Biomass

Characterization of Bio-oils from Different Pyrolysis Process Stepsand Biomass Using High-Resolution Mass SpectrometryPatrícia V. Abdelnur,*,† Boniek G. Vaz,‡ Jose D. Rocha,† Marlon B. B. de Almeida,§

Marco Antonio G. Teixeira,§ and Rosana C. L. Pereira§

†National Center for Agroenergy Research, Brazilian Enterprise for Agricultural Research (EMBRAPA), Parque Estacao Biologica,PqEB s/n°, Avenida W3 Norte, 70770-901 Brasília, Federal District, Brazil‡Chemistry Institute, Federal University of Goias, Campus Samambaia, 74001-970 Goiania, Goias, Brazil§Cenpes, Petrobras, Avenida Horacio Macedo, 950, Cidade Universitaria, Ilha do Fundao, 21941-915 Rio de Janeiro, Rio de Janeiro,Brazil

*S Supporting Information

ABSTRACT: Next-generation biofuels have been widely investigated because they have particular advantages compared to first-generation biofuels. Pyrolysis is an example of a thermochemical route extensively used in oil and coal industries worldwide toproduce these biofuels. Strategies for low-cost upgrading are among the biggest challenges facing the adoption of bio-oils in thedevelopment of commercial biofuels. Specific biomass sources could be the best option for generating bio-oil with the requiredproperties. For this, it is necessary to understand the composition of these biomasses and their bio-oils. Here, we analyzed bio-oilsamples from the fast pyrolysis of different biomasses collected during two different steps of the process by direct-infusion high-resolution mass spectrometry. First, a comparative study of two common high-resolution mass spectrometers, quadrupole time-of-flight mass spectrometry (Q-TOF MS) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), wasperformed to validate the methodology and to investigate the differences in mass discrimination and resolution. FT-ICR MSshowed the best performance because of its unsurpassed resolution and accuracy. We apply the common petroleomics tools tointerpret the mass spectra obtained. The FT-ICR MS analysis reveals that bio-oils are dominated by Ox species. The class profileof bio-oils was strongly affected by the biomass and steps of the pyrolysis process.

■ INTRODUCTION

Much has been invested worldwide in the generation of arenewable chain of fuels based on biomass derivatives, whichhas been called next-generation biofuels. These have particularadvantages compared to first-generation biofuels; they are non-food materials and could provide a real reduction in greenhousegas emissions. Biomass-based fuels could be generated fromlignocellulosic biomass, such as woody crops, agriculturalresidues, and wastes. Some examples of these advanced biofuelsare algae biodiesel, butanol, cellulosic ethanol, hydrotreatedvegetable oil, biomass to liquid diesel, and biosynthetic gas.1

The main technologies described that produce these biofuelsare based on biochemical and thermochemical routes. Pyrolysisis an example of a thermochemical route extensively used in oiland coal industries worldwide. Its application in biomassconversion is still innovative with pilot- and demonstrative-scaleprojects. Variations in technology and operation conditions canmake changes in the process of pyrolysis. Torrefaction, alsoknown as a mild form of pyrolysis, occurs at temperatures inthe range of 250−300 °C, producing mainly torrefiedbiomasses and low yields of acidic pyrolignous extracts ascondensable liquids.2 Slow pyrolysis, also known as carbon-ization, aims to produce high yields of charcoal yet is able toproduce significant amounts of tar if an appropriatedcondensation system is connected to the furnace. In Brazil,10 million metric tons of charcoal is produced yearly, to beused mainly as a bioreductor in steel and iron alloy production.3

Fast pyrolysis produces higher bio-oil (BO) yields compared toconventional pyrolysis because of the high heating rates, lowresidence times, and small particle sizes of the appliedfeedstock. In this study, samples were collected via a fastpyrolysis pilot plant in a 10−20 kg/h−1 capacity.4

