Applied Energy 126 (2014) 1–12

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Combustion, performance, regulated and unregulated emissions

of a diesel engine with hydrogen addition
J.H. Zhou ⇑, C.S. Cheung, C.W. Leung
Department of Mechanical Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong

h i g h l i g h t s

 Two distinct ULSD–H2 combustion modes are observed at high engine load.
 H2 addition can improve the engine performance at medium to high engine loads.
 H2 addition is effective in reducing CO2, CO and PM emissions (mass and number).
 Influence of H2 addition on NOx emission and NO2/NOx ratio is engine load dependent.
 H2 addition is effective in reducing examined unregulated emissions.

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

Article history: An experimental investigation was conducted on the combustion, performance, regulated and
Received 26 November 2013 unregulated emissions of a diesel engine with naturally aspirated hydrogen at the engine speed of
Received in revised form 27 February 2014 1800 rev min1 under five engine loads. Hydrogen was added to provide 10%, 20%, 30% and 40% of the
Accepted 31 March 2014
total fuel energy. Improvement of engine performance can be achieved at medium to high loads. At
Available online 22 April 2014
90% load, abnormal combustion occurs with more than 30% hydrogen addition as indicated by the drastic
increase of peak heat release rate, shortened ignition delay and combustion duration. CO/CO2 and seven
Keywords:
kinds of unregulated emissions (except for formaldehyde) can be efficiently reduced. More than 30% of
Diesel engine
Hydrogen
hydrogen addition can reduce the HC emission at low to medium loads. The percentage reduction of
Combustion NOx emission is engine load dependent, being positive at low loads and negative at high loads. Drastic
Unregulated emissions increase of NO2 is observed at low to medium engine loads. Reductions on particulate mass concentra-
Particle emission tion, particle number concentration and diesel thermal pyrolysis intermediates (olefins and benzene)
are associated with the inhibition of polycyclic aromatic hydrocarbons (PAHs) formation. All the
unregulated emissions increase at 90% load.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction on gasoline–hydrogen or pure-hydrogen fueled spark ignition en-

gines [5–8] before but more concerns have been turned to diesel
Coupled with the growing economy in different parts of the engines recently.
world, there is increasing difficulty in relying on fossil fuel to fulfill Some experimental investigations have been conducted to ex-
the energy demand. Also there is growing concern on problems plore the effect of hydrogen addition on the performance and emis-
arising from global warming and environment deterioration asso- sions of single-cylinder diesel engines. Saravanan et al. [9,10]
ciated with the usage of fossil fuel. Therefore, there is strong moti- compared carburation, port and manifold injection systems for
vation in looking for alternative fuels for different applications, hydrogen addition and demonstrated that either choice could re-
including that for motor vehicles. Hydrogen is a potential renew- duce HC, CO and CO2 and increase thermal efficiency while the last
able fuel for internal combustion engines [1], gas turbines [2], fuel one gained better emission reduction. However, the side effect of
cells [3], etc. It has the potential advantages of ultra-low pollutions increased NOx emission exists probably due to higher combustion
and high efficiency for these applications, as well as long-term temperature associated with hydrogen addition. Accordingly, die-
availability [4]. Many efforts have been devoted to investigations sel engine equipped with exhaust gas recirculation (EGR) was
investigated [11,12]. Results indicated that optimized EGR level
⇑ Corresponding author. Tel.: +852 6157 3803; fax: +852 2365 4703. could offset the NOx emission to that of diesel fuel operation with-
E-mail address: [email protected] (J.H. Zhou). out apparent deterioration in both thermal and fuel efficiencies.

http://dx.doi.org/10.1016/j.apenergy.2014.03.089
0306-2619/Ó 2014 Elsevier Ltd. All rights reserved.
2 J.H. Zhou et al. / Applied Energy 126 (2014) 1–12

Nomenclature

m_H2 mass flow rate of hydrogen (g/s) Pmax peak in-cylinder pressure (Bar)
_
mULSD mass flow rate of ULSD (kg/s) Qmax peak heat release rate (J/deg)
LHVH2 lower heating value of hydrogen (MJ/kg)
LHVULSD lower heating value of ULSD (MJ/kg) Abbreviations
/H2 air air-to-fuel equivalence ratio of the aspirated hydrogen– ULSD ultra low sulfur diesel
air mixture EGR exhaust gas recirculation
/ULSDH2 air air-to-fuel equivalence ratio of in-cylinder diesel– HCCI homogeneous charge compression-ignition
hydrogen-air mixture LTC low temperature combustion
AFRst
H2 stoichiometric air–fuel ratio of hydrogen UDDS urban dynamometer driving schedule
AFRst
ULSD stoichiometric air–fuel ratio of ULSD CFD computational fluid dynamics
hSOC start of combustion (°CA) BMEP brake mean effective pressure
hEOC end of combustion (°CA) BTE brake thermal efficiency
uid ignition delay (°CA) BSFC brake specific fuel consumption
uCD combustion duration (°CA) TNC total number concentration
upremix diesel premixed combustion phase (°CA) GMD geometric mean diameter
udiffusion diesel diffusion combustion phase (°CA)

