Applied Energy 180 (2016) 5265

Contents lists available at ScienceDirect

Applied Energy

journalhomepage:www.elsevier.com/locate/apenergy

Cold start idle emissions from a modern Tier-4 turbo-charged diesel engine
fueled with diesel-biodiesel, diesel-biodiesel-ethanol, and diesel-biodiesel-
diethyl ether blends

Murari Mohon Roy (Associate Professor), Jorge Calder (Graduate Student), Wilson Wang (Professor), Arvind
Mangad (Graduate Student), Fernando Cezar Mariano Diniz (Undergraduate Summer Research Student)

Mechanical Engineering Department, Lakehead University, Thunder Bay, Ontario P7B 5E1, Canada

highlights

Diesel-biodiesel blends with additives ethanol and diethyl ether are tested at idle. In biodiesel
blends, B20 with ethanol additive had cloud points below 25 LC.
Biodiesel blends with additives emitted much lower CO emissions than diesel.
Additives were found effective to reduce the increase in NOx from biodiesel blends. Ethanol additives
reduced HC emissions in B100 blends significantly at idling.

article info abstract

Article history: This study investigated the emissions of a modern (Tier 4) 4-cylinder direct injection (DI) diesel engine at idling with no load
Received 1 June 2016 conditions. Three idling speeds: low (800 rpm), medium (1000 rpm) and high (1200 rpm), respectively are considered. Two
Received in revised form 4 July 2016 additives (5% and 15% by volume), ethanol and diethyl ether (DEE) were mixed with biodiesel-diesel blends B20, B50 and
Accepted 18 July 2016 Available online 29 B100. B100 was produced from canola oil. Engine was tested from cold start to warm up in real world conditions. Emissions
July 2016
analysis was con-ducted for carbon monoxide (CO), carbon dioxide (CO 2), nitric oxide (NO), nitrogen dioxide (NO 2), oxides
of nitrogen (NOx), and unburned hydrocarbons (HC). Investigation results show that, CO and NO x emis-sions decrease, but
Keywords:
Diesel engine HC emissions increase after warm-up than cold start. Diesel-biodiesel blends with additives produce lower CO emissions then
Biodiesel neat diesel; ethanol and DEE additives can reduce NOx emis-sions in diesel-biodiesel blends, and increasing biodiesel content
Additives reduced HC emissions.
Ethanol and DEE
Emissions 2016 Elsevier Ltd. All rights reserved.
Idling

1. Introduction
Extensive use of the compression ignition (CI) engine in mining,
construction and transportation as well as new emissions regula-tions has
increased interest in developing cleaner diesel engines. Biodiesel has become
a promising alternative to convention diesel fuel due to its ability to run in CI
engines with little to no modifi-cation [1]. Biodiesel feedstock includes up to
350 oil producing crops globally, animal by-products, waste grease, and
various other sources [2]. Over the last decade biodiesel output has grown
from 0.8 to 14.7 billion litres annually [3]. In 2010, the Canadian
Environmental Protection Act Bill C-33 mandated 5% renewable
Corresponding author.
E-mail address: mmroy@lakeheadu.ca (M.M. Roy).
content in gasoline by 2020 and 2% renewable content in diesel fuel and
heating oil by 2012 [3]. Most renewable fuel in Canada comes from the
production of Ethanol from corn and wheat [4]. Vaillencourt et al. [5]
developed the Times-Canada model which predicts that energy consumption
is expected to increase by 42% by 2050. Canola oil is the major source of
biodiesel production in Canada. Canola oil is converted using the process of
transesterifica-tion. Transesterification or alcoholises is a process by which fat
or oil reacts with an alcohol in the presence of a catalyst to form an ester and
glycerol [6,7]. The increasing number of diesel passenger, and heavy duty
diesel vehicles have resulted in regulation of CI combustion emissions [8].
The most commonly regulated emis-sions are CO, HC, particulate matter
(PM), and NOx. Biodiesel are attractive because they have the potential to
decrease PM, CO, and HC emissions [9].

http://dx.doi.org/10.1016/j.apenergy.2016.07.090 0306-
2619/ 2016 Elsevier Ltd. All rights reserved.
 M.M. Roy et al. / Applied Energy 180 (2016) 5265 53

