Investigation Results for Combustion Residue of Marine Diesel Engines 29

Technical Papers

Investigation Results for Combustion Residue of Marine Diesel Engines*

Toshikazu Takase**, Makoto Yamawaki**,

Mitsuo Takahashi**, Takaaki Inoue**,
Kiyomasa Shinbori***, Yoshihiko Kon***, Hiroki Oida***

In the present situation, some parts of marine diesel engines are being improved upon. But the combustion
chamber and exhaust space, where dust and residue are generated by using poor quality marine fuel oil, are still
trouble-some factors. And still, some causes of engine troubles have not yet been made clear.
In this investigation, we analyzed the combustion residue which was collected from overhauling the main
engine and the generator engine on seven motor ships among those operated by Mitsui O.S.K. Lines.
Then, we investigated the formation of combustion residue.

1. Introduction 2.1 Objective Ships

The development of long stroke and other im-
provements have been introduced for low-speed diesel
engines for marine use, but the fuel oil is still degraded,
and at the present time, the combustion chamber and
exhaust gas piping system are adversely affected by the
operation of the engine.
In the operation of ship, combustion troubles and
damage to the turbocharger and exhaust gas econo-
mizer cause not only operational difficulties but also
negative factors associated with high cost and labor. It
is very important to clean the inside of the exhaust gas
piping system at time of engine maintenance. How-
ever, not a few items have not yet been clarified even
after various examinations have been performed on the
causes of engine troubles.
In this paper, the analysis on the combustion
residue sampled from the part of the overhauled engine
of the objective ships in dry-dock, and the examination
of the formation of combustion residue are described.
2. Method of Investigation
Seven ships in dry-dock are selected among those
engaged in service, and the combustion residue formed
in the main engine and the generator engine, and the
fuel oil and the lubricating oil, are sampled for analysis
from these objective ships. In addition, the structural
members of the combustion engines, etc., is studied by
reference to various literature.
* Translated from Journal of MESJ Vol.33, No.1
(Manuscript received Sep.5, 1997)
** Mitsui OSK Line, Ltd.(Ohota-ku Tokyo)
*** Japan Marine Surveyors & Sworn Measurers' Associa-
tion (Tyuou-ku, Tokyo)
Particulars of the objective ships (Ship A ~ Ship G)
are shown in Table 1.
2.2 Test Samples
(1) Combustion residue
The test samples were taken from the parts speci-
fied in Table 2 of the objective ships according to
the overhaul condition of the equipment when the
ships were in dry-dock.
(2) Fuel oil
The test samples were replaced by the analysis
data on the fuel oil used by the objective ships in
the past two years.
(3) Lubricating oil
The test samples of the main engine cylinder oil
and the D/G system oil which were used during
this survey period were taken from the storage
tanks.
2.3 Items for Analysis
The test samples and the applied analysis items in
the survey are as follows.
(1) Combustion residue
Composition analysis Total sample/toluene
insolubles
PH Toluene insolubles/ aqueous suspension
Elemental analysis Total sample/toluene
insolubles
Thermal analysis Total sample (TG/DTA)
Metal analysis Ash alkali fusion (fluores-
cent X-ray, ICP, atomic absorption, etc.)
X-ray diffraction Toluene insolubles
Layer system Combustion residue (Scanning
electronic microscope/EDX elemental analysis)
Gas chromatography analysis Toluene solubles

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30 Investigation Results for Combustion Residue of Marine Diesel Engines

Table 1 Particulars of Objective Ships

Table 2 Test sample No. of combustion residue 3. Results of Analysis

3.1 Results of Analysis (Combustion Residue)

The analysis results of the combustion residue are
shown in Table 3.

3.2 Outline of Components of Combustion Residue

The composition of the combustion residue are
roughly classified as follows.