High level of hydrogen addition was attempted by Roy et al. [13] in previous studies. However, there is lack of study involving hydro-
a super-charged diesel engine and they validated that up to 90% gen addition from low to high fuel energy substitution against
substitution of diesel fuel energy by hydrogen could be achieved engine loads, with regard to the influence on combustion parame-
which contributed to ultra-low smoke, CO and HC emissions. ters, such as ignition delay, and combustion duration. Hence it is
Additionally, charge dilution by N2 or CO2 (EGR) could inhibit worthwhile for further investigation on either engine performance
NOx formation and suppress engine knocking. Hydrogen was also or emissions coupled with the combustion characteristics. With
introduced to diesel engine operated under advanced combustion regards to engine emissions, size and number of diesel particulate
modes. Hydrogen addition in a homogeneous charge compres- are well recognized as being even more crucial than mass for
sion-ignition (HCCI) engine with adjustable compression ratio health issues [25,26]. Hydrogen addition can reduce the diesel par-
was studied by Guo et al. [14,15]. They observed that hydrogen ticle mass but its effect on particle size and number concentration
addition narrowed the operational compression ratio range and in- has not been sufficiently elucidated. Moreover, despite certain
creased the knocking tendency, but CO/NOx emissions decreased hydrocarbon species, such as aldehyde, alkene, alkyne, and cyclic
with no significant influence on HC emission. Miyamoto et al. hydrocarbons are considered as extremely toxic [27–29], to the
[16] pointed out that delayed injection timing and EGR combined authors’ knowledge, there is also lack of investigation on the effect
with hydrogen addition could achieve low temperature combus- of hydrogen addition on these unregulated emissions. In this study,
tion (LTC) so as to reduce both smoke and NO emissions. hydrogen is added to substitute 10–40% of the total fuel energy
Research has also been extended to multi-cylinder diesel en- applied to a diesel engine, at 10% interval, at five engine loads
gines, including both light-duty and heavy-duty types. Shin et al. and at an engine speed of 1800 rev min1, to investigate the
[17,18] conducted experimental study on a turbo-charged com- influence on engine performance, regulated and unregulated
mon-rail split-injection light-duty diesel engine, with 31% EGR ra- gaseous emission and particulate emissions.
tio and 10% of total fuel energy substitution by hydrogen, and
found brake specific NOx emission reduced by 25%, compared with
diesel fuel operation. Hydrogen addition could also reduce the 2. Experimental apparatus
maximum in-cylinder pressure and made the combustion smooth-
er especially at high EGR level. Shirk et al. [19] employed hydro- The engine tested in this study was a natural-aspirated direct-
gen-assisted operation on a light-duty diesel vehicle with 10% injection diesel engine. The engine specifications can be found in
total fuel energy substitution by hydrogen and tested the vehicle Table 1. The arrangement of experimental facilities is shown in
under urban dynamometer driving schedule (UDDS). They believed Fig. 1. The diesel engine was mounted on an eddy-current
that a small amount of hydrogen addition could be applied to mod- dynamometer while the engine torque and speed were controlled
ern diesel vehicles without adverse impact on vehicle performance by the Ono Sokki testing management system. The in-cylinder
and emissions. Several investigations have been conducted on hea- pressure was measured by a piezoelectric sensor (type 6056A,
vy-duty diesel engines with naturally-aspirated hydrogen by Li
et al. [20–23]. In their studies, they observed low combustion effi-
Table 1
ciency of hydrogen, as indicated by the high concentration of un-
Engine specifications.
burned hydrogen in the exhaust gas, at low engine loads [20];
and uncontrolled combustion associated with sharp increase of Engine model ISUZU 4HF1
peak in-cylinder pressure and peak heat release rate occurred Model year 1995
when high level of hydrogen was added at high engine load [21]. Displacement/(cm3) 4334
Special attention has been paid on the drastic increase of NO2 Compression ratio 19.0:1
Bore  stroke/(cm) 112  110
emission as a result of hydrogen addition. Lilik et al. [24] applied Configuration Natural aspirated, inline 4-cylinder
a computational fluid dynamics (CFD) model in their study and Rating power/(kW/rev min1) 88/3200
their result showed that the increase of NO2 emission could be Rating torque/(N m/rev min1) 285/1800
attributed to the increase of HO2 radical. Injection timing 8 BTDC
Injection pump Bosch inline type
The above literature review shows that evaluation on engine
Injection nozzle Hole type with 5 orifices
performance and regulated emissions was the focal point of
 J.H. Zhou et al. / Applied Energy 126 (2014) 1–12 3

Surge tank
Fuel tank

Air
Digital mass
flow controller ULSD
Mixing
H2 chamber and air filter

Electronic balance

Eddy Current Dynomometer

Cylinder Pressure Sensor

Combustion analyzer
Injector Shaft encoder

Heated sample line Two stage dilutor

Exhaust gas
TEOM
HC
NO/NOx 2nd

CO/CO2

Electrical Heater SMPS

O2 Multi-gas analyzer
Gaseous analyzers Dry compressed air

Fig. 1. Arrangement of experimental facilities.