Due to the extended idling periods that heavy-duty vehicles exhibit, idling
emissions have been the subject of increasing laws, and regulations from
policy makers [10]. In Canada, the Depart-ment of Natural Resources has
posted idling reductions campaign strategies and by-law strengths/weaknesses
for municipalities [11]. Natural Resources Canada has also released a
campaign for commercial shipping fleets titled FleetSmart, which is aims to
reducing idling time of transport trucks [12]. Regulations are left up to
municipalities to develop and enforce. In Ontario (Canada), 37 municipalities
have regulated idling to some extent [11]. In the city of Kingston (Ontario),
all vehicles must not idle for more than 3 min out of every hour, with
exceptions for cold weather, parades, emergency vehicles, etc. [13]. In
contrast the city of Thun-der Bay (Ontario) only regulates idling at gas
stations where three or more axel vehicles can idle for 5 min out of every hour
and all other vehicles for 2 min out of every hour [14]. The study in [10]
compared the emissions of medium duty diesel engines to gasoline trucks,
and previously studies heavy-duty diesel engines. As typi-cally reported the
study found that the diesel engines exhibited lower fuel use, higher NO x
emissions, and PM emissions while idling. The medium sized diesel engines
exhibited lower fuel use and idle emissions than the heavy-duty diesel
engines.
While operating in mining, construction, and transportation, diesel engine
can experience periods of low operation efficiency. A study in [15] examined
equipment operational efficiency, which is the ratio of which a piece of
equipment is in use vs running idle. Operation efficiency of construction
equipment can range from 85% to 41%. As operational efficiency decreased
the percentage of unnecessary CO 2 emissions increases [15]. This study only
looked at CO2; unnecessary emissions for other regulated emissions would
follow a similar pattern. Another study in [16] explored the rela-tionship
between emissions from mechanical fuel injection (MFI) and electronic fuel
injection (EFI) of heavy-duty diesel vehicles during idle; it was found that
overall EFI diesel engines emitted less CO, HC, and PM than MFI engines.
However, EFI engines emit-ted higher NO x emissions due to advanced timing
in idle condition. Similarly, transport trucks can idle up for extensive periods
of time. For example Frey and Kuo [17] examined the use of auxiliary power
units (APU) for idling reduction in long haul trucks. Long-haul trucks can idle
for more than 2000 h per year. Idling reduction strategies are especially
important in long-haul trucks that experi-ence extreme hot or cold
temperatures, where diesel engines are used as power units for cabin air
conditioning and heating. The use of APUs was found to significantly
decrease fuel use, and emis-sions of CO2, NOx, and PM in mild climates. In
more extreme cli-mates observed in much of Canada, idling rates must
increase when temperatures drop well below freezing.
tiple idle states at 800 and 1200 rpm. The tests found that increases of HC and
NOx emissions were present at idle conditions but not at high rpm conditions,
concluding that low engine speed has significant effect on emissions when
using biodiesel. An addi-tional study from An et al. [22] also concluded that
partial load and idle conditions have significant impact on CO emissions,
brake thermal efficiency (BTE) and brake specific fuel consumption (BSFC).
These studies support that when considering changing fuel blends the idle
condition emissions must also be studied. The next step for moderate climates
is to test the full range of engine condi-tion emissions on biodiesel with good
low temperature properties.
Alcohols can be used in CI engines as alternative fuels when blended
with diesel or biodiesel. Alcohol can also improve the low temperature
properties of biodiesel and biodiesel blends. Yil-mez et al. [23] tested
biodiesel with ethanol as an additive at 3%, 5%, 15% and 25% in a diesel
engine generator. Engine tests were conducted from 0% (no load) to 90% load
from two resistive heating units. Cooling effects and oxygen content of
alcohols were primary factors that affected emission reduction. Test results
showed that the blends increased CO emissions compared to diesel at low
load conditions, but there is no significant change in CO emissions at high
loads based on fuel types or blends. Ethanol blended fuels reduced NOx
emissions for all concentrations. HC emissions were found to depend heavily
on operating conditions. Up to about 40% load, HC with blends is much
higher than that of diesel fuel, and at loads higher than 40%, the HC levels of
blends and diesel fuel is pretty much similar. 2.5%, 5%, and 7.5% ethanol by
volume was added to waste pork lard biodiesel [24]. Single cylinder diesel
engine was tested at 1500 rpm for 0%, 20%, 40%, 60%, 80%, and 100% load
conditions. Ethanol addition was found to reduce CO, HC and smoke
emissions when compared to neat biodiesel, and the reduction is higher at
high loads. It was found that HC emission reductions would decrease with
increase in ethanol additive. Etha-nol was found to increase NOx emissions
for all biodiesel-ethanol blends, and higher the load, the higher the NOx
emissions was. Bio-diesel with ethanol additive was tested on a supercharged
DI diesel engine in [25] at a speed of 1500 rpm with loads from 20% to
100%. It was found that NOx emissions increase with loads, and addition of
ethanol in the blends helps reducing the NOx emissions. Test results also
showed that ethanol was able to increase CO and HC emissions at all loads,
whereas these increases were reduced when supercharged. Ethanol-biodiesel
blends were tested in a multi-cylinder diesel engine and a single-cylinder low
temperature com-bustion diesel engine in [26]. Three test conditions were
examined: 1500 rpm at 3 bar Brake Mean Effective Pressure (BMEP); 2500
rpm and 6 bar of BMEP; and 4000 rpm at full load. In general, higher NOx
and smoke and lower CO and HC were obtained at

Since Diesel engines typically experience high periods of idling, biodiesel

research must also consider the idle condition. Biodiesel could be used in
conjunction with other idling/emission reduction strategies to optimize Table 1
Test results of biodiesel according to ASTM 6751.
vehicle fleet use. Rahman at al. [18] exam-ined the effect idling had on
Jatropha biodiesel emissions. Biodiesel was found to be an attractive CO, and Test name Test method ASTM Results
HC emission reduction strat-egy. These reductions come at the expense of Limit

increased NOx emis-sions. In a study [19], the performance and emissions of Free glycerin (mass%) ASTM D6584 Max. 0
0.02
a diesel engine when fueled with biodiesel produced from waste cooking oil
Total glycerin (mass%) ASTM D6584 Max. 0.112
were examined. Lowest engine rpm tested was 1500 rpm, study found that 0.24
HC emissions vary greatly with engine speed, however CO and PM emissions Flash point, closed cup (LC) ASTM D93 Min. 169
depend more on engine load. NO x emissions were slightly increased with 130
biodiesel blends. Singh et al. [20], tested the emissions from a diesel engine Water & sediment (vol.%) ASTM D2709 Max. 0
0.505
fueled with biodiesel and hydro processed renewable diesel (HRD). Using the
TAN (mg KOH/g) ASTM D664 Max. 0.14
European stationary cycle an idle condition was tested as one of thirteen 0.5
modes. B100 was found to be more effective in reducing PM, CO, and HC Sim. dist., 50% recovery (LC) ASTM D2887 N/A 359.8
emissions, but HRD reduced NOx by 29% and brake specific fuel Cetane index ASTM D976 N/A 50
(2 variables formula)
consumption. A study on waste cooking oil [21], included mul-
Copper corrosion, ASTM D130 Max. 3a 1a
3 h @ 50 LC (rating)
54 M.M. Roy et al. / Applied Energy 180 (2016) 5265

