WATER POLLUTION CONTROL RESEARCH SERIES 15080 DJQ 04/70
ULTRASONIC EMULSIFICATION
OF OIL TANKER
CARGO
U.S. DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMINISTRATE
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ULTRASONIC EMULSIFICATION OF
OIL TANKER CARGO
Feasibility Study Using an Ultrasonic Process to
Emulsify Petroleum to Reduce Oil Slick Hazards
in Event of Spillage at Sea
FEDERAL WATER POLLUTION CONTROL ADMINISTRATION
DEPARTMENT OF THE INTERIOR
-by
SONICS INTERNATIONAL, INC.
7101 Carpenter Freeway
Dallas, Texas 75247
Program No.
15080 DJQ 04/70
April, 1970
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FWPCA Review Notice
This report has been reviewed by the Federal
Water Pollution Control Administration and
approved for publication. Approval does not
signify that the contents necessarily reflect
the views and policies of the Federal Water
Pollution Control Administration.
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ABSTRACT
As a pollution preventive concept, the ultrasonic emulsification of oil for marine
transportation has been tested for feasibility. Two crude oils and a common fuel
oil were emulsified and tested. The emulsions are characterized as stable, dis-
persible in sea water, not unduly toxic and with reduced fire hazard potentials.
This laboratory study shows that oil emulsions can be created by ultrasonics in
a continuous process at tanker loading rates. Limited economic evaluation shows
the concept to be meritorious and reasonable.
PURPOSE OF PROJECT
The purpose of this project was to study the feasibility of producing emulsified
oil at a rate comparable with conventional tanker loading rates and to investigate
the economic and ecological factors.
SCOPE OF PROJECT
To determine blender design parameters and emulsified oil characteristics, two
crude oils and one fuel oil were chosen. A Libyan light oil, a Venezuelan
oil and #6 Fuel Oil were used.
Only two emulsifiers were used and they were base-neutralized sulfonated nonionics.
These are compatible with sea water and of low toxicity.
The emulsions tested were oil-in-water. Oil was the internal phase and 97% of
the total. Water and chemical was the external phase and 3% of the total. The
tests on the emulsions were to determine: stability under simulated transporta-
tion conditions, dispersibility in sea water, toxicity to fish, and product altera-
tion. Included were tests with safety aspects: evaporation rates, flash points,
vapor pressures and rupture leak tests.
An economic study was made which shows emulsification costs of about 20 cents
per barrel without considering possible offsets or side benefits.
This report was submitted in fulfillment of Contract 14-12-559 between the Federal
Water Pollution Control Administration and Sonics International, Inc.
KEY WORDS
Continuous Process Ultrasonics Emulsification
Petroleum Emulsion Stability Dispersion
Toxicity Safety Flammability
Tanker Transportation Spills
Water Pollution
iii
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CONTENTS
Section Title
ABSTRACT iii
LIST OF FIGURES vil
LIST OF TABLES x
CONCLUSIONS 1
RECOMMENDATIONS 4
INTRODUCTION 7
3.1 Problem Background 7
3.2 Case History - Summary of Torrey Canyon
Catastrophe 10
3.3 Problem Definition 10
3.4 Purpose of Project 11
3.5 Scope of Project 12
SELECTION OF OILS AND PREPARATION AND
TESTING OF EMULSIONS 14
4.1 Selection of Oils 14
4.2 Preparation of Test Emulsions 14
4.2.1 Selection of Emulsifiers 14
4.2.2 Emulsification Procedure 15
4.2.3 Emulsion Storage 15
4.3 Emulsion Stability 17
4.3.1 Method 17
4.3.2 Emulsion Stability Data 19
4.3.3 Discussion of Emulsion Stability 19
4.4 Dispersion of Emulsion in Sea Water 33
4.4.1 Method 33
4.4.2 Emulsion Dispersion Data 34
4.4.3 Discussion of Emulsion Dispersion 34
iv
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CONTENTS CONTINUED
Section Title
4.5 Evaporation Rate Tests 39
4.5.1 Method 44
4.5.2 Evaporation Rate Data 61
4.5.3 Discussion of Evaporation Rates 61
4.6 Increased Safety 62
4.6.1 Flash Point Determinations 62
4.6.1.1 Method 62
4.6.2.2 Flash Point Data 62
4.6.2 Vapor Pressure Determinations 63
4.6.2.1 Method 63
4.6.2.2 Vapor Pressure Data 63
4.6.3 Rupture Leakage Tests 63
4.6.3.1 Methods 63
4.6.3.2 Rupture Leakage Data 64
