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ABSTRACT

Fifty-eight tests were conducted in the field using the modified one-litre test tanks and the modified five-pound test tank engulfed in a pool f i e to determine the failure characteristics of the tanks under BLEVE conditions. Ten ladings were used having a wide variety of physical properties: acetaldehyde, acetone, ammonia, methanol, n-butanol, propane, n-pentane, R-12, R-114 and water. Five remnant patterns were observed for failed tanks: single hole, crosslike teardown, two-piece teardown, three-piece teardown and shatters. It was found that for one-litre tanks the mechanical integrity af the tanks was significantly reduced when the wall thickness was reduced below 60% of the normal wall thickness (0.64 mm). However, the type of failure as determined by remnant patterns for the test tanks at a given failure pressure was similar for the wide variety of ladings used. The violence of the tank failure increased with an increase in pressure and can be quantified by 'Iear work" based on examination of the remnants of the test tank. The ratios of the tear work to the available work and of the tear work to the actual work were detennined. Mathematical models have been developed and used for predicting the lading temperatures in the tank and the surface temperatures dong the circumference of the tank, during the period prior to a pressure relief valve opening. The models give good approximations of m e a s c d values of the liquid and vapor lading temperatmes.

It was proposed that methanol should be used as a possible mode1 fluid for the one-

litre test tank if failure in the two-phase region is required to simulate prototype tanks with
propane as lading.

iii

ACKNOWLEDGMENTS

1 wouid like to express my deep gratitude and appreciation to my supervisor, Dr.

Frank R. Steward for his invaluable guidance, encouragement and support throughout this study.
1 would iike to thank d l the staff of the workshop and stores of the Department of

Chemical Engineering for assistance in carrying out experiments and for procuring the required matenals. The faculty members of the Department of Chemicai Engineering are appreciated for their interesthg discussion and suggestions. Special thanks are forwarded to the former chief technicial and technicial, Mr. A. Knappe and Mr. B. Hawkins for their assistance in fabricating experimental apparatus.
1 would like to express my sincere gratitude to Dr. Somchai Osuwan who believes

in my ability and encouraged me to pursue this study. Many thanks are due to al1 the graduate students of ChE-UNB, with a special mention to Mr. Ibrahim Karidio, Mr. Xiao Zhu Zhang, Ms. Elizabet Cruz Torres for wonderfd fiiendships 1 have received and Mr. Boonrod Sajjakulnukit for continued assistance in carrying out experiments. Last but not the least, 1 am greatly indebted to my parents, whom 1 love and missed so much during a long period of study in Canada, for their love and support throughout this work. 1 am also thankful, for those whose nmes are not cited here but who, in one way or another have been supportive during this work.

TABLE OF CONTENTS
Page

Abstract

. .............................................................. ti.

Acknowledgrnents Tableofcontents ListofTables ListofFigure Nomenclature Chapter 1 Chapter 2

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

iv
v
x

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

..........................................................
.........................................................
Introduction

xi xv

................................................ 1
................................ 4

Theories and Literature Review

BLEVE Related Research

....................................- 4

Superheated Liquid and Liquid Spinodal Chapter 3 Vent and Burn Experiments Apparatus

. . . . . . . . . . . . . . . . . . . . . . . . Il

..................................16

................................................ 17 ............................................ 18

Test Conditions Test Procedure

............................................. 19

Experirnental Results

....................................... 22
.............................. 23

3.4.1 Location of Fust Rupture

3 .4.2 Delay Tirne

........................................ - 2 3
................................... 24
............................... 24

3.4.3 Volume of Propane

3.4.4 Temperature of Propane

Page

3.4.5 Rupture Size

........................................ 24

3.4.6 Summary of Results

.................................. 25

Discussion

................................................ 25

3.5.1 Location of First Rupture

3 S.2 Delay Time

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

25

......................................... 26

3.5.3 Rupture Size and BLEVE

3.6

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

26

Conclusion

............................................... 28
....... 32
32

Chapter 4
4.1

Flow From Pressure Relief Valves with Various Orifice Sizes Single-Phase Flow
4.1.1 Vapor Flow

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

......................................... 32
......................................... 33

4.1.2 Liquid Flow

4.2

Two-Phase Flow

........................................... 38

Chapter 5
5.1

Modelling for Heating of Lading and Cylinder by Extemal Heat Source 45

Mode11

..................................................47 ...................................
48

5.1.1 Metal Heat Balance

5.1.2 Vapor Space Heat Balance 5.1.3 Liquid Space Heat Balance Mode111

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

................................................. 53

5.2.1 VaporPhase

........................................ 55 ....................................... - 5 7

5.2.2 Liquid Phase

Page
Chapter 6
6.1

Experirnental Apparatus ........................................................................

Test Tank Modification .........................................................................
6.1.1 One-Litre Test Tank .................................................................. 6.1.2 Five-Pound Test Tank ...............................................................

Filling of Ladings .................................................................................. Instrumentation ..................................................................................... Pool-Fire Source ....................................................................... Radiation Shield ........................................................................ Pressure Measurement ..............................................................

Temperature Measurement ........................................................

Pressure Relief Valves and Orifices ...........................................

Blast Pressure Measurement ......................................................

Data Acquisition Systems .......................................................... Video and Still Photographs ...................................................... Thermal Video System ..............................................................

Experimental Setup ...............................................................................

6.4.1 Test Site ........................... . . .................................................. 6.4.2 Test Tank and Pool-Fire Source ................................................ 6.4.3 Data Acquisition Systems ..........................................................
6.4.4 Video and Infked Carneras ......................................................

Test Procedure .....................................................................................

vii
.

Chapter 7

Results .................................................................................................. Comprehensive Outcome ...................................................................... Pressure and Temperature Profiles ........................................................ Fireball. Vapor Cloud and Blast Pressure...............................................

Pattern of Fail Tanks .............................................................................

Pressure at failure Corresponding to Mechanical Condition ................... Theoretical and Actual Work Available at Failure .................................. Length of Tear and Work to Tear Tank ................................................ Estimated Heat Flux .............................................................................
Chapter 8

Analysis and Discussion ........................................................................

Lading Materials ...................................................................................

Pressure and Temperature ..................................................................... Pressure Relief Valve and Orifice Size ..................................................
8.3.1

Effect of PRV Set Pressure ....................................................... Effect of Orifice Size ................................................................ ..

8.3.2

Fireball and Vapor Cloud ..................................................................... Pressure at Failure Corresponding to Mechanical Condition .................. Work Available at Failure ...................................................................... Effects of Lading and Fil1Level on Type of Failure ...............................

Time to Failure .....................................................................................

Prediction of Lading Temperature by the Developed Models ................. viii

Page

8.10 Methanol as a Test Fluid Chapter 9 References Appendix A Appendix B Appendix C Appendix D

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

135

Conclusiom and Recomrnendations

........................... 136

........................................................... 138
Lading Temperature and Pressure Profiles for Small Scale BLEVE Tests ................................................... 143
Surface Ternperaure Profiles for Small Scale BLEVE Tests Pressure-Enthalpy Diagrams for Some Ladings Used Sample Calculations of Work Available at Failure

........ 172

............. 185

. . . . . . . . . . . . . . . . 192

LIST OF TABLES

Table 3.1 Table 5.1

Test matrix and test conditions

............................... - 2 0

Available models for predicting the consequence of f i e attack (Moodie. 1988) ............................................ 46 Test conditions on small scaie BLEVE tests

Table 7.1 Table 7.2 Table 7.3 Table 7.4 Table 7.5 Table 7.6 Table 8.1 Table 8.2 Table 8.3 Table 8.4 Table 8.5 Table 8.6

.................... - 8 3

Measured quantities for srnail scale BLEVE tests

................. 84
........... 86

Summary of ranges of variables and measured quantities

Pressure at failure correspondhg to mechanical condition of the test tanks .................................................... 96 Available and actual work dong with work to tear tank for the test tanks ................................................... 100 Heat flux estimated fiom the experimental data

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

101

Relevant physical properties of ladings used for small s a l e BLEVE tests .................................................... 103 Comparison of size and duration of fireballs fiom small scale BLEVE tests with caiculated values .................................. 114 Size and duration of vapor clouds fiom small scale BLEVE tests Scale and failure type effects on work available at failure

. . . . 116

. . . . . . . . . . 120

Effects of lading. fil1 level and wall th4cness on type of failure

. . . . . 128

Relevant physical properties and constants used in the models developed ............................................... 130

LIST OF FIGURES

Figure 2.1 Figure 2.2 Figure 3.1 Figure 3.2 Figure 3.3 Figure 3.4 Figure 3.5 Figure 4.1 Figure 4.2 Figure 4.3 Figure 4.4 Figure 5.1 Figure 5.2 Figure 5.3 Figure 5.4

Pressure-Specific volume diagram with liquid spinodal Pressure-Temperature diagram with liquid spinodal The apparatus for Vent and Burn experiments

. . . . . . . . . . . . . 13

............... 13

.................... 18
................ 21

Experirnental setup for Vent and Burn experiments Sequence of the fmt rupture in the vapor space Sequence of the first rupture in the liquid space

................... 29

................... 30
..... 31

Comprehensive scenarios for the h t rupture in the vapor space

Critical mass flow rate for propane vapor vs. orifice size at various PRV set pressures .......................................... 36 Time to empty a propane tank at 85% fil1 level vs. orifice size at various PRV set pressures for single phase vapor flow . . . . . . . . . . . . .36 Critical mass flow rate for liquid propane vs.orifice size at various PRV set pressures ..........................................37

Tirne to empty a propane tank at 85% fill level vs. orifice size at various PRV set pressures for single phase liquid flow . . . . . . . . . . . . . 37
Cross sectional diagram of cylinder used for Mode1 1 Diagrams of systems used for Mode1 II

.............. 48

......................... 54

Trpical lading temperature profiles for the test tank at 85% liquid fill propane by Mode1 1 and Mode1 1 without radiation ................ 65
ypical metal surface temperature profiles for the test tank at 85% liquid fill propane at various positions dong circumference by Mode1 1 and Mode1 1without radiation (heat flux=12.5 kW/mq . . . . . . 65

Page
Figure 5.5 Typical lading temperature profiles for the test tank at 85% liquid fill propane by Model II and Model II without radiation (heat flux= 12.5 kW/m2) .................................... - 6 6 Typical metd surface temperature profiles for the test tank at 85% liquid fill propane at various positions dong circumference by Mode1 II and Mode1 II without radiation (heat flw=12.5 kW/&) . . . . . 66 Typical lading temperature profiles for the test tank for various liquid propane fil1 levels by Model II (Heat flux=13 kW/mz) .......- 6 7 Typical lading temperature profiles for the test tank at 85% liquid fill propane for given uniform heat fluxes by Model II (Heat flux=13 kW/m2) ...................................... . 6 7 Schematic of the modified one-litre test tank

Figure 5.6

Figure 5.7 Figure 5.8

Figure 6.1 Figure 6.2 Figure 6.3 Figure 6.4 Figure 6.5 Figure 7.1 Figure 7.2 Figure 7.3 Figure 7.4 Figure 7.5 Figure 7.6 Figure 7.7

..................... 70

Schematic of the modified five-pound test tank Photograph showing the test setup

.................. - 7 2

............................ -80

Photograph showing the test setup during fire Photograph showing the test setup after failure

....................80
................... 8 1

Typical temperature and pressure profiles of tank with propane aslading .................................................89 Typical surface temperature profile of tank with propane as

......... 89
.......90

Illustration of surface temperature from infiared image system

Fireball produced fiom tank filled with propane at 85% FV (Tank 47) .91 Fireball produced fiom tank filled with propane at 5 1% FV (Tank 49) .91 Fireball produced fiom tank filled with methanol at 80% FV (Tank 33) 92 Fireball produced from tank filled w t n-pentane at 80% FV (Tank 43) 92 ih Characteristics of failed-tank patterns xii

Figure 7.8

.......................... - 9 4

Figure 7.9 Figure 8.1 Figure 8.2 Figure 8.3 Figure 8.4
Figure 8.5

Failure pressure vs. wall thickness for the test tanks . . . . . . . . . . . . . . .95 Vapor pressure vs. temperature for ten ladings used Remnants of ten test tanks after failure

. . . . . . . .. . . . . . 104

. . . . . . . . . . . . . . . . . . . . . . . . . 105

Effect of orifice size installed in PRV on one-litre test tanks

. . . . . . . . 1 11

Theoretical work vs. initial per cent liquid fil1 for one-litre tank for propane ................................................. 121 Theoretical work vs. initial per cent liquid fill for one-litre tank for water ................................................... 121
Actual work vs. initial per cent liquid fill for one-litre tank for propane 122

Figure 8.6 Figure 8.7 Figure 8.8 Figure 8.9 Figure 8.10 Figure 8.1 1

Actual work vs. initial per cent liquid fill for one-litre tank for water Work to tear tank vs. pressure at failure for one-litre tanks

122

. . . . . . . . . 123

Ratio of tear work to available work in tank lading % vs. pressure at failure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123 Ratio of tear work to achial work performed by tank lading % vs. pressure at failure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124 Ratio of tear work to theoretical work in tank lading % vs. pressure at failure for medium scale test tanks . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125 Ratio of tear work to achial work perfonned by tank lading % vs. pressure at failure for medium scale test . . . . . . . . . . . . . . . . . . . . . . . . 125 Ratio of tear work to theoretical work in tank lading % vs. pressure at failure for large scale test tanks . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . 126 Ratio of tear work to actual work performed by tank lading % vs. pressure at failure for large scale test tanks . . . . . . . . . . . . . . . . . . . . . 126 Cornparison of measured lading temperature for Tank 47 with calculated lading temperature obtained fiom Models I and II without Radiation (heat flux=13 kW/m2) . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . 132 xiii

Figure 8.12
Figure 8.13
Figure 8.14

Figure 8.15

Page

Figure 8.16

Comparison of measured lading temperature for Tank 47 with calculated lading temperatures obtained fiom Models 1 and II (heat flux=13.1 kW/m2) .................................... 132 Comparison of measured lading temperature for Tank 2 with calculated lading temperatures obtained fkom Models 1 and II (heat flux=14.4 kW/m2) .................................... 133 Comparison of measured lading temperature for Tank 3 with calculated lading temperatures obtained fiom Models 1 and II (heat flux=12.6 kW/m2) .................................... 1 3 3 Comparison of measured lading temperature for Tank 11 with calculated lading temperatures obtained fiom Models 1 and II (heat flux=13.1 kW/m2) .................................... 134 Comparison of measured lading temperature for Tank 12 with caiculated lading temperatures obtained fiom Models 1 and II (heat flux=16.6 kW/m2) .................................... 134

Figure 8.17

Figure 8.18

Figure 8.19

Figure 8.20

NOMENCLATURE

coefficient in Eq.(5.4 1) area of the PRV coefficient in Eq.(5.4 1) coefficient in Eq.(5.4 1) valve coefficient specific heat, kJkg coefficient in Eq.(SA 1) acceleration due to gravity, 9.8 1 m/s2 dimensional constant, 1 kg.m/N.s2 specific entbalpy, k l k g specific heat ratio wall thickness, m mass, kg molecular weight, kg/kmol polytropic exponent coefficient in Eq.(4.8) pressure, kPa radius, m universal gas constant, 8.3 144 N.drno1.K specific entropy, k.i/kg.K tirne, s temperature, "Cor K volume, m3 qdisr critical compressibility

Greek Symbols

coefficient of volurnetric thermal exp on, K-l density, kg/m3 diffrentiai critical pressure ratio constant, 3.14 15927 specific volume, m3/kg angle, radian Stefan-Boltzmann's constant, 5 . 6 7 10-' ' kW/m2.K4 ~ acentic factor

Superscripts

critical interface vapor interface liquid metal initial vapor

xvi

Chapter 1

INTRODUCTION

A Boiling Liquid Expanding Vapor Explosion (BLEVE) is recognized as one of the

worst types of accidents that can occur in a tank car derailment or in a pressurized storage tank failure in a chernical process plant. A BLEVE is an explosion involving the rapid vaporization of liquid (Boihg Liquid) and the rapid expansion of vapor (Expanding Vapor) when a vessel fails. Fire is the most common cause of failure. Two types of ideaiized fire exposure are of'ten used to represent extreme fue behaviors: impingement and engulfinent.
A fireball results f o the explosion if the lading in the vessel is flammable, and the im

fkagments of the vessel can travel a considerable distance, 500 meters or more. The fireball

and flying hgments combined with the blast pressure can damage objects in the vicinity of the failwe. Despite the fact that the term BLEVE has been used for almost four decades, the understanding of a BLEVE is far fiom complete. Accidents that led to a BLEVE have been reported with the loss of life and property. In 1984, the largest disaster of this type occurred

in Mexico City killing more than 500 people, injuring more than 7,000, and damaging over
7,000 buildings. To understand BLEVEs and so to help prevent and mitigate such disasters,

experiments have been performed over a wide variety of conditions with tanks containing a liquefied gas.

In BLEVE research a test with a tank smaller than 40 litres would be considered a
smail scaie test. Recentiy, however, test tanks with a capacity of 1 litre or less have been used for small scale tests. The advantages of such small scaie tests are: Reduced cost; hcreased safety; Less personnel required;

Simpler experiment design.

However, the drawback of small scale tests is the difficulty in scaling up the results to full scale tanks. In a BLEVE the hazardous ladings are liquefied gases such as LPG, ammonia,

chlorine, and vinyl chloride. These materials are gases at atmosphenc pressure and normal
temperatures but are liquefied by pressurization for storage and transportation. However, there are some hazardous liquid materials such as methanol, propanol, and acetone that are flammable and used as fiels and raw materials in chernical plants. These liquids also have a potential to cause catastrophic darnage if an accident occurs. Therefore, questions arise as to the behavior of materials which are normally liquids at ambient temperature when heated under pressure: Do such materials BLEVE in a manner similar to liquefied gases? Could these materials be substituteci for liquefied gases in BLEVE research to improve safety, economy and the condition of tanks at test conditions? Research has been conducted on tanks in a wide range of sizes. Attempts to scaie up data from small and medium scale tests to full scale tanks have not been particularly succeesful mainly due to the complexity of the variables involved and the difference in

3
vesse1 geometry. Scaling up has aiso been unsuccessful because the BLEVE's phenornenon is not well understood. The objective of this study was to obtain a database on the resuits of small scale

BLEVE tests with various ladings and using an engulfhg pool fire to produce failw. The
data can be compared with that of the more restrictive number of tests made on larger tanks. Such a cornparison could lead to scale up relations for assessing full scale BLEVE potential under a given set of circumstances.

The following is the outline of this Ph.D. thesis. Theories and literature review are
presented in Chapter 2. In Chapter 3 Vent and Burn experiments are summarized. The review of flow fiom pressure relief valves with various orifice sizes is summarized in Chapter 4. Chapter 5 presents models for heating cylinders with a given heat flux on the surface used to predict vapor, liquid and cylinder surface temperatures over time.Chapter 6 describes in detail the expenmental apparatus including experimental setup, test procedure

and instrumentation. The complete resuits of the experiments are contained in Chapter 7. The
analysis and discussion of the resuits are provided in Chapter 8. Finaily, Chapter 9 presents conclusions and recommendations for future work.

Chapter 2

THEORIES AND LITERATURE REVIEW

Even though severai theones such as the SLT (Superheat Lirnit Temperature) of Reid
(1 979), shock waves of McDevitt et al. (1 990), BLBCE (Boiling Liquid Bubble Collapsed

Explosion) of Venart et al.(1993), Hot and Cold BLEVEs of Birk et al.(1994) have been put forward to explain the BLEVE phenomena, BLEVEs are not well understood and the means to mitigate such a failure is practically NI. Various types of research have been conducted

on many scales to help overcome this hazard. This chapter summarizes bnefly the previous
work on the studies undertaken to explain the underlying causes of a BLEVE.

