DOE/EV/06020- 1 uc-11

DOE/EV/06020--1
D E 8 2 015891

Final Report

Vaporization, Dispersion, and Radiant Fluxes From LPG Spills

-

Technicaf Report
Published: May 1982

Prepared by: Applied Technology Corp. P.O. Box FF Norman, OK 73070 Under Contract No. DE-AC05-78EV-06020 Prepared for:

U S . Department of Energy
Assistant Secretary for Environmental Protection, Safety and Emergency Preparedness Office of Operational Safety Washington, DC 20545

DISCLAIMER This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency Thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

DISCLAIMER Portions of this document may be illegible in electronic image products. Images are produced from the best available original document.

Technic01 Report Documentotion Page

1.
Rep011 N o .

2.

Government Accession N o .

3.

R e c i p i e n t ' s Cotolog N o .

DOE/EP-0042
4. T i t l e and Subtitle

I
D.

DOE/EP-004 2
5. Report
Dote

V a p o r i z a t i o n , D i s p e r s i o n , and R a d i a n t F l u x e s from LPG S p i l l s

7.
Author's)

J ; R.
9.

Welker and W.

Cavin

8.

Perlarming Orgonixotion Report N o .

ATC-112-FR-D
10. Work U n i t N o . ( T R A I S ) 11. Contract
or Grant N o .

Performing Orgonixation Name and Address

A p p l i e d Technology Corp. 401 W e s t Main S t r e e t , S u i t e 220 Norman, OK 73069

12.
Sponsoring Agency Name ond Address

DE-AC05-78EV-06020
13.
T y p e o f Report and P e r i o d Covered

Department of Energy (EP-32) O p e r a t i o n a l S a f e t y Programs 20545 Washington, DC

U.
S.
15.
Supplementary N o t e s

I-

F i n a l Report Task D

14. Sponsoring Agency Code

T h i s r e p o r t w a s p r e p a r e d under t h e c o g n i z a n c e o f D r . John M. S a f e t y Programs, U. S. Department o f Energy (EP-32).

16.
Abstroct

Cece, O p e r a t i o n a l

Both b u r n i n g and non-burning s p i l l s o f LPG ( p r i m a r i l y p r o p a n e ) w e r e s t u d i e d . Vapor. z a t i o n r a t e s f o r p r o p a n e s p i l l s on s o i l , c o n c r e t e , i n s u l a t i n g c o n c r e t e , a s p h a l t , s o d , rood, and polymer foams were measured. Thermal c o n d u c t i v i t y , h e a t t r a n s f e r c o e f f i : i e n t s , and s t e a d y s t a t e v a p o r i z a t i o n r a t e s w e r e d e t e r m i n e d . Vapor c o n c e n t r a t i o n s w e r e measured downwind of open p r o p a n e p o o l s 25, 1 0 0 , 400, ind 1600 f t 2 i n a r e a . A G a u s s i a n d i s p e r s i o n model m o d i f i e d f o r area s o u r c e s p r o v i d e d i good c o r r e l a t i o n o f measured c o n c e n t r a t i o n s . E m i t t e d and i n c i d e n t r a d i a n t f l u x e s from p r o p a n e f i r e s were measured. L f f e c t i v e f l u x e m i t t e d a t t h e f l a m e s u r f a c e w a s a b o u t 50,000 B t u / h r - f t 2 .
A few t e s t s i n which p r o p a n e w a s s p r a y e d i n t o t h e a i r showed t h a t a t m o d e r a t e l y ligh s p r a y r a t e s a l l t h e p r o p a n e f l a s h e d t o v a p o r o r a t o m i z e d ; no l i q u i d c o l l e c t e d In t h e ground.

Simplified

' l a m e r a d i a t i o n models w e r e a d e q u a t e for p r e d i c t i n g r a d i a n t f l u x e s ; t h e maximum

17. K e y Words

18.

Distribution Slotement

L i q u e f i e d p e t r o l e u m g a s , v a p o r d i s p e r s i o n T h i s document i s a v a i l a b l e from: v a p o r i z a t i o n rates, b o i l o f f rates, flame National Technical Information Service r a d i a t i o n , LPG, LPG f i r e s , LPG s p i l l s , 5285 P o r t Royal Road f i r e modeling. 22161 S p r i n g f i e l d , VA
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TABLE OF CONTENTS

Page
EXECUTIVE SUMMARY INTRODUCTION

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

5-1

s-1

REPORT NO

D I S P E R S I O N OF VAPORS FROM LPG S P I L L S INTRODUCTION

e

......

1-1
1-1 1-1
1-2

............ RESULTS . . . .. . D I S C U S S I O N O F RESULTS. . . . . . . . . . . . . . CONCLUSIONS . . . . . . . . . . . . . . . . . . . REFERENCES . . . . . . . . . . . . . . . . . . . 1 . R A D I A T I O h FROM LPG F I R E S . . . . . . . . . . . . 1 INTRODUCTION . . . . . . . . . . . . . . . . . . MEASUREMENT PROCEDURE . . . . . . . . . . . . . . RESULTS . . . . . . . . . . . . . . . . . . . . . S I M P L I F I E D FLAME RADIATION THEORY . . . . . . . . DISCUSSION O F RESULTS . . . . . . . . . . . . . . CONCLUSIONS . . . . . . . . . . . . . . . . . . . REFERENCES . . . . . . . . . . . . . . . . . . .
PROCEDURE AND MEASUREMENT

1-6 1-23
1-24

11-1
11-1

1 1 I11-4

11-12
11-20

11-33

11-34

I11

VAPORIZATION OF PROPANE FROM S P I L L S ONTO S O L I D SURFACES

............... INTRODUCTION . . . . . . . . . . . . . . . . . . MEASUREMENT PROCEDURE . . . . . . . . . . . . . . PROPANE VAPORIZATION THEORY . . . . . . . . . . . RESULTS . . . . . . . . . . . . . . . . . . . . . D I S C U S S I O N O F RESULTS . . . . . . . . . . . . . . CONCLUSIONS . . . . . . . . . . . . . . . . . . . REFERENCES . . . . . . . . . . . . . . . . . . .
'

111-1 111-1

111-2

111-6

111-16
111-27

111-53
111-54

TABLE O F CONTENTS..

Continued

Page
APPENDIXA REPORT NO IV

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

A-1

. . . . . . . . . . iv-1 INTRODUCTION . . . . . . . . . . . . . . . . . . . 1v-1 PROCEDURE . . . . . . . . . . . . . . . . . . . . 1v-1 RESULTS AND D I S C U S S I O N . . . . . . . . . . . . . . 1v-4 CONCLUSIONS . . . . . . . . . . . . . . . . . . . 1v-10
S P I L L S O F PRESSURIZED PROPAPJE

ii

LIST OF FIGURES Figure

S-1.

Executive Summary Comparison of Average Measured and Calculated Propane Concentrations, Run 2 7 5 - 1 .

Page

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

s-3

S-2.

Vapor Concentration Downwind of Propane Pool Showing Effects of Application of High Expansion Foam. Comparison of Measured and Calculated Radiant Fluxes. Comparison of Measured and Calculated Weight of Propane Vaporized for Test No. P-54 Mass Transfer Factors from Propane Vaporization, Report I

...........

S-6

S-3.

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

S-8

S-4.

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

s-11

S-5.

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

S-14

1 .

Sample of Strip Chart Recording of Propane Concentrations. (The Recorder Pens are Offset by About the Distance of the Two Peaks Marked "Sensor 1" and "Sensor 2."). Correction for Zero Drift During Vapor Dispersion Tests. Comparison of Average Measured and Calculated Propane Concentrations, Run 2 9 2 - 1 . Comparison of Average Measured and Calculated Propane Concentrations, Run 2 7 5 - 1 . Comparison of Average Pleasured and Calculated Propane Concentrations, Run 2 9 7 - 1 .

..

1-3
1-10

2.

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

3.

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

1-12

4.

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

1-13

5.

1-14

6.

Vapor Concentration Downwind of Propane Pool Showing Effects of Application of High Expansion Foam.

6 3

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

1-19
1-20

7.

Response of Average Propane Concentration , to Application of High Expansion Foam iii

LIST O F FIGURES--Continued Figure

1. 2.
3.

R e p o r t I1 L o c a t i o n o f R a d i o m e t e r s Near T e s t P i t Example o f f r o m LPG

Page 11-3 11-5

11-17
11-22

..... Radiometer Readings Fires. . . . . . . . . . . . . . . .

Geometry Used f o r C a l c u l a t i o n of View Factors. Surface Radiant Fluxes f o r Propane Fires

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

4.

5.
6.

S p e c t r a l Transmittance of Sapphire Radiometer Window Comparison of Flame H e i g h t s w i t h P r e d i c t i o n of T h o m a s ( 1 9 6 3 )

11-27

11-30 11-32

7.

Comparison of M e a s u r e d and C a l c u l a t e d Radiant Fluxes. R e p o r t II I

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

1. 2.

A p p a r a t u s f o r Weighing Propane During Vaporization T e s t s .

111-1

W e i g h t o f P r o p a n e Remaining A f t e r S p i l l i n t o Perlite Concrete P i t S u b s t r a t e Temperature P r o f i l e s f o r Perlite Concrete.

111-17

3.
4.

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

111-25

W e i g h t Remaining F o l l o w i n g S p i l l of Propane i n t o P e r l i t e Concrete P i t Containing G r a n i t e Chips.

111-26

5.
6.

W e i g h t of P r o p a n e V a p o r i z e d , P l o t t e d Versus

&-. . . . . . . . . . . . . . . . . .

111-29

Comparison o f M e a s u r e d a n d C a l c u l a t e d Weight o f Propane Vaporized f o r T e s t N o . P-54 E f f e c t o f T h e r m a l C o n d u c t i v i t y on Calculated Vaporization iv

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

111-31 111-32

7.

LIST O F FIGURES--Continued Figure

8.
9.

R e p o r t 111--Continued E f f e c t o f Heat T r a n s f e r C o e f f i c i e n t on C a l c u l a t e d V a p o r i z a t i o n

Paae

.........

111-33 111-38
111-42

Comparison o f C a l c u l a t e d and Measured S u b s t r a t e Temperatures Mass T r a n s f e r F a c t o r s from P r o p a n e Vaporization E f f e c t o f Wind S p e e d on Pool Temperature.

...........

10.
11.
12.

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

111-45 111-46 111-59

Pool T e m p e r a t u r e F l u c t u a t i o n s C a u s e d by C h a n g e s i n S o l a r R a d i a t i o n Level.

....
...

13.
14.

Propane Vaporization Following Pouring o f 2 0 l b o f Marble C h i p s i n t o P r o p a n e . Propane Vaporization Following S p i l l i n t o S t y r e n e Foam P i t a n d S t y r e n e Foam P i t C o n t a i n i n g Marble C h i p s Report I V

......

111-51

1. 2.

Setup f o r Propane Spray T e s t s . L o c a t i o n o f Measuring Equipment f o r Propane Spray T e s t s . Vapor Plume f r o m D i s c h a r g e o f P r e s s u r i z e d Propane a t 180 lb/min

........

IV-2

..........

IV-3

3.

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

IV-5

4.

T e m p e r a t u r e s , Tank P r e s s u r e , a n d W e i g h t L o s s f o r Ambient Temperature Propane Discharge.

IV-7

LIST OF TABLES Table Report I Summary of Wind and Evaporation Data Summary of Average Gas Concentrations Downwind of Propane Pools (a) Ratio of Predicted Concentration to Measured Concentration (a) Page

1 .
2.

......

1-7

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

1-8

3 .
4.

...........

1-15
1-22

Peak-to-Average Concentration Ratios for Propane spills (a). . . . . . . Report I1

1.

Summary of Radiometer Data

...........

11-8

Report III 1 .
2.
3.

.............. Substrate Identification . . . . . . . . . . . .

Heat Transfer Properties for Solid Substrates

Data for Spills of LPG on Various Substrates

111-19 111-24 111-35

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

vi

. . .

. .

....

EXECUTIVE SUMMARY INTRODUCTION In 1979 and 1980, tests were performed to determine the effectiveness of some fire control and extinguishing agents for liquefied petroleum gas al. 1980).
(LPG) LPG

fires (Johnson, et be spilled, The

Those tests required that

ignited, and then attacked with fire fighting agents. sequence followed during the tests was much the same a s

expected for an accidental spill and fire, and it was possible to obtain information on dispersion of radiation from
LPG LPG

vapor and

fires during the same test series.

The fire control tests did not require a sudden release of

\

LPG,

s o there were some limitations on the infor-

mation that could be gained without major modifications to the test program. The most important limitation was that

the LPG was spilled slowly, so that transient behavior could not be studied. Therefore vapor dispersion and flame radi-

ation studies were made only for steady state conditions. "Steady state" refers to the vaporization rate of fuel. Both vapor concentrations and flame radiation fluctuated during the tests because of atmospheric properties. In addition to the observations made in conjunction with the fire control tests, small scale tests were conducted to study the vaporization of
LPG

spilled on solid

s-1

s u r f a c e s a n d t h e b e h a v i o r o f LPG l e a k i n g from c o n t a i n e r s a t h i g h p r e s s u r e and ambient t e m p e r a t u r e s .

T h i s r e p o r t is d i v i d e d i n t o f o u r s e c t i o n s , each o f which d i s c u s s e s one of t h e s u b j e c t a r e a s .

Each s e c t i o n i s

written a s a separate report.

The LPG u s e d i n a l l t e s t s was

c o m m e r c i a l p r o p a n e , g e n e r a l l y more t h a n 9 7 p e r c e n t p u r e i f s u p p l i e d a t a m b i e n t t e m p e r a t u r e and 8 0 p e r c e n t p u r e i f supplied a s a refrigerated liquid.

I.
D I S P E R S I O N OF VAPORS FROM LPG S P I L L S

P r o p a n e was u n l o a d e d i n t o c o n c r e t e p i t s 5 , 1 0 , 2 0 , and 4 0 f t s q u a r e f r o m e i t h e r a m b i e n t t e m p e r a t u r e o r r e f r i g erated storage. F i l l i n g t i m e f o r a d e p t h o f 3 i n c h e s was

a b o u t a h a l f h o u r t o 2 h o u r s , s o t h e p o o l s had r e a c h e d ap-

proximately steady vaporization r a t e s before dispersion

t e s t s began.

F i v e g a s s e n s o r s were p l a c e d i n t h e v a p o r

plume downwind o f t h e s p i l l a s n e a r t h e mean plume c e n t e r l i n e a s c o u l d b e d e t e r m i n e d f r o m wind d i r e c t i o n m e a s u r e ments. C o n c e n t r a t i o n s were m e a s u r e d f o r p e r i o d s f r o m 1 0 t o Wind s p e e d , wind d i r e c t i o n , and p r o The

2 0 min f o r m o s t t e s t s .

p a n e v a p o r i z a t i o n r a t e were m e a s u r e d d u r i n g t h e t e s t s .

dispersion data i n t h i s r e p o r t a r e primarily averages of t h e measured d a t a f o r t h e t e s t d u r a t i o n s . F i g u r e S - 1 shows t h e a v e r a g e p r o p a n e c o n c e n t r a t i o n downwind o f a 5 - f t s q u a r e p i t c o n t a i n i n g p r o p a n e . p l o t s were o b t a i n e d f o r a l l o f t h e t e s t s .

s-2

Similar

A Gaussian

CALCULATED

MEASURED

10
DISTANCE FROM CENTER, FT

100

FIGURE

S-1.

COMPARISON O F AVERAGE MEASURED AND CALCULATED PROPANE CONCENTRATIONS, RUN 275-1.

s-3

d i s p e r s i o n model m o d i f i e d f o r a r e a s o u r c e s was u s e d t o p r e d i c t t h e c o n c e n t r a t i o n based on t h e v a p o r i z a t i o n r a t e ,

t h e wind v e l o c i t y , a n d a t m o s p h e r i c s t a b i l i t y .
T h e atmo-

s p e r h i c s t a b i l i t y c l a s s was d e t e r m i n e d on t h e b a s i s o f wind direction fluctuations.

T h e l i n e drawn t h r o u g h t h e d a t a i n

F i g u r e S-1 shows t h e c a l c u l a t e d c o n c e n t r a t i o n .

Similar cal-

c u l a t i o n s were made f o r a l l t e s t s and compared w i t h t h e t e s t data. R a t i o s o f c a l c u l a t e d c o n c e n t r a t i o n t o measured

The

c o n c e n t r a t i o n were d e t e r m i n e d f o r e a c h d a t a p o i n t . a v e r a g e o f t h e r a t i o s was 1 . 0 3 , 0.54.

w i t h a standard deviation of

The f a c t t h a t t h e a v e r a g e i s s o n e a r 1 . 0 i s somewhat

s u r p r i s i n g because propane vapors a r e u s u a l l y thought t o l a y e r along t h e ground s i g n i f i c a n t l y .

The a p p a r e n t l a c k o f

l a y e r i n g i s a p p a r e n t l y d u e t o t h e q u i t e low v a p o r i z a t i o n r a t e s (about 5 lb/ft2-hr) a n d m o d e r a t e l y h i g h wind s p e e d s .

L a y e r i n g was p r o n o u n c e d i n o n e t e s t o n t h e 4 0 - f t p i t w h e r e
t h e a t m o s p h e r e was s t a b l e a n d t h e wind s p e e d was v e r y low.

The r a t h e r h i g h s t a n d a r d d e v i a t i o n o f c a l c u l a t e d t o m e a s u r e d propane c o n c e n t r a t i o n is n o t s u r p r i s i n g because of v a r i a t i o n

i n atmospheric p r o p e r t i e s and t h e d i f f i c u l t y of o b t a i n i n g

a c c u r a t e d a t a f o r v e r y low v a p o r i z a t i o n r a t e s a n d low p r o pane c o n c e n t r a t i o n s .

The l a c k o f l a y e r i n g d u r i n g t h e s e tests s h o u l d n o t be t a k e n a s a n i n d i c a t i o n t h a t p r o p a n e v a p o r s w i l l n o t form

layers.

Low wind s p e e d s , s t a b l e a t m o s p h e r i c c o n d i t i o n s and

high vaporization r a t e s w i l l a l l tend t o cause l a y e r i n g ,

s- 4
t '

e s p e c i a l l y w h e r e t h e t e r r a i n is s u i t a b l e .

Larger s p i l l s o r

h i g h e r v a p o r i z a t i o n r a t e s from p r e s s u r i z e d r e l e a e s c a n l e a d t o f o r m a t i o n o f l a r g e p l u m e s whose b e h a v i o r c a n n o t be a d e q u a t e l y p r e d i c t e d by s i m p l e G a u s s i a n m o d e l s , b u t w i l l r e q u i r e models where g r a v i t y e f f e c t s a r e t a k e n i n t o a c c o u n t .

T e s t s u s i n g l i q u e f i e d n a t u r a l g a s ( L N G ) h a v e shown t h a t t h e c o n c e n t r a t i o n o f g a s downwind o f a n LNG s p i l l c a n be r e d u c e d by c o v e r i n g t h e p o o l w i t h h i g h e x p a n s i o n foam,

e v e n t h o u g h t h e v a p o r i z a t i o n r a t e was i n c r e a s e d .

F i g u r e S-2

shows t h e r e s u l t s o f a s i n g l e t e s t i n w h i c h h i g h e x p a n s i o n foam was a p p l i e d t o a p o o l o f p r o p a n e . The v a p o r c o n c e n -

t r a t i o n i n c r e a s e d s h a r p l y a s foam was a p p l i e d , r e f l e c t i n g a v a p o r i z a t i o n r a t e more t h a n d o u b l e t h a t b e f o r e foam appl i c at i o n

.
In

P e a k c o n c e n t r a t i o n s m e a s u r e d d u r i n g t h e t e s t s were

u s u a l l y t h r e e t o f o u r times t h e a v e r a g e c o n c e n t r a t i o n .

o n e test a peak concentration 3 5 t i m e s t h e average w a s mea-

s u r e d , b u t t h e r e a s o n was b e c a u s e t h e s e n s o r w a s o f f t h e plume c e n t e r l i n e a n d w a s c o n t a c t e d i n f r e q u e n t l y d u r i n g t h e

t e s t by s h o r t p u f f s o f v a p o r .
t h e r e f o r e a b n o r m a l l y low.
11.
8

The a v e r a g e c o n c e n t r a t i o n was

R A D I A T I O N FROM LPG FIRES

R a d i a t i o n f l u x e s were m e a s u r e d f o r f i r e s b u r n i n g above p i t s 5, 1 0 , 20, and 40 f t s q u a r e a t s t e a d y s t a t e burning rates. Both n a r r o w a n d w i d e a n g l e r a d i o m e t e r s were

s-5

TIME, MIN

FIGURE S-2.

VAPOR CONCENTRATION DOWNWIND O F PROPANE P O O L SHOWING , E F F E C T S O F A P P L I C A T I O N O F HIGH E X P A N S I O N FOAM.

u s e d , s o t h a t b o t h t h e e f f e c t i v e flame s u r f a c e f l u x and t h e i n c i d e n t f l u x a t a g i v e n l o c a t i o n could be measured.

The

m e a s u r e m e n t p e r i o d was u s u a l l y a b o u t h a l f a m i n u t e , a l t h o u g h t e s t s a s l o n g a s 10 m i n u t e s were r u n t o i n v e s t i g a t e t i m e effects. F l u x e s were m e a s u r e d d u r i n g t h e s t e a d y s t a t e p a r t

o f t h e b u r n , b e f o r e t h e f i r e was a t t a c k e d w i t h f i r e f i g h t i n g agents.
R e s u l t s were o b t a i n e d f o r a wide r a n g e o f wind

s p e e d and wind d i r e c t i o n . The f l a m e r a d i a t i o n was modeled a s s u m i n g t h e f l a m e t o be a s u r f a c e emitter. The e f f e c t i v e s u r f a c e f l u x was

d e t e r m i n e d on t h e b a s i s o f narrow a n g l e r a d i o m e t e r measurements t o b e
q = 50,000
1

- e x p (-0.126

D)

1
and D

where q is t h e e f f e c t i v e s u r f a c e f l u x i n B t u / h r - f t 2 ,

is t h e width of t h e s q u a r e p i t i n f e e t .

The r a d i a n t h e a t i n g

r a t e s expected a t t h e w i d e angle radiometers w e r e c a l c u l a t e d

b a s e d o n a t i l t e d c y l i n d e r model.

The f l a m e h e i g h t a n d t i l t The

a n g l e were p r e d i c t e d from l i t e r a t u r e c o r r e l a t i o n s .

b a s i c i n p u t d a t a t o t h e model were f l a m e b a s e s i z e , a v e r a g e

wind s p e e d , a v e r a g e wind d i r e c t i o n r e l a t i v e t o t h e r a d i o m e t e r , and d i s t a n c e from t h e f i r e t o t h e r a d i o m e t e r . Figure S-3 fluxes.

i s a comparison o f t h e measured and c a l c u l a t e d

R a t i o s o f c a l c u l a t e d f l u x t o m e a s u r e d f l u x were The a v e r a g e o f t h e r a t i o was 1 . 0 The c l o s e

6 3

determined f o r each run.

w i t h a standard deviation of about 16 percent.

s-7

16,000

12,000

8000

4000

0
0 4000 8000

12,000 2

16,000

CALCULATED RADIANT FLUX, BTU/HR-FT

FIGURE S-3.

COPTPARISON O F MEASURED AND CALCULATED RADIANT FLUXES.

S-8

c o m p a r i s o n o f m e a s u r e d and c a l c u l a t e d f l u x e s i n d i c a t e s t h a t
t h e s i m p l i f i e d s u r f a c e e m i s s i o n model i s a d e q u a t e f o r p r e -

d i c t i n g r a d i a n t f l u x e s f o r propane f i r e s .
111.

V A P O R I Z A T I O N OF PROPANE FROM

S P I L L S ONTO SOLID SURFACES

I f LPG i s s p i l l e d o n a s o l i d s u r f a c e i n t h e o p e n atmosphere, i t begins t o b o i l . After about 15 minutes t h e

s o l i d c o o l s enough t h a t t h e v a p o r i z a t i o n r a t e , w h i c h h a s b e e n d e c r e a s i n g , becomes r e l a t i v e l y c o n s t a n t . Active

boiling has stopped, but vaporization continues u n t i l a l l

t h e LPG i s g o n e . T e s t s were r u n t o d e t e r m i n e t h e v a p o r -

i z a t i o n r a t e s f o r propane and t o d e t e r m i n e t h e p h y s i c a l p r o p e r t i e s o f t h e s o l i d s u b s t r a t e s o n t o w h i c h i t was p o u r e d . Two g e n e r a l t y p e s o f t e s t s were p e r f o r m e d ; c l o s e d t e s t s i n w h i c h a p o l y s t y r e n e foam l i d was p l a c e d o v e r t h e t e s t p i t ,

a n d o p e n t e s t s i n w h i c h t h e p o o l s u r f a c e w a s e x p o s e d t o wind

and/or s o l a r r a d i a t i o n d u r i n g t h e test.

I n some o f t h e

l a t t e r t e s t s , s t e a d y s t a t e v a p o r i z a t i o n r a t e s were m e a s u r e d

a s w e l l a s t r a n s i e n t r*ates.

In a closed test t h e vaporization rate decreases continuously. A f t e r a s h o r t time, t h e v a p o r i z a t i o n r a t e is

i n v e r s e l y p r o p o r t i o n a l t o t h e square r o o t of e l a p s e d t i m e and t h e t o t a l q u a n t i t y vaporized is p r o p o r t i o n a l t o t h e

square r o o t o f e l a p s e d t i m e .

The p r o p o r t i o n a l i t y c o n s t a n t s

a r e r e l a t e d t o t h e thermal c o n d u c t i v i t y , h e a t c a p a c i t y , and
s-9

density of the solid, so if density and heat capacity are measured independently, the effective thermal conductivity of the solid can be determined. When propane is first spilled, the boiling rate is limited by the heat transfer coefficient between solid and liquid. The effective heat transfer coefficient can be

derived from the vaporization data taken during the first few minutes of a closed test once the thermal conductivity has been determined.
A

mathematical model can then be used Figure

S-4

to describe the vaporization curve.

shows the

weight of propane vaporized during a test in which perlite concrete was used as the solid substrate. The line drawn

through the data is from the mathematical model, using the thermal conductivity and heat transfer coefficient derived from the vaporization data. very accurately. Thermal conductivities and heat transfer coefficients were determined for gravel concrete, sand concrete, concrete containing vermiculite and perlite as fillers, clay soil, plywood, and asphalt containing crushed rock aggregate. The thermal conductivities determined from the vaporThe model reproduces the data

ization data were higher than those found from literature sources for similar materials. Temperature measurements in

some of the substrate materials indicate that the thermal conductivity is higher when the substrate is cold than when the substrate is at ambient temperature, which may be the

s-10
. .

G
I
I I

c
I I
I

TEST NO. P-54 PERLITE CONCRETE

MEASURED

- CALCULATED

I
0

10

20

I 30

40

I 50

I 60

TIME, M I N
F I G U R E S-4. COMPARISON O F MEASURED AND CALCULATED WEIGHT O F PROPANE VAPORIZED FOR T E S T NO. P-54.

reason the effective thermal conductivities were higher than those found in the literature. Literature values were gen-

erally available for ambient temperature, but not for lower temperatures.
A few tests were run to investigate the behavior of

propane when it was spilled onto surfaces covered with small rocks. When poured onto granite chips with a typical thick-

ness of about 0.15 inches, the additional heating from the chips was rapid enough that the chips were cooled in the
time required to pour the propane.

When propane w a s poured

onto larger marble chips, the time required for cooling the chips was about 3 minutes.
A

first-order heat transfer

model could reproduce the results successfully. Heat transfer coefficients were in the range to be expected based on correlations in the literature. Boiling

of propane spilled onto ambient temperature solids is generally within the transition region between nucleate and film boiling. Variations in heat transfer coefficients can Tests on similar

be substantial in the transition region.

materials under similar conditions gave relatively reproducible results. Heat transfer coefficients were usually

larger for higher density substrates, which would be expected because active boiling would occur longer than for low density substrates. Low density substrates would cool

more quickly, thus reducing boiling at the interface to a shorter period.

s-12

Mass t r a n s f e r f a c t o r s were d e r i v e d f r o m t h e s t e a d y s t a t e vaporization r a t e data. F i g u r e S-5 i s a c o r r e l a t i o n

o f t h e mass t r a n s f e r f a c t o r s a s a f u n c t i o n o f t h e Reynolds number. The p r o p a n e v a p o r i z a t i o n d a t a i n c l u d e r e s u l t s f r o m

tests o n c i r c u l a r p i t s 5 f t 2 i n a r e a up t o t e s t s on s q u a r e p i t s 400 f t 2 i n a r e a . Some d a t a p o i n t s f r o m e a r l i e r v a p o r -

i z a t i o n r a t e m e a s u r e m e n t s on h e x a n e a n d c a r b o n d i s u l f i d e a r e included. They show good a g r e e m e n t w i t h t h e p r o p a n e t e s t

r e s u l t s e v e n t h o u g h t h e b o i l i n g p o i n t s a r e much h i g h e r . Heat t r a n s f e r c o e f f i c i e n t s f o r t r a n s f e r between t h e c o l d

p o o l and warm a t m o s p h e r e c o u l d n o t b e d e t e r m i n e d f r o m t h e
available data. The t e m p e r a t u r e o f t h e o p e n p r o p a n e p o o l s d r o p p e d s u b s t a n t i a l l y b e l o w t h e b D i l i n g p o i n t when t h e p o o l s were a l l o w e d t o v a p o r i z e f o r more t h a n a few m i n u t e s . The s t e a d y

s t a t e t e m p e r a t u r e d e p e n d e d p r i m a r i l y on wind v e l o c i t y , b u t
t h e p r e s e n c e o f s o l a r r a d i a t i o n a l s o a f f e c t e d p o o l tempera-

ture.

