fertilizer inputs to energy crop plantations, and assumed electricity mixes for pyrolysis oil production.     

Production and characterization of bio-oil and biochar from rapeseed cake

New and renewable fuels are the major alternatives to conventional fossil fuels. Biomass in the form of agricultural residues is becoming popular among new renewable energy sources, especially given its wide potential and abundant usage. Pyrolysis is the most important process among the thermal conversion processes of biomass. In this study, the production of bio-oil and biochar from rapeseed cake obtained by cold extraction pressing was investigated and the various characteristics of biochar and bio-oil acquired under static atmospheric conditions were identified. The biochar obtained are carbon rich, with high heating value and relatively pollution-free potential solid biofuel. The bio-oil product was presented as an environmentally friendly green biofuel candidate.     

Utilization of lignin: A sustainable and eco-friendly approach

The use of renewable carbon sources as a substitute for fossil resources is an extensively essential and fascinating research area for addressing the current issues related to climate and future fuel requirements. The utilization of lignocellulosic biomasses as a source for renewable fuel/chemicals/mesoporous biochar derivative is gaining considerable attention due to the neutral carbon cycle. The cellulose and hemicellulose are highly utilized components of biomass, and on the other hand, lignin is a plentiful, under-utilized component of the lignocellulosic biomass in 2G ethanol and paper industry. Significant researchers have contributed towards lignin valorization, with a central goal of the production and upgradation of phenolic, unstable, acidic and oxygen-containing bio-oil to valuable chemicals or fuel grade hydrocarbons. This review is aimed to present the lignin valorization potential from pretreatment of biomass as an initial step to the final process, i.e., lignin bio-oil upgradation with mechanistic pathways. The review offers the source, structure, composition of various lignocellulosic biomasses, followed by a discussion of various pre-treatment techniques for biomass depolymerization. Different thermochemical approaches for bio-oil production from dry and wet biomasses are highlighted with emphasis on pyrolysis and liquefaction. The physical, chemical properties of lignin bio-oil and different upgradation methods for bio-oil as well as its model compounds are thoroughly discussed. It also addresses the related activity, selectivity, stability of numerous catalysts with reaction pathways and kinetics in a broad manner. The challenges and future research opportunities of lignin valorization are discussed in an attempt to place lignin as a feedstock for the generation of valuable chemical and fuel grade hydrocarbons.     

An overview of empty fruit bunch from oil palm as feedstock for bio-oil production

Empty fruit bunch (EFB) from oil palm is one of the potential biomass to produce biofuels like bio-oil due to its abundant supply and favorable physicochemical characteristics. Confirming the assertion, this paper presents an overview of EFB as a feedstock for bio-oil production. The fundamental characteristics of EFB in terms of proximate analysis, ultimate analysis and chemical composition, as well as the recent advances in EFB conversion processes for bio-oil production like pyrolysis and solvolysis are outlined and discussed. A comparison of properties in terms of proximate analysis, ultimate analysis and fuel properties between the bio-oil from EFB and petroleum fuel oil is included. The major challenges and future prospects towards the utilization of EFB as a useful resource for bio-oil production are also addressed.     

A comprehensive review on lignocellulosic biomass biorefinery for sustainable biofuel production

The increasingly severe environmental pollution and energy shortage issues have demanded the production of renewable and sustainable biofuels to replace conventional fossil fuels. Lignocellulosic (LC) biomass as an abundant feedstock for second-generation biofuel production can help overcome the shortcomings of first-generation biofuels related to the “food versus fuel” debate and feedstock availability. Embracing the “circular bioeconomy” concept, an integrated biorefinery platform of LC biomass can be performed by employing different conversion technologies to obtain multiple valuable products. This review provides an overview of the principles and applications of thermochemical processes (pyrolysis, torrefaction, hydrothermal liquefaction, and gasification) and biochemical processes (pretreatment technologies, enzyme hydrolysis, biochemical conversion processes) involved in LC biomass biorefinery for potential biofuel applications. The engineering perspective of LC biofuel production on separate hydrolysis and fermentation (SHF), simultaneous saccharification and fermentation (SSF), simultaneous saccharification and co-fermentation (SSCF), and consolidated bioprocessing (CBP) were also discussed.     

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.