21 BLEVE Related Research .

Anderson et al. (1974) conducted a full scale test with a 60 tonne tank car (RAX 20 1) that was 18.3 m long and 3.05 m in diameter. The tank car was instmented and filled with liquefied petroleum gas (LPG) 95% of capacity. A large JP-4 pool fue was used to engulf to
and heat the tank car. Temperature, pressure, liquid level, and valve lie were recorded as a

fnction of time. The tank car failed catas-ophicailybreaking into at ieast 63 fragments via stress-rupture 24.5 minutes after ignition. At failure, the surface temperature in the region of the initiai fiacture site was approxirnately 650C and the tank pressure was 2.41 MPa.nie

temperatures of a propane torch f i e produced by the operating relief valve were 1040O to C 1 180OC. The authors analytically derived an expression to determine the heat flux to the wetted surface of the tank. In the experiment, this heat flux was detennined as an average value of 2.50 cas-cmz (105 kW/m2). Reid (1978, 1979) reviewed and described how superheated liquids couid be prepared. Reid suggested that the superheat limit temperature, SLT, represents the temperature at which extremely rapid homogeneous nucleation occurs. It was s h o w that thermodynamic analysis yields values of the SLT close to those found experimentally. Reid suggested that the SLT of liquid mixtures can be evaluated by thermodynamic or kinetic theory. In 1979, Reid proposed that: "Rapid depressurization of hot, saturated liquids may result in an explosion. The temperature of the hot liquid mut, however, be above the superheat limit temperature at one atmosphere, and the drop in tank pressure must be very rapid." It should be noted that this proposed mechanism was related to the behavior of the hot liquid as the tank was rapidly depressurized afer failure of its metal wall. Reid explaineci
that the liquid was saturated pnor to failure and the bulk liquid should boil thereby reducing

the temperature to a value compatible with the lower pressure caused by failure of the metal wall. However, if there were no nucleating sites in the bulk of the liquid to initiate the boiling process, the bulk liquid would be superheated. If the bulk temperature was sufliciently above the expected boiling point, a superheated liquid-vapor explosion would occur, creating strong
and damaging shock waves.

Appleyard (1 980) tested and evaluated "EXPLOSAFE which was proposed for the reduction of BLEVEs. EXPLOSAFE is an intemal system of an expanded aluminum foi1

with a honeycornb-like structure. The manufacturer of this material claimed it would increase

the heat transfer from the vapor space surface temperature and preserve the strength of the
tank contacting the vapor space whea it was subjected to a fire. Tests were carried out on six
115 scale tank cars, four of which were each equipped w t a different kinds of ih

EXPLOSAFE. The tanks with the EXPLOSAFE did not rupture while the others (without
EXPLOSAFE) failed during the tests. Appleyard concluded that two tf the systems were effective in reducing wall temperatures. However, fire conditions varied fiorn test to test.

Kim-E and Reid (1983) developed a thermodynamic model to indicate what ranges
of initial pressure and temperature wodd allow a spinodal state to be attained on rapid

depressurization. The spinodal state was defined as the limit of stability at which homogeneous nucleation must occur. To validate their model, the authors conducted experiments using a seven liter vessel containing liquid (or supercritical) carbon dioxide.
The vessel was designed such that rapid venting was achieved by driving a pointed spike

verticaily against a rupture disc. In the thkteen experiments conducted, a soinodal state was not achieved during depressurization. The explanation given by the authors was that:

"Unless the theory (or calculated spinodal pressures) is in error, we simply have to conclude that in the smdl pressure vesse1 used, vapor formation was immediate and reduced the rate of pressure drop significantly. The vapor could have been fomed on the wall or plunger rod or, more Iikely, the reflected shock wave resulting f?om the breakhg of the burst disc led to vapor formation in the partially superheated liquids."
Their explanatior. suggests that the type of nucleation depends on the size of the vessel used. Droste and Schoen (1 988) performed large scale fire tests with both unprotected and

thermally insulated 4.85 m3 LPG storage tanks. Three unprotected tanks instrumented and

filled with 50% propane, and exposed to a fire of fuel oil contained in a number of steel troughs under the tanks. In some cases, different initial temperatures were obtained by preheating the tanks pnor to the tests. Al1 the tanks failed after a fire lasting between 7 and
12 minutes. For these unprotected tanks, the authors found that the shell temperatures of the
tank contacting the liquid were similar to the liquid temperatures while the shell temperatures

of the tank contacting the vapor were much higher. The maximum tank shell temperature was at the top of the tank. As required by the FRG regulations, the fire tests with thermal insulated LPG storage tanks were carried out using fibrous muieral wool material stitched
with steel wire (ISOVER MD 2) as a thermal insulation. With thermal insulation and fire-

proof gasket materials for vaIves and fittings the insulated tank was able to survive 90 minutes of full fire engulfhent. This fue resistance is one of the requirements of the FRG regulations for LPG storage tanks with a capacity greater than 6 m3. Moodie et al. (1988) exposed a 5 tonne horizontal cylindncal LPG tank to kerosene pool fires in order to assess the thermal response of the tank. The tank had an internal volume
of 10.25 m3 and was instrumented for extensive rneasurements of fire characteristics

including extemal and internal tank metal temperatures, and internal pressure. Two standard relief valves were installed and set at 1.43 MPa. The same tank was used for an entire series of tests with propane fil1 levels at 22%, 36%, 38%, 58% and 72% in which the fil1 was defined as the percentage of the total tank volume occupied by liquid at Sac.The authors
found that the inner liquid wall temperatures were approxirnately 20C lower than the

correspondhg extemal wall temperatures exposed to a pool fire. They found that the temperatures near the tank sides were not significantly greater than those in the bulk liquid,

that is, there was no evidence of a hot thick layer in the liquid. The thennocouplesjust above

the initial liquid level indicated that the level rose after the pool fue was established.
However, the authors concluded that there was local slopping and violent interfacial motions induced by non-uniform heating and poor longitudinal mking, or there were large superheated gas bubbles within the bulk fluid. McDevitt et al. (1988) conducted a series of small scale tests using one liter containers filled with propane or R-12. For each test, the tank was heated to a desired temperature and then niptured with a 0.22-250 rifle bullet or by a Proparms water cannon. It was found that a BLEVE could occur when the liquid temperature was below its superheat limit temperature. The authors showed that a BLEVE occurrence appeared to be dependent on the enthalpy released at tank failure. For the specific tanks used, this value was greater

than 100.4 kJ for propane and R-12.

Venart et ai. (1988) conducted experiments to investigate the behavior and the thenno-hydraulic response of pressure liquefied gases in an externally heated horizontal cylindrical tank protected by a pressure relief valve (PRV). The forty litre test tank equipped with instrumentation for measurement of tank pressure, temperatures, mass discharge and void development was used to demonstrate the complex thermo-hydmulic response as a function of heating and valve position. It was found that high volume fills, large PRV onfice size and stratificationcaused significant flashing and swelling of the affected regions in the

tank when the PRV operated. As venting continued, if the pressure within the tank increased
the core liquid became subcooled creating vapor only near the surface, and if the pressure decreased homogeneous nucleation throughout the liquid caused saturated boiling.

McDevitt et al. (1990) conducted a series of tests using a shock tube with R- L 2 and

R-22 as ladings to explore a possible BLEVE mechanism based on the formation of pressure
waves within the tank after failure. The resuits indicated that the temperature of the fluid, the volume of the fluid and the rupture hole size were instrumental in the creation of the compression wave which could cause a BLEVE.The researchers found that the rupture hole size was an irnporiant parameter affecthg the magnitude of the pressure peak formed after rupture. This finding substantiates the theory that the pressure wave is formed by the pressure increase due to restriction of the expanding vapor within the tank. McDevitt et al. (1991) also conducted experiments simulating the procedure often called "Vent and B u m used for mitigating a possible BLEVE of a derailed tank car. More details of these experiments will be presented in Chapter 3.

Birk et al. ( 1993,1994,1996) conducted a series of medium scale tests using 320 and
400 litre automotive propane tanks. The tests involved exposing instrumented test tanks filled with 80% liquid propane to engulfing JP-4pool and propane torch fues in order to quanti@ the hazards associated with a BLEVE. The authors defmed a BLEVE as "the explosive release of boiling liquid and expanding vapor resulting fiom the catastrophic failure of a vesse1 holding a pressure liquefied gas" (Birk et al., 1996). Three types of tank failure were catagorized based on observing the event and the outcome of the tests. These were two-phasejet fire release (finite failure), single-step (Cold) BLEVE and two-step (Hot)

BLEVE. A BLEVE Map and Failure Map were empirically developed using the data fiom
the tests. The authors suggest that the BLEVE event can be explained by using simple therrnodynarnics and stress analysis. In the current report (1996), the authors performed and

10

descnbed a tank deformation analysis, a BLEVE mechanism and the factors related to the hazards fiom a BLEVE, Uicluding the suggestions for emergency response. Roberts et al. (1995% 1995b 199%) carried out large scale tests with tanks heated by an irnpinging propane jet fue. Three unprotected two tome propane tanks were instnimented with themocouples and pressure transducers, filled to 20%, 41% and 60% of capacity, and equipped with a standard PRV set to relieve at 1.72 MPag. The jet f i e was set

so that the nozzie had an equivalent orifice of 12.7 mm and was located 1.O m beIow the
axial center of the tank and 4.5 m in front of the surface of the tank. It was reported that the tanks filled at 20%, 41% and 60% of capacity were respectively brought to failure after 250,

285.5 and 2 17 s by 1.52,I.38 and 1.59 kgls liquid propane jet fies. At failure, the pressures for these tanks were 1.65,2.13 and 1.86 Mpag. The pattern of tank failure for each test was described in detail including the point of failure, failed metd length and the variation of the wall thickness along the line of failure. The authors concluded that some of the current assumptions in models used for land use planning might not be appropriate. Frost et al. (1995) conducted experiments in small scale tests using steel and glaswalled vessels to determine the conditions which lead to the greatest degree of repressurization d e r the sudden depressurization of a pressure-liquefied gas. The vessels used were rectangular, cylindrical and spherical, with volumes of 260 ml, 75 ml and 150 ml respectively. The lading matenal was R-22 which is nonfiarnmable but sirnilar to propane in thermodynamic properties. The vessels were depressurkd by rupturing a foi1 diaphragm
with a pneurnatically-actuated plunger. The parameters studied included the initial

thermodynamic state of the liquid, the fil1 volume, vent area, vesse1 wall material and

11

geometry and the presence of nucleation sites within the liquid. The authors found that for d l vessel shapes used the degree of repressurization reaches a maximum value as the initial pressure of the liquid is increased. The repressuization tirne is typically greater than the tirne for the initial pressure drop. In this experirnental investigation, the spinodal was not attained due to physical constraints such as the presence of foreign bodies and the container surfaces.

For a high initial pressure, the boiling process was dominated by heterogeneous boiling fiom
the walls of the liquid. When steel wool was placed in the vessel to promote nucleation sites

within the liquid, the degree of depressurization w s reduced while the degree of a
repressurization was increased. The authors concluded that the mode of nucleation observed depended on the degree of superheat attained by the liquid and the surface characteristics of the vessel. It was stated that it is not known how these results could be scaled to larger containers.

2.2 Superbeated Liquid and Liquid Spinodal

A superheated liquid is, by definition, at a temperature above its equilibrium boiling

point. These liquids are metastable in a thermodynamic sense. They are stable with respect to small perturbation, but if the perturbation is sufficiently large, superheated liquids will partially vaporize and form a fmal, more stable state, consisting of vapor and liquid (Reid, 1983). Liquids can be superheated because nucleation sites are required to initiate boiling.

When nucleation begins on a liquid-solid interface, it is referred to as heterogeneous

nucleation. If nucleation begins in the bulk of the liquid, it is termed homogeneous nucleation.

12 A liquid can be heated above its normal boiling point if there are no nucleation sites

to promote bubble growth. The maximum temperature to which a liquid can be superheated without phase change is defined as the superheat limit temperature (SLT). The SLT is a function of pressure, composition and the method of determination. The locus of points representing the superheat limit temperature as a fhction of pressure is called the liquid spinodal. This is illustrated in Figures 2.1 and 2.2 (McDevitt, 1990) where the region between the saturation line and the liquid spinodal is the region in which a liquid can exist above its saniration temperature under non-equilibrium conditions. Reid ( 1978) descnbes three methods of determinhg SLT: expenmental, thermodynarnic and kinetic.

Exqrimental D e t e m t i o n of Su- imite(SLT'

. .

. .

The apparatus cdled a bubble column is a column of liquid in which there is a linear temperature gradient between the top and the bottom, with the highest temperature at the top.

The temperature at the bottom of the column is well below the bubble point temperature of
the liquid to be tested. The liquid being tested must be immiscible with the s m u n d i n g liquid. A droplet of the liquid being tested is injected at the bottom of the column and allowed to rise through the column. The superheat limit temperature of the liquid is the temperature at which the liquid changes to vapor, typically producing a sharp noise.
Reid (1978) suggested that the ratio of the SLT to the critical temperature was in the

range of 0.88-0.9 for al1 liquids. Experimentally, the SLT of propane was measured as 326.2

K (53C) at one bar.

Critical Point

Figure 2.1 Pressure-Specific volume diagram with liquid spinodal

Critical Point

Satura Line

Tem perature

Figure 2.2 Pressure-Temperature diagram with liquid spinodal

The stability limit for a single component stable system c m be stated as -(aP/aVh.>O. This statement c m be used to d e t e d e the SLT and to draw the estimated liquid spinodal if an equation of state is available for a given liquid and vapor. The SLT can be evaluated at
any pressures by taking the denvative of the equation of state with respect to volume at

constant temperature and setting it equal to zero or ( a P / w = O at spinodal. For example, to

n determine the SLT at atmospheric pressure the pressure i the equation of state is set equal
to the atmosphenc pressure and both equations are solved sirnultaneously.

1w Kinetic Determution of Sy~erheat . tTemperature (SLT)

. .

. .

A superheated liquid may be thought of as a mixture of continuum liquid molecules

with many vapor embryos of different sizes (Reid, 1978). Thermodynamically, there is a critical size for the vapor ernbryo which is in unstable equilibrium with the bulk liquid for each system. To estimate the rate at which embryos attain the critical size for given experimental conditions the bubble nucleation rate, J, is theoretically descnbed as J = NLf expl-16nu3/3kT(P PJ2] where NLis the number density of liquid molecules, f i s a frequency factor of the order of
10'' s-l to account for the rate phenornena of vaporizing and condensing molecules in the

vapor embryo, o is the surface tension, P is the pressure inside the embryo and Pois the bulk liquid pressure.

By setting J equal to 1O6 bubbles/mm3ms the calculated superheat lirnit temperatures

are within a few degrees of measured values (Reid, 1978). In some cases the agreement is

15

poor if the nucleation occurs at the superheated liquid boudaries or nucleation is initiated
by the evolution of dissolved gas.

Many discussions of BLEVEs have been based, in one way or another, on the
spinodai concept: Reid (1 978,1979), Kim-E and Reid (1983), McDevitt (1 !BO), Ye (1 994), Frost et ai.(1995), Birk et aL(1993, 1994, 1996). However, there has never been conclusive physical proof that a BLEVE is necessarily related to the existence of superheated liquid being formed within the container at failure or to the subsequent vapor that is formed by the rapid depressurization.

Chapter 3

VENT A N D BURN EXPERIMENTS

Tank car derailments may damage the shell of the tank car and/or associated fittings
and piping. For potentiai flame-impingement situations it may be usefiil to punchire the tank car (Vent) and ailow the lading to b u . off (Burn) prevent or mitigate a BLEVE. This to procedure entails puncturllig a hole in the vapour section of the tank car, followed by a hole in the liquid section (McDevitt and Steward, 1991). For a typicai tank car (60 tomes), which

has a diameter of 3.O5 m and a length of 18.3 m, a 10 pound shaped charge is normally used
to produce a 50 mm diameter hole in the liquid space. However, the hole size fiom a 10
pound shaped charge placed against the vapour space varies due to a number of parameters.

Besides the basic concem about the safety in handling derailed tank cars as well as the caution required for the vent and bum procedure, a concem has arisen that the vent and burn procedure may itself cause a BLEVE. BLEVEs have been reported for damaged tank cars that were not in f i e situations and were at ambient temperature (Lewis, 1983). Therefore puncturing a hole in the tank car may induce a BLEVE if not done with suficient care.
Causing a BLEVE while atiempting to perform a vent and burn operation is unacceptable as

the purpose of the procedure is to prevent catastrophic damage. Furthemore, the following questions have arisen regarding the vent and burn procedure: What section of the tank car should be ruptured first?

What should be the time delay between the first and second rupture? What is the effect of lading temperature on the vent and bum procedure? What is the effect of lading volume on the vent and bum procedure? To answer these questions experiments were designed and conducted by McDevitt and Steward (1991). In this chapter, the details of these experiments will be presented and the results discussed.

3.1 Apparatus

One-litre propane tanks having a diameter of 7.5 cm, a length of 26 cm, and a wall thickness of 0.64 mm were used to contain the propane lading. To install the required instrumentation the pressure relief valve of each tank was removed and two 1.59 mm type-T thennocouples were inserted. One thermocouple was instailed to a depth of 25 mm and the other to a depth of 50 mm fiom the connection on the tank. The tanks were filled to the desired level with propaneThe tanks were mounted horizontally about 0.5 rn above the ground and secured to a concrete block. In some tests a propane torch was placed beneath the bottom of the tank to heat the lading to the desired temperature. The tank was ruptured either by a Constant Interval Electric Detonator (500 ms delay) or an instantaneous electric detonator, both of which have a base charge of 12 grains of PETN in an alurninum shell (blasting caps). Blasting caps were provided, instailed, and detonated by RCMP personnel. The hole size was controiled by instailing hex nuts into the wooden mounting base whereas

a standoff distance of 6.4 mm provided a hole of 3 mm in diameter. The apparatus is shown

in Figure 3.1.

One-litre Propane Tank

1
Nail

I !

Copper Wire Wooden Mounting Base

Figure 3.1 The apparatus for Vent and Burn experiments.

A high speed camera with a remote trigger was used to record the event at 4,000 fiames per second, and a VHS video carnera was employed to record the experiments. The themorneter readouts, the hi& speed camera trigger, and the blasting cap triggers were

located at the observation site, 75 m fiom the tank.

3 2 Test Conditions .
A test matrix was prepared to determine the effects of various variables: a) the

location of the f rupture; b) the delay tirne between ruptures; c) the volume of propane in h t the tank at the time of rupture; d) the temperature of propane at the time of rupture; e) the

19

rupture size. The test matrix is presented in Table 3.1. The conditions of the last three tests chosen were those which had k e n shown to produce a BLEVE when the tank was ruptured

by a 22-0.250 full metal jacketed rifle bullet (McDevitt, 1990). The previous study
(McDevitt, 1990) showed that a BLEVE would occur at 50C in tanks with a minimum lading of 422 g propane. Therefore Tests 23 and 24 were added to investigate if a charge producing a larger hole would induce a BLEVE. Test 25 was dso included in a final attempt to induce a BLEVE.

3.3 Test Procedure AAer installation of the instrumentation the tanks were taken to the propane refillstation and filled with propane via a recharging valve. A balance was used to mesure the fil1 level. The tanks were actually filled with a small excess of propane which was released prior to the test.
At the test site, the equipment such as the high speed camera, video camera, and

temperature monitoring was set up and tested. The tanks were mounted horizontally on a concrete block about 0.5 m above the ground attached to two wooden holders. A propane torch was placed beneath the bottom of the tank to act as an impinging fire. A match attached to a 90-second fuse was placed near the top of the propane torch. The experimental setup is s h o w in Figure 3.2.

Table 3.1 Test matrix and measured test conditions for Vent and Burn experiments.

Test Temperature,
O C

Volume ~iquid!

Lading M d ,
g

1st Hole Location

top

Delay,
5

I
2

ambient (20) arnbient (22) ambient (28) ambient (2 1)

40
40

bottom top bottom top bottom top bonom top bottom top bottom top bottom top bottom top bottom top bottom top (8 mm dia.) bottom (8 mm dia) 13 mm dia hole

3
4

5
6

(41) (40) (40) (42) (50) (52) (45) (40)

7 8
9

40 40 50 50 40 40

10

13
14 15
16 '

ambient (1 7) ambient (20) ambient (2 1 ) arnbient (23)

17#
18 4

19
20 21 22

40
40 40 40
50

(40) (41) (40) (46) (50)

23
244

50 50

(51)
(51)

254

he time of rupture

only a video recording provided

The value in parentheses indicates the measured test conditions.

