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Fuel 102 (2012) 737–745

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Fuel characterization and biomass combustion properties of selected native
woody shrub species from central Portugal and NW Spain
H. Viana a,c,⇑, D.J. Vega-Nieva b, L. Ortiz Torres b, J. Lousada c, J. Aranha c
a
CI&DETS. Forestry Sciences Section, Agrarian Superior School, Polytechnic Institute of Viseu. Quinta da Alagoa, 3500-606 Viseu, Portugal
b
Escuela Universitaria de Ingeniería Técnica Forestal, Universidad de Vigo, Spain
c
CITAB, University of Trás-os-Montes e Alto Douro, Apartado 1014, 5001-801 Vila Real, Portugal

h i g h l i g h t s

" Selected shrub native species from Spain and Portugal were characterized.
1
" Ashes of 1–2%, N > 0.6%, S < 0.1% and HHV of 21–24 MJ kg were found.
" Alkali metal 20–30% denote potential ash bed sintering/agglomeration and fouling risk.
" ash trace elements were below most of European limits.

a r t i c l e i n f o a b s t r a c t

Article history: Selected native shrub species from central Portugal and NW Spain, Cytisus multiflorus (broom), Erica arbo-
Received 10 November 2011 rea (heath), Pterospartum tridentatum (carqueisa) and Ulex europaeus (gorse) were characterized for phys-
Received in revised form 13 March 2012 ical, thermal and chemical properties for combustion. The studied shrub species showed ash contents in
Accepted 8 June 2012
the range 1–2%, nitrogen contents above 0.6%, and sulfur contents below 0.1% at both areas of study. A
Available online 23 June 2012
significant effect of species on Higher Heating Value (HHV) was observed, with no significant effect of
the location of study, central Portugal or NW Spain. The higher HHV (24.4 MJ kg1) was recorded for
Keywords:
heath, this species also shows the higher average carbon and lower nitrogen content values of the studied
Shrub
Biomass
species. Analysis of the chemical composition of the ashes revealed alkali metals contents of 24–30%, rep-
Heating value resenting a potential sintering, fouling and bed agglomeration risk in the combustion of the studied spe-
Ash cies. Ash As, Cd, Pb, Co, Cu, Mn, Ni, Cr, and Zn content was below national and most of European
Slagging legislation maximum levels for these elements for ash application as fertilizer, with the exception of
some of the more conservative limits for Cd, Cu, Cr, and Zn from Northern and central European countries
legislation.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction residual biomass sources [5], there is an increased interest on the
consideration of alternative feedstocks for biomass combustion,
The interest in the utilization of forest biomass for bioenergy such as native woody shrub species.
has increased exponentially in the last decades in European coun- Shrubland areas currently occupy close to 1 million hectares in
tries, as an integrated strategy for climate change mitigation, the region of Galicia, NW Spain [6] and a total of 1.9 million hect-
increasing renewable energy security and preventing forest fires. ares in Portuguese territory [7]. Furthermore, abandoned shrub-
Consequently, Portuguese [1] and Spanish [2] National strategies, land areas constitute a main fuel for the frequent wildfires in
have established ambitious goals for energy production in dedi- these two countries: approximately half of the 1.5 and 0.2 million
cated biomass plants for CHP, resulting in a large potential biomass hectares burned by wildfires in Portugal and in the region of Gali-
demand in both countries. Given the limited availability of residual cia, NW Spain, in the period 2001–2010, were shrubland areas [8].
forest biomass in Portugal [3] and Spain [4], joined with a growing The regular harvesting of shrubland areas, might therefore addi-
pellet production in these two countries, potentially utilizing forest tionally be valuable for diminishing the large greenhouse gas emis-
sions associated to these frequent wildfires [9], through the
⇑ Corresponding author at: CI&DETS. Forestry Sciences Section, Agrarian Superior reduction of forest fires occurrence.
School, Polytechnic Institute of Viseu, Quinta da Alagoa, 3500-606 Viseu, Portugal. In order to evaluate their potential as a biomass feedstock for
Tel.: +351 232 446 600; fax: +351 232 426 536. combustion, there is a need for an integrated biomass and ash
E-mail address: hviana@esav.ipv.pt (H. Viana).

0016-2361/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.06.035

fixed carbon (FC%). Aboveground biomass sam- However. which particles were carefully removed with high pressure water can limit boiler efficiency. The oxygen content was obtained by subtracting from 100% Additionally. climate. was analysed.) Sweet (broom). this species-specific composition being potentially influenced by growing conditions such as sunlight. even lead to bed defluidization through application. was conducted for the four species at both areas of study. in their ashes. deposit formation and boiler corrosion (e. S. which are of particular relevance for the environmental im. (L. For each subject woody shrub species. namely a sampling plot with an area of 10 m2 was established and the the studies by Núñez-Regueira et al. ash laboratory analyses (Section 2.738 H. proximate and ultimate analysis brings relatively limited ples included leaves and all woody fractions from aboveground information when the chemical composition of the combusted bio. Analytical measurements main recent reviews in fuel and ash composition (e. Soil nutrients contents.) (common gorse or furze) and Pterospartum tri- existing native shrub species.1.19. N. Shrub characteristics and combustion properties of the selected native basic density (Db) was calculated by water displacement technique shrubs Cytisus multiflorus (L’Hér. 22 and 32 sites were sampled in Area 1 and of these two countries. 