CHAPTER1

INTRODUCTION

Rudolf Christian Karl diesel was a German inventor and mechanical engineer by
profession. He invented the diesel engine in the year 1897. The Diesel engine
became widespread in many other applications, however, such as stationary
engines, agricultural machines, submarines, ships, and much later,
locomotives, trucks, and in modern automobiles. The Diesel engine has the
benefit of running more fuel-efficiently than gasoline engines due to much
higher compression ratios and longer duration of combustion, which means
the temperature, rises more slowly, allowing more heat to be converted to
mechanical work. Diesel was interested in using coal dust or vegetable oil as
fuel, and in fact, his engine was run on peanut oil.

The Internal Combustion (IC) engine is generally used as the prime mover in
the transportation vehicles on land, water and air, power generators and in
refrigeration and air conditioning plants.Due to a wide range of applications,
the analysis of the entire process and performance of IC engines, assumes
importance.

Diesel engines are the primary power source of vehicles used in heavy duty
applications. The heavy duty engine includes buses, large trucks, and off-
highway construction and mining equipments. Furthermore, diesel engines are
winning an increasing share of the light duty vehicle market worldwide. The
popularity of the diesel engine revolves around its fuel efficiency, reliability,
and durability. High compression ratios along with relatively high oxygen
concentrations in the diesel combustion chambers are responsible for the
good fuel efficiency and low CO and hydrocarbon emissions when contrasted
to a comparable gasoline engine. The CO present in residual gas in diesel
engine is also less compared with petrol engine. However, these same factors
result in high NOx emissions. The various sources of NOx emission to the
atmosphere are motor vehicles (49%), electric utilities (25%) and other
commercial and residential sources that burns fuel (19%). The main pollutants
from diesel engines are NOx and particulate matter (PM). The particulate
matter includes the soot and unburnt hydrocarbon. The mechanism of
formations of NOx and PM in the combustion chamber of diesel engines are
contradictory and the simultaneous reduction of both is very difficult.

An overview of emissions from diesel engines and their harmful effects, the
emission norms in India and NOx control strategies are briefly introduced.

At present, due to the severity of world air pollution by substances emitted

from vehicles, emission control is being enforced more strictly, and it is
expected that the regulation requirements for emission will become even
more stringent. The demand for reduced pollutant emissions has motivated
various technological advances in passenger car diesel engines. The reduction
of engine emissions is focused on combustion technologies of diesel engines
because automotive emission regulations are becoming increasingly stringent.
As a result, technologically advanced countries are exerting efforts to develop
ecofriendly engines for vehicles through advancement of combustion at the
national level. Specifically, Bharath stage-VI will be enforced in 2020, which
mandates that the emission of NOx be reduced to a half of Bharath stage - IV
standard.

Their has been continuous research for the most efficient diesel engine which
will cause lees harm to the environment.

ENGINE EMISSION
NOx EMISSION

Nitric oxide (NO) and nitrogen dioxide (NO) are grouped

together as NOx emissions . At ambient temperatures, the
oxygen and nitrogen gases in air will not react with each
other. In an internal combustion engine, combustion of a
mixture of air and fuel produces combustion temperatures
high enough to cause chemical reactions between
atmospheric nitrogen and oxygen in the flame, producing
various oxides of nitrogen.Nitric oxide is the predominant
oxide of nitrogen produced inside the engine cylinder. One of
the primary sources of nitrogen oxides in combustion
processes is the fuel nitrogen oxide. During combustion, the
nitrogen bound in the fuel is released and forms N 2 or NO.
Fuel nitrogen oxide can contribute as much as 50% of total
pollutants when combusting oil and as much as 80% when
combusting coal. The process of formation involves the
oxidation of volatile nitrogen (low boiling point) species
during the first stages of combustion. During the release and
before the oxidation of the volatiles, nitrogen reacts to form
several chemicals which are then oxidized into NO. The
principal reactions governing the formation of NO from
molecular nitrogen are:
O+N2=NO+N
N+02=NO+0
N+OH=NO+H
NO forms in both the flame front and the postflame gases. In
engines however, combustion occurs at high pressure so the
flame reaction zone is extremely thin (~0.1 mm) and
residence time within this zone is short. Also the cylinder
pressure rises during most of the combustion process, so
burned gases produced early in the combustion process are
compressed to a higher temperature than they reached
immediately after combustion. Thus, NO formation in the
postflame gases almost always dominates any flame-front-
produced NO.
For burned gases at typical flame temperatures,NO2/NO ratio
should be negligible small.For diesel engines NO2 can be upto
10 to 30% of the total exhaust oxides of nitrogen
emissions.NO formed in the flame zone can be converted to
NO2 via the reactions as:
NO +HO2 = NO2 +OH

