AP42 Section 1.3

Reference Number: 1

Atmospheric Emissions From Fuel Oil Combustion: An Inventory Guide

U. S. Environmental Protection Agency, Washington, DC, November 1962.

999AP-2,

c

A T M 0 S P H E R I C ’

EMISSIONS FROM F U E L . O I L COMBUST’iON

I,i,

Waltcr S. Sri l l th ‘re chn i ca I Ass1 s tancr I3ran ch

ROiJCrt A. Tart Sanitary Eiigiiwering Center

The ENVIRONMENTAL HEALTH SERIES of repor ts was e s t a b - l ished 10 r e p o r t the r e su l t s of sc ien t i f ic and engineer ing ntudies of man ' s environment: The communi ty . whether urban , suhur- ban. o r r u r a l , where h e l i ves . works. and plays; the a i r , w a t e r , and e a r t h he usrn and r e - u s e s ; and the was tes h e produce8 and must d i spose of i n . a way that p r e s e r v e s t h e s e natura! r e a o u r c e s . This SERIES of r e p o r t s p r w i d e a ior profess iona l u s e r s a cen t r a l sou rce of in format ion on the i n t r a m u r a l r e s e a r c h ac t iv i t ies 0:

Divinions and Cen te r s within the Publ ic Health Se rv ice , and on the i r coopera t ive act ivi t ies with S ta t e and local agenc ie s , r e - s e a r c h inst i tut ions. and indvs t r ia l o rganiza t ions . The gsne ra l subject afe.a of r!ach repoy? 4s indic:ated by the two l e t t e r s that appear in the publication nwr'ber; the indica tors a r e

r

AP - Air Pollbtion AH - Arct ic Xea:tk E€ - Er-r i rocmcnta l Engineer ing FP - Food Pro i sc t ion OH - Occupational Health RH - Radiological Heal th W P - Water Supply

and Pol lut ion Control

Tr ip l ica te t ea r -ou t a b s t r a c t c a r d s are provided with r e p o r t s i n the SERIES to fac i l i t a te information retricv:.!. on the c a r d s for the u s e r ' s access ion number and additional key words.

:Space is provided

Repor t s in the SERIES will be d is t r ibu ted to r e q u e s t e r s , a s sup- pli.?s pe rmi t . t i f ied o n the t i t lc pagr o r to the Publ icat ions Office. Rober t A. Taft Saiii:ary Engineer ing Cen te r , Cincinnati 2 6 , Ohio.

Reques ts should be d i r e c t r d to the Division iden-

Public Health Service Publication No. 999-AP-2 I

P R E F A C E

The total inventory of pollution emitted to the atmosphere from all types of sources i n a coniniunity wi!l provide part of the basis for consideration of the pcssit.de need for ccntrol of air pollution. This review was prepared to provide a &wide for in- ventorying and controlling emissions arising from combustion ot fuel oil. Information was collected froni the !iteraturo. Addi- tional data were provided, upon request, by several power com- panies. This review is limited to information on oil used as a source of heat or power (exclusive of process heaters). The data were abstracted, assembled, and convert.ed to common units of expression to facilitate understanding.

. i

Although much has been done to increase the ..ccuracy of sampling niethods, stack sampling is not an exact science and is subject, in some cases, to significant crrors. Because of this limitation and t.he many design and operating variables, there is a wide range of values for emission of a n y given pollutant. l i terature review of this nature, where al l the publ.ished values art? impartially reported, it is appropriate to recommend those values reported most frequently. In most cases, th i s has been done. When the most frequently reported value was not compat- ible, however, with theoretical possibility, the value recommend- ed was selected in the light of good judgment.

In a

Emission values are subject to continual change as data are made available. It is expected that current investigations on the air pollution arising from the combustion of fuel oil will give more cUmp:ete information on t h i s subject. Investigatic,iis now k i n g conducted include: (1) zi survey of emissions, including polynuclear hydrocarbom, by the Division of A i r Pollution, Public Health Service, at the Robert A. Taft Sanitary Engineering Center in Cincinnati, Ohio; (2) a li terature search, by the Bureau of Mines at Laramie, Wyoming, for fuel oil desulfurization processes; (3) a study of means for removal of sulfur dioxide from flue gases, by the Bureau of Mines at the Bruceton Station, Pittsburgh, Pa. ; and (4) a survey of emissions from the com- bustion of fuel oil in residential and light industrial furnaces, sponsored by the American Petroleum Institute.

",

...I

iii

AC K N O W LE DG M EN'T

Grateful acknowledgment i s extended to Jean . J . Schuenemar,, Donald F. Walters, and William J . Schick, .I;.. , of. the Tectinical Assistance Branch, Division of Air Pollution, Public Health Service; and to Arthur A. Orning of the U . S. Elureau of Mines for the tin]? and effort they spent reviewing m d editing this report.

l v

. . Summary . . . . . . . . . . . . . . . . . . . . . . . Introduction . . . . . . . . . . . . . . . . . . . . . . Fuels . . . . . . . . . . . . . . . . . . . . . . . . . Aspect0 of Oil Combustion . . . . . . . . . . . . . . .

Oil Preparation . . . . . . . . . . . . . . . . . . Oil Combustion . . . . . . . . . . . . . . . . . . Smoke Formation . . . . . . . . . . . . . . . . . Acidic Smut ForniaLion . . . . . . . . . . . . . . .

Oxides of Nitrogen (N&) . . . . . . . . . . . . . . Theoretical Considerations . . . . . . . . . . . Emiseion Rates . . . . . . . . . . . . . . . .

Tangentially Fired Uni t s . . . . . . . . . . Horizontally Fired Units . . . . . . . . . .

Variables Affecting Emissions . . . . . . . . . Two-Stage Combustion . . . . . . . . . . . Load Factor . . . . Excess A i r . . . . . . . . . . . . . . . . Windbox Pressure . . . . . . . . . . . . . Flue Gas Recirculation . . . . . . . . . . . Fuel Pressure and Temperature . . . . . . . Other Variables . . . . . . . . . . . . . .

Sulfur Dioxide (SO21 . . . . . . . . . . . . . . . . Theoretical Considerations . . . . . . . . . . .

Sulfur Trioxide (SO3) . . . . . . . . . . . . . . . . Theoretical Considerations . . . . . . . . . . . Emission Rates . . . . . . . . . . . . . . . . Variables Affecting Emissions . . . . . . . . .

Emissions from Large Installations . . . . . . . . . . .

. :ing Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Emission Rates . . . . . . . . . . . . . . . .

Page

1

i

4

15 15 16 16 16

17 17 17 19 19 19 21 21 22 22 22 23 23 23 25 25 25 26

26 26 28 31

V

Other Gaseous Emissions . . . . . . . . . . . . . . Particulate Emissions

Emission Rates . . . . . . . . . . . . . . . . Part ic le Size' . . . . . . . . . . . . . . . . . Chemical Composition and Description . . . . . . Variables Affecting Emissions . . . . . . . . . .

Efficiency of Combustion . . . . . . . . . . Atomization . . . . . . . . . . . . . . . . Windbox A i r Admittance . . . . . . . . . . Burner Tilt . . . . . . . . . . . . . . . . Excess A i r . . . . . . . . . . . . . . . . Flue Gas Recirculation . . . . . . . . . . Sootblowing . . . . . . . . . . . . . . . .

Emissions from Small Installations . . . . . . . . . . . Oxides of Nitrogen (NOx) Shlfur Dioxide (SO21 . . . . . . . . . . . . . . . . Other Caseous Emissions . . . . . . . . . . . . . . Pa.rt iculate Emissions . . . . . . . . . . . . . . . .

Control of Emissions . . . . . . . . . . . . . . . . . : Oxides of Nitrogen (NOx) . . . . . . . . . . . . . . Sulfur Dioxide (SO2) . . . . . . . . . . . . . . . . Smoke and Organic Gases . . . . . . . . . . . . . . Acidic Smuts . . . . . . . . . . . . . . . . . . . . . Particulates . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . .

. . . . . . . . . . . . . . Sulfur Trioxide (SO$ . . . . . . . . . . . . . . .

Sulfur Trioxide (SO3) . . . . . . . . . . . . . .

References

Appendixes

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Appendix A: Detailed Data on Large Source Emissions . Appendix B: Detailed Data 011 Small Source Emissions . Appendix C: Methob of Reporting the Data .

Page

32 32 32 34 35 36 36

.

313 3a 39 39 39 39

40 40 4 1 42 43 44

45 45 45 45 46 46 46

49

55 .

vi

ABSTRACT

This review provides a hwide for the inventcrying and control of emissions arising f rom the combustion of fuel oil. Informa!ion was collected from the published literatur? and other sources. The report is limited to information oil oil used as a source of heat or power (exclusive of process heaters!. The data were abstracted, assenlbld, 2x2 Caiivnried to conimon un i t s of ex- pression to facilitate understanding. factors were established that can be applied to fuel oil combustion t.o determine the magnitude 0 1 air-cmtaminating emissions. Also discussctl a r e the compositions of fuel oils: the preparation and combustion of fuel oil; and the rates of emission, their variables, and their control.

From these data, emission

v i i

~ 3

Steam generation plants operate over a wide range of con- ditions, and designs of larger plants vary widely. The rates cf emissions from these units are afiected by variable operating conditions and by nature of the fuel used. An indication of how emissions ;re affected by operating variables is given in Table 2.

