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Renewable Energy 77 (2015) 377e385

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Particle and NOx emissions of a non-road diesel engine with an SCR


unit: The effect of fuel
€inen a, Ari Va
Mari Pietika €rvi a, *, Tanja Kolli a, Mika Huuhtanen a,
€liheikki a, Kati Oravisja
Seppo Niemi b, Sampo Virtanen c, Toomas Karhu c, Riitta L. Keiski a
a
Environmental and Chemical Engineering, Faculty of Technology, University of Oulu, P.O. Box 4300, FI-90014, Finland
b
Department of Electrical Engineering and Energy Technology, University of Vaasa, P.O. Box 700, FI-65101 Vaasa, Finland
c
Turku University of Applied Sciences, Joukahaisenkatu 3 A, FI-20520 Turku, Finland

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

Article history: Diesel engines are challenged to reduce their emissions. Nitrogen oxides (NOx), hydrocarbons, particulate
Received 12 February 2014 matter and carbon dioxide are most important regulated diesel emissions. The legislation is driving for
Accepted 11 December 2014 the use of renewable fuels in vehicles but all the impacts of those on emission control technology are not
Available online 2 January 2015
clear yet. In this study the number and chemical composition of particles emitted from a non-road diesel
engine with and without a selective catalytic reduction (SCR) unit were investigated. Common diesel fuel
Keywords:
oil (DFO) and untreated rape seed oil (RSO) were used as fuels. The NOx reduction activity of the fresh
Diesel fuel oil
SCR catalyst was also investigated. The results indicated that the fuel had a great impact on the particles
Untreated rape seed oil
Nanoparticles
emitted from the engine. The particle number was 10e100 times higher when RSO was used as fuel
Diesel engine compared to DFO. The DFO particles contained carbon in significantly higher proportions compared to
Catalysis the RSO particles. Metals, such as Fe and Cu, were also found in the DFO particles. For both fuels the NOx
Nitrogen oxides reduction activity was 79% with a SCR converter. As a conclusion, the use of the SCR converter decreased
the number of particles in general but increased the number of the nanoparticles.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction component may lead to an increase in another. One solution is to


use selective catalytic reduction (SCR) technology and to optimize
Diesel engine exhaust gas includes several substances (e.g. the combustion conditions in the engine in such a way that leads to
carbon monoxide (CO), nitrogen oxides (NOx), particulate matter the reduction of particle emissions and fuel consumption [2]. In the
(PM), sulfur oxides (SOx), aldehydes, polycyclic aromatic hydro- SCR technology a large amount of NOx emissions are reduced by
carbons (PAHs), and metals), which are resulting from the com- using a catalytic converter and urea solution. Conventionally in the
bustion process, the combination of the engine design and the fuel SCR applications for both stationary and transient emission sources
characteristics, and may be harmful to both the environment and vanadium-based catalysts are used [3,4].
human health [1]. In Europe and USA, the diesel fuel for mobile Based on the information gathered from epidemiological and
machineries contain very low amount of sulfur compounds. One of toxicological studies, air pollutants including particles from com-
the challenges in diesel engines is the simultaneous removal of NOx bustion processes are considered harmful to human health with
and particle emissions, because the technique for reducing one several health impacts such as cardiovascular and respiratory ef-
fects [5] as well as an increase in morbidity and mortality [1,6,7].
Diesel engine exhaust gas has also been classified as a human
carcinogen (Group 1) by the International Agency for Research on
Abbreviations: CO, Carbon monoxide; DFO, Diesel fuel oil; EC, Elemental carbon; Cancer (IARC) [8]. Regarding the health effects of diesel exhaust gas,
EDS, Energy-Dispersive X-ray Spectroscopy; ELPI, Electric Low Pressure Impactor;
the focus has been on ultrafine particles, but also e.g. nitrogen
FESEM, Field Emission Scanning Electron Microscope; IARC, International Agency
for Research on Cancer; NOx, Nitrogen oxides; OC, Organic carbon; PAH, Polycyclic
oxides have harmful effects on airways and on the whole respira-
aromatic hydrocarbon; PM, Particulate matter; RSO, Rape seed oil; SCR, Selective tory system such as airway inflammation in healthy people and
catalytic reduction; SOx, Sulfur oxides. increased respiratory symptoms in people with asthma [9]. Ultra-
* Corresponding author. Tel.: þ358 50 543 7323; fax: þ358 2 9448 2304. fine particles may easily penetrate deep into the lungs [11e14], and
E-mail address: kati.oravisjarvi@oulu.fi (K. Oravisj€
arvi).

