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Article history: The explosion features of nicotinic acid dust in atmosphere of methane and air at different concentrations of
Received 4 February 2010 either dust or gaseous fuel are studied. Experimental measurements of the pressure history, deflagration
Received in revised form 15 July 2010 index and flammability limits are performed by the standard 20 l Siwek bomb though adapted for such hybrid
Accepted 30 August 2010
mixtures.
Available online 7 September 2010
Data show non linear effect of explosion severity and the synergistic effects when hybrid mixtures explode.
Results allow the definition of five different regimes of the gas/dust/air mixture explosion in the plane dust
Keywords:
Dust explosion
concentration vs. fuel concentration.
Hybrid explosion © 2010 Elsevier B.V. All rights reserved.
Nicotinic acid
Deflagration index
1. Introduction shown that if methane or propane is admixed to PVC dust in air, the
lower explosion limit of the dust/gas/air mixture decreases with
More than one century ago, in 1885, Engler [1] observed that increasing the gas concentration by a second order equation which is
mixing coal dusts with methane at a concentration lower than the known as the curve for flammability limit of hybrid mixtures.
methane lower flammability limit (i.e. 2.5% in air), would allow the The data of Gaug, as referred by Hertzberg & Cashdollar [14], for
explosion of the dust/gas mixture, hence producing unexpected hydrogen addition to cornstarch dust, also have showed significant
hazardous conditions. deviation from Le Chatelier's relationship, thus indicating that a
Since that, many studies have been performed to reveal the origin higher amount of dust is required to render the system flammable
of such behaviour and also to measure the ignition propensity of such with respect to that predicted on the basis of Le Chatelier's Law.
dust/gas mixtures frequently named “hybrid” mixtures [2–11]. Concerning the explosion severity, the explosion parameters
The most extensive work on hybrid mixtures has involved the (maximum pressure and deflagration index) have been mea-
measurements of the lean flammability limits of coal dust with sured extensively at changing the dust and gas concentrations
methane addition [7,12]. For these mixtures, it was found that dust [11,15–18]. But it is not yet clarified whether the dust or the gas is
concentration required for flammability conditions may be predicted driving the explosion phenomena at changing the dust/gas ratio and
by Le Chatelier's Law, originally developed and adopted for homoge- the fuel/air ratio.
neous gas mixtures [13]. This curve is a straight line between the lean Dufaud et al. [15,16] have studied the influence of pharmaceutical
flammability limits for pure coal dust and pure methane, and the dusts and their associated solvent (ethanol, di-isopropyl ether,
weighting factor for each fuel is its content in the mixture. toluene) concentrations on maximum pressure and maximum rate
Le Chatelier's law was derived by the concept of a constant limit of pressure rise. Their results on hybrid mixtures have highlighted a
flame temperature for a given class of fuels. In the case of methane and promotion effect on the combustion kinetics and on the rate of
coal dust mixtures such temperatures are comparable and then the pressure rise for poor mixtures. Furthermore, they have noticed that
linear trend is valid. the maximum value of the deflagration index is found for dust/gas (or
However, Cashdollar [8] has found some deviation from Le dust/vapors) rather than for the pure fuels, thus concluding that there
Chatelier's rule when methane mixes with Pocahontas coal, which is are more than simple additive effects on explosion severity.
characterized by low content of volatiles. Bartknecht [4] has also These studies were performed in the equipment ad hoc developed
for dust explosion tests in which ignition of the dust/air suspension is
performed by using two chemical igniters of total 10 kJ. The
contribution of the gas in the gas/dust/air mixtures with respect to
⁎ Corresponding author. explosion severity and ignitability may be significantly influenced by
E-mail address: dibenede@irc.cnr.it (A. Di Benedetto). such ignition energy.
0032-5910/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2010.08.069
82 A. Garcia-Agreda et al. / Powder Technology 205 (2011) 81–86
Experiments were carried out in triplicate: the standard deviation The data of the deflagration index from Dahoe & de Goey [24],
and the accuracy of our data are Pmax ≤ ± 5% and KSt ≤ ± 15%. Cashdollar et al. [25] and Mashuga & Crowl [26] are also shown, but a
significant difference is found due to the highly turbulent conditions,
2.2. Theoretical evaluation which establish inside the bomb at a delay time tv = 0 used in the
present paper.
