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Applied Thermal Engineering 18 (1998) 963980

Control of oxides of nitrogen from diesel engines using


diluents while minimising the impact on particulate
pollutants
N. Ladommatos, S. Abdelhalim, H. Zhao
Department of Mechanical Engineering, Brunel University, Uxbridge, Middlesex, UB8 3PH, U.K.
Received 5 February 1998

Abstract
The investigation was conducted on a high-speed direct-injection diesel engine and was concerned
with the eects of exhaust gas recirculation (EGR) on diesel engine combustion and emissions. In
particular, the eects on combustion and emissions of carbon dioxide (CO2) and water vapour (H2O),
principal constituents of EGR, were analysed and quantied experimentally. The eects of increased
inlet temperature and thermal throttling of the inlet charge, both arising from the use of hot EGR, were
also investigated. Finally, tests were carried out during which the CO2 added to the engine air ow
increased the charge mass ow rate to the engine, rather than displacing some of the oxygen (O2) in the
inlet air. It was found that when CO2 or H2O displaced O2 in the inlet charge, both the chemical and
thermal eects on exhaust emissions were small. However, the dilution eect was substantial, and
resulted in very large reductions in exhaust NOx at the expense of higher particulate and unburnt
hydrocarbon emissions. Higher inlet charge temperature increased exhaust NOx and particulate
emissions, but reduced unburnt hydrocarbon emissions. Reduction in the inlet charge due to thermal
throttling reduces NOx emissions but raises all the other pollutants. Finally, when CO2 was additional
to the inlet air charge (rather than displacing O2), large reductions in NOx were recorded with little
increase in particulate emissions. # 1998 Elsevier Science Ltd. All rights reserved.
Keywords: Diesel combustion; Exhaust gas recirculation; Diesel pollutant emissions

1. Introduction
EGR is one of the most eective techniques currently available for reducing NOx emissions in
internal combustion engines. However, the application of EGR also incurs penalties. In the
case of diesel engines these include worsening specic fuel consumption and particulate
emissions [17]. In particular, EGR aggravates the trade-o between NOx and particulate
1359-4311/98/$19.00 # 1998 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 9 - 4 3 1 1 ( 9 8 ) 0 0 0 3 1 - 3

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emissions, especially at high loads [7, 8]. The application of EGR can also aect adversely the
lubricating oil quality and engine durability [911].
1.1. The eect of EGR on engine operation
Fig. 1 summarises the eects of EGR on the inlet charge composition of a diesel engine. In
the example of Fig. 1, 25% of the inlet air ow rate is removed and replaced by an equal
volume ow rate of hot EGR. It can be seen that the eect on the inlet charge is, rstly, a 14%
reduction in the charge mass ow rate. This is due to the reduction in the engine volumetric
eciency as a result of the rise in inlet charge temperature. Secondly, some of the inlet air is
displaced by carbon dioxide (CO2) and water vapour (H2O), which are principal constituents
of EGR. Thus, the application of hot EGR reduces the nitrogen (N2) ow rate to the engine
by about 15% and the oxygen ow rate by 19%. About one-fth of the reduction in the O2
ow rate is due to its displacement by CO2 and H2O present in the EGR, and the remainder
due to reduction in volumetric eciency.
The displacement of inlet charge with CO2 and H2O can alter the combustion process in
several ways, three of which will be considered in detail in this paper. The rst major eect to
be considered will be the reduction of oxygen concentration within the engine cylinders that is
available for combustion; this eect will be referred to as the dilution eect. The second eect
to be considered will be the higher specic heat capacities of both CO2 and H2O in comparison
to that of oxygen; this eect will be referred to as the thermal eect. Both CO2 and H2O can,
potentially, dissociate at the high temperatures prevailing during combustion and the products
of dissociation participate in the combustion process; this eect will be referred to as the
chemical eect of EGR.

Fig. 1. The eect on engine inlet charge of replacing 25% of the inlet air with hot (7008K) EGR (diesel engine at
32:1 AFR).

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When EGR is mixed with inlet air supplied to a diesel engine, the temperature of the inlet
charge to the engine increases; this can aect signicantly the compressed-charge temperature
and the combustion process. The higher inlet charge temperature also reduces the charge
density and the mass of inlet charge admitted to the engine cylinders. This eects will also be
considered in some detail in this paper.