Table 2
Fuel properties of biodiesel-diesel blends, ethanol series blends and DEE series blends.
2 Density (g/ml) Cloud point (LC) HHV (kJ/kg)
Viscosity (mm /s)
Diesel 1.90 0.82 40 45,573
Ethanol 0.80 0.80 114 (freezing point) 29,700
Diethyl ether 0.23 0.71 116.3 (freezing point) 36,892
B100 4.32 0.88 2.6 40,296
Biodiesel diesel blends 21.2
B20 2.68 0.84 44,517
B50 3.20 0.85 13.2 42,934
Ethanol additive series 25.4
B20E5 2.22 0.84 43,776
B20E15 2.11 0.83 26.6 42,295
B50E5 2.58 0.85 14.6 42,273
B50E15 2.55 0.84 14.8 40,949
B100E5 4.15 0.88 2.4 39,766
B100E15 3.92 0.87 2.8 38,707
DEE additive series 22.6
B20DE5 2.20 0.83 44,136
B20DE15 1.93 0.82 22.6 43,374
B50DE5 2.51 0.84 13.8 42,632
B50DE15 2.12 0.83 13.9 42,028
B100DE5 3.85 0.87 2.6 40,126
B100DE15 2.87 0.85 5.4 39,785

Table 3 were found to be effective in reducing smoke levels, which allowed for
Engine specifications. greater use of exhaust gas recirculation (EGR) system to reduce NOx and PM
Engine specification
emissions. Ethanol blends allowed for increase in operating range of the LTC
single cylinder engine, again due to reduction in smoke levels. In the study
Engine make and model Cummins QSB 4.5 T4L
Engine type Inline 4-Cylinder
[27], pentanol and butanol were added to biodiesel at 10% and 20% to
Number of cylinders Four examine effects on par-ticulate emissions. Experiments were performed at a
Bore Stroke 102 mm 138 mm constant engine speed of 3000 rpm and at three engine loads, corresponding
Swept volume 4.5 L to 25%, 50% and 75% related power, respectively. All the compo-nents
Compressions ratio 17.3:1
(organic carbon, diesel particulate mass and water-soluble organic carbon)
Rated power 97KW @ 2300 RPM
decreased significantly with loads, whereas ele-mental carbon increased with
loads. Blended fuels were found to be effective in reducing particulate mass
and elemental carbon emissions, as well as lowering the emissions of particle-
higher-load higher-speed condition (2500 rpm, 6 bar) than lower-load, lower- phase polycyclic aromatic hydrocarbons (PAHs) at all loads. Park et al. [28],
speed condition (1500 rpm, 3 bar) for all fuel types, and ethanol blended fuels examined the addition of biodiesel and additive to bioethanol
showed lower NOx, but higher CO and HC emissions than that of diesel fuel.
The ethanol blended fuels

Fig. 1. Schematic diagram of engine test.

 M.M. Roy et al. / Applied Energy 180 (2016) 5265 55
Table 4

Measurement devices.

Measurement devices
Method of detection Species Measured unit Range Resolution Accuracy
NovaGas 7466 K
Electrochemical/infrared detector CO % 010% 0.10% 1%
Infrared detector CO2 % 020% 0.10% 1%
Electro chemical NO ppm 02000 ppm 1 ppm 2%
Electro chemical NO2 ppm 0800 ppm 1 ppm 2%
Electro chemical O2 % 025% 0.10% 1%
Infrared detector HC ppm 10 020,000 ppm 10 ppm 1%
Dwyer 1205A
Electro chemical CO ppm 02000 1 ppm 5%
ExTech EA10 ( )200 LC to 1360 LC
Temp 0.1 LC 0.1 LC 0.3%

Sensidyne AP-20S
Chemical Formaldehyde ppm 135 ppm 0.5 ppm 5%
Chemical Acetaldehyde ppm 5140 ppm 2 ppm 5%