http://dx.doi.org/10.1016/j.renene.2014.12.031
0960-1481/© 2014 Elsevier Ltd. All rights reserved.
378 €inen et al. / Renewable Energy 77 (2015) 377e385
M. Pietika

at this particle size, metals that are adsorbed on the surface of the measurements were carried out with a turbocharged, intercooled
particles are able to enter the body and further to blood circulation, non-road high-speed diesel engine using an Electric Low Pressure
which exposes tissues and organs to toxic effects of these harmful Impactor (ELPI) and the chemical analyses for the measured par-
species [15,16]. Along with size, also the chemical composition and ticles were conducted using a Field Emission Scanning Electron
solubility of diesel particles, as well as the particle dose, are sig- Microscope (FESEM-EDS). The concentrations of NOx were analyzed
nificant factors influencing their toxicity on human [16]. The par- using a chemiluminescence detector. Untreated rape seed oil was
ticles themselves or the components adsorbed on particles, such as chosen as a model biodiesel for this study, because it represents the
organics or metal ions, may have an ability to generate reactive “worst case scenario” and it may have its own markets in medium-
oxygen species, and thereby can cause oxidative stress in biological and slow speed power plant engines [34].
systems [17]. Especially, transition metals such as cobalt (Co),
copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), vanadium (V)
2. Materials and methods
and titanium (Ti), contribute to the oxidative capacity of PM [18].
Because of the harmfulness of diesel exhaust [8] it is extremely
2.1. Particle measurements
important to find other cost-effective solutions for energy pro-
duction and transportation. Renewable energy sources and fuel
Particle measurements were carried out in the Internal Com-
derived from those are one option since for example the EU targets
bustion Engine laboratory at Turku University of Applied Sciences
the 20% share of renewable energy in total energy consumption by
using an ELPI (Dekati Ltd, Finland). ELPI measures the particle size
2020 [19]. Due to the EU legislation [20] the use of bio-based fuels
distributions of particles from 7 nm to 10 mm of their aerodynamic
has already increased in the transport sector. Unfortunately, this
diameter. The ELPI measurement system yields particulate number
has also caused unwanted effects e.g. the NOx reduction efficiency
concentrations in 12 non-overlapping size bins covering the whole
of the vanadium-based catalysts has proven to decrease due to the
measurement size range and they are described as their mean
impurities, like phosphorus (P), calcium (Ca) and potassium (K),
values (0.021 mm; 0.041 mm; 0.077 mm; 0.128 mm; 0.199 mm;
which are present in biofuels [4,21].
0.306 mm; 0.485 mm; 0.775 mm; 1.234 mm; 1.937 mm; 3.041 mm;
The combustion of diesel-vegetable oil mixtures produces more
6.187 mm).
particles than the combustion of diesel fuel [22,23]. It has also been
In the experiments a modern turbocharged, intercooled direct-
detected that particles from the combustion of diesel and vegetable
injection non-road diesel engine was used (Table 1). For the eval-
oils differ in structural and compositional ways. Nanoparticles from
uation of particle emissions of the non-road engine the ISO 8178 E2
the seed oils appear as clusters of hollow spherules, while nano-
driving cycle was used (Table 2). The engine was loaded by means
particles from diesel fuel are composed of solid spherules [22].
of a Schenck W-400 eddy-current dynamometer. The engine loads,
Diesel particles are typically agglomerates consisting mainly of
i.e., speed and torque, were exactly the same for both fuels. The
spherical primary particles of about 15e40 nm in diameter [10].
intake air flow into the engine was determined with an ABB Sen-
Diesel particles are known to consist of a solid elemental carbon
syflow instrument and the fuel mass flow rate by means of a co-
(EC) core and a volatile organic carbon (OC) layer on the surface
riolis mass flow meter. The duration of the particle measurements
[24,25]. It has been reported that more OC and less EC have been
was 40 min including all the stages of the driving cycle. The mea-
emitted from biodiesel combustion compared to conventional
surements were conducted with a fresh SCR converter or without
diesel applications [26,27]. The biodiesel term are generally used
any after-treatment method in order to find out the effect of the
for ethyl esters or fatty acid methyl originating from vegetable oils
SCR converter on the emitted number and chemical composition of
and animal fats whose properties are good enough to be used in
particles. An aqueous urea solution, 32.5% (AdBlue®) was used as
diesel engines [28]. More research is though needed in order to
the reducing agent and it was injected into the exhaust gas stream
confirm these findings and to find out more about the chemical
before the catalytic converter. The catalytic converter has been
composition of particles from renewable energy sources.
provided by industry and the details are proprietary information.
There is a wide range of biomass available that can be used to
The sampling line of the ELPI was connected to a slipstream
produce biofuels, e.g. deriving from agricultural and forestry
from the engine exhaust through a two-stage diluter. At the first
products, as well as from residues and waste from forestry and
heated and insulated stage of the diluter, the exhaust gas was
agrifood stuffs industry [20] and therefore the used biofuels may
diluted with air at 200  C. At the second unheated stage of the
have a significant role in particle emissions. Depending on the used
diluter, the exhaust gas was diluted with air at room temperature.
fuel, particle emissions in number and chemical composition may
The dilution ratio varied with load being within 77e95 throughout
differ widely. In addition, it is important to ensure that new tech-
the measurement cycle and the sample flow of ELPI was 10.3 l/min.
nologies provide sustainable solutions in view of both human
All the measurements were carried out in the same conditions to
health and the environment. In the aspect of health effects, it is still
enable the comparison. A schematic sampling set-up is presented
unclear, whether the use of renewable energy sources can lead to
in Fig. 1.
health benefits or not. For example [29] found a remarkable in-
In the measurements a traditional low-sulfur (sulfur content
crease in mutagenicity of exhaust emissions, when using rape seed
8 ppm) diesel fuel oil (DFO) and a low-quality raw bio-oil, which
oil (RSO) as fuel compared to common diesel fuel.
was chosen to be untreated rape seed oil (RSO), were used. The
There are several articles discussing effects of renewable fuels
trace elements in DFO and RSO were analyzed in the Biofuel Lab-
on on-road diesel engine emissions e.g. [23,26,27,29] and their
oratory at the University of Vaasa. From the DFO K, Ca, P,
health aspects [29]. However, less studies have been reported
concerning the non-road engines and machineries. Emissions from
non-road diesel engines using renewable fuels have been reported Table 1
from construction machines (ethanol) [30], generators (butanol) Specifications of the used engine.
[31,32] as well as agricultural machineries (seed oil) [33]. Engine AGCO Power 49 CWA
In this research the number, size and chemical composition of Cylinder number 4
particles emitted from diesel fuel oil (DFO) or RSO fueled engine Swept volume 4.9 dm3
with and without an SCR catalyst was studied. Also NOx reduction Combustion chamber Direct injection
Injection system Common rail
activity of the used SCR catalyst was investigated. The particle
€inen et al. / Renewable Energy 77 (2015) 377e385
M. Pietika 379

