1.

INTRODUCTION

Today world is facing dangerous problem of ‘Air Pollution’.

The major cause is obviously emissions from automobiles. With the
intentation to protect public health. Several nations are issuing
stricter and stricter regulations for both solid and gaseous exhausts.
In particular the trend is to restrict the limit of Particulates and NO X
emissions.

Diesel engines are reliable, fuel efficient, durable, easy to

repair, inexpensive to operate, less CO & HC. However their future
applications will greatly depend on the successful solutions of their
NOX and Particulate Matter (PM) emissions. As the two pollutants are
difficult to controlled simultaneously by only one of the control
measures.

To assure survival of diesel engines, research work is going

on to find effective solutions to control diesel exhausts, especially
Particulates & NOX.

PLASMA-the Fourth State of Matter [5] has found increasingly

wide applications in various industries. Some of them are especially
for treatment of Particulates & NOX. However very few are concerned
with the treatment of diesel Particulates.

In this paper, Plasma technology is discussed for exhaust

aftertreatment. Corona Discharge Device (CDD) The Corona Discharge
[6]
Device (CDD) significantly reduces HC, CO and Nox emissions and
non thermal Plasma (NTP) Reactor [3] which removes both Particulates
as well as NOX are discussed here.

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 2. THEORY BEHIND PLASMA TECHNOLOGY

2.1 WHAT IS PARTICULATE?

Particulates are results of incomplete combustion of diesel

engines & lubricating oil. Anything collected on plastic coated fibre
glass test filter at temperature below 125° F (51.7° c) and excluding
condensed water droplets is known as diesel particulates.

Nature of particulates: a) solid.

b) Liquid compounds.

Size: single particulate – about 0.01um

Large chain – about 10-30 um [3]
Composition: Diesel particulate = Black smoke soot + HC.

Effects of Diesel Particulates

1) Aggregate Chronic Lung Problems of Bronchis and
Emphysema,
2) Effect Mortality and Morbidy,
3) Affect visibility or opacity,
4) Mutagenic,
5) Most adverse effect is those particulates are carcinogenic.

Causes of Particulate Emissions

1) Interaction of Unburnt mixture with CC Wall.

2) Poor Atomization.
3) Local fuel rich or lean zone.
4) Late Injection.
5) Incomplete Combustion of fuel.

Control Methods: –

1) To improve CC design & fuel Injection.

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2) To Control Engine parameters.
3) Exhaust Aftertreatment.

Due to optimization of Diesel Engines, first two methods are

not suitable. The third way seems not only easiest to follow in future
but especially the only one assuring survival of C.I. Engines as such.
However; the problems to be solved in order to get effective filtering
systems are considerable. In particular, it must work automatically,
suitably without failure for long periods & have acceptable cost.

Current aftertreatment methods:

The systems for particulate removal can be grouped as
A. Particulate Traps or Filters.
E.g. Ceramic traps or Steel Wool Filters. etc.
Limitations:
1. Increase in back pressure.
2. Low filtration efficiencies.
3. Limited capacity per unit volume.
B. Regenerators:

The accumulations of particule on the trap cause a progressive

increase of back pressure. The convenient method is to carry an
effective oxidation process using regenerators it requires high
temperature.

Methods of Regeneration:
A. Increasing trap temperature system.
1. External energy system.
2. Throttling regenerators.
B. Reduction of Activation energy
3. Catalytic fuel additives.
4. Catalytic converters.
Limitations:
1. Poor durability.

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 2. Thermal stresses cracking & melting of substrate.
3. Increase in back pressure decreases oxidation efficiency.
4. Lead is carcinogenic.

2.2 WHAT IS PLASMA?

Plasma is often called as “Fourth State of Matter”, the other

three being solid, liquid, and gas. Sir William Crookes, an English
physicist, identified a fourth state of matter now called as Plasma, in
1879[5]. Plasma in stars and. Plasma in the stars and in the tenuous
space between them makes up over 99% of the visible universe and
perhaps most of that which is not visible.

The Plasma state is gaseous collection of electrically charged

particles with nearly equal numbers of negative particles and positive
ions. Though they can exist at low temperature, they are typically
come in existence when gases are heated at very high temperature.