Kistler Co., Inc.) and the pressure signal was amplified with a Hydrogen with a purity of 99.999% was naturally aspirated
charge amplifier (type 5011B, Kistler Co., Inc.). A crank-angle enco- along with air into the intake port through a tube of 0.2 m diameter
der was employed for crank-angle signal acquisition at a resolution and 2 m in length which was connected to the inlet side of the air
of 0.5 °CA. The intake and exhaust gas temperatures were filter to enhance mixing between air and hydrogen. A surge tank
measured by K-type thermocouples. For gaseous emissions, total was designed to eliminate the pressure fluctuation within the
hydrocarbon was measured with a heated flame ionization detec- hydrogen pipeline generated from the hydrogen storage cylinder.
tor (HFID, CAI Inc.); NO/NOx were measured with a heated chemi- The air filter also functioned as the mixing chamber in order to
luminescent analyzer (HCLA, CAI Inc.). CO and CO2 were measured well premix the hydrogen–air mixture. For this setup, there is no
with non-dispersive infrared analyzers (NDIR, CAI Inc.). O2 was change in the intake system arrangement which is desirable to
measured with a portable gas analyzer (Anapol AG). All the gas- keep the volumetric efficiency the same with the original operation
eous emissions were directly sampled from the engine exhaust [38]. Hydrogen flow was controlled and measured by a digital mass
pipe. The unregulated gas analyzer is a multi-component Ion flow controller (Alicat Co., Inc.). Additionally, two flash back arres-
Molecule Reaction (IMR) mass spectrometer (V&F Airsense Net) tors (Witt Co., Inc.) were equipped on the hydrogen and surge tank
which allows dynamic test of carbon-based unregulated emissions pipelines.
in low concentration. The gas sample was directly taken from the In this study, the engine was operated at five engine loads with
exhaust pipe and maintained at 190 °C to the analyzer. The brake mean effective pressures (BMEPs) of 0.08, 0.25, 0.41, 0.58
detailed operation principle of the analyzer has been described and 0.71 MPa at 1800 rev min1, corresponding to around 10%,
elsewhere [30–32] and has been employed in various studies 30%, 50%, 70% and 90% of full load. Hydrogen was added to substi-
[33–36]. Unregulated gaseous emissions including formaldehyde, tute 10%, 20%, 30% and 40% of the total fuel energy, and designated
acetaldehyde, ethylene, propene, 1,3-butadiene and BTX (Benzene, as H10, H20, H30 and H40, respectively. The energy substitution
Toluene, Xylene) were measured. The regulated and unregulated ratio of hydrogen was computed based on Eq. (1).
gas analyzers were warmed up for 1 h and calibrated with standard
gases. For particulate emissions, a two-stage Dekati mini-diluter m_H2  LHVH2
H2 energy substitution ratio ¼ ;
was employed for diluting the exhaust gas for particle sampling. _  LHVULSD þ m_H2  LHVH2
mULSD
The dilution ratio calculation method can be found in [37]. In the ð1Þ
present study, the first-stage dilution ratio varied from 6.1 to 8.9,
and the second-stage dilution ratio varied from 59.4 to 87.7, where m_H2 and mULSD
_ are the mass flow rates of hydrogen and ULSD,
depending on the engine operation condition. The first-stage di- in kg/h, respectively; LHVH2 and LHVULSD are the lower heating val-
luted exhaust gas was delivered to a tapered element oscillating ues of hydrogen and ULSD, in MJ/kg, respectively. To adjust a certain
microbalance (TEOM 1105, Rupprecht & Patashnick Co., Inc.) for percentage of hydrogen energy substitution, both the amount of
measuring particulate mass concentration, and the second-stage ULSD and the amount of hydrogen have to be adjusted. After several
one was connected with a scanning mobility particle sizer (SMPS, trials on the measurement of ULSD and hydrogen mass flow rates,
TSI Inc.) for measuring the particle size distribution and number we can attain the hydrogen energy substitution ratios to within
concentration. The SMPS consists of a TSI 3071A differential 10 ± 2, 20 ± 2, 30 ± 2 and 40 ± 2%.
mobility analyzer (DMA) and a TSI 3022 condensation particle The air-to-fuel equivalence ratio of the aspirated hydrogen–air
counter (CPC). mixture /H2 air and the in-cylinder diesel–hydrogen–air mixture
4 J.H. Zhou et al. / Applied Energy 126 (2014) 1–12

equivalence ratio /ULSDH2 air are computed based on Eqs. (2) and Table 3
(3), respectively. Experimental uncertainty (95% confidence level) and standard errors.

Parameters Uncertainty/(%) Parameters Standard error/(%)

m_ air HC 8.6 BSFC 1.1
uH2 air ¼ ; ð2Þ
AFRst _
H2  mH2
CO 5.1 BTE 1.1
CO2 0.45 GMD 1.6
NOx 2.6 TNC 2.5
_ air
m NO2 4.2 TEOM 2.3
uULSDH2 air ¼ ; ð3Þ Unregulated emissions <5
AFRst
ULSD  m _
ULSD þ AFRst _
H2  mH2

where m _ air is the mass flow rate of intake air; AFRst st

H2 and AFRULSD are
the stoichiometric air–fuel ratios for hydrogen and ULSD, 3. Results and discussions
respectively.
We employed the method mentioned in Ref. [39] to calculate the 3.1. Engine combustion characteristics
AFR and based on the AFR and mULSD _ we can get m _ air . Since the
hydrogen added would replace part of the intake air, so we con- The effect of hydrogen addition on peak in-cylinder pressure
verted the flow rate of air from mass basis to volume basis and de- and heat release rate are shown in Figs. 2 and 3, respectively, in
ducted the occupied hydrogen volume fraction so as to get the real which the data have been averaged over 400 cycles. Some impor-
intake air flow rate. The measured or calculated diesel fuel and tant information derived from the measured in-cylinder pressure
hydrogen consumption rates, hydrogen energy substitution ratio, and heat release rate data is computed and shown in Table 4. Start
air-premixed hydrogen equivalence ratio, air–diesel–hydrogen of combustion (hSOC) is defined as the crank angle of rapid pressure
equivalence ratio are shown in Table 2. rising as identified from the in-cylinder pressure data. End of com-
The engine was run for several minutes at each testing bustion (hEOC) is defined as the crank angle with 95% accumulated
condition after the cooling water reached 80 °C under close-loop heat release. Ignition delay (uid) is defined as the interval of
control and the exhaust gas temperature became stable (±1 °C). injection timing (8 CA BTDC) and hSOC. Combustion duration
The gaseous emissions and the particulate mass concentration (uCD) is defined as the interval between hSOC and hEOC. Diesel
were continuously sampled for 5 min and the average results are premixed combustion phase (upremix) is defined as the interval
presented. The gaseous emissions were converted from volumetric between hSOC and the end of rapid decrease of heat release rate
concentrations to brake specific emissions by employing the SAE and diesel diffusion combustion phase (udiffusion) is defined as
J1088 method [40]. The steady state tests were repeated three the interval between the end of upremix and hEOC.
times to ensure that the data are repeatable within the experimen- At 10% load (BMEP = 0.08 MPa), with the increase of hydrogen
tal uncertainties of the measurements. The experimental addition, there is gradual decrease of peak in-cylinder pressure
uncertainties and standard errors are shown in Table 3. The uncer- (Pmax) and peak heat release rate (Qmax) along with retardation of
tainties were evaluated at 95% confidence level using the commer- hSOC. uCD extends due to the lengthened udiffusion and hydrogen is
cial statistical software Origin. Experimental results obtained from probably ignited during udiffusion. According to the experimental
the different hydrogen energy substitutions were compared using results of Gatts et al. [20], poor combustion efficiency of hydrogen
the two-tailed Student’s t-test to verify if they are significantly was observed when the engine was operated at 10% load and that
different from each other at 95% significance level. unburned hydrogen in the engine exhaust increased almost

Table 2
Fuel consumptions and equivalence ratios.

