penthouse spring 1987

2
SPRING 1987 DAVID N. FRENCH . INC., METALLURGISTS ONE LANCASTER ROAD VO~. V , N O. 1 NORTHBOROUGH. MASSACHUSETTS 01532 (617) 393-3635 A VIEW FROM THE PENTHOUSE: USEFUL INFORMATION FOR THE WORLD OF BOILERS REDUCING CONDITION CORROSION A l l fossil fuels contain both hydrogen and carbon in various amounts and compounds. Natural gas s nearly pure methane, CH4, 75% carbon and 25% hydrogen by weight. Fuel oils usually have less carbon and more hy- drogen. Coals ar e widely different in their composition but a l l contain carbon and other hydrocarbons. A l give off heat energy when burned and a l l behave in a similar fashion when burned with a ir i n a boiler. The hydrogen, H 2 , component burns first and completely in a i r or oxygen, 02, to water vapor, H20: :.H2 + O2 = 2H20 EQ 1 and gives off considerable heat energy. T h e carbon, C, behaves in a different fashion. There a r e two common oxides of carbon, carbon monoxide, CO, and carbon dioxide, C02. De - pending on the relative amount of air, (oxy- gen) one or both of these oxides of carbon will Form, thus: 2 c + 0 2 = 2 C 0 EQ 2 c + 02 = C02 EQ 3 Combinations of hydrogen and carbon in fuel, eg. CH4, will burn to water vapor and carbon monoxide or carbon dioxide: CH4 + 2 0 2 = C 0 2 + 2H20 EQ 4 2CH4 + 302 = 2CO + 4H20 EQ 5 What i s important in EQs 4 and 5 i s the ratio of oxygen to methane, 2/1 in EQ 4 and 3/2 in EQ 5 . A s an aside, with very oxygen, the carbon won't burn a t al l and comes out of the flame a s soot or carbon black: CH4 + 02 = C + 2H20 EQ 6 The oxygen-methane ratio here i s 1/1. E Q 6 i s the basis for the manufacture of carbon black used as a pigment in paints and auto- mobile tires. Unburned carbon gives a candle i t s light. Carbon particles a r e heated to a glow by the combustion of the hydrogen in the wax. Prove this for yourself by holding a clean piece of steel or glass well above a burning candle for a few minutes. Boiler steels develop oxidation and cor- rosion resistance by the formation of an iron oxide scale in air or oxygen, to wit: 4 F e + 3 0 2 = 2Fe2O3 EQ 7 Once this oxide forms, the steel below i s protected from further oxidation. There a r e th5ee oxides of iron, FeO, Fe203, and Fe304. The temperature and oxy- gen concentration will determine which oxide will form when steel i s oxidized in a boiler. Conversely, the manufacture of steel from iron ore, mainly Fe203 plus impurities, starts with the reduction of iron oxide by carbon or car- bon monoxide: 3C + ~ e ~ 0 ~ 2 F e + 3 C 0 EQ 8 When methane i s burned with less oxygen than shown in EQ 4 for complete combustion to carbon dioxide and water vapor, conditions ar e said to be "off stoichiometric" or "reducing". The ratio of CO/C02 can be large enough to destroy the protective oxide scale on the external surface of the furnace tubes. "Re- ducing condition corrosion" i s the name given to this attack on the boiler. Figure 1 shows a cross section of a waterwall tube wasted by this mechanism. What we have discussed i s a simple, single fuel system with pure methane a s a fuel. Most real situations involve impure fuels that con- tain measureable amounts of sulfur. Sulfur burns in a ir to sulfur dioxide and sulfur trioxide: S + O2 = SO 2 E Q 1 1 These gases do enough damage alone, but under reducing conditions the sulfur i s in the form of hydrogen sulfide, H2S. When reducing condi- tions exist along a furnace wall, some of the protective iron oxide scale will be replaced by sulfides. CO + 2H2S + Fe203 = 2FeS + 2H20 + C 02 E Q 1 3

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Page 1: Penthouse Spring 1987

