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ARTICLE IN PRESSG ModelAAP-3446; No. of Pages 10

Journal of Analytical and Applied Pyrolysis xxx (2015) xxx–xxx

Contents lists available at ScienceDirect

Journal of Analytical and Applied Pyrolysis

journa l h om epage: www.elsev ier .com/ locate / jaap

low pyrolysis of different Brazilian waste biomasses as sources of soilonditioners and energy, and for environmental protection

arta Eliane Doumer a, Gregorio Guadalupe Carbajal Arízaga b, Dimas Agostinho da Silva c,arlos I. Yamamoto d, Etelvino Henrique Novotny e, Jandyson Machado Santos f,uana Oliveira dos Santos f, Alberto Wisniewski Jr. f, Jailson Bittencourt de Andrade g,ntonio Salvio Mangrich a,f,g,∗

Department of Chemistry, Federal University of Paraná – UFPR, 81531-990 Curitiba, PR, BrazilDepartment of Chemistry, University of Guadalajara, Marcelino García Barragán 1421, CP 44430 Guadalajara, Jalisco, MexicoDepartment of Forestry Engineering and Technology, Federal University of Paraná – UFPR, 80210-170 Curitiba, PR, BrazilDepartment of Chemical Engineering, Automotive Fuel Analysis Laboratory (LACAUT), Federal University of Paraná – UFPR, 81530-990 Curitiba, PR, BrazilEmbrapa Soils, Rua Jardim Botânico 1024, 22460-000 Rio de Janeiro, RJ, BrazilDepartment of Chemistry, Federal University of Sergipe – UFS, 49100-000 São Cristóvão, SE, BrazilNational Institute of Science and Technology: Energy & Environment, 40170-290 Salvador, BA, Brazil

r t i c l e i n f o

rticle history:eceived 10 November 2014eceived in revised form 9 March 2015ccepted 12 March 2015vailable online xxx

eywords:low pyrolysishemical compositionaste biomass

unctional groupsiochario-oil

a b s t r a c t

This paper explores the viability of producing energy and agricultural soil conditioners with biocharsand bio-oils from the pyrolysis of biomasses that in some cases are potential environmental pollutants.This approach addresses the need to develop sustainable production systems that minimize pollutionand soil degradation, and meet the demand for renewable fuels. Large volumes of biomass from differentsources are available in Brazil, including Eucalyptus crop residues (CE), castor meal (CM), coconut pericarp(CP), sugarcane bagasse (SB), and water hyacinth (WH). CM char and SB bio-oil are good prospects forenergy generation. Characterization using DRIFT, 13C NMR, and van Krevelen diagrams indicated that aftercarbonization, aromatic structures were predominant in the biochars produced from the CP, CE, and SBbiomasses, while aliphatic groups were abundant in the biochars from CM and WH. Analysis using EPRshowed that unpaired electrons were preferentially located on carbon atoms in the case of the CP, CE,and SB biochars, with EPR g values around 2.0030, while the CM and WH biochars presented g valuesaround 2.0035, indicating that the unpaired electrons were closer to oxygen atoms. In terms of bio-oil
chemical composition, the most abundant compounds were 3-pyridinol and furans (WH), phenols (CP),and hexadecanoic, octadecanoic, 9,12-octadecenoic (z,z), 3-docosenoic, and 5-docosenoic acids (presentonly in the CM bio-oil). The bio-oils from SB and CE were quite similar and the main compound was 1,2,6-hexanetriol. The biomass sources studied produced reasonable amounts of bio-oil, and could compete assuitable raw materials for biofuel production.
© 2015 Elsevier B.V. All rights reserved.

. Introduction

Biomass can be converted into fuel and chemical feedstocky thermochemical pyrolysis routes (gasification, liquefaction and

Please cite this article in press as: M.E. Doumer, et al., Slow pyrolysis of

and energy, and for environmental protection, J. Anal. Appl. Pyrol. (20

olid charring) [1]. Pyrolysis is usually divided into three modes:ast, intermediate, and slow. The mode and the conditions of pyrol-sis can influence the relative proportions of the gas, liquid, and

∗ Corresponding author at: Department of Chemistry, Federal University of Paraná UFPR, 81531-990, Curitiba, PR, Brazil. Tel.: +55 4133613182; fax: +55 4133613006.

E-mail address: [email protected] (A.S. Mangrich).

ttp://dx.doi.org/10.1016/j.jaap.2015.03.006165-2370/© 2015 Elsevier B.V. All rights reserved.

solid products obtained. Slow pyrolysis uses a low heating rate,with a long vapor residence time, and is used to maximize theyield of solid products (biochar) [2]. The liquid fraction (bio-oil)contains organic compounds such as alkanes, aromatic hydrocar-bons, phenol derivatives, and small amounts of ketones, esters,ethers, sugars, amines, and alcohols [3]. These liquid products,obtained under optimum conditions, can be utilized as syntheticfuels or raw materials in the chemical industry. The calorificenergy content of bio-oil is close to that of petroleum [1,4,5].

different Brazilian waste biomasses as sources of soil conditioners15), http://dx.doi.org/10.1016/j.jaap.2015.03.006

The solid fraction, a charcoal-like product called biochar, is car-bon rich (65–90%), with oxygen-containing functional groups onthe surface and aromatic structures [6] that provide resistance

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Fig. 1. Raw biomass, biochars, and pyrolysis setup used. (a) Biomass (left) and resulting biochar (right) of the materials: water hyacinth (WH), sugarcane bagasse (SB),c silicats sed.

