UTILIZATION OF COAL-DERIVED LIQUID FUELS

I N A COMBUSTION 'IWRBINE ENGINE

A. V. C a b a l , M. J. Dabkowski, R. H. Heck, T. R. S t e i n
Mobil Research and Development Corporation, Paulsboro, New J e r s e y

R. M. Chamberlin, P . R. Mulik, P. P. Singh

Westinghouse Research Laboratories, P i t t s b u r g h , Pennsylvania

W. C. Rovesti
E l e c t r i c Power Research I n s t i t u t e , Palo Alto, C a l i f o r n i a

1.0 INTRODUCTION

A number of processes a r e c u r r e n t l y being developed on a l a r g e s c a l e

t o produce l i q u i d f u e l s from c o a l ( 1 ) . I t i s a n t i c i p a t e d t h a t t h e s e c o a l l i q u i d s
w i l l supplement t h e ever decreasing s u p p l i e s of petroleum crude now r e f i n e d t o
produce g a s o l i n e , d i s t i l l a t e s , and r e s i d u a l f u e l o i l . However, d e t a i l e d
a n a l y s i s of t h e s e coal l i q u i d s shows t h a t they a r e more aromatic and contain
more nitrogen and oxygen than do corresponding f r a c t i o n s from petroleum(2.3).
I n a d d i t i o n , c o a l l i q u i d s containing r e s i d u a l f r a c t i o n s high i n asphaltenes,
a r e incompatible when blended with t y p i c a l petroleum f u e l s ( 4 ) . Some
preliminary r e s u l t s have been reported on t h e combustion of heavy c o a l l i q u i d s
.
i n r e s i d e n t i a l b o i l e r s (5) and of s y n t h e t i c j e t f u e l i n a v i a t i o n t u r b i n e s (6)

The purpose of t h i s work w a s t o e v a l u a t e t h e use of raw and hydrotreated

heavy d i s t i l l a t e c o a l l i q u i d s from t h e Solvent Refined Coal (SRC) and H-Coal
processes f o r use i n heavy duty u t i l i t y t u r b i n e s . P r e s e n t l y , t h e s e t u r b i n e s
account f o r about nine p e r c e n t of t h e i n s t a l l e d power generation c a p a c i t y
i n t h e U.S. Most of t h i s c a p a c i t y is dedicated t o peak load generation where
high r e l i a b i l i t y and t h e a b i l i t y t o p u t t h e c a p a c i t y on-line r a p i d l y a r e of
c r i t i c a l importance. I n t h e f u t u r e , gas t u r b i n e capacity i s expected t o grow
f o r intermediate and base load a s high temperature combined c y c l e systems a r e
introduced f o r power generation.

I n considering f u e l s f o r use i n t h e s e p l a n t s , c e r t a i n fundamental

combustion p r o p e r t i e s must be e s t a b l i s h e d i n order t o a s s u r e s a f e , e f f i c i e n t ,
and clean combustion of t h e s e f u e l s . R e l i a b l e u t i l i z a t i o n includes t h e
determination of t h e operating l i m i t s of t h e combustion t u r b i n e with r e s p e c t
t o corrosion, erosion, and deposition. Dependable operation of t h e combustor
without t h e occurrence of flame-out, f o u l i n g o r overheating of t h e combustor
basket i s a l s o required f o r s a f e operation on coal-derived f u e l s . Furthermore,
t h e time and power l o s t during shutdown t o c l e a n o r r e p a i r hardware i s an
important f a c t o r t o be considered. F i n a l l y , emissions from t u r b i n e s burning
coal-derived l i q u i d s must meet p r o j e c t e d s t r i n g e n t EPA standards f o r oxides
of s u l f u r and nitrogen.

D i s t i l l a t e c o a l l i q u i d s from t h e H-Coal and SRC processes were

evaluated i n a l a b o r a t o r y t u r b i n e combustor passage. The t e s t f u e l s consisted
of r a w coal l i q u i d s and t h e same l i q u i d s hydroprocessed a t s e v e r a l s e v e r i t y
l e v e l s t o produce a d d i t i o n a l t e s t f u e l s of varying aromatic and nitrogen content.
Each f u e l w a s c h a r a c t e r i z e d by p h y s i c a l , chemical, and compositional a n a l y s e s ,
and was evaluated i n a small laboratory combustor a t simulated commercial t u r b i n e

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conditions. It should be noted h e r e t h a t due t o t h e l i m i t e d f u e l q u a n t i t y
a v a i l a b l e , flows i n t h i s combustor were approximately 300 t i m e s smaller than
those i n f u l l s c a l e engines, so t h a t c a u t i o n should be exercised i n i n t e r p r e t i n g
t h e trends d e t e c t e d .

2.0 EXPERIMENTAL

2.1 HYDROPROCESSING OF COAL LIQUIDS

Samples of d i s t i l l a t e c o a l l i q u i d s from t h e SRC p i l o t p l a n t i n

Wilsonville, Alabama, and t h e H-Coal p i l o t p l a n t i n Trenton, New J e r s e y , were
hydrotreated i n a fixed-bed hydroprocessing p i l o t u n i t of t h e Mobil Research
and Development Corporation. Commercial nickel-molybdenum and cobalt-molybdenum
c a t a l y s t s were employed f o r t h e H-Coal and SRC samples r e s p e c t i v e l y . Each
l i q u i d was hydroprocessed a t s e v e r a l s e t s of processing conditions. SRC r e c y c l e
s o l v e n t processed a t t h r e e d i f f e r e n t s e v e r i t i e s and H-Coal d i s t i l l a t e processed
at two d i f f e r e n t s e v e r i t i e s w e r e s e l e c t e d f o r t h e tests. The e n t i r e l i q u i d
product w a s u t i l i z e d f o r t h e SRC l i q u i d , while t h e product from t h e H-Coal
d i s t i l l a t e w a s d i s t i l l e d t o o b t a i n a 350F+ sample f o r t h e t u r b i n e t e s t a .

F i v e g a l l o n s of each of t h e raw c o a l l i q u i d s , two g a l l o n s of each of

t h e SRC hydrotreated l i q u i d s and t h r e e g a l l o n s each of the hydrotreated H-Coal
l i q u i d s were s e n t to t h e Westinghouse Research Laboratories i n P i t t s b u r g h for
t e s t i n g i n t h e small s c a l e t u r b i n e combustor.

2.2 COMBUSTION TESTS

I n order t o e v a l u a t e t h e e f f e c t of burning coal-derived l i q u i d f u e l s

i n commercial combustion t u r b i n e s , it was necessary t o reproduce as a c c u r a t e l y
as p o s s i b l e t h e gas residence time, temperature and aerodynamics of a combustor
operating on conventional f u e l s . Because of t h e l i m i t e d q u a n t i t i e s of coal
l i q u i d s a v a i l a b l e f o r t h e s e tests, a subscale combustor was designed and its
performance evaluated on No. 2 d i s t i l l a t e f u e l t o demonstrate combustion and
emission c h a r a c t e r i s t i c s r e p r e s e n t a t i v e of f u l l s c a l e combustors. Tests were
performed a t f u e l flow r a t e s of 1.6 gph with nominal operating c o n d i t i o n s
f i x e d a s follows:

Combustion air p r e s s u r e 3.0 atm

Combustion a i r temperature 500'F
Combustion a i r flow 0.1 Ibs/sec
Fuel p r e s s u r e 100 p s i g
Fuel flow 1.6 gph
Atomizing a i r p r e s s u r e 70 p s i g
Atomizing a i r flow 3-5% of f u e l flow
Reference v e l o c i t y 7 ft/sec
Combustor e x i t temperature l8OO'F
Primary zone residence time a0.05 s e c
Heat r e l e a s e r a t e a1200 BTU/sec f t 3
combustor cooling air flow %40% t o t a l a i r
Diluent a i r flow %20% t o t a l a i r
Combustor pressure drop 23% of i n l e t p r e s s u r e

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 The combustion t e s t passage i s shown i n Figure 1. A bank of r o t a r y
compressors s u p p l i e s compressed a i r , through an i n d i r e c t l y f i r e d p r e h e a t e r , t o
t h e t e s t passage. This system is designed t o d e l i v e r 6.5 lb/sec of a i r a t a
p r e s s i r e of 6 atm and a maximum temperature of 800'F. The d e s i r e d q u a n t i t y o f
combustion a i r i s metered by a sharp edged o r i f i c e and forwarded t o t h e
combustor while t h e remaining a i r i s bypassed and u l t i m a t e l y dumped near t h e
end of t h e t e s t passage. The t e s t f u e l is burned i n a four-inch diameter
combustor and t h e r e s u l t a n t h o t g a s flows through t h e passage p a s t a back p r e s s u r e
valve which i s p a r t i a l l y closed t o maintain a set p r e s s u r e i n t h e t e s t passage.
Thermocouples mounted on t h e combustor a r e used t o measure and monitor t h e
combustor w a l l temperature. 'Tho thermocouples a r e placed d i r e c t l y a f t e r t h e
combustor t o measure t h e temperature of the h o t combustion products. The exhaust
products a r e then passed through a mixing device and an a r r a y Of s i x thermocouples
measures t h e mean bulk exhaust temperature'of t h e g a s e s . The temperatures of t h e
thermocouples are recorded on a twenty-four p o i n t recorder. F u r t h e r downstream,
provisions e x i s t f o r mounting t e s t p i n s and f o r procuring samples of t h e exhaust
gas f o r both emission analyses and smoke number determinations. A much l a r g e r
sample flow r a t e than necessary i s used t o minimize sampling l i n e i n t e r f e r e n c e
and keep t h e residence t i m e small. The sample gas i s d r i e d and f i l t e r e d and
passed t o v a r i o u s analyzers.

In a t y p i c a l run t h e combustion test passage was f i r s t f i r e d with

No. 2 f u e l and allowed t o run u n t i l t h e s e t standard t e s t conditions were reached.
The item with t h e longest t i m e constant was t h e a i r p r e h e a t e r . I t g e n e r a l l y took
about an hour before t h e combustion a i r temperature was up t o t h e t e s t design
p o i n t . When t h e required combustion a i r temperature w a s reached t h e a i r flow
through and t h e p r e s s u r e i n t h e combustion t e s t passage was set a t t h e d e s i r e d
l e v e l . The f u e l flow was s e t t o give an exhaust mixed temperature of approximately
1800F. The combustion t e s t passage was run u n t i l s t e a d y - s t a t e conditions were
achieved and t h e base-line d a t a f o r No. 2 f u e l w a s obtained. Smoke Numbers, CO2,
CO, N 4 ( and unburned hydrocarbon l e v e l s i n t h e exhaust were measured. A two
color pyrometer was s i g h t e d through a view p o r t t o o b t a i n t h e flame temperature
i n t h e primary zone.

By Slowly t u r n i n g o f f t h e No. 2 f u e l o i l needle valve and t u r n i n g on

t h e coal-derived l i q u i d f u e l valve a switchover with a n e g l i g i b l e excursion from
t h e s e t t e s t condition was obtained. When t h e t r a n s i t i o n was complete, d a t a
were taken every f i f t e e n minutes.

