Characterization of bio-oils from the fast pyrolysis of white oak and sweetgum

Conversion of lignocellulosic biomass into bio-oil through fast pyrolysis process is considered one of the promising routes to supplement conventional fossil oil. Future bio-refineries require production large amounts of bio-oil from several biomass types. Characterization of the produced bio-oils is important to determine their suitability as bio-refinery feedstock. In this study, bio-oils were produced from white oak and sweetgum woods in an auger reactor at 450°C. The yields of char, liquid, and gas were calculated. The physical characterization of bio-oils was performed based on the investigation of different properties, such as pH, density, viscosity, water content, acid value, and molecular weight distribution of bio-oil components. The chemical compositions of the bio-oils were also investigated by gas chromatography/mass spectrometry and Fourier transform infra-red analyses. The physicochemical properties of the produced bio-oils were comparable to those obtained from similar woody biomass and the oils were suitable for fuel production.     

Oily Products from Mosses and Algae via Pyrolysis

In this study, the fuel properties of mosses and algae, and the effect of pyrolysis temperature on the yield of bio-oil from moss and alga samples, were investigated. The yield of bio-oil from pyrolysis of the samples increased with temperature. The yields were increased up to 750 K in order to reach the plateau values at 775 K. The maximum yields were 39.1, 34.3, 33.6, 37.0, 35.4, 48.2 and 55.3% of the sample for Polytrichum commune, Dicranum scoparium, Thuidium tamarascinum, Sphagnum palustre, Drepanocladus revolvens, Cladophora fracta and Chlorella protothecoides, respectively. The bio-oil yield for Chlorella protothecoides (a microalga sample) rose from 5.7 to 55.3% as the temperature rose from 525 to 775 K, and then gradually decreased to 51.8% and was obtained at 875 K with a heating rate of 10 K/s. Formulas can be developed to calculate higher heating value (HHV) of different moss and alga samples. The calculated HHV using these new correlations showed mean differences ranging from ?2.3% to +0.06%. The equation developed in this study showed good agreement with experimental results on moss and algae samples. The HHVs for bio-oils from mosses 21.5–24.8 MJ/kg and the HHVs for bio-oils from algae and microalga 32.5 and 39.7 MJ/kg, respectively, were obtained at temperature ranging from 775 to 825 K. In general, algae bio-oils are of higher quality than bio-oils from mosses. In general, microalgae bio-oils are higher quality than bio-oil from wood.     

Effects of torrefaction on the physiochemical properties of oil palm empty fruit bunches,mesocarp fiber and kernel shell

In this work, the effects of torrefaction on the physiochemical properties of empty fruit bunches (EFB), palm mesocarp fiber (PMF) and palm kernel shell (PKS) are investigated. The change of properties of these biomass residues such as CHNS mass fraction, gross calorific value (GCV), mass and energy yields and surface structure when subjected to torrefaction process are studied. In this work, these materials with particle size in the range of 355–500 μm are torrefied under light torrefaction conditions (200, 220 and 240 °C) and severe torrefaction conditions (260, 280 and 300 °C). TGA is used to monitor the mass loss during torrefaction while tube furnace is used to produce significant amount of products for chemical analyses. In general, the study reveals torrefaction process of palm oil biomass can be divided into two main stages through the observation on the mass loss distribution. The first stage is the dehydration process at the temperature below than 105 °C where the mass loss is in the range of 3–5%. In the second stage, the decomposition reaction takes place at temperature of 200–300 °C. Furthermore, the study reveals that carbon mass fraction and gross calorific value (GCV) increase with the increase of torrefaction temperature but the O/C ratio, hydrogen and oxygen mass fractions decrease for all biomass. Among the biomass, torrefied PKS has the highest carbon mass fraction of 55.6% when torrefied at 300 °C while PMF has the highest GCV of 23.73 MJ kg⁻¹ when torrefied at the same temperature. Both EFB and PMF produce lower mass fraction than PKS when subjected to same torrefaction temperature. In terms of energy yield, PKS produces 86–92% yield when torrefied at light to severe torrefaction conditions, until 280 °C. However, both EFB and PMF only produce 70–78% yield at light torrefaction conditions, until 240 °C. Overall, the mass loss of 45–55% of these biomasses is observed when subjected to torrefaction process. Moreover, SEM images reveal that torrefaction has more severe impact on surface structure of EFB and PMF than that of PKS especially under severe torrefaction conditions. The study concludes that the torrefaction process of these biomass has to be optimized based on the type of the biomass in order to offset the mass loss of these materials through the process and increase the energy value of the solid product.     

