35

CHEMICAL REDUCTION OF SULFUR TRIOXIDE AN.D PARTICULATES

FROM HEAVY OILS

Robert P. Bennett

Apollo C h e m i c a l Corporation, Whippany. New J e r s e y 0798

INTRODUCTION

T h e r e h a s been a significant i n c r e a s e in interest in the scientific

application of fuel additives to r e s i d u a l fuel oils t o solve f i r e s i d e b o i l e r problems,
a s well a s additives t o reduce a i r pollution f r o m burning of r e s i d u a l fuels. T h i s
interest s t e m s from: 1) r e s t r i c t i o n s on particulate and NO, e m i s s i o n s imposed
by t h e Environmental P r o t e c t i o n Agency, 2) the higher p r i c e of fuel and t h e
d e s i r e f o r i n c r e a s e d efficiency, 3) the need t o eliminate costly cold end
c o r r o s i o n , 4) community relations that r e q u i r e the eliminating of acid s m u t
e m i s s i o n s and c h a r a c t e r i s t i c blue white plume caused by the condensation of
SOg.
T h e s e fireside p r o b l e m s can b e reduced o r eliminated by instituting
improved operating p r o c e d u r e s plus t h e u s e of one o r m o r e a d d i t i v e s added t o
t h e fuel oil o r to the f u r n a c e burning the r e s i d u a l fuel.
Effective fuel additives have been shown to be limited t o t h o s e that contain
a metal. However, t h e choice of additive f o r any p a r t i c u l a r b o i l e r depends upon
t h e needs of the b o i l e r and the p a r t i c u l a r environmental r e q u i r e m e n t s .
In g e n e r a l , fuel additives should provide b o i l e r c l e a n l i n e s s , high
t e m p e r a t u r e vanadium c o r r o s i o n protection, prevention of l o s s of operating
capacity by maintaining design s t e a m t e m p e r a t u r e s , cold end ( a i r h e a t e r ) corrosion
protection, reduction of stack e m i s s i o n s f r o m hydrocarbon p a r t i c u l a t e m a t t e r and
sO3. and improvement in t h e handling c h a r a c t e r i s t i c s of a s h in t h flue g a s in
oil-fired b o i l e r s equipped with p r e c i p i t a t o r s and stack collectors. The significant
fuel additives in u s e today usually contain MgO (with o r without s m a l l amounts of
aluminum oxide o r h y d r a t e ) , manganese, and MgO with manganese.
The u s e of magnesium oxide a s a fuel additive, p r i m a r i l y f o r t h e c o n t r o l
of vanadium slag, h a s been known f o r a number o f ' y e a r s (1). T h e addition
of MgO-based products t o t h e fuel o i l or furnace will r a i s e t h e fusion point of
the a s h if used a t a Mg:V weight r a t i o of 1. 5 to 1 ( m o l a r r a t i o of Mg:V of 3:l).
P r o p e r l y treated a s h will b e soft, but voluminous. The i n c r e a s e d a s h b u r d e n
on the b o i l e r can lead t o bridging and blockage in t h e boiler a n d i n c r e a s e d
particulate emissions. With todays low sulfur, low a s h fuels, t h e u s e of MgO,
at l e a s t a s a s l u r r y added t o the f u e l oil is no longer justified generally.
The purpose of this p a p e r i s t o review the u s e of c h e m i c a l s added t o the
fuel t o improve combustion, t h e r e b y reducing unburned c a r b o n p a r t i c u l a t e , and
t o reduce the formation of SO3 in t h e flue g a s , t h e r e b y reducing plume opacity
and acid smut e m i s s i o n s .
Additionally, b e c a u s e additives in the fuel add to the a s h b u r d e n of t h e
boiler, a n alternate a p p r o a c h f o r attacking the problems of cold end c o r r o s i o n
and acid smut e m i s s i o n s h a s b e e n developed. T h i s is a cold end feed of a
p r o p e r l y constituted neutralizing additive, applied d i r e c t l y into t h e p r o b l e m a r e a s
only and added strictly in p r o p o r t i o n t o t h e amount of SO3 p r e s e n t in the flue gas,
t h u s minimizing the t r e a t m e n t r a t e and reducing t h e problem of e m i s s i o n s t o the
atmosphere.
 F U E L O I L TREATMENT

