1 Article

2 Investigation of the Olive Mill Solid Wastes

3 PelletsCombustion in a Counter- Current Fixed Bed
4 Reactor
5 Mohamed Ali Mami1, Hartmut Mätzing2, Hans-Joachim Gehrmann2, Dieter Stapf 2,
6 Rainer Bolduan3 andMarzouk Lajili1*
7 1 University of Monastir, Preparatory Institute of Engineering Studies of Monastir (IPEIM), Ionized and
8 Reactive Media Studies Research Unit (EMIR), 15 Avenue Ibn El Jazar Monastir 5019, Tunisia;
9 [email protected]
10 2 Karlsruhe Institute of Technology (KIT), Institute for Technical Chemistry (ITC), Hermann-von-
11 Helmholtz-Platz 1,76344 Eggenstein-Leopoldshafen, Germany,[email protected];hans-
12 [email protected]; [email protected]
13 3 EIFER - European Institute for Energy Research, Karlsruhe Institute of Technology (KIT), Emmy-Noether -
14 Str. 11, 76131, Karlsruhe, Germany; [email protected]

15 * Corresponding author: [email protected]; Tel.:+216-73500277/GSM +216-97369126

16 Abstract:Combustion characteristics and gaseous emissions of olive mill solid wastes pellets:olive
17 pomace(OP) and olive pits(OPi) were carried out in an updraft counter-current fixed bed. Along the
18 combustion chamber axis and under a constant primary air flow rate, gas mixture components such
19 as O2, organic carbon (Corg), CO, CO2, H2O, H2, SO2, and NOx(NO + NO2) were analyzed and
20 measured. Also, the bed temperatures, and the mass loss rate were measured in function of time,
21 whereas, the reaction front positions were determined as well as the ignition rate and the reaction
22 front velocity. It was found that the exhaust gases are emitted in acceptable concentrations comparing
23 to the combustion of standard wood pellets presented in the literature (EN 303-5). It is shown that
24 the bed temperature increased from the ambient value to a maximum value ranging from 750 to
25 1000°C in accordance with what was previously published in the literature. The obtained results are
26 encouraging for considering olive mill solid waste pellets as promising alternative biofuels for heat
27 and/or electricity production.

28 Keywords: Olive Mill Solid Wastes (OMSWs); fixed bed combustor; pellets; combustion parameters;
29 gaseous emissions

30 1. Introduction
31 Agro-industrial by-products seem to be a pragmatic path for providing a diminution of the CO2
32 and NOxemissions in comparison to fossil fuels [1-3].Among these by-products, Olive Mill Solid
33 Wastes (OMSWs) which are generated in huge quantities present serious environmental problems
34 for leading Mediterranean countries in olive oil industry such as Spain, Italy, Greece and Tunisia.
35 However, these lignocellulosic biomasses constitute a promising source of renewable energy
36 [4,5].Indeed, these residues can be separated as olive pomace (OP) and olive pits (OPi). Olive pits
37 (OPi) are among the most important bio-fuels in Spain [6] and most of it was used in combustion
38 processes in order to produce thermal energy [7], owing to its low moisture content, high heating
39 value, uniform size and high bulk density [8]. Using this material as a biofuel, can be economically
40 viable and offers an alternative to the industry instead of using the fossil fuels [9].Despite this, there
41 are few studies which have been dedicated for analyzing the components and valorizing the olive
42 stones in an energy conversion process [5]. Nevertheless, the utilization of olive pomace as a
43 combustible is highly appreciated [10,11].Besides, mechanical densification of OP and OP iallows the
44 manufacturing of cylindrical pellets (15-30 mm length and 5-6 mm diameter) which is a suitable path

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 Energies 2018, 11, x FOR PEER REVIEW 2 of 18

