Extraction and hydrolysis of levoglucosan from pyrolysis oil

Fermentable sugar obtained from lignocellulosic material exhibits great potential as a renewable feedstock for the production of bio-ethanol. One potentially viable source of fermentable sugars is pyrolysis oil, commonly called bio-oil. Depending on the type of lignocellulosic material and the operating conditions used for pyrolysis, bio-oil can contain upwards of 10 wt% of 1,6-anhydro-β-d-glucopyranose (levoglucosan, LG), an anhydrosugar that can be hydrolyzed to glucose. This research investigated the extraction of levoglucosan from pyrolysis oil via phase separation, the acid-hydrolysis of the levoglucosan into glucose, and the subsequent fermentation of this hydrolysate into ethanol.Optimal selection of water-to-oil ratio, temperature and contact time yielded an aqueous phase containing a levoglucosan concentration of up to 87 g/L, a yield of 7.8 wt% of the bio-oil. Hydrolysis conditions of 125 °C, 44 min and 0.5 M H₂SO₄ resulted in a maximum glucose yield of 216% (when based on original levoglucosan), inferring other precursors of glucose were present in the aqueous phase. The aqueous phase contained solutes which inhibited fermentation, however, up to 20% hydrolysate solutions were efficiently fermented (yield = 0.46 g EtOH/g glucose; productivity = 0.55 g/L h) using high yeast inoculums (1 g/L in flask) and micro-aerophilic conditions.     

Lignin Pyrolysis Components and Upgrading—Technology Review

Biomass pyrolysis oil has been reported as a potential renewable biofuel precursor. Although several review articles focusing on lignocellulose pyrolysis can be found, the one that particularly focus on lignin pyrolysis is still not available in literature. Lignin is the second most abundant biomass component and the primary renewable aromatic resource in nature. The pyrolysis chemistry and mechanism of lignin are significantly different from pyrolysis of cellulose or entire biomass. Therefore, different from other review articles in the field, this review particularly focuses on the recent developments in lignin pyrolysis chemistry, mechanism, catalysts, and the upgrading of the bio-oil from lignin pyrolysis. Although bio-oil production from pyrolysis of biomass has been proven on commercial scale and is a very promising option for production of renewable chemicals and fuels, there are still several drawbacks that have not been solved. The components of biomass pyrolysis oils are very complicated and related to the properties of bio-oil. In this review article, the details about pyrolysis oil components particularly those from lignin pyrolysis processes will be discussed first. Due to the poor physical and chemical property, the lignin pyrolysis oil has to be upgraded before usage. The most common method of upgrading bio-oil is hydrotreating. Catalysts have been widely used in petroleum industry for pyrolysis bio-oil upgrading. In this review paper, the mechanism of the hydrodeoxygenation reaction between the model compounds and catalysts will be discussed and the effects of the reaction condition will be summarized.     

Characterization of Bio-oil and Bio-char from Pyrolysis of Palm Oil Wastes

The residues from the palm oil industry are the main contributors to biomass waste in Malaysia, and these wastes require extra attention with respect to handling. The biomass waste is a renewable resource that can potentially be used to produce absorbents, fuels, and chemical feedstocks through the pyrolysis process. In this study, the wastes of palm shell, empty fruit bunches, and mesocarp fiber were characterized and then pyrolyzed in a fixed-bed reactor under the following conditions: a temperature of 500 °C, a nitrogen flow rate of 2 L/min and reaction time of 60 min. After pyrolysis, characterization of the products with an emphasis on the bio-oil and the bio-char was performed using various approaches (including Karl Fischer water-content tests, FTIR, SEM, TGA and CNH/O analyses). The results showed that the pyrolysis of palm oil wastes yielded more bio-oil than bio-char or non-condensable gases. The results also indicated that all of the bio-oils were acidic and contained high levels of oxygen. The bio-oils heating values were low and varied from 10.49 MJ/kg to 14.78 MJ/kg. The heating values of the bio-chars (20–30 MJ/kg) were higher than those of the bio-oils. Among the biomasses studied in this work, palm shell contained the highest level of lignin and showed the highest levels of bio-char yield and fixed and elemental carbon in the raw and bio-char form.     