. r

Table 2. EFFECTS ON EMISSIONS OF INCREASING OPERATING VARIABLES a

~~

Increasing operating variables -

Percent load

Fuel temperatwe

Fuel pressure

Excess a i r

Percent C02 in stack

Dirt in firebox

Flue gas recirculation

Flame temperature

Stack temperature

Percent sulfur in oil

Percent ash ill Qil

I

D

D

I

D

I

D

I

- - -

I

I

I

I

D

I

- I

I

I

D

Particulates

-

D

D

D

I

I

1

D

D

I

I

a I means increase; D means decrease: - means no change. Information was collected from the published literature and

~ .- frdm other sources on stationary equipment for combustion of oil, mainly furnaces, boilers, and power plants (exclusive of process heaters). All data obtained have been included in t h i s - report, even thougn some zre very probably inaccurate, The pollution sources are divided into two categories, large (1,000 hp or larger) and small (smaller than 1,000 hp). Unless other- wise stated, the emissions a re reported in parts per million (ppm), by volume, or grains per standard cubic foot (griscf), corrected to 12 percent C02, or in pounds of pollutant per 1,000 pounds of oil fired. One standard cubic foot (scf) is taken as one

4 ATMOSPHERIC EMISSIONS !

at 32OF and 1 atmosphere of pressure , on a dry basis. !In oil conibustion, 12 percent C02 in the. stack gas corresponds to approximately 25 percent excess air or 5.5 percent 02 in :he stack gas. Thc newer boilers i~c~irnially operate with atmat ' 14, percent C 0 2 in the stack. When ,i boiler is referred to as

,operating at "'rlorml'al load, " i t is usua r ly operating at about 85 percent of its niaviniuni continuous capacity.

Detailed emission hints, a r e given in appendlxes A. and €3. Appendix A contains data 'for large sources, 'and Appendix B,. data for small sources. Appendix C i l lustrates the method used i n t h i s report for graphically pretienting the data.

erhture. to uniform te rms for t h i s report, when neceqsary. Thzse factm-s wcre a s fo1:ows:

:

I

! !

! !

Several factors were used to convert yalues found i n the l i t -

1

I-,~I)I oil I 42' KaI 1-11) o i l fi'rrd 1,000 h p

, Percent. C02

215 sef of stack gas at 12 'percent C02 (dry) 34, F j ~ O - I l ) stcam h r = 2, 500-11, oil h r (assuming

16.2 - 0: 775 X (where X - percent 0 2 i n the 75 ptr.crrit efficihicy) !

I stack) When data on c:oniposition of residual o i l we're not given in material reviewed, the. following fukl analysis was assumed: !

' 96 percen; car.bon,! 10 percc'iit hydr'ogen, and'the balance . . H20, 02, N2, su l fur : and ash: 18,300 Dtu Ib; 12O API* or

8.2 11, gal. !

!

FUELS ! ,

I

Crude oil used as raw material i n .petrheum refining,consists of a W ~ ! P s e r i e s of hydrocarlxxis varying from dissolved, fixed Kases to heavy, ,nearly solid compounds. ' Certain fractions of crude IwttroIruin, yhichl may'tw separated by siniple distillation, hzve the t.eccssary properties lo'r use hs a fuel oil. Some hydro- carlxxis sq i tabk for fuel oil are also produced by thermal or

! catalytic cracking. ,Except i n unusual land relatively unimportant 'circumstances, the onlv roniniercial I i q w l lurli s!ifl.icienhy

iractihns OI petrolcum oil. 2 I cheap for powci. ceiier&n and for industrial Iicating'are certain --

. .

FROM FUEL OIL COMBUSTION 5

The fuel oi ls used in small installations (smaller than 1,000 hp, o r 34,500-lb s team/hr , or 2,500-lb oili'hr) are generally

kind of file1 oil used depends upon the s ize of the unit. The mGst common fuel for domestic units is grade 2. Larger units, up to 200 hp, generally take grade 4; up to 1,000 hp, grades 4 to 6; above 1,000 hp, gradc 6 exclusively, or residual oils. Use of kerosene and diesel oil is usually confined to units smaller than 200 hp.

. kerosene, diesel fuel, and grades 1 through 6 fuel oils. The

Typical properties of t!ie light petrolsum fuels are shown in Table 3. Tables 4 and 5 stxw the NBS* Commercial Standards Specifications for fuel oils and general classifications of fuel oils, respectively. Table (j shows the maximum, minimum. and average gravity (in API) and sulfur content for fuel oils used in five regions of the United States. The regions are shown i n Figure 1. Table 7 shows the sa les of distillate fuel oils (grades 1 through 4.and kerosene) and residual fuel oils (grades 5 and 6 and some crude oil) in each s ta te for 1960. 6

The fuel oil used most in boilers producing s team at a ra te of 34,500 lb/hr or greater (1,000 hp or more) is called Bunker C. Other names for Bunker C and s imilar oils arc: residual, high-viscosity, heavy, grade 6, or Pacific Standard 400.2, 4 The range of prope,rties for t h i s fuel, as used in the 7Jnited States i n 1961, is listed in Table 8.

Grade 6 fuel oil is residual oil - a residue left after the lighter fractions, fuel-oil dist i l lates, kerosene, arid gasoline have been removed from the crude oil. by distillati in. During th is process the ash-forming constituents and sulfur-bearing com- pounds originally present in the crude oil are concentrated in the residual portion. With the development of improved refining processes, l a rger proportioris of the charged crulln Lire removed as distillate arc! motor fuel stock, leaving l e s s res-dual oi!, which may contain higher concentrations of sulfur and asti than residual oi ls of a few yea r s ago. 7

42-gallon barrel , at 60°F. The heat content ranges from 18,000 to 19,OOO Btu/lS, the average being 18,300. 2, 4 , Residua.1 fuel

1.0 perc nt water, 0. 5 percent nitrogen, and the remainder sulfur and ash. 5, The sulfur content of residual oi ls is usually about 1.6 percent. 5 In 1961, however, the sulfur concentration varied i n The United States from 0.34 to 4 percent, by weight (,Table 8).

i Bulk fuel oil is sold in the United States in multiples ol the , .-

- oil is approximately 36 percent carbon, 10 percent hydrogen,

- .-- * N U S N n ! w n d Lturrsb 0 1 Slan!lmI,:

., Table 3. TYPICAL PROPERTIES OF LIGHT PETROLEUM PRODUCTS (Reference 3)

Fuel properties ~ ~~

Gravity, API, 600F

Initial boiling point, O F

Distillation:

10% recovered at O F

50% recovered at OF

90% recovered a t OF

End point, O F

Flash point (P-M)a, O F

Viscosity, Saybolt sec, 100°E

Diesel index

Sulfur, %

Cetane No., ASTMC

Conradson carbon residue, 10% bottoms

Ker osen el

41. 9

336

370

437

510

546

130(TCC$

... ... 0.037

...

0.01

Premium diesel oil

37. 1

360

426

502

585

646

164

35. 1

55.8

0.41

I

0.07

a (P-M) - Pensky-Martens closed t e s t e r (ASTM C93-42).

(TCC) - Tag closed-cup tes ter (ASTM 956-36).

ASTM - American Society f n r Testing Materials.

.

1 -

7 FROM FUEL OIL COMBUSTION

The composition of the a s h in fuel oils varies greatly: the presence of a large number of elements has been detected. Normally, sulfur, aluminum, calcium, iron, nickel, silicon, sodium, and vanadium are found in complex orgarlic forms in the oil. Other elements have also been found in the a sh in very small quantities: barium, chlorine, chromium, copper, gold, lead, molybdenum, silver, strontium, thallium, tin, uranium, and zinc. 7, 8 A general analysis of the a sh from oils (after burning under laboratory conditions) from different a r e a s is shown in Table 9.

Figure I . tvographicol area8 01 the national SUN^^ 01 Lurner fuel ~ i l , . Bur*u:. of Yimr regionr, 1961 (Relerence 5).

I

Y

3 1 t:

c

. -

* 0

VI 4

- w L1 e N m 3 z 3

1

N

m VI 0 (0 m I

4 OP I

I I -

P 4

0 0

VI A 0 m -4 m

0

VI e N W

7 L

? w

8 - ~

e

N I W

c

i

N W al VI

W & P 0

8 0

- 4 al

4 0 W a 0 VI

1 e L

w W W cn 4 OD 0 ?

e . . Y "

4 w . ra W m 0 0 0 0

4

a m

Iablc 6. PAWERTIES OF FUEL OILS USED I N THE U. S. - 1961 ttIelcrence 5 )

- 2_

Fuel 011

urd. - 1

2

4

S

8

he1 oil

grade

I

2

4

5

8

Proprrly

"API. OOOF sulfur. rVq

'AFT, OO°F NIfUI.. wci

"Am, OO°F ul fur . 441

'AFT, OO°F .ulfur. wvg

'Am, OO°F sulfur. wt/q

--

Properly

'Am, 6OoF aulfur. wt/B

'Am, 80°F nulfur. VIP?,

MOP mulfur, a;:

'Am. Sn°F sulfur, W / l .

'API. 00°F ,ullur. W l a

U a l c r n rcglon ~~

Mln Avg Mu

39.s 41.9 40. 2 0.001 0.069 0. I7

20.6 3s. 3 43.8 O.M o.am 0.0s

F.0 21.4 31.0 @. 18 0.84 2. 12

7 . 1 17 .2 21.9 0.28 1.17 2 .50

-3.33 12.: 19.1 0. 53 1. 3,! 3. 40

Rocky Mounllln reglon

Mln Avg Mu

39.S 41.8 4S.7 0.006 0.113 0.41

ai . I 35.7 40.1 0.029 0.324 1.00

10.0 10.0 31.0 1.12 1.43 1 . s

1.9 12.7 20.8 0.28 1.84 3,s

1. 5 9 . 3 19. I 0.s10 2.02 4 .0

Soulhcrn r r g l m

Mln Avg Mu

39.8 42.7 44.7 0.01 0.008 0.11

31. 1 SS. S 47.7 0.04 0.249 0.72

IO. 9 a 27.9 0.27 a I . ea

12.s 15.2 17.0 G.28 1.77 .3 . 10

5 . 4 X!.J 14.3 0.34 1.5u , 3 .38

Wcalcrn r e a m ~

Mln Avg Mu

3). 0 40.7 40. 7 <O.Wl 0.131 0.31

21.1 34.9 43.0 0.029 0.119 0.93

10.0 18.4 31.0 1.32 a 1. s

2 . 1 12.0 17.0 0.90 1.83 3 . 5

I . 5 7 . 0 13. 4 0.80 1 . 91 4 . 0

Ccnlral reglm

19.5 42.5 40, 1

4. I ao. s 27.8 0.21 0.80 2. 12

1 . 4 io. s 20. I 0 .57 1 .52 3 . 5

4 . 3 3 10.1 23.0 0.43 1.47 4 . 0

183 163

I88 180

31 ai

M 04

I44 I44

42.3 0.084

35.3 0. 286

20. 7 0.99

IS. 0 1. sa

IO. s 1. eo

a No averages were complttd alncc only lwo namplcr w r i t reprcstntcd Inr lhl8 IcBI,

!