Sulfur in heavy f u e l o i l i s oxidized readily t o sulfur dioxide. A

portion of this s u l f u r dioxide is f u r t h e r oxidized t o sulfur trioxide. The
extent of conversion of the SO2 to SO3 is dependent upon the p e r c e n t of
e x c e s s air and a l s o o n t h e p r e s e n c e of oxidation c a t a l y s t s in t h e fuel,
g e n e r a l l y vanadium o r nickel. Additionally, the b o i l e r i r o n tube s u r f a c e s
c a n themselves a c t a s a c a t a l y s t f o r t h i s reaction. T h e quantities of t h e s e
c a t a l y s t s will v a r y c o n s i d e r a b l y i n different fuel o i l s , so that t h e p e r c e n t
conversion, a t a n y given l e v e l of e x c e s s air, will v a r y with t h e fuel and
b o i l e r cleanliness. I t i s difficult to p r e d i c t t h e SO3 content of t h e combustion
products of a given f u e l so, t h e r e f o r e , t h e exact dew point of t h e flue g a s i s
difficult t o forecast. An e m p i r i c a l c o r r e l a t i o n h a s been p r e p a r e d a s shown
i n F i g u r e 1. I t is s i m i l a r t o t h e e x p e r i e n c e s of o t h e r s ( 2 , 3 . 6 ) who h a v e
s h w n t h e variation of SO3 concentration a s a function of 0 2 concentration.
F u e l s examined h a v e v a r i e d f r o m a low vanadium content of below 50 p a r t s
p e r million up t o f u e l s of 300 p a r t s p e r million. Obviously, t h e b e s t situation
i s t o obtain the data f o r e a c h p a r t i c u l a r unit. However, t h i s g r a p h h a s been
e x t r e m e l y useful a s a f i r s t approximation f o r a unit w h e r e t e s t data a r e not
available.
T h e sulfur content of the fuel oil obviously affects t h e p a r t s p e r million
of SO3 in the flue gas. A s expected, a s t h e sulfur l e v e l of t h e f u e l i n c r e a s e s ,
so d o e s the absolute amount of SO3 in t h e flue g a s up t o a maximum level.
Again, a n e m p i r i c a l c o r r e l a t i o n of p a r t s p e r million of s03, i n relation to t h e
p e r c e n t excess a i r and t h e s u l f u r i n t h e fuel, can be obtained a s shown in
F i g u r e 2. T h i s a l s o i s s i m i l a r to r e s u l t s of previous w o r k e r s , such a s
Laxton (2), o r Rendle et al. (7), both of whom used experimental furnaces.
Note t h a t a reduction in f u e l sulfur f r o m 2. 5 t o 1. 570 r e s u l t s i n a reduction
i n dew point of only about 7 ° F a b o v e a n e x c e s s a i r of 10%.
F r o m t h e s e two c u r v e s , it b e c o m e s obvious that i n o r d e r t o reduce
SO3 with any given fuel, t h e g r e a t e s t effect would be obtained by reducing the
p e r c e n t excess air at which t h e unit i s fired. Decreasing the e x c e s s air a l s o
h a s t h e advantage of d e c r e a s i n g BTU losses and increasing unit efficiency.
However, excess air g e n e r a l l y c a n only b e reduced t o a limited extent,
b e f o r e flue g a s c o m b u s t i b l e s b e g i n to i n c r e a s e rapidly. T h i s in turn r e s u l t s
in a d e c r e a s e i n efficiency o r even unsafe firing conditions, as well a s
unsightly black plumes. T h e u s e of a combustion catalyst will reduce
substantially the amount of c o m b u s t i b l e s i n the flyash, and thus make it
f e a s i b l e t o operate continuously a t reduced o r at low l e v e l s of e x c e s s oxygen.
T h e latter in t u r n f u r t h e r r e d u c e s SO3 generation.