BMEP (MPa) FUEL H2 (%) _ ULSD (g/s)

m _ H2 (mg/s)
m uH2 air uULSDH2 air
0.08 ULSD 0.00 0.67 0 – 6.59
H10 10.66 0.66 27.90 67.18 6.06
H20 20.25 0.62 55.80 33.36 5.83
H30 30.43 0.54 83.70 22.09 5.90
H40 41.17 0.45 111.60 16.46 6.06
0.25 ULSD 0.00 1.11 0 – 4.02
H10 11.22 1.09 48.83 38.19 3.64
H20 21.43 1.01 97.65 18.87 3.51
H30 29.90 0.84 126.95 14.41 3.78
H40 40.44 0.69 166.01 10.92 3.94
0.41 ULSD 0.00 1.74 0 – 2.56
H10 10.45 1.62 66.96 27.73 2.46
H20 20.43 1.38 125.55 14.58 2.57
H30 29.72 1.21 181.35 9.95 2.59
H40 40.58 0.98 237.15 7.51 2.72
0.57 ULSD 0.00 2.16 0 – 2.06
H10 10.78 1.89 80.91 22.87 2.09
H20 21.20 1.61 153.45 11.58 2.17
H30 30.89 1.33 210.65 8.51 2.31
H40 40.73 1.26 306.90 5.70 2.07
0.71 ULSD 0.00 2.78 0 – 1.60
H10 10.64 2.48 104.63 17.58 1.59
H20 20.70 2.09 193.30 9.21 1.66
H30 29.56 1.82 270.63 6.52 1.69
H40 40.21 1.61 383.64 4.47 1.60
 J.H. Zhou et al. / Applied Energy 126 (2014) 1–12 5

90 At 70% load (BMEP = 0.57 MPa), due to the increase of in-

Peak in-cylinder pressure/(Bar) 85 ULSD cylinder gas temperature, the combustion efficiency of hydrogen
H10 is considered to be almost the same as diesel fuel as suggested
80 H20 by Gatts et al. [20], thus even a relatively small amount of
H30
75 H40 hydrogen energy substitution (H10 and H20) leads to an increase
of Pmax and Qmax. With H30 operation, diesel fuel developed turbu-
70
lent flame can propagate in the hydrogen–air mixture and a second
65 heat release peak is formed due to premixed hydrogen–air com-
60 bustion. The combustion process can be divided into three stages:
diesel premixed combustion, hydrogen premixed combustion and
55
diesel–hydrogen diffusion combustion. With further increase of
50 hydrogen addition to H40, the second heat release peak in udiffusion
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
BMEP/(MPa) weakens and moves towards the first heat release peak (which
occurs in upremix), indicating that hydrogen premixed combustion
Fig. 2. Effect of hydrogen addition and engine load on peak in-cylinder pressure. begins earlier and thus the two heat release peaks almost merge
together. Therefore, no clear boundary for the three combustion
stages can be identified. Owing to the fast burning rate, both
linearly with the increase in hydrogen addition. Similarly, in pres- upremix and udiffusion decrease, and accordingly uCD is shortened.
ent study, the combustion efficiency of hydrogen is low with H10 At 90% load (BMEP = 0.71 MPa), with H10 and H20 operation,
and H20 operation due to the over-lean hydrogen–air mixture. there is a slight increase in Pmax and Qmax. However, with H30
The substitution of hydrogen reduces size of the diesel plume and H40 operation, combustion is intensified. The heat release rate
and hydrogen is probably ignited by the hot oxygen-containing profile transforms to a single-peak bell shape, where drastic
diesel combustion products as suggested in Ref. [41]. Therefore, increase of Pmax and Qmax, compared with diesel fuel operation, is
only limited amount of hydrogen–air mixture can be ignited while observed. Apparent extension of upremix by 44.3% indicates that
the rest of the hydrogen directly escapes into the exhaust. The ef- the combustion of diesel fuel and hydrogen finishes during upremix.
fect of hydrogen addition on engine combustion at 30% In addition, the entire combustion phase is advanced as indicated
(BMEP = 0.25 MPa) and 50% loads (BMEP = 0.41 MPa) are similar by the shortened uid which decreases by 34.9% and 39% for H30
and thus the later is plotted in Fig. 3. Due to the improvement in and H40 operation, respectively. It is commonly accepted that, un-
hydrogen combustion efficiency as a result of the increase of der diesel–hydrogen dual-fuel operation, hydrogen is ignited by
hydrogen in the hydrogen–air mixture, there is an apparent the pilot diesel fuel under most engine operation conditions due
increase of heat release rate during udiffusion, especially for H40 to its high auto-ignition temperature. However, this investigation
operation. captured two special features: a sharp decrease of uid, and a drastic

50 90
ULSD 80 ULSD
H10
Heat release rate/(J/deg)

Heat release rate/(J/deg)

40 H10
H20 70 H20
H30 60 H30
30 H40 H40
50
BMEP=0.08 MPa BMEP=0.41MPa
40
20
30

10 20

10

0 0
-5 0 5 10 15 20 25 30 -5 0 5 10 15 20 25 30
Crank angle/(CA) Crank angle/(CA)

120 150
ULSD ULSD
100 H10
Heat release rate/(J/deg)

120 H10
Heat release rate/(J/deg)

H20 H20
H30 H30
80
H40
90 H40
60 BMEP=0.57MPa BMEP=0.71MPa
60
40

30
20

0 0
-5 0 5 10 15 20 25 30 -5 0 5 10 15 20 25 30
Crank angle/(CA) Crank angle/(CA)

Fig. 3. Effect of hydrogen addition and engine load on heat release rate.
6 J.H. Zhou et al. / Applied Energy 126 (2014) 1–12

Table 4
Effect of hydrogen addition and engine load on combustion parameters.