blended diesel fuel. The test engine was operated at an engine speed of 1200 modern Tier-4 engine that can be fueled by B20 biodiesel blends with very
rpm, and the injection pressure of 120 MPa. Biodie-sel addition was found to small modifications. The warm up engine condition will be examined with
be effective in reducing HC emissions, as well as CO and soot emissions at respect to emissions. Reductions or increases of various emissions will be
early injection timing. compared to the results of neat diesel. Satisfactory fuel blends will be
Diethyl Ether (DEE) is an isomer ether of butanol, which is pro-duced identified for use in heavy duty diesel engines for various weather conditions.
from ethanol. DEE exhibits a high cetane number, high oxy-gen content and
high flammability, and mixes well with diesel and biodiesel blends.
Rakopolos examined DEE blends at various load conditions in [29]. DEE
blends were found to decrease NO x emis-sions when compared to ethanol (a) 800 rpm
blend emissions. DEE blends were found to decrease CO emissions, and Diesel B20 B20E5 B20E15 B50
increase unburned hydrocar-bons [29]. Kannan and Marappan [30] examined B50E5 B50E15 B100 B100E5 B100E15
DEE blended with biodiesel at 5%, 10%, 15%, and 20% by volume. Satya et 90
al. [31] investigated the effects of addition of DEE to B20 biodiesel blends at 80
5% and 15% by volume. Due to the higher latent heat of evapo-ration, DEE 70
was found to reduce emissions of NO x with increasing effectivity as high 60
volume of DEE is added [30,31]. Additionally, DEE was found to increase 50
HC and CO emissions when compared to neat biodiesel. Higher oxygen 40
content of DEE caused the smoke opacity to exhibit a reduction when 30
compared to biodiesel [30]. 20
10
0
In a previous study biodiesel blends were tested on a small DI diesel 0 5 10 15 20 25 30
engine in [32], and higher biodiesel content was found to reduce CO
Time (min)
emissions. HC emissions were reduced at higher loads. Biodiesel content
produced higher NOx emissions than neat diesel. Another study [33] (b) 1000 rpm
conducted by Roy et al., biodiesel-diesel blends and biodiesel-diesel-kerosene 90
blends were tested with additive Wintron XC30 at 2% by volume on a small 80
DI diesel engine. Blends were found to be more effective in reducing CO and 70
HC emissions than neat diesel operation. Kerosene-biodiesel blends were 60
found to be effective in reducing NOx emissions. In another previous study 50
40
by Roy et al. [34], a water-scrubbing and air-dilution exhaust gas after 30
treatment system was developed and tested on a DI diesel engine. It was 20
found that NOx, CO and CO2 emissions could be reduced by up to 80% by 10
0
the after treatment system. 85% smoke reduction was also accomplished with
0 10 20 30
installation of the after treatment system. High idle conditions were tested in a
previous study with pure and waste oil canola biodiesel [35]. CO and HC Time (min)
emissions from diesel-biodiesel blends were lower than neat die-sel. NO x
(c) 1200 rpm
emissions were slightly higher when biodiesel-blends were used in higher 100
concentrations than 5 vol.%.
80
60
The effects of ethanol and DEE as additives to biodiesel and bio-diesel
40
blends have been examined at various engine conditions. Ethanol and DEE
were chosen for this study due to their common ability to improve cold flow 20
properties of fuel blends. Where a gap in knowledge exists is in the warm-up
0
period of multiple speed idle conditions. Temperature fluctuations in a
0 5 10 15 20 25 30
moderate climates support the need for more idling research to be conducted
on winter ready biodiesel. Additionally, the engine being tested is a
Time (min)

Fig. 2. Exhaust temperatures of ethanol series over warm-up from cold start.
56 M.M. Roy et al. / Applied Energy 180 (2016) 5265

2. Materials and methods viscosity, and cloud point of tested fuels [38,39]. All fuel samples were found
to have higher cloud points than neat winter diesel. All B20 biodiesel diesel
2.1. Materials blends exhibited cloud point lower than 20 LC.

Materials used for experimentation include the following: low sulfur

diesel purchased from a local fuel pump throughout the experiment. Pure
canola oil purchased from a local supermarket. Ethanol, methanol and sodium
hydroxide pellets are obtained through Lakeheads Chemical Engineering
Lab. Diethyl ether was obtained from a local vendor.
2.2. Biodiesel production and fuel properties
Transesterification or alcoholysis is the reaction of a fat or oil with an
alcohol to form esters and glycerol [36]. Transesterifica-tion is considered
one of the best approaches to produce biodiesel due to simplicity and
relatively low cost. The process of biodiesel production performed was
transesterification of canola oil in the presence of methanol [37]. One litre of
canola oil produced approx-imately 1 L of biodiesel. Glycerol was separated
from biodiesel, and then biodiesel was washed twice. Volumetric collection
efficiency after washing averaged 80%. Biodiesel production quality was
tested according to ASTM 6751 standards, which can be found in Table 1.
Fuel samples were sent to Intertek laboratory in Hamilton (Ontario) to
determine cold flow properties using ASTM D5773 standards. Table 2
summarizes the related properties of density,
2.3. Selection of fuels and fuel blends
In this study, ultra-low sulfur diesel (ULSD) and canola biodiesel (B100)
are used as the main fuels. The cloud point (CP) of the used diesel and canola
biodiesel was 40 LC and 2.6 LC, respectively. The most important challenge
of using biodiesel in Canadian win-ter conditions is its inferior cold flow
properties (CP is an important one). Ethanol and DEE have been chosen as
the additives to improve (lower) the CP of the fuels or fuel blends. Ethanol
and DEE have very low freezing points, 114 LC and 116.3 LC, respec-tively.
Therefore, lower CP was expected for ethanol and DEE blended diesel-
biodiesel fuels. As the main purpose of this study was to improve the cold
flow properties of biodiesel fuel blends, and ethanol and DEE have extremely
low freezing points, blending of these additives was kept as low as possible
(up to 15%). Further-more, we kept in mind that as ethanol has a very low
cetane num-ber ( 8), this would deteriorate the combustion and emissions in
diesel engines with higher percentage. DEE would have been used with
higher percentage as its cetane number is very high (125). However, its higher
cost is kept in mind. Furthermore, to compare ethanol and DEE results,
similar percentages of both the additives were chosen. In this study, ethanol
and DEE were mixed 5 vol.% and 15 vol.% with biodiesel-diesel blends B20,
B50 and B100.