In ordinary gas each atom contains an equal number of

positive and negative charges; the positive charges surrounded by an
equal number of negatively charged electrons, and each atom is
electrically neutral. A gas becomes Plasma when the addition of heat
or other energy causes a significant number of atoms to release some
or all of their electrons. The remaining part of those atoms is left with
a positive charge and the detached negative electrons are free to move
about. Those atoms and resulting electrically charged gas are said to
be “ionized”. When enough atoms are ionized to significantly affect the
electrical characteristics of the gas, it is “Plasma”.

Plasma can be accelerated and steered by electric and

magnetic fields, which allows it to be controlled and applied. Plasma
research is yielding a greater understanding of the universe.

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 3. WORKING OF PLASMA TECHNOLOGY

3.1 CORONA DICHARGE DEVICE

The Corona Discharge Device, called the CDD, was developed to

increase the in-use efficiency of the exhaust gas aftertreatment system
by mitigating the negative effects of undesirable material in the
exhaust gas of the engine. The CDD permits the vehicle’s catalyst to
remain highly efficient during the full life of the vehicle. This allows
the vehicle to meet in-use compliance regulations both during any
emission test and also, during it’s actual on-road use with a minimum
of precious metals in the catalyst.

3.1.1 THE CDD SYSTEM. [6]

1. It converts low voltage direct current battery power to a high

voltage high frequency supply. This is done in the power
module.
2. The high voltage high frequency supply is delivered through the
cable to an electrode to an electrode of a barrier discharge
device, which has alternate electrode and dielectric barriers. as
shown in figure 3.1.
3. The corona generated through the dielectric by means of this
barrier discharge creates non-thermal Plasma in the exhaust
gas. This takes place in the CDD itself as seen in Figure 3.2.
The corona is found in the gap between the dielectric material
and the ground.
4. The exhaust gas is directed, at a significant space velocity,
through the corona so as to alter the exhaust gas constituent
chemistry, creating radicals.
5. The radicals continue to be generated in a continuation reaction
sequence that combine with and prevent material, such as

5
 sulfur, from contaminating the precious metal in the catalyst,
keeping the catalyst more highly efficient.

3.2 The CDD PROCESS. [3]

1. Point Source Generation of Highly Active Species

A fraction of the exhaust flow (between 5% to 20%

depending on flow conditions passes through the electric discharge
region of the CDD. The CDD produces radicals, such as Hydroxyl
(OH), and other Oxidizing species, such as O3 and NO2 in the exhaust
gas.

2. Gas Phase Reactions Enable Radicals to Reach the

Catalyst

Downstream of the CDD, various radicals, such as OH,

generated by the CDD initiate gas phase reactions that generate
oxidized hydrocarbon species (HCO), convert NO to NO2, and
subsequently regenerate OH radicals. This reaction mechanism
enables short-lived radicals, which are generated at the CDD, to reach
the catalyst surface.

3. Radical Species Change the Catalyst Surface and

Enhance Catalytic Activity

Fuel sulfur, even at levels as low as 30 ppm, is a significant

poison to the catalytic activity of platinum group metals (PGM) such
as Pt, Pd, or Rh. catalytic activity is a strong function of the surface
coverage of the PGM sites. Small changes in the sulfur surface
coverage of the catalyst, when the coverage is in the range of 15% -
25%, significantly alters the overall catalytic activity. The OH and NO2
produced by the CDD, and propagated by subsequent gas phase
reactions, act to reduce the sulfur coverage. It shows that both OH

6
and NO2 react with the sulfur on the PGM surface and with nearby
oxygen, to liberate the sulfur to the gas phase in the form of SO or SO2
. Such reaction mechanisms are known as a Rideal-Eley process.

Figure 3.1 CDD Cross Section

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 Figure 3.2 Exhaust flow and process model.

3.2 NON THERMAL PLASMA REACTOR

Full scale packed NTP prototype systems (active volume

2600 cm6) were tested on a vehicle and PM removal was determined
by gravimetric, opacity, ultrafine particulate and PAH measurement. A
schematic of the NTP reactor design can be seen in Figure 3.3

The exhaust gas from diesel engine is passed through

perforated inner electrode. The gas then moves in region of Plasma
between inner amounts outer electrode over the packing material such
as ceramic bed, soot etc. and then goes out through rear portion of
reactor.