Production and characterization of phenolic compounds by flash pyrolysis of palmyra palm

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. This study deals with the characterization of the pyrolysis oil obtained from palmyra palm fruit bunch (Borassus flabellifer) produced by flash pyrolysis in the maximum yield. The pyrolysis oil was analyzed to determine its elemental composition and heating value. The chemical composition of the pyrolysis oil and fractions was investigated using various chromatographic techniques such as Fourier transform infra-red (FTIR) spectroscopy, gas chromatography–mass spectroscopy (GC-MS), and ¹H NMR spectroscopy. The bio-oil product was presented as an environmentally friendly green biofuel candidate. The analytical results showed that the pyrolysis bio-oils were very complex mixtures of organic compounds and contained a lot of nitrogenated and oxygenated compounds such as, phenols, aliphatic hydrocarbons, pyridines, amines, ketones, and so on.     

Utilization possibilities of palm shell as a source of biomass energy in Malaysia by producing bio-oil in pyrolysis process

Agriculture residues such as palm shell are one of the biomass categories that can be utilized for conversion to bio-oil by using pyrolysis process. Palm shells were pyrolyzed in a fluidized-bed reactor at 400, 500, 600, 700 and 800 °C with N₂ as carrier gas at flow rate 1, 2, 3, 4 and 5 L/min. The objective of the present work is to determine the effects of temperature, flow rate of N₂, particle size and reaction time on the optimization of production of renewable bio-oil from palm shell. According to this study the maximum yield of bio-oil (47.3 wt%) can be obtained, working at the medium level for the operation temperature (500 °C) and 2 L/min of N₂ flow rate at 60 min reaction time. Temperature is the most important factor, having a significant positive effect on yield product of bio-oil. The oil was characterized by Fourier Transform infra-red (FT-IR) spectroscopy and gas chromatography/mass spectrometry (GC-MS) techniques.     

Techno-economic performance analysis of bio-oil based Fischer-Tropsch and CHP synthesis platform

The techno-economic potential of the UK poplar wood and imported oil palm empty fruit bunch derived bio-oil integrated gasification and Fischer-Tropsch (BOIG-FT) systems for the generation of transportation fuels and combined heat and power (CHP) was investigated. The bio-oil was represented in terms of main chemical constituents, i.e. acetic acid, acetol and guaiacol. The compositional model of bio-oil was validated based on its performance through a gasification process. Given the availability of large scale gasification and FT technologies and logistic constraints in transporting biomass in large quantities, distributed bio-oil generations using biomass pyrolysis and centralised bio-oil processing in BOIG-FT system are technically more feasible. Heat integration heuristics and composite curve analysis were employed for once-through and full conversion configurations, and for a range of economies of scale, 1 MW, 675 MW and 1350 MW LHV of bio-oil. The economic competitiveness increases with increasing scale. A cost of production of FT liquids of 78.7 Euro/MWh was obtained based on 80.12 Euro/MWh of electricity, 75 Euro/t of bio-oil and 116.3 million Euro/y of annualised capital cost.     