The measured peak pressures of the mixtures dust/air and The adiabatic pressure as calculated by means of the CEA code is
methane/air were compared with the theoretical adiabatic pressure. also shown. The calculated values are higher than the peak pressure
Such parameter was computed by means of the CEA (Chemical measured due to the effect of heat losses.
Equilibrium with Applications) thermo-equilibrium code [23].
Furthermore, we calculated the equilibrium volatile content and the 3.2. Nicotinic acid explosion
volatile product distribution of nicotinic acid by using the CEA code.
The CEA code allows the calculation of the equilibrium conditions The nicotinic acid is an organic compound classified as a B-vitamin.
by minimizing Helmholtz energy at constant temperature and It belongs to the B-vitamin sub-class known as Niacin (Vitamin B3),
volume; or by minimization of Gibbs free energy, for the chemical with the molecular formula C6H5NO2 (Fig. 3). It is used mainly in
equilibrium at constant temperature and pressure. pharmaceutical industries and also is a reference dust for testing dust
explosion.
3. Results The sample structure has been analysed by means of scanning
electron microscopy. SEM images of nicotinic acid, reported in Fig. 4 at
In the following we report the explosion results obtained in our two different magnifications, show that the sample is composed of
equipment for each fuel (methane and nicotinic acid) and then we smooth-faced prismatic particles.
discuss the results of the explosion behaviour of their mixture at Details of the granulometric distribution of the nicotinic acid are
changing the CH4/nicotinic acid ratio. given in Table 2.
The simultaneous TGA-DSC test (N2 flow rate of 100 ml/min;
3.1. Methane explosion heating rate of 20 °C/min) carried out on the nicotinic acid sample
revealed the absence of moisture in the dust. Furthermore, in the
The explosion behaviour of methane has been widely studied and explosion tests we used cylinder dry air rather than ambient air.
it is well known in the literature. The complete combustion of the nicotinic acid is the following:
Conversely, few papers deal with the explosion behaviour measure-
ments of methane/air mixtures in the standard conditions of dust/air 2C6 H5 NO2 þ 25=2O2 →12CO2 þ 5H2 O þ N2 : ð1Þ
explosion in the 20 l bomb, at quiescent conditions [24–27].
In the present work the ignition of methane/air mixtures is
From this equation, it is possible to calculate the stoichiometric
performed at the same conditions as the dust runs (gas mixture
dust concentration, which results in C = 168 g/m3.
injection and tv = 0; spark ignition) in order to allow the comparison
In Fig. 5 the maximum pressure (Pmax,) attained in the sphere and
between the pure fuel behaviour and the gas/dust/air behaviour.
the deflagration index (KSt) are shown as a function of the dust
Fig. 2 shows the maximum pressure and the deflagration index as
concentration. It appears that the maximum value of both Pmax and KSt
measured for the methane/air explosion with respect to the fuel
is attained at about C = 600 g/m3, which is much higher than the
concentration. The literature data for the deflagration index as reported
calculated stoichiometric value, C = 168 g/m3. These data are similar
by Senecal [27], Bartcknect [28] and NFPA [29] are also given. These
to those found in the literature [15,30–32] and reported in Table 3. In a
values were obtained in apparatus different from the 20 l spherical
previous paper Di Benedetto and Russo [33] showed that the
bomb and are significantly lower than those found in our experiments.
explosion of dust can be modelled as the explosion of its volatiles.
In order to get insights into this difference, we have calculated the
thermodynamic distribution of the volatiles of nicotinic acid by using
the CEA code. In this regard, we have found that in the range of
temperatures from 700 °C to 1800 °C the volatile content ranges from
25% up to 26% in weight. This result definitely agrees with the ratio
between the stoichiometric dust concentration and the value at which
the maximum pressure and deflagration index occur (168/
600=0.28). In the following the experimental data are compared
with the thermodynamic values estimated at the respective equiva-
lent dust concentration Ceq calculated as follows:
Ceq = C = f ð2Þ
Fig. 4. SEM images of nicotinic acid at 2500 × (up) and 8000 × (down) magnification.