Table 7. SALES OF FUEL OILS IN 1900, thousand barrels (Reference 8)

I i

I -

-

Alabama Alaska Arlzona Arkansaa Calilornla

Colorado Connectlcut Delaware Dlslrlcc of Columbla Florlda

Georgla Hawall Idaho lllliiols Indlana

Iowa Kansas Kentucky Loulslana ;5Ial!W

Maryland Massachusetts Mlchigan Mlnnesota Mlsslsslppl

Mlsswrl Montana Nebraska Nevada New Hampshlre

New Jersey New Mexlco New York North Carollna North Dakota

Ohlo Oklahoinv Oregon Pennsylvanla Hhode ISlMd

Soulh Carollna South Dakota Tennessee Texas Utah

Vermont Vlrginla Washlngton West Vlrglnla Wlsconaln

Wyomlng

U. S. total --

Dl8tll l l te fuel olla (Grades 1 lo 4 and kerosene)

I

1,007 1,723 540 307

4. 977

1,137 21,043 2,478 2,544

1, e73 145

2,825 32,490 20,415

3,120

8.445 1,039 1,470 1.484 0,539

10,600 40,594 20,739 11.339

89

I, 202 1.205 2,004 589

4,240

40,7Q9 764

71,480

2,376

13,833 017

0,093 30,827 7,819

9. e0.s

3,375 2,254 928

5,340 1,112

1.814 9.312 13,220

407 19,322

1,015 - 477,402

Realdual fuel 011s (Grades 5 and 8 and crude

011 used as fuels)

4,202 895 95 474

7a.000

1,185 14,450 8,081 2,387 28,970

0,413 5.013 201

25,070 12,850

1,021 2,248

SI4 8,590 5,742

10,490 38.942 11,242 0,303

33n

2,970 I. 950 377 202

2,324

42.705 108

76,588 4,537 055

11,3R1 I , :G8 8,453 42,643 9,501

4,634 58 104

21,40S 5,552

498 17,448 9,179 1,451 4,215

1,710

540,872 -

Table 8. PROPERTIES OF GRADE 6 FUEL OIL. 1961 a

Property

Gravity, OAPI

Flash point PenskyLMartens closed tester, 6,

Viscosity, Furol, at 12ZoF, sec

Sulfur content, wt %

(Reference 5)

Min Max

- 3.33 23.0

15. 2 365

13.7 415

0.34 4.00

Ramsbottom carbon residue on 100% sample, 4.9 23. 6

rex.

1.6

8 .9

5 .3

2.5

0 .3

1 , 4

1. 5

30.8

1.0

42.1

4 .6

Ash, wt % 0.002

Water and sediment, vol %

Pour poin!, OF -10

a The extreme ranges of various properties of fuel oil

found in the !:lilted States in 1961.

Pa.

0. 8

97.5

0.7

0 .2

0 .2

_ _ _ _

0. 1

_ _ 0 .9

.-

Table 9. ANALYSIS OF ASH IN VARIOUS OILS. a* (Reference 9)

as vrt 8

Reported

MnO 1 0.3

"205 5. 1

NiO 4. 4

Na2O 9.5

K 2 0 _ - s o 3 15.0

Chloride - -

38.8

17.3

8. i

1.8

0.4

Trace

0. 5

8.9

_ _ 10. 8

.-

31.7

31.8

12.6

4.2

- - Kan.

10.0

19.1

4.8

1 .3

Trac

0.4

0.6

23.6

0. 9

36.4

6. 1

52.8

19.1

6. 1

9.1

Trac

14.0

1.4

-- - -

2.6

--

12.1

18.1

l a . 7

0. a

Trace

38.5

10.7

_ _ 7.0

_ _ -

I

i . . :

!

?

i

i

I

.

a After burning under laboratory conilltion.