3.0 RESULTS AND DISCUSSION

3.1 HYDROPROCESSING RESULTS

The SRC r e c y c l e s o l v e n t was hydroprocessed over a commercial CoMo/A1203

c a t a l y s t (Cyanamid WS-1441A) a t t h r e e s e v e r i t y l e v e l s while t h e H-Coal d i s t i l l a t e
was hydroprocessed over a commercial NiMo/A1203 c a t a l y s t (Ketjen 153s) a t two
s e v e r i t y l e v e l s . Table 1 l i s t s t h e p r o p e r t i e s of t h e feeds and hydroprocessed
l i q u i d products from t h e s e runs. Also shown i n Table 1 a r e t h e processing
conditions, y i e l d s of a l l products, and degree of heteroatom (0, N , S ) removal.
For t h e SRC r e c y c l e s o l v e n t , t h e p r e s s u r e w a s held constant a t 2500 p s i g f o r
a l l t h r e e runs. The two h i g h e s t s e v e r i t y runs were made a t %715'F and space
v e l o c i t i e s of 0.8 and.0.4 consuming 2260 and 2800 SCF H2/Bbl r e s p e c t i v e l y . For
t h e lowest s e v e r i t y r u n , t h e temperature w a s decreased t o 678'F and t h e space

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v e l o c i t y increased t o 2.9 LHSV. This r e s u l t e d i n a hydrogen consumption of
1140 SCF/Bbl. I n a l l c a s e s , t h e y i e l d of cg+ l i q u i d product was g r e a t e r than
98 %. The s u l f u r removal was g r e a t e r t h a n 85% f o r a l l t h r e e c o n d i t i o n s while
t h e oxygen and nitrogen removal v a r i e d from 30 t o 95%.

The H-Coal d i s t i l l a t e was processed a t 1500 p s i g and 2.9 space

v e l o c i t y f o r t h e mild s e v e r i t y run and a t 2500 p s i g and 0.5 space v e l o c i t y f o r
t h e high s e v e r i t y run r e s u l t i n g i n chemical hydrogen consumptions of 570 and
1730 SCF/Bbl r e s p e c t i v e l y . The temperature w a s approximately 700'F f o r both
runs. Again, s u l f u r removal w a s g r e a t e r than 95%while oxygen and n i t r o g e n
removal varied from 40 t o 99%.

The r a w and hydrotreated I-Coal d i s t i l l a t e were d i s t i l l e d t o remove

t h e m a t e r i a l b o i l i n g below 350F. These, together with t h e as received r a w and
hydrotreated SRC r e c y c l e s o l v e n t , were used a s t h e t e s t f u e l s f o r t h e combustion
t e s t s . Table 2 lists t h e chemical and p h y s i c a l p r o p e r t i e s o f t h e c o a l l i q u i d
f u e l s . Also shown a r e t h e p r o p e r t i e s of t h e N o . 2 petroleum f u e l used i n t h e
canbustion tests. I n g e n e r a l , t h e c o a l l i q u i d s have lower API g r a v i t i e s : are
higher b o i l i n g ; and contain l e s s hydrogen ( i . e . , more aromatic) and more s u l f u r ,
n i t r o g e n , and oxygen than t h e petroleum f u e l . The t r a c e metal elements a r e
s i g n i f i c a n t i n t h e raw SRC r e c y c l e s o l v e n t and H-Coal d i s t i l l a t e ; hydroprocessing
reduces these metals t o l e v e l s e q u i v a l e n t t o t h e N o . 2 petroleum f u e l . The r a w
SRC r e c y c l e s o l v e n t c o n t a i n s only 7.4 w t % hydrogen with 74 % of t h e carbon
atoms i n aromatic r i n g s t r u c t u r e s while t h e raw H-Coal d i s t i l l a t e c o n t a i n s 9 . 1 w t
% hydrogen and 55% aromatic carbon. The most severely hydroprocessed SRC r e c y c l e
s o l v e n t and H-Coal d i s t i l l a t e s t i l l c o n t a i n 34 and 27% aromatic carbon
r e s p e c t i v e l y compared t o 19%aromatic carbon i n t h e No. 2 petroleum f u e l . In
a d d i t i o n , severe hydroprocessing increased t h e h e a t of combustion of t h e c o a l
l i q u i d s equivalent t o t h a t of N o . 2 f u e l .

3.2 TURBINE ENGINE SIMULATION RESULTS

3.2a) F u e l Forwarding and Atomization

Due t o t h e s m a l l q u a n t i t i e s of f u e l a v a i l a b l e , t h e constant p r e s s u r e
r e c i r c u l a t i n g f u e l system designed f o r u s e w i t h t h e t e s t passage could n o t be
used. Instead a small tank p r e s s u r i z e d with n i t r o g e n was used a s a source of
c o n s t a n t pressure f u e l . The f u e l nozzle assembly chosen f o r t h e s e t e s t s w a s t h e
conventional a i r a s s i s t atomizing type used r e g u l a r l y with N o . 2 f u e l i n t h e
combustion test passage. This type nozzle c o n s i s t s of an o r i f i c e and a c o n i c a l
swirl element which produces a r a p i d r o t a t i o n of t h e o i l w i t h i n t h e c o n i c a l s w i r l
chamber. The a i r t o a s s i s t i n atomization i s brought c l o s e t o t h e o r i f i c e by
an a i r swirler where it mixes w i t h t h e o i l i n a highly t u r b u l e n t manner. The
a i r s w i r l e r i s kept i n p l a c e by a cap t h a t goes over t h e whole assembly. A
second cap i s used t o keep t h e nozzle cool and t o o b t a i n an a i r flow p a t t e r n
a t t h e head of t h e combustor s i m i l a r t o t h a t i n a f u l l s c a l e combustor.

Studies were conducted t o determine whether t h e r e g u l a r f u e l nozzle

assembly designed f o r flow r a t e s of t e n t o t h i r t y g a l l o n s p e r hour would give
good atomization i n t h e one t o two g a l l o n s p e r hour range if smaller f u e l nozzles
were employed. The small s c a l e f u e l nozzles were mounted i n a s u i t a b l e enclosure
i n t h e l a b o r a t o r y and No. 2 f u e l was pumped i n t o t h e nozzle a t a p r e s s u r e of
100 P s i . The spray p a t t e r n was observed v i s u a l l y and photographs were taken.

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 I t w a s found t h a t t h e degree o f atomization w a s b e t t e r than t h a t
observed with t h e l a r g e r nozzles. N o i n d i v i d u a l d r o p l e t s o r d r i p p i n g s could be
seen and when t h e atomizing a i r w a s turned on t h e spray was e f f e c t i v e l y atomized.
From t h i s t e s t , it was concluded t h a t t h e hollow cone s p r a y p a t t e r n produced by
t h e s m a l l s c a l e nozzle w a s s u i t a b l e f o r t h e c o a l l i q u i d combustion s t u d i e s .

3.2b) Combustion and Emission C h a r a c t e r i s t i c s

The complete r e s u l t s of t h e combustion tests on t h e seven c o a l derived

f u e l s are t a b u l a t e d i n T a b l e 3. This table a l s o p r e s e n t s d a t a f o r t h e base No. 2
petroleum f u e l . This f u e l w a s run p r i o r t o t h e combustion of each coal-derived
l i q u i d and t h e values reported i n Table 3 r e p r e s e n t an average f o r a l l base l i n e
runs.

SRC Recycle Solvent:

SRC r e c y c l e s o l v e n t ( 7 . 4 w t % H) w a s t h e f i r s t c o a l l i q u i d t e s t e d .
The t r a n s i t i o n from N o . 2 f u e l t o t h e SRC r e c y c l e s o l v e n t w a s f a i r l y smooth
and s t e a d y - s t a t e conditions were e a s i l y e s t a b l i s h e d i n t h e combustion t e s t
passage. The most s i g n i f i c a n t change observed w a s t h e s h a r p i n c r e a s e i n N4(
emissions from t h e base l i n e f u e l . However, a f t e r about an hour of t e s t i n g it
became evident t h a t t h e combustor w a l l s were n o t maintaining a uniform temperature
and were showing s i g n s of e r r a t i c temperature f l u c t u a t i o n s . Based on t h e s e
observations, i t was speculated t h a t coke d e p o s i t i o n and burning was taking place
on t h e combustor w a l l s . A small i n c r e a s e i n smoke number a t t h e time of f u e l
t r a n s i t i o n was observed b u t i t e v e n t u a l l y d e c l i n e d t o v a l u e s l e s s than t h o s e
observed f o r t h e No. 2 f u e l . Apart from t h e d i f f e r e n c e c i t e d above no o t h e r
major observations w e r e noted during t h e f i r s t one and one-half hours of t e s t i n g
with t h e r e c y c l e s o l v e n t . However, a f t e r about one and one-half hours of running
it became evident t h a t t h e combustor had burned o u t . The t e s t passage housing
t h e combustor developed a d u l l red h o t s p o t and t h e t e s t w a s terminated after
"4.6 hours of running. On opening t h e t e s t passage and observing t h e damage it
w a s noted t h a t a l a r g e p o r t i o n of t h e combustor dome and a s e c t i o n of t h e
combustor wall had burned through. Coke d e p o s i t s were. found b o t h on t h e
combustor w a l l and a t t h e nozzle. The combustor can before and a f t e r t h i s t e s t
is shown i n Figures 2A and 2B.

The second f u e l t e s t e d w a s t h e most s e v e r e l y hydrotreated r e c y c l e

s o l v e n t (11.0 w t % H) using a new combustor can i d e n t i c a l t o t h e one t h a t w a s
destroyed. The base l i n e t e s t conducted with t h i s combustor using No. 2 f u e l
produced higher N4( and UHC readings. However, such v a r i a t i o n s i n combustor
emission c h a r a c t e r i s t i c s are not unusual e s p e c i a l l y a f t e r r e p l a c i n g combustors.
The t r a n s i t i o n from N o . 2 f u e l t o t h e c o a l l i q u i d was made smoothly and t h e t e s t
w a s conducted with no problems. A f t e r t h e t e s t , t h e combustor was opened and
no evidence of any coke d e p o s i t s were found. The combustor w a l l showed no h e a t
d i s t r e s s e f f e c t s and t h i s test a l s o yielded f a i r l y low smoke numbers.

A moderately hydroprocessed r e c y c l e s o l v e n t (10.3 w t % H ) w a s t h e t h i r d

f u e l t e s t e d . The i n i t i a l attempt t o switch from N o . 2 f u e l t o t h i s hydroprocessed
l i q u i d w a s n o t very successful. It was found s w n a f t e r t h e t r a n s i t i o n t h a t t h e
combustor wall temperature r o s e appreciably. This n e c e s s i t a t e d termination of
t h e experiment and disassembly of t h e passage t o check t h e f u e l nozzle assembly
and combustor can f o r coke formation. I t w a s found t h a t t h e nozzle was fouled
by a small carbon d e p o s i t . The can was r e l a t i v e l y c l e a n except f o r two small
s p o t s where coke had deposited. Evidently, a d i s r u p t i o n of t h e f u e l spray p a t t e r n
by t h e carbon deposited on t h e nozzle w a s r e s p o n s i b l e for t h e i n c r e a s e i n w a l l
temperature observed.

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 After cleaning t h e nozzle and c a n , a second attempt w a s made using
t h i s f u e l . This time t h e t r a n s i t i o n from No. 2 f u e l to t h e moderately hydro-
processed recycle s o l v e n t (10.3 w t % H) w a s s u c c e s s f u l and t h e run was made
without any d i f f i c u l t y . The wall temperatures as w e l l a s t h e N& emissions
were s u b s t a n t i a l l y higher with t h i s c o a l l i q u i d compared t o N o . 2 f u e l . On t h e
o t h e r hand, smoke w a s s a t i s f a c t o r y . A f t e r t h e run, t h e t e s t passage w a s opened
and examined f o r d e p o s i t s . Evidence of coking on the can w a l l was noticed. A
l a r g e p i e c e of coke was found on t h e l a s t s t e p of t h e can and another attached
t o t h e dome. Other carbon d e p o s i t s were a l s o found on t h e wall of t h e t e s t
passage. I n a d d i t i o n , t h e nozzle had moderate coke deposition.