An additional f a c t o r is t h a t t h e u s e of a combustion catalyst, which i s a
m e t a l , w i l l a l s o help t o d e s t r o y the catalytic p r o p e r t i e s of t h e f u e l m e t a l s by
c h e m i c a l reaction. P r e v i o u s w o r k e r s (1) have shown that operation at low
e x c e s s air a l s o f a v o r s the f o r m a t i o n of t h e lower oxides of vanadium, V2O3
and V204, which l e a d s t o high-melting a s h and a minimum of c o r r o s i o n and
fouling.
T h e use of a m a n g a n e s e c a t a l y s t f o r t h e reduction of SO3 i s shown i n
T a b l e 1. Note t h a t at given oxygen levels (Units 2 and 3) t h e r e is a sub-
stantial reduction i n SO3 with t r e a t m e n t . T h e d a t a for Unit 1 show both the
reduction obtained f r o m reduction of e x c e s s oxygen and t h e additional benefit
of manganese t r e a t m e n t . T h e S O 3 content w a s determined by t h e well known
E P A Method 8.
I
i
'\
37
P a r t i c u l a t e e m i s s i o n s consist of inorganic a s h f r o m t h e fuel, unburned
c a r b o n f r o m incomplete combustion, and c o r r o s i o n products. Flue gas ash
loading f r o m any p a r t i c u l a r fuel should b e f a i r l y constant at steady operating
'i conditions. However, the carbon content c a n v a r y depending on t h e c o m p l e t e n e s s
of combustion and on e x c e s s a i r levels.
!!. A number of m e t a l s a r e known t o be effective a s combustion catalysts. They
c a n r e d u c e particulate loadings i f they p r o m o t e m o r e complete burning of the
\ c a r b o n portion. A r e c e n t p a p e r by G i a m m a r (4) points out the effectiveness
of manganese f o r this purpose. It h a s b e e n found that manganese can be used
a s a n inorganic s l u r r y (5, 10) o r in the f o r m of a t r u l y soluble organometallic
species. The inorganic type i s most economical f o r u s e in heavy fuels w h e r e
\
h i g h e r concentrations of manganese a r e r e q u i r e d , a s c o m p a r e d to distillate fuels.
In a typical example, a r e f i n e r y w a s r e q u i r e d t o b u r n heavy asphaltic bottoms
in a package b o i l e r producing 200,000 lbs. of s t e a m p e r hour at. 9 0 0 ° F superheat
t e m p e r a t u r e and 900 psi. superheat p r e s s u r e . T r e a t m e n t of t h e pitch with
45 ppm Mn produced a d e c r e a s e in flue g a s p a r t i c u l a t e s f r o m 0.17 t o 0.04 mg/SCF
\
with a corresponding reduction of c a r b o n content of the particulate f r o m 72% t o
31%.
F o r g a s t u r b i n e s and package b o i l e r s , t h e soluble f o r m often b e c o m e s t h e
additive of choice b e c a u s e of the e a s e in handling, p a r t i c u l a r l y since the requisite
p a r t s p e r million of manganese i s low enough so that t h e e x t r a c o s t for supplying
a soluble f o r m of manganese is considered t o be economical.
I n addition to the reduction in acidic e m i s s i o n s and p a r t i c u l a t e e m i s s i o n s
obtained by the use of a manganese combustion c a t a l y s t and reduced e x c e s s a i r
level operations, t h e r e i s often a significant i n c r e a s e i n efficiency obtained. This
c a n b e directly t r a n s l a t e d into fuel savings and d o l l a r s a s shown i n T a b l e 2. This
efficiency i n c r e a s e alone often justifies t h e u s e of a fuel additive.