7–9 biomass samples.d ¼ qv . volatile matter (VM%) taneous determination of CHN was carried out in a Leco TruSpec and ash yield (A%). dried and weighted to determine the dry aboveground biomass Fuel calorific properties are known to be influenced by biomass per hectare (t ha1). in.41W. of biomass at constant volume in dry basis was determined 2. [13]).2. Area 2. calorific value were randomly selected from the harvested biomass for fuel and (e.2. where it was divided by species. oven others. neither any of the 2.2. The simul- moisture content (w%). is relatively scarce.g. belowground root biomass mass is not also considered [16]. The analysis of ing CEN/TS 15104:2005 [35] European Standard for determining physical and thermochemical properties of the shrub biomass Carbon (C). it would be of interest to study whether tion were: Cytisus multiflorus (L’Hér. particularly given the potential samples were taken for proximate and ultimate analyses. central Portugal have an effect on the calorific properties of the Ulex europaeus (L. Shrub biomass measurement and sampling for fuel and ash following the CEN EN 14918:2009 [37] The HHV in dry basis was analysis calculated by the Eq.0500 N.2. shrub species in this area.1. Moreover. [16. Available information on biomass charac. where qv. tion. The determination evaluation of the potential of shrub ashes should consider the of ash content (dry basis) was carried out at 550 °C ± 10 °C accord- monitoring of relevant minor and trace elements contents in the ing to CEN EN 14775:2009 [32] The volatile matter content (dry ashes. Moisture content (wet basis) was determined following the ciated ash slagging and fouling risk.gr. composition (e. in Area 1 of study. dentatum (L. respectively.1.) Willk (carqueisa).1. in joules per gram. (2) proximate analysis. also called gross calorific value (GCV). including relevant the sum of (C. Therefore. (6) ash chemical composition. available water.1. basis) was determined at 900 °C ± 10 °C according to CEN EN pact of the potential ashes reutilization as fertilizer (e.g.gr ð1Þ ð100  M ad Þ The areas of study were Centre – North Portugal (Area 1). Ulex europaeus (L. 06°140 17’W to 42°500 5000 N. extending from 39°110 5300 N. chemical properties such as basic density (e.0600 N. H. and/or fuel proximate and ultimate analysis (e. Material and methods The higher heating value (HHV).) (heath). Sulfur content determination was done value (Higher and Lower Heating Value) and (5) energy density cal- in a Leco SC-144DR using direct combustion and infrared detec- culation. terization and specific combustion properties of native woody Within each site. Erica australis (L.gr is the higher . / Fuel 102 (2012) 737–745 characterization for the main native species in the shrubland areas June to August 2007. extending from dry (moisture-free) fuel.gr. [11]). qv. available shrub characterization studies for these na. Ultimate analysis the main genus present in the Mediterranean native shrubland Elemental composition of shrub biomass was measured follow- areas of NW Spain and North-Central Portugal. biomass. geo.g.g. for aboveground biomass determination.) Sweet (Spanish or Portuguese the different local soil and climate conditions from NW Spain and white broom). soil pH and The selected species for study of biomass and ash characteriza- nutrients [16]. [10]). minor and trace elements contents.) (Spanish or Portuguese heath).) (gorse) and Pterospartum tridenta- tum (L. S and ash) contents in percentage. [10] and Elvira and Hernando aboveground biomass within that plot was clipped. among ported to the laboratory. (4) calorific Elemental Determinator. by cut- ash slagging and fouling risk in biomass fuels with high mobile ting representative small fractions of the exposed root system. nor any of the main ash composition databases (e. and the studies from Fernandes and hermetically closed containers to prevent moisture loss and trans- Pereira [12] and from Fernandes and Rego [13] in Portugal. Viana et al.g. Higher and lower heating values 2. [17–19]).3.20]). tive species have only focused on selected biomass physical and representative of all the sampled aboveground biomass fractions.2. (1) [37]: 100 2. [21–26]). (3) ultimate analysis (C. an integrated European Standard CEN EN 14774-1:2009 [31]. 15148:2009 [33]. thermal and chemical characterization of biomass. Hydrogen (H) and Nitrogen (N) and CEN/TS including: (1) basic density (Db). 7°260 25. together with a scarcity of information on the ash compo- sition for shrub species in general: for instance. From the analysis sample.g. is scarce. Erica australis and expressed as dry weight per unit volume [34]. placed into [11] in NW and central Spain. 7°310 10. Additionally. in percentage by mass. Sampling for biomass and ash analysis graphic location. specially alkali metals. Shrub biomass measurement qv . Mad is the moisture in 42°560 26. these species being representative of 2. 2. the present work aimed to study the fuel and ash tween the sum of volatile matter and ash contents from 100. O. N). namely 15289:2006 [36] for Sulfur (S) content in solid biofuels. In spite of its All samples were prepared according to the technical specifica- relevance on combustion efficiency. slagging and fouling risk.89W to 42°310 28. In addition. occupying homogeneously at least one hectare.) Willk (carqueisa).g.d is the higher heating value at constant volume of the 08°190 0200 W and NW Spain (Area 2). Fixed carbon content (%) is the difference be- Consequently. [27–29]). Proximate analysis and basic density clude any information on shrub ashes composition and/or the asso. 2.2).2. soil types.g. 2. H. tions CEN/TS 14780:2005 [30] for sample preparation for the phys- information on the ash composition of these native shrub species ical. however. [14–16]).