Figure 3.2 Experimental setup for Vent and Burn experiments

22 For the tests with a 0.5-second delay, one of the blasting caps inserted into the wooden mounting bases was an instantaneous detonator and the other was a Constant Interval Detonator, with a delay of 500 ms.Both caps were connected to one circuit. The first one detonated imrnediately, when the button was pushed, and the second one detonated 500

ms later. For the tests with a 2-second delay, two instantaneous detonators were used. These
were comected to two separated circuits and discharged on cornmand. Once the blasting caps were iri place, the equipment ready and functioning, the fuse
was lit and RCMP personnel moved to the observation site. At the end of the 90 seconds the

match was lit which in turn lit the propane torch. When the test temperature had been achieved, the high speed camera operator started the camera and cued the RCMP personnel to detonate the blasting caps. The temperature of liquid in the tank was recorded. A video recording was made for each of the tests.

3.4 Experimental Results

The measured test conditions are given in Table 3.1. Video recordings of each test show the fireball size and duration including the effect of the second rupture. The high speed films show clearly the initial rupture, the initial venting, the ignition and development of the fireball, and in some cases the effect of the second rupture. Al1 tanks were ruptured irectly above and below the tank centerline to insure that the rupture was in the top (vapor) or bottom (liquid) section. A hole of approximately 3 mm in diarneter in both the top and the bottom of the tank resulted fiom the detonation of the blasting cap through the hex nut.
A discussion of the effect of the variables studied foltows.

23
3.4.1 Location o f First Ru~ture

Changing the location of the first rupture provided the most visually different effect. Experirnentally, the tanks which were vented i the top first produced a propane jet which, n in some cases, ignited and burned as a flame shooting into the air. When the bottom of the

tanks was ruptureci, a large vaporizingjet was expelled toward the ground. A propane cloud
was formed near the ground and was ignited, by either the propane torch or flying sparks, producing a large fireball which fonned alrnost immediately. Mer the top was mptured the vapor released also produced a propane jet. Significantly, the high speed films show that in most cases the release of the liquid caused the tank to move slightly. Observations taken

fiorn the high speed films are shown in Figures 3.3,3.4 and 3 S. It should be noted that the
tirne period in Figures 3.3,3.4 and 3.5 is less than one second.

3.4.2 Delav Timg

From the video and high speed carnera the difference in fireball behaviour could not be detected between tests with 0.5 s delay and those with 2 s delay. However, the thought
was that a longer delay would result in more propane escaping through the top hole, if the

first rupture is in the vapor section, therefore, a smaller freball should result when the liquid is released. In Test 15, the second blasting cap could not be detonated after two seconds but was finally detonated aller 60 seconds. This allowed the pressure and temperature inside the

tank to drop substantially, as indicated by the fiost formed on the outside of the tank.

3.4.3 Volume of P r o ~ a

Tanks were filled with 25,50 and 95 v% liquid propane. The tanks that were filled
with 95 v% resulted in the largest fireballs. The differences arnong 25,50 and 95 v% tests

were primarily the size of the fvebails produced by the rupture in the liquid section of the

tank.

3.4.4 Tem~erature Proof

The rneasured test temperatures are given in Table 3.1. There were no observed difference in tests at different temperatures but with other parameters the same. None of the
tanks BLEVEed. A temperature of 40C was selected because that is the maximum ambient

temperature to which a propane tank railcar or truck rnight be subjected in Canada. In a previous study (McDevitt, 1990) it was shown that BLEVEs could be induced at 50C and

95 v%.

3.4.5 m

e S&

For Tests 9 and 10 BLEVEs should have occurred based on the cntenon given by McDevitt (1990). However, in that investigation thz tanks were ruptured with a 22-0.250 rifle bullet which produced two holes of 6.4 mm diameter (one entering and one exiting). The hole diameter has been s h o w to affect the formation of pressure waves when a PLG
tank is ruptured (McDevitt, 1990). Therefore Tests 23 and 24 were conducted but BLEVEs

still did not occur. Test 25 was carried out by using two blasting caps side by side to produce
a 13 mm diameter hole in the top of the tank.A BLEVE did not occur with this larger hole.

3.4.6 Summaw o f Results

1) T&

that were first ruptured in the vapor space produced a propane jet followed

by a frebail d e r the liquid space was ruptured. The release of the liquid caused

the tank to move slightly; 2) Mien the first rupture was in the liquid space, a fireball formed immediately. Afier the vapor space was ruptured a propane jet fomed;

3) The difference in delay tirne (between 0.5 s and 2 s) had no significant effect on
tank failure. For the test with a iielay time of 60 s fiost formed on the bottom half

of the tank before the second rupture; 4) A greater volume of liquid propane resuted in a larger fireball;
5) Lading temperatures had no observable effect;

6) None of the tanks BLEVEed in the tests.

3.5 Discussion
3.5.1 Location of F i r s t t u r q

Puncturing the tank in the vapor section first wili result in a decrease in tank pressure

and eventually in cooling of the lading. The subsequent rupture of the liquid section will empty the tank rapidly and cause a fireball. On the other hand, rupturing the tank in the liquid section first will result in a more rapid release of propane and produce a larger fireball. The subsequent rupture of the vapor section seems to have little effect on the process. However a previous study (McDevitt, 1990) showed that a rupture in the liquid space c m

26

produce higher amplitude shock waves in the liquefied gas tanks. Therefore puncturing the liquid space fvst is probably more dangerous and more likely to result in a BLEVE.

3.5.2 Del- Time

Rupturing the tank in the vapor space fist with a longer delay before ruptunng the tank in the liquid space would result in more propane leaving through the first holeThis couid therefore result in a smaller firebail when the second hole in the liquid space is made.

From the tests conducted it can be estimated that for a hole diameter of 3 mm in the vapor
space, the delay times of 0.5 s and 2 s would release 2 and 9 g of propane, respectively. Relative to the weight of propane in the tank the amount of propane released was not significant.Therefore the difference in the time delay between 0.5 s and 2 s interval did not significantly change the amount of propane in the tank at the time of the second rupture. However it should be noted that one of the tests, Test 15, produced an interesting result which leads to the following suggestion: once the vapor space has been punctured the propane should be allowed to vent until there is significant evaporative cooling (the formation of fiost on the tank). When the fiost appears on the tank, the second rupture should be made (the tank will be at a significantly lower pressure).

353 Rur>ture S b and B U V E ..

Tests 9 and 10 were expected to BLEVE. When BLEVEs did not occur, Tests 23 and 24 were repeated with the same conditions except for larger holes (8 mm diameter). Test 25 did not produce a BLEVE even though it was perfonned with a rupture size of 13 mm. In

27

fact the rupture hole size created in Test 25 was much larger than the ones that caused a BLEVE for similar tanks in a previous study (McDevitt, 1990). The difference between the previous study which resulted in a BLEVE and this work was that the tanks in which a BLEVE occurred had a second exit hole, produced fiom the inside to the outside of the tank
with the exit of a builet. It is postulated that the exit hole weakened the metal in the region

of the hole by tearing outward which allowed the tank metal to continue to tear. In a typical BLEVE the tank is caused to fail by the intemal pressure which causes the tank hole to fail
outward resuiting in damage similar to that caused at the exit hole. However in the vent and

burn both holes were caused by the shaped charges which pushed the tank metal into the tank
rather than producing the tearing action of a hole forming in an outward direction. Al1

BLEVEs induced by the rifle bullet involved tank tearing initiated at the bullet exit hole.
The total surface area of a typical tank car is approximately 190 m If a vent and bum ' .

is carried out on the tank, the area of a 5 cm diameter hole produced with a 10 pound shaped charge is 0.002 m2. The ratio of the area of the hole to the surface area is therefore
1.O5 x IO-'. The total surface area of a one liter propane tank is 70 m2. Therefore the ratio of

the hole area of an 3 mm diameter hole to surface area of the tank is 1.O x

If the

experiments conducted were to be linearly scaled up to the full scale tanks, the rupture size would have been 0.5 m. Therefore, the holes i the one litre tanks in these vent and burn n experiments can be considered as a severe case compared to an actual vent and burn procedure. Since a one litre tank and a typical tank car are made of different materials and have different wall thicknesses, it is difficult to make a direct comparison about the rupture size required to BLEVE the full scale tanks.

3.6 Conclusions
1) The high speed films indicated that it would be safer to puncture the vapor space

of the tank before the liquid space of the tank;

2) It is useful to delay the puncture of the liquid space after the vapor space by a
certain period of time to allow the tank to cool by vapoxization and thus give a reduced pressure within the tank before the second puncture occurs.

Figure 3.3 Sequence of the fust rupture in the vapor space; a) Propane jet pmduced by a vapor release b) Subsequent liquid space rupture causing the tank to move slightly C) Fireball resulting immediately h m a liquid release

Figure 3.4 Sequence of the first rupture in the liquid space; a) Liguid release causing the tank move b) Resulting fireball c) Subsequent vapur space rupture under engulfing firebail

Figuw 3.5 Comprehensive scenarios for the first rupture in the vapor space

Chapter 4

FLOW FROM PRESSURE RELIEF VALVES WITH

VARIOUS ORIFICE SUES

A pressure relief valve (PRV) is usually a spring loaded valve which will open once

the pressure in the vesse1 exceeds a certain set pressure. The pressure relief capability of any particula.PRV varies greatly with the flow regime of the fluid during its passage through the
valve. Two typical flow regimes - single phase and two phase - were reviewed in this study.

For any flow regime, the mass flow rate, m, is expressed as

m = C&G

(4- 1)

where

C is the valve coefficient; A, is the minimum or critical area of the PRV; G is the mass flux.

4.1 SinglePhase Flow

4.1.1 V a ~ o Flow r

If the mass flux for the vapor, G , is choked flow based on the following assurnptions:
i) the vapor obeys the ideal gas equation of state;

, ii) the specific heats C and C, are constant;

iii) the vapor undergoes an isentropic process,

the resulting expression c m be written as (Sallet, 1979)

when the ratio of the vessel pressure to atmospheric pressure is

where

Po is the vesse1 pressure;

Pm is the atmospheric pressure;
p, is the density of the vapor at the vessel pressure;
gc is the dimensional constant (1

kgm/Ns2);

k is the specific heat ratio (CdC,) of the lading.

4.1.2 w

d Flow

If the orifice is in the liquid space and the lading stays liquid during the entire flow
process fiom the vessel through the orifice to the atmosphere, the mass flux for the liquid,

G,, can be obtained h m incompressible fluid flow relationships. By assuming that the fldd

is incompressible and the flow is inviscid and that nonconservative body forces are

neglected, the resulting expression is (Sallet, 1979)

where

p, is the density of the liquid;

g, is the dimensional constant (1 kgrn/NsZ);

g is the acceleration due to gravity;

Po is the vesse1 pressure;

, is the atmospheric pressure; P
az is the difference in elevation between the liquid level and the orifice.

For single-phase flow, the mass flow rate for the vapor through the orifice in the PRV can be determined fiom Eqs.(4.1) and (4.2) if the onfice size and the valve coefficient are specified. Similarly, the mass flow rate for the liquid can be calculated fiom Eqs.(4.l) and
(4.3). These equations were used for determinhg the mass released from the tank through

the orifice in the PRV under the test conditions for small scde tests. Calculations on mass flow rates for various orifice sizes installed in the PRV were performed using propane as lading under the given conditions for small scale tests. In this
study the PRV was always installed in the vapor space of the tank. The flow of vapor

released through the PRV was assumed to be choked flow and the pressure within the tank was assurned to be equal to the PRV set pressure and remain constant throughout the release. Valve coefficients are nomially experimentally obtained. They Vary as to types and

35

manufacturers (Sallet, 1979). The valve coefficients used in this study were taken as 0.89

for choked vapor flow and 0.65 for liquid flow (Sallet, 1979).
Figure 4.1 shows the mass flow rate for the propane vapor versus the orifice size at given PRV set pressures. As s h o w in Figure 4.1, the mass flow rate increases as the orifice size is increased at a given PRV set pressure. However, an increase in mass flow rate is less significant if the orifice sue is smaller than 0.2 mm at given PRV set pressure. Figure 4.2 presents the calculated results for the time to empty a propane tank at 85% fill level versus
the orifice size at given PRV set pressures. It can be seen that an increase in orifice size

decreases the tirne to empty the tank.

If the PRV happens to be installed in the liquid space of the tank, the mass flow rate
of the lading for various orifice sizes and the time to empty a propane tank can be determined in a similar manner. Such calculations using equations for single-phase liquid flow provide the results s h o w in Figures 4.3 and 4.4. Figure 4.3 presents the m a s fIow rate for the liquid propane versus the orifice size at given PRV set pressures. Figure 4.4 shows the calculated time to empty a propane tank at 85% fill level versus the orifice size at given

PRV set pressures. As can be seen, for any particular orifice size, the mass flow rate of the
liquid is greater than that of the vapor and the tirne to empty a propane tank for the liquid flow release is much smaller than that for the vapor flow release. However, it should be noted that, for liquid flow, the pressure within the tank would not decrease significantly even though the mass flow rate of the lading is much higher.

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Orifice Size, mm

Figure 4.1 Critical mass flow rate for propane vapor vs. orifice size at various PRV set pressures

2500 2000
V)

Po

1.?2 MPip

A
O

Po

2.48 MPag

1500

Po

6.62 MPip

i=
1000 -

500
O

m
0

A
A
1
1

A 1

A
1

A
L

A
l

I
A
1

I
1

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Orifice Sire, mm

Figure 4.2 Time to empty a propane tank at 85% fil1 level vs. orifice size at various PRV set pressures for single phase vapor flow

0.035

Po

0, 0.03 d

cn

1.72 MPag

P z 0 c
V)

r' 0.025 Po

0.02

Po

2.41 MPmg
A

ab

5.52

I A
O

II

a 0.015 0.01

2 O .Ci

(D

A
0

m
A

*t0.005 O

O + O

a
1

:'
A
1

I
4
I
1

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Orifice Size, mm

Figure 4.3 Critical mass flow rate for liquid propane vs. orifice size at various PRV set pressures

0.4

0.5

0.6

Orifice Size, mm

Figure 4.4 Time to empty a propane tank at 85% fil1 level vs. orifice size at various PRV set pressures for single phase liquid flow

4.2 Two-Phase Flow

Two-phase flow through an orifice is considerably more complicated than single-

phase flow. For several decades the topic has been studied and nurnerous reports of
theoretical and experimental studies have been published by many authors (for example, Starkrnan et al., 1964; Henry and Fauske, 197 1;Sdlet, 1979; Hutcherson et al., 1983; Sallet

and Somers, 1985; Seynhaeve et al., 1994 etc.) providing a nurnber of modeis used for
predicting the m a s flow rate for two-phase flow. In particular, the following models have been developed and used as standard approaches:

Homogeneous Eauilibnum Mode1 CHEM)

Developed by Starhan et al. (1964) this mode1 is based on the following assumptions:

..

a) the average velocities for the phases are equal;

b) thermodynamic equilibrium exists between the phases;

c) the process undergoes an isentropic expansion.

The mass flow rate prediction resulting fkom these assumptions is

where

h, is the enthalpy at stagnation; ,

xE is the equilibrium quality;

h,, is the enthalpy of liquid at equilibrium;

h is the enthalpy of vapor at equilibrium; ,

y,is the specific volume of liquid at equilibrium;
I is the specific volume of vapor at equilibrium. ,

The critical flow rate of HEM can be obtained by selecting the downstream pressure
for which the maximum flow rate is achieved.

Homoeeneous Frozen Mode1 (HFW

In this modei the following assumptions are made (Henry and Fauske, 1971):
a) the average velocities for each phase are equal;
b) there is no heat or mass transfer between the phases;

c) the vapor behaves like a perfect gas when it expands isentropicdly; d) the kinetic energy is due only to the vapor expansion; e) the critical flow rate is defmed by gas-dynamic principles.

Based on the assumptions above the critical flow rate can be obtained as

in which the two-phase specific volume, u, is expressed as

where the subscript O indicates the stagnation, k is the specific heat ratio (CdC,,) and
the critical pressure ratio, q, can be simplified to

when (1 - x,-Jq0 / (xoug ) 1.

Henry-Fauske Mode1 Henry and Fauske (1 971) introduced a coefficient, N, that allows oniy a fiaction of
the equilibrium vapor generation to occur. The term N is correlated as a function of b o a t equilibrium quality, xE,. This non-equilibnum mode1 is derived fiom the following assumptions: a) the phase velocities are equal;
b) no heat or mass transfer occurs durhg the expansion;

c) the expansion is isentropic on each phase. d) the vapor behavior can be described by a polytropic process, at the throat. e) the liquid phase is incompressible. f) the mass transfer rate at the throat can be conelated by:

where the subscript t stands for at the throat and

N =x,, 10.14,

xEt5 O 14 .

(4.9)

and
N = 1,
x , > 0.14
(4.1O)

Based on the assumptions above the cntical flow rate expression cm be written as

G,

nP

(1 -xo)N d, s - ( S S ) dP

xoCpg(lln M ) - c

P(sgo - s , ,)

where s,, is tl 2 entropy of vapor at equilibrium;

s,, is the entropy of liquid at equilibrium;

s is the entropy o f vapor at stagnation; ,
s,,

is the entropy of liquid at stagnation;

n is the thermal equilibriurn polytropic exponent which is given by

The two-phase momentum equation, under the restrictions listed above, can be integrated between the stagnation and throat locations to yield

With a combination of Eqs.(4.11) and (4.13) the transcendental expression for the
critical pressure ratio c m be described as

where

(1 -X~)NP,s d, -

,ln - c(/

- MC)

and

For given stagnation conditions of Po and x, a solution of Eq.(4.14) gives predictions of both the critical pressure ratio and flow rate. Al1 the models mentioned above are for a thoroughly dispersed mixture. For an orifice or short tube through which the discharge of initially subcooled or saturated liquid

has a unique separated flow pattern (Henry and Fauske, 1971) the transcendental expression
for Mo-phase compressible flows through orifices is proposed and written as:

where C is the discharge coefficient of the orifice.

44

The critical pressure ratio expression above cm be solved to yield a prediction for the

maximum flow rate.

Since various orifices were used in the present study Eq.(4.20)can be used to predict

the mass flow rates fiom the test tanks under the two-phase conditions.

The following statements are important to remember when considering the pressure
relief provided by the opening of a pressure relief valve under various conditions:
1) Equations for the mass flow of material through an orifice indicate that the mass
flow of liquid is approxirnately 5 times that of vapor through the sarne size orifice

at the same tank pressure;

2) The same equations show that the volume of flow through the orifice for vapor is 2 timss that of volume of liquid for the same size orifice at the sarne tank
pressure. This means that pressure relief is more effective for vapor phase flow through the orifice;
3) If some liquid is entrained into the vapor leaving the orifice this reduces the vapor

flow and thus pressure relief capabilities of the pressure relief valve.

Chapter 5

MODELLING FOR HEATING OF LADING AND CYLINDER

BY EXTERNAL HEAT SOURCE

Models for predicting the consequences of f i e attack on a liquefied gas storage tank have been developed for over two decades under different circumstances by many workers using a variety of assumptions and numerical techniques. A number of models involve engulfing pool fires (Moodie, 1988) which are described in Table 5.1. Most of the models listed in Table 5.1 have been specifically used for total pool fire engulfinent. However, some
can be modified to mode1 partial engulfinent or radiant heating. To date, such models remain

in the development stage and need M e r validation to improve their reliability. Consequently, complex models do produce detailed predictions but they have not been validated due to a lack of detailed data for large scale systems; simple models often give little information (Birk et& 1994). In this study simple models have been used for predicting the lading and surface temperatures of a tank enguifed in a pool fie. These models were developed employing the principles of heat transfer and thermodynamics. The conceptual basis for the rnodels entailed subjecting an uninsdated cylindncal tank in a horizontal position to total pool fire engulhent. Pool fire engulhent provides a unifonn heat flux to the tank. The tank was not equipped with a PRV,consequently the total mass of the lading in the tank was constant. This

46

situation models one of the worst type of accidents, that is, when the PRV of the tank does
not fnction at its set pressure for the entire process.

Table 5.1 Available models for predicting the consequences of f i e attack (Moodie, 1988)
Modes of rm altack
rnodelled

Versel Contents
modelled

Cornrnents Protedion

+ code h pibYedomm
w
cubold baseci modal r h

MCAR

d do t o z nu

Unhsulilsdh Itlmai paaclbn

Curmnt UN8 Coda (19811)

unhui~nd

~lld.n g h cwnpufar n ~
for ralsf vent s l z h whkh rlso

hcMm danmihait wurca.

NOrullnerdaJb

Unhsulmal

Mde wilb Min muthe for

gu 111a6 vaueLI only

Two models were developed in detail based on various assumptions.