COLD END TREATMENT

So f a r , we have d e s c r i b e d the benefits of using fuel additives to r e d u c e

SO3 e m i s s i o n s and t o d e c r e a s e unburned c a r b o n p a r t i c u l a t e e m i s s i o n s . Even with
t h e s e t r e a t m e n t s , it h a s been found that a n u m b e r of units suffer f r o m varying
d e g r e e s of cold end c o r r o s i o n with resulting a i r h e a t e r blockage and wastage.
Even with low sulfur fuels, many units e x p e r i e n c e cold end problems.
T o minimize t h e s e p r o b l e m s one can r e d u c e SO3 content totally o r r a i s e
t h e exit g a s t e m p e r a t u r e above the dew point. Two methods of doing the l a t t e r
a r e available: 1) s t e a m coils in the a i r duct u p s t r e a m of the a i r h e a t e r can b e
u s e d t o r a i s e the t e m p e r a t u r e of the incoming a i r f o r combustion. This r e s u l t s
i n a h i g h e r m e t a l t e m p e r a t u r e a t t h e cold end of the a i r h e a t e r . 2) An a i r
h e a t e r by-pass d a m p e r u p s t r e a m of the a i r h e a t e r c a n b e u s e d t o b y - p a s s a
portion of the incoming a i r for combustion around t h e a i r h e a t e r . This also
r e s u l t s in a higher t e m p e r a t u r e a t the cold end of t h e a i r h e a t e r . Both of
t h e s e methods r a i s e the exit g a s t e m p e r a t u r e and s a c r i f i c e unit efficiency. A
4 0 ° F change in exit g a s t e m p e r a t u r e is g e n e r a l l y equivalent to 1% in unit
efficiency.
An alternate, o r supplementary t r e a t m e n t , depending on b o i l e r operations,
i s t h e injection of a cold end, free-flowing, neutralizing powder ( 8 ) , a p r o c e s s (10)
which has been perfected o v e r s e v e r a l y e a r s . T h i s m a t e r i a l is usually applied
a f t e r t h e economizer and h a s the advantage of only being added in proportion to the
f r e e SO3 p r e s e n t . In t h i s way, the acidic conditions a r e n e u t r a l i z e d with minimum
burden on the system.
 38 i
T o i l l u s t r a t e t h e s u c c e s s of this a p p r o a c h , l e t us c o n s i d e r s e v e r a l c a s e
histories.

EXAMPLE I

A 220 MW p r e s s u r i z e d unit with a L j u n g s t r o m air h e a t e r had both severe

c o r r o s i o n and a i r h e a t e r pluggage p r o b l e m s which r e q u i r e d a high exit gas
t e m p e r a t u r e of 3 0 0 ° F t o p r o t e c t t h e cold end. T h e #6 f u e l o i l contained 400 pprn
vanadium and 2. 5'7~ sulfur. F u e l u s e r a t e w a s 302 bbl/hour o r 12,684 gallons
p e r hour. MgO, i n the f o r m of a s l u r r y , w a s added t o t h e f u e l o i l i n an attempt
t o solve the c o r r o s i o n and pluggage p r o b l e m s and a c i d s m u t emissions. This
approach was u n s u c c e s s f u l b e c a u s e of e x c e s s ash and blockage within t h e boiler.
It w a s t h e r e f o r e decided t o t r y cold end feed. T h e a c i d dew point of the
untreated unit w a s 300°F. w h e r e a s the exit g a s t e m p e r a t u r e w a s only 305°F. I
Using a feed rate'of neutralizing agent of 0.19 lbs. /bbl., t h e dew point was
reduced t o 1 8 0 ° F o r e s s e n t i a l l y a w a t e r dew point. T h i s allowed a s a f e
reduction in exit g a s t e m p e r a t u r e to 2 6 5 ° F by shutting off s t e a m a i r p r e h e a t e r s
and closing air h e a t e r b y - p a s s ducts. T h e economic gain f r o m t h e s e features
alone w a s over $200,000 annually. Additional benefits w e r e reduced corrosion
and maintenance c o s t s and improved unit p e r f o r m a n c e because of no a i r heater
pluggage with t r e a t m e n t .
During t h e c o u r s e of this investigation, we w e r e again a b l e to demonstrate
that j u s t the reduction in e x c e s s a i r alone is not sufficient t o reduce t h e SO3
to a low enough l e v e l t o p r o t e c t the cold end of t h e unit. F i g u r e 3 shows the
efiect of e x c e s s a i r reduction on SO3 g e n e r a t i o n i n the untreated unit at
constant load. Dropping t h e e x c e s s a i r l e v e l f r o m 12 t o 5% reduced t h e SO3
content f r o m 80 ppm to 30 ppm, but s t i l l r e s u l t e d i n a dew point of 290°F.
T r e a t m e n t with additive a t 12% a i r reduced t h e SO3 to 16 ppm and reduction I
to 5% air at t h e s a m e t r e a t m e n t r a t e reduced t h e SO3 t o 2 ppm allowing safe
operation a t a n exit g a s t e m p e r a t u r e of only 265°F.
I n considering a s a f e exit g a s t e m p e r a t u r e , it must b e r e m e m b e r e d that
i t i s not j u s t t h e a v e r a g e cold end m e t a l t e m p e r a t u r e , but t h e minimum metal
t e m p e r a t u r e u n d e r t h e p o o r e s t operating t e m p e r a t u r e s and t h e duration of these
conditions against which p r o t e c t i o n must be provided. By t h e u s e of the
neutralizing additive, one not only stops t h e c o r r o s i o n completely, but often
a l s o p i c k s up the added economic benefits of being a b l e t o safely t u r n off water
o r steam a i r h e a t e r s a n d / o r close a i r h e a t e r by-pass dampers.