S h a l l o w p o o l s r e s p o n d t o wind a n d s o l a r r a d i a t i o n

c h a n g e s more r a p i d l y t h a n d e e p p o o l s .
IV.

SPILLS OF PRESSURIZED PROPANE

Most p r o p a n e i s t r a n s p o r t e d a n d s t o r e d i n t h e U n i t e d S t a t e s a s a p r e s s u r i z e d l i q u i d a t ambient temperature. About o n e - t h i r d o f t h e l i q u i d v a p o r i z e s when t h e p r e s s u r e i s

reduced t o atmospheric p r e s s u r e under e q u i l i b r i u m conditions. In n e a r l y a l l a c c i d e n t a l releases, t h e propane

S-13

10-

m
\ N

I1

-n

F I G U R E S-5.

MASS TRANSFER FACTORS FROPI

PROPAPIE VAPORIZATION.

S-14

discharges a t high v e l o c i t y , atomizing t h e l i q u i d a s i t s p r a y s i n t o t h e atmosphere.

A

b r i e f s e r i e s o f t e s t s was r u n i n a n e f f o r t t o

d e t e r m i n e t h e f r a c t i o n o f l i q u i d t h a t would f a l l t o t h e g r o u n d a s i t was r e l e a s e d from h i g h p r e s s u r e s t o r a g e a t ambient temperature. L i q u i d p r o p a n e was f l a s h e d t h r o u g h

h o r i z o n t a l t u b e s i n t o t h e open a t m o s p h e r e a t r a t e s up t o 1 8 0 lb/min.
N o l i q u i d propane accumulated i n t h e s p e c i a l l y

d e s i g n e d , i n s u l a t e d t r a y p l a c e d b e n e a t h t h e d i s c h a r g e plume i n any t e s t . The plume t e m p e r a t u r e d r o p p e d a s low a s -70F, The l i q u i d was p a r -

indicating t h e lack of equilibrium.

t i a l l y a t o m i z e d and p a r t i a l l y v a p o r i z e d a s i t s p r a y e d from
t h e d i s c h a r g e t u b e s , and t h e d r o p l e t s t h a t were f o r m e d

d u r i n g d i s c h a r g e were s o s m a l l t h a t t h e y v a p o r i z e d b e f o r e t h e y reached t h e ground.

T h e r e was n o t e v e n a marked

t e n d e n c y f o r t h e plume t o f a l l t o t h e g r o u n d d u r i n g t h e brief discharge.

The r e s u l t s o f t h e s e b r i e f tests and o t h e r o b s e r -

v a t i o n s d u r i n g t h e t e s t program i n d i c a t e t h a t a c c i d e n t a l s p i l l s o f p r o p a n e from a m b i e n t t e m p e r a t u r e s t o r a g e w i l l n o t c a u s e l i q u i d a c c u m u l a t i o n e x c e p t i f t h e r e is a l a r g e quant i t y s p i l l e d , t h e s p i l l d u r a t i o n is l o n g , and t h e s p r a y is d i r e c t e d downward t o a s o l i d s u r f a c e t h a t i n t e r f e r e s w i t h f o r m a t i o n o f t h e s p r a y plume.

@
S-15

REPORT I DISPERSION OF VAPORS FROM LPG SPILLS INTRODUCTION In a study of LPG fire control and extinguishment, approximately 100 tests were run in which propane was spilled into concrete or earthen pits and ignited (Johnson, et al., 1980). Propane concentrations downwind of the

spills were measured before ignition for 21 of the tests. Vapor dispersion measurements were run on spills in pits 25, 100, 400, and 1 6 0 0 ft2 in area. Concentrations

were measured at approximately ground level as nearly directly downwind from the pits as possible. PROCEDURE AND MEASUREMENT Propane was unloaded into concrete pits directly from either pressurized o r refrigerated storage.
*

Because of

large losses due to flashing and atomizing of the liquid, ambient temperature storage was used only for the smaller test pits. Purity was greater than 97 percent for the

ambient temperature propane and 80 percent for refrigerated propane. The time required for filling the pits ranged from

about a half hour to about two hours, s o when concentrations were measured, the vaporization rates were at or approaching

steady state.

The pools o f liquid propane, usually about 3 The

inches deep, were subcooled and had ceased boiling.

1-1

pits were nominally 5, 10, 20 and 40 ft square and 2 ft deep. In most tests, 5 catalytic bead gas sensors were placed downwind o f the pools after unloading had been completed.
T h e placement was as near the centerline of the

propane plume as could be determined from observing the plume and considering the average measured wind direction. The gas sensors were calibrated immediately before they were placed in order to minimize the effects of zero drift. Both

wind speed and wind direction were monitored continuously during the tests.
The propane evaporation rate was measured

using a bubbler connected to a low pressure transducer. pool temperatures were measured using a thermocouple,

The The

fire control report by Johnson, et al. (1980) contains more detail on the liquid measuring technique and the pit design. The gas sensors measured concentrations continuously, and the outputs were recorded by strip chart recorders, In addition, outputs were recorded in digital Figure 1

form on magnetic tape at intervals of about 2 sec.

shows an example of the output o f a strip chart recorder.

RESULTS

The gas concentration at a fixed point varies during a test because of atmospheric turbulence and changes in wind speed and wind direction. Atmospheric turbulence causes
n

smaller fluctuations in concentration, but the changes are

1-2

r-i

w
P;

rl

3NVdOtId JiN3383d

1-3

more rapid than those caused by changes in the average wind velocity and direction. The turbulence also results in

changes in instantaneous wind speed and direction, but not in average wind speed and direction. There is a rela-

tionship between wind speed and turbulence level, but the average wind speeds during the tests reported here did not change substantially during most of the tests, so no changes in turbulence level would be expected during a test. Wind

direction changes were related to the atmospheric turbulence rather than changes in average wind direction during the tests. The test period was usually about 10 to 2 0 minutes, although a few longer runs were made. No differences in

average gas concentrations were noted that could be attributed to test length. The gas sensors frequently exhibited a In most tests, there were

zero drift during the tests.

enough points where no gas was present at the sensor to enable a correction for zero drift to be made. In all cases

where zero drift could be measured from the records, the change was found to be linear with time. In the few cases

where no zero points could be found for data measured during the test, the zero reading at the end of the test was used as the basis of constructing a linear zero drift line. The causes of zero drift were apparently from both the sensors themselves and from the electronic control and measurement portion of the circuit.
1-4

Small zero drifts were

n o t e d on a l l s e n s o r s ; o n e c h a n n e l o f m e a s u r e m e n t and c o n t r o l showed l a r g e z e r o d r i f t s o n n e a r l y e v e r y t e s t , r e g a r d l e s s o f
w h i c h s e n s o r head was a t t a c h e d t o i t .
T h e a v e r a g e g a s c o n c e n t r a t i o n s were c a l c u l a t e d from

t h e i n s t a n t a n e o u s r e a d i n g s by s i m p l y a v e r a g i n g t h e i n s t a n -

taneous r e a d i n g s over t h e period of t h e tests.

The concen-

t r a t i o n s on t h e d i g i t a l d a t a p r i n t o u t were s i m p l y summed and

t h e n d i v i d e d by t h e number o f p o i n t s i n t h e s u m t o g e t t h e

average.

z e r o d r i f t c o r r e c t i o n was a p p l i e d w h e r e z e r o
T h e c o r r e c t i o n was b a s e d on t h e z e r o

d r i f t had o c c u r r e d .

r e a d i n g a t t h e end o f t h e run and z e r o p o i n t s t h r o u g h o u t t h e run. C o n c e n t r a t i o n a v e r a g e s were f o u n d i n two o t h e r ways

One o f t h e ways was a g r a p h i c a l

f o r a few of t h e tests.

i n t e g r a t i o n o f t h e d a t a a s r e c o r d e d by t h e a n a l o g r e c o r d e r .
T h e s t r i p c h a r t r e c o r d was a v e r a g e d by m e a s u r i n g t h e a r e a

under t h e concentration-time

t r a c e w i t h a p l a n i m e t e r and The d i g i t a l d a t a

d i v i d i n g by t h e time c o v e r e d by t h e t e s t .

were t h e n u s e d t o r e c o n s t r u c t a s e c o n d c o n c e n t r a t i o n - t i m e
c u r v e , w h i c h was a v e r a g e d u s i n g t h e same p r o c e d u r e . Both o f

t h e s e a v e r a g e s were t h e same a s t h e a v e r a g e t a k e n d i r e c t l y from d i g i t a l d a t a , w i t h i n t h e l i m i t s o f a c c u r a c y p o s s i b l e ,

s o t h e c o n c e n t r a t i o n s r e p o r t e d f o r a l l t e s t s were a v e r a g e d

f r o m t h e d i g i t a l d a t a , which was t h e f a s t e s t a n a l y t i c a l procedure. A v e r a g e wind s p e e d and d i r e c t i o n were a l s o f o u n d by

averaging t h e d i g i t a l recordings.

They were a v e r a g e d o v e r

1-5

the same period as the concentrations so that the results would be for consistent times. The standard deviation of

wind direction was also determined directly from the digital data. Wind direction standard deviations are useful in

estimating the atmospheric stability category, which is important in data correlations and predictions of vapor concentration. Table 1 is a summary of the evaporation and wind data from the vapor dispersion tests. Because of the rela-

tively short test duration and the slow evaporation rate at steady state, it was frequently impossible to measure the evaporation rate accurately, so the evaporation rate data are missing for a number of tests. The atmospheric

stability listed for each run is based on the standard deviation of wind direction a s recommended by Gifford
(1968).

Table 2 is a summary of the average propane concentration downwind of the p o o l . The distances for which

concentrations are given are measured from the center of the pool. DISCUSSION OF RESULTS Figure 1 shows a section of a strip chart recording of propane concentration. The data from the chart can be

used to determine the average concentration through a graphical integration process, but it is easier to average the concentrations from tables of data.
1-6

This procedure was

TABLE 1 .

SUMMARY OF WIND AND EVAPORATION DATA.

Run No.

(a) Pit Width ft

Evap Rate

lb/f tL-hr

Wind Ave mi/hr

Speed
0

mifir

Wind Ave Deg

. .

Dir.
(J

Deg

Stab.

Run Time min

275-1 276-1 281-2 285-1 291-1 292-1 293-1 293-2 296-1 297-1 297-3 297-4 298-1 298-2 302-1 313-1 334-l b (
334-2

5 5 10 1 0 10
10 10 10 10 10

5.98

--

4.50

----

'10.1 20.6 6.9 1. 09 14.0 17.5 19.9 20.8 9.6 9.7 8.2 8.5 4.5 4.8 16.7 15.5 5.3
6.2

2.6 4.2 2.1 2.2 3.4

4.0 4.4 46 . 2.3 2.9

205 8 200 54 180 193 185 182 212 226 212 207 214 226 138 349 254
264

20.8 12.2 20.4 13.6 16.4 15.7 13.6 13.4 14.4 15.5 13.6 15.2 18.7 22.5 13.6 10.2 16.7
18.7

D
B D
C

18 19 51 20 17 10 17 10 9 20
10 11 19 12 15

--5.62 4.61 4.03

D
D

D
C

10 10 10 10 10
20 20
20

--

4.36 3.45 5.80

2.4 2.3 1.3 1.5 3.5 3.1 1.5

1.7

D
C
C

B D

-4.93
10.9

D
C
C

28 30
6

347-1 365-1 011-1

40
40 40

----

14 (c) 3.5(c)
8.4

---

339 335 (c) 31

--

9.5

E
F

15
18

1.7

88 .

16

(a)Nominal size; actual pit width is 5 inches larger than nominal size.

(b) Following application of high expansion foam.

(c)Estimated from airport weather data.

1-7

TABLE 2.

S M A Y OF AVERAGE GAS CONCENTRATIONS DOWNWIND OF PROPANE POOLS U MR

(a)

Run No.

Dist. f t

Conc
%

Dist. f t

Conc.
%

Dist. it

Conc.
%

Dist. f t

Conc
%

Dist. f t

Conc.
%

275-1 276-1 281-2 285-1 291-1 292-1 293-1 293-2 296-1 297-1 297-3 297-4 298-1 298-2 302-1 313-1 334-1 334-2 (b) 347-1 365-1

7.7 7.7 15.2 15.2 15.2 10.2 10.2 10.2 10.2 10.2 10.2 10.2 10.2 10.2 10.2 30.2 30.2 30.2 80.2 60.2 40.2

0.44 0.54 0.45 0.38 0.69 0.89 0.64 0.60 1.35 0.45 0.68 0.61 1.71 1.20 0.90 0.40 0.54 2.01 0.92 4.19 0.88

12.7 12.7 25.2 25.2 25.2 15.2 15.2 15.2 15.2 15.2 15.2 15.2 15.2 15.2 15.2 50.2 50.2 50.2 100.2 100.2 60.2

0.19 0.20 0.24 0.18 0.51 0.61 0.63 0.58 1.02 0.13 0.35 0.30 1.06 0.71 0.63 0.29 0.29 0.62 0.71 2.23 0.55

17.7 17.7 35.2 35.2 35.2 25.2 25.2 25.2 25.2 25.2 25.2 25.2 25.2 25.2 25.2 90.2 70.2 70.2 140.2 140.2 80.2

0.11 0.16 0.19 0.12 0.30

22.7 22.7 55.2

--

0.07 0.08 0.08

--

55.2 35.2 35.2 35.2 35.. 2 35.2 35.2 35.2 35.2 35.2 35.2 130.2 90.2 90.2 180.2 180.2 100.2

0.16 0.21 0.24 0.21 0.24 0.05 0.14 0.13 0.27 0.19 0.29 0.05 0.10 0.23 0.25 0.86 0.29

12.7 12.7 25.2 55.2 25.2 55.2 55.2 55.2 55.2

0.20 0.26 0.24 0.06 0.39 0.14 0.10 0.11 0.15

0.40 0.35 0.32 0.40 0.11 0.25 0.23 0.37 0.31 0.47 0.09 0.16 0.36 0.43 1.23 0.37

'

--

--

I
03

55.2 55.2 55.2 55.2 55.2 210.2 110.2 110.2 220.2

0.06 0.06 0.09 0.07 0.11

0.03 0.08 0.15 0.14

--

---

011-1

( a ) D i s t a n c e s are m e a s u r e d f r o m pool c e n t e r ; c o n c e n t r a t i o n s a r e i n mole p e r c e n t . (b) o l l o w i n g a p p l i c a t i o n o f h i g h e x p a n s i o n foam. F

followed for all tests.

Notice that Figure 1 shows some

points where the concentration apparently drops to zero and then rises again. These zero points may change during the The

test, but the change is approximately linear with time. zero drift was corrected by assuming a linear change over the test period.

Figure 2, which is plotted from 30-second

averages of the data, shows how the corrections were made. The average gas concentration over a 30-sec interval was plotted as a function of time. Periods when short term

average concentrations stayed constant or increased linearly without peaks corresponded to zero gas concentration at the sensor. These periods of zero gas concentration represent

times when the wind direction changed enough that the sensor was no longer in the gas plume. At the end of each test,

the gas sensor was removed from the plume before the pool was ignited.
A

separate baseline was established at that

Calibration after test
. (

time, as illustrated in Figure 2 .

runs showed that the span had not changed, so no adjustment in span was required. The zero adjustment was equivalent to

integrating the measured gas concentration above the baseline, as represented by the shaded areas in Figure 2. The

curves such as those shown in Figure 2 are simplified by the averaging process; they were used only to establish the zero baseline.
n

Actual average concentrations were determined by

point-by-point data sampled at about 1- to 2-second intervals during the tests.

1-9

- ' .

SENSOR 3

-.80

2 0
a
E+
H

-.40

SENSOR 4 SENSOR REMOVED FROM PLUME

cr:
z
W
I 0

2 E

-1.2

-2.0

1.2

SENSOR 5

SENSOR RGMOVED

.40

-.40

1
0

10

12

14

16

18

!
1

TIME, M I N

FIGURE 2 .

C O R R E C T I O N F O R Z E R O D R I F T D U R I N G VAPOR D I S P E R S I O N TESTS.

simple Gaussian dispersion model can be used to

predict the concentrations downwind of a propane pool based on the evaporation rate, the wind speed, and the atmospheric stability. Such a model, modified to account for source

area, was used to predict concentrations for the conditions under which the tests were run. Figures 3 through 5 show These

the results of predictions for three of the tests.

three runs were chosen to illustrate cases in which the predicted concentrations were less than, about equal to, and greater than the measured concentrations. were drawn for the other tests. Similar curves

In general, the slopes for

all the calculated curves match the experimental data well. That result is to be expected because the curves for atmospheric stability parameters all have about the same slope for the distances of these tests. The Pasquill stability

classes were used for the calculations; the stability parameters were extrapolated to the shorter distances of the tests. The ratio of the calculated concentration, Cc, to the measured concentration, Cm, was calculated for each of the runs. The results are summarized in Table 3 . The aver-

age of all the ratios is 1.03 and the standard deviation is 0.54. The relatively large standard deviation is not sur-

prising because of the variation in atmospheric properties and the difficulty of obtaining accurate data for slow

evaporation rates and low propane concentrations.

1-11

The fact

10

1
A

CALCULATED MEASURED

0
0.1

0.01

10
DISTANCE FROM CENTER, FT

100

FIGURE

3.

COMPARISON O F AVERAGE PEASURED P.UD CALCULATED PROPANE CONCENTRATIONS, RUN 292-1.

1-12

--

CALCULATED MEASURED

I
1

*I
10

100

DISTANCE FROM CENTER, FT

FIGURE 4 .

COMPARISON O F AVERAGE NEASURED AND CALCULATED PROPANE CONCCMTW.TIOMS RUN 2 7 5 - 1 .

1-13

I I

I
n

CALCULATED MEASURED

0.1

0.01

I
10

100

DISTANCE FROM CENTER, FT

F I G U R E 5.

COMPARISON O F AVETXA(3-E flEASURED AND CALCULATED PROPANE CONCENTRATIONS,

RUN 297-1.
1-14

TABLE 3.

R A T I O OF P R E D I C T E D CONCENTRATION TO MEASURED C O N C E N T M T I O N

(a)

Run

Dist.

Dist c/m

.
JCm
1.05 0.85 0.92 1.56 0.35 0.44 0.43 0.45 0.61 3.54 1.49 1.53 0.89 0.75 0.59 0.93 1.66 1.45 0.72 1.17 0.87

Dist.

No.

ft

ft

ft

cccm

Dist. ft

Dist. c/m

ft

c , Cc

275-1 276-1 281-2 285-1 291-1 292-1 293-1 293-2 296-1 297-1
H

7.7 7.7 15.2 15.2 15.2 10.2 10.2 10.2 10.2 10.2 1 0 .2 10.2 10.2 10.2 10.2 30.2 30.2 30.2 80.2 60.2 40.2

1.00 0.52 1.07 1.18 0.49

0.49 0.61 0.63 0.67 1.62 1.12 1.20 0.86 0.75 0.60 1.10 1.70 0.86 0.67 0.93 0.80

12.7 12.7 25.2 25.2 25.2 15.2 15.2 15.2 15.2 15.2 15.2 15.2 15.2 15.2 15.2 50.2 50.2 50.2 100.2 100.2 60.2

17.7 17.7 35.2 35.2 35.2 25.2 25.2 25.2 25.2 25.2 25.2 25.2 25.2 25.2 25.2 90.2 70.2 70.2 140.2 140.2 80.2

1.00 0.75 0.63 1.58 0.33

0.35 0.46 0.50 0.95 2.18 1.28 1.04 1.32 0.77 0.49 1.44 1.81 1.50 0.86 1.62

22.7 22.7 55.. 2

--

1.00 1.00 0.63

--

55.2 35.2 35.2 35.2 35.2 35.2 35.2 35.2 35.2 35.2 35.2 130.2 90.2 90.2 180.2 180.2 100.2

0.31 0.38 0.46 0.52 1.08 2.80 1.57 1.08 1.07 0.68 0.52 1.60 1.90 1.52 1.12 1.88 1.07

12.7 12.7 25.2 55.2 25.2 55.2 55.2 55.2 55.2

1.00 0.73 0.92 1.67 0.46

0.29 0.60 0.55 0.93

--

--

P
VI

297-3 297-4 298-1 298-2 302-1 313-1 334-1 334-2 (b) 347-1 365-1 011-1

55.2 55.2 55.2 55.2 55.2 210.2 110.2 110.2 220.2

1.83 1.17 1.44 0.86 0.73 1.00 1.67 1.67 1.57

--

--

1.00

--

--

( a ) D i s t a n c e s a r e measured from pool c e n t e r .

(b)Following a p p l i c a t i o n of h i g h expansion. f o a m .

that over the average of 21 tests the predicted concentrations were close to the measured concentrations is a little surprising. Propane vapors are more dense than air,

particularly at the boiling temperature, and it was expected that concentrations would be higher than predicted from a model that assumed neutral buoyancy because the vapors would tend to layer and suppress dispersion. There would also be

a tendency for dense vapors to disperse laterally under the influence of gravity. Because of the limited number of

sensors available, it was not possible to monitor concentrations in enough locations to determine if lateral spread was occurring. However, it would require an unusual coin-

cidence for lateral spread to compensate for layering in so many tests. Also, the slope of the concentration versus

distance curves matches the predicted slopes, which would not be true if strong lateral spread occurred. Thus, for

these relatively small tests and low evaporation rates, a Gaussian model modified for area sources but assuming neutral buoyancy provides satisfactory estimates of vapor concentrations. Most of the propane pools were ignited as soon as the gas sensors could be removed from the plume. At the low

evaporation rates and moderate wind velocities present during the tests, there was little burning of the vapor plume beyond the edges of the pit. One exception to this general This test used the 40-ft

statement occurred in Test 365-1.

1-16

6Id
square pit. Propane was piped into the pit during the late Fuel afternoon of a day when the wind speed was quite low. unloading was quite slow because the excess flow valve on the storage tank would close periodically, requiring a waiting period for the pressure to equalize before flow could be restarted. Consequently, it was near sundown when About halfway through the

the dispersion test began.

dispersion test, the sensor nearest the pit (at 60 ft from pool center) increased its reading and then decreased sharply, indicating that it had been saturated with propane. (At concentrations above about 4 percent, the gas sensor output decreases as the concentration increases.) The wind

speed decreased near the end of the run to about half a mile per hour and the wind direction sensor stopped functioning because there was insufficient wind to turn it. By the time

the gas sensors had been removed from the test area and the
p o o l w a s ignited, a flammable l a y e r of vapor about a f o o t

thick extended from about a pool diameter upwind to 3 or 4 pool diameters downwind. The width of the flammable layer

was about 1 diameter in one crosswind direction and 2 diameters in the'other*crosswind direction. This flammable

layer formed relatively quickly and covered an area about 10 times the pool area, illustrating the layering effect that can occur if'wind speeds are low. The layering occurred

with a very low vaporization rate, and it can be expected that layering will occur in the immediate area for faster
1-17

vaporization rates at higher wind speeds.

These tests do

not show the relationship between wind speed and vaporization rate that would result in layering or other gravityinduced effects. They do show that any gravity-induced

effects are not important for the pool sizes and vaporization rates present during the tests unless the wind speed

is very low (less than about 3 mi/hr).

In tests using liquefied natural gas, it has been shown that applying high expansion foam to the pool will reduce the methane concentration downwind of the pool. similar test was run during the propane test series.
6 shows the result.

One Figure

The concentration of propane at 5 loca(The concen-

tions is shown for a period of 20 minutes.

trations are 30-sec averages taken from digital data records.) High expansion foam with an expansion ratio of

about 500:l was applied about 13 min after the start of the portion of the record shown. The propane concentration

downwind of the pool increased immediately in response to the foam. The increase was caused primarily by the

increased vaporization rate following foam application. Figure 7 shows the average concentrations for the five sensors. Concentrations following foam application were 2 The vapor-

to 3 times as high as before foam application.

ization rate more than doubled when foam was applied, indicating that increased vaporization is the most important factor in causing higher concentrations. The slope of the

1-18

I
I I I

I // /

1\u

+a
0 0

I 0
N

E+ h

1-19

1c

0 BEFORE FOAM
0
A F T E R FOAM

0
1

0
0

0
01 .

0.01

100

1000

DISTANCE FROM CENTER, FT

FIGURE 7 .

RESPONSE OF AVERAGE PROPANE CONCENTPATION TO A P P L I C A T I O N OF H I G H EXPANSION FONT.

I -.2 0

average concentration curve after foam application is slightly steeper than the curve before foam application. Calculations using dispersion models for line sources indicate that the reason may be that the propane vapor does not penetrate the foam uniformly, but tends to be released near the downwind edge of the pit. That result is to be

expected because foam was applied at the upwind edge of the pit and the foam layer was deeper at the upwind edge of the pit than at the downwind edge. The propane concentrations shown in Table 2 and compared to calculated concentrations in Table 3 are averages. The data were also surveyed to determine the peak Table 4 contains the

concentrations during the tests.

results, presented in the form of peak-to-average concentration ratios. The results show peak concentrations from

about 1.5 to 35 times as high as the average Concentrations. The lower peak-to-average ratios generally were found when wind velocities were higher than 10 to 15 mi/hr, even though the atmosphere was moderately unstable (Pasquill B) during some of the tests. The faster wind speed apparently

promotes more uniform mixing and less plume meandering. At slower wind speeds the phenomena are a little different. If the atmosphere is stable, a s in Run No.

365-1, the peak-to-average ratios are low even for low wind

speeds.

However, for unstable atmospheres, such as in Run The

No. 334-1, peak-to-average ratios are higher.

1-21

TABLE 4.

PEAK-TO-AVERAGE

CONCENTRATION RATIOS FOR PROPANE SPILLS (a)

Run No.

Dist. Ft

/Ca

P
2.6 1.8 3.0 4.2 1.8 1.8 1.7 1.9 2.0 3.3 2.5 2.3 3.6 5.3 1.7 1.9 7.8 3.3 1.5

Dist. Ft

/Ca

Dist. Ft

pica
6.6 4.1 5.4 4.8 2.0 2.2 2.2 1.9 2.7 6.5 3.1 3.4 12.4 7.5 3.0 3.0 9.9 1 . 11 2.6 1.6 3.4

Dist. Ft

/Ca

Dist. Ft

cP/Ca
4.7 2.2 4.2 6.0 1.9 2.6 2.8 2.2 3.9

275-1 276-1 281-2 285-1 291-1 292-1 293-1 293-2 296-1 297-1 297-3 297-4 298-1 298-2 302-1 313-1 334-1 334-2 (b) 34 7- 1 365-1 011-1

7.7 7.7 15.2 15.2 15.2 10.2 10.2 10.2 10.2 10.2 10.2 10.2 10.2 10.2 10.2 30.2 30.2 30.2 80.2 60.2 40.2

12.7 12.7 25.2 25.2 25.2 15.2 15.2 15.2 15.2 15.2 15.2 15.2 15.2 15.2 15.2 50.2 50.2 50.2 100.2 100.2 60.2

3.7 2.3 4.2 5.6 2.1 1.8 1.6 1.9 2.1 9.4 2.9 3.5 5.8 6.6 1.8 1.8 9.2 8.4 2.2 1.6 2.8

17.7 17.7 35.2 35.2 35.2 25.2 25.2 25.2 25.2 25.2 25.2 25.2 25.2 25.2 25.2 90.2 70.2 70.2 140.2 140.2 80.2

22.7 22.7 55.2

--

--

5.4 8.1 8,. 5 3.3

55.2 35.2 35.2 35.2 35.2 35.2 35.2 35.2 35.2 35.2 35.2 130.2 90.2 90.2 180.2 180.2 100.2

12.7 12.7 25.2 55.2 25.2 55.2 55.2 55.2 55.2

2.8 2.2 2.3 4.2 9.8 3.9 3.7 15.3 5.7 2.9 2.8 9.7 10.2 2.7 3.1 4.6

--

--

I
N N

55.2 55.2 55.2 55.2 55.2 210.2 110.2 110.2 220.2

4.2 5.2 35.0 8.6 3.0 3.3 7.3 9.9 2.2

--

2.3

---

---

( a ) D i s t a n c e s a r e m e a s u r e d f r o m pool c e n t e r . ( b ) F o l l o w i n g a p p l i c a t i o n of h i g h expansion foam.

difference is due primarily to the difference in the magnitude of wind direction changes when the atmosphere is unstable. In Run No. 298-1, the average wind direction did not correspond to the direction of the sensor array.
As

the

distance from pool to sensor increased, the sensors were further from the plume centerline and the plume drifted across them less frequently. The average propane concen-

tration measured during this test was therefore lower than would have been measured if the sensors had been on the centerline. In Run 298-1, the gas sensor 5 5 ft from the pit

read zero during most of the test, and the few times the plume reached the sensor the concentrations were relatively high, causing high peak-to-average concentration ratios. These high peak-to-average ratios can be expected whenever concentrations are measured near the extreme edges of the
p a t h of a m e a n d e r i n g p l u m e .

