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$A p{l OEM THE AMERICAN SOCIETY OF MECHANICAL ENGINEERS

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/' i 345 E 47 St., New York, N.Y. 10017

The Society shall not be responsible for statements or opinions advanced in papers or
in discussion at meetings of the Society or of its Divisions or Sections. or printed in
its publications. Discussion is printed only if the paper is published in an ASME
journal or Proceedinps.Released for general publication upon presentation. Full
credit should be given to ASME. the Technical Division. and the author(s).

Copyright © 1981 by ASME

G. E. Krulls
Gas Turbine Vanadium Inhibition
Consulting Engineer, The mechanism of gas turbine vanadium inhibition is discussed as well as corrosion,
Vidak Associates, hot gas path deposition and exhaust gas emissions. A cost comparison is presented
Delanson, N.Y. for the various types of inhibition based on a typical power plant situation. A brief
Mem. ASME description is provided of three different kinds of inhibition systems. The aim of
this paper is to provide the gas turbine user with a practical evaluation of the
various inhibition processes.

INTRODUCTION have melting points considerably above that

of vanadium pentoxide by itself. The most
Vanadium which is found in gas turbine prevalent compound, magnesium ortho vanadate
heavy fuel oils (crude and residual) is has a melting point of about 2200°F. The
present in the form of an organic porphoryn other two are lower about 1700°F and 1400°F
compound. This compound forms vanadium for the pyro and meta forms respectively.
pentoxide, (V205) when undergoing combustion According to the equilibrium diagram, there
in the gas turbine. The vanadium pentoxide are intermediate compounds being formed and
dissolves the nickel and chromic oxides which so there is actually a range of melting points.
protect the turbine blades from hot corrosion. Vanadium pentoxide melts at about 1200°F.
If nothing is done to prevent this, the blades The reactions that take place are:
will corrode very rapidly and will have to be
replaced after a very short life. V205 + 3MgO = 3McO V205 ORTHOVANADATE
Many researchers have tried to find ways V205 + 2MgO = 2MgO V205 PYROVANADATE
of removing vanadium from fuel oil but no V2O5 + McrC = MgO V2o5 METAVANADATE
economical method has yet been found. Instead In order to obtain an adequate reaction
of removing the vanadium, it was found that a with all of the vanadium pentoxide, it has
practical way to avoid hot corrosion is to been found through experience that the ratio
inhibit vanadium with a magnesium compound. of magnesium to vanadium must be 3:1. This
This then forms new compounds which have a is four times the stoichiometric ratio.
high enough melting point to pass through the Usually 3.25:1.0 ± 0.25 is used for tolerance
gas turbine without fluxing out on the reasons.
bladino.
It should be understood that the
What follows is a discussion of the inhibition process is very complex and that
various types of inhibitors, the equipment there are many second and third order effects.
needed and how to use the equipment as well For instance, the presence of sodium affects
as information on the chemistry of inhibition. the melting point of vanadium compounds.
Inter-relationships between trace elements of
MECHANISM OF INHIBITION sodium, magnesium, vanadium and silicon were
formerly taken into account. Now they are
When magnesium is added to a gas turbine
pretty much ignored.
fuel in any of a number of compounds, it will
combine with vanadium pentoxide to form Other compounds can also be used for
magnesium orth, pyro, and meta vanadates which inhibition such as calcium compounds or
chromic oxide but these tend to form very
hard and difficult to remove deposits.
Aluminum compounds have also been used. If
Contributed by the Gas Turbine Division of THE AMERICAN SOCIETY OF aluminum sulfate is used in the water washing
MECHANICAL ENGINEERS for presentation at the Gas Turbine Conference & solution of the fuel washing process it will
Products Show, March 9-12, 1981, Houston, Texas. Manuscript received at react with calcium to put calcium in and take
ASME Headquarters December 22, 1980. aluminum out, i.e. aluminum sulfate turns to
Copies will be available until December 1, 1981. calcium sulfate. Many tricks and processes
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have been tried over the years but the
magnesium compounds have been proven best.
HOT GAS PATH DEPOSITION
When there is considerable vanadium
present, then the problem of deposition also
increases as well as the amount of
particulates present in the exhaust. As long
as calcium is kept to a minimum, the deposits
can be fairly easily removed. This usually
requires water washing and perhaps even nut-