45 for solidbiofuels production because of the high energy density and the economic viabilityat
46 competitive costs [12,13].
47 Indeed, the combustion behavior of these pellet types either mixed with other residues or only
48 derived from the OMSWs has been studied in small powered pellets boilers (<50 kW).These
49 investigations have shown that olive solid residue pellets are ecologically beneficial and, they can be
50 considered as an environmental friendly energy source for producing heat and/or electricity [14-16].
51 However, the combustion of such biofuels in fixed/fluidized beds was rarely reported in literature.
52 Furthermore, these high calorific pellets have not been commonly used in large-scale combustion
53 systems until now.
54 González et al.[14] have studied the combustion of different pellets made from olive stones (olive
55 pits), tomato and cardoon (Cynaracardunculus) in a mural boiler used for domestic heating (11.6kW).
56 The results were compared to the forest wood pellets recommended as standard fuels. The authors
57 have shown that when using olive stones pellets, characterized by lower percentages of S and N
58 contents, they obtained a significant decrease of NO x and SO2 emissions. These biofuels represented
59 the most favorable and attractive fuels from an environmental point of view by comparison to the
60 tomato, the cardoon and the forest wood pellets.
61 In fact, Miranda et al.characterized the combustion of OMSWs such as olive kernels (pits or
62 stones), olive pomace and pulp separately in their original state[17]. They have carried out the
63 combustion tests in a prototype furnace in order to analyze the main associated emissions: CO,
64 CO2,NOx, N2O, SO2, and O2. They concluded that the olive kernels and olive pomace combustion
65 presented a good efficiency. Due to the high importance of the subject,some laboratories are currently
66 investigating in fixed/fluidized beds reactors in order to simulate the combustion process of
67 industrial plants fed with these solid biofuels [18]. The choice of the fixed bed reactor is based on its
68 simplicity model, but allowing the determination of the independent characteristic numbers, needed
69 for the scale up to industrial energy supply [19-21].
70 To the best of our knowledge, the combustion of olive solid residues as OP and OPi in a counter-
71 current fixed bed reactor was not reported yet in literature. Therefore, combustion pellets tests were
72 carried out in the 40 kW batch fixed bed reactor “KLEAA” at KIT (Germany) [22,23]. In order to
73 measure the combustion characteristics of these samples, the axial temperature evolution in the bed
74 was measured. This allows determining the position of the reaction front in function of time during
75 the combustion process. In addition, the mass loss is measured continuously. Also, gaseous emission
76 as CO, CO2, H2, H2O, O2 and organic carbon (Corg) were analyzed and measured as well as some
77 highly pollutant products: SO2 and NOx (NO+ NO2). Consequently, scale independent characteristic
78 numbers such as reaction front velocity uRF, ignition rate IR, mass conversion rate MCR and specific
79 heat release rate HR were derived. These specific numbers can serve to quantify and to assess the
80 combustion quality. All obtained results are compared to similar studies in the literature and also to
81 the standard wood pellets (EN-303-5).

82 2. Materials and Methods

83 2.1. Samples preparation

84 Olive pomace (olive cake) OP and olive pits OPi used in this study were obtained from Zouila
85 Oil Press Company located in the Sahel region of Tunisia (Mahdia-Tunisia). About 6 kg pellets were
86 prepared from the biofuels at EIFER (European Institute for Energy Research, Karlsruhe, Germany):
87 100% olive pomace (OP) with a die compaction rate of 1:5 (conical pressing) and 100% olive pits (OPi)
88 with a compaction rate of 1:4 at 24 mm press channel length both. The used pellet press is a Kahl lab
89 scale flat matrix press 14-175 (with a maximum olive pellet production in the range 15-20 kg/h). The
90 specific optimum rotation frequency was determined to be 85 Hz and the optimum temperature for
91 stable pellets in literature was 75°C. The pellets were in compliance with the German and European
92 standards (EN 303-5, EN 17225-6). After pelletization and air-cooling, the pellets were stored for 24 h
93 under room conditions in order to equalize any moisture differences as shown in Table 1.
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94

95 Table 1. Operating pelletization condition

Pelletizer performance 100% olive pomace(OP) 100% olive pits(OPi)

Pelletizing temperature(°C) 60 51

Biomass moisture (% w.b.) 14.7 15.3

Pellet moisture (% w.b.) 12.4 13.7

96 (% w.b. is the percentage on wet basis)

97 Table1 indicates that the moister content decreases after pelletization. This decrease is due to the
98 evaporation caused by the rising of temperature during the pelletization process. Finally, the
99 obtained products are moisture-balanced cylindrical pellets of 6 mm diameter and 20-30 mm length.

100 2.2. Samples characterizations

101 2.2.1. Raw samples characterizations

102 Ultimate and proximate analysis of the raw samples as olive pomace (OP), olive pits (OPi) and
103 sawdust (S) are summarized in Table 2.

104 Table 2.Raw materials characteristics

Samples Equivalent Ultimate analysis Proximate analysis

formulad.b.a.f.a (% d.b.) (% d.b.)
%C %H %O %N %S %ash %FC %VM

Olivepomace(OP) CH1.54O0.56N0.024 52.2 6.7 39.6∗ 1.5 0.08 5.1 18.9* 76

Olive pits (OPi) CH1.97O0.92N0.018 41.4 5.2 50.89∗ 0.91 <0.2 0.8 15.2* 84

Sawdust (S) CH1.49O0.6N0.0035 51.5 6.4 41.9∗ 0.2 0.01 0.5 14.5 75

Spruce wood[24,25] CH1.41O0.59N0.0033 51.9 6.1 40.9∗ 0.3 0.3 1.7 18.1 80.2

Wood [26,27] CH1.46O0.6N0.0016 51.6𝑏 6.3b 41.5𝑏 0.1 0.1b 1 17 82

PalmKernels[3,27] CH1.52O0.58N0.038 51 6.5 39.5 2.3 0.27 5.2 17.5 77.3

OP (Turkish) [28] CH1.36O0.53N0.021 51.3 5.85 36.9 1.27 0.08 4.51 17.9 71.17

OP(Italy)[29] CH1.57O0.91N0.034 44.2 5.8 48.2 1.8 - 5.4 29.6 65

OPi(Spain)[17] CH1.71O0.57N0.0009 52.2 7.48 40.0 0.06 <0.1 0.56 18.5 80.94

OPi(Spain) [30] CH1.6O0.82N0.0019 44.80 6 49.09∗ 0.1 0.01 1.4 13.8 74.4

105 % d.b. is the percentage on dry basis

106 *Calculated by difference: %O=100-(%H+%C+%N),
107 %FC = 100 – (%ash + %VM),
108 adry basis ash free