C ONC LUS I O N S

Propane vapor concentrations were measured along the plume centerline for more than 20 tests in which propane was evaporating at steady state from p o o l s up to 1600 ft2 in area. A simple Gaussian model modified to account for area

sources was found to be satisfactory for predicting the

w
/7

average concentrations using wind speed and vaporization rates taken during the tests. Atmospheric stability could
1-23

be estimated from the standard deviation of wind direction measurements. High expansion foam applied to the pool

surface increased the vaporization rate and thereby increased vapor concentrations downwind of the p o o l . REFERENCES

1.

Johnson, D. W., et a l . , "Control and Extinguishment of LPG Fires," Report No. DOE/EV-6020-1, U. S . Department of Energy, Washington, DC (August, 1980) Gifford, F. A . , Jr., in Slade, D. H., (ea.), Meteorology and Atomic Energy, TID-24190, U. S . Atomic Energy Commission (July, 1968).

2.

1-24

R E P O R T I1
R A D I A T I O N FROM LPG F I R E S
INTRODUCTION

D u r i n g t h e s t u d y o f LPG f i r e e x t i n g u i s h m e n t and c o n t r o l , a p p r o x i m a t e l y 1 0 0 t e s t s were r u n i n w h i c h p r o p a n e was s p i l l e d i n t o c o n c r e t e o r e a r t h e n p i t s and i g n i t e d . s t e a d y b u r n i n g r a t e s were r e a c h e d t h e f i r e s were e x t i n guished o r controlled (Johnson, e t a l . ,
1980)

When

Radiometers

were l o c a t e d n e a r t h e t e s t p i t s d u r i n g t h e f i r e s t o m e a s u r e
radiation fluxes. o m e t e r s were u s e d . Flame r a d i a t i o n t e s t s were r u n on p i t s 25, 1 0 0 , 4 0 0 , and 1600 f t 2 i n a r e a . G e n e r a l l y r a d i a t i o n f l u x e s were meaBoth n a r r o w a n g l e and w i d e a n g l e r a d i -

s u r e d from t h e c r o s s w i n d d i r e c t i o n ; r a n g e s o f r a d i a t i o n r e c o r d e d were f r o m l e s s t h a n 2 0 0 0 B t u / h r - f t 2
Btu/hr-ft
2

t o nearly 14,000

.
MEASUREMENT PROCEDURE

Two t y p e s o f r a d i o m e t e r s were u s e d d u r i n g t h e t e s t s . The w i d e a n g l e r a d i o m e t e r s were Gardon-gage w i t h a viewing a n g l e o f 150 d e g r e e s . type instruments

They were w a t e r c o o l e d

c o n t i n u o u s l y d u r i n g t h e t e s t s , and were a l l o w e d a l o n g p e r i o d o f s t a b i l i z a t i o n b e f o r e a t e s t began s o t h a t t h e c o o l i n g w a t e r was m a i n t a i n e d a t a c o n s t a n t t e m p e r a t u r e throughout a test. The w a t e r was n o t r e c i r c u l a t e d .

11-1

The wide angle radiometers were fixed at an elevation 5 ft above the top of the pit and were placed in a generally crosswind direction one and two pit widths from the edge of the pit. ment. Figure 1 shows the general arrange-

The radiometer sensors were vertical and sapphire

windows were used to protect the sensors from convective effects , The narrow angle radiometer was placed one pit width from the edge of the pit 1.5 ft above the pit edge, It was

aimed across the downwind edge of the pit at a n upward a n g l e of about 15 degrees to ensure that the entire viewing cone was filled with flame surface. In one 1600-ft2 test a

second narrow angle radiometer was located approximately 15 ft above the pit edge at a distance of about 175 ft from the pit. The viewing circle at that distance was less than 25

ft in diameter so that the entire viewing cone was filled with flame surface. (The same narrow angle radiometer was

used for most of the tests to aid in determining fire control or extinguishment time, but the flames were not large enough to fill the entire viewing angle.) The narrow

angle radiometers used calcium fluoride windows to protect the sensing element. The view restrictors were purged to

prevent fogging of the window by dirt or fire fighting agents and cooled with water to provide stable view restrictor temperatures.

11-2

5 FT

-\

WDWIDE ANGLE

NARROW ANGLE

+r:7

1
1.5 FT

FIGURE 1.

LOCA.TION OF RADIOP.IETERS NEAR TEST P I T .

A l l radiometers were insulated and wrapped with foil

to reduce the heat input to the radiometer body.

All

electrical leads and water lines were either insulated and wrapped with foil or buried to protect them. The radiometer

outputs were recorded in digital form on magnetic tape for all runs. During some runs, analog recordings were also Figure 2 shows an example

made on a strip chart recorder. of the analog data.

RESULTS
As shown by the radiation flux recording in Figure

2,

the radiant energy incident at some point near a propane Both short term and

fire varies during the fire's duration. long term variations occur.

Short term variations are due

primarily to fluctuations in flame size and shape caused by turbulence within the flame. Some of the short term vari-

ations are too rapid to be detected by the radiometers; they are generally unimportant in practical heat transfer considerations because responses faster than a few seconds are seldom important. Short term fluctuations may have some
. ,

important effects if rapid spectral flux measurements are made. In such measurements, misleading results may be

inferred if the changes in both spectral and integrated fluxes due to flame turbulence are not properly accounted for. Long term variations in radiant flux occur a s the flame increases in size immediately after ignition and as
11-4

5000

3:

d:

3 E

FIGURE 2.

EXAMPLE O F R A D I O M E T E R R E A D I N G S FROM LPG F I R E S .

11-5

t h e flame s i z e d e c r e a s e s during burnout

(or f i r e control).

V a r i a t i o n s may a l s o o c c u r d u r i n g b u r n o u t a s t h e f u e l composition changes. In outdoor tests such a s these, t h e

wind c a u s e s c h a n g e s i n r a d i a n t f l u x i n c i d e n t a t a p o i n t b e c a u s e t h e f l a m e i s blown i n d i f f e r e n t d i r e c t i o n s b y t h e wind.

T h e f l a m e i s t i l t e d f r o m v e r t i c a l a s t h e wind s p e e d

i n c r e a s e s , and t h e f l a m e i s r o t a t e d a r o u n d i t s b a s e a s t h e wind d i r e c t i o n c h a n g e s . Both t h e t i l t i n g and t h e r o t a t i o n

change t h e flame o r i e n t a t i o n with r e s p e c t t o a radiometer,

so t h a t incident f l u x readings vary.

Narrow a n g l e f l u x measurements show s h o r t term v a r i a t i o n s i n r a d i a n t f l u x c a u s e d by some o f t h e same f a c t o r s r e s p o n s i b l e f o r s h o r t term v a r i a t i o n s i n r a d i a n t

f l u x i n c i d e n t on a p o i n t n e a r t h e f i r e .

T h e l o n g term

v a r i a t i o n s f o r n a r r o w a n g l e r a d i o m e t e r s a r e more n o t i c e a b l e f o r small f i r e s than f o r l a r g e f i r e s because t h e v a r i a t i o n s i n f l a m e t i l t and d i r e c t i o n c a u s e t h e p a t h l e n g t h t h r o u g h

t h e flame t o change.
As t h e f i r e s become o p t i c a l l y t h i c k ,

t h e v a r i a t i o n s c a u s e d by p a t h l e n g t h c h a n g e s become unim-

p o r t a n t , s o t h a t t h e c h a n g e s i n l o n g term f l u x r e a d i n g s by n a r r o w a n g l e r a d i o m e t e r s a r e d u e more t o c h a n g e s i n f u e l composition o r viewing p o s i t i o n i n t h e flame than t o changes

i n path l e n g t h due t o changes i n flame d i r e c t i o n .
The r a d i a t i o n f l u x e s c o n s i d e r e d most i m p o r t a n t f o r

a s s e s s i n g p o t e n t i a l f i r e damage a r e t h o s e a s s o c i a t e d w i t h t h e steady s t a t e portion of t h e f i r e .

11-6

The r a d i a t i o n f l u x e s

. . .-

. . . .. . . .

- . .- -. .

- . .. .

. . .-

- . .... . - . .. .-

d i s c u s s e d i n t h i s r e p o r t were a l l m e a s u r e d d u r i n g t h e s t e a d y s t a t e burning period.

T h e d u r a t i o n o f t h e m e a s u r e m e n t was

u s u a l l y a b o u t h a l f a m i n u t e , a l t h o u g h some m e a s u r e m e n t s were made f o r p e r i o d s o f 1 0 m i n u t e s o r l o n g e r . The s h o r t mea-

s u r e m e n t p e r i o d was a r e s u l t o f t h e d e s i r e t o c o n s e r v e f u e l and t h e f a c t t h a t t h e p r i m a r y g o a l o f t h e t e s t s was t o determine f i r e suppression parameters.

T h e few l o n g e r d u r a -

t i o n t e s t s were r u n t o p r o v i d e a s s u r a n c e t h a t no e r r o n e o u s i n t e r p r e t a t i o n o f t h e r e s u l t s would o c c u r .
The l o n g e r d u r a -

t i o n d a t a showed no p h e n o m e n o l o g i c a l d i f f e r e n c e s f r o m t h e d a t a o f s h o r t e r d u r a t i o n tests. Because t h e r a d i a t i o n

f l u x e s were m e a s u r e d d u r i n g t h e s t e a d y b u r n i n g p o r t i o n o f
t h e t e s t s , no d a t a o n f l u x c h a n g e s d u r i n g b u r n o u t were

recorded. T a b l e 1 c o n t a i n s a summary o f t h e r a d i a t i o n f l u x measurements.

T h e p i t d i m e n s i o n s shown i n T a b l e 1 a r e t h e

nominal dimension.

A c t u a l p i t w i d t h s were 5 i n c h e s g r e a t e r
A l l p i t s were s q u a r e .

t h a n t h e nominal width.

The p i t s

were 2 f t d e e p and t h e f u e l d e p t h was u s u a l l y 3 t o 6 i n c h e s .

A l l t e s t s were r u n o u t d o o r s u n d e r a m b i e n t wind c o n d i t i o n s .

T h e wind s p e e d and d i r e c t i o n shown i n t h e t a b l e were mea-

sured a t a location near the instrument building.

The s h o r t

term f l u c t u a t i o n s i n wind d i r e c t i o n a n d s p e e d may b e

d i f f e r e n t a t t h e t e s t a r e a , b u t t h e a v e r a g e s , a s shown i n T a b l e I, a r e n o t e x p e c t e d t o b e s u b s t a n t i a l l y d i f f e r e n t .
11-7

TABLE 1.

SUMMARY OF RADIOMETER DATA

Run
No.

Plt Width Ft

Speed Mh p

Wind Direction Degrees

R a d i a n t F l u x Measured Narrow Angle Front Rear 2 B t u / h r - t

Radiant Flux Calculated Front Rear Btu/hr- t

Ratio ,
Front

% ' %
Rear

248-1 248-2 261-1 261-2 268-1A 268-1B 268-2 268-3 268-4

H
H

5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 10 10 10 10

7.8 4.3 7.4 7.4 10.1 7.8 9.0 7.2 8.3 18.3 14.8 6.1 7.7 12.5 20.6 20.6 19.7 6.5 12.1 12.4 10.1

1 93 1 91 51 344

32,700 33,600

5 I 310 7,980
6 ,100 4,610

2,630 4 I 030 4 ,710 2,830 3,770 3,530 3,770 3,420 4,590 3,180 2 ,940. 3,890 4 ,1 2 0
2 ,570

4,287 4,667 6,822 4,083 4,854 5 ,205 6,314 5,305 5,217 4,422 4,553 5,048 5,275 4,215 3,874 3,831 3 ,8 7 4 9,674 6,517 6 ,5 6 1 6,232

2 I 260 2,449 4,593 2,207 2,969 3,428 4,484 3,415 3,805 2,805 2,653 2,825 3,575 2,226
2,216 2,218 2 ,2'16

0.807 0.585 1.118 0.886 0.814 0.817 1.059 0.932

0.859 0.608 0.975 0.780 0.788 0.971 1.189 0.999 0.829 0.882 0.902 0.726 0.868 0.866 1.045 1.253 1.108 1.202 0.875 1.024 0.936

---

-----

161 150 128 152 139 154 168 171 146 193 355 358 355 154 216 2 18 227

---

----18,100
2 6 ,900 27 ,500 27,800 29 ,200

5 ,960 6,370 5,960 5,690

---

---

co

270-2A 270-2B 270-3B 2 70- 3C 275-2

2 76- 1 B 276-2 2 76- 3 A

4,740 4 ,880 6,500 7,050 5,290 3,930 3,520 3,520 7,690 6 ,870 6 ,040 6,320

0.933 0.933 0.777 0.748 0.797 0.986 1.088 1.101 1.258 0.949 1.085 0.986

---

------25 ,1 0 0 39,800 42,000 42,600

2,120 1,770 2 ,000 4,170 3 ,100 2,620 2,620

281-3 283-2 283-3 283-4

5,013 2,711 2,682 2,452

TABLE 1 .

SUMMARY OF RADIOMETER DATA--Continued

Run
NO

Pit Width Ft

Speed blph

Wind Direction Degrees

R a d i a n t Flux Measured Narrow Angle Front Rear 2 Btu/hr- f t

R a d i a n t Flux Calculated Front Rear Btu/hr-ft2

Ratio, q

/%
Rear

Front

283-5 283-6 283-7 284-3 284-4 284-5 284-6 289-2 289-3 289-4 289-5 291-2 291-3 291-4 291-5 291-6 296-2A 296-2B 298-4 298-5 298-6 299-2 319-1 319-2

10 10 10

13.6 12.6 14.2 9.1 8.2 7.8 9.9 4.0

.86 , .

220 222 222 358 345 343 314 5 6 126 117 123 178 174 176 163 176
233 204

40,100 42,100 41,700

5,630 6,590 6,180 7,700 7,560 7,280 7,280

3 ,690 3,450 3,330 3,100

6,624 6,544 6,710 7,567 7,032 6,963 6,229 13,333 15,772 7,686 7,899 7,832

2 ,658 2 I 599 2,642

1.177 0.993 1.086 0.983 0.930 0.956 0.856

1.176 0.949 1.057 0.995 0.952 0.971 0.797

10 10 10 10
10 10 10 10

3,672 3,284 3,232 2,470

H H
\o

7.1 7.8 12;6 12.2 11.3 20.4 17.3 4.4 4.6 8.5 8.7 3.5 14.4 15.6 6.7

34I 000 27 ,200 28,000 30,600

32 ,900 35,900 3 ,500 9 37,000 36,700

--6,790 7,360

--7,203 8,160 3,762 3 ,912 3 ,860

--1.170 1.135

--I 061 . 1.109

---

---

---

10 10 10 10 10 10 10
10 10 10
10
10 10

7,270 7,170 6,930

---

---

6,430 6,320 6,990 6,460 6,320 7,980 6,350 6,180 6,460 2,380 2,960
3 ,010 2,970 3,800

---

1.057 1.102 1.130

---

7,604 5,985 6,889 6,323 7,141 9,059 6,946 6,884 5,491

3,690

1.183 0.947 0.986 0.979 1.130 1.135 1.094 1.114 0.850 1.096 1.069 0.902 1.134 1.167 1.193 1.006 0.690

44,900

---

2,608 3,164
2 I 716 3,367 4,436
3 ,125

215 192 167

34,700 35,000 33,300 30,500

200 230 257

2,620 6,730" 10,400"

6,773 7,181

TABLE 1 .

S M A Y OF RADIOMETER DATA--Continued U MR

No.

Run

Pit Width Ft

Speed MPh

Wind Direction Degrees

Radiant F l u x Measured Narrow Angle Front , Rear

Btu/hr-ftL

Radiant Flux Calculated Rear Front Btu/hr-tL

Ratio, q
Front

/%
Rear

320-1 323-1

10 10 10 10 10 10

10.1 8.7
7** 7** 7** 7**

211 154 14 8 308 315 160 195 174 169 167 160 135 158 163 162 53 59 55

26 ,100 20 ,700

7,420 8,100
9 ,060 7 ,970 6,730 7,280

7 ,550" 5,630* 5 ,710 4,520 3,450 3,690 3,280 5 ,280 3,280 3,520 3,170 3 ,400 3,060 3 ,1 7 0 3,870 3,280 2 ,580 4,502 2,510

6,517 9,407 8 ,598 8,236 5,870 6 ,0 1 8 8 ,6 4 8 7,077 8,610 8,333 8,337 8,150 6,804 7,873 8 ,612 8,432 6,442 8 ,7 8 4 5,990

6,181 5,872 4 ,336 4,096 2 ,375 2,515 4 ,470 3 ,2 5 1 4,043 3,900 3 ,805 3,844 3 ,0 3 6 3,685 4 ,099 4,005 2,803 4,195 2,682

0.878 1.161 0.949 1.033 0.872 0.827 1.228 0.683 1.299 1.117 1.257 1.100 1.011 1.025 1.162 1.227 11 1 . 1 1.040 1.081

0.819 1.043 0.759 0.906 0.688 0.682 1.363 0.616 1.233 1.108 1.200 1.131 0.992 1.162 1.059 1.221 1.086 6.932 1.069

360-1 360-2 360-3 360-4 330-1 337-1

H . H

-------

---

20 20
20 20 20

14.3 15.5 20.5 12.5 21.8 5** 6** 6** 3.5** 4** 6.5 0.8 7.8

30,100

7,040
10 ,360

--28 ,700 26,300 27,900 35 ,600 36 ,400 35 ,100 33 ,600 34,100 29 ,200

344-1 344-2 344-3 353-1 353-2

6,630 7 ,460 6,630 7,410 6 ,730 7,680 7 ,410 6,870 5,800 8,450 5,540

20 20 20 20 20 20 40 40

. 355-1
355-2A 355-2B 002-1 365-2 011-2

49 ,600

---

" R a d i o m e t e r i n g e n e r a l l y downwind d i r e c t i o n f r o m f i r e . **Wind v e l o c i t y estimated from a i r p o r t weather data.

I n a f e w t e s t s , r a d i o m e t e r r e a d i n g s were n o t obt a i n e d f o r o n e o r more r a d i o m e t e r s .

I n t h e case of t h e

n a r r o w a n g l e r a d i o m e t e r s , d a t a were s o m e t i m e s t a k e n w i t h t h e r a d i o m e t e r l o c a t e d , i n a p o s i t i o n where t h e v i e w i n g a n g l e
i n c l u d e d background a s w e l l a s t h e flame.

T h e s e d a t a were

n o t i n c l u d e d i n T a b l e 1.

The r e a r r a d i o m e t e r was moved t o a The p u r p o s e However,

l o c a t i o n downwind o f t h e f i r e f o r a few t e s t s .

was t o c h e c k f i r e c o n t r o l f l u x e s a t t h a t l o c a t i o n .

s u c h d a t a p r o v e d n o t t o b e u s e f u l , s o t h e r a d i o m e t e r was

moved b a c k t o i t s p o s i t i o n 2 p i t w i d t h s f r o m t h e c r o s s w i n d
s i d e of t h e p i t .

B e c a u s e o f v a r i a t i o n i n wind d i r e c t i o n , t h e " c r o s s w i n d " a n d "downwind" s i d e s o f t h e p i t a r e n o t e x a c t l y

9 0 d e g r e e s o r 1 8 0 d e g r e e s from t h e wind d i r e c t i o n .

The

r a d i o m e t e r s were p l a c e d a t a s i d e o f t h e p i t t h a t would u s u a l l y be c r o s s w i n d , i . e . , t h e y would v i e w t h e f l a m e a t a Once p o s i -

d i r e c t i o n 9 0 d e g r e e s f r o m t h e wind d i r e c t i o n .

t i o n e d , t h e w i d e a n g l e r a d i o m e t e r s were not moved u n t i l

t e s t s were r u n on a d i f f e r e n t p i t .

The n a r r o w a n g l e r a d i for nearly every

o m e t e r s had t o b e r e p o s i t i o n e d a n d re-aimed

f i r e b e c a u s e o f c h a n g e s i n flame t i l t a n d f l a m e d i r e c t i o n .
I t was d i f f i c u l t t o p r o v i d e p r o p e r a i m i n g o f t h e n a r r o w

a n g l e r a d i o m e t e r because t h e p o s i t i o n c o u l d n o t be c h a n g e d o n c e t h e f i r e was s t a r t e d . .Therefore, narrow angle

r a d i o m e t e r d a t a a r e l e s s r e l i a b l e t h a n wide a n g l e r a d i o m e t e r data.
11-11

SIMPLIFIED FLAME RADIATION THEORY The data in Table 1 can be used to develop a method for predicting radiation fluxes from propane fires. The

goal is to provide a relatively simple technique that will provide acceptable accuracy for engineering design purposes. A turbulent flame burning propane is a reasonably complex system. The fuel vaporizes at a liquid pool surface Wind and buoy-

and begins to mix with the surrounding air.

ancy forces cause the flame to be turbulent, s o that fuel and air are mixed throughout the flame volume. Combustion,

w h i c h involves the breakdown of the fuel molecule and its

reaction with o x y g e n from the air, may occur at any point in the flame column, although it does not occur at all points in the column simultaneously. The actual combustion zones

are not very thick because the final mixing-combustion process takes place at the molecular level. (If mixing is

complete before combustion, the resulting premixed flame has none of the red color characteristic of diffusion flames.) The combustion zones are probably less than a few centimeters thick, but there are many of them, s o to the naked eye, and to most instruments, the flame appears to be continuous. In reality, for any given path through the flame,

there are many constantly changing locations where combustion occurs.

As

combustion occurs, energy is radiated from the hot gases and hot carbon

flame from two types of sources: particles.

The primary emission from hot gases is from

11-12

water and carbon dioxide.

Emission from these two gases The bands are strongest at microns. Radiation at The

occurs in fairly broad bands.

wavelengths of 2.7 microns and 4.3

these two wavelengths is invisible to the naked eye. characteristic red-orange flame color originates from

radiation emitted by hot carbon particles that are formed as the fuel molecules lose their hydrogen. Radiation from the

hot carbon particles resembles the radiation from solid surface; it is distributed more or less along a continuum. Because the flame emits (and absorbs) radiant energy throughout its volume, it is not strictly a surface emitter. Techniques were developed in the 1960's to describe the radiation process in flames based on the use of volume emission and absorption coefficients (Love, 1968; Shahrokhi,
1965; Pfenning, 1970).

More recently similar methods that

rely on use of flame temperatures have been considered (Markstein, 1974). Both methods require relatively sophis-

ticated techniques for obtaining data that enables them to be used for predictive pu'rposes. Either can be sufficiently

simplified to enable relatively easy predictions of radiant fluxes to a flame's surroundings. Starting with the assumption~thatthe flame can be considered as a continuous absorbing, emitting medium, the radiant intensity at any point in the flame can be described by the basic transport equation
@

11-13

where

IA(X)

=
=

monochromatic radiant intensity at point x distance within flame

J A = monochromatic volumetric emission

coefficient

6,

monochromatic extinction coefficient

Equation 1 assumes isotropic emission within the flame and extinction proportional to local intensity.
J,

includes

both the continuum radiation f r o m hot c a r b o n particles and

the band radiation from emitting gases. absorption and scattering.

B,

includes

Application of Equation 1 to determine radiant fluxes from a fire requires knowledge of the emission and absorption coefficients. cannot be easily obtained. Such data are not available and Simplifications can be made that Assume

make predictions possible with more limited data.

that Equation 1 is to be applied to a flame having a hemispherical shape and that the radiant intensity is to be measured at the center of the flame. The monochromatic

radiant flux at the center of the flame can be found by integrating Equation 1. Then

11-14

lu

where R is the radius of the hemisphere and integration covers the entire hemispheric volume.
TJA

The result is

qh

- Bh

(1 -

(3)

The total radiant flux may be found by integrating Equation

3 over all wavelengths where there is significant emission,

Radiant emission from flames of other shapes to objects outside the flame can be found from equations similar to Equation 4 . Assume that the form of Equation 4

can be used to describe the radiant energy emitted at a flame surface, and assume that the flame can then be considered
as

a surface emitter.

T h e s u r f a c e f l u x can t h e n

be written as

where

qs = flux emitted from flame surface

qsm = maximum surface flux for an optically thick flame b

=

flame extinction coefficient

D = distance through the flame

11-15

The t e r m qsm i s r e l a t e d t o t h e i n t e g r a t e d a v e r a g e o f J A / B X a n d b is r e l a t e d t o t h e i n t e g r a t e d a v e r a g e o f B A ' The

d i s t a n c e t h r o u g h t h e f l a m e i s m o s t c o n v e n i e n t l y t a k e n t o be
t h e distance across the f u e l source.

I n t h e c a s e of a pool

f i r e , t h a t d i s t a n c e is t h e d i a m e t e r o f a c i r c u l a r p o o l o r t h e l e n g t h of t h e s i d e of a r e c t a n g u l a r p o o l .
T h e r a d i a n t f l u x i n c i d e n t a t some p o i n t o u t s i d e a

f l a m e c a n be c a l c u l a t e d a s

where F i s a g e o m e t r i c v i e w f a c t o r t h a t c a n be c a l c u l a t e d a s

where

dA1 = t a r g e t a r e a , t a k e n a s a d i f f e r e n t i a l e l e m e n t
A2 = e m i t t i n g a r e a of

flame

r = d i s t a n c e from t a r g e t e l e m e n t t o flame a l o n g
a l i n e f r o m dA1 t o dA2

a,

= a n g l e b e t w e e n n o r m a l t o dA1

and t h e l i n e

from dA1 t o d A Z

0, = a n g l e b e t w e e n n o r m a l t o dA2 and t h e l i n e
f r o m dA1 t o dA2 F i g u r e 3 shows t h e g e o m e t r y f o r a f l a m e w i t h a c i r c u l a r base. E q u a t i o n 7 m u s t be i n t e g r a t e d o v e r t h e e n t i r e

e m i t t i n g a r e a o f t h e f l a m e t h a t c a n be s e e n by t h e t a r g e t

11-16

FLAME

FIGURE 3.

GEOIIETFtY USED FOR 'CALCULATION OF VIEW FACTORS.

11-17

element dA1.

The view factor depends only on the geometry Values of view factors for some

of the flame-target system.

target-flame systems are available in the literature (Rein, et al., 1970; Howell and Siegel, 1969; Raj, 1977, for example). Generalized computer solutions can be written to Flame size,

obtain view factors not otherwise available.

shape, and orientation with respect to the target must be known in order to calculate the view factors. The flame height can be estimated from the correlation of Thomas (1963):

where

L = flame height
D = pool diameter m
=

burning rate

pa = air density
g = gravitational acceleration

The p o o l diameter is the width for square pools and the equivalent diameter
4 (pool area) Deq = pool perimeter

can be used for other rectangles. The flame will be tilted by the wind, changing the flame target geometry. The flame angle can be estimated

from Welker and Sliepcevich (1970) :

11-18

tan 4 cos

'

3.2

("iaPa)

0.07

($)

0.7

(z)

-0.6

where

@ = flame angle measured from vertical

D = flame diameter
a '
=

ambient air density

1-1 = ambient air viscosity

u = wind speed g = gravitational acceleration

P

fuel vapor density

The units to be used in the foregoing equations can be any consistent system. The emission coefficient has

units of energy/time-area-unit

of solid angle-unit of

wavelength, for example, and fluxes have units of energy/area-time.

length-'.

The extinction coefficients have units of

Equations 9 and 10 h a v e empirical coefficients,

and are written in dimensionless form so that any consistent set of units may be used. Some of the radiant energy emitted by a fire is absorbed by the atmosp'here. wavebands centered near 1.9, Absorption is strongest in 2.7, and 4.3 microns. These

bands are due to absorption by water vapor and carbon dioxide in the atmosphere. Flames also emit radiation at

these wavelengths, but the emission bands are wider than the absorption bands, so not all of the radiation emitted by a
11-19

flame in the emission bands is absorbed by the atmosphere. If an absorption band is particularly strong, hall the radiation absorbed by that band will be absorbed fairly near the flame. ,absorbers The 2.7-micron and 4.3-micron bands are strong

.
DISCUSSION OF RESULTS

Table 1 lists the radiation fluxes measured by narrow angle radiometers for fires in square pits from 5 to
4 0 ft wide.