Water
(2) Fuel oil content Non-solid
Combustion Toluene Oil content
Density residue solubles
Calcium sulfide
Kinematic viscosity Toluene Solid carbon
insolubles Calcium carbonate
Flash point Inorganic part
(solid) Earth and sand, iron rust,
Pour point catalyst, etc.
Water content Metal (salt, oxide), etc.
Bottom sediment and water
Carbon residue
Sulfur (1) Outline of main composition
Asphalten The main composition of the deposit of the com-
Ash bustion residue is solid toluene insolubles common to
Vanadium each ship though in different amounts. The major
Sodium components are calcium carbonate (CaCO3), derived
Silicon from the alkali additive in the lubricating oil (cylinder
Aluminum oil), and its sulfides (CaSO4), and solid carbons such as
Xylene equivalent soot formed through incomplete combustion. The
CCAI components contained in the toluene insolubles are
(3) Main engine cylinder oil and D/G system oil derived from the lubricating oil or the fuel oil.
General properties The content of the toluene solubles (oil part) which
Metal analysis is non-solid and water content are small on the whole.

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 Investigation Results for Combustion Residue of Marine Diesel Engines 31

Table 3 Results of analysis (combustion residue)

February 1999 (31)

32 Investigation Results for Combustion Residue of Marine Diesel Engines

As the engine is operated, these residues gradually

adhere to or are deposited in the exhaust gas system,
and it is estimated that the deposits vary according to
the combustion conditions, temperature, the pressure,
gas flow speed, etc., in the system.

Water content
Because a large volume of water is contained in the
combustion product, as shown in the following formu-
lae, it is, of course, believed that water is contained in
the residue. However, in reality, the temperature in the
exhaust gas piping system is high, and as a result the
possibility that water is condensed and taken into the Fig. 1-1 pH (combustion residue)
residue is low, and the water content of the residue is
relatively low.
to become corrosive sulfuric acid (strong acid). The
sulfuric acid adheres to the deposis in the exhaust gas
[(Combustion product of fuel oil (1 ton)]Perfect combustion
Carbon (86wt.%) : 860kg carbon dioxide : 3,153kg/1,605m3 as gas pipes and the residue indicates acidity.
Hydrogen (10wt.%) : 100kg water : 900kg/1,120m3 as gas The sulfur oxide is neutralized with the LO addi-
Sulfur (3wt.%) : 30 kg sulfur dioxide : 60kg/ 21m3 as gas tive (alkali) on the lubrication surface of the cylinder
Others (1wt.%) : 10kg
Total 1,000kg 4,150kg/2,746m3 as gas
liner or the piston ring into calcium sulfide. However,
not all the sulfur oxide in the exhaust gas is neutralized
and most of it (SO2 or SO3) is discharged as exhaust gas.
Toluene solubles However, part of the sample residue indicates
The toluene solubles is the produced when the neutrality or alkalinity. That is, two samples of B01
petroleum component in the fuel oil or the lubricating (PH=6.7) and D03 (PH=11.6) are higher in PH com-
oil is not completely burned and discharged from the pared to other samples, and it is confirmed by X-ray that
engine, i.e., the unburnt petroleum component. The calcium carbonate (CaCO3) is contained in these samples
unburnt oil part in the exhaust gas is essentially mini- in addition to calcium sulfide (CaSO4). Calcium car-
mal if the combustion condition is excellent, and the bonate is the additive in the cylinder oil which is
existence (content) of the unburnt oil part in the residue neutralized with SOx and discharged. Also, because
reflects the combustion conditions (complete/incom- the alkali is always excessive on the lubrication surface
plete) in the engine. of the cylinder liner, the residue in the engine is one of
Toluene insolubles the causes of alkalinity.
The toluene insolubles forms about 80-90% of the Fig. 1-2 shows the plotted relationship between
residue, and consists of a combustible part (solid car- the content ratio (Ca/S ratio) of calcium to sulfur in the
bon) and ash (inorganic matter). residue and PH of the residue. The PH of the residue
The amount of solid carbon becomes high toward with a higher calcium content compared with sulfur is
the exhaust gas economizer on the downstream side of high, proving the above-mentioned prediction.
the exhaust system from the turbocharger immediately Because the exhaust gas is acid gas containing
behind the combustion chamber, while the content of SOx and NOx, the alkali additive discharged from the
ash tends to be lower.
(2) PH
The PH of the combustion residue suspended in
water indicates acidity (PH:2-4) with most samples.
(Fig. 1-1) On the other hand, from the results of the
fluorescent X-ray and X-ray diffraction, it is confirmed
that Calcium sulfide (CaSO4) is the major component
of the inorganic material, and also that SOx in the
combustion product is incorporated in the combustion
residue. However, the major component in the residue
from the generator engine is not calcium but iron.
Sulfur in the heavy oil is burnt into sulfur dioxide (SO2),
and a part of it is further oxidized and reacts with water Fig. 1-2 Relationship between pH and calcium