Fast Pyrolysis Behavior of Banagrass as a Function of Temperature and Volatiles Residence Time in a Fluidized Bed Reactor

A reactor was designed and commissioned to study the fast pyrolysis behavior of banagrass as a function of temperature and volatiles residence time. Four temperatures between 400 and 600°C were examined as well as four residence times between ~1.0 and 10 seconds. Pyrolysis product distributions of bio-oil, char and permanent gases were determined at each reaction condition. The elemental composition of the bio-oils and chars was also assessed. The greatest bio-oil yield was recorded when working at 450°C with a volatiles residence time of 1.4 s, ~37 wt% relative to the dry ash free feedstock (excluding pyrolysis water). The amounts of char (organic fraction) and permanent gases under these conditions are ~4 wt% and 8 wt% respectively. The bio-oil yield stated above is for ''dry'' bio-oil after rotary evaporation to remove solvent, which results in volatiles and pyrolysis water being removed from the bio-oil. The material removed during drying accounts for the remainder of the pyrolysis products. The ''dry'' bio-oil produced under these conditions contains ~56 wt% carbon which is ~40 wt% of the carbon present in the feedstock. The oxygen content of the 450°C, 1.4 s ''dry'' bio-oil is ~38 wt%, which accounts for ~33 wt% of the oxygen in the feedstock. At higher temperature or longer residence time less bio-oil and char is recovered and more gas and light volatiles are produced. Increasing the temperature has a more significant effect on product yields and composition than increasing the volatiles residence time. At 600°C and a volatiles residence time of 1.2 seconds the bio-oil yield is ~21 wt% of the daf feedstock, with a carbon content of 64 wt% of the bio-oil. The bio-oil yield from banagrass is significantly lower than from woody biomass or grasses such as switchgrass or miscanthus, but is similar to barley straw. The reason for the low bio-oil yield from banagrass is thought to be related to its high ash content (8.5 wt% dry basis) and high concentration of alkali and alkali earth metals (totaling ~2.8 wt% relative to the dry feedstock) which are catalytic and increase cracking reactions during pyrolysis.     

Engineering ethanologenic Escherichia coli for levoglucosan utilization

Levoglucosan is a major product of biomass pyrolysis. While this pyrolyzed biomass, also known as bio-oil, contains sugars that are an attractive fermentation substrate, commonly-used biocatalysts, such as Escherichia coli, lack the ability to metabolize this anhydrosugar. It has previously been shown that recombinant expression of the levoglucosan kinase enzyme enables use of levoglucosan as carbon and energy source. Here, ethanologenic E. coli KO11 was engineered for levoglucosan utilization by recombinant expression of levoglucosan kinase from Lipomyces starkeyi. Our engineering strategy uses a codon-optimized gene that has been chromosomally integrated within the pyruvate to ethanol (PET) operon and does not require additional antibiotics or inducers. Not only does this engineered strain use levoglucosan as sole carbon source, but it also ferments levoglucosan to ethanol. This work demonstrates that existing biocatalysts can be easily modified for levoglucosan utilization.     

Crop Management Impacts Biofuel Quality: Influence of Switchgrass Harvest Time on Yield, Nitrogen and Ash of Fast Pyrolysis Products