It is seen by introducing a packing material in NTP reactor it

is possible to increase the residence time, which allows complete
oxidation to be achieved more economically than previously predicted.
It happens because certain species from the exhaust can adsorb or
trap and be removed from the gas phase.

Experiments were performed to confirm the NTP oxidation of

diesel soot in packed reactors and to explore the mechanisms involved
in the process. NTP reactors had the capability of being operated
empty, or being filled with packing material such as ceramic beads,
fibre filters, foams or monoliths as desired.

The vehicle used in the tests was a 1994 model LTI Fairway
London Taxi equipped with a Nissan 2.7l IDI diesel engine In the
vehicle experiments the Plasma system was fitted in place of the
vehicle's original muffler and was designed to have a similar

8
backpressure characteristic over the operating load and speed range
of the engine. The pressure drop across the packed NTP system was
20 mbar at 1500 rpm full throttle increasing to 90 mbar at 3500 rpm
full throttle.

Figure 3.3 Photography of plasma reactor

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 Figure 3.4 Cut-away of the NTP reactor

4.EXPERIMENTAL RESULTS AND DISCUSSIONS

[6]
4.1 EXPERIMENTAL RESULTS FOR CORONA DICHARGE DEVICE

(A) Table 4.1 illustrates percentage reductions in hydrocarbons (HC),

carbon monoxide (CO) and oxides of nitrogen (NOx) when a Litex CDD
is used with fuel having sulfur content from 0 to 300 parts per
million.

(B) Figure 4.1 illustrates additional reductions in pollutants when a

catalytic converter, poisoned by driving 50,000 miles (80,650
km.)With high-sulfur fuel, is run for 50 hours with a Litex CDD in the
exhaust

(C) The following figures illustrate automobile exhaust emission levels

across varying fuel-sulfur levels during engine testing of the Corona
Discharge Device. In every case, the top line represents exhaust
emissions with the CDD turned off, while the bottom line represents
emissions with the CDD turned on.
Figure 4.2 indicates that the CDD can reduce hydrocarbons
by 33 percent even in fuel that contains zero sulfur.
Figure 4.3 indicates that the CDD can reduce oxides of
nitrogen by more than 50 percent.

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 Figure 4.4 indicates that a CDD-equipped automobile
running on fuel with a sulfur level of 100 ppm emits the same amount
of carbon monoxide as an unequipped car running on 30 ppm.

Fuel sulphur
level HC CO NOX
Parts Per Million
0 33% 58% 54%
30 31% 61% 55%
100 26% 50% 46%
300 26% 40% 22%

Table 4.1 Harmful emission reduction using CDD.

Figure 4.1 Emissions v/s

hours of operation.
Figure 4.2 THC v/s fuel

sulphur.

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 Figure 4.3 CO v/s fuel sulphur.

Figure 4.4 NOX v/s fuel sulphur.

4.2 EXPERIMENTAL RESULTS FOR NON THERMAL PLASMA

REACTOR. [3]

4.2.1 LABORATORY BASED EXPERIMENTAL SYSTEM.

Laboratory scale experiments were conducted on a small

scale NTP system (active volume 200 cm6) in order to confirm
oxidation of carbonaceous PM and to explore the mechanisms
involved.

In the laboratory experiments a bank of gas analysers and

an FTIR spectrometer were used to study the composition of the
gaseous exhaust emissions. PM measurements were performed by
filter paper sampling (Whatman GFA). Exhaust was provided by a
Lombardini diesel generator set (5 kVA rating), working at 3.6kW

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loading and running on RF73 diesel fuel containing between 350 ppm
and 500 ppm Sulphur

The exhaust gas composition was typically NO- 500ppm,

NO2 - 10 ppm, CO2 - 4.2.4%, O2 - 15.25%, H2O - 3.0 %, Total
hydrocarbons (THC) in C1 equivalent - 300ppm, N2 - balance, PM -
0.06 g/h (equivalent to a challenge of 0.78 g/h in the full scale
prototype system).