Hydrothermal liquefaction of macroalgae: Influence of zeolites based catalyst on products

Hydrothermal liquefaction (HTL) of Ulva prolifera macroalgae (UP) was carried out in the presence of three zeolites based catalysts (ZSM-5, Y-Zeolite and Mordenite) with the different weight percentage (10–20 wt%) at 260–300 °C for 15–45 min. A comparison between non-catalytic and catalytic behavior of ZSM-5, Y-Zeolite, and Mordenite in the conversion of Ulva prolifera showed that is affected by properties of zeolites. Maximum bio-oil yield for non-catalytic liquefaction was 16.6 wt% at 280 °C for 15 min. The bio-oil yield increased to 29.3 wt% with ZSM-5 catalyst (15.0 wt%) at 280 °C. The chemical components and functional groups present in the bio-oils are identified by GC-MS, FT-IR, ¹H-NMR, and elemental analysis techniques. Higher heating value (HHV) of bio-oil (32.2–34.8 MJ/kg) obtained when catalyst was used compared to the non-catalytic reaction (21.2 MJ/kg). The higher de-oxygenation occurred in the case of ZSM-5 catalytic liquefaction reaction compared to the other catalyst such as Y-zeolite and mordenite. The maximum percentage of the aromatic proton was observed in bio-oil of ZSM-5 (29.7%) catalyzed reaction and minimum (1.4%) was observed in the non-catalyst reaction bio-oil. The use of zeolites catalyst during the liquefaction, the oxygen content in the bio-oil reduced to 17.7%. Aqueous phase analysis exposed that presence of valuables nutrients.     

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.     

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。     

Catalytic pyrolysis of biomass: Effects of pyrolysis temperature,sweeping gas flow rate and MgO catalyst

Cotton seed, as a biomass source, is pyrolysed in a tubular fixed-bed reactor under various sweeping gas (N₂) flow rates at different pyrolysis temperatures. In the non-catalytic work, the maximum bio-oil yield was attained as 48.30% at 550 °C with a sweeping gas flow rate of 200 mL min⁻¹. At the optimum conditions, catalytic pyrolysis of biomass samples was performed with various amounts of MgO catalyst (5, 10, 15, and 20 wt.% of raw material). Catalyst addition decreased the quantity of bio-oil yet increased the quality of bio-oil in terms of calorific value, hydrocarbon distribution and removal of oxygenated groups. It was observed that increasing the amount of catalyst used, decreased the oil yields while increased the gas and char yields. Bio-oils obtained at the optimum conditions were separated into aliphatic, aromatic and polar sub-fractions. After the application of column chromatography, bio-oils were subjected into elemental, FT-IR and ¹H NMR analyses. Aliphatic sub-fractions of bio-oils were analyzed by GC–MS. It was deduced that the fuel obtained via catalytic pyrolysis mainly consisted of lower weight hydrocarbons in the diesel range. Finally, obtained results were compared with petroleum fractions and evaluated as a potential source for liquid fuels.     

Optimum conditions for maximising pyrolysis liquids of oil palm empty fruit bunches

As production of palm oil is expanding, a more efficient use of oil palm biomass to obtain more energy from oil palm plantations is investigated. The work was carried out on a fluidised bed bench scale fast pyrolysis unit, with the objective of determining the important conditions and key variables which are required to maximise the liquid yield and its quality. The investigation on the impact of reactor temperature, varying residence time by changing the nitrogen flow rate and combined impact of ash content and particle size on the product yields is presented. The properties of the liquid product were analysed and compared with wood derived bio-oil and petroleum fuels. It was found that in all cases the liquid product separated into two phases presenting difficulties for fuel applications, which are critically discussed. Potential solutions are also proposed which include upgrading of the liquid for fuel applications and other useful applications.     