2. Experimental facility and methodology


2.1. Facility
The engine used for the tests was a four-cylinder, 2.5 l, direct-injection, naturally-aspirated,
light-duty diesel engine with bowl-in-piston combustion chamber. The engine was modied so
as to separate the inlet and exhaust ports for cylinder number one (no. 1) [36]. The other
three cylinders remained in operation and shared inlet and exhaust systems. Provision was
made to inject various gaseous diluents (CO2, Ar, N2, O2, He) and water in the inlet system of
the no. 1 cylinder. A thermostatically-controlled electric heater was located upstream of the
inlet to the cylinder no. 1 so as to allow the inlet charge temperature of this cylinder to be
varied independently. Thermostatically-controlled electric tape-heaters were used in the no. 1
intake down-pipe, which was also insulated, in order to ensure that all the injected water
entered the no. 1 cylinder in the superheated vapour state. The rst cylinder was also equipped
with a fuel-injector needle-lift sensor and a ush-mounted piezoelectric pressure transducer.
The desired constant timing of 108 crank angle (CA) before top dead centre (BTDC) was
maintained precisely constant by mechanically locking the injector pump cam ring at this
timing. The injector needle-lift and the cylinder gas pressure signals were monitored and
recorded by means of a high-speed (up to 1 M Samples/s), 12-bit computerised data acquisition
system sampling every 0.58 CA using the degree pulses from the crank-shaft encoder. The tests
were conducted at 2000 r/min (constant speed) and constant fuel consumption equivalent to
that of about 40% load. The fuel consumption and the inlet-charge mass to the no. 1 cylinder
were kept constant for all tests, irrespective of the inlet charge composition and temperature;
also the same batch of diesel fuel was used throughout all the tests. Table 1 summarises the
engine test conditions. More information on the test facility and methodology can be found in
references [36].
2.2. Combined eects of CO2
In order to isolate the dilution, thermal, and chemical eects of CO2 (a principal constituent
of EGR) a number of carefully controlled engine tests were carried out. In a rst series of tests
the three eects, combined, were investigated by progressively substituting some of the O2 in
the inlet air to the engine by CO2, whilst maintaining the total charge mass ow rate and the
fuel mass ow rate to the engine constant. The way this was achieved is explained in detail in
refs [3, 4].

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2.3. Isolation of the dilution eect


In order to isolate the dilution eect, both the thermal and chemical eects had to be
eliminated. This meant that some of the O2 in the inlet air had to be removed and replaced by
a chemically inert gas which had the same specic heat capacity as O2. Therefore, some O2 was
progressively removed from the inlet air and replaced by an equal mass of a mixture of N- and
argon (Ar). The proportions of N2 and Ar in this mixture were chosen carefully so that the
mixture had the same specic heat capacity as O2 throughout the temperature range 600
30008K. Since the mixture of N2 + Ar was chemically `inert' and had the same specic heat
capacity as O2, the thermal and chemical eects of CO2 were eliminated and only the dilution
eect remained. For example, a mixture of 18.3% O2 + 81.08% N2 + 0.62% Ar has the same
specic heat capacity as air (23.3% O2 + 76.7% N2) throughout the temperature range 600
30008K.
2.4. Isolation of the chemical eect
In order to isolate the chemical eect, both the dilution and thermal eects had to be
eliminated. This meant that the O2 concentration in the inlet charge to the engine now had to
be kept constant and some of the N2 in the inlet air replaced by CO2. However, since CO2 has
a higher specic heat capacity than N2 that it was replacing, the thermal capacity of the inlet
charge to the engine would have increased, contrary to what was desired. Thus, in order to
keep the inlet charge thermal capacity constant (and equal to that of air), an additional
amount of N2 in the inlet air was removed and replaced by a carefully controlled amount of
Ar which has a much lower specic heat capacity than N2. In this way, the higher specic heat
capacity of CO2 was oset, and the thermal eect of CO2 was eliminated.
2.5. Isolation of the thermal eect
In order to isolate the thermal eect, the dilution and chemical eects had to be eliminated.
This meant that the O2 concentration in the inlet charge to the engine had to be kept constant
and some of the N2 in the inlet air replaced by an inert gas of higher specic heat capacity
than the N2 that it was replacing. The inert gas chosen to replace N2 was helium, He, which
has a substantially higher specic heat capacity than N2. Thus, the specic heat capacity of the
inlet charge was progressively increased, high-lighting the thermal eect on engine emissions.
2.6. Isolation of the inlet-temperature eect
In another series of tests, the temperature of the inlet charge was progressively raised from
40 to 1208C in order to study the eect on emissions of higher inlet charge temperatures
associated with hot EGR. For this test the inlet charge mass to the no. 1 engine cylinder was
kept constant (9.0 g/s) as was the fuelling rate for no. 1 cylinder (0.202 g/s). O2 concentration
was also kept constant (inlet charge composition 17.3% O2, 81.95% N2, 0.75% Ar), as was the
injection timing (108CA BTDC).