The radiometers were usually placed so that

they viewed the flame across the downwind edge of the pit. Radiometer location was critical because if the fire was tilted too far by the wind or if the wind direction changed, the radiometer viewing cone might not be filled with flame and the radiometer readings would be erratic and inconsistent. The windows on the narrow angle radiometers were made of calcium fluoride, which has a nearly flat transmission curve from about 2 microns to about 8 microns, and transmission from 1 micron to 2 microns averages about 80 percent.
A l l the strong radiation from hydrocarbon fires is

contained within the band from 1 micron to 8 microns.

The

narrow angle radiometers were calibrated at the factory using a blackbody source. Calibration was checked using a

blackbody following the tests, and the calibration was identical. Calibration was performed on the basis of the
11-20

crs
i n c i d e n t r a d i a n t f l u x , s o t h a t no c o r r e c t i o n s were r e q u i r e d because of t h e small flraction of energy r e f l e c t e d o r a b s o r b e d by t h e window. The f l a t t r a n s m i s s i o n c u r v e o b v i a t e d a need t o c o r r e c t f o r t r a n s m i s s i o n a t v a r i o u s wavelengths, and because a l l t h e incident r a d i a t i o n s t r u c k t h e window a t n e a r l y r i g h t a n g l e s , no c o r r e c t i o n f o r r e f l e c t i o n f o r g r a z i n g r a d i a t i o n was n e c e s s a r y .
T h e n a r r o w a n g l e r a d i o m e t e r d a t a were u s e d t o d e t e r -

mine v a l u e s o f qsm f o r u s e i n p r e d i c t i n g r a d i a n t f l u x e s . The p r o c e d u r e f o l l o w e d was t o a v e r a g e t h e m e a s u r e d n a r r o w angle r a d i a n t f l u x e s f o r a period of h a l f a minute t o s e v e r a l minutes. The v a l u e s t h u s o b t a i n e d were u s e d t o

determine the c o e f f i c i e n t s q

and b i n E q u a t i o n 5. The sm a v e r a g e d n a r r o w a n g l e r a d i a n t f l u x e s v a r i e d from r u n t o r u n ,

The s o l i d l i n e i n F i g u r e 4 i s c a l -

a s shown i n F i g u r e 4 .

c u l a t e d f r o m E q u a t i o n 5 w i t h qsm o f 5 0 , 0 0 0 B t u / h r - f t 2
= 0.126 f t - l .

and b

The m e a s u r e d n a r r o w a n g l e f l u x e s shown i n F i g u r e 4 v a r y s u b s t a n t i a l l y from t h e l i n e drawn t o r e p r e s e n t t h e d a t a , a n d some e x p l a n a t i o n i s - r e q u i r e d .

First, the data

p o i n t s a r e shown p l o t t e d ' a s a f u n c t i o n .of f l a m e d i a m e t e r .

T h e r e were a c t u a l f i r e s from* p o o l s n o m i n a l l y 5,

1 0 , 20, and

40 f e e t wide.

However, t h e -wind d i r e c t i o n was f r e q u e n t l y

n o t p e r p e n d i c u l a r t o t h e r a d i o m e t e r , , s o t h a t t h e flame w a s blown i n a d i r e c t i o n t h a t i n c r e a s e d t h e v i e w i n g p a t h l e n g t h . The p a t h l e n g t h s were c o r r e c t e d f o r t h e w i n d d i r e c t i o n

11-21

NOMINAL FIRE S I Z E

FLAME DIAMETER, FT

FIGURE 4 .

SURFACE RADIANT FLUXES FOR PROFANE F I R E S .

69

e f f e c t , and t h e r e s u l t i s t h e " d i a m e t e r " p l o t t e d i n

F i g u r e 4. Some o f t h e n a r r o w a n g l e r a d i o m e t e r f l u x e s a r e w e l l below t h e l i n e . These a r e most l i k e l y t e s t s where t h e f u l l

r a d i o m e t e r v i e w i n g c o n e was n o t c o m p l e t e l y f i l l e d by t h e flame. The l i n e was drawn w i t h a b i a s t o w a r d t h e h i g h e r

f l u x e s b e c a u s e t h e y were j u d g e d t o be more r e l i a b l e . Narrow a n g l e r a d i o m e t e r d a t a were o b t a i n e d f o r o n l y one of t h e 40-ft

tests.

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

t h e p i t , and a s e c o n d n a r r o w a n g l e r a d i o m e t e r a b o u t 1 7 5 f t away f r o m t h e f i r e g a v e e s s e n t i a l l y t h e same r e a d i n g s . The

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

less than 2 percent.

The n a r r o w a n g l e r a d i o m e t e r f l u x e s were n o t c o r r e c t e d f o r a t m o s p h e r i c a b s o r p t i o n f o r two r e a s o n s .
First,

no m e a s u r e m e n t s were made o f t h e s p e c t r a l e n e r g y d i s t r i bution. Second, t h e r e s u l t s from t h e 4 0 - f t

test indicate

t h a t a b s o r p t i o n is r e l a t i v e l y weak beyond t h e a r e a i m m e d i a t e l y surrounding t h e f i r e . Standard methods o f calcu-

l a t i n g t h e a t m o s p h e r i c t r a n s m i s s i v i t y a r e b a s e d on b l a c k b o d y r a d i a t o r s , and b e c a u s e t h e flame is n o t a b l a c k b o d y r a d i a t o r , t h e a b s o r p t i o n may be l e s s t h a n p r e d i c t e d , p a r t i c u l a r l y a t l o n g e r d i s t a n c e s f r o m t h e f i r e , b e c a u s e b o t h water v a p o r and c a r b o n d i o x i d e a r e r e l a t i v e l y s t r o n g a b s o r b e r s i n t h e i r a b s o r p t i o n wavebands.

11-23

The n a r r o w

g l e radiometer data represent t h e efAs s u c h , qsm i s

f e c t i v e s u r f a c e r a d i a n t f l u x from t h e f i r e .

a n i n t e g r a t e d a v e r a g e o f t h e r a d i a n t f l u x e s from a number o f r e a c t i n g zones w i t h i n t h e flame.

T h e f l u x may v a r y w i t h

b o t h t i m e and p o s i t i o n i n t h e f l a m e .

Within t h e response

c a p a b i l i t y of t h e radiometers, t h e t i m e v a r i a t i o n i n f l u x f o r t h e 4 0 f t f i r e s was l e s s t h a n 5 p e r c e n t o f t h e a v e r a g e . When t h e f u l l v i e w i n g c o n e o f t h e r a d i o m e t e r was v i e w i n g t h e

f i r e , f l u c t u a t i o n s i n r a d i a n t f l u x f r o m t h e 10- a n d 2 0 - f t
f i r e s were u s u a l l y l e s s t h a n 1 0 p e r c e n t .

F l u c t u a t i o n s from

the 5-ft

f i r e s were a l i t t l e l a r g e r .

No l o n g term c h a n g e s

i n n a r r o w a n g l e r a d i o m e t e r r e a d i n g s were n o t e d i n t h e f e w
f i r e s t h a t were m o n i t o r e d t h r o u g h b u r n o u t .
However, t h e

p r o p a n e b u r n e d was n e a r l y 98 p e r c e n t p u r e , s o no c h a n g e s d u e t o f u e l c o m p o s i t i o n would h a v e been e x p e c t e d .

The s m a l l

d i f f e r e n c e between radiometer r e a d i n g f o r narrow a n g l e r a d i o m e t e r s 4 0 f t and 1 7 5 f t from t h e f i r e i n d i c a t e s t h a t t h e r e

a r e no s t r o n g v a r i a t i o n s i n r a d i a n t o u t p u t i n t h e p o r t i o n s
o f t h e f l a m e w h e r e t h e f l a m e i s n o t b r o k e n up. Table 1 a l s o lists t h e r e s u l t s of wide angle r a d i o m e t e r measurements f o r propane f i r e s .
The wide a n g l e

r a d i o m e t e r s were u s u a l l y p o s i t i o n e d o n e and two p i t diam-

e t e r s from t h e e d g e o f t h e p i t .

T h e l o c a t i o n was c h o s e n t o

be i n t h e d i r e c t i o n crosswind t o t h e p r e v a i l i n g wind, b u t o n c e t h e r a d i o m e t e r s were p o s i t i o n e d , t h e y were n o t moved d u r i n g t h e t e s t s on a p i t o f g i v e n s i z e .

11-24

A v e r a g e wind

direction varied during the tests, so the flame may have been blown toward or away from the radiometers during a test. Table 1 lists both wind speed and wind direction

averaged over the same period that the radiometer readings were averaged. These are not necessarily the same averages

as those measured for the full duration of the test (from ignition to extinguishment)

.
Cor-

The wide angle radiometers used sapphire windows to protect the sensing element from convective effects.

rections to the measured data were required to obtain the actual incident flux at the radiometer location. The trans-

missivity of the windows is best from about 1 micron to 4 microns. At wavelengths less than 1 micron and greater than Factory calibrations of

4 microns, transmission decreases.

the wide angle radiometers was done using a group of tungsten filament lamps with quartz tubes surrounding the filament.
The quartz tubes d o not transmit beyond about 5

nicrons and transmission for quartz begins to decrease sharply at about 3.5 microns. Calibration checks were per-

formed on each wide*angle radiometer using a blackbody source. window. Checks were made both with and without the sapphire With the window removed, the blackbody calibration However, with the window At a given

matched the factory calibration.

in place, a consist.ent difference was found.

63

radiometer output, the actual incident flux based on blackbody radiation, was about 20 percent greater than the flux
11-25

indicated by the factory calibration curves.

Because the

flame radiation is not blackbody radiation, additional corrections were required. The windows were removed from the wide angle radiometers and the transmittance measured for radiation incident at several angles. Figure 5 shows the result. Mea-

surement at wavelengths less than those shown by the solid lines were not possible with the equipment available, but manufacturers data indicate that the transmittance remains about constant at wavelengths down to 1 micron. The average

transmittance of the windows for flame radiation was calculated from

where

average transmittance for wavelengths between X1 and X 2

= A = transmittance at wavelength A = emissive power of flame at wavelength X

Spectral emission data were not available for propane, s o data for large estimate 7.
LNG

fires (Raj, et al., 1979) were used to

LNG

The error introduced by using

emission data

instead of propane data is not expected to be large because the major emission bands are found at about the same wavelengths. The emission measurements for
LNG

were made

from a distance of 775 ft, so there was little radiation

11-26

1.0

-- - - - - - - - -

---------

I
I N C I D E N T ANGLE

0.8

0.6 '

0.4

-- - - - - - - - 1
S A P P H I R E WINDOW

0.2'

I 3

WAVELENGTH, MICRONS

F I G U R E 5.

SPECTRAL TPANSMITTANCE O F S A P P H I R E RADIOMETER WINDOW.

detected at the wavelengths where atmospheric absorption is strong. Sapphire transmittances are high and relatively

constant at those wavelengths where atmospheric absorption is strong, so the effect on average transmittance is minor. The average transmittances found from the sapphire transmittance data and LNG flame radiation are listed in Table 2 .

TABLE 2 .

AVERAGE TRANSMITTANCE FOR FLAME RADIATION THROUGH SAPPHIRE WINDOWS. Averaue Transmittance
0.909

Incident Angle
90

45 30 15

0.845 0.423 0.028

The average transmittance decreases rather sharply as the angle of incidence changes between 45 degrees and 15 degrees. At angles of incidence less than 15 degrees, sap-

phire reflects most of the incident radiation of all wavelengths. Correction to the wide angle radiometer data was

required because of the reflection at l o w incident angles. The approximate incident angles for the radiation from the flames were calculated and the radiant flux data were corrected accordingly. The wide angle radiometer fluxes shown in Table 1 have been corrected for both flame transmittance through the
11-28
n

c13

r a d i o m t e r window and i n c i d e n t r a d i a t i o n a n g l e .

Thu

the

data l i s t e d represent the radiant flux incident a t the radiometer location.

N o c o r r e c t i o n h a s been a t t e m p t e d f o r

a t m o s p h e r i c a b s o r p t i o n t o d e t e r m i n e what t h e f l u x m i g h t h a v e been i n t h e absence of a b s o r p t i o n .

T h e n a r r o w a n g l e r a d i o m e t e r d a t a were u s e d i n

c o n j u n c t i o n w i t h E q u a t i o n s 5 a n d 6 t o compare " p r e d i c t e d " and m e a s u r e d i n c i d e n t f l u x e s . E q u a t i o n s 5 and 6 , combined

w i t h t h e narrow a n g l e radiometer d a t a , r e s u l t i n

-0.126 q = 50,000
F

E q u a t i o n 1 2 is a d i m e n s i o n a l e q u a t i o n i n which t h e i n c i d e n t f l u x is i n B t u / h r - f t 2 and D m u s t have t h e u n i t s o f f e e t .

( O t h e r u n i t s may b e u s e d w i t h s u i t a b l e c o n v e r s i o n s . ) The p r o c e d u r e f o l l o w e d i n p r e d i c t i n g r a d i a n t f l u x e s r e q u i r e d t h e c a l c u l a t i o n of r a d i a n t view f a c k o r s . The f l a m e

h e i g h t and a n g l e s r e q u i r e d f o r t h e v i e w f a c t o r c a l c u l a t i o n s
were o b t a i n e d f r o m E q u a t i o n s 8 t h r o u g h 1 0 .
A few flame

l e n g t h m e a s u r e m e n t s were p o s s i b l e .

The m e a s u r e d f l a m e

l e n g t h s a r e compared t o t h e Thomas p r e d i c t i o n i n F i g u r e 6 , a n d t h e m e a s u r e d v a l u e s a r e w e l l r e p r e s e n t e d by t h e Thomas equation. The m e a s u r e d v a l u e s were t a k e n f r o m m o v i e s o f t h e

f i r e s and were a n a v e r a g e o f t h e f l u c t u a t i n g f l a m e l e n g t h . B u r n i n g r a t e s u s e d i n E q u a t i o n 8 were c a l c u l a t e d f r o m -0.208 0.32

D

V = 0.13

11-29

0.1
I I

5 x 5
10 x 10
2 0 x 20

0 0

I
I I I I

0.1

FIGURE 6 .

COMPARISON O F FLAME HEIGHTS WITH P R E D I C T I O N OF THOMAS ( 1 9 6 3 ) .

11-30

where V is the linear regression rate in in/min.

Equation

13 is based on burning rates measured during the fire

control and extinguishment tests (Johnson, et al., 1980). Flame tilt angles were calculated using Equation 10 and the average wind velocities measured for the period during which the radiation measurements were made. The

camera locations used to film the fires were chosen to provide coverage for determining extinguishment or control time, and the resulting photographs and movies were not useful for measuring flame tilt angles, s o no comparisons of measured and predicted flame angles were possible. The

flame azimuthal angles were assumed to be the same as the mean wind direction angles measured during the radiation tests. The view factors were calculated using as basic input only the wind speed and wind direction measured during the tests and the radiometer position.
A l l other input

parameters were calculated based on previously-available information. Once the view factors had been calculated,

Equation 12, based on the narrow angle radiometer data, was used to calculate the expected incident radiant flux at the wide angle radiometer locations. Table 1 includes a listing

of the calculated fluxes and Figure 7 shows a comparison of measured and calculated fluxes. Figure 7 does not show all

the data for cases where calculated and measured fluxes were

nearly equal because of overcrowding on the graph.

11-31

16,000

'/

12,000

8000

4000

0 0 4000
8000

12,000

16 ,001

CALCULATED '~ADIANT FLUX, BTU/HR-FT

F I G U R E 7.

COMPARISON O F FIEASURFD P N D CAJJCULP.TFD F$.DIANT

FLUXE

11-32

Table 1 also contains a list of the ratio of calThe overall average culated flux, qc, to measured flux, qm of the ratio of qc/qm is 0.998 with a standard deviation of about 16 percent. This result indicates that the simplified

method of predicting the radiant flux from a propane fire is adequate for most purposes. If the spectral distribution of

energy from a propane fire is required, the spectral

I

emission curves for LNG fires (Raj, 1979) can be used as a good approximation.
CONCLUSIONS

The radiant fluxes from propane fires can be predicted with good accuracy using a simple flame emission model. The maximum radiant emission flux for free-burning

propane diffusion flames is about 50,000 Btu/hr-ft2, and fires from 5 to 4 0 ft in width follow an emission curve derived by simplifying a basic transport model. Predicted

radiant fluxes incident at locations near the flame show close correlation to measured fluxes. Flame height and

angle of tilt predicted by models from the literature are adequate for modeling flame geometry.

11-33

REFERENCES

1.

J o h n s o n , D. W . , e t a l . , " C o n t r o l a n d E x t i n g u i s h m e n t o f LPG F i r e s , " R e p o r t N o . D O E / E V - 6 0 2 0 - 1 , U. S . D e p a r t m e n t of E n e r g y , W a s h i n g t o n , DC ( A u g u s t 1 9 8 0 ) .

Love, T.
J . , R a d i a t i v e Heat T r a n s f e r , C h a r l e s E . Merrill P u b l i s h i n g C o . , Columbus, OH ( 1 9 6 8 ) .

2.

3.

S h a h r o k h i , F . , " N u m e r i c a l T e c h n i q u e f o r C a l c u l a t i o n of R a d i a n t E n e r g y F l u x t o T a r g e t s f r o m F l a m e s , " Ph.D. D i s s e r t a t i o n , U n i v e r s i t y o f Oklahoma, Norman, OK ( 1 9 6 5 ) . P f e n n i n g , D. B . , " R a d i a t i v e T r a n s f e r f r o m Laminar D i f f u s i o n F l a m e s , " Ph.D. D i s s e r t a t i o n , U n i v e r s i t y o f Oklahoma, Norman, OK ( 1 9 7 0 ) . M a r k s t e i n , G. H . , " R a d i a t i v e E n e r g y T r a n s f e r f r o m Gaseous D i f f u s i o n F l a m e s , " 1 5 t h I n t e r n a t i o n a l Symposium on C o m b u s t i o n , The C o m b u s t i o n I n s t i t u t e ( 1 9 7 4 ) .
R e i n , R.
G., et al., "Radiation View Factors f o r T i l t e d C y l i n d e r s , " J. F i r e and F l a m m a b i l i t y , - 1 4 0 ( 1 9 7 0 ) . 1,

4.

5.

6.
7.

H o w e l l , J. R . ,
R a j , P.

a n d R. S i e g e l , T h e r m a l R a d i a t i o n H e a t T r a n s f e r , Vol. 11, NASA SP-164, W a s h i n g t o n , DC ( 1 9 6 9 ) .

8.

P. K . , " C a l c u l a t i o n o f T h e r m a l R a d i a t i o n H a z a r d s f r o m LNG F i r e s - - A R e v i e w o f t h e S t a t e - o f - t h e - A r t , " P r o c e e d i n g s , AGA O p e r a t i n g S e c t i o n , American G a s A s s o c i a t i o n , A r l i n g t o n , VA ( 1 9 7 7 ) .

9.

Thomas, P . H . , "The S i z e o f F l a m e s f r o m N a t u r a l F i r e s , " N i n t h I n t e r n a t i o n a l Symposium on C o m b u s t i o n , Academic P r e s s , N e w York ( 1 9 6 3 ) . W e l k e r , 2 . R . , a n d C. M. S l i e p c e v i c h , " S u s c e p t i b i l i t y of P o t e n t i a l T a r g e t Components t o D e f e a t by T h e r m a l A c t i o n , " U n i v e r s i t y o f Oklahoma R e s e a r c h I n s t i t u t e R e p o r t No. OURI-1578-FR, Norman, OK ( 1 9 7 0 ) .
R a j , P.
P . K . , e t a l . , " E x p e r i m e n t s I n v o l v i n g Pool and Vapor F i r e s f r o m S p i l l s o f L i q u e f i e d N a t u r a l G a s on Water," R e p o r t N o . CG-D-55-79, U . S . Coast G u a r d , W a s h i n g t o n , DC (Varcli 1 9 7 3 )

10.

11.

11-34

R E P O R T I11
V A P O R I Z A T I O N OF PROPANE FROM S P I L L S
ONTO S O L I D SURFACES

INTRODUCTION

I f p r o p a n e o r o t h e r flammable l i q u e f i e d g a s i s s p i l l e d , i t w i l l immediately begin t o vaporize.

The vapor

plume t h u s formed w i l l be f l a m m a b l e f o r a d i s t a n c e f r o m t h e area of the s p i l l . The v a p o r i z a t i o n r a t e i s o n e o f t h e

p r i m a r y f a c t o r s d e t e r m i n i n g t h e s i z e o f t h e f l a m m a b l e plume. The v a p o r i z a t i o n r a t e d e p e n d s o n t h e t h e r m a l p r o p e r t i e s o f t h e s o l i d o n t o which p r o p a n e i s s p i l l e d a n d o n t h e s o l i d temperature. The s o l i d s u b s t r a t e w i l l u s u a l l y be much

warmer t h a n t h e p r o p a n e , b u t i t s s u r f a c e w i l l c o o l r a p i d l y .
The v a p o r i z a t i o n r a t e w i l l d e c r e a s e a s t h e s o l i d c o o l s u n t i l
a c o n d i t i o n is reached w h e r e h e a t t r a n s f e r t o t h e l i q u i d i s

b a l a n c e d by t h e h e a t r e q u i r e d t o v a p o r i z e t h e l i q u i d .

As

t h e h e a t t r a n s f e r r a t e and v a p o r i z a t i o n .rate decrease, h e a t t r a n s f e r from t h e a t m o s p h e r e and e n e r g y a v a i l a b l e from s e l f c o o l i n g of t h e l i q u i d a l s o provide energy r e q u i r e d t o vaporize the liquid. E v e n t u a l l y , a s t e a d y s t a t e c o n d i t i o n may b e

r e a c h e d i n which h e a t and m a s s - t r a n s f e r a r e b a l a n c e d and t h e v a p o r i z a t i o n r a t e becomes c o n s t a n t .

111-1

MEASUREMENT PROCEDURE

A mass b a l a n c e s y s t e m was c o n s t r u c t e d t o weigh t h e

s u b s t r a t e and p r o p a n e c o n t i n u o u s l y . diagram of t h e a p p a r a t u s . b a l a n c e d on a p i v o t .

Figure 1 is a schematic

I t c o n s i s t s of a s t e e l frame

One end o f t h e f r a m e s u p p o r t s t h e t e s t Counter-

p i t and t h e o t h e r i s a t t a c h e d t o a l o a d c e l l .

w e i g h t s a r e p l a c e d on t h e e n d o f t h e f r a m e n e a r t h e l o a d
c e l l t o b a l a n c e t h e f r a m e and i n c r e a s e t h e s e n s i t i v i t y o f

measurement.

F u l l s c a l e movement o f t h e s e n s i n g e l e m e n t o f i n c h e s , s o t h e frame is
The e n t i r e
I t c a n be

t h e load c e l l is less t h a n 0.01

m a i n t a i n e d i n a l e v e l a t t i t u d e a t a l l times.

a p p a r a t u s i s mounted o n a n o u t d o o r c o n c r e t e p a d .

used c o m p l e t e l y i n t h e open, i n t h e s h a d e , o r i n t h e shade

w i t h s h e l t e r i n g t o reduce wind e f f e c t s .
A l l t e s t s were r u n

o u t d o o r s t o a v o i d s a f e t y p r o b l e m s c a u s e d by p o t e n t i a l accumulation of flammable v a p o r s i n d o o r s .
T h e o u t p u t s i g n a l f r o m t h e l o a d c e l l was r e c o r d e d o n

b o t h a s t r i p c h a r t r e c o r d e r and on m a g n e t i c t a p e .

The

a p p a r a t u s was c a l i b r a t e d b e f o r e e a c h t e s t by l o a d i n g i t w i t h l e a d b r i c k s o f s l i g h t l y g r e a t e r m a s s t h a n t h e mass o f p r o p a n e t o be s p i l l e d d u r i n g t h e t e s t .
T h i s procedure assured

u s e of t h e w i d e s t p o s s i b l e p o r t i o n of t h e t r a n s d u c e r range
a s w e l l a s checking f o r proper o p e r a t i o n . The z e r o p o i n t o f

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

o f d i f f e r e n c e s i n t e s t p i t w e i g h t and b a l a n c e l o a d i n g , b u t
t h e span c a l i b r a t i o n remained c o n s t a n t throughout t h e t e s t

111-2

H H H

I
W

Figure 1 .

Apparatus f o r Weighing Propane During Vaporization Tests.

series.

The b a l a n c e s y s t e m , when c a l i b r a t e d i n d o o r s , o r

o u t d o o r s u n d e r no wind c o n d i t i o n s c o u l d r e c o r d c h a n g e s o f a b o u t 0 . 0 5 l b , w h i c h i s a b o u t 0 . 2 p e r c e n t o f t h e mass o f t h e i n i t i a l propane s p i l l f o r most t e s t s . Many t e s t s were r u n

when t h e r e was low t o m o d e r a t e w i n d , and t h e w i n d g u s t s c a u s e d random v a r i a t i o n i n t h e r e c o r d e d w e i g h t b e c a u s e o f movement o f t h e t e s t p i t .

s h i e l d e d from wind e f f e c t s ,

When t h e t e s t p i t s w e r e p a r t i a l l y t h e w e i g h i n g a c c u r a c y was a b o u t

o n e p e r c e n t o f t h e amount o f p r o p a n e s p i l l e d , o r a b o u t a q u a r t e r t o a t h i r d of a pound. I n some t e s t s where t h e

w e i g h i n g f r a m e a n d p i t were n o t s h i e l d e d a n d wind s p e e d w a s h i g h , random v a r i a t i o n s i n r e c o r d e d w e i g h t o f more t h a n 5 l b

were f o u n d .

I n c a s e s where t h e wind f l u c t u a t i o n s were

p r e s e n t , d a t a were a v e r a g e d o v e r a b o u t a 10-sec p e r i o d , 5
s e c b e f o r e t h e time b e i n g c o n s i d e r e d a n d 5 s e c a f t e r .

This

p r o c e d u r e produced r e a s o n a b l y c o n s i s t e n t d a t a e x c e p t f o r q u i t e s t r o n g , g u s t y winds.
In a d d i t i o n t o t h e p r o p a n e w e i g h t , t h e p r o p a n e tem-

p e r a t u r e , wind s p e e d , s o l a r f l u x , and s u b s t r a t e t e m p e r a t u r e

were m e a s u r e d f o r e a c h t e s t .

Ambient t e m p e r a t u r e , h u m i d i t y ,

a n d b a r o m e t r i c p r e s s u r e were r e c o r d e d f o r m o s t t e s t s . The g e n e r a l t e s t p r o c e d u r e was t o s e t up t h e l o a d

c e l l and t e s t p i t on o p p o s i t e e n d s o f t h e w e i g h i n g f r a m e ,

b i a s t h e w e i g h t s o t h a t t h e l o a d c e l l was s e t n e a r t h e end o f i t s e f f e c t i v e s p a n , and c a l i b r a t e t h e l o a d c e l l . Propane

was t r a n s f e r r e d from a n a m b i e n t t e m p e r a t u r e s t o r a g e t a n k t o

111-4

a s p i l l bucket.

I n t h e f i r s t t e s t s , t h e s p i l l b u c k e t was However,

i n s u l a t e d t o minimize b o i l o f f b e f o r e t h e s p i l l .

r e g a r d l e s s of t h e c a r e used i n t r a n s f e r r i n g t h e propane, s u b s t a n t i a l s u b c o o l i n g o c c u r r e d , s o t h a t t h e p r o p a n e was s o m e t i m e s more t h a n 3 0 d e g r e e s F b e l o w i t s n o r m a l b o i l i n g point. S u b c o o l i n g t o t h a t e x t e n t was l a r g e e n o u g h t h a t

b o i l i n g o f t h e p r o p a n e on t h e s u b s t r a t e d i d n o t r a i s e t h e b u l k of t h e l i q u i d t o t h e b o i l i n g p o i n t . Therefore, an

u n i n s u l a t e d b u c k e t was u s e d f o r t r a n s f e r r i n g p r o p a n e d u r i n g most t e s t s . I n a d d i t i o n , warm p r o p a n e g a s was b u b b l e d

t h r o u g h t h e p r o p a n e l i q u i d i n t h e s p i l l b u c k e t t o warm t h e l i q u i d t o t h e b o i l i n g p o i n t b e f o r e i t was s p i l l e d . The u s u a l p r o c e d u r e was t o p o u r t h e l i q u i d p r o p a n e i n t o the p i t a s rapidly a s possible without splashing o r sloshing. The t i m e r e q u i r e d d e p e n d e d on t h e amount s p i l l e d ,

b u t was u s u a l l y 1 0 t o 1 5 s e c o n d s f o r a s p i l l o f 25 t o 3 0 l b . The t e s t p i t s were c o n s t r u c t e d f r o m a v a r i e t y o f materials. Whenever p r a c t i c a b l e , t h e r m o c o u p l e s were p l a c e d

i n t h e f l o o r of t h e p i t t o monitor t h e temperature p r o f i l e . The f l o o r a r e a o f t h e t e s t p i t s was u s u a l l y 5 f t 2 , b u t i n a few cases t h e m a t e r i a l used f o r t h e p i t bottom could n o t be o b t a i n e d i n a l a r g e enough p i e c e , s o s m a l l e r p i t s were constructed.
T h e p i t s i d e s were u s u a l l y a b o u t 4 i n c h e s

t h i c k a n d t h e p i t b o t t o m s were 4 t o 6 i n c h e s t h i c k .