The cleaned nozzle and can w e r e p u t back i n t h e t e s t passage and t h e

f o u r t h f u e l , a mildly hydrotreated r e c y c l e s o l v e n t , (8.9 W t % H ) , was t e s t e d .
The t r a n s i t i o n from No. 2 f u e l t o t h e c o a l l i q u i d w a s made and no major problems
were e n c x r r t e r & d i x i n g Lhis rr. Uowever, it was found t h a t during t h e course
of t h e run t h e combustor wall temperature c o n t i n u a l l y increased from an i n i t i a l
l e v e l of 1265F t o 1810F. Smoke l e v e l s as w e l l as N% l e v e l s were higher than
with No. 2 f u e l . On termination of t h e r u n , t h e t e s t passage was disassembled
and a l a r g e coke p i e c e w a s found l y i n g i n t h e passage. F u r t h e r examination
revealed t h a t it had been a t t a c h e d t o t h e nozzle and probably came off a t t h e
time t h e f u e l w a s turned o f f . The coke p i e c e remaining on t h e nozzle i s shown
i n F i g u r e 3.

H-Coal D i s t i l l a t e :

The f i r s t H-Coal f u e l t e s t e d w a s t h e s e v e r e l y hydrotreated product

(11.7 w t % H1. The base l i n e t e s t d a t a using No. 2 f u e l o i l i n d i c a t e d t h e
same order of emissions a s f o r t h e p r e v i o u s base l i n e t e s t s . The t r a n s i t i o n
from N o . 2 f u e l t o t h e s e v e r e l y h y d r o t r e a t e d H-Coal d i s t i l l a t e was r e l a t i v e l y
smooth and t h e t e s t was completed with no problems. After t h e run, t h e t e s t
passage was opened and t h e combustor examined. N o evidence of any coke
d e p o s i t s on e i t h e r t h e combustor can o r o n t h e nozzle were found. The f a c t t h a t
t h i s f u e l was clean-burning i s a l s o evidenced by t h e low smoke numbers measured
(Table 3 ) . The mildly hydrotreated H-Coal product (10.5 w t % H I w a s t h e second
H-Coal f u e l t e s t e d . I n i t i a l l y , t h e combustor w a s f i r e d with N o . 2 f u e l and t h e
base l i n e operating c h a r a c t e r i s t i c s obtained. The t r a n s i t i o n t o t h e c o a l l i q u i d
w a s r e l a t i v e l y smooth. I t w a s found on t r a n s i t i o n t h a t both t h e combustor wall
temperatures and Nq( emissions i n c r e a s e d s l i g h t l y and then gradually decreased
over t h e run. Otherwise, no s i g n i f i c a n t changes were observed. After t h e run,
t h e t e s t passage w a s opened up and a g a i n examined. N o evidence of any coke
buildup e i t h e r on t h e combustor can o r on t h e nozzle w a s found.

The cleaned nozzle and t h e can were p u t back i n t h e t e s t passage and

t h e t h i r d H-Coal f u e l , raw H-Coal d i s t i l l a t e (9.1 w t % H ) , was t e s t e d . The
passage was s t a r t e d on N o . 2 f u e l and b a s e l i n e d a t a were taken. The changeover
from No. 2 f u e l t o raw H - C o a l d i s t i l l a t e was made without any problems. However,
it w a s found that during t h e i n i t i a l p a r t of t h e test run t h e combustor w a l l
temperature was much higher than with N o . 2 f u e l . Therefore, i n o r d e r t o prevent
t h e l i k e l i h o o d o f any damage t o t h e combustor can t h e l a t t e r p a r t of t h e t e s t
run w a s completed a t a reduced exhaust g a s temperature. The measured Nq( l e v e l s
were higher i n comparison t o t h e No. 2 f u e l . On termination of t h e t e s t , t h e
t e s t passage was disassembled and, through t h e combustor c a n w a s found t o be
f r e e of coke d e p o s i t s , a buildup of coke around t h e nozzle was observed.

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Data Analysis:

Raw c o a l l i q u i d f u e l s d i f f e r from petroleum-derived f u e l s i n t h a t t h e y

a r e very aromatic and, as such, are hydrogen d e f i c i e n t . Hydrotreating of t h e s e
f u e l s c o n s i s t s of c a t a l y t i c a l l y adding chemical hydrogen t o t h e f u e l . Hydrogena-
t i o n also decreases both t h e heteroatom and aromatic content of t h e l i q u i d .
Hence, t h e hydrogen c o n t e n t of t h e c o a l l i q u i d s i s an important parameter and
it i s used as an index of f u e l q u a l i t y i n t h e p r e s e n t a t i o n of m o s t of t h e emission
and combustion r e s u l t s presented below.

In Figure 4 , t h e emissions of C02, CO, UHC, NOx and smoke a r e shown

p l o t t e d a g a i n s t t h e weight percent hydrogen i n t h e f u e l . The C 0 2 emissions
(Figure 4A) i n t h e exhaust do not show any appreciable t r e n d with t h e hydrogen
content o f t h e f u e l .

CO emissions, p l o t t e d i n F i g u r e 4B a s a function of f u e l hydrogen

c o n t e n t , do not show any d e f i n i t e t r e n d . However, t h e CO emissions a r e q u i t e
low and a c c e p t a b l e i n s p i t e of t h e s m a l l s i z e of t h e combustor t e s t e d and t h e
s i g n i f i c a n t quenching e f f e c t s observed under t h e s e conditions.

In Figure 4C, t h e unburned hydrocarbons a r e p l o t t e d a s ppm of

e q u i v a l e n t CH4 i n t h e d r y exhaust gas. The emissions a r e a g a i n low and
acceptable. The s l i g h t i n c r e a s e of UHC with i n c r e a s i n g hydrogen c o n t e n t f o r t h e
SRC derived f u e l s and n o t f o r t h e H-Coal derived f u e l s i s probably due t o t h e
low b o i l i n g p o i n t c o n s t i t u e n t s p r e s e n t i n t h e former. These w i l l tend t o mix
earlier and more r a p i d l y with t h e can cooling a i r and subsequently be quenched
o u t . The quenching e f f e c t i s increased due t o t h e combustor w a l l temperature
being lower w i t h t h e high hydrogen f u e l s .

I n Figure 4D, t h e N4( emissions a r e shown p l o t t e d a g a i n s t hydrogen i n

t h e f u e l . These emissions decrease with increased hydrogen c o n t e n t of t h e f u e l .
This i s as would be expected, f o r w i t h increased hydrogenation of t h e c o a l
l i q i d s , t h e bound n i t r o g e n c o n t e n t i s decreased leading t o reduced N 4 ( i n t h e
exhaust. A n average value of N 4 ( emissions f o r No. 2 f u e l f o r a l l t h e base
l i n e t e s t s i s 148 ppm a s shown by t h e d a t a p o i n t f o r t h i s f u e l . Thus, it is
apparent t h a t i n o r d e r t o meet t h e EPA proposed r u l e s regarding N 4 ( emissions
increased d e n i t r o g e n a t i o n of coal l i q u i d s i s d e s i r a b l e from t h e t u r b i n e
designers p o i n t of view. However, even f o r N o . 2 f u e l (0.008 w t % Nitrogen)
it i s not easy t o meet t h i s EPA r u l e and t u r b i n e designers a r e looking f o r and
working on a l t e r n a t i v e combustion systems. For example, if t h e premixed combustor
concept is developed then o t h e r parameters, i . e . , evaporation t i m e , i g n i t i o n
delay, e t c . w i l l become of o v e r r i d i n g importance r a t h e r than N 4 ( emissions.

The average smoke number measured i s displayed i n Figure 4E. Although

low smoke numbers were i n d i c a t e d it i s speculated t h a t they were n o t r e a l l y
t h a t low f o r a l l of t h e f u e l s t e s t e d . The reason f o r t h i s thought is t h a t
when t h e raw SRC r e c y c l e s o l v e n t (7.4 w t % H) w a s t e s t e d t h e smoke increased
immediately a f t e r t h e t r a n s f e r t o t h e coal-derived l i q u i d and then s t a r t e d t o
decrease. Large carbon p a r t i c l e s were found on t h e passage w a l l s , e t c . , and
t h e l i n e connecting t h e smoke meter t o t h e passage w a s found h e a v i l y laden
with s o o t . The l i n e , t h e r e f o r e , could be f i l t e r i n g o u t t h e smoke p a r t i c l e s . A
similar sudden i n c r e a s e i n smoke and subsequent decrease w a s a l s o observed on
switching t o t h e mildly hydrotreated SRC r e c y c l e s o l v e n t . Thus, t h e l i n e d o u t
readings l i s t e d i n Table 3 a r e s u s p e c t f o r t h e SRC r e c y c l e s o l v e n t f u e l s .

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 For the H-Coal t e s t series, t h e smoke sampling l i n e was replaced
with a s h o r t l i n e avoiding sharp bends ( t o avoid carbon o r moisture s e p a r a t i o n
and subsequent carbon d e p o s i t i o n ) from t h e passage t o t h e smoke meter and a
much h i g h e r flow r a t e was used. I t was observed during t h e s e s e r i e s of t e s t s
t h a t t h e smoke numbers observed varied from 0 t o 1 f o r both t h e H-Coal f u e l s
and N o . 2 fuel: as such t h e maximum v a l u e of 1.0 was p l o t t e d on F i g u r e 4E f o r
H-Coal f u e l s .

The r e l a t i v e N4( measured with coal-derived f u e l s divided by t h e base

l i n e NOx measured with N o . 2 f u e l i s p l o t t e d i n Figure 5 a s a f u n c t i o n of t h e
, n i t r o g e n content of t h e f u e l . I t should be noted t h a t t h e N4( values observed
f o r t h e s e v e r e l y hydrotreated SRC r e c y c l e s o l v e n t (11.0 w t % H) and H-Coal
d i s t i l l a t e s (10.5 and 11.7 w t % H ) are lower t h a n or e q u i v a l e n t t o N o . 2 f u e l
even though t h e c o a l l i q u i d s have a s l i g h t l y higher n i t r o g e n c o n t e n t . I n t h e s e
c a s e s , t h e c o n t r i b u t i o n due t o f u e l bound n i t r o g e n i s more than compensated f o r
by ths reduced theirn,al I:& proiluetion rzite. T h i s i s i n agreement w i t h t h e
lower exhaust temperatures observed f o r t h e s e f u e l s (compared t o N o . 2 f u e l ) .
The average combustor w a l l temperature w a s always higher using t h e coal-derived
f u e l s as compared t o No. 2 f u e l . This is due t o the higher thermal r a d i a t i o n
from t h e s e f u e l s . A p o s s i b l e exception, as shown below, t o t h e previous comment
on combustor w a l l temperatures i s the most s e v e r e l y hydroprocessed H-Coal f u e l
( 1 1 . 7 w t % H).
I n Figure 6A, t h e average combustor w a l l temperature f o r SRC derived
f u e l s i s p l o t t e d from f i f t e e n minutes b e f o r e switchover t o c o a l f u e l s t o t h e
time t h a t e i t h e r t h e w a l l temperature was unacceptable or t h e f u e l w a s exhausted.
Curve A is f o r t h e raw r e c y c l e s o l v e n t (7.4 w t % H) and as can be seen t h e w a l l
temperature increased by almost lOOOF a f t e r t r a n s f e r t o t h e c o a l l i q u i d . Over
t h e f i r s t p a r t o f t h e t e s t the w a l l temperature increased by almost ZOOOF t o
1680'F a s compared with an average gas temperature of 1800F. I t is speculated
t h a t a t t h i s p o i n t t h e combustor was destroyed s i n c e t h e wall temperature began
t o behave i n an erratic manner. F i n a l l y , a f t e r about n i n e t y minutes of o p e r a t i o n
t h e d e s t r u c t i o n of t h e combustor became obvious due t o t h e presence of a h o t
s p o t on t h e passage w a l l .