Unit/CA BMEP = 0.08 MPa BMEP = 0.41 MPa

ULSD H10 H20 H30 H40 ULSD H10 H20 H30 H40
hSOC 2.9 3.1 3.2 3.5 3.4 2.2 2.4 2.5 2.7 2.5
hEOC 28.6 29.4 30.1 31.2 31.9 42.1 42.3 42.9 42.6 40.3
uid 10.9 11.1 11.2 11.5 11.4 10.2 10.4 10.5 10.7 10.5
/premix 9.2 9.5 9.1 8.5 8.6 8.5 7.8 7.7 6.5 5.8
udiffusion 16.5 16.9 17.8 19.1 19.9 31.3 32.0 32.1 32.7 32.0
/CD 25.7 26.3 26.9 27.7 28.5 39.8 39.8 40.5 39.2 37.8
BMEP = 0.57 MPa BMEP = 0.71 MPa
ULSD H10 H20 H30 H40 ULSD H10 H20 H30 H40
hSOC 1.5 1.6 1.6 1.6 1.2 0.3 0.3 0.3 2.6 2.9
hEOC 50.0 50.1 48.9 46.7 45.1 56.4 56.7 55.7 53.6 52.6
uid 9.5 9.6 9.6 9.6 9.2 8.3 8.3 8.3 5.4 5.1
/premix 7.6 7.6 7.2 6.9 6.3 8.2 8.7 8.8 11.8 11.9
udiffusion 40.9 40.8 40.2 38.2 37.6 47.8 47.7 46.6 44.3 43.6
/CD 48.5 48.5 47.4 45.1 43.9 56.0 56.4 55.4 56.1 55.5

increase of Pmax and Qmax which may denote abnormal combustion et al. [45] suggested that the wall heat flux of hydrogen flame would
in diesel–hydrogen dual-fuel engine. There is little possibility for be several times higher than that of diesel fuel combustion when
auto-ignition of hydrogen since engine knocking is not detected. wall temperature was low (low engine load). Thus, the higher
However, under extreme engine operating conditions, such as thermal loss due to wall heat transfer could be another reason for
near-stoichiometric hydrogen–air mixture or high in-cylinder gas poor engine performance.
temperature, surface-ignition or pre-ignition of hydrogen by hot At 50% load, except for H10 operation, the BTE and BSFC can re-
spots (carbon deposits, cylinder wall, piston bowl etc.) may occur turn to that of diesel fuel operation with slight improvement.
[1,42]. In addition, high level of hydrogen addition may also modify Although the peak heat release rate with hydrogen addition is still
the diesel oxidation chemistry and uid of diesel fuel would accord- lower than that for diesel fuel operation during upremix, diffusion
ingly decrease as suggested by Arrarwal et al. [43]. combustion is enhanced due to hydrogen combustion. Compared
with diesel fuel operation, the higher heating value and faster
3.2. Engine performance flame propagation speed of hydrogen lead to faster and more
complete diesel–hydrogen combustion and hence higher thermal
The brake thermal efficiency (BTE) and brake specific fuel con- efficiency.
sumption (BSFC) were calculated using Eqs. (4) and (5) [44]. At high loads, hydrogen becomes effective in improving engine
performance. With H30 operation, 12.5% increase of BTE and 11.1%
T  2pn
BTE ¼ ; ð4Þ decrease of BSFC are achieved at 70% load. The above-mentioned
_  LHVULSD þ m_H2  LHVH2
mULSD ‘‘three-stage’’ combustion is probably favorable for improving
engine performance. Compared with H30 operation, H40 operation
BSFC ¼ ½m _ H2 =ðT  2pnÞ;
_ ULSD þ ðLHVH2 =LHVULSD Þ  m ð5Þ has similar heat release rate profile, however, engine performance
where T refers to the engine torque in Nm, n refers to the engine deteriorates. Probably, the extremely high burning rate of
speed in rev min1. The results are shown in Fig. 4. In general, en- hydrogen within the extended upremix consumes a large amount
gine performance interacts closely with the combustion process. of oxygen which reduces oxygen available during udiffusion for
With hydrogen addition, engine performance is always poorer than diesel fuel combustion, resulting in incomplete combustion and
diesel fuel operation at 10% and 30% loads. For example, at 10% load, hence lower thermal efficiency. In addition, the short quenching
the decrease of BTE is 117% and the increase of BSFC 12.8%, on distance of hydrogen flame may also increase wall heat transfer
average of H10 to H40 operations. This is mainly due to the low especially when hydrogen combustion is close to stoichiometric
combustion efficiency of hydrogen under low engine loads as condition such that high flame speed can cause intensified
indicated by the decrease of Pmax and Qmax. In addition, Owston convection [1,46].