I n some

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

s i d e s were made f r o m p o l y s t y r e n e foam o r p o l y u r e t h a n e foam

111-5

b e c a u s e o f t h e p r o b l e m s e n c o u n t e r e d i n making w a l l s o f t h e substrate material.

When p o l y s t y r e n e foam was u s e d f o r p i t

w a l l s i t was c o v e r e d w i t h a l a y e r o f 0.6-mil

polyethylene t o

p r e v e n t d e g r a d a t i o n by d i r e c t c o n t a c t w i t h p r o p a n e . Many t e s t s were run w i t h t h e p r o p a n e p o o l open t o t h e atmosphere. When t h i s p r o c e d u r e was f o l l o w e d , i t was

p o s s i b l e t o e s t i m a t e t h e c o n t r i b u t i o n s of s o l a r r a d i a t i o n and a t m o s p h e r i c c o n v e c t i o n t o t h e v a p o r i z a t i o n p r o c e s s . In

o t h e r t e s t s , t h e p r o p a n e was p o u r e d i n t o c o v e r e d p i t s w h e r e t h e e f f e c t s o f t h e o u t s i d e e n v i r o n m e n t were s m a l l ,

The

covered t e s t s enabled t h e e s t i m a t i o n of thermal c o n d u c t i v i t y and s u r f a c e - t o - l i q u i d heat transfer coefficients.

I n s e v e r a l t e s t s g r a n i t e o r m a r b l e r o c k s were p l a c e d

i n t h e bottom of t h e p i t t o s i m u l a t e t h e e f f e c t s of g r a v e l
o r rock s u r f a c e s .
The v e r y r a p i d v a p o r i z a t i o n of propane

s p i l l e d o n c r u s h e d r o c k s u r f a c e s c a u s e d some m e a s u r e m e n t problems b e c a u s e s e v e r a l pounds o f propane c o u l d be vapori z e d i n t h e 1 0 t o 1 5 seconds r e q u i r e d t o pour i t i n t o t h e pits.

A f e w t e s t s were

r u n i n w h i c h r o c k s were p o u r e d i n t o

p r e v i o u s l y cooled propane p i t s ,
P R O P A N E VAPORIZATION T H E O R Y

When p r o p a n e i s s p i l l e d on a s o l i d s u r f a c e , i t s t a r t s t o v a p o r i z e i m m e d i a t e l y a t u s u a l a m b i e n t temperatures. I n m o s t c a s e s t h e h e a t t r a n s f e r r a t e from s o l i d

n

t o l i q u i d i s f a s t enough t h a t b o i l i n g o c c u r s f o r a s h o r t

111-6

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

Later, a s heat

t r a n s f e r from t h e s o l i d d e c r e a s e s , b o i l i n g s t o p s , b u t v a p o r ization continues, with t h e heat required f o r vaporization b e i n g s u p p l i e d by r a d i a t i o n o r c o n v e c t i o n from t h e a t m o s p h e r e , o r from s e l f - c o o l i n g of t h e l i q u i d , i n addition

t o c o n d u c t i o n from t h e s o l i d s u r f a c e .
T h e t o t a l r a t e o f h e a t t r a n s f e r a v a i l a b l e t o cause

v a p o r i z a t i o n from a p r o p a n e p o o l on a smooth s u r f a c e c a n b e c a l c u l a t e d from a h e a t b a l a n c e ,

+
where

9 ,

+ qr + 9 ,

= = = = =

heat transfer rate available for vaporization heat conduction t o s o l i d surface h e a t t r a n s f e r from a t m o s p h e r e h e a t t r a n s f e r from s o l a r r a d i a t i o n s e n s i b l e h e a t r a t e from s e l f - c o o l i n g
is u s u a l l y

qc qa qr
9s

T h e h e a t t r a n s f e r r a t e from t h e s o l i d , q c ,
_ . !

dominant a t t h e s t a r t of t h e s p i l l . surface
C001St

However, a s t h e s o l i d Both q, and

9,

decreases relatively rapidly.

q r a r e r e l a t i v e l y c o n s t a n t and c h a n g e p r i m a r i l y b e c a u s e o f changes i n ambient c o n d i t i o n s .

t r

As t h e p o o l c o o l s ,

a rela-

t i v e l y s m a l l amount o f e n e r g y i s e x t r a c t e d f r o m t h e p o o l itself.
I t ' s importance is u s u a l l y i n determining t h e pool
4

temperature r a t h e r than i n causing s u b s t a n t i a l vaporization of liquid. I f t h e p r o p a n e p o o l i s d e e p enough t o p e r s i s t

111-7

longer than 15 minutes to half an hour, the atmospheric convection and solar radiation terms become dominant as source of heat. Heat transfer from the solid surface can be found by considering a heat balance within the solid. the solid has constant thermal properties. can then be found from
k a2T 2 ax
aT = pc -

Assume that Its temperature

at

where

T = temperature within the solid

= =

thermal conductivity distance within the solid solid density solid heat capacity

p =

t = time Equation 2 is written for one-dimensional application. There is rarely a need to consider two-dimensional forms for spills of liquefied gases. Assuming that the solid is at a

uniform temperature when the spill occurs, T = T

0

a t t = O When

(3)

where To is the initial temperature of the solid.

propane initially contacts the solid surface, the heat transfer rate is limited because by convection between the solid and li.,quid. Thus, one boundary condition is
111-8
n

where

convective coefficient between propane and solid

T = temperature of liquid propane in pool P Normally, the solid can be treated as being semi-infinite,
so the second boundary condition is

for large values of x, i.e.,

at depths where the solid has

not yet been cooled by propane. The solution to Equation 2, along with its initial and boundary conditions, is

T - Tp = e r f ( - ) . e x p ( ~ + ~ ? ) e r f c ( ~ + ~ )

(6)

T0 - T P

2 m

&

where

is the thermal diffusivity, k / m .

The rate of heat transfer from the solid to the liquid propane is

= h(T

T P

111-9

a t x = 0 (the s o l i d s u r f a c e ) , so, s u b s t i t u t i n g (T
Equation 6,

- TP ) f r o m

q C = h(To

- TI? ) exp

(e)

erfc

() m

Any c o n s i s t e n t s e t o f u n i t s may be u s e d ; n o t e t h a t h 2t / k p c
is u n i t l e s s .

E q u a t i o n 8 c a n a l s o be w r i t t e n i n t h e form

(To
c I =

T ) P

fi Y exp y2 e r f c Y

where

The f u n c t i o n

f ( ~ ) fi Y exp y2 e r f c Y =

i s between 0.95 and 1 . 0 f o r v a l u e s o f Y g r e a t e r t h a n 3 ,

which i n d i c a t e s t h a t t h e h e a t t r a n s f e r c o e f f i c i e n t h is i m p o r t a n t p r i m a r i l y f o r times

t < % 3

h2

111-10

6rs
is

The t o t a l h e a t t r a n s f e r f r o m s o l i d t o l i q u i d o v e r a t i m e t c a n b e found by i n t e g r a t i n g E q u a t i o n 8. The r e s u l t

QC

h(To

TP)

() y[

(exp y 2 e 2 f c Y r

- 1) +

-1

(13)

Jii
A t long

w h e r e Qc i s t h e t o t a l h e a t t r a n s f e r f r o m t h e s o l i d .

times E q u a t i o n 1 3 r e d u c e s t o

The e l a p s e d time b e f o r e E q u a t i o n 1 4 a p p l i e s d e p e n d s o n t h e t h e r m a l p r o p e r t i e s of t h e s o l i d and t h e h e a t t r a n s f e r c o e f ficient.

Qc
A

value of

Y = 8 is required t o b r i n g t h e value of

c a l c u l a t e d from Equation 1 4 t o w i t h i n 1 0 p e r c e n t o f t h e

v a l u e c a l c u l a t e d f r o m E q u a t i o n 13. The r a t e o f h e a t t r a n s f e r from t h e a t m o s p h e r e c a n b e c a l c u l a t e d from

9 ,

= ha

('a

TP)

where

ha = c o n v e c t i v e c o e f f i c i e n t between a i r and propane

T

= ambient a i r temperature

V a l u e s f o r ha d e p e n d o n t h e p o o l s i z e a n d t h e w i n d v e l o c i t y . They a r e t y p i c a l l y a b o u t 1 t o 2 Btu/hr-ft2-OF,

so the heat

brs

t r a n s f e r r a t e from t h e a t m o s p h e r e t o t h e p o o l i s o n l y a few

111-11

p e r c e n t o f t h a t from t h e s o l i d u n t i l t h e s o l i d s u r f a c e cools. A t m o s p h e r i c h e a t i n g i s more i m p o r t a n t f o r s o l i d s

w i t h low v a l u e s o f t h e p r o d u c t k p c a t s h o r t e r times a f t e r

the spill. The s o l a r r a d i a n t f l u x i s a l s o s m a l l compared t o t h e i n i t i a l h e a t t r a n s f e r r a t e from t h e s o l i d .

I t is about t h e

same m a g n i t u d e a s t h e c o n v e c t i v e f l u x , and i s i m p o r t a n t o n l y f o r s p i l l s t h a t a r e d e e p enough t o b e l o n g - l a s t i n g . The p r o p a n e p o o l i s n o t i n e q u i l i b r i u m w i t h t h e a t m o s p h e r e , s o p r o p a n e will c o n t i n u e t o v a p o r i z e e v e n i f t h e h e a t t r a n s f e r f r o m t h e s u r r o u n d i n g s becomes v e r y low.

The

e n e r g y r e q u i r e d t o v a p o r i z e t h e p r o p a n e c a n come from s e n s i b l e heat released a s t h e pool cools. h e a t c h a n g e i s g i v e n by

dT

The r a t e o f s e n s i b l e

9s

= p HC

p
L

dt

where

pL =

propane l i q u i d d e n s i t y

H = pool depth
CL = s p e c i f i c h e a t of

l i q u i d propane

I f t h e p o o l t e m p e r a t u r e i s a t t h e b o i l i n g p o i n t , qs

i s z e r o and r e m a i n s z e r o u n t i l t h e h e a t t r a n s f e r r a t e

( p r i m a r i l y q c ) becomes low enough t h a t t h e p o o l b e g i n s t o cool. Until t h a t time, t h e v a p o r i z a t i o n r a t e can be c a l -

c u l a t e d from
111-12

rll

4 -

where

m = mass e v a p o r a t i o n r a t e

AH^

= h e a t of v a p o r i z a t i o n o f propane

T h e t o t a l mass e v a p o r a t e d up t o a n y time b e f o r e t h e p o o l

c o o l s below t h e b o i l i n g p o i n t i s

Q,
M =

+ Q,

Q,

AHv

where

Qa = q a t

(19)
(20)

Q, = q r t
and t is t h e d u r a t i o n of t h e s p i l l . q r a r e assumed t o be c o n s t a n t ,
I f t h e p o o l d r o p s below i t s b o i l i n g p o i n t ,

N o t i c e t h a t b o t h qa a n d

t h e va-

p o r i z a t i o n r a t e no l o n g e r c a n be d e t e r m i n e d by h e a t t r a n s f e r c o n s i d e r a t i o n s o n l y , b e c a u s e n o t a l l h e a t added t o t h e p o o l must result i n vaporization. Therefore, once subcooling

b e g i n s , v a p o r i z a t i o n r a t e s m u s t be c a l c u l a t e d f r o m mass transfer considerations. For s u b c o o l e d p o o l s , t h e v a p o r -

i z a t i o n r a t e may b e e s t i m a t e d f r o m

m =

kg pv P

111-13

where

g
V

= =

mass t r a n s f e r c o e f f i c i e n t
vapor p r e s s u r e of propane

P = atmospheric pressure

The m a s s t r a n s f e r c o e f f i c i e n t d e p e n d s p r i m a r i l y o n t h e wind v e l o c i t y , b u t i s a l s o a f f e c t e d by p o o l s i z e and p r o p a n e

properties.

The v a p o r p r e s s u r e d e p e n d s o n l y o n p o o l temT h e r e f o r e , once t h e pool b e g i n s t o c o o l , a t a

perature.

t i m e t h a t c a n be d e t e r m i n e d a s

w h e r e rn i s c a l c u l a t e d f r o m E q u a t i o n 1 7 u s i n g

t h e p o o l t e m p e r a t u r e m u s t be found by i n t e g r a t i n g E q u a t i o n
1 6 and f i n d i n g t h e d e c r e a s e i n p o o l t e m p e r a t u r e c a u s e d by

vaporization.

The i n c r e m e n t a l q u a n t i t y o f p r o p a n e v a p o r i z e d

d u r i n g a n y p e r i o d , a s c a l c u l a t e d from E q u a t i o n 2 1 , must be b a l a n c e d by t h e q u a n t i t y o f e q u i v a l e n t e n e r g y s u p p l i e d by q c , q a , q r , and qs.

A s t e p w i s e c a l c u l a t i o n c a n b e made f o r

successive t i m e increments t o determine vaporization r a t e s and t h e t o t a l q u a n t i t y v a p o r i z e d a t a n y time. E q u a t i o n 13, which g i v e s t h e h e a t t r a n s f e r r e d from t h e s o l i d t o t h e propane,
is based on t h e assumption t h a t

t h e s o l i d s u r f a c e i s s m o o t h and f l a t .

I n many p r a c t i c a l

c a s e s o f i n t e r e s t , t h e s u r f a c e w i l l be c o v e r e d by r o c k s o r g r a v e l , and t h e p r o p a n e w i l l v a p o r i z e r a p i d l y u n t i l t h e

111-14

rocks o r gravel cool.

The a d d i t i o n a l h e a t t r a n s f e r t o t h e

p r o p a n e c a n be e s t i m a t e d i f t h e r o c k s a r e s m a l l enough t h a t t h e y c a n b e assumed t o be a t a u n i f o r m t e m p e r a t u r e a s t h e y c o o l following t h e propane s p i l l . p e r a t u r e is

T h e u n i f o r m r o c k tem-

Tr - T To - T
where

h r = c o n v e c t i v e c o e f f i c i e n t between r o c k s and p r o p a n e
Ar
= t o t a l surface area of rocks

Mr

= t o t a l mass o f r o c k s

Cr = s p e c i f i c h e a t o f r o c k s
T h e v a l u e o f Ar d e p e n d s o n b o t h t h e s i z e and s h a p e o f t h e
rocks and t h e t o t a l m a s s of t h e r o c k s . If

the rocks are a l l

t h e same s h a p e , a n d u n i f o r m i n s i z e , t h e r a t i o A r / M r

is an

i n v e r s e f u n c t i o n of rock s i z e .

If t y p i c a l rock dimensions

a r e o n t h e o r d e r of a c e n t i m e t e r o r two, h r is r e a s o n a b l y i n d e p e n d e n t o f r o c k s i z e and i s a b o u t t h e same m a g n i t u d e a s

h

( f o r c o n v e c t i v e t r a n s f e r between p i t bottom and p r o p a n e )

111-15

RESULTS

F i g u r e 2 shows t h e r e s u l t f o r two t y p i c a l t e s t s , i n
t h i s c a s e , s p i l l s of propane i n t o a 5 - f t 2 p e r l i t e c o n c r e t e

pit.

I n T e s t P-15, a b o u t 40 l b o f p r o p a n e w a s ' p o u r e d

into

t h e p i t , which was u n c o v e r e d and e x p o s e d t o b o t h s u n a n d

wind,

A f t e r a b o u t 15 m i n u t e s , t h e v a p o r i z a t i o n r a t e becomes

r e l a t i v e l y c o n s t a n t u n t i l t h e propane h a s e n t i r e l y vaporized. During t h i s c o n s t a n t r a t e v a p o r i z a t i o n p e r i o d , t h e

l i q u i d i n t h e p i t is s u b c o o l e d , r e a c h i n g a t e m p e r a t u r e of -82'F. I n T e s t P-54, a b o u t 3 0 l b o f p r o p a n e was p o u r e d i n t o However i n T e s t P-54 t h e p i t

t h e same p e r l i t e c o n c r e t e p i t .

was c o v e r e d w i t h a p o l y s t y r e n e foam l i d t h a t p r e c l u d e d b o t h wind and s o l a r r a d i a t i o n from r e a c h i n g t h e p r o p a n e .

The

v a p o r i z a t i o n r a t e was l o w e r f o r T e s t P-54, a n d o n l y a b o u t 1 5
l b v a p o r i z e d i n t h e h o u r t h e t e s t was r u n , compared t o a

t o t a l v a p o r i z a t i o n o f a b o u t 4 0 l b f o r T e s t P-15. u s e d i n T e s t P-54

The l i d

p r e v e n t e d v a p o r i z a t i o n c a u s e d by non-

e q u i l i b r i u m b e t w e e n t h e p o o l and t h e v a p o r a b o v e i t , s o t h e pool did not subcool.

T h e l i q u i d t e m p e r a t u r e a f t e r an hour

o f v a p o r i z a t i o n remained a t t h e b o i l i n g p o i n t of propane. S i m i l a r t e s t s were r u n u s i n g g r a v e l mix c o n c r e t e , sand mix c o n c r e t e , v e r m i c u l i t e c o n c r e t e , c l a y s o i l , sandy s o i l , p o l y e t h y l e n e foam, p o l y s t y r e n e foam, plywood, s o d , s a n d , a s p h a l t , and p o t t i n g s o i l ' a s t h e s u b s t r a t e m a t e r i a l s . I n a few t e s t s g r a n i t e c h i p s o r m a r b l e c h i p s were p l a c e d on
111-16

40

OPEN

30

0
On

TEST NO.

P-15

COVERED

L
0

/ '
0
0 0

20-

O 0

O0
O o o

0
" 0

0800
O o o O O O q 0000

O o 0 s

10-

TEST NO. P-54

o0o0

"0

no
1

0
1

TIME, MIN

F i g u r e 2.

W e i g h t of P r o p a n e R e m a i n i n g A f t e r S p i l l i n t o P e r l i t e C o n c r e t e P i t .

t h e s u b s t r a t e s u r f a c e t o i n v e s t i g a t e t h e e f f e c t s of rock

coverings. T a b l e 1 i s a summary o f t h e r e s u l t s o f t h e s p i l l
t e s t s , g i v i n g t h e i n i t i a l c o n d i t i o n s , t h e measured t h e r m a l

p r o p e r t i e s , a n d t h e s t e a d y s t a t e v a p o r i z a t i o n r a t e where
t e s t s were u n c o v e r e d a n d s t e a d y v a p o r i z a t i o n r a t e s were

achieved.

T a b l e 2 is a key t o t h e s u b s t r a t e a b b r e v i a t i o n s

u s e d i n T a b l e 1 a n d i n c l u d e s s u b s t r a t e d e n s i t y and h e a t

capacity.

Figures A-1

t h r o u g h A-79

i n t h e Appendix a r e

p l o t s showing t h e w e i g h t of propane remaining i n t h e t e s t p i t a t any t i m e f o l l o w i n g t h e s p i l l . a s shown i n t h e f i g u r e s and T a b l e 1. Ambient t e m p e r a t u r e , i n i t i a l s u b s t r a t e temperature,

Test durations varied

p r o p a n e t e m p e r a t u r e , wind s p e e d , and s o l a r r a d i a t i o n f l u x

were m e a s u r e d f o r m o s t t e s t s .
v a l u e s a r e i n c l u d e d i n T a b l e 1.

Summaries o f t h e m e a s u r e d

I n some t e s t s t h e s u b s t r a t e

t e m p e r a t u r e s were m e a s u r e d a t v a r i o u s d e p t h s b e l o w t h e s u r face. F i g u r e 3 shows t h e m e a s u r e d s u b s t r a t e t e m p e r a t u r e s

f o r t e s t P-54. F i g u r e 4 i s t h e r e s u l t s f o r a t e s t i n which p r o p a n e was p o u r e d o n t o g r a n i t e c h i p s o v e r a p e r l i t e c o n c r e t e s u b strate.

The v a p o r i z a t i o n r a t e i s v e r y r a p i d a t t h e s t a r t o f

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

pour b e c a u s e o f t h e r e l a t i v e l y h i g h v e l o c i t y o f propane vapor leaving through t h e pouring spout i n t h e p i t cover. By t h e time t h e p o u r i n g was c o m p l e t e , t h e g r a n i t e c h i p s ,

111-18

c
TABLE 1. DATA F O R SPILLS OF LPC ON VARIOUS SUBSTRATES

c
____----TEMPERATURE --------TEST I D PIT SIZE (SO-FT) TEST
LENGTH

AIR
(OF)

(MINI

PIT (OF)

INIT. LIQ
(OF)

STEADY STATE (OF)

AVERAGE WIND SPEED (MPH)