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2.7. Isolation of the thermal throttling eect


To simulate the reduction in inlet mass ow rate arising from the use of hot EGR (reduction
in inlet charge density), the inlet air mass ow rate to the no. 1 cylinder was progressively
throttled from 10 to 8.5 g/s in steps of 0.5 g/s, whilst maintaining the inlet charge temperature
constant.
In a subsequent series of tests, only the nitrogen in the air was progressively reduced, whilst
the oxygen mass ow rate to the engine was kept constant. This was achieved by injecting into
the inlet manifold calculated amounts of oxygen and helium, while throttling the inlet charge
air (Helium was injected as well in order to keep the specic heat capacity of the inlet charge
the same as for air). These tests allowed the following question to be answered: when the inlet
charge mass is reduced isothermally, is it the reduction in the charge mass itself that is
important, or is it the consequent reduction in the amount of oxygen mass rate to the engine
that controls emissions?
2.8. Compensation for changes in ignition delay
The various changes to the engine inlet charge composition and temperature altered the
length of the ignition delay period. These changes in ignition delay caused changes in
particulate and other exhaust emissions, for example, by increasing the proportion of
premixed-fuel burning, or by retarding the bulk of the combustion process further into the
expansion stroke. On the other hand, the dilution, chemical and thermal eects of CO2 also
caused additional modications to the combustion process which occurred after the ignition
delay period. It was felt desirable to isolate the eects on exhaust emissions of changes in
ignition delay and account separately for such changes. This was done by using a commercial
ignition improver (2-ethyl hexyl nitrate) in small concentrations (typically 3000 ppmv). By
using the ignition improver it was possible to shorten the ignition delay back to the level
without inlet charge diluents. Thus any increase in delay due to the introduction of diluents in
the inlet charge to the engine could be oset, and the eect of increased delay could be
accounted for separately.

3. Results and discussion


3.1. Eects of CO2 on emissions
Fig. 2 shows the reduction in exhaust NO emissions due to the replacement of O2 in the
inlet charge by CO2. For this gure, the O2 concentration in the inlet charge was gradually
reduced from 23.3%(m) (by mass) to 16.3%(m) by replacing it with CO2. The gure also
shows how much of this reduction is accounted for by the dilution, chemical, and thermal
eects. It can be seen from this gure that when O2 equivalent to 7% of the inlet charge mass
is replaced by CO2 (that is, when O2 in the inlet charge is reduced from 23.3 to 16.3%), the
reduction in NO is very substantial; the NO concentration in the exhaust is reduced to one-

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Fig. 2. Eects on nitric oxide emissions of carbon dioxide replacing oxygen in the inlet charge.

tenth of its original level. It is also interesting to note that once O2 in the inlet charge is
reduced from 23.3 to 17.3% (i.e. 6% of the inlet charge is replaced by CO2), strong
diminishing returns set in, with very little additional reduction in NO being obtained with
further substitution of O2 in the charge.
Fig. 2 also shows that the reduction in O2 concentration (dilution eect) accounts for most
of the observed reduction in NO. The dissociation of CO2 and its participation in the
combustion process (chemical eect) is seen to have had a much smaller eect on NO
emissions. The high specic heat capacity of CO2 (thermal eect) hardly inuenced the NO
emissions at all.
In order to isolate the eects on NO of the increase in ignition delay, the following test
was run: the O2 concentration in the inlet charge was reduced from 23.3 to 17.3%(m) and
the O2 was replaced by a mixture of N2 + Ar having the same mass and specic heat capacity
as the oxygen being replaced. This replacement of O2 in the inlet charge had the eect of

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Fig. 3. Nitric oxide emissions at constant inlet oxygen concentration (17.3%(m)) with ignition delay progressively
reduced using cetane improver.

prolonging the ignition delay from 7.98CA (when the engine was running with air only) to
11.78CA. Whilst the engine continued to run at this condition, the ignition delay was
progressively reduced from 11.7 back to 7.78CA by adding gradually increasing amounts of
ignition improver (2-ethyl hexyl nitrate) to the engine fuel. Fig. 3 shows that the eect
of ignition delay alone on NO is rather small in comparison with the eects of reducing
the oxygen available for combustion. Plots similar to that in Fig. 3 were produced for the
other exhaust emissions (NOx and Particulates) and the eects of ignition delay were conrmed
to be of secondary importance in comparison with the dilution eect on the levels of these
emissions.
Fig. 4 shows that the particulates increased more than four-fold when the O2 concentration
in the inlet charge was reduced from 23.3 to 16.3%(m) by replacing it with CO2. Fig. 4 also
shows clearly that the reduction in O2 availability for combustion (dilution eect) is responsible