EXAMPLE I1

E v e n with low sulfur f u e l (0. 30/0), u n i t s which cannot reduce e x c e s s a i r

levels have a need f o r cold end protection. For example, a 350 MW pressurized
b o i l e r with a Ljungstrorn air heater w a s experiencing significant cold end
corrosion. T h i s unit burned #6 o i l of about 14 pprn vanadium and 0.3% sulfur.
E x c e s s a i r was 1570. F u e l consumption w a s 600 bbls. / h r . o r 25,200 gallons
p e r hour. The exit g a s t e m p e r a t u r e w a s 2 7 0 ° F . but t h e acid dew point was
273"F, equivalent t o 10 p p m , of SO By applying the powdered neutralizing
agent to the cold end a h e a d of t h e a3.'i r h e a t e r s at a r a t e of 0.033 lbs./bbl,
t h e dew point wa's reduced t o 1 5 0 ° F o r 0 ppm, SO3. By shutting t h e by-pass
d a m p e r s , a 30°F reduction in exit g a s t e m p e r a t u r e could b e safely achieved.
F u e l consumption alone h a s b e e n cut by 14,000 bbls. a y e a r , which at c u r r e n t
p r i c e s is a savings of $182,000.
 39
CONCLUSIONS

I n summary, we have reviewed the production of SO3 a n d unburned

particulate f r o m burning heavy oils. F o r m a t i o n of SO3 l e a d s to, c o r r o s i o n of
t h e cooler p a r t s of t h e boiler, such a s t h e a i r h e a t e r and duct work, and c a n
produce a visible plume and acidic emissions. Unburned p a r t i c u l a t e leads to
excessive e m i s s i o n s and a visible plume. Mechanical c o r r e c t i o n s alone
usually a r e not sufficient t o eliminate t h e s e problems. T h e u s e of a manganese
combustion catalyst allows operation a t low e x c e s s a i r l e v e l s , and consequently
low SO3 levels, without the a d v e r s e formation of unburned c a r b o n p a r t i c u l a t e
matter. T h e u s e of lower e x c e s s a i r l e v e l s i m p r o v e s unit efficiency and
s a v e s fuel.
Additionally, neutralization of r e s i d u a l SO3 b y application of a neutralizing
additive i n powder f o r m into the cold end of t h e b o i l e r allows operation at
lower flue g a s t e m p e r a t u r e s b e c a u s e of t h e lowered a c i d dew point. Air
h e a t e r s and cold end duct work a r e thus protected while l o w e r exit g a s
t e m p e r a t u r e s improve unit efficiency.
The combination of t h e s e two approaches: the u s e of c h e m i c a l i n t h e
hot end f o r combustion improvement, and c h e m i c a l i n t h e cold end f o r a c i d
neutralization, l e a d s t o significant savings with heavy f u e l o i l u n i t s while at
t h e s a m e t i m e minimizing o r eliminating e m i s s i o n s p r o b l e m s (9).

REFERENCES

1. Reid, W. T . , "External C o r r o s i o n and Deposits, American Elsevier,

New York, New York, 1971.

2. Laxton, J. W . , i n "The Mechanism of C o r r o s i o n by F u e l I m p u r i t i e s , "

Butterworths, London, 1963, pp. 228-237.