Table 2 using Field Emission Scanning Electron Microscope (FESEM, Zeiss


Test cycle (ISO 8178 E2) used in particle measurements with SCR or without any ULTRA plus) equipped with Energy-Dispersive X-ray Spectroscopy
after-treatment method.
(EDS) in the Center of Microscopy and Nanotechnology at the
Speed (rpm) Load (%) Torque (Nm) Measurement time in ELPI (min) University of Oulu. Analyses were made from three different points
1500 100 700 8 of each ELPI foil. Generally, the analyses were done using area
1500 75 525 20 measurement, but in some cases only a dot analysis was possible
1500 50 350 6 due to the low amount of particles on the foil. Reliable chemical
1500 25 175 6
analyses for particles bigger than ~2 mm could not be done, because
Total 40
of the low amount of particles collected in the ELPI foil during the
measurement. The results are presented as weight percentages
(wt-%) of each element.
magnesium (Mg) and sodium (Na), and from the RSO Mg, K, Na, Ca,
P, Cu, Fe, Mn, V, aluminum (Al), silicon (Si), and zinc (Zn) were
2.3. NOx reduction
analyzed. The detection limit in the chemical analysis of DFO and
RSO was 1 ppm.
The catalytic activity measurements were conducted using the
same engine (Table 1), SCR catalyst element and fuels (DFO and
2.2. Chemical analyses of particles RSO) as in the particle measurements. The ISO 8178 E2 driving cycle
(Table 2) was also used. The concentrations of NOx were analyzed
Chemical analyses were made for the particles gathered to the using a chemiluminescence detector (Eco Physics CLD 700 EL ht C).
ELPI foils during the particle measurements. The ELPI foils are After the baseline measurements the catalyst was aged for 61 h in
mainly aluminum (Al, 99 wt-%) and iron (Fe, 1 wt-%). Analyses for exhaust gas at ~340  C using RSO as a fuel. The measurements for
determining the chemical composition of particles were performed NOx concentrations were repeated after the ageing procedure. NOx

