Biorefineries: Current activities and future developments

This paper reviews the current refuel valorization facilities as well as the future importance of biorefineries. A biorefinery is a facility that integrates biomass conversion processes and equipment to produce fuels, power, and chemicals from biomass. Biorefineries combine the necessary technologies of the biorenewable raw materials with those of chemical intermediates and final products. Char production by pyrolysis, bio-oil production by pyrolysis, gaseous fuels from biomass, Fischer–Tropsch liquids from biomass, hydrothermal liquefaction of biomass, supercritical liquefaction, and biochemical processes of biomass are studied and concluded in this review. Upgraded bio-oil from biomass pyrolysis can be used in vehicle engines as fuel.     

Performance assessment of hydrogen production from a solar-assisted biomass gasification system

In this study, we investigate a solar-assisted biomass gasification system for hydrogen production and assess its performance thermodynamically using actual literature data. We also analyze the entire system both energetically and exergetically and evaluate its performance through both energy and exergy efficiencies. Three feedstocks, namely beech charcoal, sewage sludge and fluff, are considered as samples in the same reactor. While energy efficiencies vary from 14.14% to 27.29%, exergy efficiencies change from 10.43% to 23.92%. We use a sustainability index (SI), as a function of exergy efficiency, to calculate the impacts on sustainable development and environment. This index changes from 1.12 to 1.31 due to intensive utilization of solar energy. Also, environmental impact of these systems is evaluated through calculating the specific greenhouse gas (GHG) emissions. They are determined to be 17.97, 17.51 and 26.74 g CO₂/MJ H₂ for beech charcoal, sewage sludge and fluff, respectively.     

Investigation of municipal sludge gasification potential: Gasification characteristics of dried sludge in a pilot-scale downdraft fixed bed gasifier

This study presents the research results acquired from conducting municipal sludge gasification in a downdraft type gasifier at pilot scale. The assessment of the results was not only focused on syngas characteristics, but also on the gasification residues: char ash and glassy material. The gasification temperature was varied from 1000 to 1150 °C during the gasification trials. The produced high quality syngas was transferred to the engine to generate the electricity. About 1 kWh electrical power was achieved for approximately 1.2 kg municipal sludge gasified. Most of the heavy metals available in the sludge was found as fixed form in the glassy material. The gasification residues evaluated as valuable materials regarding their characteristics have reuse potential for different beneficial usage alternatives. Based on the costs for the investment and operation and incomes, the return on the investment for this pilot scale system was roughly found as 3.3 years. This study showed that the municipal sludge had an important fuel merit and the energy recovery from the sludge was possible via the gasification application. In this paper, the research results were discussed in detail to make better insight to full-scale applications as a promising alternative for sludge disposal.     

Biohydrogen production from oil palm frond juice and sewage sludge by a metabolically engineered Escherichia coli strain

Biohydrogen is considered a promising and environmentally friendly energy source. Escherichia coli BW25113 hyaB hybC hycA fdoG frdc ldhA aceE has been previously engineered for elevated biohydrogen production from glucose. In this study, we show that this strain can also use biomass from oil palm frond (OPF) juice and sewage sludge as substrates. Substrate improvement was accomplished when hydrogen productivity increased 8-fold after enzymatic treatment of the sludge with a mixture of amylase and cellulase. The OPF juice with sewage sludge provided an optimum carbon/nitrogen ratio since the yield of biohydrogen increased to 1.5 from 1.3 mol H₂/mol glucose compared to our previous study. In this study, we also reveal that our engineered strain improved 200-fold biohydrogen productivity from biomass sources compared to the unmodified host. In conclusion, we determined that our engineered strain can use biomass as an alternative substrate for enhanced biohydrogen production.     

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。     

Hydrogen transfer during co-liquefaction of Elbistan lignite and biomass: liquid product characterization approach