8/7/2019 Penthouse Spring 1987

http://slidepdf.com/reader/full/penthouse-spring-1987 1/2

SPRING 1987

DAVID N. FRENCH . INC., METALLURGISTS

ONE LANCASTER ROAD V O ~ . V , NO . 1

NORTHBOROUGH. MASSACHUSETTS 01532

(617) 393-3 635

A VIEW FROM THE PENTHOUSE: USEFUL INFORMATION FOR THE WORLD OF BOILERS

A l l f o s s i l f u e l s c o n t a i n b o t h h y dr og e n

i n v a r i o u s a m o u n t s an d c o m po un ds .i s n e a r l y p u r e m e t h a n e , C H4, 7 5 %

o n a n d 2 5% h y d r o g e n b y w e i g h t . F u e l

i l s u s u a l l y h a v e l e s s c a r b o n a n d m o r e hy -

C o a l s are w i d e l y d i f f e r e n t i n t h e i r

a l l c o n t a i n c a r b o n a nd o t h e r

A l l g i v e o f f h e a t e n e r g y when

a l l b e h a v e i n a s imi la r f a s h i o n

en b u r n e d w i t h a i r i n a b o i l e r .

T h e h y d r o g e n , H 2 , c o m p o n e n t b u r n s f i r s t

d c o m p l e t e l y i n a i r o r o xy g e n , 0 2 , t o w a t e r

H 2 0 ::.H2 + O2 = 2H20 EQ 1

d g i v e s o f f c o n s i d e r a b l e h e a t e n e r g y . T h e

b e h a v e s i n a d i f f e r e n t f a s h i o n .

a r e t w o common o x i d e s o f c a r b o n , c a r b o nO, a n d c a r b o n d i o x i d e , C 0 2. De-

i n g on t h e r e l a t i v e a m ou nt o f a i r , ( o x y -

o r b o t h o f t h e s e o x i d e s o f c a r b o ni l l Form , t h u s :

2 c + 02 = 2C 0 EQ 2

c + 02 = C02 EQ 3

i o n s o f h y d r o g e n a n d c a r b o n i n f u e l ,

CH4, w i l l b u r n t o w a t e r v a p o r a n d c a r b o nn o x id e o r c a r b o n d i o x i d e :

CH4 + 2 0 2 = C02 + 2H20 EQ 4

2CH4 + 3 0 2 = 2CO + 4H20 EQ 5

i s i m p o r t a n t i n EQs 4 a nd 5 i s t h e r a t i o

o x yg e n t o m e th a n e , 2 / 1 i n EQ 4 a nd 3 / 2 i nQ 5 . A s a n a s i d e , w i t h v e r y l i t t l e o x y g e n ,

e c a r b o n w o n ' t b u r n a t a l l a n d c o m es o u t o f

e f l a m e a s s o o t o r c a r b o n b l a c k :

CH4 + 0 2 = C + 2H20 EQ 6

o xy ge n- me th an e r a t i o h e r e i s 1/1. EQ 6

s t h e b a s i s f o r t h e m a n u fa c t u r e o f c a r b o nu s e d as a p i g m e n t i n p a i n t s a nd a u t o -

t i r e s . U n bu rn ed c a r b o n g i v e s a c a n d l e

t s l i g h t . C a r b o n p a r t i c l e s a re h e a t e d t o a

o w by t h e c o m b u s t i o n o f t h e h yd r o g en i n t h e

x . P r o v e t h i s f o r y o u r s e l f by h o l d i n g a

s t e e l o r g l a s s w e l l a b o v e a

d l e f o r a f ew m i n u t e s .

B o i l e r s t e e l s d e v e l o p o x i d a t i o n a n d c or o s i o n r e s i s t a n c e by t h e f o r m a t i o n of a n i r

o x i d e sca l e i n a i r o r o x y g e n , t o w i t :

4 F e + 3 0 2 = 2Fe2O3 EQ

O nc e t h i s o x i d e fo r m s , t h e s t e e l b e l o w i s

p r o t e c t e d f ro m f u r t h e r o x i d a t i o n .