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astor meal (CM), coconut pericarp (CP), and Eucalyptus crop residues (CE); (b) borochematic diagram of the reactor arrangement; (e) photograph of the equipment u

o biological degradation [7]. Biochar has shown potential as aatural fertilizer [8–14] and as a solid biofuel [8,15]. The indige-ous Amazonian peoples prepared biochar by pyrolyzing (charring)lant debris, producing the substance known as Terra Preta de

ndios. Biochar contains both refractory and labile portions [13], andan be produced from various waste biomass sources, includingoody biomasses [2,6,16–18], municipal waste [19], and agri-

ultural residues [1,9,10,12–15]. According to the Internationaliochar Initiative (IBI), it is estimated that by the year 2050 about0% of all crop and forestry residues may be converted to biocharor use as soil conditioners and for energy production [11]. Cur-ently, lignocellulosic wastes are not fully utilized in Brazil, withome being burned and reduced to ash and CO2, increasing green-ouse gas (GHG) emissions, without energy recovery [20]. In thisontext, value can be added to biomass by using it for energyroduction, as an excellent alternative to fossil fuels [21], as wells to produce soil conditioners [13], taking advantage of the facthat waste biomass is low-cost, renewable, and available in largeuantities.

Several studies have demonstrated that the quality and chemicalomposition of biochar depend on the feedstock and the produc-ion conditions [13,16,17,22]. However, few detailed studies haveeen carried out in Brazil using biomass wastes such as those con-idered here. In this work, we studied biomass derived from wateryacinth (WH), an aquatic plant widely utilized to clean wastewa-



er in ponds, which if not frequently removed can cover the entireater surface and hinder the process. This biomass is abundant

n Brazil, it is estimated that the annual WH generation from the

e reactor loaded with biochar; (c) reactor inside the electrically heated furnace; (d)

Brazilian Paraguay river floodplain reach about 0.8 to 2.4 × 107 t ofdry biomass [23]. Another biomass is Eucalyptus crop residue (CE)from planted forests, which if left in the environment can contami-nate the soil surface and fresh waters, due to its action as a reducingagent [24]. Currently planted area of Eucalyptus forests is 5.4 millionhectares, in Brazil [25]. Sugarcane bagasse (SB) from the sugar andalcohol industries is also abundant in Brazil and is used to producethermal electricity. In Brazil, 700 million tons of sugarcane wereproduced in 2014 [26]. Castor meal (CM), which is available fromthe Brazilian biodiesel industry [27], is known to be highly toxicto animals. In 2014, Brazilian production of castor berries was of37.900 t [26]. Green coconut pericarp (CP), from coconut process-ing industries and the consumption of coconut water [28], whichis very common on Brazilian beaches, can pose a substantial riskto public health. Coconut pericarp halves are concave and retainrainwater, enabling the development of Aedes aegypti, the mosquitothat transmits dengue fever, chikungunya, and yellow fever, amongother viruses, mainly in countries with tropical climates [29,30]such as Brazil, where around two billion of the fruit are producedevery year [26].

For the reasons described above, it was decided to study slowpyrolysis processes, using the biomasses CE, CM, CP, SB, andWH to produce biochar, bio-oil, and syngas. The solid productsobtained were characterized using physicochemical and spectro-scopic methods in order to determine their suitability for use


as biofuels or soil conditioners. The composition of the bio-oilwas investigated using gas chromatography/mass spectrome-try (GC/MS) in order to relate the chemical structures to the

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al and Applied Pyrolysis xxx (2015) xxx–xxx 3

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Table 1Higher heating values (HHV, MJ kg−1) of the biomass, biochar, and oil samples (asreceived).

Material HHV (MJ/kg)

BiomassCE 18.85 ± 0.14CM 21.25 ± 0.04CP 23.46 ± 0.07SB 17.27 ± 0.49WH 14.36 ± 0.21

BiocharCE 25.32 ± 0.17CM 22.74 ± 0.84CP 25.97 ± 0.58SB 24.35 ± 0.45WH 17.24 ± 0.13

Bio-oilCE 27.49 ± 0.03CM 27.69 ± 0.17CP 30.23 ± 0.03

ARTICLEAAP-3446; No. of Pages 10

M.E. Doumer et al. / Journal of Analytic

haracteristics of the products and their potential for use as biofuelsr feedstocks for the chemical industry.

. Materials and experimental procedures

.1. Biomass and pyrolysis

The biomass sources were water hyacinth (WH), sugarcaneagasse (SB), castor meal (CM), coconut pericarp (CP), and Euca-

yptus crop residues (CE). The sugarcane bagasse was provided byhe sugar and alcohol company Melhoramentos S.A. (Brazil). Theastor bean (Ricinus communis L.) residues from the biodiesel indus-ry were collected in the form of castor meal and the mesh sizeas 2 mm. The triturated coconut pericarp was from trees (Cocosucifera) grown in Bahia State (Brazil). The Eucalyptus crop residue

rom the species Eucalyptus grandis and Eucalyptus saligna was pro-ided by Granfor (Brazil) and was ground to a mesh size of 5 mmsing a hammer mill. The water hyacinth (Eichhornia crassipes) wasbtained from wastewater stabilization ponds in the municipalityf São Cristovão (Sergipe State, Brazil) and received in mesh size.85 mm. All the biomass samples were air-dried before pyrolysis.