Model 1: Lading in tank in two phases with different heat transfer coefficients Iiom the tank wail in each phase, without mass transfer between phases;

Model II: Lading in tank in two phases with difierent heat transfer coefficients fiom the tank wail in each phase, with mass transfer between phases.

5.1 ModeII

The following assumptions were used to develop the fvst model.

a) the heat flux on an outside cylinder surface is constant and uniform;

b) the outside surface looses heat by radiation; c) the heat transfer to each phase in a cylinder is given by a constant uniform heat transfer coefficient between the wall and the fluid phase;

d) the matenal in each phase has a uniform temperature (the lading is not thermally
stratified); e) heat transfer between phases is governed by a constant uniform heat transfer coefficient; f) there are no radial temperature gradients in the tank wall;
g) the physical properties of the material are independent of temperature.

Figure 5.1 shows a schematic of the cylinder used in the derivation of the heat transfer relations used in ModelI.

Figure 5.1 Cross sectionai diagram of cylinder used for Mode1 I

For two-dimensional transient heat transfer in the metd (factoring in the radial and circumferential transfer but neglecting the radial temperature gradient of the metal), and onedimensional transient heat transfer in the vapor and liquid, the governing equations can be obtained fkom heat baiances on each phase of the material for a unit length of cylinder.The derivation of these equations are individually descnbed as follows:

5.1.1 JMeaHeat B -

In general a heat balance for a system c m be written as

heati, - heat,, = heaa,

where

heat,, is the heat entering the system; heak, is the heat leaving the system; heat, is the heat accumulation within the system.

From Figure 5.1 a transient heat balance on a control volume of metal, dB, in contact

with the vapor phase neglecting radial temperature gradients within the metal is given by

where

Tm is the metal temperature;

0 is the angle dong the circumference;
q is the heat flux given on the outside surface;

r is the radius of the cylinder; k is the thermal conductivity of the metal;

is the wall thickness of the cylinder;

h, is the heat transfer coefficient to the vapor; ,

TV is the vapor temperature;

q

, the heat loss due to radiation; is

p,,, is the density of the metal;

Cp, is the specific heat of the metal;

is time.

50

It is assumed that the cylinder behaves as a blackbody emitting radiation fiom a surface at the surface temperature. The heat loss due to radiation is then given by
q ,

= UT,

where G is the Stefan-Boltzmann constant (5.67~ kW/m2.K4). 1(Y"

Substitution of Eq. (5.3) into Eq. (5.2) with rearrangement yields

The first term gives the flux of heat by conduction in the circumferential direction.Tne

second term on the lefi side represents heat flux fiom the outside surface entering the cylinder.

The third term is convection to the vapor phase within the vessel. The 1st term on the lefi side
of the equation gives radiation emitted from the outside wall.The right side of the equation gives heat accurnulating within the tank metal control volume.
When the angle almg the circderence moves across the interface between the vapor

and liquid, the third term on the lefi side of Eq45.4) is changed such that the vapor temperature, TV, becomes the iiquid temperature, T, and the heat tramfer coefficient to vapor,

4, becomes the heat transfer coefficient to liquid, hl. Therefore, the equation for the metal in
ih contact w t the liquid phase becomes

5.1.2 V

Since it is assumed that there is no thermal stratification within the vapor phase its control volume is taken as the total volume of vapor space in the cylinder. The amount of heat entering into the volume of vapor space by convection fiom the metal surface is

where 8 is the angle at the liquid-vapor interface (see Fig S.l).The amount of heat ieaving ,
the vapor space and entering the liquid space by convection through the interface is

where h, is the interfacial heat transfer coefficient and 4 is the area of the interface. The
arnount of heat accumulation within the vapor volume is

where

p,

is the density of the vapor,

Cpvis the specific heat of the vapor; Vv is the volume of the vapor.

Therefore, the vapor-space heat balance, by making use of Eq. (5.1). gives

5.1.3 Liquid Space Heat Balance

It is also assumed that the liquid space is heated as an entity and not stratified. The liquid receives heat from the metal surface with which it is i contact and through the vaporn liquid interface. The resulting equation is

where

p,

is the density of the liquid;

Cp, is the specific heat of the liquid;

V, is the volume of the liquid.

For Mode1 1the goveming equations used for determinhg the metal surface, vapor and liquid temperatures were respectively Eqs. (5.4), (5.9) and (5.10). The following initiai and

boundary conditions applied were: at

t=O,

T,=T,=T,=T,;

at 0 = O,

t3Tm/a0= O (symmetry);

0 = n,
where T, is the initial tempeature.

aT,,,/Xi = O (symmetry).

The PDEs were solved by a finite difference technique using the Crank-Nicolson method dong with the Thomas Algorithm. To determine the surface temperature distribution
in the metal Simpson's rule was employed for the evaluation of the integral to determine

vapor and liquid temperatures of the lading.

5.2 Model II

This mode1 includes al1 the phenornena of Model 1 but in addition allows mass to be transferred between the liquid and vapor. in order to account for the mass transfer, equations
of state are required for the liquid and vapor phases including a vapor pressure relationship.

Model II is based on the following asswnptions:

a) the heat flux on the outside cylinder surface is constant;

b) the outside surface looses heat by radiation.
c) the heat transfer coefficients to each phase h m the cylinder wall are independent

of temperature and tirne; d) the material in each phase has a uniform temperature (the ladhg is not thermally stratified);

e) there are no radial temperature gradients in the cylinder wall; f) the specific heat of the material in each phase is constant; g) the ideal gas law applies to vapor phase;
h) the equation of state for the liquid uses the coefficient of volumetrk expansion of

the liquid as a function of temperature. The vapor and liquid were individually considered as each being an open system having heat and mass transfer across the boundary between the two phases. The heat balance on the metal cylinder wall was determined in the same manner as for Model 1 (Eqs. 5.5, 5.1 1,
5.12 and 5.13). Figure 5.2 illustrates the systems used in the derivation for Model II.

(b)

Figure 5.2 Diagrams of systems used for Model 11: (a) Vapor; (b) Liquid

5.2.1 V a ~ o Phasg r

From Figure 5.2 (a) the open system equation on the vapor in differential form with respect to t h e can be written as

where

Q is the heat absorbed;

t is tirne;
W, is the "shaft" work;

U is the intemal energy;

h, is the enthalpy of the mass entering or leaving the vapor;

and

m is the mass entering or leaving the vapor.

The "shaft"work can be expressed in t e m of the volume and pressure of the system

dW, = - V d P

where V is volume and P is pressure. Since the w r c m also be written as ok

VdP = d ( P V )

- PdV.

Introducing Eqs. (5.16) and (5.17) into Eq.(5.14) and rearranging yields

Since

where

H is the enthaipy of the system; M is the m a s in the system; h is the specific enthalpy.

For the vapor phase equation (5.18) becomes

where M,, h, and Vvare the mass, specific enthalpy and volume of the vapor in the system, respectively.

From a m a s balance the mass enterhg or leaving the system is equal to the change

of mass in the system,

If it is assumed that the vapor leaving the system has the sarne enthalpy as the vapor within the system (that is, h,= hB)and the reference state is liquid at 25 O and 1 atm pressure C

The vapor-phase equation, therefore, becomes

where M, = f (T); = f (T); = f (T). V, P

5.2.2 Ligaid P h a s

Similarly the open system equation on the liquid phase in differential form with
respect to tirne r e f e r ~ to Figure 5.2 (b) can be rewritten as g

but

By using the same concept as the denvation for the vapor-phase equation which is

Eq.(5.20) the liquid-phase equation can be obtained as

where

M, is the mass of the liquid in the system;

h, is the specific enthalpy of the liquid;

V, is the volume of the liquid in the system.

A mass balance on the liquid phase gives the mass entering or leaving the system as

equal to the change of mass in the system,

Substitution of Eq. (5.26) into Eq. (5.25) and rearrangement yield

59

By taking the reference state as liquid at 25 O and atmosphenc pressure the specific C

enthalpy of the liquid can be obtained fiom

If it is assumed that h, is the enthalpy of saturated vapor,

hl-h, = -ahvap

where &a,

is the heat of vaporkation.

By substituthg Eqs.(5.28) and (5.29) into Eq.(5.27)the liquid-phase equation becomes

where Ml = f (T); V,= f (T); P = f (T).

For Mode1 II it is assumed that the heat transfer between the liquid and vapor is dominated by radiation and natural convection at the interface such that the heat flux terms for each phase can be expressed as follows:

vapor:

liquid:

where hinf the natural convective heat transfer coefficient at the interface. is

A mass balance on an entire cylinder as a closed system gives the following equations:

MT=M1+Mv

(5.33)
(5.34)

v,
since V, = M,uIand V,
= Mvuv,

=Vl+Vv

where q and u are the specific volume of liquid and vapor respectively. ,

Thus the change of mass and volume with respect to thne cm be obtained as

and

The liquid volume also expands when heated. The specific volume of the liquid cm
then be expressed by introducing the coefficient of volumetnc thermal expansion of liquids,P,

as

where

u,, is the specific volume of the liquid at the reference state;

T is the reference temperature and ,

for T, < 340 K for propane (Reid et al., 1987).

For an ideai gas the specific volume of the vapor can be written as

It is assurned that the pressure within the cylinder is equal to the vapor pressure of the

lading and is a h c t i o n of the liquid temperature,

P = P,exp (B)

where

B = [a(T) + b(T)'-'+ c(TI3+ d(T)6]1T;

T = 1-TI/ Tc; Pcis the critical pressure;
a,b,c, and d are constants for the lading used.

The heat of vaporization,

a, be expressed as (Reid et al., 1987) can

where o is the acentric factor and equal to 0.153 for propane.

63

Introducing Eq.(5.3 1) into Eq.(5.23) and Eq.(5.32) into Eq.(5.30), the governing equations for the energy balances on the vapor and liquid phases, yields a set of equations for determining the vapor and liquid temperatures versus time. The technique for solving the PDEs utilized in Model 1 was also irnplernented for Model II. Although the major difference between Model 1 and Model II was allowing mass transfer between the phases, another two cases for each model were developed in the same manner: with and without the heat loss due to radiation on the surface of the cylinder. Therefore, four models were used to predict the lading and surface temperatures under the given conditions. Figures 5.3 presents the liquid and vapor lading temperatures predicted by Model 1

(MOD 1) and Model 1without radiation (MOD VNOR) versus time for the cylinder equivalent
to the test tank at 85% liquid fiil propane. Figure 5.4 shows the metal surface temperatures predicted by Model 1 and Model 1 without radiation versus tirne for a similar cylinder. Figure 5.5 gives the liquid and vapor lading temperatures predicted by Model II (MOD

II) and Model II without radiation (MOD II/NOR) versus time for the cylinder equivalent to
the test tank at 85% liquid fil1 propane. Figure 5.6 presents the metal surface temperatures

predicted by Model II and Model II without radiation versus tirne for a similar cylinder.The results obtained fiom the models will be compared and discussed with the experimental data fiom the test tanks in Chapter 8. Figure 5.7 shows the effect of the liquid fil1 levels on the lading temperatures for cylinders siinilar to the test tanks with a given uniforrn heat flux. The change in liquid fil1 levels does not affect the liquid temperatures which rise almost linearly with time. The vapor

64

temperatures start to rise rapidly until reaching their maximum values and drop significantly when the liquid propane expands hilly within the test tanks. Apparently, the maximum vapor temperatures decrease as the liquid fi11 levels are increased.

Figure 5.8 presents the effect of the given uniform heat fluxes on the iading
temperatures for similar cylinders at 85% liquid fiU propane. As can be seen, the rate of lading temperature augmentation changes significantly as the given uniform heat flux is increased.

In Figures 5.7 and 5.8 the vapor temperature eventually falls rapidly to the liquid
temperature. This corresponds to the point when the tank becomes liquid full.

2 0 / ,,
O

20

40

60

80

1O 0

120

Time, s
MOD 1- Tliq
a

MOD 1- Tvap

MOD IINOR-Tliq

MOD IINOR-Tvap

Figure 5.3 Typical lading temperature profiles for the test tank at 85% liquid propane by Model 1 and Model 1 without radiation (heat flux = 12.5 k W h 2 )

60

Time, s

Figure 5.4 Typicai metal surface temperature profiles for the test tank at 85% liquid propane at various positions along circumference by Model 1 and Model 1 without radiation (heat flux = 12.5 kW/m2)

20

Fm , ,
O

, ,

10

20

30

40

50

Time, s

60

70

rn

MO0 Il-Tliq

MO0 Il-Tvap

MOD IIINOR-Tliq

MOD IIINOR-Tvap

Figure 5.5 Typical lading temperature profiles for the test tank at 85% liquid fil1 propane by Model II and Model II without radiation (heat flux = 12.5 kW/m2)

Figure 5.6 Typical metal surface temperature profiles for the test tank at 85% liquid fil1 propane at various positions dong circumference by Model II and Model II without radiation (heat flux = 12.5 kW/m2)

0 O

, 1 20

rn

40

60

80

1O0

120

140

Time, s

Figure 5.7 Typical lading temperature profiles for the test tanks for various liquid propane fil1 levels by Model II (heat flw = 13 kW/m2)

60

80

Time, s

Figure 5.8 Typical lading temperature profiles for the test tanks at 85% liquid propane for given uniform heat fluxs by Model II

Chapter 6

EXPERIMENTAI, APPARATUS

Details of the equipment, instrumentation and test procedure are presented in this chapter. The design of the apparatus was based on a typical situation where a tank car is subjected to pool-fire engulhent. The focus of the experiments was mechanical and thermalinduced BLEVEs. The experiments were designed to induced a BLEVE in a safe environment.

6.1 Test Tank Modification

6.1.1 One-Litre Test T

The tests were conducted with one-litre commercial propane tanks having an outside diarneter of 75 mm, a length of 260 mm, and a wall thickness of 0.64 mm. To permit quantitative measurement of the event the test tanks were modified as follows:

The tanks were instrumented with a pressure measuring device and one or more thermocouples to monitor tank pressure and temperature during the test until the tank failed or the pool f i e ceased;

Since the test tanks were to be engulfed with a pool fire, their original

ih charging and relief valves were removed and replaced wt strong bolts to

69

prevent leakage at these locations. A stronger recharging vaive was assembled and installed in a new location to fil1 the tank with the desired lading. The test tanks were modified by the following procedure. The original charging and relief valves were removed and replaced with two 6.35 mm bolts. A 6.35 mm NPT stainless steel union was installed at 25 mm fiom the center of the tank to accept a 6.35 mm TP3 16L stainless steel tube 1.O7 m long. At the other end of the tube a 6.35 mm NPT stainless steel ball valve was connected to allow the various ladings to be charged. A 3.18 mm NPT stainiess steel union (for a one-thermocouple tank) or a multiconductor feed through (for a three-thennocouple tank) was installed at the opposite end but the same distance as that of
the 6.35 mm NPT union. Either a 3.18 mm diameter type-T thermocouple was inserted into

the tank through the 3.18 mm union or three 1.59 mm diarneter type-T thennocouples were inserted through the multiconductor feed through. For a one-thermocouple fitting, the thermocouple was inserted to a depth of 65 mm fiom the top of the tank to measure the liquid lading temperature. For a three-thennocouple fitting, the first thermocouple measuring the liquid temperature was inserted to a depth of 65 mm. The second one was kerted to varying depths depending on fil1 level to measure the temperature near the interface. The third themocouple was inserted to a depth of 10 mm to measure the vapor temperature. To weaken the tank wall a shaved surface 10 mm wide and 50.8 mm in length was made on the top of the tank next to the steel tube fitting containhg the ball valve. The shaving was made to various depths to yield a desired wail thickness at this point. This ailowed the tanks to fail at a lower pressure. The test tank is schematically illustrated in

Figure 6.1.

6.1.2 Five-Pound Test Tank

A five-pound commercial propane tank having an outside diameter of 235 mm, a

height of 178 ~nm, a wall thiclmess of 2.20 mm was used as a supplemental test tank in and order to investigate the effects of tank size and the thermal response of propane lading of the two phases, that is, liquid and vapor. The five-pound tank was modified in the following way. The tank handle was rernoved fiom the top of the tank to allow for installation of instrumentation. The original charging valve coupled with a pressure relief valve was removed and replaced with a 15.88 mm-6.35mm NPT stainless steel reducing union to be fitted with a 6.35 mm TP3 16L stainless steel tube of 1.O7m long. At the other end of the tube a 6.35 mm NPT stainless steel bal1 valve was comected to allow the lading to be charged. Two 3.1 8 mm NPT unions were used; one was installed on the side 50 mm frorn the base of the tank, and the other was installed on the top of the tank 100 mm fiom the reducing union.Two 3.1 8 mm diarneter t p - themiocouples were inserted through the 3.1 8 yeT

mm NPT unions to measure the vapor and liquid lading temperatures. Figure 6.2 shows the
diagrarn of the modified five-pound test tank.

6.2 Filling of Ladings

The ladings used in this study consisted of two common types of materials; liquefied gases and liquids. S x liquid ladings were employed; acetaldehyde, acetone, n-butanol, ni pentane, methanol, and water. Four liquefied gases were used; ammonia, propane, R-12 (dichlorodifluoromethane), and R-1 14 (1,2-dichloro-1,1,2,2-tetrafluoroethane). those For ladings which are liquids at room temperature the Iading could be added directiy thmugh the charging valve. If the lading was a gas at room temperature the following procedure was used.
A container was partially filled with dry ice. The test tank was placed in the container

and covered with dry ice to induce a low temperature within the tank.The valve acting as a

recharging valve was connected to a regulator of the lading supply tank through an adaptor.

The thermocouple was connected to a digital themorneter readout to monitor the temperatwe
inside the tank. When the temperature in the tank reached a value below the normal boiling point of the lading, the valve was opened to aliow the lading to flow into the tank where it condensed into a liquid. The temperature w i t b the tank increased during filling until the lading no longer flowed into the tank. The valve was closed and disconnected fiom the supply tank.The tank was then purged through the valve and allowed to decrease in temperature. This procedure was repeated until the tank was filled with the desired weight

of lading.

6 3 Instrumentation . 6 3 1 PooEFire Source ..

A round steel container (Pan) with a diameter of 0.6 10 m and a height of 51 mm was

filled with a fuel to provide a pool fxe. By knowing the burning rate of the fuel and the length of time that the fuel was to bum the amount of fuel required in the pan could be determined. In this study methanol and 2-propanol were used as fels depending on the lading king tested. A heavy-duty steel stand 1 m x 1 m x 0.5 m height was used to support the pan above the ground. On the top of the stand a steel fiame 1 m
x

1m

1 m containing

double layers of 50.8 mm mesh fencing metal net was p k e d over the pan containing the fiiel and the test tank to protect the personnel and instrumentation against flying fiagrnents of the failed tank.This metal fencing also allowed the tank pieces to be collected after the tank failure.

6 3 2 -eu ..

..

A radiation shield was used in some cases in order to reduce the radiation from the

surface of the test tank engulfed in a pool fie. The radiation shield was fabricated of thin steel sheet metal with dimensions of 300 mm by 100 mm mounted on four copper rods 200

mm in length.

6 3 3 Pressure Me..
A pressure transducer manufactured by Tram Metrics Inc., mode1 P21AX, with an

operating range of 0-3000 psig (0-20.69 MPag) was connected with a tee fitting to the valve

75

used for charging the lading. A data acquisition board instailed in a PC (personal cornputer) was used to log the pressure data.

For a tank with one thennocouple, a 3.18 mm O.D. thennocouple was used to measure the liquid temperature. For a tank with three therrnocouples, 1.59 mm O.D. therrnocouples were used to rneasure the vapor, interface, and liquid temperatures. The length of the therrnocouples in both cases was 0.914 m. This allowed the connections to the data acquisition system @AS) to be a sufficient distance from the pool fire to prevent damage to the connections.

6.3.5

5 Orifices
A pressure relief valve (PRV)manufactured by NUPRO Co., SS-4R3A series, can

be adjusted for nominal cracking pressure ranges by using calibrated springs. It was installed

on the other branch of the tee fitting. The pressure-relief settings studied were in a range of
250-800 psig ( 1.72-5.52 MPag).
An orifice disc was mounted at the outlet of the PRV to regdate the Ming releasing

from the tank when the tank pressure reached the PRV set pressure. The orifice sizes ranged fiom 0.1- 1.O mm in diameter.