Fe. ing Vamvuka and Zografos [44] Fuel bulk density depends on the utilized biomass logistics: chipping.21% to 1. In addi- tion to average biomass values for each species. of the biofuel. slagging trend can be expected [45]. according to the following expressions [17.gr. Fe2 O3 ceived (MJkg1). in joules 2. The following slagging and fouling indices were calculated from The LHV was calculated as (Eq.34 kg alkali MJ1 slag- vaporization (constant pressure) for water (moisture) at 25 °C [J/g ging and fouling is certain to occur according to Miles et al. RS biofuel. A sensitivity analysis of the effects of Higher biomass values were found for broom (Citisus multiflo- varying this average bundling density value on ±25% on calculated rus). of the biofuel. The most feasible option for the shrub fuels under study consists on fuel bundling after harvesting.net.17 kg alkali received [w%].45]: qp. 3. Mn. etc. if 2.net.d is the lower heating value in dry basis at constant Fe2 O3 þ CaO þ MgO þ Na2 O þ K2 O pressure.18.2. followed by gorse (Ulex europaeus) at both areas of study. BDar the bulk density. after an ash digestion with Nitric acid – HNO3 (65%).6 and 26 t ha1 (dry basis) for an average plot in the areas of to CEN/TS 15290:2006 Solid biofuels – Determination of major ele. Results and discussion paction into bundles can be very variable depending on the machinery used and type of biomass residues (e. Since 3. qp.ar combustion. qp. whereas the slagging risk should be high at SI < 2. [39. very high trend [45].0 < RS < 2. Cu.2. Shrub biomass measurement it was not the purpose of this paper to explore these issues. a seasonal range . of the moisture-free biofuel. The com. volume weight of the BAI ¼ ð9Þ Na2 O þ K2 O biofuel as received (kg m3 bulk volume). bundling. 2wðHÞd  0.d ð1  0:01Mar Þ  24:43Mar ð3Þ Alkali Index (AI) [17] was calculated according to the following equation: where qp. high trend.6. in joules per gram. in percentage by mass of the index [45] was calculated according to the following equation: moisture-free biofuel.net. [43].ar ¼ qp. Similarly. 24. 3.net. in joules per gram. obtained at resulting in an average total aboveground biomass (Bt) sum of 550 °C following CEN EN 14775: 2009 [32] was analysed according 18.40]). 8½wðOÞd þ wðNÞd  ð2Þ Base to acid index [45] was calculated according to the follow- ing equation: where qp. in percentage by mass.d  212. Al. Zn and Ni Proximate analysis and basic density results are shown in was done by Graphite furnace atomic absorption spectroscopy Table 2. Proximate analysis lizing a Boric acid – H3BO3 (4%) neutralization for the first elements Ash percentage ranged from 1.2. Proximate analysis and basic density nation was done by flame atomic absorption spectrometry (FAAS). if AI > 0.56% for the shrub above- as recommended by Baernthaler et al. ground biomass of the studied species. Co. Descriptive statistics of the shrub biomass sampling plots at the dues (285 kg m3 [39]) reported in the literature was utilized for two areas of study are shown in Table 1.43 is the correction factor of the enthalpy of MJ1 probable slagging and fouling. Mar is the moisture content as Higher Heating value (MJ kg 1) at w% = 0%. Hydrofluoric acid – HF (40%).4.net.ar is the lower heating value at constant pressure.75. Na.2. according to 1 Fernández Llorente and Carrasco García [18] Ear ¼ q BDar ð4Þ For evaluating the risk of bed agglomeration in fluidised bed 3600 p. (GF-AAS). Mg. i. qp. the following bed agglomeration index (BAI) [44] where Ear is the energy density of the biofuel as received was calculated according to the following equation: (MWh m3) of bulk density). 3. Ash Si. Hydrogen peroxide – H2O2 (30%). Pb. low w%. 3600 1 the conversion factor Being that: bed agglomeration occurs when BAI < 0. energy density was additionally performed. (4) [38]. If AI > 0. Viana et al.ar the lower heating value as re.gr.2. and the measurement of ash As. in joules per gram. w(O)d is the oxygen content.15.6. d The LHV at constant pressure at a required moisture content where S is S in percentage from elementary analysis if RS < 0. Cr. in ðK2 O þ Na2 OÞAð%Þ joules per gram. the biomass distri- 2.net. an average value of bulk density for green bundles for logging resi. Cd. The chemical composition of the biomass ash.1.net.44. of the biofuel with moisture content as received AI ¼ ð7Þ HHV Mar. [17] per 1 w% of moisture].6.5. Average biomass values for the studied species (Bi) are of a similar range to the values measured in NW Spain shrubland [10]. to Eq. Ti. uti. if 0. was calculated as the following equation: fouling trend.d is the higher heat. All the studied species providing an initial estimate of the energy density of the shrub were characterized by a high weight of fine fractions of <6 mm.6. qv. Ca.d is the lower heating value at constant pressure in dry ba- where A(%) is the ash percentage obtained at 550 °C and HHV is the sis. according Being that: no slagging should be expected at values of SI > 2. H.d ¼ qv . follow- for the energy units (MJ to MWh).g. if RS > 2.net. K. (2)) [37]: ash chemical composition (Table 5).1. of the moisture-free (dry) Being that: if B/A < 0. ments [41] and CEN/TS 15297:2006 Solid biofuels – Determination of minor elements [42]. / Fuel 102 (2012) 737–745 739 heating value at constant volume of the fuel as analysed.. The following sintering index (SI) [18] was calculated according to the following equation: 2. B=A ¼ ð5Þ SiO2 þ Al2 O3 þ TiO2 ing value in dry basis. Ash slagging and fouling indices per gram.6 < RS < 2. bundles after harvesting. P determi. w(H)d is the hydrogen content. of the biofuel. in percentage RS ¼ ðB=AÞSd ð6Þ by mass. study in central Portugal and NW Spain. medium trend.e. w(N)d is the nitrogen content. Fuel energy density CaO þ MgO The energy density as received (Ear) was calculated using the SI ¼ ð8Þ Na2 O þ K2 O lower heating value as received and the bulk density. Ash chemical composition bution for an average mixed shrubland plot is given in Table 1. respectively.