109 bAverage value

110 - Not determined

111 Tables 2 and 3 show the ultimate and proximate analyses and the energy characteristics of the
112 used raw materials. These characteristics are compared with those found in literature for different
113 agro-industrial wastes. All analyses were carried out at the Chemical and Microbiological Institute
114 UEG GmbH (Germany). Ultimate, proximate and energy contents were made according to the
115 standards analytical methods for solid fuels.HHV is measured by the calorimetric bomb and the LHV
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116 is then calculated using(Eq. 1).The energy density (ED) is obtained by the multiplication of the bulk
117 density 𝜌𝐵𝐷 and the low heating values (LHVs) (Eq.2).

118
9%𝐻+%𝑀
119 𝐿𝐻𝑉 = 𝐻𝐻𝑉 − 𝐿𝑣 (
100
) (1)

120
121 𝐸𝐷 = 𝜌𝐵𝐷 × 𝐿𝐻𝑉 (2)
122

123 Table 3.Energy contents in the raw materials

Samples LHV (MJ/kg) 𝝆𝑩𝑫 (kg/m3) ED (GJ/m3)

Olive pomace(OP) 17.9 539 9.6

Olive pits (OPi) 17.29 764 13.20

Sawdust (S) 16.4 103 1.689

Spruce wood[24,25] 18.1 105 1.9

Palm Kernels[26,27] 17.0 500 8.5

OC (Turkish)[31] 19.6 591 11.58

OC (Jordan)[32] 23.056 558 12.86

OPi (Spain) [33] 14.7** 651.9** 9.85

Oke(Greece) [34] 19.36 573 11.09

Rice Husks [35] 14.9 200 2.820

124 OC: Olive cake, Oke: Olive kernels

125 ** As received

126 Furthermore, Table 2 shows higher Nitrogen contents for OP and OPi by comparison to sawdust
127 (0.2%) and wood (0.1%). This further will be responsible of the higher nitrogen oxides emissions.
128 In addition, the ash content in the two samples (OP and OPi) seems to be higher (3% and 4.7%)by
129 comparison to 0.5% for sawdust. For the two samples,the Energy density is higher than many
130 biomasstypes in Table 3. Hence, the pelletization process is an officially compulsory process allowing
131 at the same time the increase of the energy density and making biomass biofuels easier to transport
132 and storage with a higher hardness anddurability [36,37].

133 2.2.2.Pellets samples characterizations

134 Two pellets samples were prepared from the olive pomace and olive pits samples as 100% olive
135 pomace (OP) and 100% olive pits (OPi).The main chemical characteristics of the produced pellets are
136 summarized in Table 4. These obtained analyses are compared to the current standard wood pellets
137 and to other pellets in literature.We observes that the prepared pellets show typical compositions
138 when compared to other biomasses available in the literature [16,17,38].
139 The ash content was determined using a muffle furnace for which the temperature is fixed at
140 815°C.One noticed that the obtained values remain inferior to those fixed by the European
141 normalization (<5%).In addition, Nitrogen content,respecting the EN-15104 normalization, is
142 respectively 1.26% for OP and 0.61% for OPi. These values are relatively higher than 0.11%obtained
143 for wood pellets. For the sulphur content, there isn’t any problem (<0.1% for both samples).

144
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145

146 Table 4.Pellets characteristics

Samples Equivalent Ultimate analysis (% d.b.) Proximate analysis

formulad.b.a. (% d.b.)
f.a

%C %H %O %N %S %ash %FC %VM

100% OP CH1.3O0.57N0.021 49.5 5.4 37.92∗ 1.26 <0.1 2.9 17.7* 79.4

100% OPi CH1.65O0.74N0.011 46.5 6.4 46.49∗ 0.61 <0.1 1.9 15.7* 82.4

wood CH1.4O0.63N0.002 46.3 5.4 39.4 0.11 0.022 0.3 24.3 75.4
pellets

OP(Spain) CH1.52O0.49N0.032 51.48 6.56 34.8 1.98 <0.1 5.55 17.28 77.18
[16]

OP(Spain) CH1.65O0.47N0.007 4 6.4 25.4 0.4 0 2.3 16.2 72.7

[17]

147 *Calculated by difference

148
149 Table 5.Energy contents in the pellets samples

150 Samples LHV 𝝆𝑩𝑫 (kg/m3) ED Du

(MJ/kg) (GJ/m3)
(% w.b.)