shelling equipment. If the turbine can not
be shut down and cooled frequently for wash-
ing then not-shelling can remove deposits
under load. Quite often both cleaning
techniques are used.
Ninety percent of the deposits formed
are magnesium oxide and magnesium sulfate.
Magnesoim oxide is by far the hardest to re-
move. Both species are in equilibrium ac-
cording to:
MgSO4 MgO + So3
Increased temperature drives the re-
action to the right whereas increased sulfur
and pressure drives it to the left, As one
can see, this is in the right direction for
modern gas turbines with increasing pressure
ratios.
Silicon is known to be a good additive
for the flocculation of deposits which makes
them less adherent and easier to remove.
This can be added in a number of forms such
as organo silicon compounds or magnesium
silicate (Talc).
EXHAUST GAS EMISSIONS
If goverment regulations limit the
amount of particulates allowed in exhaust
gases then this will also limit the amount
of vanadium that can be tolerated in the
fuel. If we assume that all the particluate
emissions are due to inhibition of vanadium,
we can calculate a limit on vanadium due to
this. As an example, assume that the
regulatory limit on particulate emissions is
0.12 LB/MBTU. 1 Now we can calculate the
limit as shown in Appendix A to be a maximum
allowable amount of vanadium of 150 PPM.
In reality we must also consider how
much ash is present in the fuel. If there
is 0.1% ash (a typical amount for residual
fuel), this would reduce the vanadium limit
to 83 PPM maximum. In addition, if a silicon
compound is used this would again lower the
allowable vanadium level to a considerable
degree. If the silicon were added with
magnesium in the form of Talc (magnesium
silicate), this would reduce the allowable
vanadium level to 47 PPM.
FOOTNOTE:
1. 0.12 LB/MBTU = 51.6 kq or 51.6 Kilograms
per tera Joule. tj
Ii
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Other numbers can be evaluated by the use of
the equation shown below. See also Appendix
A.
26.47V + 10 4 A = XH
where
V = Vanadium in fule oil - PPM
A = ash in raw fuel oil - %
X = allowable particulates in exhaust -
LB/MBTU
H = higher heating value of the fuel-
BTU/LB
This equation is based on particulates being
made up of:
3MgO • V2O5 magnesium ortho vanadate
MgSO4 magnesium sulfate
MgO magnesium oxide
SiO2 silicon dioxide
ash
where the magnesium compounds formed are
based on magnesium added to fuel being 4.643
times the stoichiometric ratio which is an
addition rate of 3.25:1.00 Mq:V. The
magnesium that remains is assumed to form
compounds 90% of which are MgSO4 and 10% MgO.
It can readily be seen that environmental
regulations can radically affect allowable
fuel quality. Without this factor the old
limit of 500 PPM vanadium would be feasible.
COST OF VANADIUM INHIBITION
There are a number of possible ways to
inhibit vanadium. The more common compounds
are:
1. Magnesium sulfonate
2. Magnesium Naphthanate Oil Soluble
3. Organic Silicon Compounds
4. Magnesium Sulfate, Aqueous
5. Magnesium Sulfate, Emulsified
6. Magnesium Oxide, Oil Suspension
7. Magnesium Hydroxide, Suspension
8. Magnesium Silicate (Talc) Oil Suspension
Of these the first two are by far the most
expensive magnesium compounds. If you wish
to add oil soluble silicon compounds to re-
duce gas path deposits, these are even more
expensive.
The fourth compound listed has been well
proven and is quite reasonable in cost. It
does however require a fairly complex capital
equipment installation and a more difficult
operation. It must also be injected just
prior to combustion as it tends to separate
rapidly form oil. This means quality control
is difficult as the use of certification tanks
with this is not feasible. In addition, the
Epsom Salt must first be dissolved in water
to a known concentration with controlled
temperatures to prevent recrystallization.
The fifth item is taking aqueous Epsom
Salt one step further and emulsifying it so
that it can be added prior to the
 certification tanks without danger of
settling. This adds one more complication
however.
The sixth item has also been well proven
but it is the most abrasive and often con-
tains too much calcium as well as being ex-
pensive. It has a hardness of 6.0 - 6.5 on
the NEC Scale compared to about 1.0 for Talc.
The seventh item is much like the sixth
but is bulkier because of water of hydration
being present. It is not as abrasive though,
having a hardness of 2.0 - 2.5 on the MHO
Scale.
That brings us to the eighth item Talc.
It is the least expensive and contains a
large amount of silicon to combat deposition.
Silicon comes along practically free as you
pay for the magnesium and get silicon as a
by product.
Now to get a comparison of these in-
hibitors see Table No. 1 that follows:
TABLE NO. I_