Although upgrading bio-oil from fast pyrolysis of biomass is an attractive pathway for biofuel production, nitrogen (N) and mineral matter carried over from the feedstock to the bio-oil represents a serious contaminant in the process. Reducing the N and ash content of biomass feedstocks would improve process reliability and reduce production costs of pyrolytic biofuels. This study investigated: (1) How does switchgrass harvest date influence the yield, N concentration ([N]), and ash concentration of biomass and fast pyrolysis products? and (2) Is there a predictive relationship between [N] of switchgrass biomass and [N] of fast pyrolysis products? Switchgrass from five harvest dates and varying [N] from central Iowa were pyrolyzed using a free-fall reactor. Harvestable biomass peaked in August (8.6 Mg ha^?1), dropping significantly by November (6.7 Mg ha^?1, P?=?0.0027). Production of bio-oil per unit area mirrored that of harvested biomass at each harvest date; however, bio-oil yield per unit dry biomass increased from 46.6 % to 56.7 % during the season (P?=?0.0018). Allowing switchgrass to senesce lowered biomass [N] dramatically, by as much as 68 % from June to November (P?<?0.0001). Concurrently, bio-oil [N] declined from 0.51 % in June to 0.17 % by November (P?<?0.0001). Significant reductions in ash concentration were also observed in biomass and char. Finally, we show for the first time that the [N] of switchgrass biomass is a strong predictor of the [N] of bio-oil, char, and non-condensable gas with R ² values of 0.89, 0.94, and 0.88, respectively.     

Hybrid thermochemical processing: fermentation of pyrolysis-derived bio-oil

Thermochemical processing of biomass by fast pyrolysis provides a nonenzymatic route for depolymerization of biomass into sugars that can be used for the biological production of fuels and chemicals. Fermentative utilization of this bio-oil faces two formidable challenges. First is the fact that most bio-oil-associated sugars are present in the anhydrous form. Metabolic engineering has enabled utilization of the main anhydrosugar, levoglucosan, in workhorse biocatalysts. The second challenge is the fact that bio-oil is rich in microbial inhibitors. Collection of bio-oil in distinct fractions, detoxification of bio-oil prior to fermentation, and increased robustness of the biocatalyst have all proven effective methods for addressing this inhibition.     

热烟气气氛下生物质在流化床反应器中快速热解制取生物油

在对操作流化速度进行冷态实验以及流化床温度稳定性进行测试的基础上,研制了新型流化床反应器,并使用玉米秸秆为原料,探究了热烟气气氛下快速热解制取生物油的最佳反应温度以及床料。在最佳热解条件下,对糠醛废弃物、木糖废弃物以及海藻进行了实验研究,得到了各产物产率,并对得到的生物油进行了物理特性分析。结果显示,在最佳操作流速下,当温度为500 ℃时使用白云石为床料可以获得最大生物油产率。4种原料中玉米秸秆的生物油产率最高,达到42.3 wt%。在最佳热解条件下获得了4种物料不同含量的重油和轻质油,其中重油的物理特性差别很小,重油的热值比轻质油的热值高很多。不可冷凝气的高位热值是6.5?8.5 MJ/m3,因此不可冷凝气体可以作为一种燃料气被加以利用。     

Subcritical Water Hydrolysis of Microalgal Biomass for Protein and Pyrolytic Bio-oil Recovery

Microalgae are a promising source of protein and biofuels. This study involved the extraction of soluble proteins from raw microalgae using subcritical water hydrolysis followed by pyrolysis of the resulting spent microalgal biomass for bio-oil production. The extraction process produced solubilized protein in amounts up to 10 wt% of the dry biomass. The effects of hydrolysis temperature (150–220 °C), process time (90–180 min), and initial pH (2–12) on the chemical compositions and reactivity of the spent biomass as biofuel intermediates were investigated. It was found that when the temperature and time increased, the protein and carbohydrate fractions of the spent biomass were reduced, while their lipid fraction increased. A low initial pH led to lower protein content in the spent biomass. Compared with the raw microalgae, the spent biomass gave a higher yield of pyrolytic bio-oil that contained much less of the N-containing compounds and higher amounts of long-chain fatty acids (C₁₆) and C₁₄–C₂₀ long-chain hydrocarbons. In addition, enhanced energy recovery and a reduction in the energy consumption of the pyrolysis process were the other benefits acquired from the protein extraction. Therefore, subcritical water hydrolysis was considered to be an effective process to recover solubilized proteins, enhance the properties of the spent biomass, improve the energy balance of the subsequent pyrolysis process, and raise the quality of the bio-oil.     