100% OP 19.02 820 15.59 88.02

100% OPi 18.38 785 14.42 85.11

wood pellets 17.45 660 11.51 89.6

OP (Spain)[16] 20.36 780 15.8 -

OP(Tunisia)[38] 19.23 920 17.69 -

151
152 In Table 5 the LHV values are ranging between 17.45 and 20.36 MJ/kg. The energy density values
153 of our samples seem to be encouraging (14.42 GJ/m3 for OPi and 15.59 GJ/m3 for OP).On the other
154 hand, the durability (Du) which is determined in function of the percentage of fine particles leaving
155 the pellets after appropriate mechanical tests shows acceptable percentages with high regression
156 factor (R2=0.985)[39]. Indeed, the durability is a physical property which ensures us about the
157 prepared pellets to be easily handled during its transport and storage without big problems[40].
158 Values of durabilityforboth prepared samples(OP) and (OPi) are in the same range of the standard
159 wood pellets. Also, obtained durability(88 - 89%) for the peanut hull pellets for which the moisture
160 content varied between 6% and 13%,is in agreement with our results [41].

161 3.Combustion Test

162 The experimental studies were carried out in a batch fixed bed reactor (KLEAA) characterized
163 by a nominal power of 40kW. This device is located at the Institute for Technical Chemistry (ITC) at
164 the Karlsruhe Institute of Technology (KIT) in Germany.
165 The counter-current fixed bed reactor KLEAA hasthree main components: the combustion
166 chamber with the fixed bed and a heated furnace, the post combustion chamber (secondary
167 combustion chamber) and the flue gas cleaning system, which incorporates a heat exchanger, a bag
168 filter and a carbonabsorber.
 Energies 2018, 11, x FOR PEER REVIEW 6 of 18

169 The facility is suited to perform tests of several kilograms of solid fuel samples. The fuel bed
170 has a volume of 10 liters. The furnace and the secondary combustion chamber can be heated
171 electrically up to a temperature of 1100°C. The major components of the installation are represented
172 schematically in Figure 1. A more detailed description of the facility is available elsewhere [21-23].

173

174 Figure 1.Sketch of the KLEAA fixed bed facility at ITC, Karlsruhe, Germany.
175
176 The fixed bed has a height up to h = 250 mm and a diameter d = 230 mm. It is equipped with
177 thirteen K-type thermocouples which are arranged in 20 mm intervals along the chamber axis in
178 order to measure the central bed temperature as shown in Figures2a and 2b.

179
180 Scheme 1. The fixed bed reactor

181

182 Two experimental tests were performed with the biofuel pellets:
183  3.5 kg of 100% olive pomace (OP).
184  3.75 kg of 100% olive pits (OPi).

185 The pellet samples are introduced into the combustion chamber. Then, the combustion chamber
186 is moved to be connected to the hot furnace and the fixed bed is heated by radiation from the hot
 Energies 2018, 11, x FOR PEER REVIEW 7 of 18

187 furnace wall (900°C). The primary air is supplied at the bottom of the fixed bed via a sintered metal
188 plate. The flow rate of primary air was kept constant at 10 Nm3/h corresponding to a primary airflow
189 equal to 310 kg/h/m2. The temperatures of the primary and the secondary air (25 Nm3/h) temperature
190 were about 25°C. In addition, a water-cooled pipe is used to the gases analyzers in order to transport
191 the measurement of the gas concentrations above the bed in particular in the freeboard zone. CO,
192 CO2 and H2O are analyzed by infrared techniques, Corganic by flame ionization, O2 by a paramagnetic
193 system and H2 by heat conductivity. Furthermore, the trace gases such as NO, NOx, N2O and SO2were
194 also measured at the outlet of the post-combustion chamber. CO2, CO, H2O and O2were in addition
195 determined. An appropriate heat exchanger has served to heat the water recovery system. After
196 combustion, the fly ash is emitted and collected in a special box under the grate via the ash filter. The
197 higher-pressure regulator allows imposing a depression in the plant of about 50Pa.
198 Due to the absence of similar works in literature, the obtained results will be only compared to
199 some previous experiments conducted with conventional wood pellets under almost similar
200 conditions [21-23,42,43].