TYPE OF PRODUCT Mg Si i COST COST COST USAGE COST SPACE

WT.% WT.% $/LB Mg'$ /LB SiI PRODUCT' LB/MO S/MO FT3

JOIL SOLUBLE MAGNESIUM 8 0 8.37 $6.70/GA 66,864 44,800 7132

!OIL SOLUBLE SILICON 0 6 ---- 15.38 $9.50/CA 89,150 84,692 9509

CRYSTALLINE MAGNESIUM SULFATE 9.76 0 1.02 -$0.10/GA 54,700 5,445 5610

AQUEOUS MAGNESIUM SULFATE 5.00 I 0 1.02 ------ I $0.55/GP. 106,784 5,445 4007

(EMULSIFIED MAGNESIUM SULFATE 3.80 0 4.72 ------ S1.89/GP,139,656 8,435 5322

SUSPENDED MAGNESIUM OXIDE 19.8 0 2.52 - $5.00/GAL 26,962 13,453 2157

SUSPENDED MAGNESIUM HYDROXIDE 13.6 0 3.31 -- --- $4.50/GAL 39,256 17,671 3140

POWDERED MAGNESIUM SILICATE 1820 2830 0.79 0.52 $0.15/GALL 29,660 4,452 3042

SUSPENDED MAGNESIUM SILICATE 6.27 9.57 0.79 0.52 /GAL 85,148 4,452 6812

Table No. 1 was generated based on the 9. COSTS HERE PRE CALCULATED EXCLUSIVE OF
following: SHIPPING.
BASIS: 10. THE FIGURES PRESENTED ARE FOR TYPICAL
PRODUCTS IN THE FORM THAT THEY ARE
1. FUEL FLOW - 200 GPM.
AVAILABLE.
2. OPERATING TIME - 173 HRS. MO .
11. THERE IS ALSO AN OIL SOLUBLE INHIBITOR
3. VANADIUM - 100 PPM. ON THE MARKET WHICH HAS BOTH MAGNESIUM
AND SILICON CONTAINING 6z% OF EACH AT
4. RATIO OF MAGNESIUM:VANADIUM - BY WT.
$10.00/GALLON.
3.25:1.
5. MAGNESIUM SULFATE CONCENTRATION IN 12. 75 PER CENT OF SPACE IS USED WHEN STOR-
ING DRUMS FOR 6 MO. STORAGE.
WATER (MgSO4) BY WT. - 25%.
6. MAGNESIUM SOLIDS SUSPENSION CONCENTRA- 13. 90 PER CENT OF SPACE IS USED WHEN
STORING BAGS SUCH AS MAGNESIUM SULFATE
TION IN OIL - BY WT. - 33%.
(TALC) AND MAGNESIUM SULFATE HEPTAHYDRATE
7. EPSOM SALT IS CALCULATED @ $6.00 PER (EPSOM SALT) FOR 6 MONTHS STORAGE.
100 LB.
14. LABOR COSTS FOR MIXING AND HANDLING ARE
8. EMULSIFIER IS CALCULATED @ $6.00 PER EXCLUDED.
GALLON.