In this study, Elbistan lignite (EL) and manure were liquefied under catalytic conditions in an inert atmosphere. Red mud, tetralin, and distilled water were used as a catalyst and solvent, respectively. The liquefaction studies were carried out under catalytic conditions in the catalyst concentration of 9%, solvent/solid ratio of 3/1, reaction time of 60 min, waste/lignite ratio of 1/3, and at temperature of 400°C. Stirring speed and initial nitrogen pressure were kept constant at 400 rpm and 20 bar, respectively. At the end of liquefaction process, the soluble liquefaction products were separated by successive solvent extraction to preasphaltene, asphaltene, and oils. Oil products characterized by H-NMR to be able to differ hydrogen transfer from manure to EL surface. To obtain the hydrogen transfer way, liquefaction experiments conducted under inert atmosphere which does not related to hydrogen reaction, other above experimental conditions were kept same but only solvent type changed. The reason of using distilled water instead of tetraline is tetraline known as hydrogen donor but not water. Because water behaves supercritical conditions during the liquefaction stage. EL liquefied alone while using tetraline however EL liquefied with manure with using distilled water as a solvent. The obtained oil products form both experiments characterized by H-NMR. The radical groups diffraction and range values are not changed significantly shows that manure behaved as an hydrogen donor. So, EL with manure is the one great option to reduce cost of hydrogen source for direct coal liquefaction plant.     

Anaerobic co-digestion of sewage sludge with switchgrass: Experimental and kinetic evaluation

Sewage sludge removal via anaerobic digestion provides energy production in addition to waste minimization. Several strategies, such as anaerobic co-digestion, were developed to increase energy production from sewage sludge by improving C/N balance. In this study, anaerobic co-digestion of sewage sludge with an energy crop, namely switchgrass, was evaluated. As a result of studies implemented at different mixing ratios, maximum methane production was measured as 272.06 mLCH₄/gVS at the mixing ratio of 0.4:0.6 (sewage sludge:switchgrass). According to modified kinetic models used for interpretation of synergetic and/or antagonistic effects, anaerobic co-digestion has a synergetic effect on biogas production from both biomass.     

Effects of solvents and catalysts in liquefaction of pinewood sawdust for the production of bio-oils

Liquefaction of biomass with proper solvents and catalysts is a promising process to produce liquid biofuels and valuable chemicals. In this study, pinewood sawdust was liquefied in the presence of various supercritical solvents (carbon dioxide, water, acetone, and ethanol) and catalysts (alkali salts and acidic zeolites). The liquid, gas and solid products were analyzed using GC–MS, FT-IR, elemental analyzer, ¹H NMR, ¹³C NMR. The experimental results showed that both solvent and catalyst can significantly improve the liquefaction process by increasing the yield of liquid oil and suppressing the formation of solid residue. K₂CO₃ showed the best performance by doubling the yield of bio oil. Meanwhile, the maximum bio-oil yield (30.8 wt%) and the minimum solid residue yield (28.9 wt%) were obtained when ethanol was employed as the solvent. Solvents can also strongly affect the distribution of liquid products. 2,4,5,7-tetramethyl-phenanthrene and bis(2-ethylhexyl) phthalate were the premier compounds in liquid product as supercritical carbon dioxide is used as solvent while 2-methyl-naphthalene became the main composition when water is used as solvent.     

Influence of fuel ashes on corrosion of surface coatings cladded by CMT method

The aim of the present research was to investigate the influence of different biomasses and sewage sludge ash (at 650°C for 1000 h and 2000 h, respectively) on the surface of weld cladded (Cold Metal Transfer technique, CMT) stainless steels 309 and 310. The biomass ashes were rich in K₂O, CaO, SiO₂, whereas sewage sludge ash in P₂O₅, CaO, Fe₂O₃, and SiO₂. Characterization of the stainless steel cross-section and surface after the corrosion process inducted by the presence of ash were carried out by scanning electron microscopy (SEM) with EDAX analysis. Phase analysis of corrosion products was made by X-ray diffraction (XRD). Chromium, nickel, and iron oxides were the main oxides which occurred after the corrosion test. It has been proved that biomass ashes have the corrosive properties (because of their chemical composition) and are more aggressive than the sewage sludge ash for that kind of materials.     

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.     

The influence of organic and inorganic fertiliser application rates on UK biomass crop sustainability

Bioenergy and energy crops are an important part of the UK’s renewable energy strategy to reach its greenhouse gas reduction target of 80% by 2050. Ensuring the sustainability of biomass feedstocks requires a greater understanding of all aspects of energy crop production, their ecological impacts and yields. This work compares the life-cycle environmental impact of natural gas and biomass from two energy crop systems grown under typical UK agronomic practice. As reported in previous studies the energy crops provide significant reductions in global warming potential (GWP) compared to natural gas. Compared to no fertiliser application, applying inorganic fertiliser increases the GWP by 2% and applying sewage sludge increases the GWP by a lesser extent. In terms of an equivalent GWP savings per unit area of land, the emissions associated with fertiliser production and application can be offset by a yield increase of <0.2 t/ha. However, very large increases in eutrophication and acidification levels are incurred compared to the natural gas reference case when applying either fertiliser. For sewage sludge the impact of varying the allocation factor between the function of wastewater treatment and that of crop growth is also illustrated.     