Different biomass sources could be a good option forgenerating BOs with specific properties. BO is the condensableproduct fraction originating from biomass fast pyrolysis,exhibiting some interesting features: it is liquid, presents higherenergy density than the original material, and is easy to pumpand transport over large distances. However, BO has to beupgraded to reach suitable fuel properties. Strategies for low-cost upgrading are among the biggest challenges facing theadoption of pyrolysis BO in the development of commercialbiofuels.A considerable number of studies have been performed

investigating BO properties and chemical compositions toverify their potential as biofuel.5−9 The most commontechnique used to identify BO samples is gas chromatog-raphy−mass spectrometry (GC−MS). However, this techniqueis limited to identifying small-chain and nonpolar compounds,usually requiring one-step derivatization to analyze polarcompounds. Only lightweight compounds in BO can be

Received: May 1, 2013Revised: September 26, 2013Published: September 30, 2013

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© 2013 American Chemical Society 6646 dx.doi.org/10.1021/ef400788v | Energy Fuels 2013, 27, 6646−6654

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analyzed by GC−MS analysis, owing to the low injectortemperature in GC. However, some polar compounds, suchacids and alcohols, can be identified, which is dependent uponthe chromatographic column used in GC separation.10−12 MShas been shown to be a powerful technique for detecting polarcompounds using an electrospray ionization source (ESI−MS).Direct-infusion mass spectrometry (DIMS) analysis has beenwidely used to detect and identify many chemical compoundsin different matrices, such as food,13,14 fuels,15 andbiofuels.16−19 Some advantages of this technique are minimalsample preparation steps, faster analyses, and a wider range ofcompounds detected at the same injection. Smith and Lee20

have analyzed BOs using laser desorption ionization−massspectrometry (LDI−MS) and have detected a complex natureof them compared to non-phenolic compounds. Recently, ESI−MS has been used to detect a wide range of compounds(“phenolics and sugarics”) in BOs produced from red oak,21

pine pellets, and peanut hull22 biomasses.In the present study, BO samples originating from the

pyrolysis of different biomasses were analyzed by DIMS usingquadrupole time-of-flight mass spectrometry (Q-TOF MS).However, a considerable amount of compounds was detected,and the spectrum was quite similar to that generated forpetroleum samples (showing a Gaussian shape of m/z ions),confirming the high complexity of BO samples. Afterward, theBO samples were analyzed through ultrahigh-resolution massspectrometry (UHRMS), using Fourier transform ion cyclotronresonance mass spectrometry (FT-ICR MS),11,12 which hasevaluated precision for petroleomic experiments as measuredby repeatability and reproducibility.23 Petroleomic tools wereused to characterize each sample according to their oxygen andcarbon classes and double-bond equivalents (DBEs).5,11,24

Additionally, samples collected in two different steps of thefast pyrolysis process of each biomass [BO and light bio-oilfraction (LBOF)] were analyzed by DIMS. A differentspectrum profile was obtained for each step of the process,inferring a specific chemical composition for each step.

■ EXPERIMENTAL SECTIONChemical Reagents and Samples. High-performance liquid

chromatography (HPLC)-grade methanol was purchased from Merck

(Rio de Janeiro, Brazil) and used without further purification.Ammonium hydroxide was obtained from Sigma-Aldrich (Rio deJaneiro, Brazil).

BO samples originating from the fast pyrolysis process of differentbiomass samples (eucalyptus, eucalyptus bark, cellulosic mud, waterhyacinth, and pine) were analyzed. Eucalyptus samples were collectedfrom a pulp and paper plant. These samples are representative of theindustrial process and are produced in large amounts in Brazil.Eucalyptus bark was collected from a debarking process beforechipping the trunks. Primary cellulosic mud was collected at the end ofthe pulping process during filtration and purification of pulp. Waterhyacinth was collected under Brazilian Environment Institute(IBAMA) rules from the Paraguay River near Corumba in the stateof Mato Grosso do Sul.25 Pine wood biomass sample was supplied byBTG (Enschede, Netherlands).