(a) 800 rpm

Diesel B20 B20DE5 B20DE15 B50
B50DE5 B50DE15 B100 B100DE5 B100DE15

100
90
80

60
70

50
40
30
20
10
0
0 5 10 15 20 25 30
Time (min)
(b) 1000 rpm
100
80

60

40

20

0
0 5 10 15 20 25 30
Time (min)
C)

100 (c) 1200 rpm

Temperature (deg.

80
60
40
20
0 5 10 15 20 25 30
0
Time (min)

Fig. 4. Diesel-biodiesel blends CO emissions over warm-up

Fig. 3. Exhaust temperatures of DEE series over warm-up from cold start.

from cold start.

 M.M. Roy et al. / Applied Energy 180 (2016) 5265
Table 2 shows that different percentages of ethanol and DEE lower the CP of
different fuels and blends by as much as 5.4 LC (CP of 26.6 LC for B20E15
compared to the CP of 21.2 LC for B20).
2.4. Engine and test procedure
2.4.1. Engine under study
Engine being studied is a Cummins Tier 4 Final QSB4.5 inline 4-cylinder
turbocharged engine with high pressure common rail injection system, and a
diesel particulate filter. The QSB4.5 is designed mainly for use in agriculture,
mining, and construction. A dual tank fuel system was installed for switching
between vari-ous test fuels. Specifications of the test engine can be found in
Table 3.
2.4.2. Engine test procedure
The engine was tested at three idling conditions: 800 rpm, 1000 rpm, and
1200 rpm with no engine load. Engine was tested for 30 min, starting from a
cold start for each test. CO, CO 2, NO, NO2, HC, O2, and exhaust temperature
readings were taken at 0, 5, 10, 20, and 30 min intervals, respectively. The
probe was inserted for 2 min for each test. This is because we noticed that to
get a stable maximum NOx reading, it takes about 2 min. Peak
Fig. 5. Diesel-biodiesel blends NOx emissions over warm-up from cold start.
57
reading of each component was taken for every test. For 0 min data, the probe
was inserted just after starting the engine and kept 2 min for getting maximum
readings. Therefore, 0 min data is basi-cally from 0 to 2 min peak values.
Similarly, 5 min data is 46 min peak values and so on. At each data point, for
example diesel fuel, 800 rpm, 0 min, we tested the engine in three different
times/days for three readings, and the average of these three readings of CO,
NOx and HC is presented in the next sections. Similar strategy was used for
other fuels and test conditions for other intervals. An average cooling period
of 8 h was used between each engine test to ensure cold start conditions.
When changing fuel type, engine was run for a short period on neat diesel
then fuel was switched to the next test fuel. Fuel consumption was measured
by weighing detachable fuel tank before and after each test. Engine was tested
in outdoor conditions with a temperature range from 20 LC to 25 LC.
2.5. Exhaust emissions and temperature measurement
The test apparatus was designed and constructed so that all exhaust
measurements were taken 6 in. into the exhaust pipe. The apparatus was held
in the middle of the pipes approximately 1 in. from the opening of the
catalytic converter. NO, NO2, HC, O2 and CO2 emissions were measured
using a NOVA gas 7466 K analyzer. NO and NO2 sensors both have a
resolution of 1 ppm. HC sensor has a resolution of 10 ppm. CO 2 sensor has a
resolution of 0.1% of gas analyzed. CO emissions were measured using a
Dwyer 1205A handheld CO analyzer with a resolution of 1 ppm and an
accuracy of 5% of reading. Temperature of exhaust gas
Fig. 6. Diesel-biodiesel blends HC emissions over warm-up from cold start.
58 M.M. Roy et al. / Applied Energy 180 (2016) 5265
Fig. 7. Average CO emissions (ethanol series) (a) low idle, (b) medium idle, and (c) high idle.
temp was measured using an EXTech Easyview 10 with a resolu-tion of 0.1
LC and an accuracy of 0.3% of reading. Formaldehyde and Acetaldehyde
emissions were measured using a Sensidyne AP-205 colorimetric gas
detector. Acetaldehyde tube has a measuring range of 5140 ppm and can
detect as up to 2 ppm. Formaldehyde tube has a range of 135 ppm and can
detect as low as 0.5 ppm Fig. 1 illustrates the engine test set up. Further
information on measurement systems used can be found in Table 4.
3. Results
3.1. Warm-up period from cold start
3.1.1. Average exhaust temperature of fuel blends during warm-up Figs. 2 and
3 illustrate temperature measurements taken from the exhaust pipe of the test
engine for ethanol and DEE series,
respectively during engine warm up. Overall exhaust gas tempera-tures begin
low and increased until they reach steady state at around 20 min. A significant
change is observed from engine start to about 510 min. At engine start (Fig.
2), diesel and diesel-biodiesel blends without ethanol show temperatures of
5065 LC at 800 rpm, 5373 LC at 1000 rpm and 7082 LC at 1200 rpm;
whereas diesel-biodiesel blends with ethanol additives show on average about
20% lower temperature (3556 LC) at 800 rpm, 22% lower (3662 LC) at
1000 rpm and 26% lower (4172 LC) at 1200 rpm. However, after engine
warmed up (30 min), the change in temperatures with or without ethanol is
negligible. The average temperature at 800 rpm is approximately 74 LC and
that at 1000 rpm and 1200 rpm are about 81 LC and 85 LC, respectively. It
seems that higher latent heat of evaporation of ethanol played a significant
role at engine start up to about 5 min, that made exhaust temperatures 20
26% lower.
significant
Fig. 3 shows similar trend to that of Fig. 2, that is, there is
change in temperatures from engine start up to about
 M.M. Roy et al. / Applied Energy 180 (2016) 5265
Fig. 8. Average CO emissions (DEE series) (a) low idle, (b) medium idle, and (c) high idle.
510 min, especially for the DEE added fuel blends, and steady states reach at
around 20 min. However, DEE added fuel blends show lowest temperatures
(2226 LC) at different engine speeds than that of ethanol added fuel blends
(3541 LC) at engine start. After engine warmed up, the average temperatures
of DEE added fuel blends are 66 LC, 68 LC and 76 LC, respectively for 800
rpm, 1000 rpm and 1200 rpm, which is 1015% lower than the average
temperatures of ethanol added fuel blends. Highly volatile DEE (boiling point
34.4 LC) seems to be responsible for such low tem-peratures, especially at
engine start.
3.1.2. Emissions of diesel-biodiesel blends during warm-up
Peak emissions measurement from 0, 5, 10, 20 and 30 min intervals were
taken to examine the characteristics of emissions over the warm-up period.
For simplicity only diesel-biodiesel blends were included in Figs. 46, which
represent average CO, NOx, and HC emissions from cold start to warm-up. In
Fig. 4, CO emissions just after the cold start is the lowest, then increased in
the time interval of 515 min, and finally decreased towards 20 and 30 min
intervals. Average CO reductions after warm up from cold start were 30.0%,
27.9% and 26.5% for 800, 1000 and 1200 rpm, respectively. The lowest CO
during the cold start could be due to the adsorption on the cold exhaust
manifold and tail pipe surfaces. In the intermediate intervals higher CO seems
due to des-
59
orption at higher surface temperatures. In 2030 min interval, the engine
became warmed up with stable combustion and lower fuel consumption to
maintain the engine speeds with the lowest CO emissions. Biodiesel blends
showed lower CO emissions than that of diesel fuel, and B100 produced 40
60% lower CO than diesel at all engine conditions. This is attributed to
oxygen content in bio-diesel that makes better combustion of biodiesel
blended fuels over diesel fuel. Fig. 5 shows that NOx emissions decrease
signifi-cantly for all fuel blends over warm-up. Average NO x reductions for
all fuel blends are 48.9%, 42.68% and 36.3% for 800, 1000 and 1200 rpm,
respectively. Probably low-temperature NOx (prompt NOx) is formed at cold
start possibly to a lean fuel mixture. Higher fuel consumption at cold start
produced higher NOx, and it gradu-ally decreased until the engine became
warmed-up. A mixed pat-tern of NOx emission is obtained for different fuels.
Biodiesel blends produced lower NOx than diesel at 800 rpm, but at 1000 and
1200 rpm, biodiesel blends produced higher NOx. Two impor-tant factors of
NOx production in diesel engines are in-cylinder temperature and availability
of oxygen. In general, biodiesel blends produce higher NOx than diesel,
because of oxygen content in bio-diesel in similar engine conditions. One
probable explanation of lower NOx with biodiesel blends at 800 rpm could be
due to higher cetane numbers that reduce ignition delay. Lower the ignition
delay, the lower the peak pressure and in-cylinder temperature
60 M.M. Roy et al. / Applied Energy 180 (2016) 5265