6.3.6 Blast Pressure Measurement

A blast pressure transducer manufactured by PCB Piezotronics Inc. mode1

PCB 1l3B5 1 w t a resolution of 0.025 psig (172 Pa) was placed 1.37 m from the test tanks ih
during several tests. This transducer was comected to the DAS to record the pressure variation with time immediately after a violent failure.

6.3.7 Data Acqgisition Svstemg

...

The data acquisition system consisted of a data acquisition board which was installed
in a PC, and a terminal box with cable comection to the sensors. Two data acquisition

systems were used and are described as follows:

A WB-FAI-B 16data acquisition board by Omega Inc. with acquisition speeds

fiom 2.5 kHz to 1 kHz was installed in a PC (486DXU33) and utilized for 0
logging the tank pressure and temperature data.
A DAS-50 data acquisition board by Keithley Metrabyte Inc. featuring high

speed from 137 Hz to 1 MHz was instailed in a PC (486DX250) was employed for logging the blast pressure data.

6.3.8 Video and SGII Photogi.aDhS

A VHS and an 8 mm video camera were used to record the entire test including tank

heating, lading release, fdlure and tank remnants. Still photographs were taken of the remnants of the tanks at the end of the experirnents.

6.3.9 Thermal Video Svstennfrared

An IQ325 Thermal Video System manufactured by FLIR Systems Inc. was used to

measure the tank surface temperatures This system contained the following: h f k e d imager with attached CRT viewfinder; image processor with keyboard; color monitor.

In addition a VCR coupled to the image processor was used to record the IR images
for later anaiysis of the data.

6.4 Experimental Setup

The setup of the experiments consisted of four parts which are individually described in the following sections.

6.4.1 Test Site

The test site was located in the University of New Brunswick woodlot approximateiy
3 km fiom the nearest highway. It is an open-cut gravel pit of 400 m2 in m a sunounded by

lines of pine trees and accessed through three dirt roads. The open area is surrounded on three sides by mounds of gravel which would collect fragments from the tank failure.

6.4.2 Test T

w Pooi-Fire Source

The pan used to contain the fuel for the pool f i e was placed in position on a steel
stand 0.5 m above the ground. The thermocouple line and the tube connected to the PRV

78

were insulated with g l a s wool. The test tank was mounted on a stand at the center of the pan which held the tank 100 mm above the base of the pan. The pressure transducer was fitted to the tank and the thermocouple was connected to the cables fiom the DAS. In some tests a radiation shield made of thin metal sheet 100 mm x 300 mm and four small copper rods
200 m m high was placed over the tank in order to reduce the radiation fiom its surface.

6.4.3 Data Acquisibon estemg

...

Each PC instaled with the DAS was set up and connected to the DAS's terminal box. From the terminal boxes cables were comected to the sensors. The application software were required by the DAS's to monitor and log the data.

6.4.4 Video and Inbared Cameraq

To create video records, two video cameras were set on tripods aimed at the tank. O One camera, I m from the tank, was used for recording close-up views of the tank. The
other, at a distance of 15 m, was employed for recording the fkball and the pst-experiment scenarios.
The IQ325 imager was set 20 m fiom the tank to capture infrared images.

6.5 Test Procedure

The test procedure consisted of the following steps: a) The test tank was mounted on the steel stand within the fuel pan;
b) The instrumentation was connected and the data acquisition was verified;

c) The liquid fuel was charged to the fuel pan;

d) Ali photographie equipment and the data acquisition were started; e) The liquid fuel in the pan was ignited with a burning wick. This was considered
time zero;

f) The data was collected continuously until the tank failed or the liquid fuel was
consumed;

g) The after effects of the test, paxticularly wih respect to the test tank, were
recorded;

h) The tank or fragments of the tanks were collected and saved.

Some photographs showing the test setup, the test setup during fire and the test setup d e r failure are presented in Figures 6.3 through 6.5.

Figure 6.3 Photograph showhg the test setup

Figure 6.4 Photograph showing the test setup during fire

Figure 6.5 Photograph showing the test setup afkr failure

Cbapter 7

RESULTS

Fifty-eight tests were conducted in the field using the tanks and apparatus described

i Chapter 6. This chapter presents the conditions under which the tests were conducted and n
the results of these tests. The results are presented in tabular form dong with some still

photographs taken nom video recordings of the tests.

7.1 Comprehensive Outcome

The conditions for al1 tests in the test program are presented in Table 7.1. Except for
the ammonia, at Ieast two tests were perfomed on each of the ladings. However, three or

more tests on each matenal was the nom. Table 7.2 presents the variables and measured quantities for a i l tests conducted. The variables studied were type of lading, lading fil1 level, PRV set pressure, orifice size, and mechanical condition of tank wall thickness.The measured quantities were maximum pressure, maximum temperature, maximum surface temperature,
tirne (to fiulure), blast pressure, pattern of failed tank rernnants and length of tear. For tanks

that failed the maximum measured quantities were those at failure. Notice that the length of tear was the s u .of distances measured on each remnant of failed tank.

Table 7.1 Test conditions on small scale BLEVE tests

TANK No.
UQUlD FlLL LWEL

MECHANICAL CONOmON OF TANK

1.72
1 .O

TYPE OF FUEL

PROPANE N-BUTANOL N-BUTANOL ACETONE ACETONE R-12 R-12 N-PENTANE WATER ACETAL 46 PROPANE PROPANE 47 48 PROPANE 49 PROPANE 50 PROPANE 51 PROPANE METHANOL 52 METHANOL 53 MrnNOL 54 55 METHANOL METHANOL 56 57 METHANOL Remarb: NIA = Not I

1 2 3 4 5 6 7 8 9 1011 1012 11 12 13 14 15 16 17 18 19 20 21 22' 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

PROPANE PROPANE PROPANE PROPANE PROPANE PROPANE PROPANE PROPANE AMMONlA WATER WATER PROPANE PROPANE WATER PROPANE WATER PROPANE PROPANE PROPANE WATER WATER WATER PROPANE MrnNOL N-BUTANOL ACETONE AC ETAL. N-PENTANE
R-12 R-114 WATER

NIA NIA
5.52 1.72 5.52 1.72

4A NIA
0.35 0.35 0.35 0.35

NIA
5.52 1.72 1.72 5.52 1.72 1.72 1.72 1.72 1.72 1.72 1.72 1.72 1.72 1.72 5.52 1.72 1.72 1.72 1.72 1.72 1.72 1.72

NIA
0.35 0.35 0.35 0.10 0.10 0.10 0.10 0.10 0.20 0.10 0.10 0.10 0.10 0.20 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10

WATER METHANOL METHANOL

R-114 R-114

NIA NIA NIA NIA NIA NIA NIA NIA NIA NIA NIA NIA NIA NIA NIA NIA
5.17 2.48 1.72 5.17 2.48 1.72 5.17 5.17 5.17 1.38 0.79 1.72

NIA NIA NIA NIA NIA NIA NIA NIA NIA NA NIA NIA NIA NIA NIA NIA
0.20 0.20 1. 0 O 0.20 0.20 0.20 0.20 0.40 0.60 0.20 0.20

METHANOL MEfHANOL MRHANOL METHANOL METHANOL MEMANOL METHANOL METHANOL PRO+MET METHANOL PROPANOL METHANOL METHANOL PROPANOL ACmONE PROPANOL MErHANOL METHANOL PROPANOL PROPANOL PROPANOL PROPANOL PROPANOL METHANOL PROPANOL METHANOL MrnNOL METHANOL METHANOL METWNOL PROPANOL PROPANOL METHANOL PROPANOL PROPANOL PROPANOL METHANOL PROPANOL PROPANOL PROPANOL PROPANOL METHANOL MEMANOL PROPANOL PROPANOL PROPANOL MEMANOL METHANOL METHANOL METHANOL METHANOL METHANOL PROPANOL PROPANOL PRO+MET MrnNOL MElfANOL

NO NO NO NO NO NO NO NO NO NO NO NO YES YES NO YES NO NO NO YES YES YES YES NO NO NO NO NO NO NO YES NO YES NO YES YES YES NO YES YES NO YES NO YES YES YES NO NO NO NO NO NO NO NO NO NO NO NO

Table 7.2 Measured quantities for small scale BLEVE tests

r ,

TANK No.

MAX
SURFACE TEMP. OF TANK

FAiLURE

TfME TO
PRV

OPENING
(SI

PATTERN OF FAllED TANK

(l ' C
1 2 3 4 5 6 7 8 9 1 1O1 1012 11 12 13 14 15 16 17
18

19 20 21 22' 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43
44

2.00 7.50' 7.50' NIA 6.90 6.90 6.41 6.55 6.55 1.61 3.79 3.79 3.79 2.59 NIA 4.48 2.46 2.00 NIA 1.72 0.97 1 .52 ,574 2.38 2.59 2.55 2.69 2.55 2.93 2.99 NIA 5.89 7.00 7.49 6.39 6.87 5.68 6.14 6.42 6.06 8.54 7.19 7.36 6.94 5.64 6.06

390 88 97 NIA 400 400 265 99 99 205 248 53 74 192 71 213 60 53 68 184 161 102

LT106
VT.275 124 114 135 ll6 120 57 95 NIA 275 186 231 106 123 LT:1O7 TT339 VT:143 201 179 154 186 1O 7 115 135 182 112

NIA NIA NIA NIA NIA NIA 250 275 325 300 375 NIA NIA NIA ,200 NIA >l5O >zoo >250 ,200 ,200 >200 ,200 MA 468 NIA 375 280 320 370 NIA 456 284 499 440 462 NIA 476 570 380 335 338

NO YES YES NO NO NO NO YES YES NO NO YES YES YES YES YES YES YES YES YES YES YES YES

NIA 130 140 NIA NIA NIA NIA 180 330 NIA NIA 100 80 380 47 720

TH TH

sw sw
TH TH
TW CL CL TH TW CL CL CL CL SH SH NIA SH SH SH SH SH SH CL SW SW CL ST CL TH
CL

72
48
37

188 108 285 217 239 182 227 185 203 60 124 NIA NIA 584 578 169 195 135 550 840 335 388 174 202 242 549 178

YES YES YES YES YES YES YES NO NO YES YES YES YES YES YES NO YES YES YES YES YES YES YES
3 L e I

sw
CL TW TH ST TW CL CL

290
466 862 542

45

I I

--

Table 7.2 Measured quantities for small scale BLEVE tests (cont'd)
k

TANK Na.

MAX. SURFACE

MAX.

46

PRESS. (WW)

TWP.
OF TANK

O
Lf:114 mi15 VTll9 LT: 67 rr: 73 VT: 72 LT475 TT:384 vr:343 LT:145 ml48 W149 LT: 87 TT: 97 VT: 98 LT: 74

(SI

TTUE TO FAKURE

Busr PRESSURE

RP@ O 1.37 m
NIA
NIA

PAiTERN OF FAlED TANK

6.68
3.38 1.87 7.06 3.52 2.89 8.12 6.39

2M 250
475

ES
YES
NO

108

47 48 49

8a
NIA
185 100 76 4 n

NIA
7.10 4.96

250
250 250 >472

YES

50
51 52 53 54

ES
YES
YES NO

VT:78
LT:234 iT:237 VT:238 LT224 NIA

rr: n

NIA

r: rm

r472
,472

NIA NIA
365

NIA NIA
5.24

5.83
1.58 1.24

55
56 57

3.00

VT:265 LT:219 ff:228 VT:242 LT: 158 TT: 158 UT:158 LT:143 K:146 UT:145 LT:l&? TT: 184 ml82

NO
YES YES

460
460

282

NIA
NIA

Remarks:

460

E S

465

NIA = Nol applicable LT = Liauid t e m m t u r e SH = shgb ho18along weakened spot CL = Crosslike teardown SW = Swelling TH = Three-piem teardown fW = Twogie leardowi ST = Shalten

86

The ranges of variables studied are presented in Tabie 7.3 dong with the variation in
meitsured quantities.

Table 7.3 Summary of ranges of variables and measured quantities

m
- -

Variable ! Measured Quantity Type of Lading

h Liquid Fill Level, O

Range
10

Arnbient Temperature, O C
PRV Set Pressure', MPag

Orifice Size*', mm Mechanical Condition of Tank Wall Thickness, mm Type of Fuel Radiation Shield with and without
1.24-8.12

Max. Pressure, MPag

Max. Liquid Temperature, O C Max. Surface Temperature, O C

53-234
>150-662

Time to PRV Opening*, s

Time to Failure, s

0-500 37-550

Pattern of Failed Tank

Length of Tear, m
iemarks:

5
0.061-1.988

"some tanks no failure tear = O

no PRV in some cases

7.2 Pressure and Temperature Profiles

For each test tank the pressure and temperature data were recorded using the data acquisition systems.Typica1 pressure and temperature versus t h e data are presented in Figure 7.1 for Tank 47 w t propane as lading. The pressure and temperature profiles of al1 ih tests conducted are given in Appendix A. The surface temperature of the tank obtained fiom the i&ared image system s h o w

in Figure 7.3 was converted into a diagram as a surface temperature profile. A typical s d a c e
temperature profile on the vapor space of the tank is shown in Figure 7.2 for Tank 7. It can be seen that initially the surface temperature increases rapidly followed by a reduced rate of increase. This phenornenon occurs because the temperature of the tank wall in contact with the vapor is higher than the temperature of the tank wall in contact with the liquid. The high thermal conductivity of the metal tank allows heat flow fiom the metal in contact with the vapor to that in contact with the liquid. This will also reduce the rate of temperature nse of
the rnetal surface in contact with the vapor. Data on tank surface temperatures versus time

for some tests are presented in Appendix B. The difficulty in obtaining the tank surface temperature was due mainly to hurnid weather conditions, especially in fog. The infkared image used for detecting the surface temperature of the test tank could not be focused precisely on the tank under these circumstances.

73 Fireball, Vapor Cloud and Blast Pressure .

Tanks which fail as a BLEVE and that contain flammable liquefied gases often, but
not always, produce a fireball. It was obsewed that the size of the fireball depended on the
mass of the lading at the time of BLEVE regardless of the type of lading if flammable. Some
photographie evidence is presented in Figures 7.4-7.7.

Figure 7.4 shows the firebail produced fiom the tank fiiied with propane at 85% fill level. Figure 7.5 shows the fireball given by the tank containhg propane at 5 1% fil1 level.
The fireballs produced fiom both methanol and n-pentane at 80% fill levels are shown in

Figures 7.6 and 7.7 respectively.The size of fireballs produced by different fill levels and ladings will be discussed in Chapter 8. The blast pressure at failure was measured for three tests at a distance of 1.37 meters

fiom the tank facing the cylindrical surface. The blast pressure varied between 4.96 and 7.10

kPa with the highest value being recorded for propane lading with the nonnal wall thickness.
The blast pressure for the methanol lading was higher than the lower value for a propane lading even though the tank failed at a lower pressure due to a very weak wallO.10 mm.

TANK 47 PROPANE, 85%, PRV:360, 0:0.20, W:0.30

Figure 7.1 Typical temperature and pressure profiles of tank with propane as lading

TANK 7 PROPANE, 85%. PRV:250. 0:0.35, W:0.38

Figure 7.2 Typical surface temperature profile of tank with propane as lading

Figure 7.3 Illustration of surface temperature fiom infrared image system

Figure 7.4 Fireball pruduced h m tank filled with propane at 85% FV (Tank 47)

Figure 7.5 Fireball produced h m tank filled with propane at S% FV (Tank 36)

Figure 7.6 Firebdl obtained h m tank containhg methsnol at 80% FV (Tank 33)

Figure 7.7 Fireball obtained h m tank containhg n-pen-

at 80% FV (Tank 43)

7.4 Pattern of Failed Tanks

The pattern of failed tanks was recorded for a l tests and presented in Table 7.2. The i type of pattem was divided into the following groups:

SH (single hole dong weakened spot) - the breach occurs about the length of the

weakened groove.
CL (crosslike teardown) - the breach occurs dong the weakened spot and moves

dong the circumferences of the end cap and the center of the tank, but the tank is still
in a single piece.

TH (two-piece teardown) - the tank is tom into two pieces; the part at which the
breach occurs and the remaining part, and while the end cap is breached, it remains attached to the main part. TW (three-piece teardown) - the end cap is tom apart where the breach occurs, the
part at which the weakened spot was made is most likely flatkned and separated

fiom the remainder of the tank.

ST (shatters) - the tank is tom into some small pieces.

The illustrations showing the characteristics of these patterns are given in Figure 7.8.

Figure 7.8 Characteristics of failed-tank patterns:

a)

SH; b) CL; c) TW; d) TH; e) ST

7.5 Pressure at Failure Corresponding to Mechanical Condition

For a cylindrical tank of a given metal the pressure at failure is mainly a function of

wall thickness. I f the wall is weakened by decreasing its thickness the pressure at failure is reduced. Table 7.4 presents the pressure at failure for the test tanks used in this study. These data are presented graphically in Figure 7.9.

0.1

0.2
ACETONE PROPANE

0.3 0.4 Wall Thickness, mm

AMMONIA
R-12

0.5

0.6
+
N-BUTANOL
WAER

0.7

ACETAL. N-PENTANE

METnANOL

R-114

Figure 7.9 Failure pressure vs. wall thickness for the test tanks

Table 7.4 Pressure at failure correspondhg to mechanical condition of the test tanks
Average Pressure at Failure

(Mm)
1.24

Remarks: WK, x mm = weakened wall thickness redud to x mm for 50.8 mm groove on top surface NM = normal wndlion The numeric in parentheses indicates a number of tanks involved

7.6 Theoretical and Actual Work Available at Failure

The theoretical work available in the tank when failure occws can be determined utilizing a pressure-enthalpy (P-h) diagram for the particular lading if the pressure at failure and tank fil1 level are known. The pressure-enthalpy diagrams for some of the ladings used in this study are given in Appendix C. The details for determining the available work are presented in Appendix D. As the lading is heated at constant volume the energy is stored in

the lading. When the tank fails this energy is released. One measure of this is the available
work (Steward and Rirksomboon, 1996). For an isentropic expansion to atmospheric pressure the difference in intemal energy is equal to the available work,

-W, = AU

at constant s

The values of the available work at the tirne of failure for each test in which failure occurred have been calculated or estimated. Estimations were made for the ladings for which precise thennodynamic data were not available, namely,acetaldehyde,acetoneand n-pentane. These values are presented in Table 7.5. Another quantity of interest is the amount of work the lading perfonns in pushing back the atrnosphere when the lading expands during failure. The process of tank failure is the lading expanding at constant enthalpy. Duhg such an expansion the lading pushes back
the atmosphere and performs work. This has been defined as the "actual work" at failure.

where

Pa is the pressure of the atmosphere;

V, is the volume of the lading at atmospheric pressure d e r expansion
at constant enthalpy; V, is the volume of the lading before the expansion, the volume of the test

tank.

Table 7.5 also presents the values of the actua work performed by the lading in pushing back the atmosphere when failure occurs.

7.7 Length of Tear and Work to Tear Tank

The length of metal tear was detemined for each test if ail pieces of the tank were recovered. These values are presented in Table 7.2. The work required to propagate a crack on the tank or work to tear the tank was calculated fiom the formula (Hahn et al., 1972 and Hahn et al., 1969)

where

R is a proportionality constant for the material, taken as 700 kJ/m2for steel; t is the thickness of the material, m; L is the length of the tear of the material, m.

99

These values are presented in Table 7.5 and range fiom 0.027 to 0.891 kl for the tests conducted.

7.8 Estimated Heat Flux

The heat flux for each test was determined if the thennodynamic data of the lading
was available. These values are presented in Table 7.6. Experimentally, propanol produces

a heat flux 2-3 times as hi& as methanol. The amount of wind during a test was a major

factor in lowering the heat flux to the tank surface. This can be seen orn the infiared image recording of surface temperatures showing a fluctuation in surface temperature when occasionally the wind blew over the test tank.