General Experimental Procedures. Fast Pyrolysis Technologyand BO Production. The pilot plant shown in Figure 1 is a circulatingfluidized-bed reactor, with a capacity of 10 kg/h, located at theBioware Company (Campinas, Brazil), where the pyrolysis runs werecarried out. Some changes in the feed capacity are expected because ofthe bulk density variation of feedstock. Pretreated biomasses with amoisture content in the range of 10−12 wt % and particle sizes from 2to 4 mm were fed from a silo (3) directly into the free board of thereactor (2), which was preheated and previously loaded with fine sandparticles as a bed in the case of thermal pyrolysis, whereas alternatively,a reactive catalyst bed could have been used. A confined feed screw(3a) located at the bottom of the silo kept a regular preset feeding rate.Air was used as the fluidization agent. A blower (1) supplied the airflow, which passed through a heater (2) and finally fed in the reactor.The process is autothermal, once the air burned about 10% of thebiomass to supply heat for the process. The reaction temperatureranged from 450 to 500 °C. As a result, the biomass was convertedinto biochar, vapor, and gas mixture. Volatile products left the reactor,dragging the finer char particles, which were separated by means oftwo insulated cyclones in series (5). A biochar reservoir (8) retainedthe biochar from the cyclones until it cooled to room temperature.After the cyclones, a two-stage recovering (condensation) system (6)separated pyrolysis liquids into two fractions. The first stage was anindirect cooler with water, and the second stage was a centrifugaldevice (condenser). The gases entered in the first stage at 200−250 °Cand left at 80−90 °C. A stream rich in water and water-solublecompounds LBOF was condensed and collected in a tank (9). Theuncondensed vapors entered in the second stage (centrifugal device),where aerosol drops coalesced and the BO was collected at 40−50 °C.

Figure 1. Biomass fast pyrolysis pilot plant (PPR 10), with 10 kg/h capacity, for (7) BO and (9) LFBO sample reservoir.

Energy & Fuels Article

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Pyrolysis gases exited on the top of centrifugal device and flowed toa combustion chamber to be burned (10). Optionally, the combustiongases could recirculate to the system from a gas distributor plate toserve as a fluidization agent and as a source of heating for the reactorbed (not shown in Figure 1). The plant operated at atmosphericpressure. Operational conditions were monitored and controlled usingsensors distributed throughout the system, which was connected to acomputer for data acquisition (11−15). Further information aboutbiomass fast pyrolysis in Brazil is described elsewhere.26,27

For each biomass processed, two samples were collected in differentsteps of the pyrolysis process, BO and LBOF, and both were analyzedby MS. BO is the oil fraction with a low water content, and LBOF isthe aqueous phase with a high water content and contains water-soluble compounds.27

BO and LBOF samples from eucalyptus, eucalyptus bark, cellulosicmud, and water hyacinth were produced at the Bioware Company(Campinas, Brazil), whereas BO from pine biomass was supplied byBTG (Enschede, Netherlands)28 via Petrobras (Rio de Janeiro, Brazil).MS Analysis. A standard solution (SS) of each BO and LBOF

sample was prepared, dissolving 10 mg of BO in 10 mL of MeOH.Then, consecutive dilutions were performed to determine an idealconcentration for each analyzer because they have differentsensitivities. The best conditions established were 0.1 mg/mL for Q-TOF MS analysis and 0.05 mg/mL for FT-ICR MS analysis, with bothsolutions containing 0.2% ammonium hydroxide in methanol.Q-TOF MS Analysis. ESI−MS analyses were performed in the

negative-ion mode in Q-TOF MS (Waters, Manchester, U.K.), withthe following conditions: capillary voltage, 1.4 kV; gas pressure, 0.3 psi;cone voltage, 35 V; extractor voltage, 4 V; source temperature, 100 °C;and desolvation temperature, 100 °C.Aliquots of 100 μL of SS were transferred to a flask containing 900

μL of methanol with a 0.2% ammonium hydroxide solution. Aftershaking for 30 s using a vortex and 5 min of centrifugation, 100 μL ofthis solution was diluted to 1 mL of the total volume with methanolcontaining a 0.2% ammonium hydroxide solution. This resultingsolution was then directly infused into the mass spectrometer.All of the ESI(−)−Q-TOF MS data were analyzed using the