1 ) I V B H data.

~~~~~ ~~~

I i

- I

ASPECTS OF OIL COMBUSTION Oil Preparation

Fuel oi ls must be vaporized before they can be burned. There are two different ways of doing this. The oil may be vaporized by heatingiwithin the burner unit or the oil may be atomized mechanically, producing fine oil droplets that may be vaporized. Burners in the first group, usually called vaporizing burners, are fired only with light oils. They are sometimes used in smal le r space hcaters with pot-type burners. They have very little application in the power field. 2Yr-y

.

1.-

If oil is to burn in the short t ime it is in the combustion chamber of a furnace, it must be in the form of small particles that expose as much sur face per unit of volume of oil as possible to the heat in the chamber. The necessary atomization of the oil may be effected i n three basic ways: by forcing oil under pressure through a nozzle, as In the '*gun-type" burner; by dse of centri- fugal force, as in the "rotary-cup" burner; and by use of s leam or air under pressilre to inject the oil into the conibustion cham- ber, as in "steam-atomization. '- Mechanical means that effect the atomization of oil i n "rotary-cup'' burners consist essentially of an oil cup, which'is driven by a motor or air turbine, and an air nozzle or ring. ,The cup spins at speeds from 3,500 to 10,000 rpm. This motion tears the oil into droplets by centri- fugal action. The s team- Jr air-atomizing burners use pressures ranging from 100 to 1,000 psi, as do the "gun-type'' burners. 10, 12

I Besides atomizing the oil to achieve rapid vaporization, the

b u n e r must a lso disperse the particles of oil in such a manner that they mix with air, stripping off l aye r s of oil from the drop- lets as they move through the air. This requires a high degree of turbulence. The great relative motion bcitween the oil and the air also produces a uniform mixture in the comhs t ion zone. 10

s t r a ine r or fi l ter to remove sludge. This filtering process pro- longs pump life, reduces burner wear, and increases the com-

I

Before the oil reaches the burner it is passed through a

bustion efficiency. 10 1 - Grades 5 and 6 oil must be heated before they can be pumped

i to the burner efficiently. For good atomization, viscosity of j I

these oils must be maintained in the range of 130 to 150 Saybolt Uliiversal. This requires heating the oil to temperatures of 170 to 2600F. 2, 10, l 1 i

I 15

t i

I

! I \

I i 1

I I 16

i i . , I

1 !Oil Combuit ion I !i I

I !

. ' I . I The* are two i inds of hydrocarbun combustion: hydroxyls- ' I tion and decomposition. Hydroxylatiod or Hue-flame 'burning

,takes place when the hydrocarbon molecules combine with oxygen 'and produce alcohols or peroxidcs that Split ,into aldehydes,

I mainly formaldehyde, and water. The aldehydes burn to form I

C02 and H20. ' Decomposition' or ye\low-flame burning takes place when the hydrocarbons 'krack" or decom'pose into lighter compounds. The lighter compounds then "crack" into carbo

I znd hydrogen, which byrn to form C42 and H2O. 2, 4, 10, 1% i

'

I . I

' ' A mixture of yellow- and blde-flame burning i s ideal: This1 type of hurning is indicated when C02 in the dry stack gas is 12 to 14 percent. This stack gas compQsition corresponds to pro-

? rigion of approximately 15 to 30 percent excess.air, depending on pruperties of the oil. 2, 4 , 10, 12 '

!

. . !

I

I Smoke Formation . . I

,. ! I

! Smoke from qil-burning units is the result of ,incomplete , combustion., An efficiently operated furnace'should not smoke, since smoke' is a sign that unburned and partially burned hydro-

' carbons are being emitted to the atmosphere. Incomplete atomi- zation of the oil caused,'l* improper fuel temperature; d i r ty , worn, or dampged burner tips: or . improgr fuel or steam pres-, suie mqy cause the furnace'to smoke. ' A poor draft or improper fuel-to-air ratiq may also cause a furnace to smoke. Other fact,ors that may causeia smoking fire ?re: poor mixing and ! insufficient turbulence of the air and oil mixture, low furnace

: temperatbres, and insufficient time for fuel to bprn combletely i n the combustion chamber, 10,' 12

.

I , . I

I I t Acidic 'Smut! Formaiion !

"Acihic smuts" a re generally. l a r re particles, approximately one-fourth inch in dianjeter, ,containi g metallic sulfates (usually iron sulfate) and carbonaceous material. Smut foSmation is a result of the condensation of water vapor andl SO3 on cold metal j

surfaces. The metal surface is defidd as cold when ifs tempera- ture i.s below the Slue-gas dew pdint, which is approximately 300OF. The.metal is corroded, f mning the Fetallic sulfap. The metallic sulfate in turnlabsorbs carbonaceous particulates from the flue as. The smut eventually ffakes off and is carried out .of the stack

k I

-. by the flue gas. 13

I . ,

I .

i I

' "

i I - i !

i r

t i I

i -

d

\ EMISSIONS INSTALLATIONS

Oxides of Nitbgen (NO,) \

\ THEORETICAL CONSIDERATION^

1 A i r contains approximately 21 lpercent oxygen (02) and 79

percent nitrogen (N2) by'volume. When oil is,oxidized with air at high temperatures, the composition of the main combustion products is essentially 12 percent Cp2, 5 p e y e n t 0 2 , and 83 percent N2, by volume. 1 Other compounds, however, are also formed in sma l l concent"rations, some of which are air pollutants. One c l a s s of pollutants is reierred tA as N%- a general t e r m that includes the oxides of nitrogen, 'such as NO, NO2, N2O4, and N2O5. During combustion, oxygen and ni rogen gas combine to fo rm NO as follows: t

If t ime permits, this reaction will continue to equilibrium, but i t does not go to completion as does the carbo? to carbon dioxide reaction. The NO will, however, react with more oxygen and form NO2 and other NOx,products. The N2 to(N0 equilibrium may shift in e i ther direction, depending upon many variables. If the concentration of one of the gases is increased, the equilibrium will shift to the opposite side. There is an abundance of nitrogen but very little oxygen present for t h i s reaction. If the amount of oxygen (excess air) is increased (without reducing the flame temperature), the NO concentration will increase also, and the reverse is true. As the NO reacts with oxygen to produce NO2, there is a reduction in the concentration of NO, which removes i t frcni the equilibrium in rraction (1) above. The NO is replaced by reaction (1) returning to equilibrium. ,

Another variable that complicates this equilibrium is the motion of the gases through zones of different temperatures, pre9sure8, and concentrations. Most 01 the NO is Iormed in the flame where very high temperatures are present. The residence t ime of the gases at this temperature is relatively short , however, and thus the NO reaction is prevented from reaching equilibrium. Figure 2 shows the theoretical concentration of. NO, assuming typical fuel analysis, typical excess air, and aaresidence time of 0. 5 second at various flame temperatures. 14

17

18 1

ATMdPHERIC EMISSONS

The main factors in NOx production are:, the flame temwer- ature (usually between 2,400 and 3, 800°F), the length of time that combustion gases are niaintalned at the flame temperature, and the amount of excess air present in the flame. Distinctly different NOx concentrations have been reported for two different basic designs of furnace, however. These designs are referred to as tangentially and horizontally fired fireboxes, The tangentially fired unit is built in such a manner that the [lame is propagated in a cylindrical form. The unit is constructed tu produce a spiral upward motion of the flame and combustion products around the walls of the cylindrical firebox. li is a rclatively new and infrequently used design.

!

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FLAME T E M P E R A T U R E . O F

Figure 2. :Theoretical lormation 01 nitric oride V I llome temperature (Rcltrcnce 14).

i

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i I1 I I

l -

i i I j

FROM FUEL OIL C~MBUSTION 19 i

,Y Units fired other than tangentially are classified as horizon- tally fired units. These units are usually fired at right angles to the walls of the firebox but they may be fired at various angles. They niay be fired on one or more sides, ok from the bottom of the firebox. The firebox may be square, rectangular, or cylindrical. Horizontal firing tends cqncentrate the hot gases in the center of the 'firebox.

EMISSION RATES I

Tangentially Fired bn i t s 1 . , I

NO, emissions'from tangentially p e d units appcar to be about one-hall as great as those normally reported for horizon- tally fired units. Only a few authors have reported on emissions from tangentially fired units. Sensenpugh reported a range of 200- to 400-ppm NOx in the stack for this type of unit. 15 Sensenbaugh and Jonakin compiled mdny li terature values for tan- gentially and horizontally fired units. \ These values ranged from 160- to 362-ppm NOx in s tacks from tangentially fired units. All the data, including the experimental values, found in the literature for tangentially fired units a\e shown in Figure 3. The numeral 2 designates two-stage combustion, which will be dis- cussed later. Figure 3 shows a n extreme NO, concentration range of 160 to 400 ppm in stack gas from tangentially fired units. The iiiost common range is 180 to 280 ppm. The most common values reported in the l i terature are between 200 and 220 ppm, which may be lower than normal: the few references available, however, permit no better representation.

14

Horizontally Fired Units

All emission data, exclusive of that relating to tangentially fired units, are grouped under the classification "Horizontally fired units. " Many general ranges for emissions from horizon- tally fired boilers have k e n reported, as follows:

Range NO, as N02, ppm References

I 330 to 915 1 . 500 to 700 15 , 100 to900 15, 16 : 3 1 0 t o 9 1 5 ' 17, 18

' 400 to 600 20 275 to 600* 19*

20 ATMOSPHERIC EMISSIONS f-

4 20

15

w l W

-I < a

: IO

2

d S

w c 0

w m LL 0

z

0 0 loo i 200 400 500

.i NO, IN STACK C I S , ppd

1 I I I 1 1 1 I I t 1 I I 1 1

I 2 3 4 5 6 7 8 1 . 9 IO I! 12 13 Ib NOs A S NO2, Ib.'l.OOO Ib OF OIL F IRE0

Figure 3. NO, emissiona'from large, tangentially fired units.

1 !

1

!

i