1O0

Table 7.5 Available and actual work along with work to tear tank for the test tanks
Tank No.
2 3 8 9 11 12 13 14 15 16 17 19 20 21 23 24 25 26 27 28 29 32 33 34 35 36 37 39 40 41 43
44

Lading Matenal Propane Propane Propane Ammonia Propane Propane Water Propane Water Propane Propane Water Water Water Methanol N-butanol Acetone Acetalde. N-pentane R-12 R-114 Methanol Methanol R-114 R-114 Propane N-butanol Atone Atone R-12 N-pentane Water Acetalde. Propane Propane Propane Propane Methanot Methanol Methanol

-Liquid Fill Failure Level Press. (MP~Q) 85 7.50' 7.50' 85 6.55 85 75 6.55 3.79 85 3.79 85 40 3.79 50 2.89' 4.48 80 85 2.46 2.00 20 1.72 20 0.97 13 80 1.52 2.38 80 2.59 80 80 2.55 75 2.69 2.55 80 80 2.93 80 2.99 80 7 .O0 7.49 80 80 6.39 80 6.87 5.68 50 80 6.14 80 6.06 80 8.54 80 7.19 80 6.94 5.64 80 80 6.06 85 3.38 51 7.06 36 3.52 2.89 49 80 8.12 1.58 80 1.24 80

45 47 49 50 51 52 55 56 57

Available Work (kJ) 42.70 42.70 31.35 80.28 27.60 27.60 45.12 23.55 120.44 29.76 8.32 20.24 9.27 64.45 31-82 20.05 27.49 30.97 34.19 28.78 26.27 35.32 37.50 32.52 32.98 37.53 22.09 28.40 30.28 37.73 40.23 121.O0 28.33 32.07 41.75 22.91 23.42 65.19 27.09 23.95

Adual Work (kJ) 13-41 13.40 13.38 24.53 11.86 11.86 21-90 8.10 38.40 11.20 3.18 13.57 4.44 26.46 11.11 13.47 13.31 15.12 11.96 11.48 11.80 18.36 19.30 13.13 13.41 11.89 13.77 14.20 14.98 13.43 13.79 45.90 14.82 11.92 13.89 7.36 7.45 20.68 12.15 10.70

Work to Tear Tank (kJ) 0.464 0.432

0.444
0.352 0.237 0.206 0.204 0.302 0.263 0.242 0.163 O 187 . o. 102 0.042 0.044 0.085 0.042 0.061 0.054 0.122 O 163 . 0.217 0.891 0.379 0.409 0.455 0.188 0.235 0.339 0.422 0.299 0.202 0.275 0.252 0.573 0.259 0.222 0.883 0.166 0.027

0 3.00 8

Remarks: estimated failure pressure at failure

4 . 1 -du!L 73

0.343

Table 7.6Heat flux estimated fiom experimental data

Tank No. Lading Material Propane Propane Propane Ammonia Propane Propane Water Water Water Water Water R-12 R-i 14 R-114 R-114 Propane R-12 R-12 Water Propane Propane Propane Propane Propane Fill Level
(%)
--

Type of Fuel Methanol Methanol Methanol Pro+Met Methanol Methanol Propanol Propanol Propanol Propanol Propanol Pro+Met Methanol Methanol Methanol Methanol Methanol Methanol Propanol Methanol Methanol Methanol Methanol Methanol

Heat Flux (kW/m2)

Chapter 8

ANALYSIS AND DISCUSSION

This chapter analyzes and discusses the results presented in Chapters 5 and 7.

8.1 Lading Materials

The ten ladings used in this study were selected on the basis of differences in their
physical properties toxicity, availability and reliability of thermodynamic data. Table 8.1 presents some of relevant physical properties of these ten ladings.

Two m i types of ladings were used, that is, liquefied gases and liquids based at an an
initial temperature of approximately 25C. Both types included flammable and nonflamrnable materials. Overall, the molecular weights range fiom 17.031 (ammonia) to
170.922 (R-14). The normal boiling points range fiom -42.1 O (propane) to 1 17.8O (n1 C C

butanol). The cntical temperature and cntical pressure of water were the highest arnong those
of the ladings used, 374.2"C and 22.05 MPa respectively. The critical compressibility of al1

ladings is in a narrow range of 0.220 (acetaldehyde) and 0.281 (propane). Lading properties
C at 25 O were used for determinhg the quantity of lading at a desired fil1 level. The properties

at atmospheric pressure were required for evaluating some quantities which were used for

M e r analysis of the data.

OOE

1O6

Figure 8.1 gives the vapor pressure versus temperature for the ten ladings. Materials with a wide variation in volatiiity were used in this study. Propane was the most volatile and n-butanol the least volatile of the ladings.

In order to investigate the effects of different ladings on type of failure the test tanks
with the sarne mechanical integrity were filled with various ladings at approximately the same fill level. When failure occurred, tanks produced a similar pattern under similar conditions. This can be seen fiom representative tank remnants in Figure 8.2. For al1 the
tanks shown in Fig. 8.2 the wall thickness was weakened at one spot dong the top surface
to 0.38 mm with a volume fill of 80%, except for the ammonia and propane ladings which

were 75% and 85% fil1 respectively. The figure shows crosslike teardown for five of the ladings. Three of the ladings produced two-piece teardown and two produced three-piece teardowns. However, the patterns indicated a sirnilar explosive violence in al1 cases. Figure 8.2 also shows that the tanks charged with acetaldehyde, acetone, methanol, n-butanol and water which are Iiquids at atmospheric pressure failed with crosslike teardowns. The tank containing n-pentane, which is also a liquid at atmospheric pressure, failed with a hnro-piece teardown. This is because the tank filled with n-pentane failed at a higher pressure (6.94 MPa) compared with the others (5.64-6.06 MPa). However, the tank charged with methanol failed at 7.00 MPa producing crosslike teardown. Al1 tanks containing ammonia, propane, R-12 and R-114 which are liquefied gases failed with twopiece and three-piece teardowns.

The type of fuel used for providing a pool fire can be disthguished by examining the
remnants (see Figure 8.2). Tanks with soot deposits or a heated metal surface after the paint

1O7

on the surface was burned off, were engulfed in a propanol pool fire; on the other hand, there were no visual effects an the surface of tanks engulfed in a methanol pool fire. Accordhg to the video recordings and rernnants of the failed tanks it was indicated that the patterns of failed tanks were similar for al1 ladings used when the tanks failed at approximately the same pressure. Since different ladings at the same pressure were at different positions on the phase diagrarns at the time of failure the nature of the tank failure does not depend on the phase present. For exarnple, Tanks 23-28 containing 80% liquid fill various ladings failed at approximately the same pressure, 2.6 MPa, producing al1 single holes. When investigated,

Tank 24 filled with n-butanol failed in the two-phase region while the remainders failed in
the single-phase region, liquid only. Moreover, Tank 8 containing 85% liquid fill propane
failed catastrophically at a pressure of 6.55 MPa which was in the single-phase region, above the critical point, producing a three-piece teardown. Tank 9 containing 75% liquid fil1

arnmonia failed at the sarne pressure, 6.55 m a , but in the two-phase region producing the
same pattern as Tank 8.

8.2 Pressure and Temperature

The lading temperature and interna1 pressure versus time for the test tanks are given
in Appendix A. Based on these data the following observations are made.

When the tank was charged with a liquefied gas, the intemal pressure of the tank
started to rise rapidly as soon as it was exposed to the pool fire. The liquid temperature

108

started to increase after a short period of tirne and increased almost linearly until failure afler

an initial period of slow rise. If the pressure relief valve opened and exhausted a significant
amount of ladin the temperature within the tank became more unifonn. When the tank was charged with a liquid, there was no signincant change in interna1 pressure on initial exposure to the pool fue. However, the liquid lading temperature started to rise shortly after exposure to the pool fire. The difference in initial effect on the intemal pressure was due to the difference in vapor pressure of the liquefied gases and the liquids at the initial temperature. In some cases the vapor and interface temperatures versus time were also recorded
to investigate the thermal response of the two phases of the lading in the test tank.The results

show that the difference in temperature can be significant between the vapor and liquid phases inside the tank for both liquefied gases and liquids. This is because there is much less
thermal capacity in the vapor phase compared to the liquid phase, primarily due to the much

lower vapor density. The heat traasfer coefficient between the tank wall and the vapor is substantially less than the heat transfer coefficient between the tank wall and the liquid (Sumathipala, 1990). However, the difference in fluid density more than compensates for the reduced heat transfer, and so the vapor temperature is raised more rapidly. Thermal stratification can occur in both the liquid and vapor phases (Anderson et al.,

1974, Droste and Schoen, 1988, Moodie, 1988, Birk et al., 1993). However, it is always
found to be greater in the vapor phase. The small tanks used in this study certainly make thermal stratification much less than that observed in larger tanks particularly in the liquid

1O9

phase. However, the data indicate a significant temperature difference between the two

phases during heating by a pool f i e before the pressure relief valve opens.
A pressure relief valve would be significant for the tanks containing a liquefied gas

or liquid when they could be exposed to fire. When engulfed in the test pool fies, the tanks without a PRV installed failed catastrophically,with the severity varying in proportion to the strength of the tanks. Of nineteen tanks without a PRV, only three tanks remained whole because of a leak at the comection of the fittings on those tanks. This leak acted as a PRV reducing the pressure in the tanks.

8.3 Pressure Relief Valve and Orifice Size

8.3.1 Effect of PRV Set Pressure

For Tanks 11 and 12 the test conditions were identical except for the PRV set pressures. The PRV set pressures were 5.52 MPa for Tank 11 and 1.72 MPa for Tank 12. Both tanks failed at the sarne pressure, 3.79 MPa, when heated. Tank 11 failed before the

PRV opened since it was set at a pressure above which failure occurred. For Tank 12, as cm
be seen in Figure A. 12, the PRV did not relieve the pressure suficiently to prevent failure. This is probably because the orifice size in the PRV was too small(O.10 mm) to allow for sufficient lading to be released and relieve the pressure in the tank. The PRV set pressure for Tank 7 was 1.72 MPa while that for Tank 9 was 5.52 MPa. The PRV set at 1.72 MPa enabled Tank 7 to remain whole by releasing suscient lading (propane) through an orifice 0.35 mm in size. This venting kept the pressure inside the tank below the failure pressure which was about 6.55 MPa for these particular tanks. Tank 9 failed

110

catastrophically d e r the PRV operated around 5.52 MPa for 6 cycles (see Figure A.8). This shows that a proper PRV set pressure is essential f r mitigating tank failure. o Theoretically, the PRV operating pressure is the pressure at which the PRV fully
opew. According to the specificationsof the PRVs, the nominal operating pressure should

0 be within 1 % of the set pressure. However, PRVs have been found to operate outside their
specifications (Ye, 1994). For the PRVs used in this study, the operating pressures for the first opening of the valves were ofien slightly above the set pressures, but within the range of the nominal operating pressure. Such behavior can be observed fiom the plots of pressure versus time in Figures A.8, A.47, AS2 and A.53.

832 Effect of Orifice Size ..

Figure 8.3 shows the effects of the orifice size,the tank wall thickness and the PRV set pressure on a BLEVE for one-litre test tanks. As can be seen, the tank with weakened wall thickness of 0.38 mm or greater will not fail if the orifice size installed in the PRV is in the range of 0.35- 1. mm and the PRV set pressure is lower than 5.17 MPa.. Al1 tanks will O fail if the PRV on the tanks is equipped with an orifice 0.20mm or smaller, regardless of the tank wall thickness and the PRV set pressure. This would suggest that an orifice size less
than 0 2 mm is too small to allow sufficient release of the lading fiom the test tanks under .0

fire engulfment. Notice that the calculated mass flow rates in Figure 4.1 show that if the orifice size is less than 0.20 mm the mass flow rate is low, 0.9 g/s. However, a tank with weakened wall thickness of 0.25 mm will not f i if an orifice 1.O mm is installed. This al

III indicates that the proper sizhg of the orifice and set pressure of the PRVs can rnitigate a

BLEVE for the test tanks. Notice that the dotted area inicates the region where experiments
have not been carried out in this study.

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.6

0.B

1.0

Orifice Sue, mm

Figure 8.3 Effect of orifice size installed in PRV on one-litre test tanks

8.4 Fireball and Vapor Cloud

Observations for the tests conducted indicated that the size of fireballs depends on
the fil1 level of the flammable ladings. However, flammable ladings usually, but not always,

produce a fireball. Upon failure, the tanks containing the nonflarnrnable ladings produce vapor clouds . Vapor clouds were also produced at failure by tanks containing flarnmable

112

lading if a fireball was not produced. The size and duration of the fireballs and of the vapor clouds were measured by means of video recordings of the tests. The size and duration of the fireballs were compared with calculated values based on the correlations proposed by
Hasegawa and Sato (1978)

where

D , is the maximum diameter of the fireball, m; m

M
is the mass of the lading, kg;

and

where

tb is the time to achieve the maximum diameter, S.

The correlations above were selected because they were recomrnended for predicting the size and duration of fieballs when the mass of ladings was less than 10 kg. The measured and calculated values of size and duration of the fireballs dong with the percent of emrs for the tanks containing flammable ladings are presented in Table 8.2. For nonfiarnmable ladings the measured values of the vapor clouds are presented in Table 8.3. The period of time fiom tank failure to dissipation of the fireball or vapor cloud (tirne to disperse) is also presented in Tables 8.2 and 8.3. As shown in Table 8.2 the experimental maximum diameter of the fireballs is in moderate agreement with that of the calculated value f o Eq. (8.1). The percent of error im

113

ranges fiom 0% to 104%. However, for the duration of the fkeballs, the measured values are not in agreement with that of the calculated values from Eq. (8.2). The percent of error ranges fiom 0% to 290%. The experimental values are in most cases much lower than the calculated vaiues. From Table 8.3 it c m be seen that the size and duration of the vapor clouds produced by tanks with nodamrnable ladings appear to be independent of the mass of the ladings. However, for the tanks filled with water the size and t h e to disperse of the vapor cloud
(steam) tended to be a h c t i o n of the mass of water at failure. In the test involving

nonfiammable ladings, Eqs. (8.1) (8.2) were not employed for determining the size and and

duration of the vapor clouds since there was no fireball of the lading and, in the case of
water, the vapor cloud was steam. Another observation fiom the video of the tests was that the fuel remaining in the pan

used for providing a pool fre can enhance the fireball produced by flammable lading when
the tank fails catastrophically. This was observed on Tanks 14 and 49 with acetone and

methanol as fuels respectively, where both tanks were charged with propane at the same fil1 level, 50%. In addition to enhancing a fueball, the fuel remaining in the pan can produce a fireball by itself if the tank containing the nonfiammable lading fails violently. The video recording of Tank 34 shows that the vapor cloud produced by R-114 drags the bunllng propanol into the a u producing a fireball after the tank fails violently. In contrast, the pool fire in the pan will be extinguished imrnediately by stem if the test tank containing water fails violently.

Table 8.2 Cornparison of size and duration of fireballs from small scale BLEVE tests with calculated values
Max, Diameter
Tank No.
Lading

of Fireball

Time to Max. Diameter

Time to Disperse

(ml
calc.

(SI
calc.

6)

3 8 11

12 14 16 17
18 22 23 24 25 27 32 33 36 37 39

Propane Propane Propane Propane Propane Propane Propane Propane Propane Methanol N-Butanol Acetone N-Pentane Methanol Methanol Propane N-Butanol Acetone

3.98

n/a
3.99 nla nla 3.99 2.54 2.04 6.30 4.53 4.59 4.55 4.22 4.54 4.54 3.38 4.58 4.54

-13.7 nla 0.0 nla nla -13.7 -27 .O -36.0 16.0 -13.3 -2.0 -30.0 -5.5 -13.5 9.2 -12.7 -1.8 -29.7

0.91 nla 0.91 n/a nla 0.91

0.70 0.62 1.18 0.98 0.99 0.99 0.94 0.98 0.98 0.83 0.99 0.98

Table 8.2 Cornparison of size and duration of fireballs fiom small scale BLEVE tests with calculated values (cont'd.)

Tank No. Lading Mass (kg)

Max. Diameter of Fireball

Time to Max.Dia.
- -

Time to Disperse %err (%)

-3.3 -44.1 -16.7 -145,9 nla -290.0 -144.1 nla nia -193.9

(9

43 45 46 47

clc.

49 50 51 52 55 56 57

N-Pentane Acetaldehyde Propane Propane Propane Propane Propane Methanol Methanol Methanol

4.22 4.52 3.97 4.00 nla 3.06 3.36 nla nla 4.43 nla

-5.5 -29.1 0.8 0.0 nla -104.0 -12.0 nla nla -47.7 nla

0.94 0.98 0.91 0.91 nla 0.78 0.83 nla nla 0.97

Remarks: vapor cloud n associated with acetone as a fuel t associated with methanol as a fuel $ vapor cloud followed by Iiquid rainout nia not applicable

Table 8.3 Size and duration of vapor clouds fiom small scale BLEVE tests
-

--

Lading

Mass (kg)
0.456 0.400 0.798 O. 199 O. 130 0.798 1. O l 1.160 1.160 1.160 1.047 1.O47 0.798

Max. Diarneter (m)

Time to Max. Diameter

lime to Disperse

(s)
Ammonia Water Water Water Water Water R-12 R-114 R-114 R-II4 R-12 R-12 Water

(s)

30 .
3.0 4.5 2.5 2.0 2.5 2.5 nla 5.0*

3 s
3.0 3.0 4.0

0.46 0.67 0.62 0.73 0.13 0.48 0.11 nla 1.05% O.4Ot 0.17 0.26 1.49

t - small vapor cloud with liquid rainout $ fireball produced by propanol as a fuel

8.5 Pressure at Failure Corresponding to Mechanical Condition

As can be seen in Figure 7.9, the data c m be divided into two regions: one below and

the other above a wall thickness of 0.38 mm. This indicates that the mechanical integrity of
the test tank can be significantly reduced when the wall thickness is weakened to greater than

60% of the nomal wall thickness of 0.64 mm. The failure pressure is reproducible to within

2 MPa for tanks with weakened wall thickness, whereas the variation of failure pressure is
somewhat greater for tanks with n o d wall thickness.

For the particdar type of tank used in this study, Figure 7.9 may be used as a guide
for determinhg whether a given thickness for the weakened spot on the tank is likely to fail

for a tank filled with a particular lading and to a particular fil1 level in the single or two-phase

117

region. For example, fiom Figure 7.9 and a pressure-enthalpy diagram for propane (Figure

C. l), it may be seen that for a tank filled with 85% liquid propane to be brought to failure
in the two-phase region, the thickness of the tank wall would have to be weakened to less
than 0.18 mm. From a safety standpoint, such a weakened wall thickness is undesirable for

any tank filled with propane to such a hi& level.

8.6 Work Available at Failure

The theoretical or available work at the time of failure, W,, is presented in Table 7.5.
For a particular lading the available work will be a function of failure pressure if the tanks
are filled to the same initial liquid level. Figures 8.4 and 8.5 present the available work at

failure versus the initial percent liquid fill for various pressures for propane and water respectively. At a given pressure it can be seen that the available work increases with percent initial liquid fil1 and reaches a maximum value at 60% to 85% liquid fill. In the range of interest the maximum value of the available work shifts to lower initial percent liquid fil1 as the pressure increases. The actual work perfomed by the lading i pushing back the atmosphere, W, , is n given in Table 7.5. The actual work is always less than the available work for each test tank. Figures 8.6 and 8.7 present the actual work at the time of failure versus the initial percent liquid fill for various pressures for propane and water respectively. The maximum actual work during the failure is obtained when the initial percent liquid fil1 is between 60% and

85%. As the pressure rises, the maximum value of the actual work shifts to lower initial
percent liquid fill.

118

The work to tear the tank or tear work required to propagate the obsenred crack over
the tank, W,, versus the failure pressure for the test tanks, is presented in Figure 8.8 dong

with the designated regions where the pattern of failed tanks was obtained. The data suggest
that the failure pressure is important in determining the pattern of failed tanks,and the pattern in tum affects the tear work. At high failure pressures the tear work was found to be essentially independent of the failure pressure. The ratios on a percent b a i s of the tear work to the available work, and the tear work to the actual work, versus the failure pressure are presented in Figures 8.9 and 8.10. As indicated, for these particdar tanks the te= work required to propagate a crack over the tank is Iess than 2.5% of the available work at the time of failure, and less than 6% of the actual work performed by the lading in pushing back the atmosphere at the tirne of failure. To investigate the scale effects on work availabte at failure those ratios indicated above were deterrnined using the data for medium scale test tanks (Birk et al., 1996) and large scale test tanks (Roberts et al., 1995a , 1995b and 199%). Figures 8.1 1 and 8.1 3 show the ratio of the tear work to the available work versus the pressure at failure for medium and large scale test tanks respectively. Figures 8.12 and 8.14 present the ratio of the tear work to the actual work versus the pressure at failure for medium and large scale test tanks respectively. For medium scale test tanks the ratio of the tear work to the available work is less

than 0.05% while the ratio of the tear work to the actual work is Iess than 0.1 2%. It should
be noted that the type! of failure for medium scale test tanks was the so-called jet release

119

(single hole) failure allowlng the lading to be released through the breach giving two-phase Bow. This type of failure will produce a jet fire if the lading is flammable. For large scale test tanks these ratios are less than 0.35% and 1.O% for the tear work to the available work, and the tear work to the actual work, respectively. It should also be noted that the large scale test tanks were brought to failure by jet-fie impingement causing the tanks to fail catastrophically as a BLEVE. Table 8.4 shows the effects of the tank scde and the type of failure on the ratios of the tear work to the available work, and the tear work to the actual work, at the time of filure. It can be seen that the ratios decrease as the tank scale increases for the same type of failure. This suggests that the smdl scale tank used in this study is more durable than larger tanks due to the higher fiaction of work required to propagate a crack over the tank.