Production of biorenewable styrene: utilization of biomass-derived sugars and insights into toxicity

Fermentative production of styrene from glucose has been previously demonstrated in Escherichia coli. Here, we demonstrate the production of styrene from the sugars derived from lignocellulosic biomass depolymerized by fast pyrolysis. A previously engineered styrene-producing strain was further engineered for utilization of the anhydrosugar levoglucosan via expression of levoglucosan kinase. The resulting strain produced 240 ± 3 mg L^?1 styrene from pure levoglucosan, similar to the 251 ± 3 mg L^?1 produced from glucose. When provided at a concentration of 5 g L^?1, pyrolytic sugars supported styrene production at titers similar to those from pure sugars, demonstrating the feasibility of producing this important industrial chemical from biomass-derived sugars. However, the toxicity of contaminant compounds in the biomass-derived sugars and styrene itself limit further gains in production. Styrene toxicity is generally believed to be due to membrane damage. Contrary to this prevailing wisdom, our quantitative assessment during challenge with up to 200 mg L^?1 of exogenously provided styrene showed little change in membrane integrity; membrane disruption was observed only during styrene production. Membrane fluidity was also quantified during styrene production, but no changes were observed relative to the non-producing control strain. This observation that styrene production is much more damaging to the membrane integrity than challenge with exogenously supplied styrene provides insight into the mechanism of styrene toxicity and emphasizes the importance of verifying proposed toxicity mechanisms during production instead of relying upon results obtained during exogenous challenge.     

熔盐热裂解生物质制生物油

为探讨热裂解条件对熔盐中生物质热裂解制生物油的影响,在自行设计的反应器中,以摩尔比为7∶6的ZnCl2-KCl混合熔盐作为热裂解的热载体、催化剂和分散剂,考察了500 ℃时添加的金属盐和生物质原料的影响,并采用气相色谱-质谱仪 (GC-MS) 对生物油的主要组成进行了分析。结果表明：添加的金属盐显著影响热裂解产物得率,稀土金属盐显著提高生物油得率,降低生物油的含水率,添加摩尔分数为5.0％ LaCl3时生物油得率为32.0％,含水率为61.5％;水稻秸秆热裂解的生物油和焦炭得率较高,稻壳热裂解的气体得率较高;金属添加盐对生物油组成有较强的选择性,LiCl和FeCl2对生物质向小分子裂解具有较强的催化作用,而CrCl3、CaCl2和LaCl3对生物油二次裂解具有抑制作用。研究结果为熔盐热裂解生物质制生物油提供了参考。     

Destabilization of mayonnaise induced by lipid crystallization upon freezing

The thermal and rheological history of mayonnaise during freezing and its dispersion stability after the freeze-thaw process were investigated. Mayonnaise was cooled to freeze and stored at ?20 to ?40 °C while monitoring the temperature; penetration tests were conducted on the mayonnaise, which was sampled at selected times during isothermal storage at ?20 °C. Significant increases in the temperature and stress values due to water-phase crystallization and subsequent oil-phase crystallization were observed. The water phase crystallized during the cooling step in all the tested mayonnaise samples. The oil phases of the prepared mayonnaise (with rapeseed oil) and commercial mayonnaise crystallized during isothermal storage after 6 and 4 h, respectively, at ?20 °C. The dispersion stability was evaluated from the separation ratio, which was defined as the weight ratio of separated oil after centrifuging to the total amount of oil in the commercial mayonnaise. The separation ratio rapidly increased after 4 h of freezing. This result suggests that crystallization of the oil phase is strongly related to the dispersion stability of mayonnaise.     