HYDROCARBON EMISSION

Hydrocarbons, or more appropriately organic emissions, are the consequence

of incomplete combustion of the hydrocarbon fuel. The level of unburned
hydrocarbons (HC) in the exhaust gases is generally specified in terms of the
total hydrocarbons concentration expressed in parts per million carbon atoms.
While total hydrocarbon emission is a useful measure of combustion
inefficiency, it is not necessarily a significant index of pollutant emissions.

Diesel fuel contains hydrocarbon compounds with higher boiling points, and
hence higher molecular weights, than gasoline. Also, substantial pyrolysis of
fuel compounds occurs within the fuel sprays during the diesel combustion
process. Gaseous hydrocarbon emissions from diesels are measured using a
hot particulate filter (at 190•C) and a heated flame ionization detector. Thus
the HC constituents vary from methane to the heaviest hydrocarbons which
remain in the vapour phase in the heated sampling line (which is also
maintained at about 190•C)

CARBON MONOXIDE

Carbon monoxide (CO) emissions from internal combustion engines are con-
trolled primarily by the fuel /air equivalence ratio. Diesels, always operate well
on the lean side of stoichiometric; CO emissions from diesels are low enough
to be unimportant.
PARTICULATE EMISSIONS

Diesel particulates consist principally of combustion generated carbonaceous

materials (soot) on which some organic compounds have become absorbed.
Most particulate material results from incomplete combustion of fuel
hydrocarbons; some is contributed by the lubricating oil. The emission rates
are typically 0.2 to 0.6 g/km for light-duty diesels in an automobile. In larger
direct-injection engines, particulate emission rates are - 0.5 to 1.5 g/brake kW .
h. The composition of the particulate material depends on the conditions in
the engine exhaust and particulate collection system. At temperatures above
500 0C, the individual particles are principally clusters of many small spheres or
spherules of carbon (with a small amount of hydrogen) with individual
spherule diameters of about 15 to 30 nm. As temperatures decrease below
500"C, the particles become coated with adsorbed and condensed high
molecular weight organic compounds which include: unburned hydrocarbons,
oxygenated hydrocarbons (ketones, esters, ethers, organic acids), and
polynuclear aromatic hydrocarbons. The condensed material also includes
inorganic species such as sulfur dioxide, nitrogen dioxide, and sulfuric acid
(sulfates). The objective of most particulate measurement techniques is to
determine the amount of particulate being emitted to the atmosphere.
Techniques for particulate measurement and characterization range from
simple smoke meter opacity readings to analyses using dilution tunnels.

EFFECTS OF NITROGEN OXIDE (NOX) EMISSIONS

 Smog is formed when NOreacts with volatile compounds in presence of

sunlight.
 Atmospheric NO eventually forms nitric acid, which contributes to acid
rain.
 NO reacts with ammonia, moisture, and other compounds to form nitric
acid vapor and related particles. Small particles can penetrate deeply
into sensitive lung tissue and damage it, causing premature death in
extreme cases. Inhalation of such particles may cause respiratory
diseases such as bronchitis. It may also worsen existing heart diseases.
METHODS TO REDUCE NOx EMISSION

EXHAUST GAS RECIRCULATION

Nitrogen oxide (NOX) emissions can be reduced by cooling some of the

exhaust gas, which is then redirected back into the charge air. This results in
the reduction of the combustion temperature and less nitrogen oxide is
produced. This process is known as exhaust gas recirculation (EGR) and is one
of the principal methods used to reduce nitrogen oxide emissions from diesel
engines.

. It was first introduced in series production in mid-2011 for Series 4000 Oil and
Gas engines in hydro-fracking applications (EPA Tier 4 emissions standard). It
was likewise intro duced in rail engines subject to EU IIIB emissions regulations
which came into force in 2012.

WATER INJECTION :

 Water injection in the form of emulsion :

The injection of water in the form of diesel-water emulsion as
alternate fuel is a possible way of reducing the NOx and PM
simultaneously. The flame temperature is reduced due o the
presence of water in the engine cylinder, as it absorbs the heat of
combustion and reduces the NOx emission.
 Water injection into the air intake manifold during the suction stroke
along with the air through a separate injector
 Water injection directly into the engine cylinder using a separate
injection pump and injection nozzle.