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 Investigation Results for Combustion Residue of Marine Diesel Engines
Reference Fig. I Relationship between dew point
and boiling point of sulfuric acid
engine is gradually neutralized in the gas atmosphere
even when the alkali additive is deposited.
In addition, because the temperature of the exhaust
gas is lower compared with the temperature of the
exhaust gas immediately behind the combustion cham-
ber on the downstream area away from the combustion
chamber, a part of the sulfur in the exhaust gas is turned
into mist as the temperature approaches the dew point
of sulfuric acid, and adsorbed in the soot or adhered
water. It can thus be concluded that the residue depos-
ited in the exhaust gas economizer indicates strong
acidity.
The relationship between the boiling point and the
dew point of sulfuric acid is shown in Reference Fig. I.
The straight line (arrow) in the figure indicates the
situation where the high-temperature gas containing
sulfuric acid is cooled, and the sulfuric acid is turned
into mist at the temperature on the dew point curve. It
(Calculated on the assumption that 2.5wt.% SO2 is changed into
SO3, and steam content is 5wt.%, and the air-fuel ratio is 35:1)
Reference Fig. II Dew point of sulfuric acid
(calculated value)
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33
is also indicated that the dew point of sulfuric acid drops
in a highly humid atmosphere.
It is thus considered possible that water can be
present in the residue in the exhaust gas pipe at high
temperatures above the dew point of water, and part of
the sulfuric acid forms the mist and adheres to the inside
of the exhaust gas pipe and is adsorbed therein.
Reference Fig. II indicates the dew point of sulfu-
ric acid in the diesel engine, showing the general
tendency between atmospheric pressure and the dew
point of sulfuric acid.
3.3 Thermal Analysis
The result of the thermal analysis on the combus-
tion residue is indicated in Fig. 2.
The mass loss in each temperature range in the TG
curve, is believed attributable to the following phenom-
ena (predicting from the components of the residue, the
range of measurement temperature, etc.):
1) Mass loss up to 120 is caused by the evaporation
of adhered water.
2) Mass loss between 120 and 330 is caused by
volatilization and combustion of the oil content,
and desorption of part of the crystal water.
3) Mass loss between 330 and 550 is caused by
combustion of the solid carbon.
4) Mass loss above 550 is caused by desorption of
carbon dioxide from crystal water or carbonate.
4. Results of Thermal Analysis and Exami-
nation
4.1 Classification of Residues by Thermal Analysis
Curve
The thermal analysis curve (TG/DTA) of the com-
bustion residue is roughly classified into three kinds of
pattern shown below.
Fig. 3 indicates the typical TG curve and DTA
curve of the combustion residue. In the figure, the
mass loss ratio in the respective temperature range of
120, 550 and 750.
Pattern I: Ca (calcium) type residue
Mass loss in TG is small, the mass loss ratio in the
range of 330-550 is 10 wt.% or less, and no large heat
generation peak is shown in the DTA curve.
Pattern II: Intermediate type residue
The mass loss ratio in the range of 330-550 in
the TG is 10-40 wt.%, and the heat generation peak is
shown in the DTA curve.
Pattern III: C (carbon) type residue
Large mass change is shown in the TG curve, the
mass loss ratio in the range of 330-550 is not less than
40 wt.%, and a sharp heat generation peak is shown in
the DTA curve.
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34 Investigation Results for Combustion Residue of Marine Diesel Engines