17) 0.38 (±0.31) 46.26) 1.48.84 (±0.6 (±0. Bt (t ha1) (db): average shrub aboveground biomass (t ha1 on dry basis).49 (±0.13) 6.2.4 (±0.6 (±4.35 (±0.88 (±0.25) <0.02) 83.32 (±0. considering all the plots of the area of study. np: number of study plots at each area of study where the species was present.1 Erica australis (Portugal) Shoot 49.62) 17.02) <0.08) 41.64 (±0.4) 89 (±9) 21.07) 15.2 (±40.6 (±0.8 (±30. Table 2 Proximate analysis and basic density of the shrub species at the two areas of study.1 (±0.3) 85 (±14) 27.80 (±0.63%.05) 80.1 (±0.81 (±0.5) Pterospartum tridentatum (NW Spain) Shoot 1.9 (±34.6 (±1.01) <0.9 (±0.69) 59. root: belowground biomass.04) 45. Ash composition will be further discussed in and Panov [47] reported values of 2.81 (±0.67 (±0.1 (±0.38 (±0. for the plots where the species was present.0 (±5.09) 44.78 (±0.42% have been reported for Ulex parvif.2) 435.9) 483.79 (±0.0) Where: shoot: aboveground biomass.5 (±22. 0.07) 80. FC% Fixed Carbon (%).53) 6.52) 0.39) 37.1 Where: shoot: aboveground biomass.6.7) 78 (±17) 85.4 (±2.1 (±12. Species Proximate analysis (% by mass.4 (±11.5%.7) Root 1.3) 26.99 (±0.30) 14. Table 3 Ultimate analysis of the shrub species at the two areas of study.57 (±0.51 (±0.3) 98 (±2) 2.7) 74 (±21) 87. %B(db) <6 mm: Percentage of aboveground biomass (dry weight) corresponding to the fraction of less than 6 mm.9 (±14.0) Root 0.9) 739.55 (±0.82 (±0.6 (±7.01) 82.1 Root 45.38) 45.6) 603.71 (±0.2) Where: ns: number of biomass sub-samples selected for biomass and ash analysis at the laboratory.9 (±0.3) Cytisus multiflorus (NW Spain) Shoot 1.2) Erica australis (Portugal) Shoot 1.01) 83.3 (±0.39) 43.5) 80 (±16) 25.04) 45.45 (±0.9 (±4.83 (±0.04) <0.09) 0.19) 2.8) Ulex europaeus 9 28 0.14) 15.2 (±0.9) 10.3) 2.86% and 0.01) <0.09) 0. VM%: Volatile Matter (%).21–0.48 (±0.740 H. were observed in NW Whereas typical ash content in wood is 0.03) 80.96 (±0.46) 16.10) 7.44) 18.84 (±0.7 (±1.45 (±0.16) 6.2 (±0.9 (±0.g. dry basis) C H O N S Cytisus multiflorus (Portugal) Shoot 46.65 (±0.50 (±0. / Fuel 102 (2012) 737–745 Table 1 Descriptive statistics of the shrub biomass sampling plots at the two areas of study.6 (±2. Ash%: Ash percentage (%).35 (±0.98 (±0. Viana et al.2 (±0. dry basis) Db (kg m3) Ash% VM% FC% w% Cytisus multiflorus (Portugal) Shoot 1.2) 99 (±1) 2.43) 6. diameter branch fractions.96 (±0.1 Pterospartum tridentatum (NW Spain) Shoot 48.08) 6. where mobile nutrients such as green studied species possibly contributed to the relatively high potassium are accumulated.3) Pterospartum tridentatum (Portugal) Shoot 1.08 (±0.65 (±0. Numbers in parenthesis are the standard deviations.9 (±2.08) 6.36) 17.2) 4.33) 0.95 (±0.2 (±10.32 (±0.1 (±53.01) <0.3 (±0.46) 6.20 (±0.75 (±0. the actively metabolising fractions such as leaves.5) 485.05 (±0.4 (±7.3) 91 (±4) 38.72 (±0.1 Ulex europaeus (NW Spain) Shoot 48.38 (±0.7) 16.09) 42.5 (±2.71–1.73 (±0.46) 46.38 (±0.5 (±77.10 (±0.1 Pterospartum tridentatum (Portugal) Shoot 47.2 (±183. Species Ultimate analysis (% by mass.17) 0.06 (±0.46 (±0.1 Cytisus multiflorus (NW Spain) Shoot 48.09) <0.06 (±0.44 (±0.65 (±0.32 (±0.30) 17.1 Ulex europaeus (Portugal) Shoot 46.3 (±4.0) 3.72 (±0. Ash values of 2.7) 408.7 (±16.9 (±9.65 (±0.7 (±2.79% respectively.71 (±0.97 (±0.0) Ulex europaeus (Portugal) Shoot 1.65) <0.6 (±3.30) 0. and in the low lorus in France [46].8) 569.20 (±0.48 (±0.8) 5.4) Ulex europaeus 9 12 0.6) Root 0.12) 42.1) Erica australis 7 9 0.3) 13.51) 52. Bi (t ha1) (db): average shrub aboveground biomass (t ha1 on dry basis).49]).29) 47. The presence of leaves and spines in the ever.01) 84.95 (±0.7 (±0.04) 44. Section 3.7 (±2.6) Erica australis 7 16 0.13 (±0.3 (±1.2 (±34.05) 82.09) 79. Numbers in parenthesis are the standard deviations. .31) 6.07) 44.9 (±13.4) Other species n 22 0.04 (±0.69) 6.47 (±0.5) 0. root: belowground biomass.4) 4.51% for Erica arborea leaves.05) 84.1) 30.8) 58 (±35) 83.3) 8.3) 1.86 (±0.28) 48.19) 14.9) 3. Numbers in parenthesis are the standard deviations.8 (±0.4) Root 0.8) Erica australis (NW Spain) Shoot 1.31 (±0.3) 0.58 (±0.02) <0.9 (±3.55) 42.01) 80.4) 28. while the ashes content of the same species twigs was 1.97 (±0. in ash content for native gorse. ash content of the shrub biomass: for instance.88 (±0.2 (±1.88 (±0.7) 2.1 Root 46.6 (±0.24 (±0.29) 16.1 Erica australis (NW Spain) Shoot 48. broom and heath of 0.04) 45.3) Pterospartum tridentatum 7 19 0.01) <0.16–0.2 (±66.71 (±0.2) Pterospartum tridentatum 7 10 0.26) 6.41) 17.08) <0.7 (±0.2 (±0.32 (±0.56 (±0.06) 6.9) 576. the ash content in Spain [10].9 (±3.8) 9.31 (±0.29) 1.9) 522.3 (±1.3 (±9.50) 18.47 (±0.6) 0.3 (±63.5) 420.85 (±0.0 (±7. can be as high as 2–5% (e.11) 45.37 (±0.4) 0.74 (±0.4) NW Spain Cytisus multiflorus 9 26 1.37 (±0. Dimitrakopoulos [16.9 (±104.5) Sum 26. w%: Moisture content wet basis (%).2 (±0. Area of study species ns np h (m) B% (db) <6 mm CC (%) Bi (t ha1) (db) Bt (t ha1) (db) Central Portugal Cytisus multiflorus 9 11 0.5) Ulex europaeus (NW Spain) Shoot 1.35) 43. CC: shrub canopy cover (%).49 (±0. h(m): shrub height (m).7 (±24.7 (±0.06) <0.1 (±10.1 Root 46.2) 417.18) 0. including leaves and twigs <6 mm.4 (±17.20) 49.8 (±5.63 (±0.5 (±89.14%.3 (±16. Db: basic Density (kg m3).1 Root 45.90 (±0.45 (±0.4 (±0.7 (±6.1) 93 (±6) 12.6 (±15.54) 58.01) 81.2) Other species n 32 0.00) 0.3) Sum 18.21 (±0.9) 417.03) 42.