4.2.2 VEHICLE BASED EXPERIMENTAL SYSTEM.

Two configurations were employed to take measurements on

the full scale NTP system, a light duty transient engine dynamometer
and a vehicle chassis dynamometer. The engine dynamometer was
connected to emissions monitoring equipment comprising, Horiba
MEXA 7200TDR and 71000DEGR gaseous analysers and a Horiba
110 DPAS particulate measuring system, which incorporates a TEOM.
The chassis dynamometer was a 65 kW Consine dyno with full
dynamic simulation housed in a thermostatically controlled test
enclosure.

4 .2.3 VEHICLE BASED EXPERIMENTS

(A) OPACITY STUDIES.

A Celesco Research smoke meter was used to measure the

opacity of the exhaust under several different sets of conditions. Tests
were conducted at 120kph steady state and under free acceleration.
The results are shown in Figure 4.5. Emissions at steady state were
low even with the standard exhaust system it can be seen that the
Plasma device significantly reduced the visible smoke emissions under
free acceleration.

(B) GRAVIMETRIC STUDIES.

The reduction in total mass of PM can be seen by reference

to Figure 4.6. Measurements were taken over the standard European

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drive cycles (ECE/EUDC), at ambient temperature of 25°C. An
additional test was performed at 0°C to simulate cold-start conditions.

(C) PM SIZE DISTRIBUTION STUDIES.

The effect on the concentration of ultrafine particulate

matter with mean diameters of less than 300 nm was tested using a
scanning mobility particle sizer (SMPS). Figure 4.7 effect of the reactor
on the ultrafine particulate distribution measured under steady state
conditions. The packed Plasma system removed 99.9% of PM of
average diameters around 60nm.

(D) PAH REMOVAL STUDIES.

The concentrations of sixteen PAHs were monitored using

gas chromatography and mass spectrometry (GC/MS). The results of
this work are shown in Figure 4.8. Amounts of these compounds in
the exhaust were reduced significantly with the use of the packed NTP
aftertreatment system.

Figure 4.5 Opacity testing Figure 4.6 Total particulate

Mass Testing

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 Figure 4.7 Ultrafine particle testing with the NTP reactor

Figure 4.8 PAH testing with the NTP reactor

4.2.4 LABORATORY-SCALE EXPERIMENTS

(A) IMPACT OF SOOT AND PACKING ON NO TO NO2 CONVERSION.

All of the results presented are for systems running on

unfiltered exhaust unless stated otherwise in the text. Figure 4.9
shows the conversion of NO to NO2 in an unpacked reactor. The
conversion increases with increasing energy density and NO2 becomes
the majority NOx species at energy densities above 25 joules per litre.

(B) PACT OF SOOT AND PACKING ON HYDROCARBON OXIDATION.

Figures 4.10 show the changes in concentrations of CO and

CO2 relative to the engine out emissions as functions of energy density
in each of the reactor configurations. Figure 4.11 shows the changes

15
in the absolute concentration of THC, measured as C1, as a function of
energy density in each of the reactor configurations. It can be seen
that when using a packed reactor with soot-filtered exhaust more of
the hydrocarbon is removed and converted to CO at a given energy
density than for the experiment when soot was present.

(C) SOOT OXIDATION IN A SYNTHETIC EXHAUST STREAM.

In order to further study the PM oxidation mechanism, the

packing material in the laboratory reactor was pre-coated in either
diesel exhaust PM or carbon black. The reactor was then operated at
70 J/l and 200_C in a CO2 free simulated exhaust comprising 90% N2
and 10% O2. The CO2 evolution was then recorded as a function of
time. The Plasma was initiated at time t=0 minutes and extinguished
at time t=240 minutes. The data from this experiment, using
Acetylene black (Denka Carbon), can be seen in Figure 4.12. A steady
state concentration of approximately 200ppm of CO2 was liberated
from the soot oxidation. After approximately 200 minutes, the CO2
returned
to zero and
visual

observation of the packing confirmed removal of the acetylene black.

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 Figure 4.9 NO and NO2 concentrations in an UN packed reactor

Figure 4.10 The

concentrations of CO. Figure 4.11 The THC concentration.