Fig. 2 Thermal analysis curve (TG/DTA)/[I]

Fig. 2 Thermal analysis curve (TG/DTA)/[II]

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 Investigation Results for Combustion Residue of Marine Diesel Engines
Fig. 3 Thermal analysis curve
The characteristics in the thermal analysis of Ca
type residue are that mass loss is small in the TG
because the amount of solid carbon is small, and the
heat generation peak in DTA is not remarkable.
However, at higher temperatures (above 550),
mass loss not accompanied by heat generation is seen,
which is presumed to be attributable to desorption of
crystal water (H2O) and desorption of carbon dioxide
(CO2) from the carbonate.
On the other hand, C type residue contains much
solid carbon, which is burned (oxidized) through heat-
ing, and mass loss (TG) accompanied by heat genera-
tion is seen. For example, a sharp and large heat
generation peak, seen around the temperature of 400
February 1999
35
(22 minutes) of the DTA curve is caused by combustion
of the solid residue. Because the amount of the inor-
ganic component is small in the C type residue, the
mass reduction attributable to desorption of crystal
water or carbon dioxide in the high-temperature region
above 550 is small. The intermediate type residue
forms the intermediate composition or the thermal
analysis curve between those of Ca type and C
type.
4.2 Standard for Classification of Type of Residues
by Thermal Analysis
Heating mass loss (in the range room temperature
~ 750) in the thermogravimetric analysis (TG) is
based on the desorption and combustion of the adhered
water, crystal water, unburnt oil, and the solid carbon
contained in the sample, and different substances are
desorbed and reduced in weight according to the range
of the heating temperature. The mass loss in the tem-
perature range between room temperature and 120 is
presumed to be attributable to the combustion of ad-
hered water, that between 120 and 550 is pre-
sumed to be attributable to the combustion of crystal
water and solid carbon, and that between 330 and
550 is attributable to the combustion of solid carbon,
respectively.
In the thermal analysis, a part of the components of
the residue is desorbed or burned in a composite man-
ner, and it is difficult to quantify the specific substance
with any degree of accuracy. However, in the classifi-
cation of the residue type substance by thermal
analysis, it is considered possible that the parameters of
incomplete combustion can be mass loss in the tem-
perature range (330-550) where the effect of crystal
water is small on the whole, taking into account the
solid carbon which can be measured in a generally
stable manner.
The classification standards of the combustion
residue using the TG loss % in the temperature range
between 330 and 550 in the thermal analysis, is
specified according to the residue type.
The residue of the main engine T/C nozzle ring is
generally small in solid carbon, and the mass loss ratio
in the temperature range between 330 and 550 is
within 10 wt.% except Ship B which is equivalent to
that of Ca type residue.
On the other hand, the mass loss ratio is above 70
wt.% in the residue high in carbon content. However,
because the inorganic component is contained in the
residue in addition to the solid carbon, no residues close
to 100 wt.% in the TG mass loss ratio are found. Thus,
the residues of not less than 40 wt.% in the mass loss
ratio are regarded as C type residue.
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36 Investigation Results for Combustion Residue of Marine Diesel Engines
Table 4 Classification of Type of Residues by Thermal Analysis
4.3 Relationship between TG Mass Loss(%) and
Carbon Contents
Fig. 5 shows the carbon content (wt.%) to the TG
mass loss in the temperature range between 300 and
500 and between 120 and 550 which is plotted
on the toluene insolubles and the total samples. It is
confirmed from the figure that the TG mass loss % and
carbon content are very strongly correlated (correlation
factor : 0.960 and 0.967), and the mass loss ratio in the
range of the prescribed temperature by the thermal
analysis can be regarded to be equivalent to the carbon