Fig. 1. A schematic sampling set-up of the particle measurements with ELPI. The sampling line of the ELPI is connected to a slipstream from the engine exhaust through a two-stage
diluter and the departing dilution air is directed to the tailpipe.
380 €inen et al. / Renewable Energy 77 (2015) 377e385
M. Pietika

conversions were calculated for the baseline measurements and 3.3. Chemical composition of particles
after 61 h of ageing.
Fig. 4 shows elemental compositions of the particles emitted
from the DFO or RSO fueled engine equipped either with or without
3. Results the SCR converter. The results are given as mean values calculated
from the analyzed points by EDS of each ELPI foil. The most sig-
3.1. Fuel quality nificant differences in element compositions between the DFO and
RSO particles are in the proportions of carbon (C) and oxygen (O).
Table 3 depicts typical properties of the burned raw rape seed oil The proportion of carbon is remarkably lower in the RSO particles
(RSO). According to the EN ISO 6245 method, the measured ash than in the DFO particles being in average 21 wt-% and 22 wt-% for
content of RSO was 0.144 wt-%. The water content of RSO was RSO, and 71 wt-% and 64 wt-% for DFO, with and without the SCR,
500 mg/kg, the acid number 2.4 mg KOH/g, and the oxidation respectively. In the DFO particles the highest proportions of carbon,
stability index 10 h. The analyzed trace elements of DFO and RSO 87 wt-% in average, were detected in particles of 0.08e0.20 mm of
are shown in Table 4. In DFO the concentrations of all the analyzed their aerodynamic size, whereas in the RSO particles the carbon
elements were below the detection limits. In turn, RSO contained content was the highest in the bigger particles (1.2e1.9 mm) having
high amounts of Ca and P and relatively high amounts of Mg and K. an average of 31 wt-%. The proportion of oxygen in the RSO parti-
Thus, the RSO fuel used may be considered as a low-quality fuel. cles of the whole size range was in average 39 wt-%, which is higher
compared to 18 wt-% in the DFO particles. In addition, the shares of
the other elements, e.g. P, Ca, and Mg, are also remarkably higher in
3.2. Particle number size distributions and engine parameters the RSO particles, i.e. in average 16 wt-%, 15 wt-% and 4 wt-%,
respectively, compared to 2.3 wt-%, 2.6 wt-% and 0.4 wt-%,
The measured particle number size distributions are presented respectively, in the DFO particles.
in Fig. 2. According to the results it is clear that the use of RSO In Fig. 5 the wt-% of the elements (other than C and O) analyzed
produced more particles compared to DFO. When the SCR catalyst from particles emitted from engines fueled either with DFO or RSO
element was used the total emitted particle numbers during the are presented as a function of particle size. The results are given as
cycle were 1.0  108 and 2.4  109 for DFO and RSO, respectively. mean values calculated from the analyzed points of the ELPI foils.
Without the catalytic converter the amounts were 1.3  108 and The emitted particles (Fig. 5) contain the same elements which
4.0  109 for DFO and RSO, respectively. Thus, smaller amounts of are present in the fuels used (Tables 3 and 4). In general, as
particles were emitted, when using the SCR converter than without mentioned earlier, the proportions of P, Ca and Mg were higher in
any after-treatment method. Depending on the size, the number of particles emitted from the engine running with RSO than with DFO.
particles emitted from the RSO fueled engine was 10e100 times Also small proportions of K were found in the particles emitted
higher compared to the number of particles emitted from the DFO from the combustion of RSO. With the exception of Mg, the line
fueled engine. Fig. 2 shows also that the use of an SCR converter shapes of these elements are very similar with each other showing
increased the number of emitted particles only in the nucleation that the highest proportions of P, Ca and K are found in the smallest