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Fig. 4. Eect on total particulate emissions of carbon dioxide replacing oxygen in the inlet charge.

for the large increase in particulates. In fact, the dilution of the inlet charge can be seen to be
greater than the overall eect of CO2. However, the detrimental eect of dilution is moderated
to some extent by the chemical eect of CO2 which reduces the particulate emissions as shown
in Fig. 4. A chemical eect of CO2 in reducing particulate emissions (possibly through
suppression of soot formation or enhancement of the soot oxidation) was also reported by
other workers [1214].
The particulate mass emitted in the exhaust was analysed for volatile organic fraction
(VOF) and carbonaceous fraction (residual). This was achieved by placing the particulate
lters for 24 h in an evacuated oven which was continuously being purged with lowpressure nitrogen at 2008C. The loss in weight was then taken as being the VOF of the
particulates. The results showed that the increase in the particulate emissions with increasing
inlet charge dilution was mainly attributable to the increase in the carbon fraction of the
particulates [3].

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3.2. Eects of HO vapour on emissions


Fig. 5 shows the eects of on NOx emissions of water vapour replacing oxygen in the inlet
charge. For this gure, the O2 concentration in the inlet charge was gradually reduced from
23.3%(m) (by mass) to 20.3%(m) by replacing it with H2O vapour. The results are very similar
to those obtain with CO2 replacing oxygen in the inlet charge. Again, the dilution eect
dominates, while both the thermal and chemical eects are very small by comparison.
Fig. 6 shows the eects on particulate emissions of water vapour replacing oxygen in the
inlet charge. As in case of CO2 replacing oxygen in the inlet charge, the dilution eect on
particulate emissions is the greatest. However, the chemical eect is greater in the case of H2O
in comparison to that for CO2 replacing oxygen in the inlet charge; the reasons for this are not
apparent. Once more, the thermal eect is very small.

Fig. 5. Dierent eects of water vapour replacing oxygen in the inlet charge on nitrogen oxides emissions.

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Fig. 6. Dierent eects of water vapour replacing oxygen in the inlet charge on the particulate emissions.

3.3. Eects of inlet charge temperature


The temperature of the inlet charge was progressively raised from 40 to 1208C whilst maintaining the inlet charge mass ow rate to the no. 1 engine cylinder constant (9.0 g/s). Fig. 7
shows the eect of gradually increasing inlet charge temperature on exhaust NO emissions,
after osetting the eects of inlet charge temperature on ignition delay. It can be seen from
this gure that when the inlet charge temperature was raised from 40 to 1208C, the exhaust
NO level increased from 60 to 170 ppmv. However, Fig. 7 shows that at least 40% of this
increase in NO could be attributed to the reduction in ignition delay. With constant injection
timing at 108CA BTDC, the shortening of the ignition delay caused combustion to take place
closer to TDC, resulting in increased gas temperature and higher NO formation rate.
Fig. 8 is particularly interesting because it shows that exhaust particulate emissions also
increased by over 50% when the inlet charge temperature was raised from 40 to 1208C.

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Fig. 7. Inuence on nitrogen oxides emissions of inlet charge temperature at constant inlet charge mass and oxygen
concentration (17.3%(m)).

Furthermore, Fig. 8 shows that virtually none of this increase can be attributed to the
shortening of the ignition. It is possible that the increasing inlet charge temperature led to an
acceleration of fuel pyrolysis in the fuel-rich regions of the spray core, resulting in accelerated
soot formation. At the same time, however, it is possible that soot oxidation was also
enhanced by the higher combustion temperature, but not to the same degree as soot formation
in the spray core.
3.4. Eects of thermal throttling on emissions
The inlet air mass ow rate to the no. 1 cylinder was progressively throttled from 10 to
8.5 g/s in steps of 0.5 g/s, whilst maintaining the inlet charge temperature constant (i.e.,

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Fig. 8. Inuence on particulate emissions of inlet charge temperature at constant inlet charge mass and oxygen
concentration (17.3%(m)).

isothermal throttling). Fig. 9 shows that throttling the inlet air has only a very small eect on
NO emissions. The small eect is due to two major but opposite eects, which tend to cancel
each other out. First, the reduction in the inlet charge air ow rate tends to raise the peak
cylinder gas temperature and NO production, because the same amount of energy is now
absorbed by a smaller trapped mass in the engine cylinder. Secondly, however, the reduction in
oxygen supply to the engine, resulting from throttling the air, tends to reduce the peak cylinder
gas temperature and NO production.
Fig. 10 shows that throttling the inlet air increases the smoke emission from the engine.
Again, this is the net result of two opposing eects. First, the reduction in the inlet charge air
ow rate tends to raise the peak cylinder gas temperature and, probably, the soot oxidation
rate, resulting in lower soot emission in the exhaust. Secondly, however, the reduction in