Comprehensive evaluation of hydro-liquefaction characteristics of lignocellulosic subcomponents

This study investigated the hydro-liquefaction behaviors of cellulose, xylan and lignin in ethanol at various temperatures. The interactions between the reaction medium and individual biomass component under different temperatures were evaluated using the Monte Carlo method. The simulation results indicated that the compatibility from cellulose and xylan system was superior to that of lignin with the elevated temperature. The liquefaction characteristics of cellulose and xylan were highly affected by temperature variation due to the existence of active chemical region and functional groups in the structures. In comparison, the reaction behavior of lignin-containing complicated polyaromatic structure was slightly dependent on the elevated temperature. The variation trend of chemical structures from solid residues was highly related to the nature of the raw feedstock. The properties of bio-oil derived from liquefaction of single biomass composition were also associated with the inherent composition of each biomass subcomponent.     

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.     

Towards sewage sludge based biofuels via thermochemical conversion – A review

Wastewater treatment leads to an increase in sewage sludge production. Sewage sludge consists, in general, of non-toxic organic matter and therefore can be utilized as a biomass resource for energy production. Energy recovery from sewage sludge via thermochemical valorization processes seems of great potential. Processes’ products can be used as bio-fuels, while minimization of the environmental impacts can be also achieved. In particular, wet sewage sludge pyrolysis-partial gasification at high temperatures and especially gasification give a new perspective for hydrogen-rich fuel gas production. Co-processing of sewage sludge with biomass improves the fuel's characteristics and enhances the processes efficiency. In addition, blends of sewage sludge with biomass contribute in diluting the inorganic and toxic compounds. Towards that direction, algae production using wastewater resources and then to be used for biofuels production seems a sustainable solution that is the reason why exploitation of such a material through thermochemical processes is under intensive discussion.     

Phosphorus recovery from the biomass ash: A review

Biomass ash, generated during the thermal chemical conversion of biomass for energy production, is an industrial by-product which is often recognized as a solid waste, but there are some useful elements in the biomass ash such as phosphorus, etc. So through some technology and methods, the biomass ash can be transferred into a useful resource. The paper mainly includes the following aspects: biomass ash composition characteristics, biomass thermal chemical conversion for phosphorus and phosphorus recovery technology from biomass ash. Through these aspects literature review, not only the whole biomass ash characteristics was made clear, but also we think that the idea of phosphorus from biomass ash is feasible, especially for some high phosphorus ash such as sludge ash, meat and bone meal (MBM) ash, etc. So the review about phosphorus from the biomass ash is very important practical significance for biomass energy, biomass ash disposal and phosphorus resource.     

Thermochemical conversion of sewage sludge: A critical review

The increasing levels of sewage sludge production demands research and development to introduce more commercially feasible options for reducing socio-economic and environmental problems associated with its current treatment. Sewage sludge may be processed to produce useful products or as a feedstock for energy generation. Initially, the characteristics of sewage sludge are discussed in terms of composition and the current options for its treatment with the associated environmental impacts. Processes to valorize sewage sludge are discussed, including heavy metal removal from sewage sludge, production of bio-char, production and use of activated carbon and use of sewage sludge combustion ash in cement and concrete. Thermochemical processes i.e., pyrolysis, co-pyrolysis and catalytic pyrolysis, also gasification and combustion for process intensification, energy and resource recovery from sewage sludge are then critically reviewed in detail. The pyrolysis of sewage sludge to produce a bio-oil is covered in relation to product bio-oil composition, reactor type and the use of catalysts. Gasification of sewage sludge focusses on the characteristics of the different available reactor types and the influence of a range of process parameters and catalysts on gas yield and composition. The selection and design of catalysts are of vital importance to enhance the selectivity of the selected thermochemical pyrolysis or gasification process. The catalysts used for sewage sludge treatment need more research to enable selectivity towards the targeted desired end-products along with optimization of parametric conditions and development of innovative reactor technologies. The combustion of sewage sludge is reviewed in terms of reactor technologies, flue gas cleaning systems and pollutant emissions. In addition, reactor technologies in terms of technological strength and market competitiveness with the particular application to sewage sludge are compared for the first time for thermochemical conversion. A critical comparison is made of the drying techniques, co-feedstocks and catalytic processes, reaction kinetics, reactor technologies, operating conditions to be optimized, removal of impurities, fuel properties, their constraints and required improvements. The emphasis of this review is to promote environmental sustainability for process intensification, energy and resource recovery from pyrolysis, gasification and combustion involving the use of catalysts.     