245 (±0. Fuel moisture values should only be regarded as indicative of the conditions at the par- Ultimate analysis results for the shrub species at the two areas ticular time of sampling at the two areas.667) 9. carqueisa. Basic density highest average carbon content for heath as in the present study.75 Ulex europaeus 1 21.1 1. the highest values corresponding to heath at Portugal area of study were lower than the corresponding carbon Fig.0 19.17 0.4 14.6 Pterospartum tridentatum 23. broom and heath found in NW Spain [10]. range of 70–86% in volatiles for woody biomass [16. [11].1 1. like in the hydrocarbons and PAH [20].6 18.71 0.02 0.1 0.56 Ulex europaeus 2 21.1 1. H. moisture at reception would be influenced both by the season of Measured shrub aboveground biomass carbon contents are sim- harvest and the logistics of harvesting and transport. samples including leaves and twigs of less than 6 mm. broom by Elvira and Hernando [11]. Table 5 Shrub ash major and selected minor elements composition.9 10. Species Area HHV (MJ kg1) LHV (MJ kg1) Ear (GJ m3) Ear (MW h m3) Cytisus multiflorus 1 22.06 0. Similar values of 500–580 kg m3. Average higher heating values of shrub species for the two areas of study Where: (letters in brackets) stand for signifficant differences at p < 0.231 (±0.49] with the 427–484 kg m3. ilar to the range of 46. these shrub aboveground biomass to ensure higher combustion efficiency and low emissions of CO.455 (±0.0 22.318) 2. Ear: Energy Density as received of the shrub fresh bundles (GJ m3 and Mw h m3).350) 11.256 (±0. Viana et al.0 12.321) 8.5–62.397 (±0. present study. actual fuel of study are shown in Table 3. .0 12.203) 2.8%.639) 7. gal showed higher density values than corresponding aboveground er values in the reported year-round seasonal ranges in moisture woody biomass samples (Table 2).3.19 0.05. broom and heath by Núñez-Regueira et al.2.02–55.75 Where: Area 1: Central Portugal.5 15.3 3.9 The observed values of Volatile matter were similar to the usual both areas of study (Table 2).0 22.1 0. Fernandes and Pereira [12] care must be taken to achieve complete combustion of the volatiles and Fernandes and Rego [13]. 1.208 (±0. LHV: Lower Heating Value (MJ kg1) at moisture content as received (see Table 2). have been higher volatile percentages and lower fixed carbon measured for reported for Spanish and Portuguese heath.2 9. / Fuel 102 (2012) 737–745 741 Table 4 Higher and lower heating values and energy density of shrub species at the two areas of study. 356–474 kg m3 and 379–500 kg m3.654) 9.5–66.454 (±0.234) 3.41 0.51% observed in NW Spain for gorse.4 15.502) 8.6 10.6 2.111 (±0.69 Cytisus multiflorus 2 22. who also found the 3.656) 7. HHV: Higher Heating Value (MJ kg1 at dry basis). Species Ash composition (% oxides referred to ash dry weight) SiO2 Al2O3 TiO2 Fe2O3 Na2O K2O CaO MgO P2O5 Cytisus multiflorus 16.5 8.2.1 18.57 Erica australis 2 24.508 (±0.6 3.144 (±0. Numbers in parenthesis are the standard deviations. as it would be ex- 3.9 11.69 0.1 17.67 Erica australis 1 24.48 0. Basic density of the shrub aboveground biomass ranged from Measured belowground biomass carbon contents results in central 404 to 498 kg m3.162) 2. content of 47.396) 2.4 0. In high volatiles content fuels.872 (±0.4–63. and 44. Belowground biomass samples from central Portu- Moisture values at the time of reception correspond to the low.488) 3.89 Pterospartum tridentatum 2 22.3 8.1 17.361) 2. furthermore.0 0.1 Ulex europaeus 33. gorse and the belowground biomass samples.3 13.365 (±0.241 (±0. 57.88 Pterospartum tridentatum 1 21.668) 11.3 Erica australis 17.702 (±0. Area 2: NW Spain.9 0.0%.117 (±0.236) 2.0 0. Ultimate analysis pected for a summer harvest of these species.071 (±0.9 18.2% for native gorse.48.

8%.65 MJ kg1 for Spanish broom.17 Probable 1. [50]). heath the species in the present study. ized deviations for the four shrub species are shown in Fig.1 5. for the native broom Cytisus scoparius.0–1. with val- paeus (gorse).2 111. Higher values were observed ious authors have noted the positive role of increasing C and for heath HHV at both areas of study. decreasing N in raising the HHV of biomass fuels (e. followed by Spanish gorse. ranging from 1.03 Low 0.9 2. showed N contents above rigal et al.5 14. carqueisa and gorse in central Spain.06.8 5808.7 739.g.3 2. followed by Ulex euro.46 and 21.61 High 0.105) nor of interaction between species and ues of <0.63% to 2. at both areas of study.8 MJ kg1 have been measured similar to the range of 0.89 Low 0.7%.0–2. values have been reported for other broom species. a General Linear Model ANOVA was per- were within typical ranges for forest biomass fuels (e.07 Occurs Ulex europaeus 0.05%.g. [10] in NW Spain is more cies: values of 24. this possibly being a consequence of the species being classified as high calorific and the latter as medium higher N content characteristic of the soils in the region (e. Lower calorific are characterized by a high nitrogen fixation capacity.6% threshold proposed by Obernberger et al.8 2.4 7287. with a seasonal sured by Elvira and Hernando [11]. High calorific values are typical of heath spe- study and from Núñez-Regueira et al. calorific species following the calorific value classification estab- Measured shrub biomass nitrogen content from the current lished by Hough [51]. All Spain [53] and a reported seasonal range from 19.94 MJ kg1. with the highest species being heath. area of study (p-value = 0. lowed by a second group formed by broom and carqueisa.6 1. scoparius.1 20.7 3212. Var- 2 areas of study are shown in Table 4.7%. as discussed in the Section 3.1 11.17 Probable 0. 