50 600

ULSD
500 H10
40 H20
BSFC/(g/kW-hr)

H30
BTE/(%)

400 H40
30

ULSD 300
H10
20 H20
200
H30
H40
10 100
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
BMEP/(MPa) BMEP/(MPa)

Fig. 4. Effect of hydrogen addition and engine load on brake thermal efficiency (BTE) and brake specific fuel consumption (BSFC).
 J.H. Zhou et al. / Applied Energy 126 (2014) 1–12 7

3.3. Regulated emissions 10

ULSD
3.3.1. BSCO2/BSCO emissions 8 H10
One of the intentions for introducing hydrogen into diesel H20

BSHC/(g/kW hr)
H30
engine is to reduce greenhouse gas emission. Fig. 5 shows the H40
6
effect of hydrogen addition on brake specific CO2 and CO (BSCO2/
BSCO) emissions. The average decreases of BSCO2 at 10% and 30%
loads are 1.5%, 5.6%, 21.5% and 25.2% in the sequence of H10 to 4
H40 operations. The percentage reduction of CO2 becomes higher
at medium to high loads and on average from H10 to H40, the 2
decreases of BSCO2 at 50%, 70% and 90% loads are 10.8%, 20.9%,
35.5% and 39.6%, respectively. In general, the percentage reduction
0
of BSCO2 by hydrogen addition depends on the engine load and is a 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
strong function against BTE and BSFC, being lower at 10% and 30% BMEP/(MPa)
loads and higher at 50%, 70% and 90% loads, and the best BSFC is
obtained with H30 operation at 70% load and the highest percent- Fig. 6. Effect of hydrogen addition and engine load on BSHC.
age reduction of BSCO2 is also achieved under the same operating
conditions.
Hydrogen addition is also effective in reducing CO emission. sequence of H10 to H40 operations, compared with that of diesel
However the percentage reduction is not affected by engine load fuel operation. The slight decrease of NOx emission at low to med-
but is affected by the amount of hydrogen added, which is possibly ium loads owes to the lowered combustion efficiency of hydrogen.
due to the overall lean burn nature of diesel engine. Compared At high loads, the fast burning rate of diesel–hydrogen mixture as
with diesel fuel operation, the reductions of BSCO are 14.9%, indicated by the sharp increase of Pmax and Qmax contributes to
29.3%, 44.7% and 53.3%, on average of the five loads, in the high in-cylinder gas temperature which enhances the formation
sequence of H10 to H40 operations. of NOx.
The changes in brake specific NO2 (BSNO2) emission are consis-
tent with results in the literature [22,24,47]. On average of the five
3.3.2. BSHC emission loads, from H10 to H40 operations, the BSNO2 is 2.01, 2.47, 3.05
Fig. 6 shows the effect of hydrogen addition on brake specific and 2.70 times of that for diesel fuel operation. Specifically, the
hydrocarbon (BSHC) emission. In general, BSHC emission is found BSNO2/BSNOx ratio increases with hydrogen addition: it ranges
to be affected by the amount of hydrogen added. Low level of from 39.9% at 10% load to 1.4% at 90% load for diesel fuel operation;
hydrogen addition (H10) increases the BSHC emission by 10.5% from 71.5% at 10% load to 2.4% at 90% load for H10 operation, and
while high level of hydrogen addition of H30 and H40 reduces from 83.3% at 10% load to 4.0% at 90% load for H40 operation.
the BSHC emission by 7.5% and 17.2%, respectively, on average of However, the conversion from NO to NO2 is not depending on
the five loads. Guo and Neill [15] suggested that the oxidation of the amount of hydrogen added, as can be seen in Fig. 7.
hydrocarbon was determined by some key radicals (OH, H, etc.)
when hydrogen was added and was probably related to the 3.3.4. BSPM emission
amount of hydrogen. For example, at 10% load, the BSHC increases Fig. 8 shows the effect of hydrogen addition on brake specific
by 18.0% and 17.2% with H10 and H20 operations, respectively, but particulate matter (BSPM) and normalized PM emission. Normal-
decreases by 3.2% and 14.7% with H30 and H40 operations, respec- ized PM emission is obtained by dividing the BSPM with the brake
tively. To conclude, only high level of substitution of diesel fuel en- specific diesel fuel consumption, expressed in mg/g-ULSD. It can be
ergy by hydrogen can contribute to the reduction of HC emission. found that except for 10% engine load at which BSPM increases by
48.3% and 63.0% under H30 and H40 operation, respectively,
3.3.3. BSNOx/BSNO2 emissions hydrogen is effective in reducing BSPM at other loads. On average
Fig. 7 shows the effect of hydrogen addition on brake specific of the other four loads, BSPM decreases by 33.4%, 50.2%, 60.9% and
NOx and NO2 (BSNOx/BSNO2) emissions. On average of 10%, 30% 69.3% in the sequence of H10 to H40 operations.
and 50% loads, BSNOx decreases by 3.9% with H40 operation, com- There are three potential influences of a gaseous fuel on soot
pared with that of diesel fuel operation. On average of 70% and 90% formation: the dilution effect which changes the amount of carbon
loads, the BSNOx increases by 16.6%, 20.5%, 24.1% and 28.4%, in the per unit mass of the air–fuel mixture; the thermal effect which

1600 9
ULSD 8 ULSD
1400 H10 H10
H20 7 H20
1200 H30
BSCO2/(g/kW-hr)

H30
BSCO/(g/kW-hr)

6 H40
H40
1000 5

800 4

3
600
2
400
1

200 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
BMEP/(MPa) BMEP/(MPa)

Fig. 5. Effect of hydrogen addition and engine load on BSCO2 and BSCO.
8 J.H. Zhou et al. / Applied Energy 126 (2014) 1–12

8 6

ULSD ULSD
H10 5 H10
7
H20 H20

BSNOX/(g/kW hr)

BSNO2/(g/kW-hr)
H30 4 H30
6 H40 H40

3
5
2

4
1

3 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
BMEP/(MPa) BMEP/(MPa)

Fig. 7. Effect of hydrogen addition and engine load on BSNOx and BSNO2.