Fig. 9. Average NOx emissions (ethanol series) (a) low idle, (b) medium idle, and (c) high idle.

is. It can be concluded from the NOx emission trend at different engine
conditions that cetane number effect is dominating at the lowest rpm
condition over oxygen content of biodiesel blends, whereas at higher engine
speeds, oxygen content in biodiesel blends is controlling over cetane number
effect. Fig. 6 illustrates that HC emissions increase over the warmup period
starting from 0 to 20 ppm readings. Average increase in HC emissions for all
fuel blends are 70.8%, 50.5%, and 64.9% for 800, 1000, and 1200 rpm,
respectively. It seems that HC formation mechanism inside the combustion
chamber is pretty much similar from the engine start up to warm-up at no-
load conditions. However, the adsorption effect is very significant during cold
start making lowest HC emissions at this condition. HC production with
biodiesel blends is significantly lower than that of diesel, especially at 1200
rpm.
Higher in-cylinder temperature at this speed and oxygen content in biodiesel
blends helped to reduce HC emissions more than 65%.
3.2. Average CO emissions for ethanol and diethyl ether series
Figs. 7 and 8 show average CO emissions of different fuel blends for
ethanol and DEE series, respectively. Average peak readings of CO emissions
over testing period from different blends were com-pared to those of pure
diesel. At low idle condition (Fig. 7a), CO emissions of B20, B50 and B100
decreased by 4.5%, 6.1% and 32.9%, respectively compared to diesel CO
emissions. At 1000 rpm (Fig. 7b)
or middle idle condition, these
reductions increased to 9.5%, 14.8% and 39.4%, respectively.
As illustrated in
 M.M. Roy et al. / Applied Energy 180 (2016) 5265 61

Fig. 10. Average NOx emissions (DEE series) (a) low idle, (b) medium idle, and (c) high idle.