Energy self-sufficiency of smallholder oil palm processing in Nigeria

The study evaluated the contribution of various energy sources to the smallholder processing of oil palm in Nigeria. Ten small-scale palm oil processing mills were visited at Elele, River State, Nigeria for sample collection. The weight of the various solid wastes generated and utilized for boiling process were measured including EFB (empty fruit bunch), PPF (palm press fiber), PKS (palm kernel shell) and chaff, while the volume of diesel used for digestion was also measured. The processing of 1 tonne of FFB (fresh fruit bunch) in the mill yields 63.4–77.1 L of CPO while the following waste by-products were generated from the FFB; 24 to 31% EFB, 23 to 28% PPF, 10 to 12% PKS and 1.4 to 2.4% chaff. Out of the total biomass generated by the mills only 12.74–22.25% EFB, 24.43–33.38% PPF, 2.71–6.71% PKS and 15.12–49.04% chaff were utilized by the various mills for fruit boiling/sterilization, indicating that the majority of biomass wastes is unutilized in the mills. The volume of diesel utilized by the mills for digestion is quite low ranging from 0.6 to 0.8 L. The gross calorific values of the waste biomass are EFB 16.970–18.537 MJ/kg, PPF 16.472–21.037 MJ/kg and PKS 19.378–21.614 MJ/kg. The total energy utilized by the mills for processing 1 tonne of FFB ranged from 2179.43 to 3014.31 MJ. Out of these, biomass energy accounted for 98.22–98.75%, while fossil fuel accounted for the remaining 1.25–1.78%. The study concluded by suggesting innovative ways of substituting the <2% fossil fuel contribution with the direct use of pre-heated palm oil to fuel the digesters.     

Impact of a pressurized hot water treatment on the quality of bio-oil produced from aspen

The bio-oil produced by fast pyrolysis is a genuine alternative to fossil resources. However an improvement of its quality is required in order to improve its application.To upgrade the quality of bio-oil, Pressurized Hot Water Treatment (PHWT) has been applied on trembling aspen whole wood chips prior to fast pyrolysis process. The pyrolysis was then performed in an auger reactor at the temperature of 723 K. The effects of PHWT on yields, physicochemical properties, and composition of bio-oils were investigated.Although PHWT does not seem to influence the bio-oil yield, which remains around 56% for both untreated and pre-treated wood, it does improve its quality. The main effect of pre-treatment is the lower water content of the oil obtained from pre-treated wood, which is thus meeting the requirements of ASTM D7544 Standard. Moreover, PHWT appeared to favor the levoglucosan production and to decrease the syringol derivatives content of the bio-oil. The elementary composition revealed an increase of the C/O ratio when the biomass was pre-treated. This is in agreement with the heating value of bio-oil from pre-treated biomass which was found to be higher than that of bio-oil from untreated biomass.     

Upgrading the lubricity of bio-oil via homogeneous catalytic esterification under vacuum distillation conditions

In order to accelerate the application of bio-oil in the internal combustion engines, homogeneous catalytic esterification technology under vacuum distillation conditions was used to upgrade the crude bio-oil. The lubricities of the crude bio-oil (BO) and refined bio-oil with homogeneous catalytic esterification (RBO_hce) or refined bio-oil without catalyst but with distillation operation (RBO_wc) were evaluated by a high frequency reciprocating test rig according to the ASTM D 6079 standard. The basic physiochemical properties and components of the bio-oils were analyzed. The surface morphology, contents and chemical valence of active elements on the worn surfaces were investigated by scanning electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy, respectively. The results show that RBO_hce has better lubricities than those of BO, but RBO_wc has worse lubricities than those of BO. The tribological mechanisms of the bio-oils are attributed to the combined actions of lubricating films and factors that will break the film. Compared with BO, plenty of phenols in RBO_wc results in corrosion of the substrate and destroys the integrity of the lubricating films, which is responsible for its corrosive wear. However, more esters and alkanes in RBO_hce contribute to forming a complete boundary lubricating film on the rubbed surfaces which result in its excellent antifriction and antiwear properties.     

Low energy consumption and high quality bio-fuels production via in-situ fast pyrolysis of reed straw by adding metallic particles in an induction heating reactor

An in-situ fast pyrolysis of biomass by adding metallic particles in an induction heating reactor was proposed to produce high quality bio-fuels. After adding metallic particles into biomass, the times required to reach complete pyrolysis during reed straw pyrolysis process were significantly reduced up to 28.9%. The yields of combustible gas and bio-oil products were significantly increased. Furthermore, higher-quality combustible gas and bio-oil products were obtained with the LHV of gas products and HHV of bio-oil (dry basis) increased by 14.2%–19.1% and 4.16%–16.35%, respectively, under 400–600 °C. The lower oxygen content and higher yields of aromatics, alkenes and alkanes contents in bio-oil were obtained after metallic particles addition. More importantly, up to 26.5% of the total energy consumption during pyrolysis process was reduced after adding metallic particles into biomass in an induction heating reactor. The results indicate that adding metallic particles into biomass in an induction heating reactor can significantly enhance the heat transfer, decomposition reaction intensity and energy utilization efficiency of biomass pyrolysis process with lower energy consumption and higher-quality bio-fuel production.     