3. Reese, J. T . , Jonakin, J.. and C a r a c r i s t i , V. Z . , Combustion, -

36. 29,
(1964).

4. C i a m m a r , R. D., Krause, H. H., Locklin, D. W . , ASME, 75-WA/CD-7.

5. Kukin, I. , "Effects of Additives on B o i l e r Cleanliness and P a r t i c u l a t e

E m i s s i o n s , I s International Meeting of t h e Society of Engineering Science,
T e l Aviv, I s r a e l , June 1972.

6. Kukin, I . , and Bennett. R. P., "Chemical Reduction of SO3, P a r t i c u l a t e s

and NOx E m i s s i o n s , I t T h e International E n e r g y Engineering C o n g r e s s ,
Chicago, Illinois, November 1975.

7. Rendle, L. K., Wilsdon, R. D., and Whittingham, G . , Combustion, -

31, 30,
(1959)

8. Kukin, I . , and Ross, A . , Combustion, 45. 14, (1974).

9. U. S. Patent 3,837,820.

10. U.S. Patent 3,692,503.

 40 I

FIGURE 1

CONVERSION OF SULFUR TO SULFUR TRIOXIDE I

I 1

5 lo 15 26
PERCENT EXCESS AIR
EMPIRICAL PERCENT CONVERSION OF S TO SO3 WITH
VARYING EXCESSAIR FOR#GOIL AND FOR COAL.

~ ~~

FIGURE 2
OEWPOINT RELATED TO FUEL SULFUR CONTENT

100 r I 308.

1.5% S

20 0.5% S

10 15 m
PERCENT EXCESS AIR

SO3 CONCENTRATION AND DEW POlNT RELATED TO EXCESS AIR

AND PERCENT FUEL SULFUR FOR#6OIL.
\
41

\
FIGURE 3
EFFECTOF EXCESSAIRON AClDDEWPOlNTATCONSTANTLOAD

5
c
240-F -
z
2 220°F -
k 2GU'F-
4

1WF -
1W'F-

140'F -
12 10 8 6 4 2
96 EXCESSAIR
CONDITIONS-
A -Untreated
0 -Treated
ARlLlTY OF ADDITIVE 7 0 REDUCE DEWPOINTALLOWING
SAFEOPERATIONATREDUCED E X I T G A S TEMPERATURE
 42

-T
TABLE I
EFFECT OF MANGANESE ON SO, GENERATION

SO3 (PPM at 3%0 2 ) Percent

Unit Untreated Treated Reduction
9.1 5.0 45.1
4.55 14.2 8.0 43.7
20.4 9.0 55.9

2.5 1.7 32.0 I

15.0 9.0 40.0

ABILITY O F MANGANESE TO REDUCE SO3 CONCENTRATION IN

DIFFERENT UNITS AT VARIOUS EXCESS AIR LEVELS.

I TABLE 2
FUEL SAVINGS FROM REDUCTION OF EXCESS
AIR ALLOWED BY U S E OF MANGANESE ADDITIVES

Unit: lWMW

Fuel: =6fueloilwithaheatvalueot 18.5006TU/lb.

FueiUseRate: Average 52,500 gallonslday

Excess Air: 30% Initial: 18.50 Ibs. airllb.of fuel

8% Final: 15.73 ibs. airllb. of fuelldiff. = 2.77 ibs air

I Additive: I 31% Mnslurryat r a t e o l l galionl12,WOgallonsfuel

I
I Heat CapaClly: I 0.237BTUllb. of airl'F
I 4

Average
Heat Loss: Exil gas temp.
AT
-
Air to preheater = 85OF (ambient)
27VF (average)
= 190°F

(2.77Ibs.alrllb. fuel) (0.2376TUllb. airlOF) (190'F)

124.7 BTUllb. fuel oil
-
Oilconsumed (avg.) = 52.500gal.lday
@ 8 IbsJgal.
@ 124.7 ETUllb. -
= 420,000 Ibs.lday
52374.000 BTUlday (saved)

I -
52.374 x 10" ETUldav 353.88 gallday (saved)
148.0006TUlgal. = 8.42 bbl.lday I
I At current price of Slllbbl., this is worth S92.62lday.
I