201 4. Results and discussions

202 4.1. Temperature Evolution in the Fuel Bed

203 Figure 3 shows the evolution of the bed temperature against time at various bed heights from
204 the bottom during the combustion process of olive pomace (OP), olive pits (OPi) and the standard
205 wood pellets measured by the thermocouples. The temperature measurements were collected at time
206 intervals of 5 seconds.
207 Starting from the bed top to the bed bottom, the temperature profiles of the pellets samples show
208 three distinct stages: (1) the ignition delay time, (2) the main combustion phase and (3) the final char
209 combustion.
210 During the ignition delay time, the bed surface is heated up slowly. Hence, it dries and ignites
211 by the radiation heat coming from the hot furnace wall. The ignition front then propagates from the
212 top of the fuel bed downwards opposite to the direction of the gas flow [44]. The ignition delay time
213 is measured by thermocouples T2 and/or T3 (blue and pink). It is determined to be 3.5 min, 3.2 min
214 and 5.1 min, respectively(Figures 3 and 4).
215 Thereafter, the main combustion phase starts, when the flame front reaches and passes the
216 thermocouples successively, the temperature increases rapidly from ambient to almost 1000°C. We
217 observe that the temperatures rise from the initial values (25 - 30°C) to reach about 880°C for wood
218 pellets, 800-875°C for OPi, and approximately 975°C for OP.The observed overshoots of temperature
219 can be explained by the highly exothermic combustion of a small amount of carbon (coke). The arrival
220 time and the position of the reaction front are derived from the inflection point of the temperature
221 curves. After the passage of the reaction front and the collapse of the fuel bed, the thermocouples
222 record the temperature of the hot combustion gas.
223 For the time interval between 30 min and 45 min (Figures3and4), the reaction front reaches the
224 bottom of the bed and the fuel bed temperaturerises again which is due to the heat generated by the
225 residual char oxidation with air (T9, T10,T12 and T13). In this stage, some of the thermocouples may
226 have much lowertemperatures than otherswhich may be due to make faster the convective cooling
227 [45].A second difference is the reached maximum temperature level, especially during the residual
228 carbon combustion. The OP generated a higher flame temperature reaching 1200°C at the flame front
229 compared to 1090°C and 1050°C respectively for OPiand wood pellets. Thehigh olive pomace pellets
230 combustion temperature can be attributed to the higher heating value (HHV) (22.03 MJ/kg, dry basis),
231 which is strongly relatedto the carbon content in this sample type (49.5%) [38,46]in comparison with
232 the 46.5% carbon content and 19.4 MJ/kg (HHV, dry basis) for OPi [14], and 46.3% carbon content and
233 18.5 MJ/kg (HHV, dry basis) for the wood pellets[47].
234
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(c
)

235
236 Figure 3.Responses of the thermocouples to the passage of the flame front.(a) 100% olive pomace(OP);(b) 100%
237 olive pits; (c) standardbiofuel wood pellets.
238
239 During the main combustion phase, which is characterized by the combustion of the pyrolysis
240 gases, this has no effect for the heat release and the fuel bed temperatures are quite similarfor the
241 different biofuel pellets.In the char burning phase, however, the heat release (HR) can be quite
242 different due to the different amounts of residual carbon (Table 6) and consequently, the maximum
243 temperatures may differ significantly.

244 4.2. Mass Loss History in the Fuel Bed, Reaction Front Velocity
245 The analysis of the experimental results leads to the determination ofsome combustion
246 parameters such as:

247 Reaction front velocity:

248
𝑑ℎ
249 𝑢𝑅𝐹 =
𝑑𝑡
(3)
250 Mass conversion rate:
251
𝑚̇
252 𝑀𝐶𝑅 =
𝐴(1−𝑌𝑎𝑠ℎ )
(4)
253 Ignition rate:
254
255 𝐼𝑅 = 𝑢𝑅𝐹 × 𝜌𝐵𝐷 (5)
256 Specific heat release rate:
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257
258 𝐻𝑅 = 𝑀𝐶𝑅 × 𝐻𝐻𝑉 (6)
259 These characteristic numbers are of a great help in order to predict and understand quantitatively the
260 combustion process in the fixed bed.Moreover, these parameters are scale independent and can be
261 used in order to describe the combustion behavior in large industrial facilities.Theyhave been
262 determined in a similar way as they were described in the literature[22, 23, 48-50].

263 4.2.1. Reaction Front Velocity

264 The position of the reaction front is obtained from the inflection point in the temperature profiles
265 shown above. In Figures4a-c, the reaction front position is plotted versus the elapsed time and, almost
266 linear curves are obtained.This result indicates a steady, uniform propagation of the flame front. For
267 the OP and OPi the reaction front velocities were foundto be 4 mm/min and 5.06 mm/min,respectively
268 (Figures 4b, 4c), while in the case of wood pellets the reaction front velocity is almost 5.33mm/min
269 (Figure4a). The regression factor (R²) for all results exceeds 0.9.

270

271 Figure 4.Reaction front positions derived from experimental pellets tests: (a) standard wood pellets;
272 (b) 100% olive pomace (OP); (c) 100% olive pits (OPi). Experimental conditions: Primary air 10
273 Nm3/h; primary air temperature 25°C and combustion chamber temperature 900°C.