1).6 1. such as gorse or broom. threshold established by Obernberger et al. the highest ranking Nitrogen content ranged from 0. formed testing the three factors species.5 150 700 300 4500 150 Sweden (Forestry) 30 30 300 400 100 7000 300 Austria (Field and grassland) 20 8 100 100 250 250 1500 100 Portugal (Agriculture)a 20 750 1000 1000 2500 300 Spain (Soils with ph < 7) 20 750 1000 1000 2500 300 Spain (Soils with ph > 7) 40 1200 1750 1500 4000 400 a Limit values of concentration of heavy metals in sludge from water treatment plants. Greece [47] and Spain [52].05 Low 0.14 High 0.06 Occurs Erica australis 2. with a N range of 1.45 Low 0.88 Low 0. characteristic of woody species being the highest ranking of 20 Mediterranean species in biomass fuels [49. who found average calorific values of and the 0.5 100 600 300 1500 100 Finland (Forestry) 30 17. 23. with an average HHV of 24.44 MJ kg1.4 3.62 MJ kg1 reported for Ulex parviflorus in France [46].44.4 409. It is interesting to note that the higher HHV was found for 3.1% of woody fuels than to the contents of >0.34 and 20.1% tion between species and area of study.1 MJ kg1 found in central with potential implications for the combustion of these fuels. fol- values found for Cytisus multiflorus (broom). a higher N content was observed (Erica scoparia). with no significant effect of neither area measured sulfur content values being more similar to average val. 20. USA). Similarly.07 Low 0. contents for aboveground biomass for all the studied species.g.59. [49] for minimizing A significant (p-value 6 0. than to the lower range of 0.06 Low 0. with an average HHV of 21. 22. with an average HHV of 21.1–0. these heating value was found. respectively.1 10204. the first three in NW Spain area of study.3 12.06 Low 0. 1. man-Keuls test revealed three groups for HHV. in the range of 6–7% and 41–45%. [16]). Using Hydrogen and oxygen content.2% S com.13 Occurs Table 7 Shrub ash trace and selected minor elements composition. A subsequently Student–New- monly found in herbaceous biomass fuels (e. For all 24.2 4. / Fuel 102 (2012) 737–745 Table 6 Ash slagging and fouling indices and risk. [49] for avoiding 21. typical of herbaceous biomass for Erica arborea in France [46]. Leguminous shrubs. of study (p-value = 0.3. Species B/A Rs Alkali Index (AI) Sintering Index (SI) Bed Agglomeration Index (BAI) B/A Slagging risk Rs Fouling risk AI Fouling risk SI Sintering risk BAI Bed agglomeration Cytisus multiflorus 2. in NW Spain.1 Ulex europaeus 4. and a third group for et al. 21.4 3.16 MJ kg1 (Fig. [53].2 4812.8%.3 293.93 High 0. this . Viana et al.1 128.1 9.2 1660. [10] study in NW Spain.8 689.05) effect of species on fuel higher sulfur-related corrosion risk in biomass boilers combustion. being also similar to the values of NOx emissions in combustion.9 7.7 Country (application) Denmark (Agriculture/Forestry) 15 120 100 30 Finland (Agriculture) 25 1.1 5.9 Pterospartum tridentatum 3. [10] found the highest shrub N content values in NW Spain gorse. accumulat. [16]). [10].9 Erica australis 4. area of study and interac- All studied species showed a sulfur content below the 0. [14.15]). such as Cytisus ing this mobile nutrient in fine fractions such as leaves or twigs. 23. Species As Cd Pb Co Cu Cr Mn Zn Ni Cytisus multiflorus 3. this species having the both the highest average C content and lowest N content in the current study and in Núñez-Regueira Higher and lower heating values for the studied species at the et al.43 MJ kg1 for this species.5–2. HHV for gorse mea- tive shrub species ultimate analysis at four seasons of harvest from sured in the current study agrees with the values reported by Mad- Núñez-Regueira et al.14 Low 1. SPSS 19 (SPSS Inc.9 101.4. who reported average HHV of N range of 1.1% to 4. Núñez-Regueira ues of 22.00 High 0.g.742 H.02 to of the studied species at both areas of study and in the data of na.3 2.07 Occurs Pterospartum tridentatum 1. Higher and lower heating values heath.667). and heath.8% Measured average HHV results are similar to the values mea- at four seasons of study.9 100. this fuels. Greece in Dimitrakopoulos and Panov study [47].32–20.16 Low 1.16].2 2290.68 MJ kg1 measured in NW Spain [10]. Average HHV and standard.6 and 23.

Ash chemical composition and slagging indices silica.2 GJ m3 to 3. Potential ash sintering. Ca. ough alkali for the ashes to melt in combustion and/or the li metal contents of 30% in gorse ash in NW Spain. A ±25% variation in the shrub bundle bulk density would result in estimated energy density values of 1.g. with a total sum for broom and gorse ashes. oxides referred to ash percentage dry weight and normalized to The Rs index suggested a low sulfur-based corrosion risk for all 100% for slagging indices calculation. deposition and corrosion in biomass com- sources such as woodchips of softwood (2. for the summer harvest scenario with the measured Results from the calculation of ash slagging and fouling indices. and Soto and Diaz-Fierros [56] measured alka. Lower heating values are highly potassium content is important as an indication of the potential for dependent on fuel moisture content and therefore the values pre.1. However. metals present in the studied fuels. Consequently. might be responsible season of harvest and associated moisture content [11].14 and 0. evaluated in the following Section 3. such as diameters larger than 3 cm.5–3.3–6. together with other nutrients encing the different HHV of species. in the combustion of herbaceous 3. [16] reported average K2O contents of 24. slagging and fouling risk is further high pressed bales (2.07 to 11. with values of 0.2. For instance. 