MassLynx 3.5 software (Waters, Manchester, U.K.). Mass spectra wereaccumulated over 60 s to generate final data ranging from m/z 50 to1000.FT-ICR MS Analysis. Aliquots of 100 μL of SS were transferred to a

flask containing 900 μL of methanol with a 0.2% ammoniumhydroxide solution. After shaking for 30 s using a vortex and 5 min

of centrifugation, 500 μL of this solution was taken and diluted to 1mL of the total volume with methanol containing a 0.2% ammoniumhydroxide solution and injected using a micro-ESI. Solvents andadditives were of HPLC grade, purchased from Sigma-Aldrich, andused as received. General ESI conditions were as follows: capillaryvoltage, 3.10 kV; flow rate, 5 μL min−1; tube lens voltage, −39 V; andcapillary voltage, −100 V.

Ultrahigh-resolution MS was performed with a Thermo Scientific7.2 T ESI−FT-ICR MS LTQ-FT ULTRA (Thermo Scientific,Bremen, Germany). A scan range of m/z 200−1000 was used, and100 microscans were collected in each run. The average resolvingpower (Rp) was 400 000 at m/z 400, where Rp was calculated as m/Δm50%, that is, by the m/z value divided by the peak width at 50% peakheight. Time-domain data (ion cyclotron resonance signal or transientsignal) were acquired for 700 ms. Microscans were co-added usingXcalibur 2.0 software (Thermo Scientific, Bremen, Germany). Themolecular weight distribution for each sample was first verified byLTQ analysis to ensure the validity of the molecular weightdistribution based on FT-ICR MS.

ESI(−)−FT-ICR MS data were analyzed using the Composersoftware (Sierra Analytics, Modesto, CA). In addition to externalcalibration, an internal recalibration was applied to the peak list (usingComposer software) prior to final peak assignment. A set of theoreticalhomologues series for a specific heteroatom class (most abundant classfor each ion mode) was selected as an internal calibrant because oftheir presence in all samples, low errors, and high average peakintensities. Similar tools used for petroleum analysis, such as classdistribution, DBE versus carbon number, and van Krevelen diagrams,were used to process these highly complex spectra.

■ RESULTS AND DISCUSSION

BO Analysis Using Q-TOF MS. Figure 2 shows ESI(−)mass spectra of BO and LBOF of water hyacinth, which werecollected from different steps of the pyrolysis process. Note thatthe mass spectra of these two samples are different, revealingdifferences in their chemical composition because of thechemical fractionation that occurred in the process. The BOsamples were collected at the end of the process and containedmany more compounds, including heavy compounds, such asO-containing compounds (Figure 2a), and the LBOF samples,collected at the beginning of the process, contained more

Figure 2. ESI(−)−MS spectrum using Q-TOF MS of (a) BO and (b) LBOF from the fast pyrolysis process of water hyacinth biomass.



“light” compounds, such as acids and sugar-derivativecompounds (Figure 2b).The highest ion intensity detected in negative mode, m/z

255 (Figure 2a), in the BO sample refers to the saturated fattyacid palmitic acid (C16:0; C16H32O2);

29 however, the highestion intensity detected in the LBOF, m/z 161, was attributed tothe sugar compound levoglucosan (C6H10O5) (Figure 2b).The high abundance of sugar-derivative compounds in the

LBOF samples was also observed for the other biomass samplessubmitted to fast pyrolysis (see Figure 1S of the SupportingInformation). This occurs because the hot product vaporsmeet, as a first step, a quench stream (water + LBOF recycled),which further condensates water and light compounds. Thisfraction contained more “light” compounds, such as acids andpolyhydroxilated compounds, which indicate derivatives of theconversion of sugar structures (Figure 2b).Comparing BO samples from different biomass sources and

processes under different stages of development, it was clearlynoticed that each one has a specific fingerprinting MSspectrum. BO from water hyacinth has more fatty acidcompounds, whereas BO from eucalyptus bark contains atriterpenoid acid (C30H46O3)