274 4.2.2. Mass Loss History

275 The mass conversion rate (MCR) is defined as the mass loss per unit area and time. It is obtained
276 directly from the measured mass of the fixed bed, and thereafter corrected by considering the ash
277 content of the fuel.
278 The ignition rate (IR)defines the quantity of fuel ignited per unit area and time due to the
279 propagation of the reaction front. This crucial parameter (IR) can be used as a scale-up parameter for
280 industrial plants and for estimating the grate position, where the reaction front reaches its limit at the
281 bottom of the fuel bed, indicating the end of the fuel combustion. In addition, the heat release rate
282 (HR) is determined from the calorific value and the mass conversion rate products (Eq.4) and
283 (Figure5)
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284 However, the specific heat release in the main combustion zone (HR I) is calculated using the
285 MCR I and the higher heating value of the fuel. In the char residual oxidation phase, this value (HR
286 II) is obtained from the MCR IIand the higher heating value of the residual coke.Besides, the HHV of
287 the coke is calculated according to (Eq.7) [51,52]:
288
289 𝐻𝐻𝑉𝑐𝑜𝑘𝑒 = 1.19 𝑌𝑐𝑜𝑘𝑒 + 14.119 (7)
290
291 Where ycoke is the mass fraction of carbon in the coke, which is approximately 0.85 for
292 lignocellulosicbiomass coke [53,54]. HHVcoke then is ≈ 30.8 MJ/kg.
293

294
295 Figure 5.Mass loss curves in the fuel bed:(a)100% olive pomace (OP); (b)100%olive pits(OPi); (c)
296 standard wood pellets. Experimental conditions: Primary air 10 Nm3/h; primary air temperature
297 25°C and combustion chamber temperature 900°C.

298 Figure5 shows the mass lossin the bed for OP, OPiand standard wood pellets in functions of
299 time. During the ignition delay time (0-3min), the mass decreases slightly. Indeed, this zone
300 corresponds to the moisture evaporation and to the start of devolatilisation. Thereafter, in the main
301 combustion phase, the mass decreases steadilyand almost linearly. In this important zone, one
302 determines the two combustion parameters described above: the mass conversion rate (MCR I) and
303 the specific heat release HR I. Finally, in the char oxidation zone, the decrease of the mass slows down
304 again. MCR II (Figure 5) and HR II (Table6) confirm this observation. It is to be reminded that the
305 parameter HR should be below 1 MW/m² in the bottom of the bed [23].
306 Nevertheless, the decrease of the heat release rate (HR II)in the third zone can be explained by
307 the small oxidation rate of carbon. Moreover, the ignition rates (IR) for OP and OPi are 0.041
308 kg/m²/sand 0.056 kg/m²/s, respectively.These values are of the same order of magnitude than the
309 standard wood pellets (0.054 kg/m²/s).

310
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311 Table6.Specification Heat Release in the fuel bed

Heat Release 100% OP 100% OPi Wood pellets

HR I (MW/m²) 1.035 0.950 0.99

HR II (MW/m²) 0.166 0.20 0.117

312

313 4.3.Gaseous emissions

314 4.3.1. Gaseous emissions analysis above the bed

315 Figure6 shows the evolution of the gas concentrations measured directly above the fixed bed
316 (called freeboard) versus the time during the combustion tests of the different samples. The
317 considered gaseous emissions are respectivelyO2 (oxygen), CO2 (carbon dioxide), H2O (vapor water),
318 H2 (dihydrogen) and Corg(organic carbon). All components are expressed in (% vol.wet basis). In
319 addition, the local air ratio constant (λ) is plotted on the right axis.
320 At the beginning of all experimental tests, only the O2 concentration in the flue gases is detected
321 in the freeboard due to the primary air supply, and then it dropped quickly from the ambient level
322 21% to zero percent. At the contrary, the H2O mass flow rises due to the fuel bed drying process.
323 After 4 to 5 min, the fuel ignites. Consequently, the concentrations of CO and CO2 increases rapidly,
324 whereas, H2, Corgand H2O are liberated. Hence, the concentration of O2is significantly decreased. Also,
325 we observe that the gaseous emissions remains at a roughly constant level when the combustion
326 phenomenon progresses, this period is called the main combustion zone or the quasi-stationary
327 combustion zone[23]. During the corresponding time interval [37 min, 56 min], the reaction front
328 reached the bottom of the bed. Consequently, one observes again the rising of the O2 concentration,
329 while the concentrations of H2 and Corgare decreasingto their minimum levels. During this period,
330 the char residue burning is enhanced showing a little increase of CO2. In contrast, CO rises also
331 steeply with the decrease of CO2 and stabilizes between 20 and 28%. This observation can be
332 attributed to the gasification process to which the residual char is subject, especiallywith the presence
333 of CO2in the medium[21]:
334
335 𝐶 + 𝐶𝑂2 → 2𝐶𝑂 (8)
336 In this zone, the olive pomace (OP) pellets are characterized by a high emission of CO which
337 rises up to 23%by comparison to 20.2%of the OPi. But, this concentration remains quietly smaller
338 than the 24.5%for the wood pellets. However, during the combustion process, these values still
339 present the highest peaksby comparison to the CO2 emissions. This growth is maybe due again to the
340 gasification process of the residual char in presence of the water steam (H2Ov) in the medium:
341
342 𝐶 + 𝐻2 𝑂 → 𝐶𝑂 + 𝐻2 (9)
343 This reaction yields the increase of CO and H2at the same time [21, 55].Moreover, Figure 6a shows
344 that the OP presents the highest amount of CO2 (about13%)by comparison to the 11% for OPi.This
345 result is due to the high percentage of carbon content (about 49.5%) compared to the 46.5% of the
346 OPi.After a combustion time of about 43 min-70 min, all the gaseous emissions tend to zero value,
347 indicating that the fuel pellets conversion is ended.
348 Therefore, the comparison of the different pellets shows that the wood pellets (Figure 6c) have
349 the more stable emissions.Such behavior may be attributed to the lower moisture content (about
350 6.5%)by comparison to the other samples. Nevertheless, the obtained results for OP and OPi remain
351 comparable to the standard wood pellets.