The most extensive N4( study was done in Los Angeles County in a joint dis t r ic t , federal, state,! and industry project. 19 In this study, the effects of many variables were studied. Results from this project showed a normal range of 275- to 600-ppm NO, at stack conditions on 63 large sources. (This included 130 tests comprising 554 stack Sam les. ) The average emission rate was

pounds of oil fired, calculated on the basis of 18,300 Btu per pound of oil fired. Other studies showed s imi la r results.

Al l the data collected for NO, emlssions for units, other

0.78 pound of NO, per 10 t? Btu, or 14.2 pounds of NOi per 1,000

- 3

than tangentially fired, are shown in Figure 4. These data show

z 460- and 480-ppm NO,. !

.:

1

an extreme range of 0 to 1,020 ppm. The normal range is 300 to i

700 ppm, and the most commonly reported values are between

554 sornplem on power plont.19

‘- 0 2 4 6 8 IO I2 14 16 18 20 22 24 26 28 30 32

NOx AS NOz. lb/1,000 Ib OF OIL FIRED

VARIABLES AFFECTING EMISSIONS ,*”

Firing Rate I

One author 22 showed that the NO, emissions varied with the fir ing rate. ws equation may tw written as:

where X is the firing rate in pounds of oil per hour, C is the percent of carbon in the oil, and NO, is nitrogen oxides 88 N02. Since oil usually contains about 86 percent carbon, the equation could read:

1. 18 I b NO,/hr = [ - 2;8] (3)

Data for horizontally fired units conformed to this equ-tion rather closely.

22 f

I !

1

E

: i i z

Two-Stage Combustion j

Two-stage combustion reduces NOx combustion, as in other types of combus 130 percent of the theoretical air is but only 90 to 95 percent is the fuel. The remainder of introduced through box. reduced the tally fired

In two-stage

In two-stage combustion, the limited oxygdn supply near the burn- er probably inhibits the formation of NOx.

Lo3d Factor

Large boilers often have a power demahd fluctuation. They normally run at about 8 5 percent of their designed load, which provides a reserve So+ peak power demand. ( Several studies indicated an average NOx decrease from 0.6 to 0.9 percent per 1 percent load decrease b l o w a 70 percent load; and an average NOx increase from 0.6 to 1.1 percent per l! percent load' increase above a 70 percent load. 19, 25 The increase in NOx concentra- tion is caused by the increased flame temperature at the higher firing rate.

\ : ! 3 :

,i j r

Excess A i r i

In electric power plants, the amount of excess air used in the combustion of oil may vary from 8 to 30 percent, in a given plant. The amount of excess a i r used in large modern plants is about 16 to 20 percent, equivalent to approximately 14 percentlC02 concentration !n the stack gas. This concentration varies with fuel composition and burner design. One author reported on a tangentially fired unit that emitted 13 percent C02 and 258-ppm NO, (corrected to 12 percent C02). A l inear relationship was established indkating that, as the C@ concentration W a s in- creased by 1.6 percent (decrease in excess air), the NO, con- centration was reduced by 29 Wrcent. This is equivalent to ai

The same author reported on a horizontally fired unit that

18 percent decrease in NOx per 1 percent increase in C02. 14

emitted 13.6-percent C02 and 700-ppm NOx (corrected to 12 percent CO2). An approximate l inear relationship was established

I

! P I FROM FUEL OIL COMBUSTION i

23

b /

indicating that, a s the C02 concentratih was increased by 0 .9 Percent, the NOx concentration was reduccd'by 32 percent. Thls is equivalent to a 35 percent decrease in N& per 1 percent in-

I 1 ' _

crease i n CO2. 14 i

E , i . i 1

The joint projec4 conducted i n Loa Andeles ,County investi- gated the relationship of excess a i r to NOifformation. This relationshi is shown: on the harsis of C021/concentration, in Figure 5. f9 The Sax concentration incqases with a decrease in C02 concentration* because N& formaqion is promoted by i surplus oxygen. +

i i Windbox Pressure 6

i

I ! i

The plenum chamber, through which the supply of combustion air is provided to all ,burners, is the "windbox. " A i r pressure in the windbox is controlled by opening or ?losing the a i r registers. The a i r registers regblate the flow of a i r in the windbox in much the same manner as an air damper regulates the flow of/hot air in domestic heating units. In one study it was found that the NOx concentratim in tile stack gas was decreased considerably when the windbox pressure'twas increased by 1 inch of water. 19

Flue Gas Recirculatich

Some plants permit a portion OS the flue gas to be recycled through the firebox. ;One author found an average NOx reduction of 1.3 percent per 1 percent flue gas recycled in a tangentially fired unit. 14 In another study it was found that N& was reduced approximately 2.5 percent per 1 rcent increase in the opening of the recirculating fan damper. ff Since recirculating the flue gas reduced the oxygen concentration and flame temerature in the firebox, the amount of NOx Iorrned was also reduced.

t i ,> 1

B

I I 1 Fuel Pressure and Temperature I

/ ! I

One study revealed that, when the fuel ,feed rate was kept constant and the pressure of the fuel oil was increased, either by decreasing the size of the burner. orifices or by decreasing the number of burners for the same fuel rate, N 4 , concentration was decreased. The study showed an average decrease of 0.17 per- cent NOx per one-psi increase in fuel pressure, when smaller orifice tips were used, 19 but these tips do not last or stay clean as well as larger tips. 14 The study also showed that, when the number of burners in 'a firebox was increased from the normal 12 to 14, resulting in a 50-psi decrease in fuel pressure, NOx

24

800

a 7 0 0

0” 0

U L? !2

w I- U w K K 0 v n j so0

z - 0-

400

300

I I ’

85% Load. 16 Burn-rs

701. Load, 16 Burners

55% Load, 12 Burners

55% Load, 16 0um.r.

200 ,‘I2 13 14 15

I P CO2 IN STACK GAS, X

E

I:

Figure 5. Elfect of excess air on emissions of nitrogen oxides from a large unit (Reference 19).

25 s .

FROM FUEL OIL COMBUSTION <

19 was decreased Iron1 12 to 10, resulting in\a 100-psi increase in fuel pressure, NO, concentration decreased 4 percent.

One author found 'that oil tcrnperature p d a small effect on NO, concentration. His data showed an avyrage of 0.3 percent decrease in NO, per OF increase i n oil tern'perature In the range

concentration increased 15 percent. number of burners

I ) !!

.I

I 4 of 207 to 277OF. 14 ', , .

Other Variables I i ' I ' I

NO, production iqcreases if deposits on boiler tubes are not removed frequently by lancing or by other 'means. 14, 19 Clean- ing the t u b e s increasdr, heat t ransfer rates,i which might be followed by a reduction in the flame tempeiature and in NO, emissions for a givenjload.

1 i around the burner to the flame to promote efficient combustion. One author found that, by removing tile appToach-cone vanes from the burners and operating with the air registers wide open, NOx concentration w a s reduced 16 percent.' 24 This niay have been a peculiarity of a specific firebox design.

i Approach-cone vanes difect the air Iloy either through or

Sulfur Dioxide (SOz) I !

I I THEORETICAL CONSIDERATIONS

Oil contains many complex organic forms of sulfur, in con- centrations ranging faom a trace to more tdan 5 percent by weight. During the combustion of oil, the sulfur in the oil is ox- idized to sulfur dioxide (SQ) in much the same way as carbon is oxidized to carbon dioxide (C@). In other words, the oxidation is virtually complete. The SQ may react with more oxygen, how- ever, forming sulfur trioxide (S@) or sulfate radicals in a com- plex equilibrium similar to those of the NOx compounds. This means that not a l l the sulfur in the oil is emitted as SQ. The variables controlling the S@ emissions are those controlling the format1011 of S@ and metellic sulfates. 7, 26, 27

The amount of sulfur emitted as SO2 may be inferred lrom a material balance. Fly a sh contains around 10 percent sulfur, and oil contains around 0.1 percent ash. Thus, about 1 percent of the sulfur in the oil ends up in the fly ash. Sulfur emitted as SO3 is probably about 1 percent of the sulfur In the oil. Thus, 98 percent of the sulfur in the oil is probably emitted as SO2,

- I

I'

ATM/OSPHERIC EMISSIONS I

I \

\ EMISSION RATES ,

Figure 6. The extreme range is from 12 to more than 100 percent of the sulfur in the fuel emitted as S02. The normal range is 85 to 100 percent. The h o s t common value is 100 percent. The 100 percent value is questionable as a r e those values above 100 percent. One of the v'alues plotted at 100 percent or greater represents a calculated value of approximately 120 percent; this impossibility indicates inaccurate sampling'and analyzing prac- tices. It would appearffrom the data and t h e material balance that the SO2 emitted in the flue gas represents about 98 percent of the su l fu r in the oil:

The data collecte'd on sulfur emissions are presented in

Sulfur Trioxide (SO31

1 THEORETICAL CONS~DERATIONS F

Theoretical e q u i l h u m considerations ,for t h e reaction

inaicate a tendency t o i a r d SO3 formation as' the temperature of the combustion gas s t i eam becomes increasingly lower than the flanie temperature. Catalytic surfaces consisting of iron oxides from the boiler tubes and the vanadium- and, iron-bearing ash deposits a r e present to accelerate the reaction. This reaction is similar to that usediin producing SO3 iri a 'contact sulfuric acid plant; i n a cornbustion:chamber, however, there is less catalyst and contact time. 7, 26

and as heat is t ransferred to the boiler, preheater, and economizer, the temperature of the gases Areduced. If the So3 conies i n contact with surfaces below the dew point of the gas, the SO3 combines with water vapor to produce sulfuric acid. The sulfuric acid reacts in turn to produce metallic sulfates on the surface that it contdcts, which reduces ttie SO3 concentration. The SO3 niarkcdly increases the dew point of the flue gases to alwut 300°F. This high dcw point of the exhaust gases may result in corrosion of the boiler and stack, and in formation of acidic smuts , as discussed in 'a previous section. 26,128,299 30931, 32,33

! \

As the products of iconibustion travel toward the stack exit,

!

.I i

~~ ~

I

/' \ ' I

s, FROM FUEL OIL COMBUSTION I 1

\ , \

27

.

n W I- K 0 a a w

0 IO 20 !30 40 50 &?O 80 :90 100 b (a CHATER 1

SULFUR I t 4 THE OIL EMITTED AS 502, 'i I

Figure 6. Pe$enl 01 sulfur In Ihe O i l emitted a s $02 lrom large units I

28 I ATMOSPHERIC $MISSONS 1 t

' !

EMISSION RATES

Lines are

I'

i 4 I

Range I Reference I