Curve B i s f o r t h e least s e v e r e l y hydrotreated r e c y c l e s o l v e n t

(8.9 w t % HI. On switchover from No. 2 o i l a s i m i l a r i n c r e a s e t o t h a t observed
f o r the raw r e c y c l e s o l v e n t w a s noted. This w a s p o s s i b l y due t o t h e onset of
coking. A sharp i n c r e a s e i n w a l l temperature a t t h e termination of t h e t e s t
was a l s o noted.

Curve C i n F i g u r e 6 A i s the d a t a p o i n t observed with t h e aborted test

using t h e moderately hydrotreated r e c y c l e s o l v e n t (10.3 w t % H). The sudden
i n c r e a s e i n w a l l temperature i s hard t o e x p l a i n except t o say t h a t i n t h e f u e l
t r a n s f e r process t h e spray nozzle p a t t e r n w a s d i s t u r b e d . On c l e a n i n g t h e nozzle
and mounting it back i n t h e passage a s a t i s f a c t o r y run (Curve D) was obtained.
However, t h e lined-out average combustor wall temperature f o r t h i s c o a l l i q u i d
w a s about 250'F h o t t e r than with t h e b a s e No. 2 f u e l .

Curve E was obtained using t h e s e v e r e l y hydrotreated r e c y c l e s o l v e n t

(11.0 w t % H ) . It appeared t o r u n s l i g h t l y lower than N o . 2 f u e l on t r a n s f e r
b u t a f t e r f i f t e e n minutes i n t o t h e run t h e temperature increased by almost 200'F.

126
 I n Figure 6B, average combustor w a l l temperature d a t a f o r t h e H-Coal
f u e l s a r e presented i n a manner s i m i l a r t o t h a t u t i l i z e d f o r t h e SRC f u e l s .
Curve A i s f o r t h e severely hydrotreated H-Coal d i s t i l l a t e (11.7 w t % H ) . This
Curve i n d i c a t e s t h a t no s i g n i f i c a n t change i n t h e can w a l l temperature occurred
when u t i l i z i n g t h i s f u e l as compared t o t h e No. 2 f u e l . Curve B is for t h e
mildly hydrotreated H-Coal d i s t i l l a t e (10.5 w t % H ) . I t w a s found t h a t a gradual
increase i n wall temperature occurred subsequent t o t h e t r a n s f e r from No. 2 o i l .
During t h e course of t h e experiment, t h e average w a l l temperature ran about ZOOOF
h o t t e r . Curve C is f o r t h e raw H-Coal d i s t i l l a t e (9.1 w t ?. H ) . Subsequent t o
t r a n s f e r from N o . 2 f u e l t o t h e c o a l l i q u i d t h e average can temperature r o s e
from approximately 1180'F t o 1675'F. To avoid p o s s i b l e damage t o t h e combustor
can i f operation was continued a t t h i s c o n d i t i o n , t h e f u e l flow was reduced
u n t i l the can temperature was i n the s a f e o p e r a t i n g regime.

3 . 2 ~ ) Corrosion, Erosion and Deposition

A t e s t period of one-three hours i s t o o s h o r t t o o b t a i n q u a n t i t a t i v e

information on t h e long-term c o r r o s i o n , e r o s i o n and d e p o s i t i o n e f f e c t s with
t h e s e stocks. However, l i m i t e d information was obtained by exposing two test
specimens ( p i n s ) of t u r b i n e a l l o y s ( I n 792 and %45) t o t h e combustion products
from the raw SRC r e c y c l e s o l v e n t . After running approximately two hours t h e
t e s t was terminated and t h e p i n s w e r e examined w i t h a scanning e l e c t r o n
microscope. Figures 7A and 7B show general scans ( 5 0 0 ~ )of t h e s u r f a c e s with
arrows i n d i c a t i n g p o s s i b l e d e p o s i t s . I r o n , s i l i c a , alumina, calcium, phosphorous,
copper and c h l o r i n e were a l l d e t e c t e d i n t h e s e scans. Longer runs are needed
t o quantify t h e u l t i m a t e e f f e c t s of t h e s e d e p o s i t s on t u r b i n e l i f e . However,
t h e analyses of t h e raw c o a l l i q u i d s (Table 2 ) and t h e d e p o s i t i o n s observed on
t h e t e s t p i n s during t h e two hour t e s t i n d i c a t e t h a t t r a c e metals may be a
problem i n t h e u t i l i z a t i o n of c o a l l i q u i d s . Although no t e s t p i n s were used
f o r t h e hydroprocessed l i q u i d s i n t h i s s t u d y , t h e analyses i n d i c a t e a s i g n i f i c a n t
decrease i n t h e l e v e l of t r a c e contaminants a f t e r hydroprocessing. This should
c o n t r i b u t e t o a longer t u r b i n e l i f e .

4.0 CONCLUSION

Combustion t e s t s on raw d i s t i l l a t e c o a l l i q u i d s from t h e H-Coal and

SRC processes r e s u l t e d i n s i g n i f i c a n t l y higher N 4 ( emissions and increased
combustor w a l l temperatures than with a comparable b o i l i n g range No. 2 petroleum
f u e l . I n a d d i t i o n , both of t h e raw c o a l l i q u i d f u e l s were high i n t r a c e metal
contents which could lead t o excessive c o r r o s i o n , e r o s i o n , and d e p o s i t i o n o f
t u r b i n e blades i n long-term s e r v i c e . Hydroprocessing was e f f e c t i v e i n
producing f u e l s of lower f u e l bound n i t r o g e n c o n t e n t , higher hydrogen
(i.e., lower a r o m a t i c i t y ) , and i n e l i m i n a t i n g most of t h e d e t r i m e n t a l t r a c e
metals. The r e s u l t i n g hydroprocessed c o a l l i q u i d f u e l s gave lower N4( emissions
i n t h e t u r b i n e combustor. Combustor wall temperatures decreased w i t h increasing
hydrogen content (i.e., higher hydroprocessing s e v e r i t y ) . The most s e v e r e l y
hydroprocessed H-Coal l i q u i d showed no i n c r e a s e i n N% nor i n c r e a s e i n combustor
wall temperature compared t o a base No. 2 petroleum f u e l . However, t h e most
severely hydroprocessed SRC r e c y c l e s o l v e n t , r e q u i r i n g t h e a d d i t i o n of 2800
SCF H2/Bbl, gave s l i g h t l y higher N% and higher combustor w a l l temperatures
than the base petroleum f u e l .

127
 S p e c i f i c conclusions based on t h e r e s u l t s of t h i s work a r e :

0 H-Coal d i s t i l l a t e and SRC r e c y c l e s o l v e n t can be r e a d i l y forwarded and

atomized.

0 I n g e n e r a l , t h e combustion w a l l temperature i s higher when burning c o a l

l i q u i d s than f o r a base No. 2 petroleum f u e l . Combustor w a l l temperature
decreases with i n c r e a s i n g hydrogen c o n t e n t o f hydroprocessed coal l i q u i d .
The most severely hydroprocessed H - C o a l d i s t i l l a t e showed no i n c r e a s e i n
w a l l temperature over t h e base petroleum f u e l . On t h e o t h e r extreme,
t h e r a w SRC r e c y c l e s o l v e n t (7.4 w t % hydrogen) caused burn-out of t h e
combustor can i n less than two hours.

0 N 4 ( emissions were 30% higher f o r t h e raw SRC r e c y c l e s o l v e n t (0.62 w t %

E.;& Bcund E i t r o g c a ) c a p a r e d t o %!e 5ase p e t r c l e u n f u e l !0.008 w t % f u e l
bound nitrogen) .
Increasing hydroprocessing s e v e r i t y decreased t h e f u e l
bound nitrogen c o n t e n t and produced f u e l s w i t h N 4 ( emissions equivalent t o
t h e petroleum f u e l .

0 Coke formation on t h e f u e l nozzle u s e d i n the combustor is a major concern

with r a w and mildly hydroprocessed c o a l l i q u i d s . These d e p o s i t s ranged from
massive f o r t h e r a w SRC r e c y c l e s o l v e n t t o n i l f o r t h e most severely hydro-
processed SRC and H-Coal l i q u i d s . The s e v e r i t y of d e p o s i t s i n f u l l s c a l e
combustors may be l e s s due to t h e i r h i g h e r flow r a t e s .

0 Unburned hydrocarbons emissions a r e a c c e p t a b l e , i n c r e a s i n g s l i g h t l y with

i n c r e a s i n g f u e l hydrogen. CO emissions a r e acceptable.

0 Smoke m i s s i o n s were l o w f o r H-Coal l i q u i d s . R e l i a b l e smoke numbers could

n o t be obtained for t h e SRC r e c y c l e s o l v e n t due t o p o s s i b l e soot and coke
formation i n t h e sample l i n e .

0 Flame temperatures were not s i g n i f i c a n t l y d i f f e r e n t f o r any of t h e f u e l s

tested as determined by o p t i c a l pyrometry.

ACKNOWLEDGMENT

The work w a s performed under EPRI P r o j e c t RP 361-2, j o i n t l y sponsored

by E l e c t r i c Power Research I n s t i t u t e and Mobil Research and Development
Corporation.

REFERENCES

(1) White, J. W., Sprague, R., McGrew, W., e d i t o r s "Clean F u e l s from Coal -
Symposium I1 Papers", I n s t i t u t e of G a s Technology, June 23-27, 1975.

(2) Callen, R. B., Bendoraitis, J. G., Simpson, C. A . , Voltz, S. E., Ind. Eng.
Chem., Prod. R e s . Dev., 15, 223 (1976).

(3) S c h i l l e r , J . E., Hydrocarbon Processing, (11, 147 (1977).

128
(4) Cabal, A . V . , V o l t z , S . E . , S t e i n , T . R . , Ind. Eng. Chem., Prod. Res.
Dev., g,58 ( 1 9 7 7 ) .

(5) Haebiq, J . E . , Davis, B . E . , DZUna, E . R . , Preprint Div. Fuel Chemistry,

Am. Chem. S O C . , ( l ) ,203 ( 1 9 7 5 ) .

(6) Nowack, C. J., Solash, J., D e l f o s s e , R . J . ; paper presented a t 82nd

National Meeting of American I n s t i t u t e of Chemical Engineers, Synthetic
Liquid F u e l s , Paper No. 19b, A t l a n t i c C i t y , N . J., August 29-September 1,
1976.

129
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T e s t of Mildly Hydrotreater2 ShC Recycle S o l v e n t
(8.9 w t % Hydrogen)

133
Figure 2a. Inconel X-750 Combustor Can Used for Combustion T e s t s

Figure 2b. Combustor Can (Side View) a f t e r T e s t

of Raw SRC Recycle Solvent

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Mildly HDT SRC Recycle Solvent (8.9 Wt 70 H I
0 Moderately HDT SRC Recycle Solvent (10.3 Wt % H )
A
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Content of the Coal-Derived Fuels. I'

136
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Figure 6A. Average Combustor Wall Temperature as a Function of Time

for the SRC Recycle Solvent Fuels.