mode size range (nanoparticles in a size range of 7e29 nm of their particle sizes when using RSO.
aerodynamic diameter). The emitted DFO particles with and The use of an SCR converter had only a minor effect on the
without a catalytic converter were 47% and 35% in the nanoparticle proportions of P, Ca, K, and Mg in particles, when using the RSO fuel.
size range (particle diameter < 50 nm), and 79% and 72% in the However, in the case of DFO, P, Ca, K and Mg are found in higher
ultrafine size range (particle diameter < 100 nm), respectively. For proportions in the particles of around ~ 0.3e0.5 mm, when the SCR
the emitted RSO particles with and without a catalytic converter, catalyst is not used compared to particles emitted with the SCR
nanoparticles contributed 19% and 17%, and ultrafine particles 72% catalyst. In all the cases the levels of K (0e0.8 wt-%) in particles
and 70%, respectively. It was also noteworthy that despite of the were significantly lower than the P, Ca and Mg levels (up to 20 wt-
particle size, the reduction level in the particle number by the SCR %).
converter is relatively similar within the detected size range. Similarity between the proportions of Si, Fe and Cu elements is
When comparing the particle number emissions generated by also seen (Fig. 5). These elements are found in particles in the cases
different fuels, the relative air-fuel ratio (lambda) has to be kept as of both fuels but the highest amounts are analyzed from the par-
constant as possible in all operating modes and for all fuels [35]. ticles bigger than 0.7 mm and smaller than 0.04 mm of their aero-
Fig. 3 depicts the lambda values at various engine loads for both dynamic size, when DFO was used without the SCR converter. The
fuels DFO and RSO. As shown, the relative air-fuel ratios were very proportions of Si, Fe, and Cu in DFO particles bigger than 0.7 mm,
similar independent of, which fuel was burned in the engine, the were in average 10 wt-%, 8 wt-%, and 9 wt-%, respectively, and in
biggest difference being 2.1%. Fig. 3 also illustrates the measured particles smaller than 0.04 mm 8 wt-%, 6 wt-%, and 10 wt-%,
brake mean effective pressures (BMEP) at each load point showing respectively. In particles emitted from the diesel fueled engine with
that the loads were almost equal for both fuels in all modes. an SCR converter, lower amounts of Si, Fe and Cu were detected.
Only in particles with a size of around 0.7 mm a slight increase in
proportions of these chemicals can be seen (Fig. 5). With the RSO
Table 3
Typical properties of the burned raw rape seed oil (RSO). fuel the SCR converter has no noteworthy effects on the amounts of
Si, Fe and Cu in the emitted particles. Zn was also found in particles
Property Unit Typical Method
emitted when RSO and diesel fuels were used. The highest pro-
Viscosity at 40  C mm2/s 32 ISO 3104 portions (6 wt-% in particles of 0.775 mm of their aerodynamic size)
Density at 20  C kg/m3 991 DIN 51757
were detected with DFO, when the SCR converter was used.
Sulfur ppm 8 ASTM D 5453
Flash point 
C >200 Sulfur (S) has its own unique shape of line compared to the other
Pour point 
C 10 ISO 3016 elements (Fig. 5). First of all, the SCR converter has an impact on
Cu corrosion 1a ISO 2160 sulfur appearance in the emitted particles. Especially in bigger
Fe corrosion 0 ISO 7120 particle sizes with both fuels more sulfur is analyzed from particles,
Iodine number g iodine/100 g 113 ISO 3961
when the SCR converter is used (with the exception at the particle
€inen et al. / Renewable Energy 77 (2015) 377e385
M. Pietika 381

Table 4
Trace elements of used rape seed oil and diesel fuel oil.

Element Mg K Na Ca P Al Cu Fe Mn Si V Zn
(mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg)

RSO 55 13 1.3 324 366 0 0 0.5 0.4 0 0 0.8


DFO < dl < dl < dl < dl < dl n.a. n.a. n.a. n.a. n.a. n.a. n.a.

n.a. ¼ not analyzed.