90% S'converted to SO2 and '

! 100% S converted do SO2 and

20

i

1 t o 5% S O ~ converted to S O ~

' 1 t0;2% s o 2 ionverted to s43 !

I ' I

1 to 5% S'converted to SO3, :

! , ' I

' 1 . to a. 5 lb SO3/1,000 lb oil,, for

I . 1

I I Figure 8 the sulfur in

I f rom 0.25 to tween 1. O'and 1.'25 percent of the sulfur in the oil emitted as SO3. Figure b: shows that stack' concentration var ies from O'to 76 ppm. The normal range var ies between 6 and 24'ppm, The most com-

'

i mdn are between 14- and 22-ppm SOa. !

. ' When the gases leave the stack, they are, cooled below the

dew point, causing much of the SO3 to combine with water vapor ' in'the surrounding gas s t d a m , sometimes producing a visible !

plume. One author reported a viaible plume at 3-ppm apd a ' conspicuous plume at IS-ppm 903. lf& The particle size of sulfuric acid mist varies from 0.5 to 6 microns, depending Lpon the amount of water vappr present. 34

. i

! i

I

I

\ I

FROM FUEL OIL COMBUSTION

8 0

10

6 0

50 E a ui 4 0 Y U u 4 0 5

54

z - " 10

2 0

I' I

I i I

I I I I I ' I

I I I

SULFUR IK THE OIL, 'i B t W T

I

Figure 7. Relo~ionshipbetwen SO3 emission aid sulfur in oi l la I.rpr units. i:

I. ;

1

30 OSPHERIC EMlSSIONS I

11

w

* w 11

A < >

a

t o c. K 0 a a- ea

d

W

IL 0

x 10

a

0

I . s . 1 0 ,I 1, 0 1 ' . !

( SULFUR IN THE OIL E d I T T E O AS SO3;;

Figure 8. Percent of ru l lur in the oil emitted os SO, Iran IorpeLnitr.

I., I,

I

2 0

v)

13 -I

> C W

0 W OL

IO

a

: s d z

0

m 0' c] Individual v a l u e s repon&

I

' Typical vo lves reported . Note: 5 0 3 valuer not cofts1at.d

w i t h .ullur content ,ol oi l .

40 50 60 70 eo 0 10 20

SO3 IN S T A C K CAS. ppm .

5%. Ib: 1,000 Ib CF OIL FIRED

Figure 9. Concentration of SO3 in stack g o w r 01 large units.

B FROM FUEL OIL COMRUSTION \ 31

- One a i t h o r found that variation of a ame temperature affected

VARIABLES AFFECTING EMISSIONS

SO3 concentrations in the stack gas. a pilot plant study and not with actual

experiment was done in

1 - plants. A plot of SO3 content (ppm) the flame temperature ! is shown in Figure 10. 35 This indicated that the per-

i

furnaces or power I

cent sulfur in the fuel converted to So3 deheased with an increase in the percent CO2 in the stack gas. Thedf data do not agree, ,

/ however, with other data collected for th i s report. i

i' I

I I

1 I 70

6C

Y U < I- m z '4C - rn

2 Y 0

U I- z W U z 2 0 0 U

i - i

' / I i I

0

FLAME TTMPERATURE. "F .

Fipue 10. Effect 01 flame lempcroture on 503 emission (Reference 39 .

\ I

32 + I \ d Y

\

\

I

I i

Other factors that may have a small effect on SO3 emission are boiler load fuel rcssure, excess air, and percent.ash in the fuel. 7 , 2 6 , 2 Q , h 31&, 33,35,37,37 These variables seem to have little significance in the for,mation of .W3, however.

I Other Gaseous Emissions

Large power plants are usually efficient operations, and therefore, should not emit unburned or partially burned hydro- carbons in significant quantities. Several references, however, have given values for emission of various organic compounds or groups of organic compounds. Since investigators have not re- ported the organic compounds in a consistent manner, e. g., hydrocarbons measured as hexane, no comparison of the results is possible. Table 104ists organic compounds found in emissions from large units, a8 reported by several investigators. Table 10 also shows some values for inorganic gases.

I

Particulate Emissions i

EMISSIONRATES ~ i

The particulate loading of stack gases depends primarily upon the efficiency of combustion and the rate of build-up of boiler deposits. The data do not follow any trend when the per- cent ash in the oil is plotted against stack loadings. When oil containing one pound of ash is introduced into a large bbiler, as little as one-half pound or as much as 10 pounds of particulates could be emitted. This emission may result from a build-up or detachment of boiler deposits, carbon in the fly ash, &SO4 reacting with the boiler or stack, or from a combination of these factors. I

Particulate loading ranges cited In the literature are 0.02 to 0.04 grains per cubic foot 14 and 1 to 5 pounds per 1,000 pounds of oil fired (0.0325 to 0.1625 gr/sct, calculated). The latter value is for low-pressure atomization. The loading was 'reduced by two-thirds when high-pressure atomizing was used. 20 All the literature value6 for particulate matter are represented in Figure 11. This figure shows an extreme range between 0.005 and 0.205 gr/scf. The normal ran(:e is between 0.025 and 0.060 gr/scf. The most c )mmonly reported values are between 0.030 and 0.035 gr/scf.

-

J ' I 1 1 i

. . .<

.

34 \ ATMOSPHERIC EMISSIONS I :

, on p0w.r plorlrr

il ; I

PARTICULATE CONCENTRATION, 9, s c l I---- , -1- 8

I I 61 3 4 I) 2 0

i .PARTICULATE, I'a 1.000 Ib OF OIL F I R E 0 I

i PARTICLE SIZE i

I 1 The s ize distribution depends upon the degree of, atomization

of the oil, the efficiency of mixing, the number of collisions be- tween f ly ash particles, the flame temperature, the design of the firebox, and the flue gas path through the boiler to the stack. 7 The lighter particles usually contain l e s s carbon and are smal le r in size. The literature shows an assortment of sizes I (Table 11).

I The larger particles a r e skeletons of burned-out fuel parti-

cles called cenospheres, which are hollow,: black, coke-like spherical particles. 46 The smal le r particles formed by the condensation of vapors' a r e of r ep i l a r shape and usually hate a niaxinium dimension of*aLK)ut 0.01 micron. 7 Good atomization usual ly reduces the n u m b e r of cenospheres.

i

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FROM FUEL OIL CdM!3USTION 35

0.4. (estimate) or BO$ less than 0.5.

I

I I

a carbm particles only. 1 CHEMICAL COMPOSITION AND DESCRIPTION

i

No general statebient can be made on the highly variable composition of fly ash from oil coinbustion. The probable c0ns:itue::ts of fly ash that may be found in! f lue hQS are as follows:

A1203, A12(S04)3, CaO, CaSO4, FezOg, Fe2(S04)3, McrO, MgS04, NiO, NiSCq,i,Si02, Na2S04, NaHS04, Na2S207, V2O3! v204, V205, ZnO, ZnS04, Na20sV205, 2Na20.V205, 3Na20. V205, 2Ni0. V2O5, 3 N i 0 - ViO5. Fe2O3' V2O5. Fe203.ZViO5, Na20. V2O4- 5v2,05 ahd. 5Na20. V2O4. I 1 V2O5. 48 The average compositions of ash kiuiid i n various oils lwfore firing are giveti in Tahle 9.'

The coniposition of the fly ash changes as the'gas leaves the

1

!

i 1

L . I

1 firelmox and t ravels through the boiler atid the internal parts of

and solidifies, some reacts with the Imiler and stack, and sonie is deposited within the unit. The fly ash conipisithin varies f roni plant to plant and from oil to oil. Table 12 show?. analyses o f fly ash froni a plant using residual oil. 46 Vanadium is u s u a l l y prrsctit i n the Ilv ash.and has Ixvn considered for use an an indi- cator OI thc 1ireseiice of f ly ash froni oil-fired uriils.

- the power plant. A s the gas cools, some of the fly a sh condenses

Rallgrs

36

“ I i reported for percent combpstibles in the fly a s h are 50 to 75 Percent; 20 30 to 40 pkrcent (but up to 94 percent); 46 and, in 31 tests in one plant, a Gariatlon from 61.1 to’95.2 percent. 23 The amount of combustiblds in fly aeh decreases with increased atomization pressure ’and flame temperature. 49 A decrease in the percent combustibles in fly a sh should accompany a decrease in stack loading; not enough data are available, however, to make a definite statement.

Recently, much attention has been focused on the emission of potentially carcinogenic substances from !various operations. These substances are !usually polynuclear hydrocarbons, of which 3,4-benzpyrene is the:most studied example. Only one author has reported information on emission of these materials from oil- burning units. Gurinoy, a Russian inves t i e to r , found 3,4-benz- pyrene i n concentrations of 0.01 percent of the soot emitted from the combustion of petroleum introduced in a‘ furnace through a spray burner, 70 Some as yet unpublished sampling data indicate that about 0.004 percent of the soot is 3,4-benzpyrene’ when oil is burned by means of{an air-atomized oil burner. 45 Tdese limited data indicate that about 0.04 to 0.10 pounds of 3,4-benz- pyrene is emitted per .million pounds of oil burned. I( ,

I

Other properties o f the fly a s h given in the l i terature are an initial pH of 3; 2o 17 !to 25 percent SO3 (which includes H2S04 droplets): 46 and a specific gravity of 2.5. 20 The amount of soluble solids reported in one reference ranged from 30 to 60 percent. 19 This range of soluble solids and other values from references (50) and (42) are represented i n Figure 12. The values range between 1.3 and 68 percent soluble solids.

JAFUABLES AFFECTING EMISSIONS

Efficiency of Combustion

Poor mixing, turbulence of the air and oil, low flame tem- peratures, and short residence t ime in the combustion zone calise l a rge r particles higher combustible content, and higher particu-

I late loadings. 12

.. J .i . .

i

! !

‘j

3

.. ,:

!

Table 12. ELEMEN 1 Elements

. Carbon

Ether, soluble

Hydrogen

Ash (800°C)

Sullates as SQ (lncl HzSO4)

Chlorldea an Cl

Nltrogen as N Q

Iron as Fez03

Chromlum as Cr%

Nlckel as NIO

Vanadium as V 2 4

Cobalt as CozO3

Slllcon as SI%

Alumlnum a s A k Z Q

Barlum as BaO

Mapneslum a s MgO

Lead a s PbO

Caldum as CaO

Sodlum a s NazO

Copper as CuO.

Tllanlum as TIOZ

Molybdenum as M a

Boron as 4% Manganese as MnOi

Zlnc as Zn@

-

. - Phosphorus a s PzO5

Strontlurn as SrO

Tltanlum a6 Ti0

I . ANALYSES OF TOTAL PARTICULATES (Relerence 46) (Data in wrcent)

i: Test A Total sollds lrom burnhg PSa 4 m 011 (collected In P laboratory electrical, PreclDI'itor at 23OoF)'

I' h., 58. Ib

2. 3

- _ _ I?. 4

17.5

_-- -__ 3.1

.M

1.8

2 . 5

.08

. 6

1.6

. 4

. 2

. I

. 2

.s

.01

-_ - . 0 2

. 01

. 0 4

--- .s . 0 4

.03

Test B Tnlal sollds lrom Mrnlng 4' API oil (collected In a glass fllter sock at 3OOoF)

18. Ib

4 . 4

--- 51.2

25 .0

. 5

. 3

3.7

. 3

13.2

4 . 7

I

- 3 J 8 . 7 /

14.8 i /

. I

!?

i . 2 1 . 4

3.0 1 t

. :::4/ OS I

. 0 4 1

. 08' I -_-

e--

--- a Pacllic Standard.

I Value prohably Includes mlnor amount of hydrogen.

30 '\

ATMOSPHERIC EMISSIONS

I

I I

0 I I 1 0 IO 20 30 40 50 m

+

' Figure 12.

FROM FUEL OIL COMB 39

1 1

Burner Tilt I