3.5
500

Normalized PM concentration/
ULSD ULSD
3.0
H10 H10
400 H20
H20
BSPM/(mg/kW-hr)

2.5 H30
H30
300
H40 (mg/g-ULSD) H40
2.0

1.5
200
1.0
100
0.5

0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
BMEP/(MPa) BMEP/(MPa)

Fig. 8. Effect of hydrogen addition and engine load on BSPM and normalized PM.

changes the flame temperature and the chemical interaction effect

which changes the reaction rate or reaction path. Gülder et al. [48] Table 5
Effect of hydrogen addition and engine loads on particle total number concentration
experimentally validated that hydrogen addition in acetylene dif-
(TNC) and geometric mean diameter (GMD).
fusion flame had negligible impact on flame temperature and thus
soot formation was influenced by the dilution and chemical effects BMEP/ ULSD H10 H20 H30 H40
(MPa)
of hydrogen, in which the chemical effect was verified as a reduc-
tion of normalized soot formation. Their results were also verified TNC/(#/cm3)
0.07 6.91E + 06 5.55E + 06 4.54E + 06 3.99E + 06 3.08E + 06
by Guo et al. [49] using numerical simulation. It is of interest to
0.25 1.29E + 07 1.04E + 07 8.00E + 06 7.04E + 06 4.88E + 06
examine the effect of hydrogen addition on the normalized PM 0.41 1.83E + 07 1.45E + 07 1.13E + 07 1.03E + 07 7.68E + 06
emission from a diesel engine as very few related studies have 0.57 2.29E + 07 2.07E + 07 1.79E + 07 1.39E + 07 1.13E + 07
been conducted before. The decrease in normalized PM emission 0.71 5.06E + 07 4.58E + 07 4.13E + 07 2.71E + 07 2.55E + 07
indicates that the reduction of BSPM relies not only on the direct GMD/(nm)
replacement of diesel fuel by hydrogen (dilution effect) but also 0.07 55.8 54.1 53.2 51.7 52.8
on the influence of hydrogen on diesel particulate formation kinet- 0.25 62.0 60.2 58.2 55.2 54.9
0.41 76.0 71.8 68.5 62.3 60.9
ics (chemical effect). 0.57 92.6 88.7 85.4 71.5 69.8
Table 5 shows the total number concentration (TNC) and geo- 0.71 121.2 116.8 107.9 98.2 91.4
metric mean diameter (GMD) of diesel particulate. In general, on
average of all loads, TNC decreases by 15.8%, 30.1%, 43.5% and
55.2% and GMD decreases by 3.9%, 7.9%, 15.6% and 17.2%, respec- in HACA reactions. The effect of hydrogen addition on PAHs
tively, in the sequence of H10 to H40 operations. Both reductions formation relies on R1 (H þ O2 $ OH þ O) and R2 (OH þ H2 $
on TNC and GMD of diesel particulate contribute to the reduction H2 O þ H), where hydrogen consumes the OH radical in R2 while
of BSPM. oxygen consumes the H radical in R1. Probably hydrogen addition
Based on the HACA mechanism (H-abstraction-C2H2-addition) makes R1 dominant than R2, which further consumes H radical. In
[50] as a soot surface growth model, ‘‘H-abstraction’’ (A1 þ H $ consequence, PAHs formation is constrained which leads to both
A1 þ H 2 , A1 refers to one-ring aromatic molecule, benzene) reductions on soot nucleation rate and soot surface growth rate,
activates the aromatic molecules with free radicals and resulting in reductions on normalized PM, TNC and GMD. Park
‘‘C2H2-addition’’ promotes further growth of polycyclic aromatic et al. [51] conducted simulation study on premixed acetylene
hydrocarbons (PAHs), as soot precursor, and soot nucleation flame with hydrogen addition and they reported similar results.
(A1 þ C 2 H2 $ A1 C 2 H2 , A1 C 2 H2 þ C 2 H2 $ A2 þ H2 , A2 refers to the However, the net soot formation rate depends on the competition
two-ring aromatic molecule). Therefore, H plays a dominant role of soot inception and oxidation rates and both of them are temper-
 J.H. Zhou et al. / Applied Energy 126 (2014) 1–12 9