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 15. TI'E PRICE OF L^;ATFF IS NC INCI, FOE D. 4. Usually (2) blenders to blend the
inhibitor into the fuel, also lead
16. TIDE CO "I' PER POUND CAF Na and Si IN
stand-by.
MIGNFSIUM :ILTC1.Tl, T N 1,'ITPE6/76 FIGURF
i.e. IF YOU PPY $0.79 PER POUND CF Mr 5. A. calibration tube to calibrate the
YOU PAY NO'1HING PER POUND OF Si lID flow through the ir,.eterina pumps.
VISA VL:RS:,.
The oil soluble inhibition system, is
From Table No. 1, it can be seen that using_ quite simple and easy to use. One rust be
an oil soluble macncsium cor'pcuno costs: very careful to prevent water from heir'
in the fuel as this tends to make the
$537,600.00 PLR YEAR
inhibitor plate out on the filters.
Usincr the gas turbine qradc Talc will cost
only: OIL SUSPENDABLE INI]IAITION
$ '3,44.00 PER YEAFI Oil suspendable inhibitors include
m.agnesiurr. oxide, n.acinesium hydroxide and
These numbers are also based on 24% aas
turbine duty cycle. Consider now the cost magnesium, silicate (Talc). For this dis-
cussion we will assume the use of Talc which
of inhibition based on a 100% duty cycle and
is received in powder form. For Talc to be
250 PPM vanadium. Ne then have expenditures
C: of use in a oas turbine, it must be of gas
turbine grade i.e. of small particle size
OIL SOLUELE 55,612,000.00 PFP YEAR and low in trace element contaminants.
1ALC $ 557 , 700.00 p YEAR Talc is typically received in 50 or 100
pound bass. The process of using Talc car. be
with a possible saving of $5 million per
completely automated or partially automatic
year.
as described here.
it should be pointed out that you can
then Talc is mixed with oil, a consider-
also buy oil soluble products containinc_?
able compaction takes place and thus the
Loth Macnesium. and Silicon. These cost about
apparent specific gravity is greatly de-
510.00 PER GALLON and contain about 6.5% of
creased over the bulk specific gravity. A
each element. That cones to $15.38 PER Lb of
test of this produced the data that follows
Macnesium or half that if you consider
in Table II,
splitting the cost with silicon. This
is the most expensive inhibitor when based
oc the price of tr.aq_nesium. It also takes
the most space for storacie and contains the
i,ost weight for shipment.
Note that the numbers in `Table No. 1 are
based on using on site water for Magnesiui-
Sulfate and therefore the water is not
shipped. The Magnesium Sulfate crystals
are hydrated though and contain a bit more
than half their weight in water. The formula
is MgSO4 . 7"20. This has a irolecular weight
of 246 of which 126 is for the seven water
molecules.

OIL SOLUBLE 160101 11 1.

Oil soluble inhibition systems typically
consist of:
1. A storage place for storing the drums in
which the material is shipped.
2. A supply tank into which the drums are
emptied periodically and frog''. which
the inhibitor is pumped.
3. Usually (2) metering pumps in a lead/
stand-by configuration.
TAPLE II
SPECIFIC APPARENT
GRAVITY SPECIFIC GRAVITY
OF OF
FRACTION OF TALC WT% FRACTION OF DIESEL OII: WT MIXTURE TPLC (CALCULATED)
38.85 61.15 1.119 1.511
23.80 76.20 1.000 1.416
16.50 83.50 0.946 1.331
8.60 91.40 0.895 1.161