30 as the highest ion intensitydetected. BOs from eucalyptus, cellulosic mud, and pinepresented similar chemical composition profiles, with levoglu-cosan having the highest detectable ion intensity.Q-TOF MS versus FT-ICR MS. Because of the high

chemical composition complexity of these samples, we useUHRMS, using ESI−FT-ICR MS, as a tool that has the powerto broadly characterize these samples at a molecular level. Theresults obtained when applying both analytical approaches werecompared: Q-TOF MS (resolution of 5000) and FT-ICR MS(resolution of 400 000).To illustrate the differences in the amount and quality of

information obtained by each analyzer, Figure 3 shows themass-scale-expanded segment at m/z 351 from the massspectrum of eucalyptus BO obtained from Q-TOF MS and FT-

ICR MS. This mass scale-expanded segment in the FT-ICRmass spectrum demonstrates baseline separation of six differentcompounds, whereas only one compound had been observed inthe Q-TOF mass spectrum. Resolution of all of those doubletsrequires a mass resolving power (m/Δm 50% at m/z 351)greater than 17 000 if the two closely spaced ion peaks havesimilar magnitudes. An even higher resolving power is requiredif their abundances are different. Such an ultrahigh resolvingpower is easily achieved by FT-ICR MS or other UHRMSs,such as Orbitrap or ultrahigh-resolution TOF MS.This infers that Q-TOF MS does not have enough resolution

to separate compounds with the same nominal mass. For adetailed and complete chemical composition characterization ofBO and LBOF samples, they should be analyzed usingUHRMS. However, Q-TOF MS could be a good option forpyrolysis process evaluation during development and opti-mization, detecting major compounds in BO and LBOFsamples, with the advantage of being a more robust and cheaperinstrument.Another important and significant difference among the two

mass spectrometers is mass discrimination; some instrumenta-tion and/or experimental conditions have a higher sensitivityfor low mass ions versus high mass ions or vice versa. Hence,the experimental conditions were carefully optimized tominimize mass discrimination for the mass range of interest.Additionally, ion source conditions and ion guide voltages wereoptimized to reduce aggregation and minimize fragmentation.Despite having performed all of these settings, the FT-ICR MSdata showed mass discrimination against very low mass ions,especially those below m/z 140 (see Figure 2S of theSupporting Information). However, the ions detected by FT-ICR MS and Q-TOF MS show similar relative abundance.In the FT-ICR MS, the ion flight time between the

quadrupole and the ICR affects the transmission of high massions versus low mass ions. The ion flight time determines howlong the ICR cell has the gate open for the ion injection, during

Figure 3. (a) ESI(−)−MS spectrum of eucalyptus BO using Q-TOF MS. Mass-to-charge (m/z) ratio from 351.00 to 351.40 using (b) Q-TOF MS(resolution of 5000) and (c) FT-ICR MS (resolution of 400 000).



which trapping of injected ions occurs through the highmagnetic field inside the cell. If sufficient time is not given,some high mass ions might not have arrived at the cell. Incontrast, if the gate is open too long, some low mass ions willbe lost. The effect of the ion flight time on mass discriminationis notorious in FT-ICR, and typically, there is no good way ofefficiently trapping ions in a very wide mass range.31 The massspectra acquisition conditions were set to reach the best way toavoid the mass discrimination.Chemical Characterization of BO by FT-ICR MS. FT-

ICR MS has been shown to be an ideal tool for the deepchemical composition characterization of BO samples,especially for its unparalleled ability to simultaneously resolveand identify thousands of peaks in complex mixtures at the levelof molecular formula assignment.22 To demonstrate the highmass accuracy obtained, tables of assignment molecularformulas for the some Ox class identified in the eucalyptusBO is include in Tables 1S−5S of the Supporting Information.In addition, petroleomic-like tools are necessary to processthese highly complex matrixes. The first data process performedwas the characterization of BO samples according to theiroxygen classes using the Composer software (Figure 4). Each