The pyrolysis reactions were conducted in a laboratory-scaleeactor, with heating from room temperature up to 350 ◦C at a ratef 5 ◦C min−1, giving a maximum time of 70 min in the reactor. Theyrolysis experiments were performed using a 2 L internal volumeorosilicate reactor (internal diameter 15 cm, height 34 cm) loadedith the biomass (300 g of SB, 300 g of WH, 550 g of CM, 350 g of CE,

r 300 g of CP). The reactor was externally heated by an electric fur-ace equipped with temperature control. A diagram of the system

s shown in Fig. 1. The pyrolysis vapors were transferred through aater condenser at 20 ◦C to separate the condensable (bio-oil) and

on-condensable gases.After each test, biochar and bio-oil were collected from the

eactor and the condenser system, respectively, to measure theass yield and remove aliquots for detailed analyses. The pyrolysis

xperiments were repeated at least three times. The mass yield ofases was calculated by difference. The bio-oil was separated intorganic and aqueous fractions using aqueous NaHCO3 solution (5%,/v), with a 1:2 (v/v) ratio of bio-oil to sodium bicarbonate solu-

ion, and the organic fraction was stored in stoppered glass flasksor subsequent analysis.

.2. Characterization of biomass, biochar, and bio-oil samples

Characterization of the biomass, biochar, and bio-oil samplesas performed using a range of analytical and physicochemi-

al methods. Measurement of the calorific values of the samplesollowed ASTM Method D240-50 and employed an IKA Model

7000 calorimeter. In the case of the bio-oil, only the organicraction was measured. The proximate analysis of the biomassnd biochar samples was conducted according to the ASTMtandard procedures for ash (ASTM D 1762-84), volatile matterASTM D 1762-84), and fixed carbon (FC) (by difference). Bio-oilolutions (100 mg mL−1) in tetrahydrofuran (THF) were deriva-ized using N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) in

ratio of 1:1, and then analyzed by GC/MS using a Shimadzuodel QP5050A instrument. An RTX-5SilMS capillary column was

sed (5% diphenyl, 95% dimethylpolysiloxane; 30 m × 0.25 mm ID,.25 �m), and 1 �L aliquots of sample were injected in splitlessode. Helium (99.999%) was used as the carrier gas, at a flow rate of

.2 mL min−1. The column temperature program was 50 ◦C (5 min),



ollowed by a ramp at 10 ◦C min−1 to 310 ◦C (14 min). The injectornd transfer line temperatures were 300 ◦C. The mass spectrome-er was operated at 70 eV in electron impact (EI) mode. The masspectrometer was operated in scan mode in the range 40–550 Da.

SB 22.66 ± 0.15WH 29.52 ± 1.24

Mid-infrared spectra of the solid samples were acquired with aFourier transform infrared spectroscopy (DRIFT) instrument (Excal-ibur FTS 3500 52 GX, Bio-Rad).

Electron paramagnetic resonance (EPR) analysis of the biocharsamples was conducted at room temperature (∼300 K), using aBruker EMX spectrometer operated in the X-band (∼9.5 GHz)with modulation frequency of 100 kHz. For the full EPR spectra(�B = 5000 G), the operational conditions were a sweep field of5000 G, center field of 3300 G, microwave power of 20 mW, andmodulation amplitude of 5 G. The organic free radicals (OFR) wereanalyzed using the g-factor region close to 2.0, with the OFR sig-nal near the center of the sweep field of 50 G, microwave powerof 0.2 mW, and modulation amplitude of 1 G. The EPR data weretreated with the aid of Win-EPR® software, and a “weak pitch”reference material (g = 2.0028) was supplied by Bruker. The OFRwere quantified using the approximation: intensity x �B2. The res-onance parameters were obtained by mathematical treatment withthe Win-EPR® software, and the electron spin concentration wasdetermined by comparison with that of the reference material.

Solid-state 13C NMR analyses were performed at a resonancefrequency of 100.6 MHz, using a Varian Inova 400 spectrometer(Varian, Palo Alto, CA, USA). Thermogravimetric (TG) and differ-ential thermal gravimetric (DTG) analyses were performed with20 mg of sample, using a Mettler-Toledo TG/SDTA 851e thermo-analyzer, under an air atmosphere, at a heating rate of 20 ◦C min−1

in the range 25–1000 ◦C. The moisture contents were calculatedfrom the loss of weight at 105 ◦C.

3. Results and discussion

3.1. Pyrolysis yields

The average pyrolysis yields of biochar, bio-oil, and non-condensable gases are presented in Fig. 2. As a first observation,the maximum production of solid, liquid, or gaseous products wasidentified in terms of the type of biomass that provided the high-est yield. In the case of solid biochar, CM provided the highestyield (74.09%), while generating the smallest amounts of liquid andgaseous products. The highest yield of liquid products (sum of theoil and water fractions) was achieved with SB (40.97%), and the


maximum production of bio-gas (20.48%) was obtained with CP.The bio-oil derived from Eucalyptus (CE) showed a higher yield

in the aqueous fraction, which represented 78.54% of the total liq-uid product of pyrolysis. The highest organic fraction percentage

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Table 2Chemical analysis of the biomasses and biochars in terms of the amounts (wt.%, drybasis) of fixed carbon, ash, and volatile matter.

Material Fixed carbon Ash Volatile matter Moisturewt.% wt.% wt.% wt.%

BiomassCE 18.61 ± 1.14 2.05 ± 0.42 79.20 ± 1.35 4.0CM 20.91 ± 0.18 8.57 ± 0.42 70.52 ± 0.58 3.0CP 28.57 ± 0.42 2.43 ± 0.09 68.99 ± 0.46 4.6SB 12.97 ± 0.58 4.00 ± 0.18 83.03 ± 0.67 6.3WH 17.43 ± 0.27 17.40 ± 0.18 65.15 ± 0.36 8.0

BiocharCE 58.26 ± 0.90 4.37 ± 0.18 37.36 ± 0.71 –CM 27.13 ± 1.08 10.35 ± 0.20 62.52 ± 0.88 –CP 64.39 ± 0.09 5.22 ± 0.18 30.39 ± 0.11 –

involatile [13]. The high N content of biochar could be an advan-tage, because it could be used to provide nutrients to the soil andincrease crop yields [35].