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Fig. 9. Eect of throttling the inlet charge on nitric oxide emissions.

oxygen supply to the engine, resulting from throttling the air, tends to reduce the soot
oxidation rate, resulting in increased soot emission. The second eect dominates the rst, and
the net result is an increase in soot (smoke) emission from the engine.
3.5. The eect of increasing inlet charge mass by CO2 addition
The basic dierence between the use of EGR in gasoline and diesel engines is that EGR
displaces air in diesel engines, whilst in gasoline engines the EGR mass is additional to the
mixture mass required for a given engine power output [6].
Tests were carried out during which, instead of CO2 displacing oxygen in the air supplied to
the engine, the CO2 mass was additional to the air mass ow rate. For these tests, the engine
was rst operated with an air ow rate of 10 g/s per cylinder, as in previous tests, and the
exhaust emissions were recorded. Then, 1 g/s per cylinder CO2 was added to the air mass ow

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Fig. 10. Eect of throttling the inlet charge on smoke emissions.

rate and the emissions were again recorded. Because the addition of 1 g/s per cylinder CO2 to
the inlet air increased the ignition delay from about 8 to 9.88CA, ignition improver was used to
shorten the ignition delay back to 88CA. Fig. 11 shows that the addition of 1 g/s per cylinder
CO2 reduced the NOx level to almost one-third, with the change in ignition delay not being
responsible for any of this reduction.
Fig. 12 shows that the addition of the 1 g/s per cylinder CO2 increase particulates by about
30%. However, almost all this increase is attributable to the increase in ignition delay. When
the increase in delay is oset by ignition improver, the particulate emissions with and without
the additional 1 g/s CO2 are at about the same level.
The results from the addition of 1 g/s per cylinder CO2 are particularly interesting because:
(i) The O2/fuel ratio supplied to the engine is not altered, unlike the case of displacing O2 by
CO2; the generation of soot and particulate emissions is not, therefore, greatly aected.

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Fig. 11. Oxides of nitrogen emissions for test with carbon dioxide added to the inlet air and ignition delay
progressively reduced using cetane improver.

(ii) The extra mass of CO2 raises substantially the total heat absorbing capacity of the inlet
charge to the engine, leading to signicant reductions in combustion temperature and
substantial reductions in NOx emissions.
The addition of CO2 to the inlet air mass ow rate appears to be a very eective way of raising
the heat absorbing capacity of the inlet charge. In contrast, when CO2 displaced O2, as in the
tests described earlier in this paper, the higher specic heat capacity of CO2 hardly raised the
overall heat absorbing capacity of the inlet charge (this is demonstrated in ref. [3] which shows
EGR raising the overall specic heat capacity of the inlet charge from 1.26 to only 1.27 kJ/
kgK, or by less than 1%).

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Fig. 12. Particulate emissions for test with carbon dioxide added to the inlet air and ignition delay progressively
reduced using cetane improver.

4. Conclusions
(i) The introduction of CO2 and H2O in the inlet charge resulted in a reduction in NOx and an
increase in the particulate emissions (which, in the case of CO2, was dominated by dry
soot).
(ii) When some of the O2 in the inlet charge was replaced by CO2 or H2O, the dominant eect
on emissions was the reduction of oxygen availability for combustion (dilution eect); the
higher specic heat capacity of the CO2 or H2O in comparison to that of the O2 it replaced
(thermal eect), had virtually no eect on emissions.
(iii) `Chemical eects', resulting from the dissociation of the CO2 or H2O, were responsible for
only moderate eects on NOx and particulates.

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(iv) Increasing the inlet charge temperature (at constant inlet charge mass ow rate) resulted in
an increase in both NOx and particulate emissions. In practice, there will be benets from
cooling the EGR, in terms of reduced NOx and particulates.
(v) Throttling the inlet charge mass at constant inlet charge temperature (isothermal throttling)
has only a small eect on exhaust NOx but raises exhaust smoke emissions substantially.
(vi) Adding EGR to the air ow rate to the engine, rather than displacing some of the inlet
air, appears to be a more benecial way of utilising EGR in diesel engines. This way may
allow exhaust NOx emissions to be reduced substantially with little penalty of increased
particulate emissions.

Acknowledgements
The nancial support of the Engineering and Physical Sciences Research Council (EPSRC)
and the technical support of Ford Motor Company are gratefully acknowledged.

References
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