352 4.3.2. Gaseous emissions analysis in the post-combustion chamber

 Energies 2018, 11, x FOR PEER REVIEW 12 of 18

353 Figure7 illustrates the distribution of the tracesof gas concentrations versus time in the flame
354 front, especially, at the outlet of the post-combustion chamber (secondary combustion chamber).
355 More exactly, we focused in this section on the analysis of NOx (nitrogen oxides), N2O (nitrous oxide)
356 and SO2 (sulphur dioxide), expressed in mg/Nm3, dry at normal temperature (25°C) and pressure. O2,
357 CO2, and CO concentrations are taken into accounts.
358

359
360 Figure 6.Concentrations of gaseous emissions analysis above the fixed bed (in the freeboard): a)
361 100% standard wood pellets, b) olive pomace (OP) and c) 100% olive pits (OPi). Experimental
362 conditions: Primary air 10 Nm3/h; primary air temperature 25°C and combustion chamber
363 temperature 900°C

364 The analysis of these figures shows that NO x emissions during the pellets combustion at the
365 secondary combustion chamber are relatively high when compared to the SO2 emission. This
366 increasing may be attributed to the combustion of fuel-N occurring in the post-combustion chamber
367 due to the higher amount of the secondary air injection. Hence, a notable increase of the temperature
368 in the medium can be at the origin of The NO formation (called thermal NO) and corresponding
369 mechanism formation is the so-called zel’dovich mechanism.
370 Furthermore, the reduction of CO is inherent to the increase of the excess air at the secondary
371 combustion chamber [56]. In contrast, Garijo et al [57] and Staigeret al. [58] indicate that an elevation
372 of the CO concentration or another carbon compound can inhibit the NO x formation due to a
373 reduction of the temperature by radiative heat absorption in the medium. In another side, NO x
374 emissions (Figure7a) of the OP showed the highest value with about 895 mg/Nm3 compared to 720
375 mg/Nm3(Figure7b) of the OPi andto almost 255 mg/Nm3(Figure7c) of the wood pellets. In fact, this
376 result is well expected because the nitrogen content in olive pomace (1.26%) is higher than wood
377 pellets (0.11%) and,than olive pits (0.61%). This observation was already mentioned in literature[59,
378 60].In addition, this NOx concentration growth can be also justified by the abundance of O2 supplied
379 at the post- combustion chamber [28]. In another side, the SO2 emissions during the combustion tests
 Energies 2018, 11, x FOR PEER REVIEW 13 of 18

380 for the pellets samples (OP) and (OPi) arepractically presented as small traces by comparison to the
381 standards biofuel (wood pellets).This fact is related to the low Sulphur contents ( ≤ 0.1)for the
382 different samples.
383

384

385 Figure 7.Trace of gases measured at the outlet of the post combustion chamber.(a) 100% OP; (b)100%
386 OPi;(c) wood pellets