3. with the highest values found fuel tended to accompany an increasing ash content.7% for herbaceous and woody fuels ashes. [18. The reported alkali index is in the lower range of typical her- noted that gorse biomass composition was characterized by high baceous fuels values of 0. resulting ashes of all the studied species. Jobson and Thomas [55] [17]. / Fuel 102 (2012) 737–745 743 explaining in part the higher HHV of woody fuels in comparison branches and twigs compared to the ashes from branches with with herbaceous fuels [16].4 GJ m3.4–1.8 GJ m3) or grass in bustion.75 proposed by Bryers [45] for the of the studied species would descend to 5. higher alkali for woody fuels or leached agricultural fuels with low slagging risk. Werkelin the authors.9 GJ m3. Fernández Llorente and Carrasco García [18].1%. Fe. was below the threshold value potassium is easily retranslocated and accumulated in low diame.21 MJ kg1.6. or potential reactions with silica bed materials. mass and ash composition: for example. with K2O contents in the ashes ranging from 10% to 20%. Na. are threshold for K in ash established by Obernberger et al. Furthermore.5 MJ kg1.2. of 2 for avoiding ash sintering in the combustion proposed by ter woody fractions as well as in leaves.2 to >2 kg alkali MJ1.9 GJ m3) [54]. was more similar to the average SiO2 ing sulfur-related corrosion risk during combustion as discussed in values of 22.44]). as evaluated by Fernández Llorente to what discussed in Sections 3. the calculated LHV values above the threshold of 0.2 (e.2 GJ m3. this content being linked to present in the shrub biomass composition. the mobile nutrient and Carrasco García [18] SI index. with low melting points. H.17 kg alkali MJ1 threshold for probable slagging and fouling All samples showed high alkali metals content. [16]. as re- study. of the probable slagging and fouling threshold from Miles et al.6. which contain en- potassium contents.6. For a wet and associated ash slagging and fouling risk.7 GJ m3) or triticale straw (1. can be influ. not measured in the current study. 0. were in the vicinity High alkali metals contents have been recorded in gorse shrub bio. for the relatively high ashes yield of the studied species: Jenkins Measured LHV of the freshly harvested shrub biomass samples et al. 3.2% for herbaceous fuels reported in the ash composition review Calculated alkali index in the present study was above the by Vassilev et al. [10] and by Fernandes and Pereira [12]. similar to the values observed in this study. inert material particles and leading to subsequent agglomeration and even defluidization of the bed [20].. particularly potassium. suggesting a ica found in the ashes would not be expected to lead to significant greater role of season of harvest and associated moisture content formation of silicates in reaction with the alkali and alkaline earth on the energy density of these fuels. sented are only representative of the calorific value correction for Alkali metals. 46. observed hard sintering and ash Energy density of fresh shrub biomass compacted into bundles deformation at temperatures below 850 °C. straw or brassica. K.1–1. have the tendency to react the particular moisture value at the time of sampling.5–2. Measured 0. Viana et al. For instance. Similarly earth metals in the ashes. [49] for minimiz- silica content in the ashes. metal contents can be found in herbaceous than in woody fuels: typically with alkali indexes values of <0. In the present sudy. Ash chemical composition: major and selected minor elements might be regarded as a potential source for the occurrence of ash Ash contents of Si.g. these K contents being (Table 4) ranged from 2. Biomass with elements vaporize and condense on boiler tubes and refractories high annual growth is abundant in alkaline elements because they [17].5. corded for the studied fuels in the areas of study by Núñez-Regue- The results of the slagging index Basic to Acid ashes (B/A). expressed as agglomeration and fusion (e. moisture contents and associated lower heating values. the studied species. alkali content reported for all the studied species in Table 3. In addition. other factors. for Erica australis at both sites.2.5 below.6% and In addition. This high content of potassium. forming sticky coatings on the surface of sity are discussed in Section 3.7% to 30. extractive content. all which represent a conservative estimate for a summer harvest sce- the studied species showed ash potasium contents above the 7% nario assuming no drying period of the biomass after harvest.2% for woody fuels than to the average value of Section 3. above.6. Ash slagging and fouling indices and slagging and fouling risk respectively.3) would be et al. are presented in Table 5. and 3. of alkali metals (Na and K) oxides ranging from 23. are summarized in Table 6. These values. Ti.1. together with 1. but in higher amounts than average reported alkali indexes are readily taken up from the soil [16]. Similarly low values of this index (SI < 0. for the four species of season harvest scenario.3. whereas heath and carqueisa ashes.3. phosphorus. in addition to the intrinsic content of silica in the fuels. respectively. Vassilev et al. ash fusion or deposition via vaporization and condensation [17]. these results being expected. given the low S Shrub ashes were mainly constituted by silica. [57] observed an increasing potassium concentration in the ranged from 7. suggests that the low content of sil- in calculated energy density values of 1. such as soil contamination associated to the process of bio- mass harvesting. The effects with the bed material or with ash silica to form eutectic mixtures of fuel moisture on effective LHV and associated fuel energy den.4 and 2.1% threshold established by Obernberger et al. [48] observed enriched K content in the ashes of young and obtained utilizing Spanish gorse ashes composition data from the biologically active tissues such as leaves. other exogenous sources of 3. below the metals (Na and K) and alkaline earth metals (Ca and Mg).16 kg alkali MJ1. Al. [17. the relative amount of alkali metals to alkaline 10. assuming a moisture content of 65%. Mg and P. with ira et al. Fuel energy density energy crops such as thistle.7 literature [56]. [49] for similar to the energy density values reported for other biomass avoiding ash melting.44]). This high alkali/ alkaline earth metals content times higher K content in the ashes of the wood of small-sized might result in a low fusion temperature of the ashes of the studied .