Table 3Elemental contents (%C, %H, %N, and %O) of the biomasses and their respectivebiochars.

Element CE CM CP SB WH

(%) BiomassC 46.82 ± 0.91 46.79 ± 0.17 47.59 ± 0.41 45.52 ± 0.22 33.59 ± 0.37H 6.33 ± 0.04 7.19 ± 0.04 5.82 ± 0.09 6.26 ± 0.01 5.81 ± 0.09N 0.16 ± 0.03 8.52 ± 0.04 0.78 ± 0.02 0.24 ± 0.03 2.11 ± 0.01Oa 44.65 ± 0.49 28.92 ± 0.49 43.38 ± 0.38 43.83 ± 0.38 41.07 ± 0.98

BiocharC 68.15 ± 0.92 54.42 ± 0.73 63.99 ± 1.98 65.02 ± 0.93 45.53 ± 1.19

Fig. 2. Mass yields of pyrolysis products from CE, CM, CP, SB, and WH.

37.69%) in the liquid product was obtained for SB. In previous work, similar yield of 32.34% of bio-oil was obtained from giant Mis-anthus at 400 ◦C [31], while Wright et al. [32] reported that thequeous phase of the bio-oil can account for more than 70%, with0% being suitable for use as a biofuel. The biomass sources stud-

ed here therefore produced comparable and satisfactory amountsf bio-oil, and could compete as suitable raw materials for biofuelroduction or for use as chemical industry feedstocks.

.2. Higher heating value

The higher heating values (HHV) of the samples of biomass,iochar, and bio-oil are given in Table 1.

For the biomasses, the highest HHV value (23.46 MJ kg−1) wasbtained for CP, and the lowest value (14.36 MJ kg−1) was foundor WH. The HHV values for biochar and bio-oil (organic fraction)

ere higher than for the corresponding biomasses. The higher HHVf biochar was due to the formation of fixed carbon, and substan-ial increments were observed for SB (from 17.27 to 24.35 MJ kg−1)nd CE (from 18.85 to 25.32 MJ kg−1), reflecting improvement inhe quality of these materials for use as fuel. The highest HHVere obtained for CP, with values of 25.97 and 30.23 MJ kg−1 for

iochar and bio-oil, respectively. The HHV values for CP bio-oil30.23 MJ kg−1) and SB bio-oil (22.66 MJ kg−1) were in agreementith those reported by Mantilla et al. [21] for empty palm fruit

34.91 MJ kg−1) and sugarcane bagasse (25.22 MJ kg−1).According to Bridgwater [33], the mean calorific value of bio-oil

s close to 17 MJ kg−1, which is equivalent to 40% of the calorificalue of fuel oil (43 MJ kg−1). Therefore, the bio-oils obtained fromhe five biomass sources in this study are good candidates for use asuel sources, because the measured calorific values reached around0% of that of fuel oil.

.3. Proximate and ultimate analyses

The results of the chemical analyses of the biomasses andiochars are given in Table 2.

Chemical analysis of the biomass samples showed that the con-ents of volatile materials ranged from 65.15 to 83.03%, with theowest and highest values for WH and SB, respectively. The lowolatiles content of WH was possibly due to the high percentage of



sh (17.40%). The ash contents of the remaining biomasses rangedrom 2.05% (CE) to 8.57% (CM).

The lowest and highest fixed carbon contents of the biomassamples were found for SB and CP, respectively, in agreement with

SB 50.44 ± 0.16 5.50 ± 0.13 44.05 ± 0.30 –WH 31.58 ± 0.26 30.54 ± 0.48 37.87 ± 0.41 –

the HHV results since a higher content of fixed carbon in the fuelshould be reflected in a higher calorific value.

Compared to the raw materials, the biochars showed increasedcontents of volatile matter and fixed carbon. The levels of volatilematter in the samples of biochar were indicative of incomplete car-bonization and suggested that volatile compounds were formedduring the thermal degradation process. The ash contents of thebiochars were also higher than found for the biomasses, as expecteddue to the mineral material remaining after carbonization. Thesefindings are in agreement with the results obtained by Özc imenand Ersoy-Meric boyu [1], who studied waste biomass from the foodprocessing industry.

Table 3 presents the elemental analyses of the biomasses. Thelowest and highest contents of C were found for WH (33.59%) andCP (47.59%), respectively. The C contents in SB, CE, and CM weresimilar to the value obtained for CP. In terms of H and N, the high-est contents were found for CM and CE. After pyrolysis, the highestC contents of the biochars were found for CE, SB, and CP (between63 and 68%). The highest percentages of H and N were obtained forCM. Carbonization caused the C contents of the biochars to increase,relative to the values for the biomasses, while the percentages ofO and H decreased. According to Al-Wabel et al. [34], the loss ofhydrogen can be attributed to the effect of temperature in breakingthe weakest bonds in the biomass structure, producing materialsthat are more carbonaceous. The same authors found enrichment inN content, compared to the original raw material, after carboniza-tion of coconut pericarp, and a similar effect was observed in thisstudy, with the exception of CM. This can be explained by the incor-poration of N into complex structures that are heat-resistant and


H 4.09 ± 0.06 6.05 ± 0.06 4.00 ± 0.11 4.19 ± 0.08 3.53 ± 0.04N 0.50 ± 0.03 7.01 ± 0.38 0.97 ± 0.03 0.55 ± 0.01 3.93 ± 0.03Oa 22.85 ± 0.71 22.14 ± 1.10 25.47 ± 1.55 24.72 ± 0.88 16.44 ± 1.25

a Calculated by difference.