Fig. 7c high idle tests once again increased reductions of CO for B20, B50,
and B100 by 26.6%, 30.5%, and 41.8%, respectively.
In Ref. [23], ethanol blended fuels result in higher CO emissions. The
authors explained the reason as follows: because ethanol has a lower cetane
number and higher heat of vaporization require-ments than diesel, ethanol
blended fuels also decrease overall cetane number and increase ignition delay,
which leads to incomplete combustion in the cylinder and results in higher
CO emissions. However, we have similar result only for B20E15. Otherwise,
significant reductions in average CO emissions than neat diesel were
observed at all idle conditions in the ethanol ser-ies. Therefore, another
explanation is important to explain the results. Addition of ethanol to fuel
blends has two opposing factors, cooling effect and volatility. Cooling effect
of ethanol is attributed
to the higher latent heat of vaporization, with ethanol and diesel having a
latent heat of vaporization of 921 kJ/kg and 232 kJ/kg, respectively [40].
Increased volatility of ethanol will also affect the combustion profile of a fuel
blend. Diesel and biodiesel have boiling point of 180340 LC, and 350 LC,
respectively. Boiling point of ethanol is significantly less than both diesel and
biodiesel at 77.8 LC. The addition of 5% ethanol by volume was found to
decrease CO emissions for all B20, and B50 blends due to volatility effect of
ethanol dominating combustion. 15% ethanol addition by volume to B20, and
B50 was found to increase CO emissions from 5% addition probably due to
cooling effect of ethanol reducing combustion temperature, which is evident
by the lowest tempera-tures of 15% ethanol added fuel blends at all engine
speeds (Fig. 2) from engine start up to about 5 min. At all idling conditions
neat
62 M.M. Roy et al. / Applied Energy 180 (2016) 5265
biodiesel with ethanol additive exhibited higher CO emissions with higher
ethanol volume percentage. The volatility effect of ethanol additive has a
lessened effect on B100 blends due to the high boil-ing point of biodiesel.
Therefore, the cooling effect of ethanol addi-tive lowers the combustion
temperature and increases CO emissions for B100 blends.
Fig. 8 shows CO emissions of DEE series at low, medium, and high idle
rpms. For all fuels (except B20DE15 at 800 rpm) and all engine conditions,
CO emissions are significantly lower than diesel. In Ref. [29], a correlation is
found between oxygen concentration in DEE and ethanol blended fuels with
CO emissions. Higher the oxy-gen percentage in the blend, lower the CO
emissions was reported. Also, DEE blended fuels showed lower CO
emissions than ethanol blended fuels at same percentage of oxygen in it. This
is under-standable that higher oxygen helps better combustion. We want to
explain the CO emissions of DEE and ethanol blended fuels from different
perspectives.
Similar to ethanol, DEE has higher volatility, and higher latent heat than
diesel and biodiesel. The boiling point of DEE is 34.4 LC
[41] and the latent heat of evaporation is 356 kJ/kg [39]. Compared to
ethanol, DEE is more volatile and should have less of a cooling effect due to
lower latent heat of evaporation. 5% addition of DEE to B20 and B50 were
found to decrease CO emissions due to increased volatility. Addition of 15%
DEE to B20 and B50 increased CO emissions from 5% DEE. Again this can
be attributed to cooling effect of DEE dominating combustion profile. Due to
reduced
Fig. 11. Average HC emissions (ethanol series) (a) low idle, (b) medium idle, and (c) high idle.
cooling effect of DEE when compared to ethanol, increases in CO emission
are less pronounced. CO emissions from B100 increased with increased DEE
at all idle conditions.
Fig. 7 indicated that all biodiesel blends from the ethanol series except for
B20E15 showed reductions in CO emissions. B100 fuel blends and B50E5
exhibited highest CO reductions across all idle conditions. Similarly, from the
DEE series in Fig. 8, B100, and B50DE5 showed promising reductions in CO
emissions compared to neat diesel. B20DE5 also proved to be effective in CO
reduction.
3.3. Average NOx emissions for ethanol and diethyl ether series
Figs. 9 and 10 illustrate the average NO, and NO 2 emissions from low,
medium, and high idle tests, for ethanol series and DEE series, respectively.
NO and NO2 emissions were combined to examine average NO x emissions
over warm-up period. Average NOx emissions over testing period were
compared to neat diesel NOx emission values. B20, B50 and B100 all emitted
higher NOx emissions than diesel. It was found that increasing volume
percentage of biodiesel would increase NOx emissions at all rpms. The
average NOx emissions trend for all fuel types tested including diesel was
that higher idle conditions caused lower average NOx emissions. This may be
attributed to over leaning in local areas of combustions due to higher air
consumption at high idle speeds. While cylinder temp increases with rpm,
idling condition does not
 M.M. Roy et al. / Applied Energy 180 (2016) 5265
create high enough temperature to facilitate greater NOx production.
At low idle, all blends with ethanol produced lower average NOx
emissions than neat diesel. As shown in Fig. 9a, B100E15 low-ered NOx
emissions at medium idle test by 4.8%. In Fig. 9c, B100E5 and B100E15
reduced NOx emissions by 3.1% and 14.1%, respec-tively. It was seen that
the addition of ethanol to biodiesel-diesel blends could reduce average NOx
emissions in all tests. B100E15 was found to be the most effective blend in
reducing average NOx emissions over the test period.
Fig. 10 demonstrates the average NOx emissions at different idling
conditions for DEE series. No blends generated lower average NOx emissions
than neat diesel. Addition of DEE to B20, B50, and B100 caused a slight
reduction of average NOx emissions from the biodiesel-diesel blends. Higher
volume percent of DEE induced lower NOx emissions. The reduction in NO x
emissions can been attributed to the higher cetane number associated with
DEE, due to lower ignition delay. Cetane number of diesel, biodiesel, and
DEE are 48, 50, and 125, respectively [33,42]. Due to very high cetane
number of DEE, we expected much higher NOx reduction with higher