A Raw H-Coal Distillate 19.1 Wt % HI

Mildly HDT H-Coal Distillate (10.5 Wt % H I
rn Severely YDT H-Coal Distillate (11.7 Wt % H I

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1000
-30 -15 0 15 30 45 60 75

R u n n i n g Time o n Coal-Derived Fuels ( M i n u t e s )

Figure 66. Average Combustor Wall Temperature as a Function of Time for

t h e H-Coal Fuels.

137
Figure 72. General Scan of I n 792 Surface (500x1 Shewing
Surface Features and a Possible Degosit ( P x r o w )

Figure 7b. General Scan cf X45 Surface (50CX) Showing

Possible Deposit (Arrow)

138
 COMBUSTION PROPERTIES OF COAL LIQUIDS FROM THE EXXON DONOR
SOLVENT PROCESS. C . W. Q u i n l a n a n d C. W. Sigmund, Exxon
R e s e a r c h and E n g i n e e r i n g C o . , P. 0. Box 4 2 5 5 , Baytown, T e x a s 77520

The Exxon Donor S o l v e n t (EDS) P r o c e s s c o n v e r t s b i t u m i n o u s , s u b - b i t u m i n o u s

and l i g n i t e coals i n t o l o w s u l f u r l i q u i d p r o d u c t s . A b r i e f d e s c r i p t i o n o f
the EDS p r o c e s s , t h e r e s u l t i n g l i q u i d p r o d u c t s a n d t h e f l e x i b i l i t y o f t h e
EDS p r o c e s s t o a l t e r p r o d u c t d i s t r i b u t i o n w i l l be reviewed.

EDS l i q u i d p r o d u c t s p r o d u c e d f r o m I l l i n o i s # 6 b i t u m i n o u s coal were b u r n e d

i n a s t a n d a r d one g a l l o n / h o u r home h e a t i n g o i l b u r n e r and a 50 HP
i n d u s t r i a l f u e l o i l b o i l e r . P h y s i c a l and chemical a n a l y s e s and combustion
e m i s s i o n d a t a f o r b o t h r a w and h y d r o t r e a t e d coal l i q u i d s w i l l be compared
to c o n v e n t i o n a l petroleum p r o d u c t s .

139
 Small S c a l e E v a l u a t i o n of t h e Combustion
and Emission C h a r a c t e r i s t i c s of SRC O i l *

L. J. Muzio and J. K. Arand

KVB, I n c . , 17332 I r v i n e Blvd., T u s t i n , CA 92680

INTRODUCTION

A p o t e n t i a l a l t e r n a t e approach t o t h e use o f petroleum-based f u e l s i n conven-

t i o n a l combustion systems i s l i q u i d f u e l s d e r i v e d from c o a l . In the present study,
t h e combustion and emission c h a r a c t e r i s t i c s o f SRC f u e l o i l (a s y n t h e t i c l i q u i d
f u e l derived f r o m c o a l ) were e v a l u a t e d in a l a b o r a t o r y b o i l e r a t a s c a l e of 3 m i l l i o n
Btu/hr. The f a c i l i t y was designed t o s i m u l a t e t h e combustion c o n d i t i o n s found i n
l a r g e u t i l i t y b o i l e r s . The s y n t h e t i c l i q u i d f u e l was produced by t h e s o l v e n t
refiiled coal p r o c e s s (1)-**a t t h e Department of Energy funded, and Gulf o p e r a t e d
Solvent Refined Coal P i l o t P l a n t .

The high n i t r o g e n c o n t e n t (approximately 1%t o 1.5% by weight) of the s o l v e n t

r e f i n e d c o a l o i l (SRCO) is p o t e n t i a l l y a cause of high n i t r o g e n o x i d e s (NOx) emis-
s i o n s from conventional combustion systems. I t i s known t h a t i n t h e combustion of
f u e l s c o n t a i n i n g chemically bound n i t r o g e n , a f r a c t i o n of t h i s n i t r o g e n combines
w i t h oxygen i n t h e a i r to form n i t r o g e n oxides which a r e emitted a s p o l l u t a n t s in
t h e f l u e gases. One p e r c e n t by weight of n i t r o g e n i n a t y p i c a l f u e l o i l has a
p o t e n t i a l of producing about 1,300 ppm ( d r y ) o f n i t r o g e n o x i d e s i n b o i l e r f l u e
g a s e s a t 3% excess oxygen i f a l l n i t r o g e n i n t h e f u e l i s converted t o n i t r o g e n
oxides. For conventional combustion c o n f i g u r a t i o n s , approximately 20% t o 50% o f
t h e f u e l n i t r o g e n i s converted to NOx w i t h t h e p e r c e n t a g e conversion d e c r e a s i n g
a s t h e n i t r o g e n c o n t e n t of t h e f u e l i n c r e a s e s . Other v a r i a b l e s such a s e x c e s s a i r
l e v e l and temperature p l a y a l e s s e r r o l e ( 2 , 3 ) . However, combustion m o d i f i c a t i o n s
can be used t o l i m i t t h e conversion of f u e l n i t r o g e n t o l e v e l s c o n s i d e r a b l y l e s s
than t h e normally encountered 20% to 50%. These methods have been s a t i s f a c t o r i l y
I
and r e p e a t e d l y demonstrated on u t i l i t y b o i l e r s . A d d i t i o n a l n i t r o g e n o x i d e s are
formed i n high-temperature b u r n e r flame zones by o x i d a t i o n of a small p o r t i o n o f
t h e n i t r o g e n i n t h e combustion a i r .

The o b j e c t i v e of t h i s s t u d y w a s t o document t h e combustion c h a r a c t e r i s t i c s

and t h e emissions of NOx, SOX, and p a r t i c u l a t e s w h i l e burning SRC f u e l o i l i n a
boiler. I n p a r t i c u l a r , t h e s e n s i t i v i t y of t h e emissions t o load and excess a i r
v a r i a t i o n s a s w e l l a s a i r p r e h e a t , s t a g e d combustion, and f l u e g a s r e c i r c u l a t i o n
were determined. These m a l l s c a l e t e s t r e s u l t s can then be used to a i d i n assess-
ing t h e performance of t h i s f u e l i n a t y p i c a l f u l l s c a l e u t i l i t y b o i l e r .

During t h e i n v e s t i g a t i o n , d i r e c t comparisons of t h e emission c h a r a c t e r i s t i c s

of t h e coal-derived f u e l were made t o t h o s e from a t y p i c a l low-sulfur #6 f u e l o i l
(0.24% n i t r o g e n by weight) and a #2 o i l w i t h a n i t r o g e n c o n t e n t of 0.024% by weight.
S e l e c t e d c h a r a c t e r i s t i c s of t h e t h r e e f u e l o i l s a r e s h o h i n Table 1 a l o n g w i t h t h e
a n a l y s i s of t h e western Kentucky c o a l from which t h e SRC o i l was d e r i v e d .
I'
*Sponsored by Gulf Mineral Resources, Co., Denver, Colorado.
**Numbers i n p a r e n t h e s e s correspond t o r e f e r e n c e s a t t h e end of t h e paper.

140
 No a t t e m p t was made t o e x p l o r e t h e p o s s i b l e changes i n s t o r a g e and handling
procedures which might be necessary t o f i r e t h e coal-derived o i l i n a b o i l e r o r i g i -
n a l l y equipped t o f i r e r e s i d u a l , d i s t i l l a t e o i l s or o t h e r f u e l s .

TABLE 1. TYPICAL FUEL CHARACTERISTICS

Western
Kentucky
Coal -
SRCO #6 O i l #2 O i l

c, wt % 72.2 86.6 86.61 86.82

H, wt % 5.0 8.38 12.25 12.69
N, w t % 1.4 1.12 0.24 0.024
s, wt % 3.6 0.26 0.28 0.11
Ash, w t % 10.5 0.008 0.016 0.003
02, wt % (by d i f f e r e n c e ) 7.3 3.63 0.6 0.35
Gross Heat of
Combustion, Btu/lb 13,150 17,040 19,150 19,190
API Gravity, 60 OF -- 8.3 2.3 32.3
V i s c o s i t y , SSU a t
140 OF -- 35.6 324 (100'F) 34

APPARATUS

The b a s i s of t h e combustion f a c i l i t y i s a modified 80-HP f i r e t u b e b o i l e r which

for t h e s e t e s t s w a s f i r e d a t a r a t e of 3 m i l l i o n Btu/hr. The combustion modeling
p r i n c i p l e s used i n d e s i g n i n g t h i s f a c i l i t y t o s i m u l a t e combustion c o n d i t i o n s i n f u l l
s c a l e u t i l i t y b o i l e r s a r e d i s c u s s e d i n Reference 4. The a p p a r a t u s , shown in F i g u r e
1, can be d i v i d e d i n t o f i v e groups of components: (1) f u e l supply, (2) a i r supply,
(3) burner, (4) b o i l e r f u r n a c e , and (5) i n s t r u m e n t a t i o n .

The o i l s were drawn from 55 g a l l o n drums and d e l i v e r e d to t h e burner with a

plunger type p o s i t i v e displacement metering pump.' During t e s t s w i t h t h e #6 o i l ,
t h e drums were heated t o raise t h e o i l t o i t s pumping t e m p e r a t u r e and e l e c t r i c a l l y
heated to its f i r i n g temperature j u s t upstream of t h e o i l gun.

A i r from an i n d i r e c t - f i r e d p r e h e a t e r passed through an i n s u l a t e d d u c t and a

v e n t u r i meter t o two v a l v e s which were t h e n used t o r e g u l a t e t h e flow s p l i t between
t h e burner a i r and second-stage a i r . For t e s t s i n v o l v i n g two-stage combustion, t h e
second-stage a i r passed down a n i n s u l a t e d d u c t , through another v e n t u r i meter, t h e n
to a p e r f o r a t e d t o r u s i n s i d e t h e combustion chamber. The secondary a i r was i n j e c t e d
from t h i s t o r u s r a d i a l l y toward t h e a x i s of t h e combustion chamber through 32 o r i -
f i c e s each 9/16" i n diameter. Downstream of t h e burner a i r v a l v e , t h e burner a i r
flow was s p l i t i n t o twu d u c t s which e n t e r t h e windbox from o p p o s i t e s i d e s . Recir-
c u l a t e d f l u e g a s , when used, was added t o t h e combustion a i r upstream o f t h e a i r
preheater.

The burner used in t h i s s t u d y w a s a s c a l e d down v e r s i o n of a t y p i c a l u t i l i t y

b o i l e r o i l burner. The b u r n e r u t i l i z e s a s i n g l e 16-vane v a r i a b l e vane-angle a i r
r e g i s t e r f o r imparting s w i r l t o t h e a i r flow. During t h e s e t e s t s , t h e vanes were
f i x e d a t 20 deg. For t h e t e s t r e s u l t s r e p o r t e d i n t h i s paper, a 30 deg. hollow cone
mechanical type atomizer w a s used to d e l i v e r t h e o i l to t h e combustion chamber.
A more complete d e s c r i p t i o n o f t h e burner can be found i n Reference 5.

The b o i l e r s h e l l was an 80-HP Scotch dry-back t y p e . A t a f i r i n g r a t e of 3

m i l l i o n Btu/hr, t h e b o i l e r ' s volumetric f i r i n g i n t e n s i t y was 38,500 Btu/hr-ft3,
which i s t y p i c a l o f o i l - f i r e d u t i l i t y b o i l e r s . The steam produced by t h i s b o i l e r
i s vented a t one atmosphere. A l s o , t h e l a b o r a t o r y b o i l e r ' s combustion chamher was
f i t t e d with a s t a i n l e s s s t e e l l i n e r to g i v e w a l l t e m p e r a t u r e s of about 800 OF, a l s o
t y p i c a l of u t i l i t y b o i l e r s .