BO sample has a different profile of oxygen compounds, whichis directly related to the biomass used in the fast pyrolysisprocess. The chemical composition analysis showed severalheteroatom classes consisting of 2−12 oxygens, except for

water hyacinth, with O2 as the most abundant class; the otherBOs have the most abundant class with 4−6 oxygens,accounting for ∼12−20% of the identified peaks, corroboratingwith previous results reported by Jarvis et al.22 and Smith etal.21

To verify the differences between the chemical compositionsof the BO samples, two BO samples from water hyacinth andeucalyptus biomasses were selected and a detailed inspection oftheir composition was performed.The oxygen class distribution was completely different for

each BO analyzed (see Figure 3S of the SupportingInformation). BO from eucalyptus contains more oxygencompounds compared to that from water hyacinth. This couldbe explained considering the thermal chemical conversion ofhemicellulose, cellulose, and lignin as reported by Yang et al.32

The pyrolysis of hemicellulose occurred quickly, with theweight loss of hemicellulose mainly happening at 220−315 °Cand that of cellulose happening at 315−400 °C. However,lignin was more difficult to decompose, because its weight losshappened in a wide temperature range of 160−900 °C and thegenerated solid residue was very high (40 wt %). Because waterhyacinth has a lower lignin content compared to eucalyptus, itis expected that its conversions mainly in H2, CO, CO2, H2O,and some oxygenated compounds are those represented inFigure 3S of the Supporting Information. On the other hand,because eucalyptus has a higher lignin content, its conversionnot is totally complete, with a high amount of oxygenatedcompounds remaining in the final product, mainly lignin-derivative compounds.25

Figure 5 shows water hyacinth and eucalyptus BO negative-ion ESI isoabudance-countoured diagrams of DBE versuscarbon for three Ox heteroatom classes (O4, O6, and O8). Theoxygen classes for both oils span different compositional spaceswith number and DBE. Water hyacinth BO contains more O4

compounds, from C8 to C22, and DBE 5−15. However,eucalyptus BO contains more O6 and O8 compounds, from C6

to C30, and DBE 2−18. In general, the lower oxygenheteroatom classes (O1−O6) have lower DBE values of 1−6,whereas the high oxygen heteroatom classes (O7 or higher)have higher DBE values (>7). This means that, in suchcompounds, an increase in DBE and carbon number is

Figure 4. Oxygen class distribution for each BO analyzed by ESI(−)−MS using FT-ICR MS.

Figure 5. DBE versus carbon number diagrams to (a) water hyacinth BO and (b) eucalyptus BO.



accompanied by a high oxygen content. Jarvis et al.22 reported asimilar trend for pine pellet BO.Chemical Characterization of BO and LBOF Samples.

Another data process was performed to compare samplescollected in two different steps of the fast pyrolysis process (BOand LBOF) using the same biomass. The samples obtainedfrom the same biomass used for FT-ICR MS characterizationwere selected to compare the results.Water hyacinth BO contains a majority of O2−O5

compounds, whereas LBOF samples are concentrated in O2−O8 compounds (Figure 6a). The high oxygen composition in

LBOF indicates the presence of high concentrations ofderivatives of the conversion of sugar structures. This occurs,as was previously explained, because there is a quenching of thetemperature at the first step of the fast pyrolysis process, whichcondenses the water, and furthermore, water-soluble com-pounds, such as sugar-derivative compounds (high oxygencomposition), are extracted at this part of the process, whereLBOF samples are collected. On the other hand, eucalyptus BOand LBOF samples could not be clearly distinguished in theoxygen class composition graph (Figure 6b), which infers thatthe separation process at the pyrolysis process was not efficientfor this biomass under the tested conditions.Further data processing was performed for these samples,