One investigator change in burner tilt, There was very little fly ash loading or com- bustible content of the fly ash when flue gas was not recirculated. When some flue gas was recitculated, however, the combustible content and loading of fly ash tended to reach a maximum with the burner tilted zero degrees from the horizontal. This would in- dicate that best operation, from the air pollution standpoint, , would result with burners inclihed either up or down. No con- clusion has been redctieed on thd combined effect of burner tilt and flue gas recirculation. 23

1

several serids of tests involving flue gas recirculation.

ii

(1 i

Excess Air i \

I , A ir

;, >

Increasing the amhnt of excess a i r usually decreases the fly ash loading and combustible content of the fly ash since more complete combustion results. ~n a series of four tests it was found that, as the oxygen concentration in the stack gas increased from 2 to 4 percent, the particulate loading flecreascd froni 0.140 to 0.020 grlscf, :respdctively. Or 8tated.another way, an increase ih the C02 content in the stack gas:from 13.1 to 14.7 percerit resulted in a:?-fold increase i n partlculnte'ioading. 23 ...... ~~, 1, '. i .f ' ' 1 ".. '

....... '.' . . . .- ... JtLl ' .. ~ . , ' . : , I ' **,':.,u,:,,;,. L \ ' - ,*. .

.;$I ,...@+?y . ,>. .. I 1. ,:, . . ; j :, I

. . . . . ,.. , Flue Cas'Recircuiation. , .

. . . . . . , . & . . . . , .,, .il:, . . . . ...,.,;. . . . . . . ,.'.*.! ,,.. ...... . i . . '-Fly aah emissio; increases as more flue

into tho fireboxj2This is owing to D cooling,of the flame acd of combustion gases.,,: One author found that,, when the burners of a 188-megawatt"p1ant were at a zero tilt.from;the ,horizontal, and when'flue &Wrecirculation was increased from O'to lS'percen1, the.fly a h loading.increased,lOO perc content . ., of the I _ . . _ fly I, ash dayed,essentiall 4

~ , , .>< ..I ~

Sootblowing ,,. .' ,,'*

. . , I . 0 ' ' .,, i, ' j ' 2 9 0 ., . <> ,. , , . . ,, ,'at,'. , _. \I ', ,* ,' ,

Sootblowing increases the particulate loading in stack gases. J

One author reportcd a. 1.7-fold increase in particulate loading during sootblowing in one operation and a 3. %fold increase in another, .above ormal emissions of 0.11 and 0.039 griscf, 4g Another author found an increase 2.' times the rcspectively. normal emloelon of 0.028 gr/ecf during sootblowing.

I

83 . L . l

... . . . . . '< ..\ I. , , .

I I

ATMOSPHE FIC E MISSIONS ' , ' i

40 \ I 1: I

\ i i

I 1 ' ' i I '\

EMISSId,NS FROM ,SMAbC INSTALLATIONS

1 F " \ . , \ I a ' ;

The terrp"bmal1 sources" refers o sources o f Jes s than 1,bOO hp (equivalent to 34,500-pounds tea,m production per hour o r 2,500 pourids of oil fired per\hour). These units are used in

power to small industrial procedses. Because of the sinaller s izes of the unitp, flame temperature is\us:ually :lower than in larger sources. i In many cases, less attention is given to treat- ment of fuel and regylatlon of comhs t ion ' a i r for small units than is usually thd case' for large' units'. . This Pften resul ts i n less

+ efficient combustion in sma l l e r units.

1

1 domestic heatin'g, commercial heating, \ land,in supplying heat and : . . 3

; I

./ I

1.1.

I I I '> 8 ' ( !

Small units, in ieneral, produce'less'N0, and more fly ash and unburned hydrocarbon's than the large sources, because,Af the reduction in fl me temperature and in combustion effici,ency. Since there is a w de Ivakiation in fuels us4d in the small sburces, emissions are reported i n pounds 'per 1, OqO pounds of oilJired. Descriptions of qm!shIoncl' and yariables affecting e'missifn ra tes

B . .

! . are s imi la r to those for large sources and 'a re covr.. ?d there. , ! (' ' . . ' i

I '

I

I , ' / ' I

. . I I ' ' r , ! ( I Q i . I

I Oxides ': , of Nitrogen (WC I I

. 1.' I ' i' i

1

. .

I 'The literavre v$ues tfor NO, emi t t ed l rom small units are i

considerably less tha;n those for large units. In a,joint/district, f'ederal, state, and ihdustry project involving measurpment of emissions from 530 tinits producing 500 horsepower or less, an

' emission faator was kstablished. :This factor was 0.49-pounds NO per lo6 Btu, ok.9-pounde NOx per'l, 009 nds;of oil fired

sources, a general value of-?. 2-pounds NO, r 1,000pounds of oil fired was established for smal l sources. Other general I

I .:: 1

per 1,000 pounds of oil* fired. The vhlues &ported in the l i terature range f rom 0 to 18 pounds per 1,000 poun48 of .oil fired,. and these' are shown in Fig& :13. The data presentiation method wed in

4. . A more reliable average valve, however, would be about 9-pounds NO der 1,000-pounds oil red based on the joint project

i (cafculated on the bath of 18,.300-Btu/lb oil). %Y , Inranother program, which included many tes t s on both large and small 1

6 , values found in the l i terature are 13- 441and 7-pounh NO,

the figure indicates t,ht the moat common value is between 0 and i '

- i

1 !

I I 1 : \ ' - I 1 . !!\ . ' , . ; , I " . ) " . . conducted in 1 os An&es County.

.,.: ..~. . . ~. ' I

,\ ,. I,

1 . . omiot-.r- , ,.

..' I i

I l i J. "

, I

FROM FUEL OIL z i I

I I i - I I I

i - I

n W I- K 0 P W K

Y

-1 a $ 5 U 0

z 0

C

. 1 I 1

! 0 Individual VOIY s reported

Typical values reported I i

I

// 4 6 8 I O / I 2 . 14 16 18 20 /

/ NO,, lb.'1.000 Ib OF OIL FIRED

,/ ' I f

Figura 13. NO, amissims lrom small units.

/

I /

I ; Sulfur Dioxide (S02) 1 .

I I I I

41

W f u r dioxide!,'emission data for small units are/shown in I i Figure 14. This distributiQn of values is similar tothat for large

sources. The extreme range is 0 to 100' percent of the sulfur in the fuel oil emitted as SO . Values up to 254 percent were re-

sumed to be 100 percent. (The error isipmbably,owing to inaccuracies in sampling and analyzing practices.) The normal range is from 70 to 100 percent, and the; most common value ie 100 percent of the sulfur emitted as SO& as it was for the large sources. For reasons discussed previously under large source emissions, 98 percent of the sulfur emitted 88 is considered a more reasonable figure.

ported. This is imkss:!, ? e, however, and such values are as-

.

. I

!

42 i \r ATMOSPHERIC EMISSIONS

!! O I '

'I I I

1 0 1 I r Ii.l I I

0 IO 20 30 40 50 kl m 80 $0 100 (OR GREATER) I !

! 1

SULFUR IN THE OIL E M l l T E D AS 502:"i I I

I' Figure 14. Sullur dloxtde emlsslans 1 Irona small

I

Sulfur Values found in the literature for sulfur tripxide emissidns

are shown in Figure 15. ,This figure shows an ex t remt ran& of 0 to 13.75 percent of sulfur in the fuel oil emitted as SO3. ,The normal range is between 0 and 1.25 percent and the most common value is between 0 and 0.25 percent of the sulfur emitted as. SO3. Figure 15 indicates, however, that there are sufficient vdlues reported to support the conclusion that about 1 h r c e n t of the sul- f u r in the oil is emitted as SO3. This conclusion would'be in more general agreement with the 903 emission from large sources.

I-' --*& a W + o! 0 n a

a

W

u W

IL 0

$

t I 0 Individual values reported

Typical valuer roportmd

,

I 2 9 13 SULFUR IN THE OIL EMITTED AS SO,, i

bn, Figure IS. Sullur trioxide emissions Iron, small units.

%! I

J FROM FUEL OIL COMBUSTION

i 1

Oth& Gaseous

43

. Smaller sources tend to compounds than

larger sources. This is owing to and lower combustion efficiency in its,. Li terature values for carbon monoxide are shown and for aldehydes, as formaldehyde, in Figure 17. range for CO emissions is 0 t o 194 pounds of oil fired. The normal range is between 0 are between 0- and fired. The is 0 to 3.3 range is 0 to 0.6 pound. and the most comm'on values are betwe/en

-

I f I

0.28nd 0.3 pcurid per '1,000 pounds of oil fiied. I

/ xi I S , . . 4

=til 0 W I- K 0 P

:s

d U 0

z 0

TypIrol values reponed

0 4 IO

CO. lb/1,000 Ib OF OIL FIRED I

Figure 16. Carbon monorido emissions from small units. I t

I

0, c I 0 Individual valves reported

U > Typic01 valves reponed 0

d z

0 W n a l i ) .2 0.5 LO 1.5

( 1 9 3.0 3.6

ALDEHYDES (AS FORYALOEHYDE), lb/l.OW Ib OF OIL FIRED

Figure 17. Aldehydes (as formaldehyde) minod from v l o l l souma.

!

I \

44 \ One author reported a variation of hyd

to 0.011 percent in the stack gas when the from 12.4 percent

smoke number has been reported range. 52 Data for other addition to these data, on commercial aiid emissions in 0.080;

for small sources.

1 Particulate Emissions The fly ash loadings Tor small sources are slightly higher

than those for large sourccs. The data a r e presented in Figure 18. The extreme range is between 0 and 10 pounds of particulate per 1,000 pounds of oil fired. The normal range is between 1 and 4 pounds of particulate per 1,000 pounds ofoil fired, and the most common values are between 1 and 2 pounds of particufatesper 1,000 pounds of oil fired.

I ' I I

r

n W

< > 0 w c K

3 IO

2 LL 0

2 d

0

' 0 lndlrldvol values reponed '

' T ~ p l c o l rolums reponed

0 I 2 3 4 5 6 7 8 9 )O

I,' :. I

COtkTROL OF \MISSIONS

Ox'jdes of Nitro en (NO,) \ . The formation of nitrogen oxides with the flame in the flame, temper;iture, the length of t ime the

and the amount of oxygen available. is I

By

measures may, howeyer, increase particulate loading because of less efficient combristion.

, Sulfur Dioxide (Soh) ' i

b I

1 Emiss!on of sulfur dioxide is a direct function of the sulfur in the fuel. Emission ofpulfur dioxide may be' reduced either'by using low-sulfur CNde oils or by removing the sulfur. ,

I ,I

Sulfur t Trioxide (SO3)

Sulfur trioxide fokmation is initially a function of the SO2 Concentration and t e m b r a t u r e (provided there is a catalyst present). As a result of reactions of the SO3 with o;her com- bustion products and with the combustion and heat transfer equip- ment, however, the SO3 actually emitted to the atmosphere shows no direct correlation with the sulfur content of the oil. 'Effective ways of controlling emissions of So3 include the use of,additives and the use of an electrostatic precipitator in the exit gas st ream.

The basic objective of using additives is to r educ t boiler deposits and corrosion. The additives are usually added with the

These compounds usually react with the SO3 and tie it up in the form of neutral salts. Some of the more common additives are oxides, carbonates, soaps, arid naphthenates of calcium, zinc, magnesium, sodium, and other metals, The additives, by forming sulfate

t

!

I l * . . fuel or added to the flue gases directly after combustion.

45

i i

I i /

c

i: i i

i !

\

46 ATMOSPHERIC EMISSIONS