< dl ¼ under the detection limit.

size of 0.775 mm (DFO), when no sulfur was detected from the ELPI exhaust gas contained (depending on the particle size) 10e100
foil). It should be noted that particles emitted from the RSO fueled times higher amounts of particulates compared to the DFO's
engine contain almost no sulfur at all. Only when the SCR converter exhaust gas (Fig. 2). The 61 h ageing with the RSO fuel weakened
is used, small amounts of sulfur are detected in particles. the NOx reduction performance of the converter significantly (not
shown) since the NOx conversion over the SCR converter decreased
approximately by 60 percentage points after the ageing [36].
3.4. NOx reduction activity
4. Discussion
In Fig. 6 the NOx conversions over the fresh SCR catalyst and the
total emitted particle numbers when the SCR converter is used Diesel exhaust gas has been classified as a human carcinogen
during the measurement cycle are shown. Contrary to particle [1,8] and thus the need for alternative solutions for diesel fuel is
number size distributions (Fig. 2) and chemical compositions of obvious. Nevertheless, in case of renewable fuels, studies about the
particles (Figs. 4 and 5) the used fuel, DFO or RSO, had a negligible health impacts are rare and research on that field is required. The
effect on the NOx conversions over the studied converter. The NOx results of this study clearly show that the amount and composition
conversions were the same for RSO and DFO, although RSO's of particles in exhaust gas are dependent on the used fuel, rape seed
oil (RSO) or regular diesel oil (DFO). Because of the observed dif-
ferences in particle number concentrations of exhaust gas the use
1E9 of RSO and DFO will result in different kinds of particle deposition
Particle number dN/dlogDp (1/cm3)

and, therefore differences in toxic and carcinogenic effects on hu-


1E8
man body. The difference in fuel properties between DFO and RSO
1E7 also affects the differences in NOx reduction activity and deactiva-
tion of the catalyst.
1000000 Higher amounts of particles are emitted from the RSO fueled
engine than from the DFO fueled engine, and therefore more par-
100000
ticles are able to enter to the respiratory system [13e15]. Thus,
10000 DFO (without catalyst) when particles from engine driven by the RSO fuel are inhaled a
DFO (SCR catalyst) higher health risk is implicated compared to DFO. According to
1000 RSO (without catalyst) recent studies most of the inhaled diesel particles deposit in the
RSO (SCR catalyst) deepest parts of the human respiratory system because of their
100 small size [13,15]. In general, fewer particles are emitted when a
catalytic converter is used than without from both RSO and DFO
10
0,01 0,1 1
fueled engines. In the nanoparticle size range (7e29 nm of their
aerodynamic diameter) though, the use of an SCR converter leads to
Particle size (μm)
an increase in the number of emitted particle. These particles may
Fig. 2. ELPI number size distributions for particles emitted from DFO and RSO fueled be formed after the SCR system by nucleation from the gaseous
engines. exhaust components [37,38]. This leads also to a probability for a

Fig. 3. Relative air-fuel ratio and brake mean effective pressure (BMEP) of the engine at different engine loads for both fuels, diesel fuel oil (DFO) and rape seed oil (RSO).
382 €inen et al. / Renewable Energy 77 (2015) 377e385
M. Pietika

Fig. 4. The elemental compositions of DFO and RSO particles when using an SCR converter and without it. The results are presented as mean values from each size range (ELPI foils).
The ELPI foils correspond to particles sizes as follows: 1 ¼ 0.041 mm; 2 ¼ 0.077 mm; 3 ¼ 0.128 mm; 4 ¼ 0.199 mm; 5 ¼ 0.306 mm; 6 ¼ 0.485 mm; 7 ¼ 0.775 mm; 8 ¼ 1.234 mm;
9 ¼ 1.937 mm.