generating carbon distribution graphs for BO and LBOF fromwater hyacinth and eucalyptus biomasses (Figure 7). Of note,water hyacinth BO had more heavy compounds with a highernumber of carbon molecules (Figure 7a). On the other hand,LBOF presented more “light compounds”, containing a lowernumber of carbon molecules in the structure (Figure 7b). Onceagain, it is possible to infer that the separation process was notefficient for the eucalyptus biomass because many compounds,including heavy compounds with high numbers of carbon, weredetected in the LBOF sample collected at the beginning of theprocess. There was no Gaussian shape to the total carbonnumber distribution graph because the abundance distribution

for highly acidic to weakly acidic species in BO is moreasymmetric than that for petroleum and because a few highlyabundant, very acidic species dominate the broadband massspectra.22

With these results, it was possible to conclude that thechemical composition of the samples is dependent upon theprocess conditions on the step of the process that they arecollected and is strongly affected by the biomass used in theprocess.

van Krevelen Diagrams of BO and LBOF Samples. Achemical composition data analysis was performed using thevan Krevelen diagram, a graph where each derivative compoundclass is detected in a specific region of the diagram.The van Krevelen diagram is obtained by plotting the ratios

H/C versus O/C. Each region of the diagram refers to aspecific class of compounds, such as lipid-, lignin-, andcondensed aromatic-derivative compounds,33 which easily andclearly make the major classes of compounds in a sampleobservable. The diagrams were plotted to BO samples fromwater hyacinth (Figure 8a), pine (Figure 8b), eucalyptus(Figure 8c), cellulosic mud (Figure 8d), and eucalyptus bark(Figure 8e). In Figure 8, the blue dots mean compoundsdetected in high relative abundance.Water hyacinth BO samples are concentrated in lipid-

derivative compounds as fatty acids (palmitic acid), whereascellulosic mud BO contains lipid- and lignin-derivativecompounds. Eucalyptus BO contains a lot of lignin-, cellulose-,and hemicellulose-derivative compounds. Levoglucosan(C6H10O5) is the most intense sugar in this sample. Pine BOcontains more cellulose- and hemicellulose-derivative com-pounds. Eucalyptus bark BO has a high concentration oftriterpenoid acid (C30H46O3).Each biomass submitted to the pyrolysis process directly

infers the chemical composition of BO. Some of them containmore sugar-derivative compounds, and others have more lignin-derivative compounds, depending upon biomass processed.BO composition is affected by biomass composition but

could be also impacted by different vapor residence times34 orcatalytic effect of the sand used in the different fluidized beds.In this study, pine and eucalyptus BOs were produced by twodifferent setups. Therefore, the chemical composition of thesesamples could be affected by the biomass and also the pyrolysisprocess.The same approach was used to compare the BO and LBOF

compositions from water hyacinth and eucalyptus. A clearseparation between BO and LBOF from water hyacinth wasnoted, as mentioned before. BO contains more lipid-derivativecompounds, whereas LBOF has lipid-derivative compoundsand also cellulose- and hemicellulose-derivative compounds(Figure 9).Eucalyptus BO and LBOF have lignin-, cellulose-, and

hemicellulose-derivative compounds. However, most cellulose-and hemicellulose-derivative compounds were extracted in theLBOF sample. This infers that the separation method workedfor both BO and LBOF samples; however, because eucalyptusBO presented a high concentration of levoglucosan, theseparation was not clear using oxygen class (Figure 6) andcarbon class distribution (Figure 7) graphs.

■ CONCLUSIONDIMS has been successfully used for analyses of BOcomposition. UHRMS, using FT-ICR MS, has shown to bean essential tool for an unequivocal characterization of BO and

Figure 6. Oxygen class distribution graph of BO and LBOF of (a)water hyacinth and (b) eucalyptus.



Figure 7. Carbon distribution graph of BO and LBOF of (a) water hyacinth and (b) eucalyptus.

Figure 8. van Krevelen diagrams of the BO samples from (a) water hyacinth, (b) pine, (c) eucalyptus, (d) cellulosic mud, and (e) eucalyptus bark.