Rodrı́guez J. showed several 2006.89:913–33. Proupı´n J. Cu (<250 mg kg1). tection Agency) advised loading. Proupín-Castiñeiras J. Totais Nacionais (2001–2010). 2011. 2010. Fuel 2009. as [1] DGGE. Vasconcelos M. nor by typical values from wood and bark ash (e. [9] Silva T. Paúl J. 5th national forest inventory information retrieval tool. 4. The measured values were well below the limits SFRH/PROTEC/49626/2009. as evaluated by [44] BAI index. Cu.8:121–8. However. Calculation of higher heating values of biomass fuels. leaching on the content of shrub biomass and ash nutrient con- Table 7 shows the content of trace and selected minor elements tents. Pereira JP. Lisboa. [61. Rodríguez-Añón JA. Main drawbacks included high N contents (>0. as well as on the [13] Fernandes PM.1– estudio piloto con aplicación a los incendios forestales. Forest waste as an alternative energy source. CIS-Madera 2000. however. A criação de uma rede de Centrais de long as fly ash is not used.g. in the combustion of the studied fuels. 2006. Santos M. including the effect of rain tion technologies. 1. particularly densified residues from Pyrenean oak forest. Cohen WB. ther work on quantifying their potential impact must be conducted Bioresour Technol 2004. Caracterização de combustíveis na serra da Arrábida. Int J Wildland Fire 1998. Bryers RW. [6] Núñez-Regueira L. Inflamabilidad y energía de las especies de sotobosque: summer (2. Jenkins BM. 15–400. Fuel 2010.544:191–8.14:239–63. p. covering a range of soil types the studied species. role in the potential effects on the environment [27]. tended for application in agricultural soils. Cu. the variability of Zn. perspectivas de aprovechamiento. carqueisa and gorse. situación actual y magnitude lower than the USEPA (United States Environmental Pro. such as co-combustion with would expectedly occur in the case of combustion of the studied low-nitrogen and high-calcium biomasses. Miles Jr TR. Padouvas E. alkali metals contents in the ashes. Conclusions Autoridade Nacional Florestal. Fuel species of the studied genus. Biomass Bioenergy 1996. and fur- evaluation of forest residues originated from shrub species in Galicia. Preventive measures.328:105–10.88:2106–12. and under a variety of soil types. Anal Chim Acta 2005. resulting in a potential NOx emis. Thermochim. Lisboa. respectively.4 GJ m3).744 H. ent combustion technologies. Monografías INIA. Co. species at the two areas of study. Some of the performed and Eng. Ni and Cu in bottom Biomassa dedicadas.6–2%) and a rel. 0–25. 1997. Estatísticas dos incêndios florestais. Cr. Mn. Estimativa de Emissões Selected native woody shrub species from NW Spain and central Atmosféricas Originadas por Fogos Rurais em Portugal. Ministério da Agricultura do Desenvolvimento Rural e das Pescas. Direcção Geral de Geologia e Energia. might deserve future investigation. should also be further explored for these and other native As. p. Gobierno de España. whereas typical trace elements References contents found in forest residues ash should present no risk. 138. met neither by some of the observed values in shrub ash. Montero I. suggesting countries such as Finland. Silva Lusitana Portugal white broom. heating value and associated energy density variations study under Silva Lusitana 1993. 2010. Energy under forest mineral soils in Mediterranean countries [28]. Hernando C. [14] Demirbas A. [12] Fernandes PM.2 GJ m3) and winter harvest scenario (1. Appl Energy 2010.10:125–38. particularly given ability of ash agglomeration and fusion in the boiler. [15] Friedl A. Denmark. The potential influence of logistics. 19. The measured values are compared to the limit and seasons of harvest. the scarcity of boiler-scale combustion studies for shrubby bio- Furthermore. Vassileva CG. A new method to estimate fuel surface area. combined with a high (20–30%) biomass fuel from elemental composition. Zn and Ni were similar to the usual Acknowledgements ranges of 3–60. Pitman [27] pointed out that. Viana et al. Rui Rocha from Leco laboratory for the assis- most conservative thresholds established by North and Central tance in elemental analysis. 15–4400 and 6–200 mg kg1. combustion conditions should be conducted. Austria. The authors would like to sincerely European countries for Cd (<1.1:237–60. Ministério da Agricultura do Desenvolvimento Rural e das Pescas. 1989. [17] Miles TR. . Research on actual emis- gether with decreasing alkaline earth metals generally result in sions and slagging and fouling risk of the studied fuels under real lower ash sintering and fusion temperatures. The applied dose and ash form plays an important 2020. Baxter LL.5 mg kg1). Measured contents of ash As. Boiler sions. Cr thank the anonymous reviewers for their highly productive sug- (<100 mg kg1). 68. Zn and Ni. / Fuel 102 (2012) 737–745 species: as illustrated by [20]. They also would like to thank Eng. established by Spanish and Portuguese current legislation for all Cristóvão Santos from Mechanical Department of the University the studied elements and below the limits from most of the Euro- of Trás-os-Montes and Alto Douro where calorific analysis were pean countries legislation as summarized in Table 7. 10–250. Rotter H. Rego FC. GIS-based analysis of geographical availability and locations of wood- dinary boilers result in heavy metal soil levels still two orders of fired power plants in Portugal. sintering [18]. [4] Bermúdez J.62]. heath. Prediction of heating values of atively high (1–2%) ashes content. Cr. in the region. Turismo y Comercio. long-term research in [5] Miranda MT. Pb. energy. Mn. increased alkali metal contents to. Baxter D. [3] Viana H. Ministerio de Industria. 24 MK kg1) and interesting energy density values both under a [11] Elvira LM. values for these elements established by the legislation on ash uti. Lopes D. Oden LL. Pereira J. Aranha J. programme [61.27–29. Piñeiro G. Acta 1999. Cd.91:215–21. [7] AFN. Sweden and UK as potential of the biomass ashes to be utilized as fertilizer. La biomasa forestal en Galicia. Cd. 1–20. Varmuza K.27–29. Further work may focus on detailed moisture content. Boiler-scale combustion tests of additives on the combustion of the studied species under differ- should be conducted to discriminate the actual slagging and foul.62]). An overview of the chemical composition of biomass. measured for all of the studied [16] Vassilev SV.2–3. Andersen LK. Energetic characterization of ecological effects of ash application is scarce [27–29]. would not be gestions for improving the manuscript. this synthesized in Haglund [58]. commonly found in Authors would like to express their acknowledgements to the wood and bark ash for these elements as reported in the literature Portuguese Science and Technology Foundation (FCT). Rojas S. such as high HHV (21– [10] Núñez-Regueira L. bed agglomeration mass fuels. and Zn (<1500 mg kg1). measured in the ashes of woody shrubby species in the region.87:2551–60. fouling [17] and bed agglomeration [44] risk deposits from firing biomass fuels. [8] AFN. FloreStat.5:27–40. Lisboa. 15–650. Arranz JI. or the incorporation species in fludized-bed reactors. enhancing the prob. [28] and [29]. Estratégia Nacional para a Energia. Measured trace and selected minor elements were below na- lization as a fertilizer in agriculture and forestry from European tional and most European thresholds for these metals. Assessment of forest biomass for use as Pitman [27] noted that applications of ash up to 10 t ha1 from or. Pb and Co. different harvesting season and logistic scenarios.to- quantification of calorific values for other native shrubby woody volume ratio using water immersion. Mouriño B. ing risk of the studied shrub species ashes under different combus. advantageous properties as biomass fuels.76:431–4. 1000–30000. The Spanish [59] and Portuguese requiring a comprehensive environmental monitoring of fly and [60] currently existing legislation with limiting values for these bottom ashes obtained under a variety of combustion technologies elements is established for sludge from water treatment plants in. ash poses a risk of exceeding permissible levels if ash is applied in [2] Plan De Acción Nacional De Energías Renovables De España (PANER) 2011– large quantities.

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