percentage of DEE in the blend. The results suggest that the effect of high
cetane number is less effective to reduce
Fig. 12. Average HC emissions (DEE series) (a) low idle, (b) medium idle, and (c) high idle.
63
NOx emissions at idling engine running conditions. The small change in
exhaust temperatures (Figs. 2 and 3) further support higher cetane number is
having smaller effect at idle conditions.
3.4. Average HC emissions for ethanol and diethyl ether series
Figs. 11 and 12 represent the average HC emissions for the etha-nol and
DEE series blends, respectively. At all tests, B20, B50, and B100 produced
less HC emissions than diesel. This can be attribu-ted to the higher oxygen
content of biodiesel-blends allowing for a more complete combustion.
Fig. 11 shows the average HC emissions of the ethanol series fuel blends.
HC emissions are product of incomplete or partial combustions of
hydrocarbons in the combustion chamber. At low and medium idle tests,
ethanol was found to decrease HC emis-sions for B20 blends. In all other fuel
blends ethanol was found to decrease HC emissions. It was seen that the
addition of ethanol to B100 blends would significantly decrease HC
emissions.
Fig. 12 illustrates the average HC emissions for the DEE series fuel
blends. Increasing DEE percentage by volume was found to increase HC
emissions from diesel-biodiesel blends at all idle conditions.
64 M.M. Roy et al. / Applied Energy 180 (2016) 5265
The most important finding of this study about HC emissions of ethanol
and DEE series is that higher percentage of ethanol helps to reduce HC
emissions, whereas HC emissions increased with higher percentage of DEE in
the blends. To explain this, we need to consider fuel properties of different
fuels and blends as well as some phenomena inside the combustion chamber.
In fuel proper-ties, oxygen content, volatility and cetane number are some of
the very important ones need to be considered during engine start and at
idling. Among phenomena inside the combustion chamber, wall-adhering,
flame-quenching and over-leaning are important ones. Lower the boiling
point (high volatility) of the fuel, more read-ily it vaporizes and mixes with
air giving more complete combus-tion. Higher oxygen content promotes
complete combustion. High cetane number fuels have low self-ignition
temperatures that help better combustion during engine start and warm-up
phase. The optimal combination of these fuel properties makes lower wall-
adhering, and less chance of over-leaning. As a result, the com-bustion is
more complete and there is less HC emissions. Very high oxygen content of
ethanol (34.3%) and good volatility (boiling point 77.8 LC) produce less HC
emissions with higher percentage of etha-nol in the blends. On the other hand,
although DEE has a very high cetane number (125), its excessive volatility
(boiling point is only 34.4 LC) creates local over-leaning. As a result, lower
temperatures, especially at engine start, which is evident from Fig. 3
(temperature is only about 2226 LC) deteriorates combustion producing
higher HC at higher percentages of DEE in the blends.
3.5. Aldehyde emissions
Formaldehyde and acetaldehyde emissions were tested after engine warm-
up at low and high idle conditions for all the fuel blends (ethanol and DEE
series). Formaldehyde readings were the same for all fuel types, 5 ppm at low
idle and 10 ppm at high idle conditions. Acetaldehyde emissions remained at
5 ppm for all fuel blends and idle conditions after warm-up. From the
aldehyde results, it is understood that aldehyde production mechanism inside
the engine during idling engine running with different fuel blends is similar.
4. Conclusion
In this work, systematic experimental analysis was conducted to examine
the emissions of biodiesel blends with ethanol and DEE. Data was taken over
a warm-up period from a cold start. Three fuel series were tested: biodiesel-
diesel blends, biodiesel-diesel-ethanol blends, and biodiesel-diesel-DEE
blends. Conclu-sions from emissions results of tested fuels are summarized
below:
(1) All B20 fuel blends exhibited cloud points below 20 LC. B20E5, and
B20E15 both have cloud points below 25 LC.
(2) From cold start to warm-up condition CO, NO x, and HC all produce
observable trends. CO and NO x saw reductions after cold start,
whereas HC emissions increased with time.
(3) B20, B50 and B100 blends produced significantly less aver-age CO
emissions than neat diesel. All fuel blends with etha-nol with the
exception of B20E15 generated lower CO emissions results than neat
diesel. Addition of 5% ethanol could decrease CO emissions for B20
and B50 fuel blends, whereas the addition of ethanol to B100 would
increase CO emissions, while still remaining under neat diesel levels.
(4) Addition of biodiesel content to biodiesel-diesel blends could increase
NOx emissions. Addition of ethanol was found to decrease NO x
emissions with additional ethanol content. NOx emissions from B100
were affected the most by ethanol content. In high idle tests, B100
blends with ethanol
produced less NOx emissions than neat diesel. It was found that DEE
content would reduce NOx emissions at all idle con-ditions for all fuel
blends. B20DE15 and B50DE15 were the only fuel blends to reduce
NOx emissions than average die-sel emissions.
(5) Increasing biodiesel content could decrease HC emissions. Ethanol
content decreased HC emissions significantly for B100 blends. DEE
content was found to increase HC emis-sions at all test conditions.
(6) On the other hand, no significant increase in aldehyde emis-sions was
found after warm-up period, and no smoke emis-sions were noticed
(visual inspection) for any fuel blends at idling conditions after engine
warm-up.
Acknowledgements
The authors would like to acknowledge the financial support from
Lakehead University, which made this project possible. Appreciation is given
to the Brazilian Government for support of this project through Science
without Borders program. Thanks are also given to Mr. Joe Ripku,
technologist in the Department of Mechanical Engineering and Debbie
Puumala, technician in the Department of Chemistry, both at Lakehead
University for their assistance throughout this project.
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