content by composition analysis. As for the TG mass
loss %, the correlation to the carbon content (composi-
tion analysis) in each temperature range is examined,
and it is confirmed that the mass loss ratio in the
temperature range between 330 and 550 is most
strongly correlated.
(36)
4.4 Condition of Combustion and Residues
Fig. 6 shows the toluene solubles and solid carbon
among the composition. As clearly shown in the figure,
the samples from the exhaust gas economizer of the
sample number 04 of each ship show abundant solid
carbon on the whole, and the conditions where soot
is deposited are clearly shown. On the other hand,
because the quantity of solid carbon is small in the T/C
samples A02-03, C02-03, D02-03, E02, F02, etc., it is
estimated that T/C is the reason why it is difficult for the
solid carbon to be deposited if the combustion condi-
tion in the combustion chamber is excellent. Thus, it is
recognized that much solid carbon in the T/C sample of
the generator engines of Ships B, E and G indicates the
possibility of incomplete combustion.
The toluene solubles (unburnt oil part) is slightly
higher in Ship B (B01), Ship E (E03), and Ship C
Bulletin of the M.E.S.J., Vol. 27, No.1
 Investigation Results for Combustion Residue of Marine Diesel Engines
Fig. 5 Carbon content and TG mass loss (%)
Fig. 6 Toluene solubles/solid carbon
generator engine (C12), and taking into consideration
that the amount of solid carbon is large, incomplete
combustion increases not only solid carbon but also the
unburnt oil part in the formation of the residue. How-
ever, the relationship to incomplete combustion is not
shown so remarkably compared with the solid carbon.
From the above-mentioned examination, it can be
recognized that the parameter to indicate incomplete
combustion of the fuel oil is solid carbon.
4.5 Characteristics of Type of Residue by Part of
Deposit
The confirmed items in the thermal analysis of the
residue samples are summarized below by deposit part.
Main engine
1) Sample from piston crown part
The sample B01 shows the intermediate type, and
contains the oil and the solid carbon.
2) T/C nozzle ring
Most of the samples are of Ca type residue, with
February 1999
37
few combustible components.
3) T/C blade
The residue of this part is classified into the
intermediate type and Ca type.
4) T/C outlet exhaust gas pipe
The D03 sample is a typical Ca type residue, and
B03 is high in solid carbon content, and of C type
residue.
5) Exhaust gas economizer
The content of solid carbon is higher for every
sample compared with that of the T/C residue
immediately behind the engine.
The main engine residue is characterized by the
fact that the carbon content becomes gradually higher
from the engine toward the exhaust gas economizer,
and changes from Ca type to C type.
In the highly humid residue, the mass loss caused
by desorption of crystal water is seen in the relatively
low temperature range (120-330) and the high tem-
perature range (550-770). It can be recognized that
the temperature range (330~550), between these
temperature ranges, is the range where the unburnt
component (solid carbon) caused by incomplete com-
bustion is measured.
Generator engine (turbocharger)
The residue of the generator engine is high in
carbon content compared with the main engine residue,
and the possibility of incomplete combustion is consid-
ered to be high. It is also characterized by the fact that
crystal water or carbon dioxide is desorbed in the high
temperature range. Though the number of samples is
small, the carbon content tends to be higher from the
combustion chamber to the turbocharger and the fun-
nel.
5. Conclusion
5.1 Deposit of Combustion Residues and Causes
As a result of the composition analysis of the
combustion residue, the major components of the
residue are calcium sulfide, solid carbon or iron.
Calcium sulfide is the product of calcium salt in
the additive of the lubricating oil which reacts with
SOx in the exhaust gas, and the solid carbon
(soot) is discharged through incomplete combus-
tion. Because iron is contained in high guantities
in the residue from the generator engine and the