AVERAGE SOLAR

RADIATION BTU/HRSO-FT

STEADY STATE BOILOFF RATE LB/SECSO-FT

CALCU LATE0 THERMAL CONDUCTIVITY 8TUdHR-

BOILING HEAT TRANSFER COEFFICIENT BTU/HRSQ-FT-O F

FT-

CG-1 CG-3
CG-4

5 5 5

32

86 82 85 80 75 66 66 54 58 48 62 56 65 50 57 52 78 78 91

80 78 78 87 82

-50 -51 -48 -50. -55

-55 -65 -48 -66

2.8 5.9 2.7 10.2 5.4

255 150 180 201 184 173 COVERED COVERED

0.00238 0.00265 0.00253 0.00296 0.00225 0.00208 0.004 1 0 -A 0.00173-A 0.00280

2.5-B 2.8-8 4.0-8

45 55 85 70 50

44
50

CS1-5 CS1-7

5
5

43 54 68 18 20 14 8

3.0-8

-63
-7 2
NA

3.6-8
3.8-8
7.4

cs1-8
CS1-23

5
5

48 60 41 30 33
45 48 62 46 26 42

-60
-4 5

6.0
COVERED COVERED

60
150

H H H

CS1-24 CSl-26 CS1-27 CS1-29 CS1-30 CS2-33 CS2-34 CS2-36 1152-37 CS2-47 CS2-50 CS2-75

5
5 5 5 5 5 5 5 5 5 5

-4 5
-45 -45 -45 -45 -45

NA
NA

36 .
3.6-8

100 100

I
P u 3

8.7

141
89 118 133 2." COVE R E D COVERED 179
COVERED COVE R E D

NA
NA NA

3.3
4.9 6.1 2.0"
COVERED
COVERED

0.00333
0.00327 0.00346 0.00306 0.00191-A

4.0-8 4.8-8 4.5-8

100
120

10
12

100
55 65

11
18 15 52 17 50

NA

3.5-8
3.7 5.4 4.6-8

-4 5
-45 -45 -48 -50 -45

NA

-45 -60
NA

0.00 20 4 -A
0.00176 0.00218-A 0.00235-A

100
55 65

3.6
COVERED COVERED

66
70

3.6
4.7

NA
NA

45
50

30

90

COVERED

COVERED

0.00 236 -A

4.1

~~~~

- P l t was s h a d e d Crom s u n NA - N o t a p p l i c a b l e A - Long-term b o l l o t f r a t e

**
8

Estimated

( p i t was s h e l t e r e d )

d e t e r m l n e d b y c o r r e c t i n g Cor s o l a r a n d a t m o s p h e r i c f l u x e s ; s e e t e x t

TABLE 1.

DATA FOR SPILLS OF L f f i ON VARIOUS SUBSTRATES--Continued

TEST I D

PIT SIZE (SQ-FT)

TEST
LENGTH (MIN)

--------AIR

TEMPERATURE

(OF)

PIT (OF)

INIT. LIQ
(OF)

--------STEADY STATE
(OF)

AVERAGE WIND

AVERAGE

SOLAR
RADIATION

SPEED (MPH)

BTU/HRSQ-FT

STEADY STATE BOILOFF RATE LB/SECSQ-FT

CALCULATED

THERMAL CONDUCTIVITY
BTU6HRFT- F

BOILING HEAT TRANSFER COEFFICIENT SQ-FT-OF BTU/HR-

P-14 P-15 P-38 P-39 P-42 P-48

5 5 5 5 5 5 5
5

78 62
14

75 72 64 64 55 59 74 92 84 65 70 55 61 61 68

82 72 47 -25 45 62 70 95 86 65 57 55
41

-60 -67
-4 5

-82 -80
NA

8.1

153 117
COVERED

0.00153 0.00180 O.OOOe5-A 0.00100 0.00082-A 0.00094-A 0 . 0 0 0 8 5-A 0.00139 0.00059-A 0.00148 0.00160 0.00233 0.001570.00071-A

0.85-8 0.90-8 0.72

NA

50 45 38
NA

11.4
COVERED

23 25 60 60 55 90 60 60 10 40 31 61 30

-45 -48 -50 -45

-60
NA

2.2
COVERED
COVERED

172
COVERED COVER E D
COVERED

0.84 0.80 0.94 0.80-B 0.96 2.0-8 2.0-8 1.0-8 0.72 0.86 0.89 1.0

40 20 20 45 25 50 30 25 35
25

NA

H H H

P-54 P-73 P-74 v-12 V-13 V-32 V-40

V-41

NA

COVERED

1
h ,

-4 5
-45 -60 -62 -50 -45 -45 -50 -50

-55
NA

2.1
COVERED

246
COVERED

5 5 5

-76 -6 2
NA

6.7 5.8 14.0

COVE R E D

183 200 125

COVERE
COVE R E O

5
5 5
5

NA
NA

38 65 85

COVERED
COVERED COVERED

v-49 v-8 3

NA
NA

COVERED
COVE R E D

0.0 0 0 8 7 -A
0.00095-A

20 30

91

NA
A

Not a p p l i c a b l e Long-term boiloff rate D e t e r m i n e d b y c o r r e c t i n g for s o l a r a n d a t m o s p h e r i c f l u x e s ; s e e t e x t

c
TABLE 1. DATA FOR S P I L L S OF LPG O N VARIOUS SUBSTRATES--Continued

c
- --- - - - - TEST ID PIT SIZE (SQ-FT) TEST LENGTH (MINI AIR (OF) STEADY STATE BOILOFF RATE LB/SECSQ-FT
B O 1 LING HEAT TRANSFER COEFFICIENT BTU/HRSQ-FT-OF

TEMPERATURE INIT. PIT LIQ (OF) (OF)

----- --- STEADY STATE (OF)

AVERAGE

WIND SPEED (MPH)

AVERAGE SOLAR RADIATION BTU/HRSQ-FT

CA LC U LATE D THERMAL CONDUCTIVITY BTULHRFT- F

CL1-20 CL1-21 CL2-57 CL2-58 CL2-59

H H H

51
64

45

48
30
65 55

-58
-63 -62 -50 -50 -45 -48 -48 -45 -45 -46 -47 -45 -48

-85 -8 5
NA

10.7 13.7 COVER E D 1.5 COVERED COVER E D 0.9 COVE R E D 2.0* COVERED COVERED COVERED 2.1

87
187
COVERED 113 COVERED COVERED 192 COVERED

0.00175 0.00223 0.00178-A 0.00170 0.00187-A

0 . 0 0 1 21 - A

NA

NA
NA

5
5

38
76 67 84

NA

60 50 40

3.4 2.8-B

100 65

5 5
5
5

-45
NA NA

80

3.5
3.2 3.5-8
NA NA NA

60
50

CL2-64 CL2-65 SS1-51 SS1-52 SS1-53 SS2-61 SS2-62 552-67 PTS-19

60
40

90
80

82
61

I
N

-53
NA

0.00198 0.00215-A 0.00161

95
NA NA NA

31
16
40 40 30 35 48

80

78 78
85

5 5 5
5

81
78 80 84

-45
NA

195
COVERED COVERED COVERED 242

0.00 1 52-A
0 . 0 0 2 7 5-A 0.00290-A 0.00287 0.02150

67

NA

NA

NA NA NA

77
82 53

NA

NA

5 5

85 58

-5 5 -45

N A
NA

3.8

137

NA

NA
A

E s t i m a t e d ( p i t was s h e l t e r e d from wind)

Not applicable

Long-term

boiloff rate

D e t e r m i n e d b y c o r r e c t i n g for s o l a r and a t m o s p h e r i c f l u x e s ; see t e x t

TABLE 1. DATA FOR SPILLS OF LPG ON VARIOUS SUBSTRATES--Continued

--------TEST I D PIT SIZE (SQ-FT) TEST LENGTH (MINI AIR

(OF)

TEMPERATURE INIT. PIT LIQ

(OF) (OF)

--------STEADY STATE
(OF)

AVERAGE

AVERAGE

WIND SPEED (MPH)

SOLAR
RADIATION BTU/HRSQ-ET

STEADY STATE BO I LOF F RATE LB/SECSQ-FT

CALCULATED THERMAL CONDUCTIVITY BTULHRET- F

BOILING HEAT TRANSFER COEFFICIENT BTU/HRSQ-E T-O F

PE-44 PE-45 PE-4 6 PS-9

35 167
40

64

73 78 -20 82 75 46 70 -40 54 74 80 86

-4 5
-50 -64 -7 3 -7 3 -86

NA NA

COVERED COVERED

COVERED
COVER E D

0.00 0 1 9 -A
0.00027-A 0.00062 0.00095 0.00133 0.00067 0.0000 6 -A 0.00039

C C
NA

20

5
5

78 80 74 70 48 73 73 58 78 84 88

2
NA

-8 2 -94

10 ..
8.5 12.8 7.9
COVERED

180
202 75 205
COVERED

5
5 5

103 60 62 125 60

NA
NA NA C

NA
NA

H H H I 1 0
h )

PS-10 PS-11 PS-56A PS-56B PS-89 PL-60 PL-63 PL-68

-100
-92
NA

NA

5 5 5
4

-6 8
-62 -52 -47 -46 -45

5
NA

-80 -68
NA

2.0. 0.5.
COVERED

144

NA
NA

10
120 120 90

0 . 3 . '
COVER E D COVERED

0.00033
0.00028-A

NA

C
C

20 45
NA

4
4

NA

COVERED 1.9

0 0 0 0 29 -A .
0.00089

-72

267

0.07-8

*+
NA A B

Estimated

( p l t was s h e l t e r e d from wind) from s u n

P i t was s h a d e d Not a p p l i c a b l e Long-term

boilotf r a t e see t e x t

D e t e r m i n e d by c o r r e c t i n g f o r s o l a r a n d a t m o s p h e r i c f l u x e s ;

T h e r m a l c o n d u c t i v i t y c o u l d n o t b e d e t e r m i n e d Cor low t h e r m a l c o n d u c t i v i t y s u b s t r a t e s i n c o v e r e d t e s t s .

TABLE 1.

DATA FOR S P I L L S OF Lffi ON VARIOUS SUBSTRATES--Continued

c
CALCULATED THERMAL CONDUCTIVITY BTU HRFT- F

TEST I D

PIT SIZE (SO-FT)

TEST LENGTH (PIIN)

______-TEMPERATURE ---------INIT. AIR (OF) PIT

(OF)

LIQ
(OF)

STEADY STATE (OF)

AVERAGE WINO SPEED

(Mf")

AVERAGE SOLAR

RADIATION BTU/HRSO-FT

STEADY STATE B O 1 LOFF RATE LB/SECSO-FT

BOILING HEAT TRANSFER COEFFICIENT BTU/HRSQ-FT-OF

SOD-66 SOD-69 SOD-70 SOD-71 SAND-17 A-43 CS/CR-76

H H H

5 5 ,

30
20 20 20
I _ ,

86

75
79

-4 5 -45 -4 5
-4 5

-4 5

COVERED

COVERED

0.00 0 8 7 -A
0.00394 0.00349
0.00406

NA NA
NA

NA NA

82 84 96 57 71 81 82 96 96 81 82 90 77 82 69 71 59 58

-48 -48 -45

1.7 2.0' 0.8

4.0

187 178 223 153 COVE R E 0 COVERED COVE R E D COVERED

COVERED COVERED
COVE R E D

5
5

74
81 57 73
86

NA
NA

NA

5
1
5 5
5

52 20

-4 5 -4 5 -4 9
-45 -50 -45
-4 5 -4 5

-4 5
NA NA NA

0.00150 0.00157-A 0.00247-A

NA

NA

COVERED

2.5 4.3

95
NA
NA
NA NA
NA NA

30
45
40

COVERED
COVER E O COVERED

P/C R-77 P/C R -7 8 CS/C R-79 P/CR-80 PS/CR-81 P/CR-82 V/CR-84

80 86 90 81
88

0.00 100-A

1.1
0.93

NA
NA
NA NA NA

0.0008 4 -A
0.00191-A

I
N W

5
5

30

COVERED
COVERED COVER E 0

3.8
1.3

30 30
30

0 . 0 0 117-A
0.00005-A

5
5

82

-45
-48

COVE R E 0

COVERED

0.00 138-A
0.00094-A

1.20

NA NA

5
5

30
20

71
70

NA

COVER E O COVERED
2.0.

COVERED COVERED 0.5''

1.1
1.8
NA

v/ne-es
V/M0-86 V/MB-87

-45
-45 -50 -45
-4 5

NA

0.00 153-A 0.00132

0.00123 0.00139

NA NA NA NA NA

45

60
56 52
54

-6 4
NA

5
5 5

10

2.0' 1.7

1 . 6 . '
0.5..
0.4"

NA
NA

V/MB-88
PS/MB-90

40.
10

-65
NA

0.5.

0.00018

NA

NA
A
B

Estlmated

( p i t was s h e l t e r e d f r o m v l n d )

P1.t w a s s h a d e d f r o m s u n Not a p p l i c a b l e L o n g - t e r m bolloff r a t e D e t e r m i n e d b y c o r r e c t i n g f o r s o l a r and a t m o s p h e c l c f l u x e s ; see text

T h e r m a l c o n d u c t i v i t y c o u l d n o t b e d e t e r m l n e d f o r low t h e r m a l c o n d u c t l v l t y s u b s t r a t e s I n c o v e r e d t e s t s

TABLE 2. SUBSTRATE IDENTIFICATION

PIT I D

SUBSTRATE

HEAT CAPACITY
( BTU/LB-~F)

CG

Gravel mix c o n c r e t e F i r s t sand mix c o n c r e t e Second sand mix c o n c r e t e P e r l i t e concrete Vermiculite c o n c r e t e Fi r st cla y/so i1 Second c l a y / s o i l F i r s t sand/= il Second sand/so i 1 Polyethylene foam Polystyrene foam Plywood ( f i r ) Bermuda sod Sand Asphalt Granite chips Marble c h i p s Potting soil

135 135 135 83

77

0.20
0.20

cs1
cs2 P

0.20 0.24
0.25

v
CL1

109 109 95 103

2.4

0.21
0.21

CL2

ss1
ss2
PE

0.19
0.20 0.40 0.27

Ps
PL

0.95 30 103 106

0.65

SOD
SN AD
A

0.20

0.19
0.20

144
165
162

GR
MI3

0.195
0.193
0.22

PTS

39

*-

Second sand/soil base

111-24

80

60

P
0

A
0

&

40

A
20

0
0

3-

A
0

0
0 0
0

A
0 0

-20

A
0
0

-40

A
0
0

1/4 in 1 / 2 in 1 in
2 in

A
-60

4 in

TEST NO. P-54

TIME, MINUTES

Figure 3 .

Substrate Temperature Profiles f o r Perlite Concrete.

111-25

TEST NO.

P/GR-80

TIME, SEC

F i g u r e 4.

W e i g h t Remaining F o l l o w i n g S p i l l o f P r o p a n e i n t o P e r l i t e C o n c r e t e P i t C o n t a i n i n g . G r a n i t e Chips.

6 d
which were a b o u t 0 . 1 5 i n c h e s i n n o m i n a l s i z e , were c o o l e d t o n e a r l y l i q u i d propane temperature.
T h i s very rapid boiling

made i t d i f f i c u l t t o m e a s u r e t h e i n i t i a l w e i g h t o f p r o p a n e , b e c a u s e t h e g r a n i t e c h i p s c o o l e d b e f o r e a l l t h e p r o p a n e was poured. S i m i l a r p r o b l e m s were e n c o u n t e r e d i n t e s t s u s i n g

l a r g e r marble c h i p s . DISCUSSION OF RESULTS

T h e v a p o r i z a t i o n d a t a shown i n F i g u r e s A - 1

through

A-79

i n t h e Appendix c a n b e u s e d i n c o n j u n c t i o n w i t h t h e

v a p o r i z a t i o n r a t e m o d e l s t o d e t e r m i n e some o f t h e e f f e c t i v e values of heat t r a n s f e r parameters required t o p r e d i c t v a p o r i z a t i o n r a t e s f o r r e f r i g e r a t e d propane i f i t is s p i l l e d on a s o l i d s u r f a c e .

I t s h o u l d b e k e p t i n mind t h a t i f p r o -

p a n e i s s p i l l e d from a m b i e n t t e m p e r a t u r e , p r e s s u r i z e d cont a i n e r s , a s u b s t a n t i a l f r a c t i o n w i l l f l a s h t o vapor immed i a t e l y and a n a d d i t i o n a l f r a c t i o n w i l l a t o m i z e . In f a c t ,

d u r i n g t h e s e p r o p a n e s p i l l t e s t s , c a r e f u l e f f o r t was req u i r e d t o a s s u r e t h a t l i q u i d samples c o u l d be withdrawn from ambient temperature s t o r a g e . F i g u r e 2 shows t h e v a p o r i z a t i o n r a t e f o r p r o p a n e s p i l l e d on a s o l i d s u b s t r a t e .

I n t h e test where t h e l i q u i d

p o o l was c o v e r e d , v a p o r i z a t i o n was c a u s e d p r i m a r i l y by h e a t t r a n s f e r by c o n d u c t i o n t h r o u g h t h e s u b s t r a t e t o t h e l i q u i d . E q u a t i o n 9 o r E q u a t i o n 1 3 c a n be used a t l o n g times a f t e r

t h e s p i l l t o d e t e r m i n e some o f t h e t h e r m a l p r o p e r t i e s .

In

111-27

these tests, the quantity of propane evaporated was measured, so Equation 13 and its long time approximation given by Equation 14 were used to estimate heat transfer parameters. Equation 14 shows that if the values of k , p, c , and
T

remain constant, the total quantity of heat transferred

from substrate to pool is

Q,
c;

= A K

The total mass o f propane boiled is then

or
M = S E

where
2Ec(To

s =

TP)

6 AHv

and S is the slope of the line obtained by plotting M versus t. Figure 5 shows such a plot for Test No. P-54.

The slope of the linear portion of the curve is 0.05

1b/f t2-sec 1/2

The density of perlite concrete used in the tests was 83 lb/ft3, obtained by direct weighing and a volume

111-28

measured by d i s p l a c e m e n t .

Specific heat of perlite concrete Using t h e i n i t i a l sub-

w a s m e a s u r e d t o b e 0 . 2 4 Btu/lb-'F.

s t r a t e t e m p e r a t u r e o f 70F a n d t h e p r o p a n e b o i l i n g t e m p e r a t u r e o f -45'F, the e f f e c t i v e thermal conductivity of

0

p e r l i t e c o n c r e t e was f o u n d t o b e 0 . 9 4 B t u / h r - f t -

F.

Once t h e t h e r m a l c o n d u c t i v i t y h a s b e e n d e t e r m i n e d
f r o m t h e l o n g term v a p o r i z a t i o n d a t a , t h e c o v e c t i v e h e a t t r a n s f e r c o e f f i c i e n t between t h e s u b s t r a t e and t h e l i q u i d c a n be d e t e r m i n e d by assuming a v a l u e f o r h and c a l c u l a t i n g the vaporization curve. The c a l c u l a t e d c u r v e w i l l b e p a r a l -

l e l t o t h e measured d a t a p o i n t s a t long times, b u t w i l l

c o i n c i d e w i t h t h e measured d a t a p o i n t s o n l y i f t h e proper e f f e c t i v e value f o r h is chosen. F i g u r e 6 s h o w s a com-

p a r i s o n o f c a l c u l a t e d and measured v a p o r i z a t i o n r e s u l t s f o r T e s t No. P-54. The l i n e d r a w n t h r o u g h t h e d a t a p o i n t s i n Btu/hr-ft0

F i g u r e 6 was c a l c u l a t e d u s i n g k = 0.94 20 Btu/hr-ft2-OF,

F and h =

a s r e p o r t e d i n T a b l e 1.

I f a test d o e s n o t r u n long enough f o r a l i n e a r r e l a t i o n s h i p t o d e v e l o p between M and

6, e th

values for

h and k c a n be approximated by f i t t i n g t h e c u r v e o f M versus t. V a p o r i z a t i o n c u r v e s c a l c u l a t e d from t h e assumed v a l u e s o f k and h a r e r e l a t i v e l y s e n s i t i v e t o t h e i n p u t values. F i g u r e 7 shows c a l c u l a t e d c u r v e s where k is v a r i e d

b y 20 p e r c e n t f r o m t h e e f f e c t i v e v a l u e , u s i n g t h e e f f e c t i v e v a l u e o f h , and F i g u r e ' 8 shows c a l c u l a t e c u r v e s where t h e

111-30

TEST NO.

P-54

PERLITE CONCRETE

0
MEASURED CALCULATED

30
TIME, MIN

40

Figure 6 .

Comparison o f Measured and Calculated Weight of Propane Vaporized f o r T e s t No. P-54.

TEST NO. P-54 PERLITE CONCRETE

h = 2 0 BTU/HR-FT~-OF

30

40

50

TIME, MIN Figure 7. Effect o f Thermal Conductivity on Calculated Vaporization.

v a l u e o f h i s v a r i e d by 2 0 p e r c e n t u s i n g a c o n s t a n t v a l u e o f k. I n Figure 7 , v a r y i n g t h e v a l u e chosen f o r k c a u s e s

c h a n g e s i n t h e s l o p e o f t h e c u r v e ; s o i t c a n be i n f e r r e d t h a t t h e thermal conductivity is incorrect. I n most c a s e s ,

k was d e t e r m i n e d from t h e s l o p e o f t h e c u r v e i n a p l o t o f M

versus

X, s o

t r i a l and e r r o r s o l u t i o n s f o r k were n o t

required.

I f , a s shown i n F i g u r e 8 , t h e s l o p e s o f t h e

c a l c u l a t e d l i n e and t h e d a t a l i n e a r e t h e same, b u t t h e m a g n i t u d e d i f f e r s by a n a p p r o x i m a t e l y c o n s t a n t a m o u n t , adjustments i n the value selected f o r h a r e required.

T h e r e were s e v e r a l t e s t s f o r which t h e t h e r m a l c o n -

d u c t i v i t y c o u l d n o t b e d e t e r m i n e d by t h e p r o c e d u r e d i s c u s s e d above. I n t e s t s s u c h a s P-15, f o r which v a p o r i z a t i o n d a t a

a r e shown i n F i g u r e 2 , t h e c o v e r was n o t p l a c e d o v e r t h e p i t , and t h e v a p o r i z a t i o n i n c l u d e d e f f e c t s o f h e a t t r a n s f e r from a t m o s p h e r i c c o n v e c t i o n , s o l a r r a d i a t i o n , and s e l f c o o l i n g of t h e l i q u i d propane.

In a f e w such cases, the

heat t r a n s f e r coef-

thermal c o n d u c t i v i t y and s o l i d - t o - l i q u i d

f i c i e n t were e s t i m a t e d by r e c o u r s e t o t h e h e a t t r a n s f e r model t h a t i n c l u d e d a l l t h e e f f e c t s p r e s e n t . The v a l u e s o f

k and h d e t e r m i n e d were a b o u t t h e same a s t h o s e f o u n d f o r

t h e c o v e r e d t e s t s , s o n o t a l l o f t h e u n c o v e r e d tests were

analyzed

.
The e f f e c t i v e v a l u e s f o r k and h a r e i n c l u d e d i n

T a b l e 1 f o r a l l t h e t e s t s where t h e y c o u l d b e d e t e r m i n e d . T a b l e 3 i s a summary o f t h e b e s t v a l u e s f o r e a c h m a t e r i a l .

111-34

TABLE 3.

HEAT TRANSFER PROPERTIES FOR SOLID SUBSTRATES

h Materia1 B t u / h r - f t 2-oF

k B t u / h r - f t-OF
EXP Lit. Ref e r e n c e

Gravel c o n c r e t e

50

2.7

Lentz and Monfore ( 1 9 6 5 )

Sand c o n c r e t e P e r l i t e concrete Vermiculite concrete C l a y soil Asphalt

100 30 30 70 95

4.0 0.9 0.9 0.2

0.2

Eshbach ( 1 9 7 5 ) Eshbach ( 1 9 7 5 )
R e i d (1980j

3.5
2.5

3-4

111-35

The e f f e c t i v e v a l u e o f k i s compared w i t h v a l u e s f o r t h e same o r s i m i l a r m a t e r i a l s f r o m l i t e r a t u r e s o u r c e s .

The t h e r m a l c o n d u c t i v i t i e s measured from t h e c o v e r e d

vaporization r a t e tests a r e generally higher than those reported i n the l i t e r a t u r e for similar materials. Similar

b e h a v i o r i s shown i n t h e d a t a o f Reid (1980), where t h e r m a l c o n d u c t i v i t i e s o f p o l y s t y r e n e foam were f o u n d t o be i n t h e r a n g e o f 0.06 Btu/hr-ft-OF,

LNG.

when t h e v a p o r i z i n g l i q u i d was

T h a t v a l u e i s a b o u t 3 t i m e s t h e v a l u e s t a t e d by foam Since

m a n u f a c t u r e r s f o r t e m p e r a t u r e s n e a r 6 0 t o 80F.

t h e r m a l c o n d u c t i v i t i e s f o r foamed i n s u l a t i o n d e c r e a s e a s t h e t e m p e r a t u r e d e c r e a s e s , t h e a c t u a l d i f f e r e n c e is g r e a t e r t h a n
is immediately a p p a r e n t .
Reid a l s o measured h i g h e r t h e r m a l

conductivity for s o l i d polyethylene than reported i n the literature. The r e a s o n f o r t h e h i g h t h e r m a l c o n d u c t i v i t i e s However, t h e v a l u e s shown i n T a b l e

is n o t r e a d i l y a p p a r e n t .

3 do r e p r e s e n t d a t a t h a t a r e r e q u i r e d f o r p r e d i c t i n g vapor-

i z a t i o n r a t e s f o r propane s p i l l s . The h e a t t r a n s f e r c o e f f i c i e n t s g i v e n i n T a b l e 3 a r e i n t h e r a n g e t o b e e x p e c t e d , b a s e d o n t h e work o f S c i a n c e

(1966).
The v a r i a b i l i t y among t h e v a r i o u s s u b s t r a t e s i s

probably due p a r t l y t o differences i n material surfaces, but may b e d u e t o t h e r a n g e o f a v e r a g e t e m p e r a t u r e d i f f e r e n c e s between propane and t h e s u b s t r a t e .
S c i a n c e showed t h a t t h e

t r a n s i t i o n r e g i o n between n u c l e a t e and f i l m b o i l i n g o c c u r r e d o v e r t e m p e r a t u r e d i f f e r e n c e s o f a b o u t 30 t o 200F

111-36

for

Gr3
propane. The v a p o r i z a t i o n d a t a u s e d t o d e t e r m i n e h e a t t r a n s f e r c o e f f i c i e n t s were l a r g e l y i n t h e t r a n s i t i o n r e g i o n , s o some d i f f e r e n c e s c o u l d b e e x p e c t e d .
The v a l u e s g i v e n i n

T a b l e 3 s h o u l d e n a b l e r e l a t i v e l y good v a p o r i z a t i o n r a t e p r e d i c t i o n s t o be made. F i g u r e 3 showed a n example o f t h e t e m p e r a t u r e p r o f i l e s measured i n t h e p e r l i t e c o n c r e t e p i t d u r i n g T e s t

No.

P-54.

The t e m p e r a t u r e n e a r t h e s u r f a c e d e c r e a s e d

r a p i d l y d u r i n g t h e f i r s t f e w m i n u t e s , t h e n d e c r e a s e d more slowly.
The t e m p e r a t u r e 4 i n c h e s d e e p remained a p p r o x i I t is p o s s i b l e t o

mately constant throughout t h e test.

p r e d i c t t h e t e m p e r a t u r e p r o f i l e s f o r a s o l i d s u b s t r a t e from Equation 16. F i g u r e 9 shows t h e r e s u l t o f s u c h c a l c u l a t i o n s The c a l c u l a t e d t e m p e r a t u r e s , shown a s

f o r T e s t No. P-54.

s o l i d l i n e s , a r e h i g h e r t h a n t h e measured t e m p e r a t u r e s a t d e p t h s l e s s t h a n about an inch i n t h e s u b s t r a t e , b u t lower

t h a n t h e measured t e m p e r a t u r e s a t d e p t h s m o r e t h a n a b o u t a n

inch.

S i m i l a r p l o t s were made f o r o t h e r t e s t s ; t h e y s h o w e d poor c o m p a r i s o n s between c a l c u l a t e d and measured temperatures, especially f o r t h e insulating materials such a s p o l y e t h y l e n e foam and p o l y s t y r e n e foam. In t h e c a s e of t h e

c o n c r e t e b a s e d m a t e r i a l s , some o f t h e d e v i a t i o n b e t w e e n meas u r e d t e m p e r a t u r e s and c a l c u l a t e d t e m p e r a t u r e s may b e d u e t o

Grs

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

p e r l i t e a t t h e surface than i n t h e bulk.

111-37

However, t h e r e a r e

G4 0

w
E+

3
ul

L9

0 -40

1/4 in
1/2

A
0

in

C -

-60

1 in 2 in 4 in CALCULATED

TEST NO. P-54

I
T I N E , MINUTES

Figure 9.-

Comparison of Calculated and lleasured Substrate Temperatures.

111-38

@
other non-consistent

results i n the data a s w e l l .

For a

given test p i t , the r a t i o (T

Tp)/(To

T ) should be

c o n s t a n t f o r a g i v e n time and d e p t h i n t h e p i t , p r o v i d e d t h e p i t p r o p e r t i e s remain c o n s t a n t from run t o run. The tempera-

t u r e r a t i o s d i d n o t remain c o n s t a n t from run t o r u n , b u t

t h e r e was n o o b v i o u s r e a s o n f o r t h e c h a n g e s .

T e m p e r a t u r e p r o f i l e p l o t s c o u l d be drawn t h a t f i t t h e d a t a a t o n e o r two d e p t h s b u t n o t a t o t h e r d e p t h s . However, t h e t h e r m a l c o n d u c t i v i t i e s r e q u i r e d f o r t h o s e c a l c u l a t i o n s c o u l d d i f f e r f r o m t h o s e f o u n d by c o n s i d e r i n g the vaporization data. The t e m p e r a t u r e p r o f i l e s m e a s u r e d d u r i n g t h e p r o p a n e v a p o r i z a t i o n t e s t s g e n e r a l l y showed h i g h e r m e a s u r e d t e m p e r a t u r e s d e e p i n t h e s u b s t r a t e t h a n t h o s e p r e d i c t e d by Equation 6 . T h a t r e s u l t i m p l i e s t h a t t h e t h e r m a l con-

d u c t i v i t y d e r i v e d from t h e v a p o r i z a t i o n d a t a i s t o o l a r g e .
However,
near t h e surface of the substrate, t h e measured

t e m p e r a t u r e s were l o w e r t h a n t h e c a l c u l a t e d t e m p e r a t u r e s , which i m p l i e s t h a t t h e t h e r m a l c o n d u c t i v i t y d e r i v e d from v a p o r i z a t i o n d a t a i s t o o low. I n r e a l i t y , t h e most l i k e l y

explanation f o r t h e behavior is t h a t t h e thermal c o n d u c t i v i t y v a r i e s w i t h t e m p e r a t u r e , i n c r e a s i n g a s t h e temperature decreases. The v a p o r i z a t i o n t e s t s p r o v i d e a n

a v e r a g e t h e r m a l c o n d u c t i v i t y t h a t i s a p p l i c a b l e f o r t h e temp e r a t u r e r a n g e of b o i l i n g o r s l i g h t l y s u b c o o l e d l i q u i d propane a t atmospheric pressure.

111-39
The thermal d a t a a r e

therefore quite good for predicting vaporization rates, but less reliable for determining temperature profiles. The mass transfer coefficient required for calculating vaporization rates for an open pool after boiling ceases and the liquid begins to subcool can be obtained from steady state vaporization measurements. Table 1 lists the

steady state vaporization rates for the tests where the pit was uncovered and steady conditions were reached. The mass

transfer coefficients were found for some of those tests. They were then used to determine the mass transfer factor
d e f i n e d by

where

jm = mass transfer factor

Gm = wind velocity in molar units

k' = mass transfer coefficient in
9-

molar units pa
=

ambient air viscosity

Pa = ambient air density D = diffusion coefficient