The tank wall thickness to diameter ratio for the small scale tanks is 0.0085 compared
to 0.0057 for full scale tanks. This indicates that the small scale tanks are relatively stronger
and can therefore withstand a higher intemal pressure before failure.

A comparison of the ratios of the tear work to the available work between the small

and medium tanks for the same type of failure (single hole), indicates that the medium tanks
required less tear work to produce a single hole failure than did the small tanks. Also, a comparison of these ratios between the small and large tanks for the same type of failure

(BLEVE), produces the same trend as seen in scaling Erom small to medium tanks.
Table 8.4 shows that the ratio of the actud work to the available work at failure is approximately 40% for al1 tank sizes.

Table 8.4 Scale and failure type effects on work available at failure

70

Propane

12.0 MPa

O ] O

1O

20

30

40 50 60 70 Initial %Liquid Fill ( 25 deg C)

80

90

100

Figure 8.4 Theoretical work vs. initial per cent liquid fil1 for one-litre tank for propane

Steam

12 MPa

v ;

10

20

30

40 50 60 70 lnitial %Liquid Fill ( 25 deg C )

80

90

100

Figure 8.5 Theoretical work vs. initial per cent liquid fil1 for one-litre tank for water

10

20

30

40 50 60 70 Initial %Liquid FiII (25 deg C)

80

90

100

Figure 8.6 Actuai work vs. initial per cent liquid fil1 for one-litre tank for propane

Steam

12 MPa

30

40 50 60 70 Initial %Liquid Fill (25 deg C )

Figure 8.7 Actuai work vs. initial per cent liquid fil1 for one-litre tank for water

Two or More Pieces

I 1 1
I

Crosslike Teardown

O O
O

Single Hole
0
X

1
1 1

a
A

:a
4

,--;
+

10
EO
1

---- X

' -- 3 - - - - - - - - - b - e - -v -0- - - - - I1

_-9

m l
9 '
1
I

X
+

./,A
<X 1

v
1

1
1
1

c0 1 '
1

4 6 Failure Pressure, MPa(g)

m
O

10

m
O

ACETAL. N-PENTANE

ACETONE PROPANE

AMMONlA R-12

METHANOL R-114

+
x

KBUTANOL WATER

Figure 8.8 Work to tear tank vs. pressure at failure for one-litre tanks

4 6 Failure Pressure, MPa(g)

Atom
O

Acetal.
O

r
v

Ammonia R-114

Methanol R-12

+
x

N-utanol Water

Kpentana

Propane

Figure 8.9 Ratio of tear work to available work in tank lading % vs. pressure at failure

-.

O , O

a x
I

figm
I

X I
1

I
8

4 6 Failure Pressure, MPa(g)

1O

Figure 8.10 Ratio of tear work to achial work by tank lading % vs. pressure at failure

-1
O

0.5

1.5

2.5

Failure Pressure, MPag

3.5

Figure 8.11 Ratio of tear work to theoretical work in tank fading, % vs. pressure at failure for medium scale test tanks (Birk et al., 1996)

1.5

2.5

Failure Pressure, MPag

Figure 8.12 Ratio o f tear work to actual work performed by tank lading, % vs. pressure at failure for medium scale test tanks (Birk et al., 1996)

1.5 2 2.5 Failure Pressure, MPag

Figure 8.13 Ratio of tear work to theoretical work in tank lading, % vs. pressure at failure at failure for large scale test tanks (Roberts et al., 1995)

O O

O.5

1.5

Failure Pressure, MPag

2.5

3.5

Figure 8.14 Ratio of tear work to actual work performed by tank lading, % vs. pressure at failure for large scale test tanks (Roberts et al., 1995)

8 7 Effects of Lading and Fi1 Level on Type of Failure .

Table 8.5 summarizes the fill levels for al1 the ladings used and the weakened wall thickness with the type of failure for small scale test tanks. Of forty four tank failures, nine failed with a single hole mode, seventeen gave crosslike teardowns, five gave two-piece teardowns, nine gave three-piece teardowns and three shanered. For most of the ladings used the tanks failed in modes of single hole and crosslike teardown. The tanks filled with methanol and R-12 to 80% of volume produced the shattered

type of failure. Tanks filled with propane to various levels al1 failed i crosslike, two-piece n

or three-piece teardown. None gave single hole or shattered failure.

The propane tanks with lower liquid fill tended to give a less violent failure, crosslike teardown, than those with higher liquid fills. However, the propane tanks with lower liquid

fil1 gave a more violent failure, three-piece teardown, when the failure pressures were raised
by cutting back on the extent to which the tank wall was weakened.These results substantiate

the earlier assertion about the work available at failure: the maximum values of both the available work and the actual work, shifi to lower initial percent liquid fill as the pressure increases.

Table 8.5 Effects of lading, fil1 level and wall thickness on type of failure

Rernarks: SH = single hole CL = crosslike teardown TW = two-piece teardown TH = three-piece teardown ST = shatters The numeric in parentheses indicates a number of tanks involved. A = weakened wall thickness reduced to O. 1O mm 0 = weakened wall thickness reduced to 0.15 mm C = weakened wall thickness reduced to 0.18 mm O = weakened wall thickness reduced to 0.23 mm E = weakened wall thickness reduced to 0.25 mm F = weakened wall thickness reduced to 0.30 mm G = weakened wall thickness reduced to 0.38 mm H = normal wall thickness which is 0.64 mm

8.8 Time to Failure

As shown in Table 7.2, The time it takes the tank fails, or tirne to failure depends on

various factors such as type of lading, fi11 level,type of fuel and mechanical condition of the
tank. For a given lading with a particular type of fuel, an increase in fil1 level and tank

strength will increase the tirne to failure. An increase in lading requires a Iarger arnount of

heat to raise its bulk temperature which in turn establishes the pressure in the tank. Since a

129 higher pressure is required to fail a tank with a thicker wall, the period of tirne required for heating the buik temperature to a higher value, to achieve that higher pressure, must be greater. For a particular tank, the tirne to failure decreases substantiaily when propanol is used as a fuel in association with a radiation shield. This is because propanol f ~ gives a e higher heat flux to the tank wall than methanol fie. A radiation shield reduces the radiation loss ffom the surface of the tank.

8.9 Predietion of Lading Temperatures by the Developed Models

The lading temperatures predicted by the models have been compared with those
obtained fiom the experiments to validate the mode12 developed in Chapter 5. Since these models assume the mass of lading in the test tank is constant, that is, there is no lading leaving the tank during the time of interest, the results are compared either with test tanks without a PRV or w t tanks equipped with a PRV but prior to the valve operating. ih The mode1 requires the application of a heat flux to the surface. The heat flux obtained from the tests was used in the comparative calculations. The calculated heat flux for each test shown in Table 7.6 was detennined fiom the increase in lading temperature for a particular period of time and the surface area of the test tank. It should be noted that the heat flux calculated by the method mentioned accounted for radiation loss fiom the surface of the tank. For some tests, the heat flux estirnates varied fkom test to test although the fuel used for the pool fire was the sarne. The variation was due primarily to wind variations which could not be controlled during a test.

130

Figures 8.15 and 8.16 show the lading temperatures predicted by al1 four models developed compared with the measured lading temperatures for Tank 47. Some constants and relevant physical properties used in the models are given in Table 8.6. As mentioned in Chapter 5, the difference between Model 1 and Model II is that Model II allows mass to be transferred between the liquid and vapor phases through the interface inside the cylinder. For each rnodel, two submodels have been developed; for exarnple, Model 1 and Model IMOR, are based on the presence or absence of radiation loss fiom the surface of the cylinder. Since the estimated heat flux accounted for radiation loss fiom the surface of the tank, the models developed under which there is no radiation loss, Models I/NOR and IINOR, were therefore used to calculate the lading temperatures which were then compared with those of the experirnents. Table 8.6 Relevant physical properties and constants used in the models developed

1
Tank:

Physical Properties 1Constants Wall thickness, m Diameter, rn Thermal conductivity of rnetal, kW/m,K Heat capacity of metal, kWlm2.K Density of rnetal, kg/ms
Ladinq: Propane

Value

Heat capacity of liquid, kJ/kg.K Heat capacity of vapor, kJ/kg.K Density of liquid @ 25"C, kgIrna Density of vapora 25"C, kglrn3 Heat transfer coefficient of liquid, kWlm2.K Heat transfer coefficient of vapor, kW1mi.K Heat transfer coefficient of liquid-vapor interface, kW/m2.K

Methanol, kW Propanol, kW

131
As can be seen in Figures 8.1 5 and 8.16, comparing the results of Model INOR and

Model IVNOR with the experimental data suggests that both models are in good agreement

with the measured values. However, Model IINOR is likely to underestimate values
compared with the experimental data, while Model WNOR appears to predict well both the liquid and vapor lading temperahires. This indicates that there is mass transfer between the liquid and vapor phases and it contributes to the distribution of heat between the phases. The heat transfer coefficient used for the liquid-vapor interface, 0.08 kW/m2.K, is 8 times higher than that used for heat ansfer between the vapor and the wall, 0.01 kW/m2.K (Sumathipala,

1990). Lower heat transfer coefficients for the liquid-vapor interface gave vapor temperatures
considerably higher than those measured. Figures 8.17 through 8.20 compare predicted liquid lading temperatures pnor to a

PRV operating with the measured values for Model VNOR and Model IVNOR. It can be seen
that the liquid lading temperatures predicted by the Model II/NOR are in good agreement

with the expenmental data.

50

Time, s
Tliq, Tank 47
P

Tvap, Tank 47
Tliq, Model ll/NOR

Tliq, Model IlNOR

Tvap, Model IlNOR

-Tvap, Model IIINOR

Figure 8.15 Comparison of measured lading temperature for Tank 47 with calcuiated lading temperatures obtained fiom Models 1 and II without radiation (heat flux = 13.1 kW/m2)

50

Time, s

Tvap, Modei I

Tliq, Model II

-Tvep, Model II

Figure 8.16 Comparison of measured lading temperature for Tank 47 with calculated lading temperatures obtained fiom Models 1 and II (heat flux = 13.1 kW/m2)

"

25

50

75

1O 0

Time, s

125

150

Tliq,Tank 2

- Tliq, Model IINOR

Tliq, Model IHNOR

Figure 8.17 Comparison of measured lading temperature for Tank 2 with calculated lading temperatures obtained fiom Models 1 and II without radiation (heat flux = 14.4 kW/m2)

25

50

75

100

125

Time, s

Tiiq, Tank 3

-fliq, Model IINOR

Tiiq. Model IllNOR

Figure 8.18 Comparison of measured lading temperature for Tank 3 with calculated lading temperatures obtained fiom Models 1and 1 without radiation 1 (heat flux = 12.6 kW/m2)

o ! .
O

. .

25

50

75

Time, s

1O0

125

Tliq, Tank 11

-Tiiq, Model IJNOR

Tiiq, Model II/NOR

Figure 8.19 Cornparison of measured lading temperature for Tank I 1 with calculated lading temperatures obtained fiom Models 1 and II without radiation (heat flux = 1 3.1 kW/m2)

niq, Tank 12

-W h , Mode1 WOR

Tiiq, Mode1 l l l N 0 ~

Figure 8.20 Cornparison of measured lading temperature for Tank 12 with calculated lading temperatures obtained fiom Models 1 and II without radiation (heat flux = 16.6 kW/m2)

135

8.10 Methanol as a Test Fluid

As stated in the earlier discussion of the strength of the test tanks versus the failure pressure, the wall thickness of the particular test tanks used in this study would have to be weakened significantly for the tank filled with a high liquid propane fil1 level were to fail in the two-phase region. It is undesirable to weaken the tank to such an extent for safety reasons. However, it is desirable to study the characteristics of PRVs inthe two-phase region at near failure conditions. With a normal wall thickness, a propane tank filled to 85%vol will fail in the liquid full region while a methanol tank filled to 80%vol will fail in the two-phase region. According to the failure pressure cmesponding to the mechanical conditions of the test tanks

shown in Table 7.4, the average failure pressure for a tank with a normal wall thickness is
7.3 1 MPa which is lower than the critical pressure of methanol, 8.10 MPa. Therefore, methanol will fail in the two-phase region for unweakened tank walls if in an appropriate fil1 level range. Since methanol is a liquid at atmospheric pressure, it is easy to charge a test tank and the tank will remah at atmospheric pressure or less depending on ambient temperatures and
the amount of air above the liquid. Since methanol will exert no significant pressure on the tank at ambient temperatures, the tanks can be weakened to any desired extent without

causing a safety problem. Methanol should, therefore, be considered as a mode1 fluid for tests carried out with the one-litre tanks used in this study.

Chapter 9

CONCLUSIONS AND FUZCOMMENDATIONS

9.1 Conclusions

The visual evidence and tank rernnants indicate that the failure of the tank was

similar for al1 ladings tested. Since some tanks failed with the ladings in the single-phase region, liquid only or above the cntical point, and in some cases the two-phase region the nature of the failure does not depend on the phases present. The ratio of the work to tear the tank to the theoretical work available within the tank was less than 2.5% for al1 tests producing a failure. The ratio of the work to tear the tank to the actud work performed by the tank was less than 6.0% for d l tests producing a failure. The ratios of the work to tear the tank to the theoretical work and of the work to tear the tank to the actual work at fdiure decreased as tank size increased. The ratios of the actual work performed by the tank to the theoretical work available within the tank at failure is similar for al1 tank sizes.

The experimental maximum diameter of the fireballs is in moderate agreement

with that of the calculated value based on the correlation proposed by Hasegawa and Sato (1978). However, for the duration of the fireballs, the measured values

137

are not in agreement with that of the calculated values. The experirnental values

are in most cases much Iower than the calculated values.

8.

A model was developed for the heating of the vapor and liquid ladings before the

pressure relief valve opens. This model was able to predict the vapor and liquid temperatures versus tirne with reasonable accuracy.
9.

The model demonstrated that the temperature of the metal in contact with the vapor
is normally 100C greater than the temperature of the metal in contact with the liquid at the time failure is likely to occur.

10.

Methanol has been identified as a possible model fluid for the one-litre test tanks
if failure in the two-phase region is desired for a wide range of pressures to

simulate prototype tanks with propane as lading.

9.2 Recommendations 1.

The characteristics of PRVs in the two-phase flow for the tanks used in this study shouid be investigated M e r using methanol as a laing in order to obtain additional data for cornparison with prototype tanks containing propane.

2.

Additional tests should be conducted to determine more precisely the conditions under which sufficient pressure relief can be expected based on orifice size, PRV setting and mechanical strength of the tank.

3.

Tests should be conducted to investigate various schemes for mitigating tank failure such as sufficient pressure relief, extemal insulation and double acting pressure relief systems.

REFERENCES

Anderson, C., Townsend, W., Zook,

J e y

and Cogwill, G., ''The Effect of a Fire Environment

on a Rail Tank Car filled with LPG; Test No.8," Report No. FRA-OR&D 75-3 1,

U.S.Deparhnent of Transportation (DOT), September, (1 974).

Appleyard, R.D., "Testing and Evaluation of the EXPLOSAFE System as a Method of Controllhg the BLEVE," Report No. TP2740, Transport Canada, (1980).

B r ,A.M., Ye, Z., Maillette, J., and Cunningham, M , ik . "Summary Report on Medium Scale
Fire Tests Investigating the BLEVE Event," Report prepared for Transport Canada,
January, (1 993). Birk, A.M., and Cunningham, M.H.,
"

The Boiling Liquid Expanding Vapour Explosion," stries, Vo1.7, N0.6~474-480,(1994).

Journal of J m s Prevention i the Procn

. .

B r ,A.M., Cunningham,M.H., Kielec, D.J., Maillette, J., Miller, T., Ye, Z., and Ostic, P., ik
"Fire Tests of Propane Tanks to Study BLEVEs and Other Thermal Ruptures: Detailed Analysis of Medium Scale Test Results," Report No. TP12498E, Transport Canada, May, (1996). Droste, B., And Schoen, W., "Full Scale Fire Tests with Unprotected and Themal Insulated LPG Storage Tanks," J o u r n a l d o u s M & & Vo1.20, pp.41-53, (1988). a&,

Hahn, G.T., Haaninen, M.F., Rosenfield, A.R., "Fracture Toughness of Materials," and
Review of Materi& Science, V01.2~38 1-404, Annual Review Inc., Pa10

Alto, CA, (1972).

Hahn, G.T., Sarrate, M., and Rosenfield, A.R., " Cnteria for Crack Extension in Cylindncal
Pressure Vessels," 210, (1969). Hasegawa, K., and Sato, K., "Experimental Investigation of the Unconfined VapourCloud Explosion of Hydrocarbons," Technical Merno-

Jownial Vo1.5, No.3, 187-

of Fire Research

btitutt&No. 12, Fire Research institute, Fire Defence Agency, Japan (1978). Henry, R.E., and Fauske, H.K., T h e Two-Phase Critical Flow of One-Component Mixtures in Nozzles, Orifices, and Short Tubes," Journal of Heat Transfer, Trans. ASME,. Series C,Vo1.93, No.2, 179-187, (1971). Hutcherson, M.N., Henry, R.E., Wollersheim, D.E., " Two-Phase Vessel Blowdown of and

an Initially Saturated Liquid-Part 1: Experimental," Trans. ASm,Vol. 1OS, 687-693, (1983).

Hutcherson, M.N., Henry, R.E., and Wollersheim, D.E., " Two-Phase Vessel Blowdown of

an Initially Saturated Liquid-Part 2: Analytical," J

ASMFd3Vol. 105,694-699, (1 983).

Jn ofT . a r

Kim-E, M.E., Reid, R.C., and "The Rapid Depressurization of Hot, High Pressure Liquids
or Supercritical Fluids," Chemical Engineering at Supercritical Fluid Conditions, Ch.3,8 1-100, Ann arbor Science, (1983). Lewis, D.J., "BLEVEs Don't Need Fires," m d o u s Cargg B u , Vo1.3, October, (1983).

McDevitt, C.A., "Initiation of a Boiling Liquid Expanding Vapour Explosion," Ph.D. Thesis,

140

Department of Chemical Engineering, University of New Bruuswick, 1990. McDevitt, C.A., Steward, FR., and Venart, J.E.S., "Boiling Liquid Expanding Vapour
' Explosion an Update," 5 Technicai Seminar on Chemicai Spills Proceedings,

Montreal, 1-14, (1988). McDevitt, C.A., Chan, C.K., Steward, F.Ra, Tennakore, K.N., "Initiation Stepof Boiling and Liquid Expanding Vapour Explosions," Proceedings of the International Conference on Major Hazards in the Transportation and Storage of Pressure Liquefied Gases - Major Hazards '90, Kingston, Ontario, (1990). McDevitt, C.A., and Steward, F R ,"Vent and Burn Experiments," Report No. TPI 1235E, .. Transport Dangerous Goods Directorate, Transport Canada, (199 1). Moodie, K., "Experiments and Model1ing:- An Overview with Particular Reference to Fire Engulfinent," Journal of Ha~adous Mz&&& Vo1.20,149- 175, (1988).

Moodie, K., Cowley, L.T., Demy, R.B., Smail, L.M., and Williams, I., "Fire Engulfinent
Tests on a 5 Tonne LPG Tank,"J o d of H d o u s Mater&, Vo1.20,55-71,

(1988). Reid, R.C., "Superheated Liquids a Laboratory Curiosity and, possibly, an Industrial Curse Part 1: Laboratory Studies and Theory," Jounial of -al Educatioa Spring, 60-87, (1 978). Reid, R.C., "Possible Mechanisrn for Pressurized-Liquid Tank Explosions or BLEVE's,"
Enmneering

Science. V01.203, No.23, 126391265, (1979).