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 The bulk specific gravity of the par-
ticular Talc in question is 0.925. The
apparent specific gravity here is calculated
from the equation:
GM - GD FD/ 100
Gh=
F T /100
where
GT= apparent specific gravity of Talc
GM= specific gravity of the mixture
GD= specific gravity of Diesel oil
FD= fraction of Diesel oil in mixture
0 vanadium of 3.25:1.0. Care must be taken
FT= fraction of Talc in mixture -
Knowing the above is important when
sizing a mixing tank as (1) volume of Talc
added to (1) volume of oil does not give (2)
volumes of mixture but rather considerably
less.
The Talc inhibition system consists of
the following,
1. A dry storage place for storing the Talc
in bags.
2. A mixing tank for suspending the Talc in
oil. The oil can be Diesel or the actual
fuel to be burned.
3. One or two blenders or propeller mixers
immersed in the mixing tank.
4. A source of the suspending oil.
5. A supply tank to hold the Talc suspension
6. Metering pumps usually in a lead/stand-
by configuration.
7. Blenders in lead/stand-by to blend the
Talc suspension into the fuel oil.
8. T: calibration tube to calibrate the flow
through the metering pumps.
9. Propeller mixers in all the tanks that
will contain the Talc such as mixing
tank, supply tanks, certification tanks
and service tanks.
The Talc is suspended in the mixing tank
usually at a ratio of about 30% Talc by
weight in the mixture. A typical mixing tank
might be about 300 gallons (1135 liters).
After the Talc is thoroughly mixed, it is
pumped to the Talc supply tanks from where
it is metered into the fuel.
A Talc inhibition system such as this is
presently in operation at two power plants
in Brazil. One has a power output of 300 MW
and the other 120 MW.
WATER SOULBLE INHIBITOR
The water soluble inhibitor often used
with gas turbines is magnesium sulfate (Epsom
Salt). It usually comes in 50 or 100 LB bags
and must be dissolved in water. The solution
can then be suspended in the oil just prior
to combustion (to prevent separation) or it
can be emulsified into the oil prior to cer-
tification and/or supply tanks. Magnesium
sulfate has the formula:
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MgSO4 . 7 H2O
A look at the atomic weights shows that
it is about 10% magnesium and 50% water. The
magnesium sulfate phase diagram will show what
other compounds with different amounts of
water of hydration are possible at different
temperatures. The above formula is stable
at normal atmospheric temperatures.
The Epsom Salt is typically dissolved in
distilled water or condensate to give an
aqueous inhibitor flow that is 3% of the fuel
flow which produces a ratio of magnesium to
in the dissolving and metering system to
prevent recrystallization.
A magnesium sulfate inhibition system
typically consists of:
1. A dry storage place for storing bags of
Epsom Salt.
2. A dissolving tank with heater.
3. Emulsification tank and emulsification
equipment if required.
4. Metering pumps usually in a lead/stand-
by configuration.
5. Blenders to mix the inhibitor in oil,
usually lead stand-by.
6. Calibration tube and appropriate valving.
7. Specific gravity measuring equipment.
8. A source of distilled water.
9. Appropriate heat tracing_ to prevent
recrystallization.
Magnesium sulfate is a well proven in-
hibitor that has been used in many installa-
tions over the years.
CONCLUSION
There are many ways to inhibit vanadium
in gas turbine fuel oils. The particular
system chosen will depend on the application,
customer preferences, amount of vanadium
present in the fuel and overall economic
considerations.
The oil soluble system takes the least
in capital equipment and is the easiest to
use. The operating cost (price of the
material for inhibition) is the highest.
Where small amounts of vanadium are present
material costs may not be a factor.
The Epsom Salt (magnesium sulfate) is the
most complex system to purchase and operate.
The material is relatively low in cost. If
it is emulsified into the fuel, that raises
the cost considerably. It has been used very
successfully in a number of applications.
The oil suspendable product is least ex-
pensive from an operating stand point and the
capital cost of equipment is intermediate
between the above mentioned systems.
 The equation repesents the forming compounds
as follows,
APPENDIX A
1st TERM Magnesium Vanadates 3MgC • V205
PARTICULATE EMISSION LIMITS 2nd TERM Magnesium Sulfate MgSO4
Particulate emissions in Gas Turbine 3rd TERM Magnesium Oxide MgO
exhausts may be limited by government 4th TERM Silicon Dioxide Si02
regulations. If this is the case, vanadium
content in fuel will also have to be limit- This equation then reduces to
ed. 2.96 V + 11.45 V = 0.424 V
The following primary compounds will
= 11.607 V = 10 4 A
form as a result of the inhibition process,
= X 26.4 V + 10 4 A = X
3MaO ' V 2 0 5 Magnesium Ortho--Vanadate

atomic weight Mg = 72 or
atomic weight 0 = 48 + 80 V = X - 10 4 A
26.4
atomic weight V = 102
This can then be solved for various
atomic weight of molecule = 302 values of X and A to determine allowable
limits for V.
MgSO4
It is realized, that the formation of the
atomic weight Mg == 24 products of combustion is not as simple as
outlined here. Depending upon the amounts of
atomic weight S = 32 magnesium pyro and meta vanadates formed less
atomic weight 0 = 64 magnesium will go to the stoichiometric
protion of this reaction and more will be left
atomic weight. of molecule = 120 for the magnesium sulfate and magnesium oxide
products producing less total particulates
Mg 0 and somewhat increasing the allowable
vanadium. There are also secondary and
atomic weight Mg = 24 tertiary compounds formed which are not con-
sidered here. However this procedure should
atomic weight 0 = 16
give one a clearer understanding of how
atomic weight of molecule = 40 inhibition affects particulate emissions and
how to easily calculate vanadium limits.
Of the magnesium added, most of it does
not go for inhibition
Ma = 72 = 0.706
V 102
i.e. out of 3.25:1 Mg:V 0.706:1 Mg:V is
required for inhibition. Magnesium is added
at 4.6 times the stoichiometric ratio. This
means that 2.54:1 out of 3.25:1 is left to
produce MgSO4 and MgO particlulates.
Typically 90% of this would be MoSO 4 and
and 10% MgO.

V - _72 V ) 9 120
102 V + (3.25
1 102 24

+ V - 7 2 V) 0.1 40
1 102 24

+ 3.25 30 60 + 10 4 A = X
1 18 28
where
X= allowable particulates in exhaust
- LB/MBTU
A= ash in fuel -
V= vanadium in fuel - PPM

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