Figure 4.12 Evolution of CO2 as a function of time.

5.PROCESS LIMITATIONS AND IMPLICATIONS FOR

PLASMA-CATALYST REACTOR DESIGNS [3]

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5.1 PROCESS EFFICIENCY.

A version of the full-scale system was run in steady state

mode with the engine running at 155 Nm torque and 2500 rpm. 2.34
gm/Hr of soot were continuously oxidized from a flow of 2700 l/min.
By varying the operating frequency of the system the Plasma power
was varied from 1400 W (31J/L) to 800 W (18 J/L). At the lower power
range, determined by the limit of resonant operation of the power
supply and reactor system, continuous oxidation was still observed.
From this we can determine an upper bound to the power required for
soot oxidation to be 0.34 kW-hr/gm.

5.2 PLASMA-CATALYST REACTOR DESIGN CONCEPTS.

In a two-stage system relying upon the Plasma oxidation of

hydrocarbons to promote NO to NO2 conversion as a precursor to NO2
reduction over a catalyst, the presence of PM may lower the number of
O atoms and hydroxyl radicals available for reaction. This will reduce
the capacity for enhanced NO to NO2 conversion. The implication is
that in circumstances where a filter may act to retain soot in the
Plasma reactor, the NOx reduction capacity of the overall system may
be reduced, unless hydrocarbon levels are high enough to allow
hydrocarbon oxidation to compete with the faster soot oxidation
process. This would suggest that the packed Plasma reactor may not
be suitable as the first stage in a Plasma-catalyst system where the
catalyst is sensitive to NO2. Even in situations where packing
materials are not used, the effects of electrostatic trapping of PM in
the Plasma region together with time-varying PM loads may have to be
considered in order to fully optimise the control strategy for a two-
stage Plasma catalyst system of this type.

The use of packed NTP reactors may however, is

advantageous for some two-stage Plasma-catalyst aftertreatment
systems. It may be possible to select packing materials that optimise

18
the chemical composition of the exhaust particularly with respect to
modifying outlet hydrocarbon compositions. In these situations a
tailored mixture of NOx and activated hydrocarbon could be supplied
to a selected NOx reduction catalyst. In addition, by utilizing catalytic
materials, which are selective to NO rather than NO2, it may be
possible to use a packed NTP system to demonstrate combined NOx
and PM removal.

6. CONCLUSION

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 The Corona Discharge Device (CDD) significantly reduces
HC, CO and Nox emissions by increasing the efficiency of existing
catalytic converters. The CDD essentially creates a “self-cleaning”
environment in which existing sulfur poisoning is reduced and new
sulfur poisoning is prevented, thereby increasing the effectiveness and
prolonging the life span of the catalyst.

The CDD is simple to install. It is easily added to an

automobile’s exhaust system with minor interface modifications.

It has been shown that a suitably designed NTP reactor,

containing a packing material designed to filter and retain
particulates, can effect the oxidation of PM in diesel exhausts at low
temperatures characteristic of passenger car operation. It has also
been shown that such a reactor is effective for oxidation of the
ultrafine fraction and PAHs present in the exhaust.

In Plasma exhaust aftertreatment systems, the carboneous

particules will effectively compete with hydrocarbon for O. for removal
of NOX, we can employ an NO catalyst; as oxidation of particulates
may deplete the key radicals necessary for NO to NO2 conversion.

For future work we need to do a long term test on Plasma

reactor for regeneration and optimize the cost.

7.REFERENCES

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1. C. Bertoli et al “Performance Evaluation of Particulate Traps for
Passenger Car Diesel Engines” SAE-SP-1247.

2. F. XiaO et al “Plasma Treatment of Diesel Particulates for a

Minibus” SAE-2000-01-1926.

3. J. Christopher Whitehead et al “ Non Thermal Plasma Aftertreatment

of Particulates –Theoretical Limits and Impact on Reactor Design”
SAE-2000-01-1926.

4. http://www.aeat.com/electrocat/sae/saepaper.htm

5. http://www.Plasmas.org/rot-Plasmas.htm

6. http://www.osti.gov/fcvt/deer2000/nowakpap.pdf

7. http://www.litexcorp.com/docs/cdd_process.pdf

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