141
 The f l u e g a s c o n c e n t r a t i o n s of NO, 02, CO, and SO2 were analyzed c o n t i n u o u s l y
using a Thermo E l e c t r o n corp. chemiluminescent n i t r i c o x i d e a n a l y z e r , a Beckman
Model 742 oxygen e l e c t r o l y t i c a n a l y z e r , a n Horiba Model PIR2000 n o n d i s p e r s i v e i n f r a -
red carbon monoxide a n a l y z e r , and a Dupont 4 1 1 photometric a n a l y z e r f o r s u l f u r d i o -
xide. Smoke l e v e l s were determined using a Bacharach smoke t e s t e r (ASTM D2156-65)
and r e p o r t e d a s Bacharach smoke s p o t numbers, t h e s c a l e of which c o n s i s t s of a s e r i e s
Of t e n s p o t s from 0 to 9. T o t a l p a r t i c u l a t e l o a d i n g s were determined using EPA
Method 5.

TEST RESULTS

The combustion and emission c h a r a c t e r i s t i c s of t h e SRC o i l were e v a l u a t e d

over a range of o p e r a t i n g parameters t y p i c a l of l a r g e u t i l i t y b o i l e r s . With t h e
e x c e p t i o n of t h e v a r i a b l e a i r p r e h e a t t e s t s , t h e test r e s u l t s r e p o r t e d were o b t a i n e d
a t a nominal c o n d i t i o n of 550 OF combustion a i r temperature and a f i r i n g r a t e o f
3 m i l l i o n Btu/hr. R e s u l t s w i l l be p r e s e n t e d f o r t h e following methods of c o n t r o l l i n g
NO:

reduced excess a i r f u e l blending

staged combustion ammonia i n j e c t i o n
f l u e gas r e c i r c u l a t i o n water i n j e c t i o n f o r smoke suppression
reduced a i r p r e h e a t f u e l a d d i t i v e s f o r smoke s u p p r e s s i o n

The methods l i s t e d i n t h e l e f t - h a n d column above were i n v e s t i g a t e d e a r l y i n t h e

testing. It was found t h a t while t h e combustion m o d i f i c a t i o n s were e f f e c t i v e i n
i'
c o n t r o l l i n g n i t r i c oxide, t h e y were l i m i t e d i n t h e i r degree of e f f e c t i v e n e s s due
to a tendency of t h e SRCO t o smoke when t h e c o n t r o l methods were f u l l y implemented.
This g r e a t e r tendency of t h e SRC o i l t o smoke t h a n t h e o t h e r f u e l s t e s t e d is thought
t o be due t o t h e high aromatic c o n t e n t of t h e c o a l - d e r i v e d l i q u i d .

The e f f e c t of excess a i r and s t a g e d combustion on t h e n i t r i c o x i d e emissions

f o r t h e SRCO a l o n g w i t h t h e #6 and # 2 o i l a r e shown i n F i g u r e 2. The open symbols
a r e s i n g l e s t a g e combustion and t h e c l o s e d symbols a r e two-stage combustion t e s t s .
During t h e staged combustion t e s t s , t h e o v e r a l l excess a i r l e v e l was maintained
a t 16% ( 3 % o v e r a l l excess 0 2 ) . F i g u r e 2 shows t h a t f o r s i n g l e - s t a g e combustion
of SRCO, t h e NO produced i s very s e n s i t i v e t o t h e e x c e s s a i r l e v e l and s i g n i f i c a n t l y
higher than t h e NO emissions from t h e #6 and #2 o i l . For two-stage combustion,
t h e NO produced reached a minimum a t a b o u t 80% AB (AB i s t h e t h e o r e t i c a l a i r a t
t h e b u r n e r and A. is t h e o v e r a l l t h e o r e t i c a l a i r ; f o r s i n g l e s t a g e combustion, AB
= A o ) , with f u r t h e r r e d u c t i o n s i n burner a i r flow r e s u l t i n g i n an i n c r e a s e i n t h e
NO emissions. This e f f e c t has been observed by o t h e r i n v e s t i g a t o r s (6-9) and i s
a t t r i b u t e d t o NO formation d u r i n g combustion i n t h e second s t a g e region.

When f l u e g a s r e c i r c u l a t i o n , a t r a t e s up t o 20%*, was u t i l i z e d i n c o n j u n c t i o n

w i t h s t a g e d combustion, no f u r t h e r r e d u c t i o n s i n t h e n i t r i c o x i d e emissions were
observed. Gas r e c i r c u l a t i o n could be expected t o have g r e a t e r e f f e c t i n b o i l e r s i n
which t h e heat r e l e a s e p e r u n i t a r e a i s v e r y high. These u n i t s would tend t o have
higher c o n t r i b u t i o n of thermal NOx, and t h e use of r e c i r c u l a t i o n would tend t o
reduce t h e thermal NO more n o t i c e a b l y .

The e f f e c t of t h e combustion a i r t e m p e r a t u r e on t h e NO e m i s s i o n s i s shown

i n F i g u r e 3 f o r t h e SRCO d u r i n g s i n g l e s t a g e combustion. This d a t a shows t h e r e
i s a s t r o n g e f f e c t of t h e combustion a i r temperature on t h e NO e m i s s i o n s (approxi-
mately 9 ppm/25 OF, a t 120% e x c e s s a i r ) and t h a t t h e s e n s i t i v i t y of t h e NO emissions
to combustion a i r temperature i n c r e a s e s w i t h an i n c r e a s e i n t h e excess a i r l e v e l .

*Mass o f r e c i r c u l a t e d f l u e gas/sum of combustion a i r and f u e l flow.

142
 Fuel b l e n d i n g was a l s o i n v e s t i g a t e d a s a means of f i r i n g t h e SRCO while l i m i t -
i n g t h e NO and p a r t i c u l a t e emissions. The NO emissions from b l e n d s o f SRCO and
#6 o i l are shown i n F i g u r e 4 f o r both s i n g l e and two s t a g e combustion.

The homogeneous g a s phase r e d u c t i o n of NO by ammonia i n j e c t i o n i n t o t h e SRCO

combustion p r o d u c t s was a l s o i n v e s t i g a t e d during t h i s study. The r e d u c t i o n s i n
NO which were achieved were i n agreement w i t h t h o s e o b t a i n e d and r e p o r t e d with o t h e r
fuels (lo).

F u l l y implementing t h e n i t r i c oxide c o n t r o l techniques w i t h t h e SRC o i l , i n

p a r t i c u l a r s t a g e d combustion, was l i m i t e d by t h e tendency of t h e o i l t o form h i g h
l e v e l s of smoke and p a r t i c u l a t e s . This e f f e c t i s i l l u s t r a t e d i n F i g u r e 5 where
t h e Bacharach smoke numbers f o r s i n g l e s t a g e and t w o s t a g e f i r i n g of t h e SRCO and
#6 o i l are compared. During t h e two s t a g e t e s t s t h e s t a c k g a s oxygen c o n c e n t r a t i o n
was maintained a t 3% (dry b a s i s ) . For s i n g l e s t a g e f i r i n g , t h e d a t a i n F i g u r e 5
show t h a t t h e SRCO t e n d s to smoke more t h a n t h e #6, n o t e t h a t even a t 40% e x c e s s
a i r (AB = 1 4 0 % ) , a No. 2 smoke s p o t i s o b t a i n e d . Although f o r e x c e s s a i r l e v e l s
above about 1 0 % to 15%, t h e performance i s a c c e p t a b l e i n t h i s u n i t . A s t r i k i n g
d i f f e r e n c e i n t h e performance i n t h e two f u e l s i s seen f o r t w o s t a g e combustion
c o n d i t i o n s . The #6 o i l produced a g r a d u a l i n c r e a s e i n t h e f l u e g a s smoke l e v e l
a s the f i r s t s t a g e was o p e r a t e d more f u e l - r i c h . With t h e SRCO, l a r g e i n c r e a s e s
i n thg s t a c k smoke l e v e l s were o b t a i n e d even a t moderate s t a g i n g c o n d i t i o n s ; a smoke
number of 9 was o b t a i n e d when t h e burner was o p e r a t e d a t A - 102%. This smoking
B T
tendency i s suspected t o be a consequence of t h e high aromatic c o n t e n t of t h e SRCO
which i s on t h e o r d e r of about 60% based on t h e carbon-to-hydrogen ratio.

This t r a d e - o f f i n NO and p a r t i c u l a t e emissions i s f u r t h e r i l l u s t r a t e d i n

F i g u r e 6. These r e s u l t s show t h a t i n t h i s p a r t i c u l a r system, s t a g e d combustion
cannot be used t o reduce t h e NO emissions below t h e 1974 EPA New Source Performance
Standards (NSPS) without exceeding t h e 1974 NSPS p a r t i c u i a t e s t a n d a r d . A similar
s i t u a t i o n w i l l l i k e l y e x i s t i n a f u l l s i z e u n i t although, q u a n t i t a t i v e l y , t h e trade-
o f f may d i f f e r from t h e l a b o r a t o r y s c a l e r e s u l t s .

A number of methods were t e s t e d t o l i m i t t h e smoke and p a r t i c u l a t e formation

while implementing staged combustion with t h e SRCO. These i n c l u d e d steam atomiza-
t i o n i n s t e a d of mechanical atomization, water i n j e c t i o n i n t o t h e combustion a i r ,
and t h e use of combustion improving f u e l a d d i t i v e s ( a l k a l i and manganese b a s e d ) .

I n t h i s u n i t t h e NO and smoke l e v e l s were s i m i l a r f o r b o t h steam a t o m i z a t i o n

and mechanical a t o m i z a t i o n . U t i l i z i n g water i n j e c t i o n i n t o t h e combustion a i r ( a t
a r a t e equal t o 7% of t h e o i l flow, volumetric basis) along w i t h s t a g e d combustion,
t h e n i t r i c oxide emissions could be reduced to about 260 ppm p r i o r to t h e o n s e t
o f smoking. .This i s a b o u t 40 ppm lower t h a n t h e l e v e l s p r e v i o u s l y o b t a i n e d w i t h
staged combustion alone.

Fuel a d d i t i v e s have been used with varying d e g r e e s of e f f e c t i v e n e s s to c o n t r o l

smoke emissions from combustion systems. A r e c e n t s t u d y by B a t t e l l e (11) has shown
c e r t a i n a d d i t i v e s t o be e f f e c t i v e i n reducing smoke w i t h s i n g l e s t a g e f i r i n g of
#6 and #2 o i l although t h e a d d i t i v e s may r e s u l t i n an i n c r e a s e o f t o t a l p a r t i c u l a t e
loadings.

During t h e p r e s e n t study, v a r i o u s a d d i t i v e s were used w i t h t h e SRCO while

f i r i n g i n a s t a g e d combustion mode. The a d d i t i v e s chosen f o r e v a l u a t i o n were:
barium naphthenate, calcium naphthenate, and CI-2 ( E t h y l Corp. p r o p r i e t a r y , manga-
nese b a s e d ) . The naphthenates produced t h e best r e s u l t s i n t h e B a t t e l l e study (ll),
with CI-2 being less e f f e c t i v e . I n t h e p r e s e n t t e s t s , t h e a d d i t i v e c o n c e n t r a t i o n s
ranged from 50 t o 350 ppm of t h e primary metal i n t h e o i l .

