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Fuel Field Manual (8)

Fuel Field Manual (8)

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Published by FREDIELABRADOR

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Published by: FREDIELABRADOR on Sep 13, 2013
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09/13/2013

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CHAPTER
6
Solving
Fuel Problems
by
Using
Chemical
Additives
A
wide range
of
fuel
performance problems
can
often
be
solved
by the use of
chemical additives. Although in some circumstances the additives used may be no
substitute
for refining
processes
such as hydrotreating, caustic washing, ordistillation, they
can
provide
an
alternative
to
further
processing.
Some chemical additives such as corrosion inhibitors, wax crystal modifiers,detergents,
and
demulsifiers provide performance which
is
difficult
to
duplicate
through
refining without adversely
affecting
some other
fuel
property. Otheradditives such
as
metal
chelators,
fuel
sweeteners,
biocides,
lubricity
improvers,
foam
control agents
and
combustion enhancers
can
also
be
used
to
solve
fuel
performance
problems.
Recent
developments
and
concern over
the
control
of
fuel
exhaust emissions
have
led to the increased use of combustion system
detergents,
oxygenates andcetane improvers
in
fuel.
Oxygenated blend components such
as
ethanol,
methyl
t-
butyl
ether (MTBE), ethyl
f-butyl
ether(ETBE),
and
f-amy!methyl
ether (TAME)
are
also used
to
help limit
the
exhaust emissions
from fuel.
Some
of the
most
frequently
utilized additives
effective
at
solving fuel-relatedproblems are described within this chapter.
A.
ANTIOXIDANTS
Over
time,oxygen will react with
fuel
components
to
degrade
the
fuel
into
a
viscous,
sludgelike mass. Fuel components most susceptible to oxidation are olefins andalicyclic
naphthenes.
Paraffins
and
aromatics
are
less susceptible
to
attack
but caneventually
be consumed by the free-radical chain reaction
process.
Hindered phenol and phenylenediamine (PDA) compounds are commonly used
and
quite
effective
at
preventing free-radical oxidative degradation
of
fuel.
They
canbe
used
in
gasoline,
kerosene,
jet
fuel,
and
certain distillates
and
lubricants.
Often,
a
synergistic
effect
can be
obtained
by
using
a
combination
of a
hinderedphenol
and a
phenylenediamine antioxidant
in the
same application.
 
1.
Hindered Phenol Antioxidants
Hindered phenol compounds usually possess
alkyl
groups on ortho and para
sites.
The
alkyl groups
are
typically
J-butyl
or
methyl
in
functionality.
The
lower cost
of
hindered phenol antioxidants makes them attractive
for use in
fuel
applications.
In
gasoline, hindered phenols are typically used at treat rates of 5 to 50
ppm.
The
limitations
placed
on jet
fuel
additives
often
control
the
rate
at
which phenolic
antioxidants
can be used.
When
contaminated or held in storage at temperatures below
6O
0
F
(15.5
0
C),
hindered phenols
may
tend
to
crystallize
and
fall from
solution
as
relatively pure
compounds.
Often
solvent dilution
of
hindered phenols
can
help
to
reduce
thetendencyof
crystal dropout,
but
will
not
completely eliminate this problem.
2.
Phenylenediamine Antioxidants
Phenylenediamine (PDA) antioxidants can be used when hindered phenols do not
perform
or whenever their cost performance overcomes that of hindered phenol
compounds.
Although
PDA
compounds
can
often
be as
much
as
four
times
the
cost
of a
hindered phenol antioxidant,
the
performance provided
by
PDAs
can
frequently
exceed that
of a
hindered phenol compound.Phenylenediamines
are
relatively weak organic bases
and can
cause burns
if
left
on the
skin
for
more than
a few
minutes. Their dark
color
makes themundesirable
for use in
fuels
or
petroleum
fractions
which have Saybolt color
specifications
>+15.
Because of their alkalinenature,they may also interact with
any
acidic compounds which
may be
present
in the
fuel
or in
tank-bottom water.
Under
extreme conditions, this interaction could result in a reduction or loss in
performance of the PDA
antioxidant.
3.
Organosulfur Compounds
Some
organosulfur
compounds
can
function
as
fuel
antioxidants
by
acting
to
decompose hydroperoxides. Organosulfides
are
believed
to
react
withhydroperoxides
to
form
sulfoxides.
The sulfoxides
then
further
react withhydroperoxides to
form
other more acidic compounds. These newly formed acidscontinuetheprocessofdecomposingandreaction with hydroperoxides. Thus,
organosulfur
compounds
function
in the
process oxidation inhibition throughhydroperoxide
decomposition.
However,
in
most
fuel
applications,
sulfur-containing
antioxidants
are not utilized.Fuel problems which can typically be solved by a
fuel
antioxidant are
-
Control
of
color change
and
darkening- Retarding the formation of deposits and varnish
-
Improvement
in the
resistance
of
fuel
to
oxidationFuel problems which cannot typically
be
solved
by a
fuel
antioxidant
are-
Reversing
of the
effects
of
fuel
degradation such
as
color change
or
deposit
formation
 
-
Effectively
controlling
the
fuel
degradation process
after
it has
progressed
significantly
-
Significantly improving
jet
fuel
JFTOT
(jet
fuel
thermal oxidation test) tube
and
screen ratings
-
Color
and
deposit formation
in
distillate
fuel
are
sometimes
difficult
to
control
by
an
antioxidant. Often, other components
are
needed.
-
Reduction
in the
existent
gum
level
of
gasolineGeneral characteristics of phenolic and PDA antioxidants are summarized in
TABLE 6-1
and
chemical structures
are
shown
in
FIGURES
6-1 and
6-2.
TABLE
6-1. Characteristics
of
Hindered
Phenol
and
Phenylenediamine
Antioxidants
Hindered
Phenol
Effective
in
most
fuel
at
5-50
ppm
Will
not
significantly degrade
fuel
color
Lower
cost per pound
Can
crystallize during storage,especially
at
temperatures below
6O
0
F
(15.6
0
C);
dilutions
are
available
to
helplower crystallization temperatures
Phenylenediamine
Effective
in
most
fuel
at
1-20
ppm
May
degrade
S
ay
bolt color
of
fuel
High cost per pound
Can
crystallize during
storage;
crystallization temperature
can be
controlled
by alkyl group
functionality;
products
are
available
with
crystallization range between
6O
0
F
(15.5
0
C)
and
-4O
0
F
(-40.O
0
C)
FIGURE
6-1.
2,6-Ditertiarybutyl
Phenol
A
typicalhindered phenol-type
fuel
antioxidant
FIGURE
6-2.
N,N'-Di-isopropyl
phenylenediamine
A
typical
phenylenediamineantioxidant
OHH
NHN
CH
CH
3
CH
3
H
3
CH
CH
3

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