T h e r e a r e t h 5 e e o x i d e s o f i r o n , FeO ,

F e 2 03 , a n d F e3 04 . T h e t e m p e r a t u r e a n d o x

g e n c o n c e n t r a t i o n w i l l d e t e r m i n e w h i c h o x i d

w i l l f o r m w h e n s t e e l i s o x i d i z e d i n a b o i l eC o n v e r s e l y , t h e m a n u f a c tu r e o f s t e e l f ro m i

o r e , m a i n ly Fe 2 03 p l u s i m p u r i t i e s , s t a r t s wt h e r e d u c t i o n o f i r o n o x i d e by c a r b o n o r c a

b o n m o n o x i d e :

3C + ~ e ~ 0 ~2 F e + 3C 0 EQ

Whe n me t ha ne i s b u r n e d w i t h l e s s o x y g et h a n s ho wn i n EQ 4 f o r c o m p l e t e c o m b u s t i o n

c a r b o n d i o x i d e a n d w a t e r v a p o r , c o n d i t i o n s

s a i d t o b e "o f f s t o i c h i o m e t r i c " o r " re d u c i n

T h e r a t i o o f C O/C02 c a n b e l a r g e e n o ug h t o

d e s t r o y t h e p r o t e c t i v e o x i d e s c a l e on t h e

e x t e r n a l s u r f a c e o f t h e f u r n a c e t u b e s . "Re

d u c i n g c o n d i t i o n c o r r o s i o n " i s t h e nam e g i v

t o t h i s a t t a c k o n t h e b o i l e r . F i g u r e 1 s h o

a c r o s s s e c t i o n o f a w a t e r w a l l t u b e w a s t e d

t h i s m ec ha ni s m.

W h at we h a v e d i s c u s s e d i s a s i m p l e , s if u e l s y s t e m w i t h p u r e m e t h a n e a s a f u e l . M

r e a l s i t u a t i o n s i n v o l v e i m p u re f u e l s t h a t c

t a i n m e a su r e a b l e a m o u n ts o f s u l f u r . S u l f u rb u r n s i n a i r t o s u l f u r d i o x i d e a n d s u l f u r

t r i o x i d e :

S + O2 = SO 2 EQ

T h e s e g a s e s d o e n ou g h da ma ge a l o n e , b u t u n dr e d u c i n g c o n d i t i o n s t h e s u l f u r i s i n t h e f o

o f h y d r o g e n s u l f i d e , H 2S. When r e d u c i n g c ot i o n s e x i s t a l o n g a f u r n a c e w a l l , so m e o f tp r o t e c t i v e i r o n o x i d e sca le w i l l b e r e p l a c e

by s u l f i d e s .

CO + 2H2S + F e 2 0 3 = 2 F e S + 2H20 + C02 EQ

Page 2: Penthouse Spring 1987

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S u l f i d e s c a l e s a re n o t a s d e n s e , h a r d ,d p r o t e c t i v e a s o x i d e sca les . T h e y a r e

o u s , q u i t e f r a g i l e , are e a s i l y a b r a d e d ,

om e o f f w i t h a s h a n d s l a g r e m o v al .

r o s i o n d e p o s i t s t h a t c o n t a i n s u l f i d e s a re

e v i d e n c e t h a t " r e d u c i n g c o n d i t i o n c o r -

o n " h a s o c c u r r e d . S u l f i d e s are a l s o t h e

c om po un d t o d e t e c t , b y m e a ns o f a

T he a p p e a r a n c e o f t h i s f o r m o f c o r r o s i o n

i l l s h o w a r a t h e r s m o o t h s u r f a c e a nd may h a v e

r e w a s t a g e , see F i g u r e 1. T h e w a l l t h i c k -

s o n t h e f i r e s i d e i s 0 . 11 9 " a n d o n t h e

i s 0 . 2 6 8 " . I f t h e c o r r o s i o n d e p os -

t s are s t i l l i n t a c t t h e y w i l l c o n t a i n s u l -S t r e s s i s n o t a f a c t o r i n t h i s m orph -