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Table 4Relative composition of bio-oil by GC/MS.

Chemical compound Molecular formula Relative area (%)

WH CP CM SB CE

1-Methylbutoxy TMS C8H20SiO 4.17 – – 0.24 0.233-Methylbutanoic acid TMS C8H18O2Si 0.55 – 0.11 – –Pentanoic acid TMS C8H18O2Si – 0.64 0.13 – –5-Methyl-furfural C6H6O2 – 0.58 – – –2-Methyl-butanol TMS C8H20OSi 1.72 1.00 – 3.14 2.131,2-Ethanediol TMS C8H22O2Si2 4.24 1.65 0.55 1.37 1.78Furan-2-ol TMS C7H12O2Si 3.97 0.35 0.77 0.14 0.373,6-Dioxy-2,7-disilaoctane TMS/2,2,4,7,7-pentamethyl TMS C9H24O2Si2 0.70 0.32 – 0.32 0.452-Pyridinol TMS C8H13NOSi – – 0.28 – –Hexanoic acid TMS C9H20O2Si 0.29 – 0.40 – –Phenol TMS C9H14SiO 3.93 27.00 2.32 1.11 0.462-Hydroxy-propanoic acid TMS C9H22Si2O3 1.81 2.09 – 1.04 0.772-Hydroxy-acetic acid TMS C8H20Si2O3 0.74 4.76 – 4.36 3.56Inosose, 2-desoxy-, o-methyloxime, tetrakis-o- TMS C19H45NO5 – – – 0.27 0.73Methyl-hexanoic acid TMS C10H22O2Si – – 0.23 – –2-Hydroxy-butanoic acid TMS C10H24O3Si 0.30 0.14 – 0.48 0.233-Pyridinol TMS C8H13NOSi 13.07 1.12 2.91 – –2-Methyl phenol TMS (Guaiacol) C10H16OSi – 0.34 – – –3-Methylcyclopent-1-en-1-ol TMS C9H18OSi – – – 2.07 1.954-Pyridinol TMS C8H13NOSi 1.36 – – – –2-Pyrrolidinone TMS C7H15NOSi – – 0.64 – –Tetrahydro-3-furanmethanol TMS C8H18SiO2 3.70 2.19 – 1.37 3.084-Methylphenyl ether TMS C10H16OSi – 1.42 1.43 0.44 –3-Methyl-3-hydroxy-butanoic acid TMS C10H24O3Si 0.53 – – 0.14 –Heptanoic acid TMS C10H22O2Si – 0.18 0.27 0.22 0.193-Methylphenyl ether TMS C9H14OSi – – 0.18 – –d-Xylo-hexonic acid,3-deoxy; g-lactone TMS5-(1,2-dihydroxyethyl)-4-hydroxydihydrofuran-2(3H)-one C15H34O5Si3 0.97 – – 0.26 0.143-Hydroxy-6-methylpyridine1 TMS C9H15NOSi – 0.19 0.25 – –2,4-Hexadienoic acid TMS C12H22SiO2 1.62 0.86 – 2.11 2.57Acetic acid, bis[(trimethylsilyl) oxyl] ester TMS C11H28O4Si – – – 0.39 0.472-Methoxyphenol TMS (Guaiacol) C10H16O2Si 0.94 2.20 1.17 1.16 1.674-Hydroxy-butanoic acid TMS C10H24O3Si2 1.81 0.84 – 0.41 0.73Benzoic acid ester TMS C10H14O2Si 0.46 0.55 – 0.18 –3,7-Dioxa-2,8-disilanonane, 2,2,8,8-tetramethyl-5-(TMS) oxy] C12H32O3Si3 5.95 1.05 1.33 0.67 0.611,2-Benzenediol bis(TMS) ether (Catechols) C12H22O2Si2 5.93 17.3 5.34 4.74 5.843-Methyl-4-hydroxybutyrate 2 TMS C11H26O3Si 0.52 0.34 – 0.25 0.47Cyclohexene, 3-(3-methyl)-hexyl TMS C16H32OSi 3.42 3.22 1.13 2.10 7.60Pentanedioic acid, ester bis TMS C11H24O4Si – – – 0.27 0.21Butanoic acid, 2,4-bis[(trimethylsilyl) oxy]- ester TMS C13H32Si3O4 0.48 0.75 – 0.57 0.553-Methyl-2-nitro-benzeneethanol TMS C11H17NO3Si – – 0.26 0.51 2.551,2,6-Hexanetriol TMS C15H38O3Si3 4.76 6.27 0.22 12.10 14.702-Ethyl-1,3- propane TMS C11H28O2Si2 1.60 1.04 2.56 0.96Undecenoic acid TMS C14H28O2Si – – 4.78 – –3-Hydroxybenzoic acid TMS C13H22O3Si2 – 1.64 – – –Levoglucosan TMS C15H34O5Si3 6.20 0.44 0.13 5.57 2.95Hexadecanoic acid, ester TMS C19H40O2Si – – 4.24 – –9,12-Octadecadienoic acid (Z,Z) ester TMS C21H40O2Si – – 2.13 – –9,12-Octadecadienoic acid (Z,Z) ester TMS C21H42O2Si – – 6.71 – –9-Octadecenoic acid TMS C21H42O2Si – – 7.21 – –

Si

Si

Si

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Octadecanoic acid TMS C21H44O2