LBOF samples, because compounds with the same nominalmass were present in the samples. Otherwise, a pre-separationstep should be performed before Q-TOF MS analysis. Inaddition, Q-TOF MS could be a good option for pyrolysisprocess evaluation, because it is a more robust and cheaperinstrument.The chemical composition of BO and LBOF samples is

strongly affected by the biomass type and process conditions.Each biomass submitted to the pyrolysis process directly affectsthe chemical composition of BO. Some of them contain moresugar-derivative compounds, and others have more lignin- and/or lipid-derivative compounds. BO produced through fastpyrolysis of water hyacinth has more lipid-derivative com-pounds; eucalyptus bark has more triterpenoid acid com-pounds; and eucalyptus, pine, and cellulosic mud have morecellulosic- and lignin-derivative compounds. These character-istics seem to be directly related to the biomass compositionand are under investigation.The analysis of the two product samples collected from

different steps of the pyrolysis process, BO and LBOF, revealeddifferent spectrum profiles for each sample. Samples collectedat the first step of condensation, LBOF, contain more sugar-derivative compounds because of the quenching of vapors,which results in water condensation and extraction of water-soluble compounds.

■ ASSOCIATED CONTENT

*S Supporting InformationESI(−)−MS spectrum using Q-TOF of (a) BO and (b) LBOFfrom fast pyrolysis of different biomasses (Figure 1S), typicalmass spectrum of a eucalyptus BO acquired in Q-TOF MS andFT-ICR MS (Figure 2S), oxygen class distribution for (a) waterhyacinth BO and (b) eucalyptus BO (Figure 3S), and estimatedmolecular formulas for the measured m/z values from ESI(−)−FT-ICR MS eucalyptus BO results for O2 compounds (Table

1S), O4 compounds (Table 2S), O6 compounds (Table 3S), O8compounds (Table 4S), and O10 compounds (Table 5S). Thismaterial is available free of charge via the Internet at http://pubs.acs.org.

■ AUTHOR INFORMATIONCorresponding Author*Telephone: +55-61-3448-2340. Fax: +55-61-3448-1589. E-mail: [email protected].

NotesThe authors declare no competing financial interest.

■ ACKNOWLEDGMENTSThe authors thank EMBRAPA and Petrobras for permission topublish this work and for the financial support.

■ REFERENCES(1) Grayson, M.; Fairley, P.; Graham-Rowe, D.; Savage, N.;Sanderson, K.; Martin, J.; Gilbert, N.; Lynd, L. R.; Woods, J.;Robbins, M.; Moraes, M. Nat. Outlook 2011, 474, S1−S43.(2) Felfli, F. F.; Luengo, C. A.; Suarez, J. A.; Beaton, P. A. EnergySustainable Dev. 2005, 9, 19−22.(3) Stamatov, V.; Rocha, J. D. Int. J. Global Energy Issues 2007, 27,217−230.(4) Mesa-Perez, J. M.; Rocha, J. D.; Cortez, L. A. B.; Jordan, R. A.Fast pyrolysis as a BTL precursor. In Sugarcane BioethanolR&D forProductivity and Sustainability, 1st ed.; Cortez, L. A. B., Ed.; EdgarBlucher Ltda.: Sao Paulo, Brazil, 2010.(5) Leonardis, I.; Chiaberge, S.; Fiorani, T.; Spera, S.; Battistel, E.;Bosetti, A.; Cesti, P.; Reale, S.; De Angelis, F. ChemSusChem 2013, 6,160−167.(6) Bayerbach, R.; Nguyen, V. D.; Schurr, U.; Meier, D. J. Anal. Appl.Pyrolysis 2006, 77, 95−101.(7) Bayerbach, R.; Meier, D. J. Anal. Appl. Pyrolysis 2009, 85, 98−107.(8) Oasmaa, A.; Elliott, D. C.; Muller, S. Environ. Prog. SustainableEnergy 2009, 28, 404−409.

Figure 9. van Krevelen diagrams of the BO and LBOF to (a) water hyacinth and (b) eucalyptus.



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