T h e r e may o r may n o t b e a l i q u i d

e p r e s e n t , see V o l . I , No. 3 o f t h i s

A n o t h e r f o r m o f " r e d u c i n g c o n d i t i o n c o r -

o n " r e s u l t s i n d e e p , f i n g e r - l i k e c ir cu m -e r e n t i a l p e n e t r a t i o n s i n t o t h e t u b e w a l l ,

ee F i g u r e 2 . T h e r e i s a l s o t h e metal l o s s

s t h e w a l l t h i c k n e s s h a s b e e n r e d u c e d com-

r e d w i t h t h e c o l d s i d e o f t h e w a t e r w a l l

u b e . T he w a l l t h i c k n e s s , e x c l u d i n g t h e

r o o v e s , i s 0 . 2 2 2" w h i l e o n t h e c o l d s i d e i t

s 0 . 2 6 0 " . T h us m o s t o f t h e c o r r o s i o n w a s t a g e

s c o n f i n e d t o t h e d e e p g r o o v e s . C o r r o s i o n

e p o s i t s a l s o c o n t a i n s u l f i d e s . T h e r e i s

s o a l i q u i d p h a s e p r e s e n t , a n d a n a x i a l

s t ress i s n e c e s s a r y . T h u s , t h i s i s a f o r m o f

o r r o s i o n f a t i g u e .

T h e m ec ha n is m r e q u i r e s t h r e e c o n d i t i o n s :

a l r e a d y w e ak en ed b y t h e r e d u c i n g c o n d i t i o n s

T h e s e c r a c k s f r o m a n a x i a l s t re s s a r e t h e n

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

t u b e s u r f a c e . W i t h r e p e a t e d c y c l e s t h e

c r a c k s g ro w i n t o t h e t u b e w a l l a s s ho wn i n

F i g u r e 2 . I n v a r i a b l y t h e a s h d e p o s i t s c o nt a i n f r e e c a r b o n f r o m u n b u rn ed c o a l a n d a re

r e d u c i n g .C o r r e c t i o n o r p r e v e n t i o n o f " r e d u c i n g

c o n d i t i o n c o r r o s i o n " i s eas ie r s a i d t h a n d o

S im p ly a s s u r e p l e n t y o f a i r t o p r o d u c e c o m

c o m bu s i on t o C 02 w i t h l i t t l e ( a t r a c e ) o r n

CO a n d c a r b o n f r e e a s h d e p o s i t s . A m e a s u r em e nt o f e x c e s s o x yg e n i n t h e c h i m n ey i s n o

e n o ug h . On a v e r a g e e v e r y t h i n g may b e OK b u

l o c a l c o n d i t i o n s may b e q u i t e d i f f e r e n t .

B u r n e r s may b e o u t o f a l i g n m e n t , f u e l a n d a

may n o t b e p r o p e r l y m i x e d , s t a g e d c o m b u s t i o

t o r e d u c e N O x pr o d u ct io n t o meet e n v i r o n m e n

r e q u i r e m e n t s may l e a d t o a f u e l r i c h c o n d i

a l o n g s om e z o n e s o f t h e f u r n a c e , e t c . A l l

t h e s e f a c t o r s a n d m o r e l e a d t o l o c a l i z e d

r e d u c i n g c o n d i t i o n s , t h e r e s u l t a n t t u b e w a

a g e , a n d f i n a l l y t u b e f a i l u r e s .

F i g u r e 1. W a t e r w a l l w a s t a g e , c o r r o s i o n

e d t e m p e r a t u r e i n c r e a s e s u p t o 2 00 °F . A s t h e

a s h r e f o r m s t h e t e m p e r a t u r e r e t u r n s t o n o r m a l F i g u r e 2 . W a t e rw a l l w a s t a g e , c o r r o s i o n f a

u n t i l t h e n e x t s o o t b l o w e r c y c l e o r s l a g f a l l P h o t o c o u r t e s y o f M r . J o h n Alice, G P U , R e

o c c u r s . P A .

T h e t e m p e r a t u r e i n c r e a s e m ay c r a c k o r

c r a z e t h e o x i d e f i l m . e s p e c i a l l v w hen i t i s

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