salts, usually SO3 sometimes up to 50 percent, but normal

to 1.5 to 7 times the pulverized coal; and fly ash from

used as adkiiiives. 1,7,26,29,30, 1 1 ;

and Organic Gases I i I *

I

Emission of d organic gases is the result of in- complete or of the oil. Some'of the more common are listed in Tabla 13. By

edission can be

I/

'I

l \Acidic Smuts P

Acidic smuts are$aused by the flue gas coming in with a surface whose temperature is below the dew flue gaa. By maintaining surface temperatyres and temperatures above thb dew point of the flue gas,

tion and prevented for ation of smuts. 13 1 I I li I

may be prevented. Ope author insulated the stack of an installa-

( I

f f

Particulates

Particulate decrease as conhst ion efficiency increases. Good com,bustion efficiency is obtained by high flame and firebox temperature, high-pressure atomization, high excess air, and low flue gas recirculation. These measures may, however, increase the NO, formation. When the particulate emission is decreased by adjustment of some of these variables, the N& emission mat increase.

Use of collectore, such as multiple cyclones, on oil-fired units is usually limited to periods when sootblowing operations are in progress. Cyclones collect particles of around 10 microns and larger, but they do not efficiently collect particles of 5 microns or less.

, I I

The use of electrostatic precipitators is, at present, limited. They are found only in those areas where restrictive legislation requires low particulate loadingh and low opacity of stack effluents. Electrostatic precipitators are generally used continuously. They iollect nearly all the particulates] including

I 1 i

i - i

i f i i

1

ImproDe~dlstake) i OLIpreasureto burner too

hlnh or to0 lOW 0 1 1 v1sCOslty too high 011 VlScOSltV too low (too

!

X X I sdmetimes

/h X X X Sometimes '1

I I ,

47

liquid droplets, such decreased 90 percent decreased by as when

loading may be

I Result ,

SmoA g Carbon iormation Pulsating

I X

t much 011 (Improper at:- fuel ratio) X X I

Excess alr (causing whlte r smoke) X I

Dirty or carbonlzed burner tlp (caused by Improper location, lnsufflclent cleanlng at regular Inter- I

flre In the boiler I 1

Cause

Insufflclent alr or toa

- Poor draft X Somefirnes X

1 ,

Carbonlzed or damaned I // atomizinu CUD (rotirv'cuD) I X I x i

Worn or damaged orlflce ] I? hole 1 x X

Improper burner adjustment I I (diffuser Dlate Drotruding I I

1.

2.

3. i

4.

5.

6.

7.

8.

9.

Chadwick, W. Conference on Washington, 155.

Perry, J. H.

I

i' I

and Com-

i ures , 1961.

Battelle Memorial 1nstitw.te. A Review of Availabfk Informa- tion on Corrosion and Deposits in Coal and Oil;-Fitred Boilers and Gas Turbines. ASME, N. Y. lq59.

Buckland, B. 0,. , Cardiner, C. M., !,and SakdcTs, D. G . Residual fuel-oil a sh corrosion. ASME Pabr 52-A- 161. 1952. ?

Thomas, W. H.' Science of Petroleum. Vol. 11. Oxford Press, London. 1938. pp. 1053-1056.

c , 1

/ / t

P

i 10. Rowley, L. N. McCabe, J. C., and SkrotTki, B. G. A. I Fuel and firing. Power, 92(12):735-782.

I 11. Roberts, E. G.! F'undamentals of fuel oi1,combustion. ! - Power Plant Engineering, 42:lll-114. 1938.

4 TC* lg4*. i <

: I Los Angeles County A i r Pollution Control District, LOS Angeles, Calif3 18 pp. Mimeo. .. I

6

1-2,Pa~~melee~W+H~Operation-of-oi-l-~rnqrs-on-steam boilers. - i

13. Blum, H. A,, Lees, B., and Rendlej L. K. Prevention of steel stack corrosion and smut emission with oil-Sired boilers. Inst. .Fuel J . , 32(217):165-171. Feb. 1959.

49

I I .

. .

i

:

!

i I

. ..

I

I

66. l'Apr. 1960.

Aug. 1960.

I

1 1 I

. . 19. Mills: J.,. L., Leudtke, !ICi D., P. F., and Perry, L. B., Emissions of m stationarv, sources in Loa Angeles. emitted by me(iium.jand Angeles County A i r Pollution Control District, Los Angeles, Calif. July . ' ,196 1. '

20., ctnney, A. L . ~ Significance of contaminants f rom centha1 power plants. Proc. First Technical'Me,eting, West ,Coast Section, APCA. dar. 25-26, 1957. pp.' :33-35.,

I 21. C h 68, R L., Lunche, R.'G., Schaffer,: N. R., and Tow,'

of nitrogen

, I . , ,. . ./

I

P. S. Total air pollution'emissions in Los JAPCA, 10(5):351-366. Oct. X960. I . '

Y emissions from combustion processes. Amer. f Ind. Hyg.

, . . . I

22. Woolrich, P. F. Methods for estimating oxides of nitrogen

/ ASS=. J., ! 22:481-,484. 1961. L

'23. JeIfefisi C. C., and Sensenbaugh, J. D.'' ' Effect of'operat- ing-variables-on-t he-stack-emission-f-rom-a-modern-power

24. Barnhart, D. H., and Diehl, E.' K.,' Control of nitrogen

. I

1 station boiler. IASME. Oct. 22, J959. ' I

I

, oxides in boiler flue gases by two-stage . . combustion. JAPCA,

25. Private communication with Pacific Cas !and.'Electric Com-

10(5)>397-406. OCL 1960..' ' I ; , : ' 1 , !

' pany. Mar. 6, 1961. . .

1

I

i 1

' 1 . . a

i

i !

! 51 i I '

.

. ,. . . . , . .

I

I I +

f .,.

.. ii

:. . . ! I 30. Jarvis; ' W. D. .. Selecti 'n and use of additives in oil-fired

boilers. Inst. Fuel'$.!. 31(214):480-491. Nov. 1958.

31. Rendie, L. KI ,' and Wilsdon, R. D. The prevention of acid condensation in oil-fire& k ' i l e r s . Inst) Fkel J., 29:372-380. 1956.

32. Flint, D., Lindsay, A. W., and Littlejohn, R. F. The effect of metal oxide smokes on the SO ' content of combus- tion gases from fuel oils: Inst. Fuel 2, 26:122-127. Sept. 1953.

33. Alexander, P. AJ:, Fielder, R. S., Jadkson, P. J., Raask, E., and Williams": T. B. Acid deposit'jm in oil-fired

34. Nelson, H. W., and Lyons, C. J. Sources and control of sulfur-bearing pollutants. JAPCA, 7:187-193. Nov. 1957.

35. Crurnley, P. H. ,!,and Fletcher, A. W. , The formation of sulfur trioxide in flue,gases. Inst. Fuel J . , 293322'327.

' I 1 . ,

i

,.:

. , boilers. Inst. Firel J . , 34:53-72. Feb. 1061.

! I Aug. 1956. - * -

36. Whittingham, G. 'The influence of carbbn smokes 49 the dew-point and sulphur trLoxlde content of flame gases. J.

37. Corbett, P. F. The determination of SO2 and SO3 in flue gases. Inst. Fuel J., 24:247-251. 1951.

. Applied Chem., 1:382-399. 1951. i I I

I'

\ \

52

j . ! .

. .

.. ., . . . . \ '6V."

, L .. ,. % 1: '..*Vi..., 1. \ 'b :d i. . ,

1 Bell, G. B. Literature review 3f concentrations: Brepiratidn,. . .-

atmdspheres. Stanford ' . SU-1816. Mealo Park,

li: C. ,' and Yocum, . s .

of low molecular Amer.

20:374-378. ;ct. 1959.

. .

I i !,,

i i' I

42. Haagen-Smit, A. J. Studies of air pollution conirol by

43. Private communication with Apra Precipitate{ Corp. June I

44. The Louisville Air Pollution Study, SEC Tech. Report, A61-4. USDHEW, Public Health SerGice, Cincinnati, Ohio.

Southern Calif.!,Edison eo. ASME 'Paper 57-SA-59. 1957. I i '

I 1, '' 1961. i 7

1961. i

I , .

/ I (

9 i

45. Unpublished data from private communications. I :. 2 8

46. MacPhee, R D.., Taylor, J. R., and Chaney, A. L. Some data on particles from fuel oil burning. Los Angeles' County A i r Pollution Control District, A i r Analysis Division.

47. Private Communication with Florida Power and Light Co. June 28, 1961. '*

< Analysis Paper'$No. 7. Nov. 18, 195?,." I

I I !

F

I

L .

4 &-Bow den ,-A,T-ri-Draper;-P;-R~~i ng , 4. The 0 ro hle ni :'I

of fuel oil deposition i n open-cycle gak turbiyes. Proc. (A) Inst. Mech. Epgr., 167:291-300. 1953. .I

'... ?j

j

1 j

. B

t 49. Clarke, J . S., 'and Hudson, G. J. Heavy oil burning. Inst. .1 B

1

Marine Engrs. Trans. , 71(5):135-157. Mad. 1959. * '

Feb. 7, 1961. ' 50. Private communication with SouthernlCalifornia Edison CO.

I

'i ab / I

I A.

I _I

; 1

.

. , ,

. (

! ,I !

53.' ! ' ,

~

F

51.

55.

56.

57.

58.

59.

60.

! 61. I .

62.

I , . , , .

48(10):1931-1934. Oct. 1956. 0 : \ [ i

Wivstad, I. Pulverized coal additives in oil firing. Tekriisk Tidskrift, Stockh., ? . , .84:509.1 1954. . I

Keck, J. W. Slurry spray huts cost of c1,eaning boilers. Electrical World, p. 130. Apr. 25, 1960.

P , 1 :

' ' I. j 1

Report of 'Informal Conference on sociated with Oil Firing. Central Board, London. Nov. 20, 1957. 52 pp. '

Fisher, G. ,..Problem'of sulfur in. residual fuels. Proc. First Technical Meeting, 'West Coast 'Section; A&A, LoS Angeles, Calif. Ma;. 25-26, 1957. pp. 1!4-:17.,// i ' Haagen-Smit, A. J J . Removal of particulate and gaseous contaminants from Ijower plant flue gases. Proc. First

Calif. 1957. pp. 102-110.

, .

4 ,k

Technical Meeting, :'West Coast Section, .APCA,

Pilpel, N. Industrial gas cleaning. Brit.

Austin, H. C., and:Sproul, W. T. for oil-fired powerlplants. Paper 1959. I I

5:542-550. A u ~ . 1960.

The

Cyclone Dust Collectors. Engineering Report Prepared for American Petroleum Institute, Division of Refining, N. Y., N. Y. Feb. 1, 195.5.

1 !

t I

!

'i I

P 63. i ?

65. .. k

Grossman, P. R; . ment in air Nov.

fuel burning equip-

.. , , .

Corbett, P. F., ;and Fereday,

boiler. :,Inst. Fuel J., f 3 , , c,;;

Faith, W. L. ' Nitrogen engineers." Chem.

content of the combustion

- ,. i!. . . 66. McCabe,' L. C. ."News of ,2(5):60. Map.1960.

67. Matty;' R. E., and SO3.

68. Cb!.ss;-R : L. and^ emissions

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: 1 . . .

. . f rom the combustion of $,1959., . ,/ . ,

. . . . ~ . , '. . . 69. . Sambrook;" K. H. combustion of

fuel oils. .Proc. Sept. 30 to Oct.. 2,: 1953. . ' Society, London. pp. 83-99. 1

of fuel on tIie.'content of 3, 4-benzpyrene in smoke gases. Gigiena i,Sanitaria, Moscow., 23(12):6-9. Dec. 1958.

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ATMOSPHERIC EMISSIONS

Ranges Hypothetica references

20- 50 14

5-45 15

20-40 16

.4PPENDIX C. MTTHOD OF REPORTING THE DATA

Eniission data report fit into three categories: ( 1 ) individual test or general values, or (3) ranges of emissions. as follows (values in p

.

iple, if the data for a given pollutant were

The histogram presenting these data would be constructed as shown in the following figure:

.

FROM FUEL OIL 95

"Rangcs" first. The rar.ge 20 to 50 from a rpw extending from 20

e reference 15 was The range 20 to

r as a square

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j histogram, the extremc range would Ix 5 to 50 ppm, the most common range 20 to 40 ppm, and the most common values between 30 and 35 ppm. The emis4ion value would be chosen as 32.5 or 33 ppm. In this histogram the hypothetical references are represented inside each square for better understandj.ng of this method of representation. In the text, however, the references are not represented, for the sake of simplicity.

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