Reid, R.C., "Rapid Phase Transitions fiom Liquid to Vapor," Advances in Chemical Engineering, Vol. 12, p. 198, Academic Press, New York, 1983.

141

Prausnitz, J.M., and Sherwood, T.K., Properties of Gases and Liquids, 4th The Reid, R.C.,
edition, p.220, McGraw-Hill, 1987. Roberts, T., Beckett, H., Cooke, Ge, and Brown, D., "Jet Fire Impignernent trial on a 41% Full, Unprotected, 2 tonne Propane Tank," Process Safety Section Project Report, Project No. R04.029, Hazard Consequences of Jet-Fire Interractions with Vessels Containing Pressurised Liquids (JIVE),IWWPW95/11, Health & Safety

Laboratory, HSE, (1995a).

Roberts, T., Beckett, H., Cooke, G., and Brown, D., "Jet Fire hnpignement trial on a 60% Full, Unprotected, 2 tonne Propane Tank," Process Safety Section Project Report, Project No. R04.029, Hazard Consequences of Jet-Fire hterractions with Vessels Containing Pressurised Liquids (JIVE), IRL/PW95/12, Health & Safety Laboratory, HSE, (1995b). Roberts, T., Beckett, H., Cooke, G., and Brown, D., "Jet Fire hnpignement trial on a 20% Full, Unprotected, 2 tonne Propane Tank," Process Safety Section Project Report,

aad Project No. R04.029, H z r Consequences of Jet-Fire Interractions with Vessels

Containing Pressurised Liquids (JIVE),IR/WPW95/13, Health & Safety Laboratory, HSE, (1 995c). Sallet, D.W., "Pressure Relief Valve Sizing for Vessels Containing Compressed Liquefied
Gases," 1 Mech E, (1979).

Sallet, D.W., and Somers, G.W., "Flow Capacity and Response of Safety Relief Valves to Saturated Water Flow," Plant and Oaerations Promess, Vo1.4, N0.4, 207-216, (1985).

142

Starkman, E.S., Schrock, V.E., Neusen, K F , Maneely, D.J., "Expansion of a Very Low . . and Quality Two-Phase Fluid Through a Convergent-Divergent Noule," Journal of

Basic Eneigee*

T m .A S W . Series D, Vo1.86, No.2,247-256, (1964).

Steward, F.R., Rirksomboon, T., "BLEVE Tests for Various Ladings," Report prepared and for Transport Canada, March, (1996). Seynhaeve, J.M., Lombre, R., Ducrocq, and Bolle, L., " Physical Modeling of Rapid Transients in Long Pipes, in Case of Vaporization: an Efficient Tool for Safety Management," Process Safetv Pro-, Vol. 13, No.2,95-100, (1994).

Sumathipala, U.K.M., "Thermohydraulics of an Extemally Heated Pressure Liquefied Gas

Tank:An Experimental Study,"Ph.D.Thesis, Department of Chernical Engineering, University of New Brunswick, 1990.
Venart, J.E.S., Sumathipala, U.K., Steward, F.R.,and Sousa, A.C.M., "Experiments on the

Thermo-Hydraulic Response of Pressure Liquefied Gases in Extemally Heated

Tanks with Pressure Relief," w

d Qxrations Pro-

Vo1.7, No.2, 139-144,

(1988).

Ye, Z., "Medium Scale Fire Tests of Pressure Liquefied Gas Tanks to Study the Boiling
Liquid Expanding Vapour Explosion (BLEVE) and Transient Two-Phase Jet Release," Ph.D.Thesis,Department of Mechanical Engineering, Queen's University, 1994.

Temperature and Pressure Profiles for Small Scale BLEVE Tests

TANK 1

PROPANE, 85%, PRV:i.72,0:0.10, W0.64

100

200

300

400

Time, s

500

Figure A. 1 Temperature and pressure profiles of Tank 1

TANK 2

PROPANE. 85%. W0.64

Temp.

--Press.

20

40

60

80

100

120

140

Time, s

Figure A.2 Temperature and pressure profiles of Tank 2

TANK 3 PROPANE. 15%. W.0.84

Figure A.3 Temperahue profile of Tank 3

TANK 5 PROPANE. 85%. PRV:1.72. 0:0.35. W:0.64

Figure A.4 Temperature and pressure profiles of Tank 5

TANK 6 PROPANE, 60%. PRV:S.52. 0:0.35, W:0.64

1O 0

200

300

400

Time, s

500

Figure AS Temperature and pressure profiles of Tank 6

TANK 7 PROPANE, 85%, PRV:l.72,0:0.35, W:0.38

Temp.

--Press.

1O 0

200

300

400

500

Time, s

Figure A.6 Temperature and pressure profiles of Tank 7

TANK 8 PROPANE, 85%. W0.38

Figure A 7 Temperature and pressure pronles of Tank 8 .

TANK 9 AMMONIA, 75%. PRV:5.52,0:0.35, W0.38

Temp.

Press.

50

1O 0

150

200

250

300

Time, s

lO 350

Figure A.8 Temperature and pressure profiles o f Tank 9

TANK 1011 WATER, 80%, PRVA .72,0:0.35, W0.38

Figure A.9 Temperature and pressure profiles of Tank 104

TANK 1012 WATER, 85%, PRVA.72, Q0.35, W:0.38

Figure A. 10 Temperature and pressure profiles of Tank 1 O/2

TANK 11 PROPANE, 85%. PRV:S.52,0:0.10, W:0.25

Figure A. 1 1 Temperature and pressure profiles of Tank 1 1

TANK 12 PROPANE, 85%, PRV:1.72,0:0.10, W:0.25

Figure A. 12 Temperature and pressure profiles of Tank 12

TANK 13 WATER, 40%. PRVA.72, 0:0.10, W0.25

Figure A. 13 Temperature and pressure profiles of Tank 1 3

TANK 14 PROPANE, 50%, PRVA .72.0:0.10. W:0.25

Figure A. 14 Temperature profile of Tank 14

TANK 15 WATER, 80%, PRV:l.X!. 0:0.10, W0.25

Temp.

Press.

Figure A. 15 Temperature and pressure profiles of Tank 15

TANK 16 PROPANE, 85%, PRV:f .Z, 0:0.20, W:0.23

40

Time, s

Figure A. 16 Temperature and pressure profiles of Tank 16

TANK 17 PROPANE, 20%. PRV:1.72,0:0.10, W:0.18

20

30

Time, s

Figure A. 17 Temperature and pressure profiles of Tank 17

TANK 18 PROPANE, IO%, PRV:l.72,O:O.lO, W.0.18

20
O

10

20

30

40

Time, s

Figure A. 18 Temperature profile of Tank 18

TANK 19 WATER, 20%. PRV:l.Z, 0:0.10, W0.18

Temp.

--Press.

1 O0

Time, s

Figure A. 19 Temperature and pressure profiles of Tank 19

TANK 20 WATER, 13%, PRV:l.72,O:O.lOI WO.18

Temp.

Press.

40

60

80

Time, s

Figure A.20 Temperature and pressure profiles of Tank 20

TANK 21 WATER, 80%. PRV:1.72,0:0.20, WO.18

Temp.

1
O

_ _ _ _ -- -- -1
100

-_
1

50

150

200

Time, s

250

O 300

Figure A.2 1 Temperature and pressure profiles of Tank 2 1

TANK 22 PROPANE, 85%, PRV:5.52,0:0.10. W0.64

Liq.Temp.

--Vap.Temp.

Press.

50

1O0

150

200

250

Time, s

Figure A.22 Temperature and pressure profiles of Tank 22

TANK 23 METHANOL,80%,PRV:1.72,0:0.IO.W:0.25

140

2.5
Temp.

k ' P 100

-2
D m
I

! a

Press.

80

60-

rn 40 C

c"

, , ,
I

1.5

5
2 e

i-

.
I I

/
/

-1

20O O

___------------/

/
/

- 0.5
1 1

50

1O 0

150

200

Time, s

O 250

Figure A.23 Temperature and pressure profiles of Tank 23

TANK 24 N-BUTANOL.80 %,PRVA .72,0:0.10,W:0.25

50

100

Time, s

200

Figure A.24 Temperature and pressure profiles of Tank 24

TANK 25 ACETONE, 80%, PRV:1.72,0:0.10, W.0.25

- 2.5
I

-2

' I

I I
I

a"
V1
V)

2
1

1
I
/

-1.5 @ -1
-0.5

/ *

20,
/

,
fl

---

__-'

-------O

_ - c

50

100

150

200

Time, s

O 250

Figure A.25 Temperature and pressure profiles of Tank 25

TANK 26 ACETAL., 75%, PRV:1.72,0:0.10, W:0.25

50

1O0

200

Time, s

Figure A.26 Temperature and pressure profiles of Tank 26

TANK 27 N-PENTANE,IO%,PRV:1.72.0:0.10.W0.25

140

3
-2.5 -2 -1.5
/

2
3
V) V)

2 $

/
I

-1

/ ,

20@

---____----I

--

/ #

- 0.5
J

50

1O 0

15 0

Time, s

200

O 250

Figure A.27 Temperature and pressure profiles of Tank 27

TANK 28 R-12.80%. PRV:I .72, 0:0.10, W0.25

Figure A.28 Temperature and pressure profiles of Tank 28

TANK 29 R-114,80%, PRV:1.72, 0:0.10, W.0.25

20

40

60

80

1O0

120

O 140

Time, s

Figure A.29 Temperature and pressure profiles of Tank 29

TANK 31 WATER. 80%, W0.64

500

1O00

1500

2000

Time, s

Figure A.3 0 Temperature and pressure profiles of Tank 3 1

TANK 32 METHANOL, 80%. W0.38

?
w
CI

150

9 a
m 100

Ternp.

Press.

i-

100

200

300

400

500

Time, s

600

Figure A.3 1 Temperature and pressure profiles of Tank 32

TANK 33 METHANOL. 80%. W0.W

250

-4

$
3
V>

-3
-2

a
-1
O 100 200 300 400 500

Time, s

600

Figure A.32 Temperature and pressure profiles of Tank 33

TANK 34 R-114, 80%, W0.38

12 0

7
-6

-5 0

-4

z
2 a
V)

B
2

60-

-3
I I

-2

Z
/
/

? - - -

_---- --I

,
I
1

-1
15 0 O 200

50

100

Time,

Figure A.33 Temperature and pressure profiles of Tank 34

TANK 35 R-T14.80%, WO.64

140

--

-6

-5
-4

-3

g 2 -2 "
" 3
V)

-1
1

-----O

--'
1 1

---

50

1O0

150

Time, s

O 200

Figure A.34 Temperature and pressure profiles of Tank 35

TANK 38 PROPANE, 50%. wo.38

20

40

60

80

100

Time, s

120

O 140

Figure A.35 Temperatme and pressure profiles of Tank 36

TANK 37 N-BUTANO& 80%, W.0.38

250

-1
O
1O 0 200

300

400

500

Time, s

600

Figure A.36 Temperature and pressure profiles of Twk 37

TANK 38 N-BUTANOL, 80%, W..0-64

.
O

200

400

600

800

Time, s

1O00

Figure A.37 Temperahue and pressure profiles of Tank 3 8

TANK 39 ACETONE. 80%, W.0.38

Temp. 'cl Press.

50

1O0

150

200

250

300

350

Time, s

Figure A.38 Temperature and pressure profiles of Tank 39

TANK 40 ACETONE. 80%. W.0.64

100

200

300

400

Time, s

Figure A.39 Temperature and pressure profiles of Tank 40

TANK 41 R-12, 80%, W0.38

Ternp.

--Press.

100

Time, s

Figure A.40 Temperature and pressure profiles of Tank 4 1

TANK 42 R-12.80%. W6 .4

-Lu ;

50

100

150

200

lO 250

Time, s

Figure A.41 Temperature and pressure profiles of Tank 42

TANK 43 N-PENTANE, 80%, W0.38

Temp.

--Press.

0 3

20
O

-20
O

50

100

150

200

Time, s

O 250

Figure A.42 Temperature and pressure profiles of Tank 43

TANK 44 WATER. 80%. W0.38

300

Time, s

Figure A.43 Temperature and pressure profiles of T n 44 ak

TANK 45 ACFTALDEHYDE. BO%, W.0.38

Temp. Press.

100

Time, s

Figure A.44 Temperature and pressure profiles of Tank 45

TANK 46 PROPANE, 83%. PRV:5.17, 0:0.20, W0.64

1O 0

Time,

Figure A.45 Temperature and pressure profiles of Tank 46

TANK 47 PROPANE, 85%, PRV:2.48,0:0.20, W:0.30

40

60

Time, s

Figure A.46 Temperature and pressure profiles of Tank 47

TANK 48 PROPANE, 82%. PRV:1.72.0:1.0, W0.25

aa
l -

g 200 - j
1

Liquid

t!

'r
I

0)

2 100A

Temp.
1
1

Press.

O O

-1

100

200

300

400

, 1 500

Time, s

Figure A.47 Temperature and pressure profiles of Tank 48

TANK 49 PROPANE. 51%, PRV:5.17,0:0.20, W0.64

Figure A.48 Temperature and pressure profiles of Tank 49

TANK 50 PROPANE, 36%. PRV:2.48,0:0.20, W0.30

20

40

60

80

0.5 1O 0
1

Time, s

Figure A.49 Temperature and pressure profiles of Tank 50

TANK 51 PROPANE, 49%. PRV:l.72, Q0.20, W0.25

Figure AS0 Temperature and pressure profiles of Tank 5 1

TANK 52 METHANOL,80%, PRV:5.17,0:0.20. W0.64

Press.

-2
O 500

,/"
I l

1O 0

200

300

Time, s

400

Figure A S 1 Temperature and pressure profiles of Tank 52

TANK 53 METHANOL,BO%, PRV:5.17,0:0.40, W:0.64

400
O
'El

0 300

Press.

Temp. ---

100

200

300

400

500

600

700

Time, s

Figure AS2 Temperature and pressure profiles of Tank 53

TANK 54 METHANOL,BO%, PRV:S.l7.0:0.60. W:0.64

200

400

600

800

Time, s

1000

Figure AS3 Temperature and pressure profiles of Tank 54

TANK 55 METHANOL,BO%, PRV:1.38, 0:0.20, W.0.15

Figure AS4 Temperature and pressure profiles of Tank 55

150

Time, s

Figure AS5 Temperature profiles of Tank 56

TANK 57 METHANOL,80%, PRV:1.72, 00.20, W0.25

200

300

Time, s

Figure AS6 Temperature profiles of Tank 57

APPENDIX B

Surface Temperature Profiles for Smaii Scale BLEVE Tests

TANK 7 PROPANE, 85%. PRV:1.72 0:0.35, W0.38

Figure B.1 Surface Temperature of Tank 7

TANK 8 PROPME, 85%, W0.38

Figure B.2 Surface Temperature of Tank 8

TANK 9 AMMON4 75% PRV:5.52 0:0.35, W0.38

Figure B.3 Surface Temperature of Tank 9

TANK 1011 WATER, 80%. PRV:1.72.0:0.35, M0.38

Figure B.4 Surface Temperature of Tank 1011

TANK 1O n WATER, 80%. PRII:1.72,0:0.35, M0.38

Figure B.5 Surface Temperature of Tank 1 012

TANK 24 NWTANOL80%, PRV:1.72,0:0.10, W0.25

50

100

150

Time,s

Figure B.6 Surface Temperature of Tank 24

TANK 27 N-PENTANE,BO%.PRV:1.720:0.1O,W:0.25

400

Figure B.7 Surface Temperature of Tank 27

TANK 28 R-12 80%.PRk1.72 0:0.10, W9.25

Figure B .7 Surface Temperature of Tank 28

TANK 29 R-114.80%. PRV:1.72 0:0.10, W:0.25

Figure B .9 Surface Temperature of Tank 29

TANK 31 WATER, aon, w . :u o

Figure B. 10 Surface Temperature of Tank 3 1

TANK 32 METHANOL 80%. WAJ.38

Figure B. 1 1 Surface Temperahue of Tank 32

TANK 33 M ~ A N Oaon, w:o.s4 L

Figure B. 12 Surface Temperame of Tank 33

TANK 34 R-114.80%. W:0.38

Figure B. 13 Surface Temperature of Tank 34

TANK 35 R-114.80%, M 0 . M

Figure B. 14 Surface Temperature of Tank 35

TANK 37 N-BUTANOL 80%, W:0.38

Figure B. 1 5 Surface Temperature of Tank 37

TANK 38 N-BUTANOL 80%. W:O.4

Figure B. 16 Surface Temperature of Tank 3 8

TANK 39 ACETONE, 80%. W:0.38

Figure B. 17 Surface Temperature of Tank 39

TANK 40 ACETONE, 80%. W0.64

Figure B.1 8 Surface Temperature of Tank 40

TANK 41 R-12,80%, W:0.38

Figure B. 19 Surface Temperature of Tank 4 1

TANK 42 R-12,80%, W:0.64

Figure 8.20 Surface Temperature of Tank 42

TANK 43 N-PENTANE, 80%. W0.38

Figure B.2 1 Surface TempeTANK 44 WATER, 80% W:0.64

of Tank 43

Figure B.22 Surface Temperature of Tank 44

TANK 45 ACETALDEHYDE, 80% k0.38

Figure B.23 Surface Temperature of Tank 45

APPENDIX C Pressure-Enthalpy Diagrams for Some Ladhgs Used

Figure C.6 Pressure-Enthalpy diagram for methanol (Perry's Ch.E. Handbook, 1990)

APPENDM ' D

Simple Calculations of Work Avaable at Failure

The theoretical work is calculated at constant entropy nom -Wr = AU or

w r =~[@I-PI~I)-&-P~VJI

(7.1)

where m is the mass of lading;

h is the specific enthalpy;

P is the pressure;

v is the specific volume;

subscript 1 denotes an initial state (where failure occurs); subscript 2 denotes a final state (at at~ospheric pressure).

Using the data for Tank 8, lading: liquid fill, %: failure pressure, MPa:
Bacsis 0.001 m3 in volume of the test tank

propane
85 6.65

Since the liquid specifk volume of propane at 25 OC is 0.00203 1 m3/kg,the mass of propane inside the tank,m, is 0.4185 kg. Referring to the pressure-enthalpy diagram for propane (Figure C. 1) and following

an 85 % liquid fil1 line (density = 418.5 m3/kg),which is closed to a saturated liquid line,
from the initial temperature of 269 K (point A) to the point where failure occurs at pressure

194

of 6.65 MPa (point B, referred to as state 1), the following data cm be obtained:

h, = 735 kJ/kg
v, = 0.002389 m3/kg
with the entropy of 4.93 kJ/kg.K.
Following the entropy line of 4.93 m g . & fiom point B, to the atmosphenc pressure

line (0.10 1 MPa, point C, referred to as state 2) yields h2 = 668

v, = 0.23809 m3/kg

Subtitution of these numerical values into Eq.(7.1) yields

W,= (0.4185 kg){ [7 5 ldkg)-(6.65 x 1 03kN/m2)(0.002389 m3kg)] (3

-[(668 kl/kg)-(O.1O 1 x 103kN/m2)(0.23809 m3/kg)])
= 31.35

kJ

Therefore, the theorztical work at failure for Tank 8 is 3 1.35 kl.

D.2

W o -

The achial work performed by the lading in pushing back the atmosphere can be
expressed as

w*= P a (V*-V,)
where P is the amospheric pressure; ,

(7.2)

V, is the volume of the lading at atr..iosphenc presssure after the expansion at

constant enthalpy;
V, is the volume of the lading before the expansion, the volume of the tank.

195

Using the data fkomTank 8, the path represented the process is h m point B to point

D shown i Figure C.1. n

At point D, the specinc volume of propane is 0.3 125 m3/kg.Thus the volume of 85%

liquid propaue, V, is O. 1332 m3.The volume of the tank,V is 0.001 m3and the atmospheric , pressure is 0 10 1 x 1 O3 kPa . Substituting these values into Eq.(7.2) yields

WA= (0.101 x 1 O3 kN/m2)(0. m3-0.00 m3) 1332 1

= 13.35

kJ

Therefore, the actual work a failure for Tank 8 is 13.35 id. :