3-Docosenoic acid ester TMS C25H50O2

5-Docosenoic acid ester TMS C25H50O2

Van Krevelen diagrams illustrating the differences in the ele-ental compositions of the biomasses and biochars are shown in

ig. 3 (a) and (b), respectively. After pyrolysis, the contents of Hnd O decrease, because the biochar becomes carbon-rich [31], asbserved in this study. The decrease in the O/C molar ratio duringarbonization is associated with dehydration reactions and resultsn a less hydrophilic surface of biochar [31], while the decrease inhe H/C molar ratio is indicative of the formation of aromatic com-ounds [34]. The highest N/C and O/C molar ratios were observed

or the CM biochar, indicating a substantial presence of nitrogen andxygen functions. The CM biochar also presented the highest H/Colar ratio, indicating that the material was aliphatic [36]. There-



ore, the CM and WH biomasses may have shown higher aliphaticontents due to the smaller particle size and less free space insidehe reactor, which might have affected the thermal gradients in theystem. The low H/C molar ratio for the CE biochar was suggestive

– – 3.51 – –– – 12.20 – –– – 2.57 – –

of the presence of aromatic compounds. In all cases, the H/C molarratios for the biomasses exceeded 1.4, which is characteristic oflignocellulosic materials [15].

3.4. Composition of the bio-oils

GC/MS analysis was used to obtain information concerning thenature of the organic compounds present in the liquid productsof pyrolysis (Table 4). Between 50 and 80% of the relative chemi-cal composition of the bio-oils produced could be identified frominvestigation of the presence of around 160 compounds in theirsilylated forms.


The most abundant product in the WH bio-oil was 3-pyridinol,with a relative percentage of up to 13%. Nitrogen compounds couldbe produced after the pyrolysis of peptides or the decompositionand condensation of amino acids [37]. It should be noted that the

dx.doi.org/10.1016/j.jaap.2015.03.006

IN PRESSG ModelJ

6 al and Applied Pyrolysis xxx (2015) xxx–xxx

pfF(ta(tw(

o2dt(s3bmo[m

ywmc

Table 5EPR spin densities (spin g−1) and g values obtained for the biochar samples.

Biochar spin g−1 g

CE 2.40 1018 2.0030CM 2.79 1017 2.0034CP 7.35 1018 2.0031SB 1.51 1018 2.0030


M.E. Doumer et al. / Journal of Analytic

resence of such compounds in bio-oil could be a disadvantageor its use as fuel, due to NOx emissions during combustion [38].uran compounds were another significant group in the WH bio-oil8.6%). Furan derivatives are formed during primary decomposi-ion of hemicellulose at temperatures above 400 ◦C [38]. The majornhydrosaccharide compound in the WH bio-oil was levoglucosan6.2%), which is formed from cellulose degradation at tempera-ures between 300 and 400 ◦C [38]. These results were in agreementith the amounts of hemicelluloses and cellulose in the feedstock

∼40%) and the low content of lignin (6.5%) [39].Phenols were the main organic compounds in the CP bio-

il, which could be attributed to the high lignin content (up to5%) of green coconut shells [40]. These compounds are formeduring the decomposition of lignin macromolecules at tempera-ures above 350 ◦C, and include catechols (benzenediols), guaiacolsmethoxyphenols), and alkyl-phenols [38]. Organic compoundsuch as hexadecanoic, octadecanoic, 9,12-octadecenoic (z,z),-docosenoic, and 5-docosenoic acids were only present in the CMio-oil. During biodiesel production, these oils remain in the rawaterial after the extraction procedure. Hydrocarbons in bio-oil

riginate from the carbohydrate and lipid groups in the biomasses37]. The presence in bio-oils of phenols and long chain fatty acid

ethyl esters (FAME) could improve their HHV [21].The bio-oils derived from SB and CE were quite similar, with

ields of up to 12% of 1,2,6-hexanetriol as the major constituent,



hich was probably produced by the weak cleavage of hexoseolecules such as glucose and mannose from cellulose and hemi-

elluloses.

Fig. 3. Van Krevelen diagrams for the biomasses (a) and biochars (b).

WH 1.67 1017 2.0035

3.5. DRIFT spectroscopy

The biomasses and biochars were characterized by infraredspectroscopy (Fig. 4). The main signals detected included bandsbetween 2850 and 3000 cm−1, corresponding to symmetric andantisymmetric stretching vibrations of aliphatic CH2 and CH3moieties [1,8,9,34]. Peaks between 1050 and 1350 cm−1 corre-sponded to C O stretching and O H deformation in phenols,ethers, esters, and primary, secondary, and tertiary alcohols [8].Peaks between 630 and 850 cm−1 corresponded to aromatic C Hbending vibration, due to the presence of adjacent aromatic hydro-gens in biochars [1,8]. The spectra of the biomasses showed somedifferences, compared to the biochars, in the region centered at1602 cm−1, where the bands attributed to C C and C N fromlignin and protein appear [9,15,34], with higher signals for thebiochars (see the magnification in Fig. 4). The broad band at around3440 cm−1, related to O H stretching of cellulose and proteins inthe biomasses, disappeared completely after carbonization. Thelignin structures of biomass produce a strong absorption at around1060 cm−1, due to C O C vibrations in ethers [15,41], which aredecomposed by pyrolysis; this band was absent in the spectra forall the chars. All the biomass samples showed an absorption peak ataround 1739 cm−1, related to the C O stretching mode of ester andaldehyde groups [42]; the intensity of this signal decreased afterpyrolysis, while the intensity of the band at 1700 cm−1 increasedfor all the biochars (see the magnification in Fig. 4). This featurehas been observed previously during the pyrolysis of lignin, andwas attributed to the formation of aromatics containing carbonylgroups [42,43]. This finding, in addition to the increased inten-sity of the 1602 cm−1 band related to aromatic C C vibrations,confirmed the formation of polycyclic aromatic compounds [9,34],in agreement with the lower H/C ratios identified from the elemen-tal analysis (Section 3.3), confirming that the structures becamemore aromatic after pyrolysis of the biomasses. The WH biomassand biochar showed different behavior, with absorption bands at3050 cm−1 characteristic of aromatic C H stretching, with lessconjugation among the aromatic rings. The spectra for the CMbiomass and biochar showed greater intensity of peaks correspond-ing to aliphatic groups (at 2930 and 2857 cm−1), compared to theother biochars, revealing a higher content of linear structures. Thepresence of a high content of aliphatic structures remaining afterpyrolysis was in agreement with the 1739 cm−1 band observed forthe CM char, indicating the presence of linear carbonyl structures,possibly from fatty acids remaining after the biodiesel productionprocess.