Kinetic modeling and optimization of biomass pyrolysis for bio-oil production

Thermo-kinetic models for biomass pyrolysis were simulated under both isothermal and non-isothermal conditions to predict the optimum parameters for bio-oil production. A comparative study for wood, sewage sludge, and newspaper print pyrolysis was conducted. The models were numerically solved by using the fourth order Runge–Kutta method in Matlab-7. It was also observed that newspaper print acquired least pyrolysis time to attain optimum bio-oil yield followed by wood and sewage sludge under the identical conditions of temperature and heating rate. Thus, at 10 K/min, the optimum pyrolysis time was 21.0, 23.8, and 42.6 min for newspaper print, wood, and sewage sludge, respectively, whereas the maximum bio-oil yield predicted was 68, 52, and 36%, respectively.     

Renewable biohydrogen production from straw biomass – Recent advances in pretreatment/hydrolysis technologies and future development

Straw is an abundant natural bioresource, especially in developing and agricultural countries. Bio-hydrogen production from this renewable biomass through biological methods is an active research area. Because of its distinctive characteristic of being rich in cellulose, straw has been extensively considered as a promising raw material for clean energy production. In this paper, the recent progress of bio-hydrogen production from straw was reviewed with the emphasis on the advances in pretreatment and hydrolysis technologies. The future development of straw-based biohydrogen production was also analyzed. Based on the physicochemical properties of straw biomass and mechanisms of bio-hydrogen fermentation, various pretreatment procedures have been developed to make the straw substrate more available for hydrogen-producing bacteria to realize large-scale bio-hydrogen production from straw. This review summarized the recent technologies of straw pretreatment and hydrolysis as well as elaborated on the bottlenecks in the field of straw biotransformation in great detail. Furthermore, based on the current technology status and potential, the challenges, prospects and future directions of the production methods were further proposed.     

Bio-oil fractionation by temperature-swing extraction: Principle and application

Bio-oils produced by direct thermal liquefaction often contain heavy components that hinder their utilization as a liquefaction medium. This paper reports a new approach to fractionate the liquefaction bio-oil into a light and a heavy fraction based on solvent extraction and temperature-swing regeneration. This approach is based on hot extraction (T ∼ 70 °C) of the light fraction of the oil with a suitable extraction solvent followed by cold (T ∼ 25 °C) de-mixing of the light fraction and the extraction solvent. In this paper, we (i) illustrate the selection of the extraction solvent and define the solvent properties required, (ii) demonstrate the potential of multistage extraction/regeneration for the bio-oil produced by direct thermal liquefaction, (iii) extend the concept to fractionate a petroleum crude oil, (iv) discuss the theoretical basis of the fractionation using polymer solution theory and, finally, (v) show a low energy requirement of the extraction process by means of process simulation, i.e., an equivalent of ∼1% of the biomass intake.     

Studies on the direct liquefaction of protein-contained biomass: The distribution of nitrogen in the products

In studies of the direct aqueous liquefaction of protein-contained biomass such as sewage sludge, nitrogen derived from proteins is distributed in both the oil and aqueous phases. The nitrogen in the oil is very difficult to remove by hydrotreatment over nickel/molybdenum catalysts. Egg albumin was used as a model protein in direct liquefaction studies of the nitrogen distribution in the products. The oil yield from albumin (10%) was much less than that obtained from actual feedstocks (typically in the range 30–40%). The nitrogen content of the oil (9%) represented less than 5% of the total nitrogen, while in the liquefaction of actual feedstocks, 30–50% of the nitrogen in the feedstock was found in the oil. No distribution of nitrogen to oil under 150°C occurred because of no oil yield. The majority of the nitrogen in albumin (80%) was distributed to the aqueous phase above 200°C. The distribution of nitrogen to oil was completed by 250°C. Sodium carbonate, used as a catalyst, prevented the distribution of nitrogen to oil. Albumin was decomposed to ammonia, not to amino acids.