solid carbon, it is estimated that iron is related to
the insufficient combustion of the lubricating oil
supply system, and it is recognized that iron is
derived from the wear of structural members in the
combustion chamber.
Most of the combustion residues indicate strong
acidity, and it is recognized that sulfur oxide
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38 Investigation Results for Combustion Residue of Marine Diesel Engines
(sulfuric acid) in the exhaust gas adheres to or is
adsorbed by the residue. Further, the content of
water, unburnt oil and metals (vanadium, etc.) of
other components is relatively low.
As for the difference in the components by part of
deposit of the residue, it is recognized that the
calcium content is apt to decrease from the com-
bustion chamber to the downstream side of the
exhaust gas pipe, while the carbon content be-
comes higher from the combustion chamber to the
downstream of the exhaust gas pipe.
5.2 Classification of Residues and Thermal Analy-
sis
The residue can be roughly classified into cal-
cium type: Ca type and carbon type: C type
through the analysis on the components of the
combustion residue, and further classified into
three groups in which the intermediate type is
added through thermal analysis (TG/DTA). The
classification of the residue through thermal analy-
sis is performed based on the content of solid
carbon, and there is a tendency that a small amount
of unburnt oil caused by insufficient combustion is
contained in C type residue.
Main engine residue changes from Ca type to C
type from the combustion chamber to the exhaust
gas economizer.
Application of the thermal analysis to the residue
is extremely effective as a means of estimating the
combustion condition in the combustion chamber,
and it is recognized that the thermal analysis is
appropriate for estimating combustion troubles
and insufficient combustion attributable to the fuel
oil with solid carbon (and the unburnt oil part) as
the index.
Discussions:
Questioner: Kenji Goto
[Question]
*Even in cases where the combustion seems ex-
cellent (a small amount of soot is adhered in the vicinity
of the piston ~ T/C), there is one case where the soot
adheres to the exhaust gas economizer and one case
where no soot adheres to the exhaust gas economizer.
Do you have any idea where the difference (what the
cause) is.
(38)
[Answer]
As for the adhesion of soot to the exhaust gas
economizer, there are factors which can not be judged
only by the condition of the combustion chamber, and
it is believed that related parameters (design, structure,
maintenance, operation, etc.) affect each other.
In the analysis results of this examination, the
carbon type residue is poor at bonding, while the
calcium type residue is hard, and calcium salt is bonded
in the highly humid atmosphere, or solidified at high
temperature. It is believed that such a difference in the
nature of the major components affects the adhesion of
the soot in the exhaust gas economizer.
Further, in the subsequent examination, the rela-
tionship between the combustion residue and the prop-
erties of the fuel oil is also examined. Among them,
there is a tendency for the carbon type residue is to be
generated easily as the aromatic component in the fuel
oil is increased (as the paraffin component becomes
smaller), and as the properties of the fuel oil are largely
different according to the supplied oil. That means, it is
considered that the soot content in the exhaust gas
economizer is affected by the properties of the fuel oil
used.
The deposits of the residue which were not exam-
ined this time will be examined in the future.
References
(1) Konishi, S., and Kamita, T.,Principle and Appli-
cation to Lubricating Oil, Publisher Corona-
sha, (1992)(IBN4-339-04311-7)
(2) Awai, N., Hanashima, O., and Yokozawa, S.,
Fuel Oils used for medium & large size marine
and land use diesel engines-Methods of usage of
low quality fuel oils and effects for air pollution,
Publisher Sankaido (1994)(ISBN4-381-10060-
3-C3053)
(3) Fujiwara, Y., Process for Diesel Paticulate
Formation,(Journal of The Japan Petroleum In-
stitute, VOL.5,255266,1990)
Bulletin of the M.E.S.J., Vol. 27, No.1