higher lung dose of nanoparticles and therefore to a higher risk of adsorption of elements (Ca, Mg, P and C) on catalyst might differ
adverse health effects [5]. greatly from each other.
When no exhaust after-treatment was used, the proportions of Ageing the catalytic converter using RSO as a fuel decreased the
Si, Fe and Cu were clearly higher in the diesel exhaust particles NOx reduction activity quickly, and after only 61 h of ageing the NOx
smaller than 41 nm of their aerodynamic diameter, compared to the conversions were dramatically lower compared to the measure-
RSO particles measured. Because of the existence of these elements ments with a fresh SCR converter with both, DFO and RSO, fuels.
in the nanoparticle size range they likely also penetrate deep into According to the literature, impurities found in the RSO fuel e.g. Ca
the lungs [11e15]. Some studies suggest that transition metals like [4,21,42] and Mg [4,21] have caused major deactivation of
Fe and Cu in diesel particles may be mediators influencing the vanadium-based SCR catalytic converters. Ca has been proven to be
airway inflammation [5,17,18,39,40]. This result e unlike the earlier a more deactivating component than Mg [4,21]. As reported [21],
statement based on particle number e supports the use of RSO as a 1 wt-% of Ca or 1.5 wt-% of Mg decreased the catalyst's relative
fuel in a view of health effects. However, when the SCR converter activity in NOx reduction by 50%. Contrary to Ca and Mg, low
was used, no significant differences between DFO and RSO particles amounts of P (<1.0 wt-%) have only a minor effect on the activity of
in Cu and Fe proportions were found. vanadium-based SCR catalysts [43]. However, the higher amount of
In this study, RSO and DFO particles were observed to contain P (4e5 wt-%) can decrease the relative activity of NOx reduction by
high amounts of carbon (Fig. 5). The proportion of carbon differed 50% [21,43].
significantly between DFO and RSO particles being much higher in In the chemical analyses of DFO particles small amounts of trace
the diesel particles. Unfortunately, the measured carbon could not elements e.g. P, Ca, K and Mg, which were not present in the DFO
be identified as elemental (EC) or organic (OC) so no conclusion can fuel, were observed. These elements were found in certain particle
be made about the fuel's effect on the OC/EC ratio of particles. In the sizes (~0.3e0.5 mm). It is well known that P, Ca and Mg are
literature (e.g. Refs. [22,26,27]) it is reported that particles from the commonly present in lubrication oils, e.g. in a study [44] the
combustion of seed oils produce hollow particles missing the core lubricating oil used contained 1250 mg/kg of P and 3300 mg/kg of
of elemental carbon. This is also expected to be the reason for the Ca, and in a study [15] the lubrication oil contained 983 mg/kg of P,
differences in the carbon contents of DFO and RSO particles in this 2491 mg/kg of Ca and 6 mg/kg of Mg. Therefore, the existence of P,
study. Also trace elements, i.e. P, Ca, K and Mg, which were analyzed Ca, and Mg in diesel particles may be due to the lubricating oil.
for high proportions from the RSO fuel, are seen in the particles These impurities were not found from the DFO particles, when the
emitted from the RSO fueled engine. All these particles can deposit SCR converter was used and though they have most likely stayed in
on catalyst's surface and cause deactivation [4,21,41] and the the catalyst surface being one of the factors influencing the
€inen et al. / Renewable Energy 77 (2015) 377e385
M. Pietika 383

Fig. 5. Weight-% of the elements analyzed from DFO and RSO particles (other than C and O) as a function of particle size. Particle size is presented as an aerodynamic diameter in a
logarithmic scale as mean values from each size range (foils).

catalyst's activity in long term. The same was also found in the case
of Si, Fe and Cu, which are most probably originated from the
abrasion of the engine, implicating that they also remain on the
catalyst surface, when the SCR converter is used.
Zn and S were found in low proportions from the emitted par-
ticles although there were only minor amounts of these compo-
nents in the used fuels. Zn and S are also known as compounds used
in lubrication oils analyzed e.g. in the study [44] as concentrations
of 1320 mg/kg and 9330 mg/kg, respectively, and in the study [15] S
was analyzed as a concentration of 4711 mg/kg. Interestingly Zn
and S were found in our study in higher amounts in particles from
the exhaust gas of the engine with the SCR converter. The highest
proportion, 6 wt-%, was analyzed from the particles of 0.775 mm of
their aerodynamic size. Zn was also found from the particles at the
same size range with the exception that in this case a diesel par-
Fig. 6. Total emitted particle numbers and NOx conversions during the measurement
ticulate filter was used as an after-treatment method [15]. The
cycle [36], when a fresh SCR catalyst was used. DFO ¼ diesel fuel oil, RSO ¼ rape seed result in our study indicates that the SCR converter is influencing
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384 €inen et al. / Renewable Energy 77 (2015) 377e385
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