143
 ~ l t hl r e e a d d i t i v e s a l t e r e d t h e smoking c h a r a c t e r i s t i c s of t h e SRCO w i t h b o t h
s i n g l e s t a g e and two s t a g e combustion. However, t h e manganese-based a d d i t i v e was
m o s t e f f e c t i v e in a c h i e v i n g l o w NO emissions ( e . g . , lower AB a t t h e b u r n e r ) . I t
was also found t h a t t h e naphthenates a l t e r e d t h e NO formation a s w e l l a s t h e smoke
formation. A s a r e s u l t , t h e NO e m i s s i o n s w i t h s t a g i n g were approximately 30 t o
50 ppm higher than f o r t h e base c o n d i t i o n without t h e naphthenate a d d i t i v e .

P a r t i c u l a t e l o a d i n g s were determined while o p e r a t i n g under staged combustion

c o n d i t i o n s w i t h t h e manganese-based a d d i t i v e (CI-2). The r e s u l t s of these t e s t s
a r e presented in Table 2.

TABLE 2. PARTICULATES AND NO EMISSIONS

WITH SRCO AND CI-2 ADDITIVE

Test No. 1 2 3 4

Additive Concentration
(ppm manganese) 0 0 0 345

A0 T o t a l A i r , % Theor. 114.0 117.1 119.0 112.9

AB Burner A i r , % Theor. 114.0 103.0 83.0 11.0

Excess 02, % dry 2.7 3.2 3.5 2.5

PPm dry 35 35 135 40

NO, ppm dry ( c o r r t o 3% 0 ) 467 344 231 226

2
Smoke Number 0 3 < 9 8.5

P a r t i c u l a t e s , lb/M8tu 0.016 0.0168 0.344 0.068

A s seen in Table 2 , t h e a d d i t i v e was e f f e c t i v e i n l i m i t i n g t h e p a r t i c u l a t e

emissions d u r i n g s t a g e d combustion. Also, t h e high p a r t i c u l a t e emission d u r i n g
T e s t No. 3 ( s t a g e d combustion w i t h o u t t h e f u e l a d d i t i v e ) i s due t o carbon formation.
F u r t h e r , t h e amount of p a r t i c u l a t e c o n t r i b u t e d by t h e a d d i t i v e d u r i n g T e s t N o . 4
is a p p a r e n t l y small. Based on t h e manganese c o n t e n t i n t h e o i l , t h e manganese would
be expected to c o n t r i b u t e t o t h e p a r t i c u l a t e s on t h e o r d e r of 0.014 lb/106 Btu.
The a s h i n t h e f u e l c o n t r i b u t e s a t most 0.004 lb/MBtu to t h e f l u e g a s p a r t i c u l a t e
loading. It appears t h a t t h e snoke emissions of t h e SRCO can b e c o n t r o l l e d on
a l a r g e r u n i t w i t h a f u e l a d d i t i v e such a s CI-2 when two s t a g e or o f f - s t o i c h i o m e t r i c
f i r i n g i s used t o reduce t h e n i t r i c o x i d e emissions. I t should be p o i n t e d o u t t h a t
tests were n o t conducted t o determine t h e minimum a d d i t i v e c o n c e n t r a t i o n n e c e s s a r y
to prevent smoke formation.

I n g e n e r a l , t h e s o l v e n t r e f i n e d c o a l o i l appears t o be a u s e f u l b o i l e r f u e l
b u t i t s high n i t r o g e n c o n t e n t d i c t a t e s t h e need f o r applying NO c o n t r o l t e c h n i q u e s
to t h e system.

Since t h e SRCO is a very good s o l v e n t , c o m p a t i b i l i t y of t h e o i l w i t h t y p i c a l

s e a l s ; O-rings, e t c , used in boiler a p p l i c a t i o n s needs to be i n v e s t i g a t e d .

The major problems encountered w i t h t h e SRCO d u r i n g t h i s s t u d y were t h e h i g h

NOx emissions w i t h o u t NOx c o n t r o l methods coupled w i t h t h e smoking tendency upon
implementation of combustion m o d i f i c a t i o n s f o r NOX c o n t r o l . However, t h e s e small

144
I
I
s c a l e t e s t s show t h a t c o n t r o l techniques a r e e f f e c t i v e i n reducing t h e NOx emissions.
The carbon monoxide emissions were a l s o found t o be l o w d u r i n g t h e t e s t s and t h e
SO2 emissions were w i t h i n t h e expected range based on t h e low-sulfur c o n t e n t Of
t h e SRCO.

b I n t h e l a b o r a t o r y t e s t s , v a r i a b l e s such a s t h e l o c a t i o n of second s t a g e a i r
a d d i t i o n , a t o m i z e r d e s i g n , a i r s w i r l s e t t i n g , e t c . were n o t f u l l y i n v e s t i g a t e d .
With a more e x t e n s i v e e f f o r t , lower NOX l e v e l s than demonstrated i n t h i s study may
be p o s s i b l e on many l a r g e s c a l e b o i l e r s . I n a d d i t i o n , low NOx d e s i g n s f o r b o i l e r s
I and burners may be expected to f u r t h e r a i d i n minimizing NO e m i s s i o n s from t h e com-
b u s t i o n of t h e SRC o i l .

CONCLUSIONS

i The f o l l o w i n g s p e c i f i c c o n c l u s i o n s can be drawn from t h e r e s u l t s of t h e s e

small s c a l e tests:

The combustion performance of t h e s o l v e n t r e f i n e d c o a l o i l i s e q u i v a l e n t t o

L
1.
t h a t o f t y p i c a l u t i l i t y type f u e l o i l s . I t i s v o l a t i l e ( s i m i l a r to #2 o i l )
and does n o t r e q u i r e p r e h e a t i n g t o a c h i e v e an a c c e p t a b l e v i s c o s i t y for pumping
or atomization.

L 2. P o t e n t i a l problems w i t h f u r n a c e s l a g g i n g and m e t a l wastage o c c a s i o n a l l y

encountered w i t h c o a l combustion should be n e g l i g i b l e w i t h SRCO because of
i t s l o w s u l f u r and a s h c o n t e n t s .
6

L 3. N i t r i c oxide emissions c o u l d be maintained a t a b o u t 0.4 lb/lO Btu f o r t h e

SRCO u t i l i z i n g combustion c o n d i t i o n s t y p i c a l of many l a r g e u t i l i t y b o i l e r s .
This was accomplished with two-stage combustion and 3% e x c e s s oxygen i n t h e
flue gas. A t t h i s c o n d i t i o n , l o w s t a c k g a s c o n c e n t r a t i o n s of carbon monoxide
and p a r t i c u l a t e s were maintained.
I 4. N i t r i c oxide emissions c o u l d be reduced below 0.3 lb/106 Btu f o r t h e SRCO by
(1) blending t h e SRCO w i t h o t h e r petroleum-based f u e l o i l s having much
lower f u e l n i t r o g e n and t h e n f i r i n g w i t h t w o s t a g e combustion, or

3 (2) u s i n g a f u e l a d d i t i v e c o n t a i n i n g manganese and t h e n f i r i n g w i t h

two s t a g e combustion.
Acceptably l o w s t a c k g a s c o n c e n t r a t i o n s of carbon monoxide, smoke, and
p a r t i c u l a t e s were o b t a i n e d .

1 5. A i r preheat has a s i g n i f i c a n t e f f e c t on t h e NOx emissions while f i r i n g SRCO.

REFERENCES

c 1. schmid, D. K. and Jackson, D. M., "Recycle SRC Processing f o r Liquid and

s o l i d Fuel," p r e s e n t e d a t t h e 4 t h Annual I n t e r i m Conference on Coal G a s i f i -
c a t i o n , L i q u i f a c t i o n , and Conversion t o E l e c t r i c i t y , U n i v e r s i t y of P i t t s b u r g h ,
P i t t s b u r g h , PA, August 2-4, 1977.

h 2. Martin, G. B. and Berkau, E. E., "An I n v e s t i g a t i o n of t h e Conversion o f

v a r i o u s Fuel Nitrogen Compounds to Nitrogen Oxides i n O i l Combustlon,"
p r e s e n t e d a t t h e A I C ~ EMeeting, A t l a n t i c C i t y , NJ, August 30, 1971.

3. Dzuna, G. R., "Combustion Tests on S h a l e O i l F u e l s " , p r e s e n t e d a t C e n t r a l

S t a t e s Section/The Combustion I n s t i t u t e , A p r i l 1976.

4. Quan, V. e t a l . , "Analytic S c a l i n g of F l o w f i e l d and N i t r i c Oxide i n Combus-

b t o r s , " paper p r e s e n t e d a t EPA P u l v e r i z e d Coal Combustion Seminar, June 1973.

145

c
1'
 5. Finney, C. S. and S o t t e r , J. G., " P y r o l y t i c O i l from Tree Bark: I t s Produc-
t i o n and Combustion P r o p e r t i e s , " A I C h E Symposium S e r i e s No. 146, Vol. 71,
June 1974.

6. Brown, R. A., Mason, H. B., Pershing, D. W., and Wendt, J . O . L . , "Investigation

of F i r s t and Second Stage V a r i a b l e s on Control of NOx m i s s i o n s i n a P u l v e r i z e d
Coal Furnace," p r e s e n t e d a t t h e 83rd N a t i o n a l Meeting, AIChE, Houston, Texas,
March 1977.

7. Pershing, D. W., Lee, J., and Wendt, J.O.L., "Fate of Coal Nitrogen Under F u e l
Rich and Staged Combustion C o n d i t i o n s , " p r e s e n t e d a t 70th Annual AIChE Meeting,
New York, November 13-17, 1977.

8. Tenner, A. R., "Method and Apparatus f o r Reducing NOX from Furnaces," United
S t a t e s P a t e n t 4,021,186, May 3, 1977.

9. Arand, J. K., "Reduction of NOx Through Staged Combustion i n Combined Cycle

Supplemental Boilers, V o l . 11," EPRI Report 224, February 1975.

10. Muzio, L. J., Arand, J. K . , and T e i x e i r a , D. P., "Gas Phase Decomposition

of N i t r i c Oxide in Combustion P r o d u c t s , " S i x t e e n t h Symposium ( I n t e r n a t i o n a l )
on Combustion, p. 199, The Combustion I n s t i t u t e , 1976.

11. Giammar, R. D. e t a l . , "Experimental E v a l u a t i o n o f Fuel O i l A d d i t i v e s f o r

Reducing m i s s i o n s and I n c r e a s i n g E f f i c i e n c y of B o i l e r s , " FEA, PB 264 065,
. January 1977.

146
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150
 C o r r e l a t i o n of F u e l N i t r o g e n C o n v e r s i o n
t o NOx During t h e Combustion o f
S h a l e O i l Blends i n a U t i l i t y B o i l e r

by
x.
M. N. Mansour:and Melvin Gersteir?"

I n an o i l f i r e d u t i l i t y b o i l e r , n i t r i c o x i d e s a r e formed
by two b a s i c mechanisms; t h e t h e r m a l f i x a t i o n o f a t m o s p h e r i c
n i t r o g e n a t e l e v a t e d t e m p e r a t u r e w i t h i n t h e f l a m e z o n e , and
t h e c o n v e r s i o n o f o r g a n i c a l l y bound n i t r o g e n i n t h e f u e l t o
NQx d u r i n g t h e combustion p r o c e s s . NOx f o r m a t i o n by t h e r m a l
f i x a t i o n , ' n o r m a l l y r e f e r r e d t o a s t h e r m a l NOx i s e s s e n t i a l l y
d e p e n d e n t upon f l a m e t e m p e r a t u r e and c o n c e n t r a t i o n o f oxygen
and a t m o s p h e r i c n i t r o g e n w i t h i n t h e f l a m e zone. The c o n v e r -
s i o n o f o r g a n i c a l l y bound n i t r o g e n t o NOx, is d i r e c t l y r e l a t e d
however, t o t h e n i t r o g e n c o n t e n t of t h e f u e l .