The mass transfer factor is determined primarily by the size of the vaporizing pool and the ambient wind velocity, combined in dimensionless form as a Reynolds number,
NR =

LG -

(30)

pa
111-40

Grs

where

N R = R e y n o l d s number
L = length

( o r d i a m e t e r ) of pool i n

downwind d i r e c t i o n
G = wind v e l o c i t y i n mass u n i t s

F i g u r e 1 0 i s a p l o t o f t h e mass t r a n s f e r f a c t o r s d e r i v e d from propane v a p o r i z a t i o n - d a t a . Data a r e i n c l u d e d t o n e a r l y 15

f o r wind v e l o c i t i e s f r o m l e s s t h a n o n e m i / h r
mi/hr.

T h e d a t a p o i n t s shown a s o p e n c i r c l e s a r e f o r c i r -

c u l a r t e s t p i t s a b o u t 2.5 f t i n d i a m e t e r .

T h e p i t s were

u s u a l l y 4 i n c h e s d e e p , b u t i n a few t e s t s p i t s a s d e e p a s 8 i n c h e s were u s e d .
As p a r t o f a g e n e r a l s e r i e s o f p r o p a n e

f i r e e x t i n g u i s h m e n t and c o n t r o l t e s t s ( J o h n s o n , e t a l . ,
1 9 8 0 ) s e v e r a l t e s t s were r u n t o m e a s u r e t h e v a p o r i z a t i o n

r a t e s of propane i n l a r g e r p i t s .

Figure 10 i n c l u d e s t h e
The l a r g e p i t s i z e s and

results of those tests a5 w e l l .

o c c a s i o n a l l y h i g h e r wind v e l o c i t i e s d u r i n g t h o s e t e s t s r e s u l t e d i n h i g h e r Reynolds numbers, s o t h e d a t a extend over a r a n g e o f R e y n o l d s numbers s p a n n i n g n e a r l y two o r d e r s o f magnitude. The p i t s 5 , 1 0 , a n d 2 0 f t s q u a r e were a l l 2 f t

d e e p a n d g e n e r a l l y c o n t a i n e d a b o u t 3 t o 6 i n c h e s of p r o p a n e d u r i n g t h e tests. The r e s u l t s i n d i c a t e t h a t t h e amount o f

freeboard did not influence t h e vaporization r a t e strongly for these tests. T h r e e d a t a p o i n t s a r e i n c l u d e d i n F i g u r e 1 0 from o t h e r s t e a d y s t a t e v a p o r i z a t i o n tests. Those v a p o r i z a t i o n

r a t e s were m e a s u r e d d u r i n g a s e r i e s o f U. S. C o a s t Guard
111-41

I-

-0.57

5.4 FT N HEXANE

A
I

1 0 . 4 FT CARBON DISULFIDE

20 FT LNG
I

I
I

A
10'

lo4

lo5

10

F i g u r e 10.

Mass T r a n s f e r Factors f r o m P r o p a n e Vaporization.

111-42

6d
f i r e f i g h t i n g t e s t s (Welker e t a l . ,
1981).

1980, Johnson e t a l . ,

T h e two h e x a n e d a t a p o i n t s were m e a s u r e d u s i n g t h e

5-ft

s q u a r e p i t and t h e c a r b o n d i s u l f i d e p o i n t was t a k e n square p i t .

These points

d u r i n g measurements on t h e IO-ft

i n d i c a t e t h a t t h e mass t r a n s f e r f a c t o r d a t a m e a s u r e d f o r p r o p a n e may b e u s e f u l f o r o t h e r l i q u i d s a s w e l l . amount o f d a t a a r e a v a i l a b l e f o r o t h e r l i q u i d s . Some s m a l l Perry

( 1 9 5 0 ) c o n t a i n s a b r i e f summary o f r e s u l t s f r o m t e s t s made mostly with water. equation

-0.2

Those d a t a a r e r e p r e s e n t e d by t h e

jm

0 . 0 3 6 NR

whereas t h e propane d a t a f i t t h e e q u a t i o n
-0.57

j,

4.4 NR

B o t h l i n e s a r e shown i n F i g u r e 1 0 .

For Reynolds numbers

between

lo5

a n d 1 06 , e i t h e r e q u a t i o n p a s s e s t h r o u g h t h e p r o However, t h e s l o p e f o r t h e p r o p a n e d a t a i s d i f The b e s t p r o c e d u r e t o f o l l o w

pane d a t a .

f e r e n t from t h e d a t a i n P e r r y .

i n e s t i m a t i n g v a p o r i z a t i o n r a t e s is t o u s e E q u a t i o n 3 2 ,
k e e p i n g i n m i n d t h a t e x t r a p o l a t i o n may l e a d t o e r r o r s .
The

v a p o r i z a t i o n r a t e s p r e d i c t e d by E q u a t i o n 3 2 a r e i n t h e same range a s t h e s t e a d y s t a t e r a t e s found f o r l i q u e f i e d n a t u r a l g a s i n t e s t s where s t e a d y s t a t e r a t e s were measured a s a b o u t

0.02

in/min

(about 8

I [

lb/ft2-sec)
111-43

(AGA 1 9 7 4 ) .

The v a p o r i z a t i o n r a t e and p o o l t e m p e r a t u r e b o t h

c h a n g e a s t h e wind s p e e d c h a n g e s .

The v a p o r i z a t i o n r a t e

c h a n g e s c a n n o t be measured e a s i l y b e c a u s e t h e change is s m a l l when compared t o t h e s e n s i t i v i t y o f t h e m e a s u r e m e n t system.

Pool t e m p e r a t u r e c h a n g e s a r e more r a p i d .

F i g u r e 11

shows p o o l t e m p e r a t u r e s a n d wind v e l o c i t y f o r a p o r t i o n o f
T e s t No.

P-9.

T h e r e i s a c o r r e l a t i o n b e t w e e n wind v e l o c i t y

a n d p o o l t e m p e r a t u r e , i n d i c a t i n g t h e e f f e c t o f wind v e l o city. The d a t a i n T e s t P-9 were t a k e n d u r i n g a p e r i o d o f The c h a n g e s i n wind s p e e d

nearly constant solar radiation.

a r e r e l a t i v e l y f r e q u e n t , s o t h e pool temperature changes a r e not large. The m o s t n o t i c e a b l e c h a n g e s o c c u r b e t w e e n 1 4 3 3

h o u r s a n d 1 4 3 6 h o u r s , when wind s p e e d d e c r e a s e s a n d p o o l temperature increases. The wind s p e e d i n c r e a s e b e t w e e n 1 4 3 6 About

and 1 4 3 9 h o u r s c a u s e s a d e c r e a s e i n pool t e m p e r a t u r e .

1 4 3 9 h o u r s t h e p o o l t e m p e r a t u r e b e g i n s t o r i s e a s wind s p e e d

decreases, b u t a sudden d r o p i n s o l a r f l u x c a u s e s a d r o p i n

pool temperature.
P o o l t e m p e r a t u r e s c h a n g e more n o t i c e a b l y i n r e s p o n s e

t o changes i n s o l a r r a d i a t i o n .

F i g u r e 1 2 shows a p l o t o f

s o l a r r a d i a t i o n a n d p o o l t e m p e r a t u r e f o r T e s t No. PE-46. The t h e r m o c o u p l e m e a s u r i n g t h e p o o l t e m p e r a t u r e r e s p o n d s quickly t o t h e changes i n r a d i a n t flux. Both t h e p o o l

t h e r m o c o u p l e and t h e s u b s t r a t e s u r f a c e may be a t s l i g h t l y h i g h e r t e m p e r a t u r e s t h a n t h e l i q u i d i n t h e pool because

n

r a d i a n t h e a t i s a b s o r b e d more e f f e c t i v e l y by t h e s o l i d
111-44

TIME, HOURS

Figure 11.

Effect of Wind Speed on Pool Temperature.

TEST NO. PE-46

TIME OF DAY, HR:MIN Figure 12. P o o l T e m p e r a t u r e F l u c t u a t i o n s c a u s e d by C h a n g e s i n S o l a r R a d i a t i o n L e v e l .

c3

surfaces.

I n f a c t , s o l a r r a d i a t i o n impinging on t h e thermo-

c o u p l e can change t h e thermocouple reading even though t h e pool t e m p e r a t u r e d o e s n o t change. Assuming t h e t h e r m o c o u p l e

bead t o b e c y l i n d r i c a l , a h e a t b a l a n c e on t h e bead shows that

d L qs
where

d L (Tb - T P )

(33)

d = d i a m e t e r o f bead
L = l e n g t h of bead

Tb = b e a d t e m p e r a t u r e

9 ,

= solar flux

h = heat transfer coefficient

T

= pool temperature

I t c a n b e shown t h a t t h e minimum v a l u e o f h i s

w h e r e k l is t h e liquid t h e r m a l conductivity,

T h e thermo-

c o u p l e b e a d s a r e l e s s t h a n 0.1 i n c h e s i n d i a m e t e r , s o f o r p r o p a n e , h i s g r e a t e r t h a n a b o u t 20 B t u / h r - f t 2 L 0 F . absorbed s o l a r f l u x o f 300 B t u / h r - f t 2 b e a d , Tb 4.8'F For a n

on t h e . * e r m o c o u p l e th

c a n b e f o u n d f r o m E q u a t i o n 3 3 t o be a b o u t
Tb

and f o r a s o l a r f l u x , o f 1 0 0 B t u / h r - f t 2 ,

is

a b o u t 1' .F 6. Btu/hr-ft2,

For a change i n s o l a r f l u x from 1 0 0 t o 300 a t e m p e r a t u r e c h a n g e of a b o u t '3.2'F would be

expected f o r t h e thermocouple i f t h e pool temperature d i d

n o t change.

The measured c h a n g e s o f a b o u t 5 t o 7'F

111-47

t h e r e f o r e show t h a t t h e p o o l t e m p e r a t u r e i s c h a n g i n g w i t h changes i n s o l a r flux. The p o o l t e m p e r a t u r e c h a n g e s q u i t e For

r a p i d l y f o r t h e s h a l l o w pool used i n t h e s e t e s t s . example, a s o l a r f l u x change o f 200 B t u / h r - f t 2 p o o l a t a r a t e o f a b o u t SF/min t h e pool d u r i n g T e s t PE-46.

w i l l heat the

f o r t h e mass o f p r o p a n e i n

Deeper p o o l s w i l l r e s p o n d more

s l o w l y t o c h a n g e s i n r a d i a n t f l u x b e c a u s e t h e l i q u i d mass i s g r e a t e r p e r u n i t of pool s u r f a c e a r e a . S e v e r a l t e s t s were r u n i n w h i c h g r a n i t e o r m a r b l e c h i p s were e i t h e r p l a c e d o n t h e p i t f l o o r b e f o r e p r o p a n e was s p i l l e d o r p o u r e d i n t o t h e p r o p a n e when s t e a d y s t a t e v a p o r i z a t i o n had b e e n r e a c h e d . The g r a n i t e c h i p s were a b o u t 0.15 The

i n c h e s i n n o m i n a l s i z e ( a q u a r i u m g r a v e l was u s e d ) .

m a r b l e c h i p s were a b o u t 0.75 i n c h e s i n n o m i n a l s i z e , a l t h o u g h t h e i r s i z e a n d s h a p e were n o t a s u n i f o r m a s w e r e

t h o s e of t h e s m a l l e r g r a n i t e c h i p s .

The b o i l o f f

from t h e

g r a n i t e c h i p s , r e g a r d l e s s o f w h e t h e r p r o p a n e was p o u r e d o n t o t h e c h i p s o r t h e c h i p s were p o u r e d i n t o t h e p r o p a n e , was a s f a s t a s pouring c o u l d b e done.

As a c o n s e q u e n c e o f t h e

r a p i d b o i l i n g , s u b s t a n t i a l p r o p a n e was e j e c t e d d i r e c t l y i n t o t h e atmosphere a s s p r a y o r d r o p l e t s .
The b o i l o f f r a t e s

c o u l d n o t b e measured, a n d e v e n m e a s u r e m e n t s o f b e g i n n i n g a n d e n d i n g w e i g h t s were n o t c o n s i s t e n t .
T h e b o i l o f f when

u s i n g t h e l a r g e r m a r b l e c h i p s was s l o w e r , b u t a b o u t a s much p r o p a n e was e j e c t e d a s m i s t o r s p r a y a s was v a p o r i z e d by h e a t i n g i f t h e p r o p a n e was p o u r e d o n t o m a r b l e c h i p s i n a

111-48

concrete pit.

I f m a r b l e c h i p s were p o u r e d i n t o a p i t con-

t a i n i n g s u b c o o l e d p r o p a n e , b o i l i n g was l e s s v i g o r o u s a n d l i t t l e o r no s p r a y was e j e c t e d . The p r o p a n e warmed a n d

b o i l e d f o r a f e w m i n u t e s b e f o r e a new s t e a d y b o i l i n g p e r i o d

was r e a c h e d .

F i g u r e 13 shows a c u r v e f o r w e i g h t r e m a i n i n g p r o p a n e when 2 0 l b o f m a r b l e

i n a p i t c o n t a i n i n g sub-cooled c h i p s was a d d e d .

About a q u a r t e r o f a m i n u t e was r e q u i r e d

t o add t h e r o c k s , and s t e a d y s t a t e v a p o r i z a t i o n was ree s t a b l i s h e d i n a b o u t 3 min. A l t h o u g h n o t shown i n F i g u r e

13, t h e s t e a d y v a p o r i z a t i o n r a t e c o n t i n u e d u n t i l t h e p r o p a n e was n e a r l y g o n e .
T h e c u r v e drawn t h r o u g h t h e d a t a i s b a s e d

on Equation 24 with t h e temperature h i s t o r y being used t o c a l c u l a t e t h e h e a t l o s t from t h e m a r b l e r o c k s . H e a t re-

q u i r e d t o w a r m t h e pool t o t h e b o i l i n g p o i n t and s t e a d y s t a t e m a s s t r a n s f e r r a t e s were b o t h i n c l u d e d i n d e t e r m i n i n g

the vaporization rate.

The h e a t t r a n s f e r c o e f f i c i e n t

between t h e m a r b l e c h i p s and t h e propane u s e d t o o b t a i n t h e c a l c u l a t e d c u r v e shown was 20 B t u / h r - f t 2 - O F . F i g u r e 14 shows two c u r v e s . The u p p e r c u r v e i s t h e

v a p o r i z a t i o n when p r o p a n e was p o u r e d i n t o a p o l y s t y r e n e foam pit. The s t e a d y s t a t e v a p o r i z a t i o n r a t e i s r e a c h e d w i t h i n a

The l o w e r c u r v e i s f o r v a p o r i z a t i o n when

m i n u t e o r two.

p r o p a n e was p o u r e d i n t o t h e p o l y s t y r e n e foam p i t c o n t a i n i n g
5 0 l b o f warm m a r b l e c h i p s .
T h e l i n e drawn t h r o u g h t h e

l o w e r d a t a was c a l c u l a t e d b a s e d o n E q u a t i o n 14 a n d t h e v a p o r i z a t i o n from t h e upper c u r v e f o r a p l a i n p o l y s t y r e n e

111-49

20

15

CALCULATED MEASURED

TEST V/Ml3-87

10 0'

3
TIMI?, M I N

Figure 13.

Propane Vaporization Following Pouring of 20 lb of Marble C h i p s into Propane.

171-50

20

1
TEST ps-89

19

STYRENE FOAM

18

0
17

bEASURED

- CALCULATED

16

15

STYRENE FOAM W/50 LB MARBLE

r\

14

TIME, M I N

F i g u r e 14.

P r o p a n e V a p o r i z a t i o n F o l l o w i n g S p i l l i n t o S t y r e n e Foam P i t a n d S t y r e n e Foam P i t C o n t a i n i n g Marble C h i p s .

111-51

foam p i t . cellent.

The a g r e e m e n t b e t w e e n t h e c u r v e a n d d a t a i s e x However, t h e h e a t t r a n s f e r c o e f f i c i e n t r e q u i r e d t o

m a t c h c a l c u l a t e d and m e a s u r e d c u r v e s was 2 0 0 B t u / h r - f t * - O F .
The r e a s o n f o r t h e d i f f e r e n c e between t h e h e a t t r a n s f e r

c o e f f i c i e n t f o r t h i s t e s t and t h e t e s t i n F i g u r e 1 3 is unknown. However, t h e r a n g e o f t e m p e r a t u r e d i f f e r e n c e s

between s o l i d ( p i t o r r o c k s ) and b o i l i n g propane is g e n e r a l l y i n t h e r a n g e where t r a n s i t i o n b o i l i n g ( b e t w e e n n u c l e a t e and f i l m b o i l i n g ) i s e x p e c t e d f o r p r o p a n e ( S c i a n c e ,

1966).

T h e r e f o r e , wide v a r i a t i o n s i n h e a t t r a n s f e r c o e f -

f i c i e n t s may b e e x p e c t e d . When s t e a d y s t a t e v a p o r i z a t i o n was r e a c h e d w i t h marble c h i p s i n t h e p i t , any marble exposed a s t h e l i q u i d l e v e l r e c e d e d was q u i c k l y c o v e r e d w i t h a l a y e r o f f r o s t ( o r hydrate). The f r o s t l a y e r a c t e d a s a w i c k , a n d t h e s u r f a c e T h e r e was no s t r o n g

of t h e rocks s t a y e d w e t with propane.

e f f e c t on s t e a d y s t a t e v a p o r i z a t i o n r a t e t h a t c o u l d be a t t r i b u t e d t o t h e wicking e f f e c t . However, i t i s p r o b a b l e

t h a t t h e wicking d i d a f f e c t t h e d a t a , because a s u b s t a n t i a l f r a c t i o n o f t h e s u r f a c e o f t h e p o o l was t a k e n u p by t h e marble, reducing d i r e c t l i q u i d t o a i r vaporization. The

w i c k i n g e f f e c t a p p a r e n t l y a d d e d e n o u g h mass t r a n s f e r a r e a t o counterbalance t h a t l o s t a s t h e l i q u i d s u r f a c e receded.

111-52

CONC LUS I ONS

The v a p o r i z a t i o n t e s t s o n l i q u i d p r o p a n e showed t h a t a c o n d u c t i o n h e a t t r a n s f e r model c o u l d b e u s e d t o p r e d i c t

t h e v a p o r i z a t i o n r a t e f o r l i q u i d p r o p a n e s p i l l e d on s o l i d

surfaces.

Two v a r i a b l e s , t h e e f f e c t i v e t h e r m a l c o n d u c t i v i t y

o f t h e s o l i d and t h e h e a t t r a n s f e r c o e f f i c i e n t f o r h e a t i n g from s o l i d t o l i q u i d were d e r i v e d f r o m t h e t e s t r e s u l t s .

T h e e f f e c t i v e t h e r m a l c o n d u c t i v i t i e s were l a r g e r t h a n t h o s e

found i n t h e l i t e r a t u r e f o r s i m i l a r m a t e r i a l s .

However,

t h e y were s i m i l a r i n m a g n i t u d e t o t h e r m a l c o n d u c t i v i t i e s f o u n d by s i m i l a r t e c h n i q u e s d u r i n g LNG s p i l l t e s t s . The

t h e r m a l c o n d u c t i v i t i e s o f common m a t e r i a l s s u c h a s c o n c r e t e and s o i l v a r y a t lower t e m p e r a t u r e s and t h e e f f e c t i v e v a l u e measured from v a p o r i z a t i o n tests r e f l e c t s t h e h i g h e r v a l u e s . Temperature p r o f i l e s w i t h i n t h e s u b s t r a t e s u p p o r t t h i s conclusion. The s t e a d y s t a t e v a p o r i z a t i o n r a t e o f p r o p a n e dep e n d s p r i m a r i l y o n wind v e l o c i t y , a n d t o a l e s s e r e x t e n t , t h e s o l a r r a d i a t i o n on t h e pool. t r a n s f e r f a c t o r s was p r e p a r e d .
A c o r r e l a t i o n o f mass

I t can be used with o t h e r

h e a t and mass t r a n s f e r d a t a t o d e t e r m i n e s t e a d y s t a t e v a p o r ization rates.

Pool t e m p e r a t u r e c h a n g e s o c c u r i n r e s p o n s e
The

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

c h a n g e s a r e d e p e n d e n t on p o o l d e p t h and a r e most pronounced f o r shallow pools.

111-53

REFERENCES
1. 2.

American G a s A s s o c i a t i o n , "LNG S a f e t y Program: I n t e r i m R e p o r t on P h a s e I1 Work," P r o j e c t IS-3-1 ( 1 9 7 4 ) .

E s h b a c h , 0. W . , and M. S o u d e r s , Handbook o f E n g i n e e r i n g Fundamentals, 3 r d e d . , John Wiley & Sons ( 1 9 7 5 ) . J o h n s o n , D. W . , e t a l . , " F i r e C o n t r o l Agent E f f e c t i v e n e s s f o r H a z a r d o u s C h e m i c a l F i r e s : Carbon D i s u l f i d e , " R e p o r t N o . CG-D-09-81, U. S . C o a s t G u a r d , W a s h i n g t o n , DC ( 1 9 8 1 ) . J o h n s o n , D. W . , e t a l . , " C o n t r o l a n d E x t i n g u i s h m e n t of LPG F i r e s , " R e p o r t N o . D O E / E V / 0 6 0 2 0 - 1 , U. S. D e p t .
of E n e r g y , W a s h i n g t o n , DC

3.

4.

(1980).

5.
.6

M a c l e a n , J . D . , " T h e r m a l C o n d u c t i v i t y of Wood," H e a t i n g , P i p i n g , and A i r C o n d i t i o n i n g , 459 ( 1 9 4 0 ) . L e n t z , A. E . , a n d G. E . M o n f o r e , "Thermal C o n d u c t i v i t y of C o n c r e t e a t Very Low T e m p e r a t u r e s , " J o u r n a l o f PCA R e s e a r c h and Development L a b o r a t o r i e s , -, 39 ( 1 9 6 5 ) . 7 P e r r y , J. H . , ed., C h e m i c a l E n q i n e e r s ' Handbook, 3 r d e d . ,
M c G r a w H i l l Book Company ( 1 9 5 0 ) .

7.

8.

R e i d , Robert C . , " B o i l i n g o f LNG o n T y p i c a l Dike F l o o r Materials , I 1 R e p o r t No. G R I - 7 9 / 0 0 2 6 , G a s Research I n s t i t u t e , Chicago (1980)

9.

S c i a n c e , C. T . , " P o o l B o i l i n g Heat T r a n s f e r t o L i q u e f i e d H y d r o c a r b o n Gases," Ph.D. D i s s e r t a t i o n , U n i v e r s i t y o f Oklahoma, Norman, Oklahoma ( 1 9 6 6 ) .

111-54

APPENDIX A
T h i s Appendix c o n t a i n s t h e v a p o r i z a t i o n d a t a f o r a l l t h e t e s t s r u n i n t h e 5 - f t 2 t e s t series. The d a t a are shown

i n g r a p h i c a l form i n t h e sequence i n which t h e y w e r e r u n . The r u n numbers a r e t h e same as l i s t e d i n T a b l e 1 i n t h e body of t h e r e p o r t . The s u b s t r a t e f o r each t e s t i s n o t e d

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

w a s open o r c o v e r e d .

Refer t o Table 1 f o r a d d i t i o n a l d a t a .

A- 1

54

40

CG-1

OPEN

L MIX CONCRETE

30
. . ,

- - 7

I I

20

* , . .

. . . . .
.....

_,-_-..-

. !

, . ! . . . . . . . . . . . / .. . . . . .

, . . . , .. .. .. . . . . . . ,
. . . . . .

. .
. I

" "

, " '. !. , . .
, I

"

. . . . . . . . . .I....... . . . . . . . . . . . . . ,..,. , ,

...

-. . , ., I! :. : ., :. : .' : .' . ;.
I , .

10
0

_..-__

. . , . . . , ,., , , , . . . . . . j . . . . . .

. --.,.- _--.

. . . . . . . . . , . . . _-... j .. ,. . , , . ! . . . . . . . I. .... .. ::j . . . . . .

. . . . . . . . . . .

' I ... ..... .... ... .. . ..

. . . . . . .

. . ( . .

.i

20

40
TIME, MIN

10 0

FIGURE A-1.

VAPORIZATION O F PROPANE FOLLOWING A SPILL ON GRAVEL M I X CONCRETE.

50

, ' , , , , , , .. ,/ , , ! . . . . . . . . ./ . . . . . . . . . . . . . .i
I .
, , ! I . . 1 . ,

'

'

-1

. . .

40

CG- 3

OPEN

--

,
I
I

GRAVEL MIX CONCRETE

30
20

-, I

. . . . . . . . ,:. . . . . .

, , , , . ,

.. .. . .. .: ,. . . .I .. . . . . . . .. . :I , , , , ,. . , , .
I

.I ::,::,:

'

1 ' : : ; ,: : , ' .:

1
*

. ,.. . . .... . ,..

" "

.......

, I

.,

10

.......
,,
I .

I .

.
,

. . . . I. , , ,

' I

......

i
20

.........
, ,
, , : . . ,
, I . , . ,

.........
I
I I I I I , . , ,

. . . '. ,.' .. / ,. ,.. . .. .. .. .. .. .. I . . ! . . . . . . .

!

, , , . I , , ) , , , , , , , !

. . . . . .!
. , ,

, . . , . .

. , . ,
(

.,,,..
a , . . .
, I . , .

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

. . . . . . .1

I
I , , , , .

'

...," , -

. ., .

60
TIME, MIN

80

100

FIG,URE A-2.

VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON GRAVEL M I X CONCRETE.

A- 2

50

40

30

28

10

I ,
I

I '
1

20

40 TIME, MIN

60

80

1@ 0

FIGURE A-3.

VAPORIZATION OF PROPANE FOLLOWING A SPILL ON GRAVEL MIX CONCRETE.

'

/ j

1/ ,7

I !

CS-5

OPEN

* , s

1
1
I

t
~

I
II

20

40

'

60

80

100

T[IME, MIN
FIGURE A-4. VAPORIZATION OF PROPANE FOLLOWING A SPILL ON SAND MIX CONCRETE.

A- 3

"

40
TIME, MIN
FIGURE A-5.

60

VAPORIZATION OF PROPANE FOLLOWING A SPILL ON SAND MIX CONCRETE.

50

40

30
20

10

20

60

100

TIME, MIN
FIGURE A-6. VAPORIZATION OF PROPANE FOLLOWING A SPILL ON SAND MIX CONCRETE.

A- 4

TIME, MIN
F I G U R E A-7. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON POLYSTYRENE FOAM.

TIME, MIN
F I G U R E A-8. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON POLYSTYRENE FOAM.

"

0
TIME, MIN
FIGURE A-9. VAPORIZATION OF PROPANE FOLLOWING A SPILL ON POLYSTYRENE FOAM.

100

50

40

30
20

10

. &

40
TIME, MIN
*

60

100

FIGURE A-10.

VAPORIZATION OF PROPANE FOLLOWING A SPILL ON VERMICULITE CONCRETE. A- 6

100

TIME, MIN
FIGURE A-11. VAPORIZATION OF PROPANE FOLLOWING A S P I L L ON VERMICULITE CONCRETE.

50

40

OPEN CONCRETE

---

a
nm

30
20

10

20
TIME, MIN
FIGURE A-12. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON P E R L I T E CONCRETE.

A- 7

50
E'-15

40

OPEN

.
, .
. .
. I

P E R L I T E CONCRETE

30

--.. . , . . .
. .

.
I

...

..

, I '

, ,
I

,
I

20

, , . , . . I , . , , , . , 7--T-.--l

: , : ,

.., . , , . , . , ) ..,
I

, . . . .
,
,

, , , ,
.
.

I
I

. , . . .

..,., . . ,, .. . .
,

-I 1

10

--

0 -

20

40
TIME, MIN

60

80

100

FIGURE A-13.

VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON P E R L I T E CONCRETE.

50
I
I

40

S-17
SAND

OPEN

- _*c---

30

20

10

20

40
TIME, MIN

60

80

FIGURE A-14.

VAPORIZATION O F PROPANE FOLLOWING A SPILL ON SAND.

50

40

30
20

10

20

40

60

80

10 0

TIME, MIN
FIGURE A-15. VAPORIZATION OF PROPANE FOLLOWING A SPILL ON POTTING SOIL.

50
CL-20 OPEN

40

CLAY SOIL

30
20

10

0 -

20

40

60

80

100

FIGURE A-1'6.

VAPORIZATION OF PROPANE FOLLOWING A SPILL ON CLAY SOIL.

A- 9

z
P ,

E P ,

TIME, MlN
FIGURE A-17. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON CLAY S O I L .

50
CS-2 3 COVERED

40

Ly

SAND M I X CONCRCTE

30
20

10
.
, : , , . , .
. I , . .

I,..

,..;.,,::I:'::".':

0
0

20
TIME, MIN
FIGURE A-18.

60

80

VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON SAND M I X CONCRETE.

A-10

5(1

40

CS-24

COVERED

SAND M I X CONCRETE

30
20

17 - 7
. , , . . , ,

I::::

10
--

20

40
TIME, MIN

60

80

10 0

FIGURE A-19.

VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON SAND M I X CONCRFTE.

50
1-Ll!...:: ..i

. . ...

~. , . . ;
OPEN

40

CS-26
SAND

rux

CONCRETE

30

20

10

1 ii
j
I

0 20

40
TIME, MIN

60

80

FIGURE A-20.

VAPORIZATION OF PROPANE FOLLOWING A S P I L L ON SAND M I X CONCRETE.

A-11

50

40

CS-27

OPEN

z
0

SAND MIX CONCRETE

= e
v)

30

z
0

28

10
____.

20

40

60

80

10 0

TIME, MIN
FIGURE A-21. VAPORIZATION OF PROPANE FOLLOWING A SPILL ON SAND MIX CONCRETE.

50
OPEN CONCRETE

40

30
20

,---.--.--.

10

20

40
TIME, MIN

60

80

100
A

FIGURE A-22.

VAPORIZATION OF PROPANE FOLLOWING A SPILL ON SAND MIX CONCRETE.

A-12

50

40

CS-30

OPEN

; 1 ;: ::::
, , , , 1 I

30
20

10

20

40
TIME, MIN

60

80

10 0

FIGURE A-23.

VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON SAND M I X CONCRETE.

50
, * I
"

40

V-32

OPEN

I I

I
I

' I
I

VEFNCCULITE CONCRETE