Gasification of torrefied oil palm biomass in a fixed-bed reactor: Effects of gasifying agents on product characteristics

Gasification represents an attractive pathway to generate fuel gas (i.e., syngas (H₂ and CO) and hydrocarbons) from oil palm biomass in Malaysia. Torrefaction is introduced here to enhance the oil palm biomass properties prior to gasification. In this work, the effect of torrefaction on the gasification of three oil palm biomass, i.e., empty fruit bunches (EFB), mesocarp fibres (MF), and palm kernel shells (PKS) are evaluated. Two gasifying agents were used, i.e., CO₂ and steam. The syngas lower heating values (LHV_syngas) for CO₂ gasification and steam gasification were in the range of 0.35–1.67 MJ m⁻³ and 1.61–2.22 MJ m⁻³, respectively. Compared with EFB and MF, PKS is more effective for fuel gas production as indicated by the more dominant emission of light hydrocarbons (CH₄, C₂H₄, and C₂H₆) in PKS case. Gasification efficiency was examined using carbon conversion efficiency (CCE) and cold gas efficiency (CGE). CCE ranges between 4% and 55.1% for CO₂ gasification while CGE varies between 4.8% and 46.2% and 27.6% and 62.9% for CO₂ gasification and steam gasification, respectively. Our results showed that higher concentration of gasifying agent promotes higher carbon conversion and that steam gasification provides higher thermal efficiency (CGE) compared to CO₂ gasification.     

Reduction of low grade iron ore pellet using palm kernel shell

Effective use of local iron ore and biomass waste as energy and material resources in iron making is an interesting economic prospect since Malaysia imports iron ore to supply its domestic steel consumption while there is an abundance of biomass waste from the palm oil industry. In this work, a composite pellet made of Malaysian iron ore with palm kernel shell (PKS) waste was subjected to reduction tests using an electric tube furnace to investigate the effect of temperature and PKS content on reduction rate. Several iron ore samples taken from different mining locations were subjected to thermal and X-ray diffraction (XRD) analysis. The rate of iron ore reduction increased with increasing temperature up to 900 °C. XRD analysis revealed that the original iron ore mainly contains iron oxide hydrate and was converted into simple hematite after heating and then become magnetite after reduction. The Fe content in the original ore increased almost 12% when 40 wt% of PKS was used. The iron oxide was successfully reduced to magnetite and small amount of wustite when up to 20 wt% of PKS was present in the mixture. Besides, 20 wt% of PKS in reduction process can reduce CO₂ emissions by almost 18.69 wt% as well as decrease carbon consumption by 19.78 wt%. Thus, the utilization of biomass as a reducing agent for low grade iron ore reduction is an attractive method for upgrading iron ore as well as reducing CO₂ emissions.     

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.     

猪体水热液化工艺参数优化及生物油特性分析

以猪体为原料,以高位热值、C元素回收率、N元素残留率作为生物油质量指标,采用响应面法研究反应温度（220~300 ℃）、反应时间（40~80 min）、固含量（10%~30%）对猪体水热转化生物油产率与质量的影响。研究结果表明：反应条件均会影响水热反应的进行且温度影响最显著,分别在不同反应条件下得到单一指标最优的生物油;生物油的最大产率为76.94%（278 ℃、64 min、29%固含量）,最大HHV值为38.63 MJ/kg（290 ℃、47 min、30%固含量）,最大C元素回收率为93.16%（260 ℃、60 min、10%固含量）,最低N元素残留率为15.52%（220 ℃、40 min、12%固含量）。生物油的元素分析结果表明水热液化可有效降低生物油中N、O元素含量,提高生物油品质。傅里叶变换红外光谱分析与热重分析结果表明,生物油的化学成分复杂且以分子量较大、碳链较长的有机物为主。     

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.