(f = 0.26). The factor f is here defined as the dust “equivalent” In Fig. 7 the corresponding data of the deflagration index are given.
concentration, according to the volatile content. The results plotted suggest that in the range of concentrations
In the experimental conditions of this work we found that the investigated, the presence of methane in a cloud of nicotinic acid
minimum explosive concentration (MEC) of the nicotinic acid is equal makes the dust more violent and reactive than the pure nicotinic acid.
to 125 g/m3. This value is higher than those found in the literature Conversely, in the conditions here investigated, it seems that the
(Table 3); this difference is probably related to the weak ignition here methane/air mixture explosions (C = 0) are much more severe than
used (spark ignition instead of chemical igniters). that of the methane/nicotinic acid/air mixtures.
In Fig. 5 the adiabatic pressure as computed by CEA is also showed. At dust concentrations below the MEC (C = 30 and 60 g/m3), the
These data are shifted in the concentration range by the factor f nicotinic acid alone is unable to ignite, but the presence of methane
(Eq. (2)). activates the explosive reaction. At dust concentration equal to the
MEC (C = 125 g/m3), the presence of methane has a significant impact
on the violence of explosion: the deflagration index increases (from
3.3. Explosion of nicotinic acid/methane air mixtures 20 to 470 bar m/s) about 20 times when increasing the methane
content from zero up to the LFL (6%).
The explosion behaviour of the methane/nicotinic acid mixture in At values of the dust concentration higher than the MEC value
air has been investigated in the conditions close to the minimum (C = 190 and 250 g/m3), the presence of methane increases the
concentration values of both methane (1% up to 7.3%) and nicotinic violence of explosion, but its influence is less significant (the
acid (30 g/m3 up to 250 g/m3). deflagration index goes from 80 up to 490 bar m/s and 120 up to
In Fig. 6 the maximum pressure is plotted vs. the methane 410 bar m/s respectively). As a result, the sensitivity of nicotinic acid/
concentration at six values of the nicotinic acid concentration in the methane/air mixtures to methane content in the non-flammable
range C = 0–250 g/m3. region of methane (bLFL) decreases when the dust concentration is in
When the dust concentration is lower than MEC = 125 g/m3 the flammable region.
(C = 0, 30 and 60 g/m3), ignition is observed at CH4 concentration It is worth noting that an inversion occurs: at dust concentration
higher than 3.6%. On further increasing the methane content the higher than MEC and at low values of the methane content, the
mixture is ignited, even if both the fuels are below their flammability highest value of the deflagration index is at the lowest dust
(or explosibility) limits. concentration; conversely, at high values of the methane content,
At MEC = 125 g/m3, the maximum pressure is slightly dependent
on the methane content. At higher values of dust concentration (190,
or 250 g/m3) the maximum pressure seems to be almost independent
on the methane content.
From these results it appears that when methane concentration is
lower than lower flammable limit (LFL) the thermodynamic para-
meters become less sensitive to the methane content when dust
concentration goes from non-flammable concentration (C b MEC) to
flammable concentration (C N MEC).
Table 2
Granulometric distribution of nicotinic acid.
Table 3
Literature data of nicotinic acid.
Pmax (bar) KSt (bar m/s) MEC (g/m3) C@ max (g/m3) Ignition Ref.
the highest value of the deflagration index is at the lowest value of the
dust concentration.
From these results it can be concluded that methane and nicotinic
acid have comparable thermodynamic pressure and then temperature
(Fig. 6). Conversely, the kinetic behaviours (Fig. 7) are quite different.
Fig. 6. Maximum pressure as a function of the methane content at different values of the
nicotinic acid concentration ( spark ignition, tv = 0). Fig. 8. Explosion regimes in the plane methane content/nicotinic acid concentration.
86 A. Garcia-Agreda et al. / Powder Technology 205 (2011) 81–86
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Acknowledgement
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