3.6. EPR spectroscopy

The EPR spectra of all the biochars showed sharp absorptionlines at around g = 2.003 (Fig. 5). The CE, CP, and SB biochars pre-sented EPR g-factors of 2.0031 and 2.0030 (Table 5), suggestingthat the unpaired electrons were nearest to carbon atoms, whereas


the WH and CM biochars presented g-factors of 2.0035 and 2.0034,respectively, which are typical of free radicals near to heteroatomsin organic structures, as occurs in ortho-semiquinones [44].

dx.doi.org/10.1016/j.jaap.2015.03.006


M.E. Doumer et al. / Journal of Analytical and Applied Pyrolysis xxx (2015) xxx–xxx 7

s (das

cdhttetrmrstp

Fr

Fig. 4. DRIFT spectra obtained for the different biomasse

The areas of the absorption curves were used to determine theoncentrations of the free radicals listed in Table 5. The highest spinensities were observed for CP, followed by CE. This was due to theigh amount of polyphenol structures, which are directly relatedo the number of free radicals (the greater the number of spins,he greater the number of phenolic groups) [44], although consid-ring the EPR g values of this kind of free radical (around 2.0030),he unpaired electrons were near carbon atoms. The organic freeadicals present in biochars might enhance the reactivity of these

aterials in soil [45]. The OFR concentrations listed in Table 5 cor-



espond to the areas of the curves due to OFR absorption. The higherpin densities observed for CP, CE, and SB were in agreement withhe 13C NMR spectra (see below) that showed that these samplesroduced the most intense absorbance related to the presence of

ig. 5. EPR spectra obtained for the biochars using a magnetic field of 5000 gauss atoom temperature (∼300 K).

hed lines) and their corresponding biochars (bold lines).

aromatic structures (Fig. 7). They were also in agreement with thehigher aromatic compound contents of these materials, inferredfrom the van Krevelen plots (Fig. 3). In addition, high spin densitiesare also associated with high levels of polyphenol structures, whichdirectly affect the number and stability of OFR, due to the pres-ence of a greater number of phenolic groups in ortho- and para-positions [44]. These phenolic groups produced during pyrolysis,as evidenced by the shift of the FTIR band from 1739 to 1700 cm−1

(described above, Section 3.5), could be responsible for the oxida-tion capacity of biochars, which is required in order to sustain theenzymatic reduction of N2O to N2.

In addition to the intense free radical signal, the SB sample pre-sented an intense wide EPR line between 2700 and 3700 gauss,caused by trivalent iron in concentrated domains [46]. The sameband appeared with less intensity in the other samples, with theexception of the CP sample, for which this absorption signal wasabsent. Samples CM, WH, and CE (almost imperceptible) also exhib-ited six lines centered at the g = 2.0 region of the spectra, attributedto the hyperfine structure (A ∼90 G) of Mn (II) ions (S = 5/2) in outersphere complexes, which is typical of reducing environments [46].The spectra for the CM and WH samples also showed a line near1500 gauss (g = 4), corresponding to Fe (III) in diluted domains [46].

3.7. Thermogravimetric (TG and DTG) analysis

The pyrolysis profiles shown by both TG and DTG curves forthe biomasses SB, WH, CE, and CP were similar, while the CMbiomass showed a distinct DTG curve (Fig. 6). For all the biomasssamples, the first weight loss indicated in the DTG curve endedat 130 ◦C, and could be attributed to the release of water. Thenext events occurred at 200–300 ◦C and 300–400 ◦C, correspond-ing to the degradation of hemicelluloses and cellulose, respectively


[17]. The profile exhibited by CM during the decomposition of cel-lulose showed the presence of two large peaks of loss mass, at345 and 373 ◦C, instead of the single peak presented by the otherbiomasses.

dx.doi.org/10.1016/j.jaap.2015.03.006



0 10 0 20 0 30 0 40 0 50 0 60 0 70 0 80 0 90 0 100 00

20

40

60

80

100

Temperature (oC)

Res

idu

al M

ass

(%)

-0,01 0

-0,00 8

-0,006

-0,00 4

-0,00 2

0,00 0

360 oC

310 oC

Mas

s L

oss

Rat

e (w

t.%

/o C)

SB

60 oC

0 10 0 20 0 30 0 40 0 50 0 60 0 70 0 80 0 90 0 100 0

20

40

60

80

100

355 oC

300 oC

Temperature (oC)

Res

idua

l Mas

s (%

) 85 oC

-0,01 0

-0,00 8

-0,00 6

-0,00 4

-0,00 2

0,00 0

Mas

s Lo

ss R

ate

(wt.%

/o C)