Engineering levoglucosan metabolic pathway in <Emphasis Type="Italic">Rhodococcus jostii</Emphasis> RHA1 for lipid production

Oleaginous strains of Rhodococcus including R. jostii RHA1 have attracted considerable attention due to their ability to accumulate triacylglycerols (TAGs), robust growth properties and genetic tractability. In this study, a novel metabolic pathway was introduced into R. jostii by heterogenous expression of the well-characterized gene, lgk encoding levoglucosan kinase from Lipomyces starkeyi YZ-215. This enables the recombinant R. jostii RHA1 to produce TAGs from the anhydrous sugar, levoglucosan, which can be generated efficiently as the major molecule from the pyrolysis of cellulose. The recombinant R. jostii RHA1 could grow on levoglucosan as the sole carbon source, and the consumption rate of levoglucosan was determined. Furthermore, expression of one more copy of lgk increased the enzymatic activity of LGK in the recombinant. However, the growth performance of the recombinant bearing two copies of lgk on levoglucosan was not improved. Although expression of lgk in the recombinants was not repressed by the glucose present in the media, glucose in the sugar mixture still affected consumption of levoglucosan. Under nitrogen limiting conditions, lipid produced from levoglucosan by the recombinant bearing lgk was up to 43.54 % of the cell dry weight, which was comparable to the content of lipid accumulated from glucose. This work demonstrated the technical feasibility of producing lipid from levoglucosan, an anhydrosugar derived from the pyrolysis of lignocellulosic materials, by the genetically modified rhodococci strains.     

Microwave induced pyrolysis of oil palm biomass

The purpose of this paper was to carry out microwave induced pyrolysis of oil palm biomass (shell and fibers) with the help of char as microwave absorber (MA). Rapid heating and yield of microwave pyrolysis products such as bio-oil, char, and gas was found to depend on the ratio of biomass to microwave absorber. Temperature profiles revealed the heating characteristics of the biomass materials which can rapidly heat-up to high temperature within seconds in presence of MA. Some characterization of pyrolysis products was also presented. The advantage of this technique includes substantial reduction in consumption of energy, time and cost in order to produce bio-oil from biomass materials. Large biomass particle size can be used directly in microwave heating, thus saving grinding as well as moisture removal cost. A synergistic effect was found in using MA with oil palm biomass.     

Preparation of levoglucosan by pyrolysis of cellulose and its citric acid fermentation

Levoglucosan (LG), 1,6-anhydro-beta-D-glucopyranose, was produced by pyrolysis of cellulose. A response surface method was used to optimize the reaction parameters: X1, temperature; X2, time required for heating cellulose from room temperature to the designed pyrolysis temperature; and X3, vacuum, and a Box-Behnken design was employed for this purpose. The optimal temperature and time were found to be 388 degrees C and 26.2 min by fixing the vacuum at 1 mm Hg. The levoglucosan prepared was fermented to citric acid by Aspergillus niger CBX-209, which was a mutant derived by gamma-ray mutagenesis of the parent strain CBX-2. The mutant could produce increasing citric acid with increasing LG purity and had a citric acid yield of 87.5% when using purified levoglucosan as the sole carbon source in a 5 day fermentation period.     

Impact of Harvest Time and Cultivar on Conversion of Switchgrass to Bio-oils Via Fast Pyrolysis

The study of the effects of harvest time on switchgrass (Panicum virgatum L.) biomass and bioenergy production reported herein encompasses a large study evaluating the harvest of six switchgrass cultivars grown at three northern US locations over 3 years, harvested at upland peak crop (anthesis), post-frost, and post-winter. Delaying harvest of switchgrass until after frost and until after winter has resulted in decreased yields of switchgrass and reduced amounts of minerals in the biomass. This report examines how changes in biomass composition as a result of varying harvest time and other factors affect the distribution of products formed via fast pyrolysis. A subset (50) of the population (n = 864) was analyzed for fast pyrolysis and catalytic pyrolysis (zeolite catalyst) product yields using a pyrolysis-GC/MS system. The subset was used to build calibrations that were successful in predicting the pyrolysis product yield using near-infrared reflectance spectroscopy (NIRS), and partial least squares predictive models were applied to the entire sample set. The pyrolysis product yield was significantly affected by the field trial location, year of harvest, cultivar, and harvest time. Delaying harvest time of the switchgrass crop led to greater production of deoxygenated aromatics improving the efficiency of the catalytic fast pyrolysis and bio-oil quality. The changes in the pyrolysis product yield were related to biomass compositional changes, and key relationships between cell wall polymers, potassium concentration in the biomass, and pyrolysis products were identified. The findings show that the loss of minerals in the biomass as harvest time is delayed combined with the greater proportion in cellulose and lignin in the biomass has significant positive influences on conversion through fast pyrolysis.     