ature-dependent. Therefore, the deterioration in soot oxidation in diesel fuel pyrolysis process. The formation of such intermedi-
rate may become more prominent than that in soot inception rate ates is strongly related to the competition of both diesel fuel ther-
at low engine load which leads to the increase of normalized PM. mal pyrolysis and oxidation rate [55] as well as the temperature
and air-to-fuel equivalence ratio. Low in-cylinder gas temperature
3.4. Unregulated emissions at low engine loads limits both diesel fuel pyrolysis and oxidation
rate which contribute to large amount of intermediates. While at
The effect of hydrogen addition on eight unregulated emissions medium to high engine loads, enhanced oxidation rate at higher
including formaldehyde (HCHO), acetaldehyde (CH3CHO), ethylene in-cylinder gas temperature reduces the intermediates. However,
(C2H4), propylene (C3H6), 1,3-butadiene (C4H6), benzene (C6H6), further increase the engine load reduces the air-to-fuel equiva-
toluene (C7H8) and xylene (C8H10) were investigated. In general, lence ratio and retards the oxidation and in return increases the
hydrogen addition is effective in reducing the unregulated emis- intermediates. Therefore, in this study, gradual decrease of the
sions except for HCHO. intermediates from 10% to 70% engine loads and slight increase
of them at 90% load are observed with diesel operation. Hydrogen
3.4.1. Formaldehyde and acetaldehyde emissions addition can reduce the intermediates effectively for engine loads
HCHO and CH3CHO are two typical aldehyde emissions emitted of 10–70%, because the addition of hydrogen reduces the C–H ratio
from diesel engine and are both classified by EPA as human carcin- and hydrogen does not contain C–C bonds, both of which reduce
ogens and may cause respiratory difficulty, eczema and sensitiza- the two intermediates as suggested by Westbrook et al. [56].
tion [52]. According to Lachaux and Musculus [53], HCHO, as an
intermediate species during diesel oxidation, was formed during 3.4.3. 1,3-Butadiene emission
the ‘‘cool flame’’ stage of diesel auto-ignition and was consumed C4H6, as a common pollutant emitted from both petrol and die-
by OH radicals during the start of the development of diesel diffu- sel engines, is also a human carcinogen which can cause acute and
sion flame. Thus the amount of final survived HCHO depends on chronic symptoms. The effect of hydrogen addition on C4H6 is
the duration of udiffusion and the available OH radical. As shown shown in Fig. 10. Due to the high reactivity of C4H6, Takada et al.
in Fig. 9, HCHO is affected with hydrogen addition due to the var- [57] suggested that it was mainly formed at low engine load within
iation on OH radical since its generation and consumption depends oxygen-rich area which was reverse to the condition for diesel par-
on the competition of R1 and R2 as mentioned before. H30 and H40 ticulate formation. It is consistent with results obtained in the
operations are found to be effective in reducing HCHO emission at present study: at low engine load, high air–fuel equivalence ratio
low to medium loads. For example, with H40 operation, brake spe- contributes to high amount of C4H6 emission and with the increase
cific HCHO decreases by 36.8% and 27.8% at 10% and 50% loads, of engine load, C4H6 gradually decreases and the lowest concentra-
respectively. However, it increases by 53.9% at 90% load. According tion is found at 70% engine load. Hydrogen addition is effective in
to the heat release rate profile, with H40 operation, udiffusion is reducing C4H6 emission. On average of 10–70% engine loads, the
lengthened at low to medium loads and extremely shortened at brake specific C4H6 decreases by 21.4%, 43.2%, 61.1% and 82.0% in
90% load which is probably related to the HCHO emissions since the sequence of H10 to H40 operations. The combustion of diesel
the duration of udiffusion represent the residence time for HCHO fuel and hydrogen consumes more local oxygen and reduces the
to be converted to other species. formation of C4H6. In addition, the increase of NO2 associated with
Hydrogen addition can reduce CH3CHO. On average of 10–70% the use of hydrogen may also lead to the removal of 1,3-butadiene
engine loads, the reductions of brake specific CH3CHO are 16.3%, [58], but this effect is limited at low to medium engine loads
37.8%, 50.2% and 57.0% in the sequence of H10 to H40 operations. according to the NO2 profile.
Arapaki et al. [54] suggested that the incomplete combustion of
paraffin formed CH3CHO emission. Hydrogen addition decreases 3.4.4. Benzene, toluene and xylene emissions
the C–H ratio and directly reduces the paraffin content which leads C6H6 is also a toxic species which can cause leukemia and can-
to the reduction of CH3CHO. At medium to high loads, the increase cer. The effect of hydrogen addition on C6H6 and BTX (total of C6H6,
of in-cylinder gas temperature due to hydrogen combustion may C7H8 and C8H10) are shown in Fig. 11. It is generally accepted that
also enhance the oxidation of CH3CHO. C6H6 is a diesel pyrolysis product, similar with C2H4 and C3H6, and
is the key species which further grows into PAHs. As shown in
3.4.2. Ethylene and propylene emissions Fig. 10, there are corresponding reductions of C6H6, C7H8 and
Fig. 10 shows the effect of hydrogen addition on brake specific C8H10 along with the reduction of normalized PM, TNC and GMD.
C2H4 and C3H6 emissions. C2H4 and C3H6 are typical intermediates The simultaneous reductions of olefins (C2H4, C3H6) and BTX

1800 300

ULSD ULSD
1500 250 H10
BS(CH3CHO)/(mg/kW-hr)
BS(HCHO)/(mg/kW-hr)

H10
H20 H20
H30 200 H30
1200
H40 H40

900 150

600 100

300 50

0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
BMEP/(MPa) BMEP/(MPa)

Fig. 9. Effect of hydrogen addition and engine load on BS(HCHO) and BS(CH3CHO).
10 J.H. Zhou et al. / Applied Energy 126 (2014) 1–12

500 350

ULSD ULSD
400 H10 280 H10

BSC2H4/(mg/kW-hr)
H20 H20

BSC3H6/(mg/kW-hr)
H30 H30
300 H40 210 H40

200 140

100 70

0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
BMEP/(MPa) BMEP/(MPa)

35

ULSD
28 H10
BSC4H6/(mg/kW-hr)

H20
H30
21 H40

14

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
BMEP/(MPa)

Fig. 10. Effect of hydrogen addition and engine load on BSC2H4, BSC3H6 and BSC4H6.

45 65

ULSD ULSD
36 H10 52 H10
BS(BTX)/(mg/kW-hr)
BSC6H6/(mg/kW-hr)

H20 H20
H30 H30
27 H40 39 H40

18 26

9 13

0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
BMEP/(MPa) BMEP/(MPa)

Fig. 11. Effect of hydrogen addition and engine load on BSC6H6 and BS(BTX).

(C6H6, C7H8 and C8H10) emissions indicate that hydrogen addition 4. Conclusions
can reduce the formation of diesel thermal pyrolysis intermediates
and inhibit PAHs formation. In this study, hydrogen was naturally aspirated to a diesel en-
It is noticed that, compared with diesel fuel operation, all the gine to substitute the total fuel energy by 10%, 20%, 30% and 40%
unregulated emissions investigated in this study increase at 90% at five engine loads, and at the engine speed of 1800 rev min1.
load with hydrogen addition. Since the consumption of O, O2 and The engine combustion characteristics, performance, regulated
OH due to hydrogen addition has strong adverse impact on the oxi- and unregulated emissions were experimentally investigated. The
dation of unregulated emissions which is even more dominant at following results have been obtained:
high load and near stoichiometric conditions. Therefore, at 90%
load, hydrogen addition enhances the formation of unregulated (1) Reductions of Pmax and Qmax associated with deterioration on
emissions compared with diesel fuel operation. Especially, for ole- BTE and BSFC are observed with hydrogen addition under
fins, the brake specific C2H4 and C3H6 emissions increase evidently low engine loads due to the low combustion efficiency of
by 86.8% and 84.6%, on average of the four hydrogen energy substi- hydrogen. Two distinct combustion modes are observed
tutions which is due to the promotion of chain reactions driven by under high engine loads. First, a three-stage combustion,
the increased in-cylinder gas temperature. including diesel premixed combustion, hydrogen premixed
 J.H. Zhou et al. / Applied Energy 126 (2014) 1–12 11

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