CE

0 10 0 20 0 30 0 40 0 50 0 60 0 70 0 80 0 90 0 100 0

20

40

60

80

100

100 oC

373 oC

Temperat ure (oC)

Res

idua

l Mas

s (%

)

345 oC

CM

-0,00 5

-0,00 4

-0,00 3

-0,00 2

-0,00 1

0,00 0

Mas

s Lo

ss R

ate

(wt.%

/o C)

0 10 0 20 0 30 0 40 0 50 0 60 0 70 0 80 0 90 0 100 020

40

60

80

100

Temperat ure (oC)

Res

idua

l Mas

s (%

)

-0,00 6

-0,00 5

-0,00 4

-0,00 3

-0,00 2

-0,00 1

0,00 0

80 oC

325 oC Mas

s Lo

ss R

ate

(wt.%

/o C)

270 oC

CP

0 10 0 20 0 30 0 40 0 50 0 60 0 70 0 80 0 90 0 100 0

20

40

60

80

100

Temperature (oC)

Res

idua

l Mas

s (%

)

WH

-0.00 5

-0.00 4

-0.00 3

-0.00 2

-0.00 1

0.00 0

330 oC

270 oC

Mas

s Lo

ss R

ate

(wt.%

/o C)

75 oC

Fig. 6. Thermogravimetric and differential thermal analyses of the five biomasses.

t9mcrd

structures of the biochars (Fig. 7). The assignment of the resonanceabsorptions was based on previous studies of a variety of biomass

The decomposition of lignin occurs slowly throughout the entireemperature range of the analysis (from ambient temperature up to00 ◦C) [47]. The reactions at 100 ◦C, mainly involve the removal ofoisture. At higher temperatures, the biomass DTG profiles show

ellulose decomposition, reflected in an intense peak in 300–350 ◦C◦



ange, and peaks at ∼275 and ∼365 C, corresponding to the degra-ation of hemicelluloses and lignin, respectively [47].

3.8. CP/MAS 13C NMR

CP/MAS13C NMR analysis was used to investigate the chemical


samples including pine cone, soybean cake, corn stalk, and peanutshell [15], as well as pitch pine [17] and Miscanthus [48].

dx.doi.org/10.1016/j.jaap.2015.03.006

ARTICLE ING ModelJAAP-3446; No. of Pages 10

M.E. Doumer et al. / Journal of Analytical and

1r

ppswCtbcaggol

ibptctcwtbt

4

pBttuaccwdw

[

[

[

[

[

[

[

[

[

[

Fig. 7. 13C NMR spectra of the five biochars.

The spectra of all the chars exhibited peaks at 0–50 ppm and50 ppm, corresponding to aliphatic carbons and phenolic groups,espectively.

A number of differences between the biochars were observed:eaks for carbohydrates in the 50–100 ppm range were onlyresent in the spectra for the CE and CM biochar samples (theame samples for which linear structures with carbonyl groupsere detected by DRIFT spectroscopy, even after pyrolysis). For

M, signals between 72 and 75 ppm, and at 105 ppm, were relatedo resonances of carbons in cellulose and hemicelluloses. The CPiochar presented a clear peak at 150 ppm, indicating that residualarbohydrates and lignin remained in the biochar after pyrolysis,nd this char also showed a signal at 173 ppm from the carboxylroups present in hemicelluloses and probably also in phenolicroups (as indicated by the DRIFT spectrum). The higher contentf phenolic groups in the CP sample probably explained the stabi-

ization of the free radicals found by EPR spectroscopy (Table 5).A signal at 130 ppm, related to aromatic carbons, was present

n the spectra for all the samples, and its high intensity coulde explained by the formation of more stable aromatic com-ounds from carbohydrates (cellulose and hemicelluloses) duringhe pyrolysis process. A peak at 29 ppm, corresponding to methylarbons of acetyl groups in hemicelluloses, was most intense forhe CM and WH chars, indicating a significant presence of theseompounds. A signal at 56 ppm, reflecting metóxy groups of lignin,as observed for the CE biochar, indicating incomplete carboniza-

ion. The presence of cellulose in the biochars could be explainedy the fact that cellulose tolerates higher temperatures, comparedo hemicelluloses.

. Conclusions

A range of characterization methods were used to analyze theyrolysis products of different biomasses abundantly available inrazil. Correlations between the data obtained by the differentechniques enabled an understanding of the physicochemical fea-ures of the products. Pyrolysis of biomass produced bio-oil withp to 70% of the calorific value of fuel oil. The biomasses CP, CE,nd SB appeared to be suitable for producing biochars with low ashontents and high calorific values. These biochars exhibited high



ontents of fixed and elemental carbon, and the OFR spin densityas located close to carbon atoms. Aromatic structures were pre-

ominant in the CP, CE, and SB biochars, while aliphatic groupsere abundant in the CM and WH biochars. The biomass sources

[

[

PRESS Applied Pyrolysis xxx (2015) xxx–xxx 9

studied produced reasonable amounts of bio-oil, and could com-pete as suitable raw materials for biofuel production or asfeedstocks for the chemical industry. These biochars could alsobe used as soil conditioners, due to their stability and chemicalcomposition.

Acknowledgments

This work was supported by CNPq, CAPES, INCT E&A, and FUN-PAR (Foundation of the Federal University of Paraná – UFPR). Theauthors are indebted to LAMIR (Laboratory of Analysis of Mineralsand Rocks – UFPR) for providing the TG/DTG analyses.

Appendix A. Supplementary data

Supplementary data associated with this article can be found, inthe online version, at http://dx.doi.org/10.1016/j.jaap.2015.03.006.

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