Preliminary investigation on the production of fuels and bio-char from Chlamydomonas reinhardtii biomass residue after bio-hydrogen production

The aim of this work was to investigate the potential conversion of Chlamydomonas reinhardtii biomass harvested after hydrogen production. The spent algal biomass was converted into nitrogen-rich bio-char, biodiesel and pyrolysis oil (bio-oil). The yield of lipids (algal oil), obtained by solvent extraction, was 15 ± 2% w/w_dry-biomass. This oil was converted into biodiesel with a 8.7 ± 1% w/w_dry-biomass yield. The extraction residue was pyrolysed in a fixed bed reactor at 350 °C obtaining bio-char as the principal fraction (44 ± 1% w/w_dry-biomass) and 28 ± 2% w/w_dry-biomass of bio-oil. Pyrolysis fractions were characterized by elemental analysis, while the chemical composition of bio-oil was fully characterized by GC-MS, using various derivatization techniques. Energy outputs resulting from this approach were distributed in hydrogen (40%), biodiesel (12%) and pyrolysis fractions (48%), whereas bio-char was the largest fraction in terms of mass.     

QTL detection by multi-parent linkage mapping in oil palm (Elaeis guineensis Jacq.)

A quantitative trait locus (QTL) analysis designed for a multi-parent population was carried out and tested in oil palm (Elaeis guineensis Jacq.), which is a diploid cross-fertilising perennial species. A new extension of the MCQTL package was especially designed for crosses between heterozygous parents. The algorithm, which is now available for any allogamous species, was used to perform and compare two types of QTL search for small size families, within-family analysis and across-family analysis, using data from a 2 × 2 complete factorial mating experiment involving four parents from three selected gene pools. A consensus genetic map of the factorial design was produced using 251 microsatellite loci, the locus of the Sh major gene controlling fruit shell presence, and an AFLP marker of that gene. A set of 76 QTLs involved in 24 quantitative phenotypic traits was identified. A comparison of the QTL detection results showed that the across-family analysis proved to be efficient due to the interconnected families, but the family size issue is just partially solved. The identification of QTL markers for small progeny numbers and for marker-assisted selection strategies is discussed.     

High yield bio-oil production from fast pyrolysis by metabolic controlling of Chlorella protothecoides

The use of renewable energy sources is becoming increasingly necessary to mitigate global warming. Recently much research has been focused on identifying suitable biomass species, which can provide high-energy outputs, to replace conventional fossil fuels. This paper reports an approach for increasing the yield of bio-oil production from fast pyrolysis after manipulating the metabolic pathway in microalgae through heterotrophic growth. The yield of bio-oil (57.9%) produced from heterotrophic Chlorella protothecoides cells was 3.4 times higher than from autotrophic cells by fast pyrolysis. The bio-oil was characterized by a much lower oxygen content, with a higher heating value (41 MJ kg(-1)), a lower density (0.92 kg l(-1)), and lower viscosity (0.02 Pas) compared to those of bio-oil from autotrophic cells and wood. These properties are comparable to fossil oil. The research could contribute to the creation of a system to produce energy from microalgae, and also could have great commercial potential for liquid fuel production.     

Separation of phthalate esters from bio-oil derived from rice husk by a basification-acidification process and column chromatography

Solid precipitate containing phthalate esters was obtained from rice-husk-derived oil through a basification-acidification process. After separation by column chromatography, the solid precipitate was divided into two mono-component fractions, two bi-component fractions and a tetra-component fraction. The major compounds of the five fractions were all consisted of phthalate esters. Especially, phthalate esters accounted for a proportion higher than 80% in both Fractions I and II. The generation and precipitation mechanisms of phthalate esters were proposed. Phthalate esters were considered to be derived from a series of complicated chemical reactions of small molecules in the biomass pyrolysis process, and precipitated from bio-oil by catalytic hydrolysis and esterification.