j !, :1
I ,

30
20
- ( c

10

20

40
TIME, MIN

60

80

100

FIGURE A-24.

VAPORIZATION OF PROPANE FOLLOWING A S P I L L ON VERMICULITE CONCRETE.

A-13

TIME, MIN
FIGURE A-25. VAPORIZATION OF PROPANE FOLLOWING A S P I L L ON SAND MIX CONCRETE.

FIGURE A-26.

VAPORIZATION OF PROPANE FOLLOWING A S P I L L ON SAND MIX CONCRETE.

Grs
W

50

40

CS-36

COVERED ,..-:
*I!

z
e

d 0
P ,
v)

30
20

0 P ,

10

20

40

60

80

100

TIME, MIN
F I G U R E A- 2 7. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON SAND MIX CONCRETE.

50
cs-37

40
W

OPEN

SAND MIX C O N C W T E

z
0
n m

P ,

30

a
v)

z 20
a
0
P ,

10

i
0

.I

.___--

20

40

60

80

100

TIME, MIN
F I G U R E A-28. VAPORIZATION O F PROPANE FOLLOWING A SPILL ON SAND MIX CONCRETE.

A-15

50

T 1i
t

40
w

ii

/
I

z
P
0
CLI CL

i
I

30
20

T !
i

iI

I1
I

v)

s
0

T i

10

bt 4i
I

I1
1

1
0 0

20

40

TIME, MIN
FIGURE A-29.
A SPILL

VAPORIZATION OF PROPANE FOLLOWING ON PERLITE CONCRETE.

50

40
I

w
'

2 0
a
&
v)

30

z 20
a
0
CL

io
0 0

, , ,

20

40

60

80

100
A

TIME, MIN
FIGURE A-30. VAPORIZATION OF PROPANE FOLLOWING A SPILL ON PERLITE CONCRETE.

A-16

TIME, MIN
F I G U R E A-33. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON P E R L I T E CONCRETE.

TIME, MIN
F I G U R E A-34. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON ASPHALT.

5(1

40

4
I /

PE-44

COVERED

30

I
I . /

POLYETHYLENE FOAM

I 7 ( 1I. ; ?
. , I . . .

: ! : ' : . . I .

20
, . . . . . .
I . . .

.. .. .. . . . , I . ,

I:

10

20

40
TIME, MlN

60

80

100

FIGURE A-35.

VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON POLYETHYLENE FOAM.

50

40
'LENE FOAM

30
1 .

20

10
:I;:,":;;:
I , . . . . . . . . .

0 0

' I "

"

20

40
TIME, MIN

60

BO

F I G U R E A-36.

VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON POLYETHYLENE FOAM.

A-19

50

40

30

20

10
0

d,I 1

20

40
TIME, MIN

60

80

100

F I G U R E A-37.

VAPORIZATION OF PROPANE FOLLOWING A SPI LL ON POLYETHYLENE FOAM.

50

40

30
20

10

20

40
TIME, MIN

60

80

100

FIGURF: A-38.

VAPORIZATION O F PROPANE FOLLOWING A SPILL ON SAND MIX CONCRETE.

A-20

TIME, MIN
FIGURE A-39. VAPORIZATION OF PROPANE FOLLOWING A SPILL ON PERLITE CONCRETE.

TIME, MlN
FIGURE A-40. VAPORIZATION OF PROPANE FOLLOWING A SPILL ON VERMICULITE CONCRETE.

TIME, MIN
F I G U R E A-41. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON SAND MIX CONCRETE.

50

.. .. .. .. .. .. .. .. . .
I

. : : :. ~ - p .T .Y .;. :. ; ! .; . !: :: .!.: :. .: j. . . . ; .: . ' .: . . . . I! : : I . . . . . . . . . . . . . . . . . , , , , , . . . . . . . . . . . . . . . . . . . . . . . ;::I:::,:,:'

f . , , ,

:I:;,

'

40

SS-51

COVERED

1 -+-*--- ,

SANDY S O I L

I
. . .
, .
. ,

30
20

. . . .
. . , .
' -_-*
. . I

, , .
I

...

, . . . . . . . . . . . . ... , . . . I . . . . . . . . . .!----

. . . / .

,.,.
I

. .. . . . . . ..

. .

i . ' . : : ; .: .. , .i ,. ..
I . , , .

.. .. .. .. ..
I

..

,.

'

10

m
.........
.
I , , . , ,

.
,

. . . . . .
' , " "
, /
'
"

. . . . . . .: *

,,,!!:::.
.

, .

.
1
,

'
. .

. ! , .
, I .

--0

, , I

. j . , . . . . . ,. ., !/ " . . . . . . . . . . , . , . . . . . . . . . . . ----- . . . . .
" _ "

'

20

40
TIME, MIN

60

BO

100

F I G U R E A-42.

VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON SANDY S O I L .

A-22

I . . , .
j .
I

, . .

SANDY S O I L
7 ,-. * : I

LL 0 a LL

U
.I . :!;j.:..I''.
1
~

.,

_-. .. - .

_ I -

. , . , . .

,,..

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

:
I

ua

z
a

-t
I

" 1. ' : : I
'

0
L

,
, , , .

,....,

. . . .., . . / .
/ I

, . , . .

1.'. :,:::

. . . .

20

40
TIME, MIN

60

80

100

FIGURE A-43.

V A P O R I Z A T I O N O F PROPANE FOLLOWING A S P I L L ON SANDY S O I L .

50

40

SS-53

COVEFCD

30
20

7 -

10
:'
*

20

40
TIME, MIN

60

80

100

F I G U R E A-44.

V A P O R I Z A T I O N O F PROPANE FOLLOWING A SPILL ON SANDY SOIL.

A-23

TIME, MIN
F I G U R E A-45. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON POLYSTYFG3NE FOAM.

40

60

TIME, MlN
FIGURE A-46.
VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON P E R L I T E CONCRETE.

50

m ,
, I I . .

40

30
20

, .

10

40
'

60
TIME, MIN

FIGURE A-47.

VAPORIZATION OF PROPANE FOLLOWING A SPILL ON CLAY SOIL.

:',,::::!I::!::::,'!
' '

50
OPEN SOIL

::::I:::::::.

, , . I . . . . .
"

:
!
, .
' :

40

::; , . ,.-.-, ; , ; : : : I : : : : : : : +
,

"

. . , , , 1I ' "; '' : . ' , , . I ,

, , ,
,

,.,./...., .
. ( . . .
I

, . , , .

.,.. .,

: . II :: : , : ( ::
.

30

I . .
, I . I .

,
., ,.
I 1

,
. ,

,
. I

. .: .. ,. .. . ,! . ,
. : , , . , i

. . . , . .

!"
,

20

-I- , . . . . I ' ,
, ...,.. ..,,.. ,!...

! '

,....: j : .

10

40
TIME, MIN
FIGURE A-48.

60

VAPORIZATION OF PROPANE FOLLOWING A SPILL ON CLAY SOIL.

A-25

tr: :
C...

id

I:.::::::::!::-::.:.- : : . : : - ! !:::-

I
. . . . . . .

I . . . . . .

..L.

....... 1

50

. ., .. .. '. ,

-1

40
, .
I .

:.::I
. , . . ,

SS-61

COVERED

. , * . . ,.,.

SANDY SOIL

30
20
-. , . . .
. . I , . ,. ., .. .. .. . ,

10
0

20

40

60

80

100

TIME, MlN
FIGURE A-51. VAPORIZATION OF PROPANE FOLLOWING A SPILL ON SANDY SOIL.

SS-62

COVEFED

z
0
n m

1
I

SANDY SOIL

p .

a
n z a

II

v)

TI

----

, ,

__I_^.

.
100

20

40

60

80

TIME, MIN
FIGURE A-52. VAPORIZATION OF PROPANE FOLLOWING A SPILL ON SANDY SOIL.

50

40
PLYWOOD

30

20

10
0

20

40 TIME, MIN

60

80

100

F I G U R E A-53.

VAPORIZATION O F PROPANE FOLLOWING

A S P I L L ON PLYWOOD.

50
CL-64

40

COVERl3D

CLAY S O I L

30
20

10

20

40 TIME, MIN

60

80

100

' F I G U R E A-54.

VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON CLAY S O I L .

A-28

50
CL-65 OPEN

40

-.

, , . . ,

- - . - ?

...

CLAY S O I L

30
,

.,
,

. . . , , '. !, . . . ., , . . ...,,

. , , . ,

, , , . .

.
,

20

I _ -

. , . , , . ,

, . . . .

. .
,

..,..
. I , ,

, ,

..,.

10
0
___.--

TIME, MIN
F I G U R E A-55. VAPORIZATION O F PROPANE FOLLOWING A SPILL ON CLAY S O I L .

TIME, MIN
F I G U R E A-56. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON SOD/SOIL.

A-29

50

7--

,. ,
1

,
.

7, . m , . I:'::'.:::

40
W

SS-67

OPEN

SANDY S O I L

z
a

L 0

30

L
v)

t a
a

z
0
P,

20

10
0

--20

40

60

80

l o0

TIME, MIN
FIGURE A-57. V A P O R I Z A T I O N O F PROPANE FOLLOWING A S P I L L ON SANDY S O I L .

50

40

PL-68

OPEN

PLYWOOD

30
20

10
I I _ -

20

40
TIME, MIN

60

80

100

" F I G U W A-58.

V A P O R I Z A T I O N O F PROPANE FOLLOWING A S P I L L ON PLYWOOD.

A-30

_ _ I

, .

, , . ,;. ,:. . . I. .y ' , ; ,,: , ,, .. . : . . ' : , . ,

.,....
, . .

,. . . . .

'

I. : , :

---,
,

. . . . . . . .
. . ./

..

: : / : .I :. : . . . .
~

, .

.
- 1

SOD-69

OPEN

&! . .. .. . . .

SOD/SOIL __. . . . . . . , . , . . . . . .
1 .

;
I
8 , .

--I----I
. . . .

,:.:/::::

..

: '

w ........
.,,:..

.. .. . .. .. .. . .
. ., , , . , ,..,..:
1 : ' 1 .
I

I
'

. . . . . . . .. .. . . ,. .. ,. .. .. ,. . ,1 ". ....... ,, . . , 1. . . . . , , . , . . . . . . . . . . . . . . .~. _._. , , I . .....

/

, ,

.. : ,;.:, I: :. :. .: ::::. ,: !.
'

" " '

i -, -

40
TIME, MlN
FIGURE! A-59.

60

80

10 0

VAPORIZATION OF PROPANE FOLLOWING A SPILL ON SOD/SOIL.

SOD-70

OPEN
I .

SOD/SOIL

,,*.,

,
. , .

,
. , . . '. . ;
,

;,..::,,. .
1 ,

I ,
7--- . >

b
v)

I.:..::::: . . . . . . . . .j . .
, , , .

,
.

. . . .I
,
,
I .

.,.,. ., , . . . . . . . .

........

. .. ,. . , . . .. . . .
, ( , .

z a
0

.
. .

, .
, ( ,

, . .
.
1 .

0,

. . . . . . . . .I

,;::::

. . . . . ,. .: ,I .. ,I .. . .. . . . . . .
, . , )
,
, * . . . I . .

..
,
I

_c_--,

.. .. .. .. .. .. .. , ,. .. !.. .. .. . . i, . ,,.*, .. ,
I

, , . , , .

.
,

40

60

100

--r3

TIME, MIN
FIGURE A-60. VAPORIZATION OF PROPANE FOLLOWING A SPILL ON SOD/SOIL.

A-31

50

A -

40

tt

SOD-71
I

OPEN

I
1

30
20

f -

10

20

40
TIME, MIN

60

80

100

F I G U R E A-61.

VAPORIZATION OF PROPANE FOLLOWING

A S P I L L ON SOD/SOIL.

P-73

OPEN

i
I

P E R L I T E COlJCRETE

! i

20

40
TIME, MIN

60

80

100

FIGURE A-62.

VAPORIZATION OF PROPANE FOLLOWING A S P I L L ON P E R L I T E CONCRETE.

8-

A-32

50
P-74 COVERED

v 1 1

, . . . , . .

. . .
, . . .

40

PERLITE CONCRETE

;. .,
,

, , . . .

. . .
.

, .

.,...
.

30
, ( , . , . , , , ,

-_._ ., . . . .. .

,
,

. .

20

,,,... -i,---i , I . ., , . . , . .

,:I
i

I .,

10
.

._.

, . . .

20

40

60

80

10 0

TIME, MIN
FIGURE A-63.
~

VAPORIZATION OF PROPANE FOLLOWING A SPILL ON PERLITE CONCRETE.

CS-75
W

COVERED

z
0

SAND M I X CONCRETE
m -

h
a
CL

..
., .
/ .

t n n z
=>
&

20
TIME, MIN
FIGURE A-64.

60

80

100

VAPORIZATION OF PROPANE FOLLOWING A SPILL ON SAND MIX CONCRETE.

A-33

TIME, MIN
FIGURF: A-65. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON SAND CONCRETE/ GRANITE C H I P S .

TIME, MIN
F I G U R E A-66. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON P E R L I T E CONCRETE/ GRANITE C H I P S .

A-34

crs

50

40

. . . . ., . ,..... !:'.;:.': .,.,. .,...., .. , , . . , . , . . . . . . .

:..,

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

30

........ .. .. .. .. . .. .. ,!. /.. .......... ....., .!.. .......(..

. . . . . . ./ . . . . . . . .......1, ......
. . . . . . . I . .
, : I "
" "

:.;

) , , . , , : I

. . , i-,
1 (

,
.
.

; . , , . , : I . . . .
, : . 1 . . , I . .

.
,

.
I

.....
8 .

. -..

j.

1 : ; : : . .. .. . . ,

I
1

' '

I !

20
4
, 4 ,

r
I

-1 . .
' I

P/GR-78

COVERED CHIPS

" I

10

---T

P E R L I T E CONCRETE/GRANITE

I
0

20

40
TIME, MIN

60

80

100

FIGURE A-67.

VAPORIZATION OF PROPANE FOLLOWING A S P I L L ON P E R L I T E CONCRETE/GRANITE C H I P S .

50

40

30
20

10

20

40

60

80

100

TIME, MIN
FIGURE A-68. VAPORIZATION O F PROPANE FOLLOWING A SPILL ON SAND MIX CONCRETE/GRANITE C H I P S .

A-35

50

40

z
0 rA

a a
n

30
20
.

z
0

a
10 -

00

20

40

60

80

100

TIME, MIN
FIGURE A-69. VAPORIZATION OF PROPANE FOLLOWING A SPILL ON PERLITE CONCRETE/GRANITE CHIPS.

50

::I
40
w
P S / G R - ~ ~ COVERED

I"i ' I

* I

B 0
p :

30

a
rA

a z 20
a a

10

20

40
TIME, MIN

60

80

100
n

FIGURE A-70.

VAPORIZATION OF PROPANE FOLLOWING A SPILL ON POLYSTYRENE/GRANITE CHIPS. A-36

TIME, MIN
F I G U R E A-71. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON PEECLITE CONCRETE/GRANITE C H I P S .

50

40

30

20

10

:I.

40
TIME, MIN
F I G U R E A-72.

60

80

VAPORIZATION OF PROPANE FOLLOWING A SPILL ON VERMICULITE CONCRETE.

A-37

50
1

40

V/GR-84

COVEWD CHIPS

VERMICULITE CONCRETE/GRANITE

:I

30
20

10

20

40

60

80

100

TIME, MIN
F I G U R E A-73. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON VERMICULITE CONCRETE/GRANITE C H I P S .

50

4Q

T
I
I.
t
i

V/MB-85

COVERED

30
20

j
r

10

r
I

II

20

40

60

80

100

TIME, MIN
FIGURE'A-74. VAPORIZATION OF PROPANE FOLLOWING A S P I L L ON VERMICULITE CONCRETE/MARBLE C H I P S .

A-38

50
' I

40
:

V/MB-86

OPEN

VERMICULITE CONCRETE/MAP?LE C H I P S

30
20

. . . . ,. ,. , . , ., ./

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. . . . . . . . I . . . . . , .

20

40

60

80

10 0

TIME, MIN
F I G U R E A-75. VAPORIZATION O F PROPANE FOLLOWING A SPILL ON VERMICULITE CONCRETE/MARBLE C H I P S .

50

40

f
1

V/MB- 87

OPEN CHIPS

VERMICULITE CONCZETE/ImRBLE

30
20

10

20

60

80

100

TIME, MIN
F I G U R E A-76. VAPORIZATION O F PROPANE FOLLOWING A S P I L L ON VERMICULITE CONCRETE/MARBLE C H I P S .

A-39

50

., < .
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40
W

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V/MB-88

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Lz: Q

: VERNICULITE CONCRETE/IVLARBLE CHIPS

30

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2 3 0 Q

20

10

20

40

80

100

TIME, MIN
FIGURE A-77. VAPORIZATION OF PROPANE FOLLOWING A S P I L L ON VERMICULITE CONCRETE/MARBLE C H I P S .

50

40

30
20

t
0

10

20

40 TIME, MIN

60

80

100

FIGURE A-78.

VAPORIZATION OF PROPANE FOLLOWING A S P I L L ON POLYSTYRENE.

A-40

z
P,

0
v)

I
I I

1 i
t

LI.

n z a

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t

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P,

r
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20

40 TIME, MIN

60

100

F I G U R E A-79.

VAPORIZATION O F PROPANE FOLLOWING A SPILL ON POLYSTYRENE/MARBLE CHIPS.

A-41

REPORT I V
S P I L L S OF P R E S S U R I Z E D PROPANE

INTRODUCTION

Most p r o p a n e t r a n s p o r t e d i n t h e U n i t e d S t a t e s i s c a r r i e d by r a i l t a n k c a r , t a n k t r u c k , o r p i p e l i n e . In

n e a r l y a l l cases, t h e propane is t r a n s p o r t e d a s a p r e s s u r i z e d l i q u i d a t ambient temperature. I f t h e p r e s s u r e on

t h e l i q u i d i s r e l e a s e d s u d d e n l y , s u c h a s when a l e a k o c c u r s ,

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

The

f r a c t i o n f l a s h e d depends on t h e s a t u r a t i o n p r e s s u r e b e f o r e
t h e pressure is released.
As t h e l i q u i d f l a s h e s t o v a p o r , and a s i t f l o w s

through a crack o r valve, strong shearing f o r c e s are-generated. The s h e a r i n g f o r c e s b r e a k t h e l i q u i d u p , a t o m i z i n g i t

T h i s s e c t i o n d i s c u s s e s t e s t s made

i n t o very small droplets.

i n a n attempt t o d e t e r m i n e h o w much propane m i g h t a c c u m u l a t e following a r e l e a s e of p r e s s u r i z e d propane. PROCEDURE F i g u r e 1 is a s c h e m a t i c diagram of t h e t e s t appa-

ratus.

A t a n k c o n t a i n i n g l i q u i d p r o p a n e was p l a c e d o n o n e

e n d o f a b a l a n c e mechanism a n d a w e i g h t t r a n s d u c e r was a t t a c h e d t o t h e o t h e r end. F i g u r e 2 shows a s c h e m a t i c o f They i n c l u d e d a

the m e a s u r i n g d e v i c e s t h a t were a t t a c h e d .

t h e r m o c o u p l e t o measure l i q u i d t e m p e r a t u r e and a p r e s s u r e

IV- 1

CSENSORS

TRANSDUCER

TANK

i \ DISCHARGE
PIPE

TO DATA RECORDER

FULCRUM

F i g u r e 1.

Setup for Propane Spray T e s t s .

NITROGEN PRESSURE LINE TANK PRESSURE GAUGE TANK PRESSURE TRANSDUCER FLOW VALVE F I L L LINE SAFETY RELIEF VALVE NOZZLE PRESSURE TRANSDUCER LIQUID LEVEL GAUGE

LIQUID LINE

LIQUID TEMP. THERMOCOUPLE

F i g u r e 2.

L o c a t i o n o f P l e a s u r i n g E q u i p m e n t for P r o p a n e S p r a y T e s t s .

transducer.

I n a d d i t i o n , t h e r m o c o u p l e s were p o s i t i o n e d

d o w n s t r e a m from t h e d i s c h a r g e p i p e t o m e a s u r e t h e temp e r a t u r e o f t h e p r o p a n e plume d u r i n g d i s c h a r g e .

A

l a r g e p o l y s t y r e n e foam t r a y was b u i l t d o w n s t r e a m

o f t h e d i s c h a r g e p i p e t o c a t c h propane d u r i n g d i s c h a r g e .
T h e t r a y was l i n e d w i t h l i g h t w e i g h t p o l y e t h y l e n e f i l m t o

p r e v e n t l o s s d u e t o s e e p a g e i n t o t h e foam o r foam deterioration.

T e s t s followed a simple p a t t e r n .

The t a n k was

c h a r g e d w i t h p r o p a n e a t a m b i e n t t e m p e r a t u r e a n d i t s own vapor p r e s s u r e ( t h e propane contained 0.25 p e r c e n t e t h a n e and 0.36 p e r c e n t i s o b u t a n e )

The t a n k p r e s s u r e was t h e n

i n c r e a s e d by a b o u t 1 5 t o 2 5 p s i by d r y n i t r o g e n s u p p l i e d through a regulator. After s t a r t i n g recording instruments,

t h e d i s c h a r g e v a l v e was o p e n e d and p r o p a n e was a l l o w e d t o flow out. The n i t r o g e n p r e s s u r e was m a i n t a i n e d a t t h e maxi-

m u m r e g u l a t o r c a p a c i t y u n t i l a l l l i q u i d was d i s c h a r g e d .

N i t r o g e n p r e s s u r e was u s e d t o a i d i n p r e v e n t i n g l i q u i d f l a s h i n g upstream of t h e v a l v e during discharge.

R E S U L T S AND D I S C U S S I O N

F i g u r e 3 shows t h e plume formed d u r i n g a p r o p a n e discharge test. The d i s c h a r g e is h o r i z o n t a l a t a r a t e t h a t

s t a b i l i z e d a t 175 lb/min a f t e r about 1 0 seconds o f flow.

T h e f l o w r a t e r e m a i n e d c o n s t a n t u n t i l t h e t a n k was e s s e n -

t i a l l y empty f o l l o w i n g t h e i n i t i a l d r o p f r o m a b o u t 400

IV-4

F i g u r e 3.

Vapor Plume from D i s c h a r g e of P r e s s u r i z e d Propane a t 180 lb/min.

lb/min.

I t was a p p a r e n t t h a t n i t r o g e n f l o w was i n s u f f i c i e n t

t o keep t h e t a n k p r e s s u r e above t h e vapor p r e s s u r e d u r i n g

t h e high flow r a t e d i s c h a r g e . F i g u r e 4 shows t h e w e i g h t o f p r o p a n e d i s c h a r g e d d u r i n g t h e t e s t , t h e t a n k t e m p e r a t u r e , and t h e t a n k p r e s sure. A f t e r an i n i t i a l d e c r e a s e i n t a n k p r e s s u r e a b o u t

e q u a l t o t h e p r e s s u r e a d d e d by t h e n i t r o g e n c a p , t h e p r e s -

s u r e d e c r e a s e d s l o w l y u n t i l t h e l i q u i d was g o n e ; t h e t a n k
p r e s s u r e was t h e n a l l o w e d t o d e c r e a s e u n t i l t h e p r o p a n e v a p o r and n i t r o g e n g a s were d i s c h a r g e d . The l i q u i d t e m p e r a -

t u r e i n t h e t a n k remained a t ambient t e m p e r a t u r e u n t i l
n e a r l y a l l o f t h e p r o p a n e had b e e n d i s c h a r g e d . t e m p e r a t u r e o f a b o u t 82'F,
A t the tank

t h e t a n k p r e s s u r e was t h e v a p o r

p r e s s u r e of propane, a g a i n i n d i c a t i n g t h a t t h e n i t r o g e n flow was t o o s m a l l t o m a i n t a i n t a n k p r e s s u r e .

T h e t h e r m o c o u p l e s i n t h e p r o p a n e plume l o c a t e d 2 a n d

5 f t from t h e n o z z l e showed t e m p e r a t u r e s i n t h e plume a s low

8' a s -5F

during discharge.

A s l o n g a s l i q u i d was b e i n g d i s -

c h a r g e d , t h e plume t e m p e r a t u r e was l e s s t h a n a b o u t -70F. The plume was t h e r e f o r e s u b s t a n t i a l l y s u b c o o l e d a s t h e small d r o p s formed d u r i n g d i s c h a r g e v a p o r i z e d . About 50 p e r c e n t

o f t h e l i q u i d d i s c h a r g e d would h a v e t o v a p o r i z e i n o r d e r t o

s u b c o o l t h e plume.

Those d r o p l e t s t h a t r e m a i n e d i n t h e

plume v a p o r i z e d v e r y r a p i d l y a s t h e y mixed w i t h t h e a i r , s o t h a t by t h e time t h e plume r e a c h e d t h e t h e r m o c o u p l e 1 0 f t f r o m t h e d i s c h a r g e p i p e , t h e plume t e m p e r a t u r e was 4 0 t o 50F, i n d i c a t i n g t h a t a l l t h e p r o p a n e was v a p o r i z e d . IV- 6

TIME, SEC

F i g u r e 4.

T e m p e r a t u r e s , Tank P r e s s u r e , and Weight Loss f o r Ambient Temperature Propane Discharge.

T e s t s s i m i l a r t o t h a t f o r which d a t a a r e shown i n

63

F i g u r e 4 were r u n f o r d i s c h a r g e r a t e s f r o m 1 3 t o 1 8 0 l b / m i n .
N o p r o p a n e was c o l l e c t e d i n t h e c a t c h t r a y d u r i n g a n y o f t h e

tests.

I n one t e s t a t a f l o w r a t e o f 180 lb/min a d e f l e c t o r

s h i e l d was p l a c e d 3 f t from t h e end o f t h e d i s c h a r g e p i p e t o

a i d i n c a t c h i n g l i q u i d , b u t no l i q u i d was a c c u m u l a t e d . Q u a l i t a t i v e t e s t s were r u n w i t h s m a l l e r t u b e s where t h e f l o w r a t e was 1.8 l b / m i n , b u t a f t e r 1 0 m i n u t e s o f f l o w , no l i q u i d

The bottom

p r o p a n e was a c c u m u l a t e d i n a n i n s u l a t e d b u c k e t .

o f t h e b u c k e t c o n t a i n e d i c e o r h y d r a t e , b u t no l i q u i d .

When

p r o p a n e was d i s c h a r g e d a t a b o u t t h e same r a t e w i t h t h e 0 . 1 2 5 i n c h d i s c h a r g e t u b e h e l d a b o u t 0 . 5 i n c h e s from a c o n c r e t e s u r f a c e , a p u d d l e o f p r o p a n e a f e w i n c h e s i n d i a m e t e r formed a f t e r about a minute. d i s c h a r g e was s t o p p e d . D u r i n g t h e LPG t e s t p r o g r a m more t h a n 2 0 0 t e s t s i n v o l v i n g s p i l l s o f l i q u i d p r o p a n e were made.
I n about half
T h e p r o p a n e v a p o r i z e d r a p i d l y when

o f t h e s e t e s t s , t h e l i q u i d p r o p a n e was t a k e n f r o m a m b i e n t temperature storage. The p r o p a n e was d i s c h a r g e d i n t o

b u c k e t s , b a r r e l s , and o p e n p i t s , and s u f f i c i e n t p r o p a n e c o u l d b e c o l l e c t e d f o r small t e s t s e a s i l y . Previous exper-

i e n c e w i t h l i q u e f i e d n a t u r a l g a s had shown t h a t c a r e had t o b e t a k e n , e v e n when d i s c h a r g e was f r o m a r e f r i g e r a t e d c a r g o , i n order t o assure t h a t t h e cold l i q u i d d i d not simply a t o m i z e and t h e n v a p o r i z e w i t h o u t f o r m i n g a p o o l . Quanti-

t i e s o f a b o u t 3 0 l b o f p r o p a n e c o u l d b e t r a n s f e r r e d from

IV- 8

6iJ

p r e s s u r i z e d s t o r a g e t o a b u c k e t i n a b o u t 15 m i n u t e s . two-thirds
to three-quarters

About

o f t h e l i q u i d f l a s h e d o r atom-

i z e d d u r i n g f i l l i n g , b u t o n c e t h e b u c k e t was f i l l e d , e v a p o r a t i o n was v e r y s l o w .
The propane f l a s h e d t o a

t e m p e r a t u r e o f -70F o r l o w e r and d i d n o t warm t o t h e b o i l i n g p o i n t u n l e s s h e a t was a d d e d t o t h e l i q u i d .

e a s i e s t way t o warm t h e l i q u i d was t o s p a r g e a m b i e n t
The

temperature vapor i n t o it.

The v a p o r c o n d e n s e d i n t o t h e

l i q u i d u n t i l t h e l i q u i d reached its b o i l i n g p o i n t . Most o f t h e l a r g e s c a l e t e s t s u s e d r e f r i g e r a t e d p r o pane a s t h e f u e l s o u r c e .

I n those tests about one-third

of

t h e l i q u i d b o i l e d away o r was a t o m i z e d d u r i n g t h e f u e l transfer to test p i t s . P a r t o f t h e l o s s was d u e t o h e a t

t r a n s f e r f r o m t h e c o n c r e t e p i t f l o o r , b u t some l o s s was c a u s e d by a t o m i z a t i o n o f l i q u i d a s i t l e f t t h e d i s c h a r g e pipe. An e x p a n s i o n chamber a t t h e e n d o f t h e d i s c h a r g e l i n e

p r e v e n t e d p a r t o f t h e loss c a u s e d by a t o m i z a t i o n , b u t t h e
l o s s was s t i l l g r e a t e r t h a n e x p e c t e d b a s e d o n e q u i l i b r i u m

c a l c u l a t i o n s f o r f l a s h i n g v a p o r and h e a t t r a n s f e r from t h e p i t floor. During one of t h e l a r g e s c a l e t e s t s , a b o u t 3000 g a l o f a m b i e n t t e m p e r a t u r e p r o p a n e was f l a s h e d i n t o a p i t 1 0 f t square. The e x p a n s i o n chamber was p l a c e d a r o u n d t h e d i s 1

charge nozzle.

When t h e d i s c h a r g e was s t o p p e d , less t h a n

5 0 0 g a l was i n t h e p i t , a n d more t h a n 8 0 p e r c e n t o f t h e p r o -

p a n e had f l a s h e d , a t o m i z e d and t h e n v a p o r i z e d , o r v a p o r i z e d a s t h e t e s t p i t cooled. IV- 9

CONCLUSIONS

I f ambient t e m p e r a t u r e propane is d i s c h a r g e d i n t o t h e a t m o s p h e r e a t r a t e s up t o a b o u t 2 0 0 l b / m i n , l a t i o n of l i q u i d w i l l occur. no accumu-

I f t h e flow is d i r e c t e d a t t h e

g r o u n d and c o n t i n u e s f o r a l o n g t i m e , some a c c u m u l a t i o n o f l i q u i d may o c c u r a f t e r t h e g r o u n d i s f r o z e n , b u t o n l y s m a l l

f r a c t i o n s of t h e t o t a l f l o w w i l l remain as l i q u i d .
I f more

t h a n a s m a l l f r a c t i o n of t h e flow is t o be accumulated a s l i q u i d during d i s c h a r g e of ambient temperature propane, an e x p a n s i o n chamber and c o n t a i n e r m u s t b e u s e d t o t r a p t h e spray. Except p o s s i b l y f o r v e r y l a r g e s p i l l s t h e atomized

s p r a y w i l l e v a p o r a t e b e f o r e i t can s e t t l e t o t h e ground.

* U.S.

GOVERNMENT PRINTING OFFICE: 1982-361-076:3095

IV-10