R e s e a r c h on t h e r e d u c t i o n o f n i t r o g e n o x i d e s produced
from t h e r e a c t i o n o f a t m o s p h e r i c oxygen and n i t r o g e n h a s been
i n p r o g r e s s f o r many y e a r s . More r e c e n t l y , a t t e n t i o n h a s been
g i v e n t o t h e f o r m a t i o n o f n i t r o g e n o x i d e s from n i t r o g e n compounds
contained within t h e f u e l . T h i s s o u r c e o f n i t r o g e n o x i d e s becomes
i n c r e a s i n g l y important a s high n i t r o g e n c o n t e n t f u e l s d e r i v e d
from s h a l e and c o a l grow i n u s e .

R e c e n t l y , combustion t e s t s have been c o n d u c t e d by

S o u t h e r n C a l i f o r n i a Edison Company t o e v a l u a t e N O x e m i s s i o n
c h a r a c t e r i s t i c s of s h a l e o i l ( 0 . 7 % s u l f u r and 2 % n i t r o g e n )
when burned i n a u t i l i t y b o i l e r . The t e s t s were c o n d u c t e d
i n a 4 5 MW Combustion E n g i n e e r i n g b o i l e r equipped w i t h s i x
_______ -
* s o u t h e r n C a l i f o r n i a Edison Company, P.O. BOX 8 0 0 , Rosemead,
C a l i f o r n i a 91770
** U n i v e r s i t y of S o u t h e r n C a l i f o r n i a , School of E n g i n e e r i n g ,
Mechanical E n g i n e e r i n g Department, L o s A n g e l e s , C a l i f o r n i a
90007- 151
f a c e mounted o i l b u r n e r s e a c h r a t e d a t 85 m i l l i o n B t u / h r . To
comply with A i r Q u a l i t y Management D i s t r i c t f u e l s u l f u r c o n t e n t
r e q u i r e m e n t s s h a l e o i l was b l e n d e d w i t h l o w s u l f u r o i l s o t h a t
t h e a v e r a g e s u l f u r c o n t e n t o f t h e f u e l blend d i d n o t exceed 0.5%.
N i t r o g e n c o n t e n t o f t h e low s u l f u r f u e l ranged between 0.2-0.25%.
The NOx e m i s s i o n was e v a l u a t e d when b u r n i n g s h a l e o i l b l e n d s u s i n g
b o t h c o n v e n t i o n a l and o f f - s t o i c h i o m e t r i c modes o f combustion.
The e m i s s i o n l e v e l s were d e t e r m i n e d f o r a d e v e l o p m e n t a l low NOx b u r n e r
( L N B ) a n d a c o n v e n t i o n a l m e c h a n i c a l a t o m i z i n g Peabody t y p e b u r n e r .

As one might e x p e c t , NOx e m i s s i o n l e v e l i n c r e a s e d a s t h e

q u a n t i t y o f s h a l e d e r i v e d o i l i n t h e b l e n d was i n c r e a s e d . The
i n c r e m e n t a l i n c r e a s e i n NOx e m i s s i o n l e v e l was p r o p o r t i o n a l t o t h e
s h a l e o i l b l e n d i n g r a t i o which s u g g e s t e d t h a t t h e i n c r e a s e i n
e m i s s i o n s was m a i n l y c a u s e d by t h e h i g h n i t r o g e n c o n c e n t r a t i o n w i t h i n
the fuel. I t was s u p e r i s i n g t o n o t e , however, t h a t t h e c o n v e r s i o n

e f f i c i e n c y o f f u e l n i t r o g e n i n t o NOx decre,ased, a s shown i n f i g u r e

1, as t h e f r a c t i o n o f s h a l e o i l ( a n d f u e l bound n i t r o g e n ) i n c r e a s e d .

I t was a l s o found t h a t c h a n g i n g b u r n e r s t o i c h i o m e t r y from f u e l

l e a n t o r i c h achieved a s u b s t a n t i a l r e d u c t i o n i n f u e l n i t r o g e n

c o n v e r s i o n r a t e , p a r t i c u l a r l y i n t h e case of t h e Peabody b u r n e r .

While a number o f e x p l a n a t i o n s c a n be o f f e r e d t o s u c h r e s u l t ,
it i s f e l t t h a t t h e r e d u c t i o n i n n i t r o g e n c o n v e r s i o n e f f i c i e n c y '

i l l u s t r a t e d i n f i g u r e 1 a p p e a r s t o b e t h e r e s u l t o f two competing
processes. (a) The f o r m a t i o n o f NOx which i n c r e a s e s a s t h e n i t r o g e n

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c o n t a i n i n g s h a l e o i l c o n t e n t i n c r e a s e s , and ( b ) t h e r e d u c t i o n o f
NOx by i t s r e a c t i o n w i t h h i g h b o i l i n g h y d r o c a r b o n s i n t r o d u c e d w i t h

t h e s h a l e o i l and which is l a t e r r e l e a s e d i n t h e combustion p r o c e s s .

The proposed model s y g g e s t s t h a t NOx i s r e d u c e d a f t e r i t i s formed -
a t e c h n i q u e q u i t e d i f f e r e n t from t h e c l a s s i c a l a p p r o a c h e s o f slowing
down NOx p r o d u c t i o n by r e d u c i n g t h e r e a c t i o n t e m p e r a t u r e . The model
assumes t h a t t h e f i r s t p r o c e s s i s a f i r s t Order r e a c t i o n w i t h r e s p e c t
t o f u e l bound n i t r o g e n and hence t o t h e c o n c e n t r a t i o n o f s h a l e o i l .
The r e d u c t i o n p r o c e s s , however, i s a second o r d e r r e a c t i o n depending
upon b o t h NOx and t h e s h a l e o i l c o n c e n t r a t i o n , where t h e l a t e r
term d e t e r m i n e s t h e r e s i d u a l hydrocarbon r e l e a s e d l a t e i n t h e p r o c e s s .
On t h i s b a s i s , t h e r e l a t i v e r a t e o f NOx p o d u c t i o n w u l d be g i v e n by:

1 d(N0x) = k l (shale o i l - k 2 (NOX (shale o i l )

N O x d t
or d(N0x) [kl - k 2 (NOX 1 d t
NOx(sha1e o i l )

A p l o t of ( NOx )
( NOx) ( s h a l e o i l ) vs. (NOx) s h o u l d be l i n e a r
f o r e q u a l r e s i d e n c e times t. Such a p l o t is i l l u s t r a t e d i n
f i g u r e 2 where a good c o r r e l a t i o n r e s u l t s .

The mechanism s u g g e s t e d h e r e c a n l e a d t o a g e n e r a l t e c h n i q u e
f o r r e d u c i n g NOx f o r m a t i o n by p r o p e r f u e l b l e n d i n g . Burner d e s i g n
p a r a m e t e r s c o u l d be a l s o s e l e c t e d t o enhance t h i s d e l a y e d f u e l
v a p o r i z a t i o n w h i l e m a i n t a i n i n g good b u r n e r f l a m e s t a b i l i t y . The

153
d e l a y e d v a p o r i z a t i o n o f f u e l , a c h i e v e d t h r o u g h t h e use of h i g h
b o i l i n g t e m p e r a t u r e h y d r o c a r b o n s or t h r o u g h o p t i m i z a t i o n of b u r n e r
d e s i g n w i l l t h e n reduce NOx g e n e r a t e d d u r i n g t h e e a r l y p h a s e o f
t h e combustion p r o c e s s . The c o n c e p t is q u i t e c o n s i s t e n t w i t h t h e
g e n e r a l c o n c e p t o f s t a g e d combustion e x c e p t t h a t s t a g i n g is
accomplished by t h e n a t u r a l s e p a r a t i o n p r o c e s s e s o c c u r i n g d u r i n g
f u e l evaporation.

* S o u t h e r n C a l i f o r n i a Edison Company
P. 0. Box 8 0 0 , Rosemead, C a l i f o r n i a 91770
** U n i v e r s i t y of S o u t h e r n C a l i f o r n i a ,
School of E n g i n e e r i n g , Mechanical E n g i n e e r i n g
Department, L o s A n g e l e s , C a l i f o r n i a 90007

ld14b

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R & D ON COMBUSTION OF SULVENT REFINED COAL. W. Downs, C. L . Wagoner,
and R. C. Carr. Electric Power Research Institute, 3412 Hillview Ave.,
Palo Alto, Calif. 94305

The technical research for transportation, preparation, and combustion

of solvent refined coal that was performed by the Babcock and Wilcox Co.,
and Combustion Engineering to permit this new fuel to be utilized in a
utility boiler will be presented.

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 BURNING SOLVENT REFINED COAL. Richard D. McRanie, Southern Company S e r v i c e s , Inc.
Birmingham, Alabama 35202
Three thousand t o n s of s o l v e n t r e f i n e d c o a l ( S R C ) , manufactured a t a P i t t s b u r g & Midway
p l a n t i n Tacoma, Washington, were s u c c e s s f u l l y shipped t o and burned i n a Georgia Power
Company 22.5 MW c o a l - f i r e d u t i l i t y b o i l e r . The t e s t demonstrated t h a t SRC can b e
shipped i n s t a n d a r d , open c o a l c a r s when t r e a t e d with a commercially a v a i l a b l e c o a t i n g
s p r a y t o minimize blowing l o s s e s . Dust c r e a t e d i n t h e conveyor system w h i l e l o a d i n g
and unloading t h e SRC can be c o n t r o l l e d w i t h a w e t t i n g a g e n t spray. SRC was s t o r e d ,
p u l v e r i z e d , and burned w i t h o n l y m i n o r m o d i f i c a t i o n s t o e x i s t i n g power p l a n t
equipment. No m o d i f i c a t i o n s were n e c e s s a r y t o t h e c o a l conveying equipment o r t h e c o a l
s t o r a g e bunkers. The p u l v e r i z e r s were modified o n l y t o t h e e x t e n t t h a t c o l d primary
a i r was used and b a l l s p r i n g p r e s s u r e was reduced. The o n l y b o i l e r m o d i f i c a t i o n was
t h e i n s t a l l a t i o n of water-cooled, d u a l r e g i s t e r b u r n e r s . Emissions t e s t s were p e r -
formed w h i l e burning SRC and demonstrated t h a t SRC i s an a c c e p t a b l e f u l e f o r meeting
c u r r e n t EPA New Source Performance S t a n d a r d s f o r SO2 and NOX. The p a r t i c u l a t e
emissions were g r e a t e r t h a n a n t i c i p a t e d due largely: t o unburned carbon, a common
problem w i t h b o i l e r s of t h i s v i n t a g e ( 1 9 4 6 ) . The p a r t i c u l a t e problem can be handled
w i t h a modern p r e c i p i t a t o r . B o i l e r e f f i c i e n c y t e s t s were performed and i n d i c a t e t h a t
e f f i c i e n c y when burning SRC i s e s s e n t i a l l y t h e same a s when burning c o a l . SRC w a s
shown t o be an e x c e p t i o n a l b o i l e r f u e l from a n o p e r a t i n g s t a n d p o i n t . Soot-blowers,
which normally have t o be used 6-12 t i m e s a d a y , were n o t used a t a l l d u r i n g t h e 18-day
t e s t burn. The amount of f l y a s h and bottom a s h i s s i g n i f i c a n t l y reduced. T h i s w i l l
reduce a s h system o p e r a t i n g time and maintenance. The f a c t t h a t SRC i s b r i t t l e a n d e a s y
t o p u l v e r i z e should reduce p u l v e r i z e r maintenance.

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