387 4.3.3. Gaseous emission conversion unit

388 Obtained gaseous emissions were corrected and converted at 10% and 13% O2. The purpose of
389 this conversion is to allow comparison between our results and those found by other authors working
390 under the same oxygen ratios (10% and 13%) as it is summarized in Table7.
391 We noticed that gaseous emissions obtained in our study with a fixed bed of 40kW are in the
392 same range with other lignocellulosicmaterials.However, the obtained NOx (NO2+NO) at the post-
393 combustion chamber were 142 ppm and 116 ppm, under 10% O2 for OP and OPirespectively. These
394 values are of the same magnitude of 113 ppm NOx obtained for the standard wood pellets. However,
395 these values are higher than value obtained with the DIN plus (54 ppm at 10% O 2) [65]. In fact,
396 NOxconcentrations were obtained with small emissions (less than 30 ppm under 13% O 2) during the
397 combustion of commercial pine pellets in a domestic wood pellets boiler (22 kW) [66].Moreover, these
398 values are more or less closer to those found in literature for various pellets such as exhaust olive mill
399 solid waste (EOMSW) (115 ppm at 10% O2), and 340 ppm at 10% O2 for olive pruning pellets [67].
400 Furthermore, SO2 emissions values varied between 14 ppm-22 ppm at 10% O2 and between 10 ppm–
401 16 ppm at 13% O2 according to the results obtained from the pellets samples. Nevertheless, these
402 values are lower than the 36 ppm at 10% O2 for the Sunflower shells [68]. Roy Mohon et al. [69] have
403 shown that combustion of grass pellet and three different types of wood pellet in a prototype pellet
404 furnace (7-32kW) emitted between 0 and 7 ppm of SO2 at 10% O2.

405
 Energies 2018, 11, x FOR PEER REVIEW 14 of 18

406 Table 7.Emissions values corrected at respectively; (a) 10% O2and (b) 13% O2

Samples O2% CO2% CO1% H2O% H2% CO2 NOx(ppm) SO2

(ppm) (ppm)
100OP 11 6.84 11.58 8 7.63 a) 1446 a) 142 a) 22

b) 1054 b) 104 b) 16

100OPi 10.37 5.85 10.64 8 7.72 a) 133 a) 116 a) 17

b) 97 b)84 b) 12

Wood pellets 9.94 7 12.62 11.57 5.26 a) 46 a) 13 for N2O a) 14

b) 34 100 for NO b) 10

b)11 for N2O

73 for NO

Spent coffee 4 5 - - - a) 2456 a) 245 for NO -

ground
b) 1785 39 for N2O
(SCG) [61]
b) 178 for NO

28 for N2O

WoodDIN 12 6 - - - b) 153 b) 19 -

plus [62]

EOMSW 12 8 - - - a)795 a) 115 -

[37] b) 578 b) 85

Sawdust(S) 12 6 - - - a) 277 a) 36 -

[37] b) 202 b) 26

Sunflower 13 - - - - a) 252 a) 55 a) 36
shells[63]

French 15 6 - - - a) 277 a) 36 a) 7
Wood pellets
[63]

Pine 13.22 4.5 - - - b) 470 b) 50 -

pellets[64]

407 OMSW: Olive Mill Solid Waste, EOMSW: Exhaust Olive Mill Solid Waste
408 1At the primary combustion chamber

409 2At the post-combustion chamber

410 4. Conclusions
411 In this paper, olive solid residues (olive pomace and olive pits) have been investigated as
412 renewable and environment friendly energy sources. We focused on the combustion of the pelletized
413 biofuels in a (40 kW) counter-current fixed bed reactor in which the two samples types were
414 tested.The temperature inside the bed and the mass loss were measured. Three distinct phases during
415 the progress of the combustion process were observed: the ignition delay time, the main combustion
416 phase and the char oxidation phase. Some crucial scale independent characteristic combustion
417 parameters were determined: Thereaction front velocity, the ignition rate, the heat release rate and
418 the mass conversionrate.
 Energies 2018, 11, x FOR PEER REVIEW 15 of 18

419 It is shown that obtained results are quite similar to the results of the standard wood
420 pelletswhich are used currently in European markets.Moreover, the gaseous emissions are produced
421 in acceptable concentrations comparing to Germany and European standards.Hence, these results
422 motivatefollow-up investigations on olive solid wastes to be used as alternative biofuels for heat
423 and/or electricity production either in household or in industrial plants.
424 Acknowledgments

425 Mohamed Ali Mami would like to thank the Doctoral School of Monastir University for the Financial Support
426 of this project. Also, the author is grateful to Zouila Company (Mahdia-Tunisia) providing him the raw biomass,
427 and also, for the technical support of EIFER, European Institute for Energy Research (Bioenergy Group) for the
428 pelletization process. Finally, the author addresses deep thanks to Mr. A. Gerigand other technical team
429 members of KIT for their assistance during the experimental tests.

430 Author Contributions:All authors are directly implicated in all phases of the paper.

431 Conflicts of Interest:The authors declare no conflict of interest.

432 Nomenclautre

433 A Fuel bed cross section [m²]

434 HHV Higher heating value [MJ∙kg-1]
435 HR Heat release rate [MW∙m-2]
436 IR Ignition rate [kg∙m-2∙s-1]
437 MCR Mass conversion rate [kg∙m-2∙s-1]
438 h Bed height [mm]
439 ṁ Mass loss rate [kg∙s]
440 u Velocity [mm∙min-1]
441 y Mass fraction [-]
442 ρ Density [kg∙m-3]
443 L Latent heat [kJ∙kg-1]

444 Subscripts and Superscripts

445 ash ash

446 RF Reaction front
447 Ccoke Carbon in coke
448 BD Bulk density
449 v vaporization

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