EXTERNAL METHODS

 SELECTIVE CATALYTIC REDUCTION (SCR)

The SCR process is more complicated and expensive which uses a
surface to catalyze for nitric oxide removal. It requires high upstream
pressure to force the flow through the catalyst.
  SELECTIVE NON CATALYTIC REDUCTION (SNR)

The SNR process relies on homogeneous gas phase reaction. The

processes are simpler, only injection of the exhaust at a specified
temperature. SNR process has shown significant NO removal at fraction
of cost of SCR. Currently three processes are utilized for SNR removal of
NO, viz., Injection of Ammonia, Injection of Urea and Injection of
cyanuric acid. When the ammonia is injected in the exhaust stream the
NO is oxidized into N2O, the NO removal is increased and the
temperature for this removal level is decreased. For further increase in
ammonia concentration, the N2O concentration in the exhaust stream is
increased and in general the overall NO removal is less.

CONTROL BY FUEL ADDITIVES

Fuel additives are added as a mixture with fuel and their chemical stability
in the mixture must be ensured for all conditions. The use of fuel additives
should not increase the emissions of environmentally harmful substances.
Oxygenates such as dimethyl ether (DME), dimethyl carbonate (DMC),
dimethoxy methane (DMM) methanol, ethanol etc.

Emulsions

An emulsion can be defined as a mixture of two liquids in which one is present

in droplets of macroscopic or ultramicroscopic size, distributed throughout the
other. Emulsions are made from the constituents spontaneously or by a
mechanical way. In spontaneous emulsions, the mixing is easy and
spontaneous. But if they don’t mix properly then a third chemical called a
surfactant is used to bind the molecules of the constituent liquids. Then a
mechanical agitator is used to mix the liquids thoroughly. After mixing them for
some time, emulsion is formed.
Types of emulsion: Depending upon the type of emulsification technique, the
emulsions are classified into two types (khan et al, 2014):

The nano-additives are used to achieve specific fuel properties and to

improve the diesel engine performance characteristics and to attain a good
engine emission control without any engine modification. Technological
advancement of nano-additives and their use in biodiesel blended fuel
combinations reduced engine out emissions, which proved to be a potential
fuel additive.

The amount of emitted harmful emission gases increases in parallel with

increasing energy consumption. This increase has forced many countries to
take various precautions and various restrictions on emitted emissions have
been carried. In this study, effects of addition of oxygen containing
nanoparticle additives on NOx emissions of diesel fuelled test engine can be
investigated. Nine different nanoparticle additives namely aluminium oxide
(Al2O3), magnesium oxide (MgO), titanium oxide (TiO2), zinc oxide (ZnO), silicon
oxide (SiO2), iron oxide Fe2O3, nickel oxide (NiO), nickel iron oxide (NiFe2O4)
and nickel zinc iron oxide Zn0.5Ni0.5Fe2O4 can be added to diesel fuel at the
dosages of 25, 50 and 100 ppm.
Nanoparticle Symbol Particle size (nm) Purity (%)
Cost ($/g)

Aluminum oxide Al2O3 30 99.99 0.67

Magnesium oxide MgO 30 99.9 0.48

Titanium oxide TiO2 10–50 99.99 0.76

Zinc oxide ZnO 50 99.9 0.52

Silicon oxide SiO2 < 30 99.99 0.67

Iron oxide Fe2O3 30 99.5 0.85

Nickel oxide NiO 30 99.9 0.57

Nickel iron oxide NiFe2 30 99.9 0.95

Nickel zinc iron oxide Zn0.5Ni0.5Fe2O4 30 99.5 0.95

Cobalt oxide Co3O4

Magnalium MgAl

Carbon nano tubes CNT

Cerium oxide CeO

 NOX CONTROL TECHNIQUES

Technique System % Remarks

Modification Reduction
of NOx

Injection Engine adjust < 30% Relatively simple to

Retardation implement, increase SFC

Increased New fuel pump, <10 % Increase the cost of fuel

injection injector and fuel line injection equipment,
pressure required increase SFC

Direct water New cylinder head, <40% Increase the cost of the
injection injectors, cam shafts injection equipment
and fuel and water
system

Water N/A <40% Stability of emulsion

emulsion
injection
Exhaust Gas Valve and pipe <30% Increased cost of the
Recirculation arrangements engine

Selective External modification <95% Urea storage required

Catalytic to engine onboard, Ammonia
Reduction slippage problems ,
additional cost to
procure and operate

Fuel additive No modification in the 20% Easy to apply

engine