4.6.4 Discussion of Increased Safety 65
4.7 Toxicity 67
4.7.1 Method 67
4.7.2 Test Apparatus 67
4.7.3 Test Fish and Experimental Water 68
4.7.4 Test Conditions 68
4.7.5 Procedure 68
4.7.6 Physical and Chemical Determinations 71
4.7.7 Determination of Median Tolerance Limit
and Discussion of Results 71
4.8 Consideration of Break-Back Methods 81
4.8.1 Introduction 81
4.8.2 Pumps 81
4.8.3 Atomization 82
4.8.4 Ultrasonic Break -Back 82
4.8.5 Chemical Break-Back 82
4. 8.6 Re-Use of "Emulsion Seed" or Water Phase 82
4.8.7 Discussion 83
4.9 Product Alteration 83
4.9.1 Methods 83
4.9.2 Product Alteration Data 84
4.9.3 Discussion of Product Alteration 84
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CONTENTS CONTINUED
Section Title Page
5 DESIGN, CONSTRUCTION, AND OPERATION OF
BENCH SCALE EMULSIFICATION UNIT 87
5.1 Basis of Design - Prior Work 87
5. 2 Design and Construction of Bench Scale Unit 87
5. 3 Operation of Bench Scale Unit and Data Collection 90
5.4 Discussion of Bench Scale Emulsification 94
6 SYSTEM CONCEPTUAL DESIGN 108
6.1 Emulsification Unit Scale-Up to Basic 100 Barrels
Per Minute Unit 108
6.2 Concept of Complete Emulsification System 108
6.3 Placement of Emulsification System 113
7 ECONOMICS OF EMULSIFICATION PROCESS 117
7.1 Introduction 117
7.2 Costs of Emulsified System for Oil Transportation 117
7.2.1 Loading Rate Considerations 117
7.2.2 Capital Costs of Equipment 118
7.2.3 Operating Costs of System 118
7.2.4 Cost of Chemical Emulsifier 118
7.2.5 Possible Gains Offsetting Emulsification Costs 121
7.2.6 Possible Procedure Modifications 121
7.3 Discussion of Economics of Emulsification Process 123
8 ACKNOWLEDGEMENT 126
9 LIST OF PUBLICATIONS CRITICAL TO STUDY 127
10 GLOSSARY OF ABBREVIATIONS AND TERMS 128
11 REFERENCES 130
APPENDICES
Appendix I Evaporation Rate Tables 132
Appendix II Disclosure of Invention of Flat-Plate
Homogenizer 160
vi
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LIST OF FIGURES
Figure Title Page
4.2-1 30-Quart Hobart Mixer 16
4.2-2 "Emulsion Seed" 16
4.2-3 Finished Emulsion 16
4.3-1 Cone Penetrometer, Modified 18
4.3-2 Motion Apparatus, Modified Ro-Tap 18
4.3-3 Stability to Ambient Temperature, Quiescent - Zueitina
Emulsions 21
4.3-4 Stability to Ambient Temperature, Quiescent - Tia Juana
Emulsions 22
4.3-5 Stability to Ambient Temperature, Quiescent - #6 Fuel Oil
Emulsions 23
4.3-6 Stability to 50° - 60°C, Quiescent - Zueitina Emulsions 24
4.3-7 Stability to 50° - 60°C, Quiescent - Tia Juana Emulsions 25
4.3-8 Stability to 50° - 60°C, Quiescent - #6 Fuel Oil Emulsions 26
4.3-9 Stability to Freeze/Thaw Cycles - Zueitina Emulsions 27
4.3-10 Stability to Freeze/Thaw Cycles - Tia Juana Emulsions 28
4.3-11 Stability to Freeze/Thaw Cycles - #6 Fuel Oil Emulsions 29
4.3-12 Stability to Simulated Ship Motion - Zueitina Emulsions 30
4.3-13 Stability to Simulated Ship Motion - Tia Juana Emulsions 31
4.3-14 Stability to Simulated Ship Motion - #6 Fuel Oil Emulsions 32
4.4-1 Time Stability of 1% Dispersed Emulsions - Zueitina 36
4.4-2 Time Stability of 1% Dispersed Emulsions - Tia Juana 37
4.4-3 - Time Stability of 1% Dispersed Emulsions - #6 Fuel Oil 38
4.4-4 Time Stability of 0.1% Dispersed Emulsions - Zueitina 41
4.4-5 Time Stability of 0.1% Dispersed Emulsions - Tia Juana 42
4.4-6 Time Stability of 0.1% Dispersed Emulsions - #6 Fuel Oil 43
4.5-1 Analytical Balances With Petri Dishes Being Weighed 44
4.5-2 Accumulative Weight Loss, full open dish, Zueitina 45
4.5-3 Evaporation Rate, full open dish, Zueitina 46
4. 5-4 Accumulative Weight Loss, full open dish, #6 Fuel Oil 47
4.5-5 Evaporation Rate, full open dish, #6 Fuel Oil 48
4. 5-6 Accumulative Weight Loss, half filled, open dish, Zueitina 49
4.5-7 Evaporation Rate, half filled, open dish, Zueitina 50
4.5-8 Accumulative Weight Loss, half filled, open dish, Tia Juana 51
4.5-9 Evaporation Rate, half filled, open dish, Tia Juana 52
4.5-10 Accumulative Weight Loss, half filled, open dish, #6 Fuel Oil 53
4.5-11 Evaporation Rate, half filled, open dish, #6 Fuel Oil 54
vii
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LIST OF FIGURES CONTINUED:
Figure Title Page
4.5-12 Accumulative Weight Loss, half filled, 1/4" vent, Zueitina 55
4.5-13 Evaporation Rate, half filled, 1/4" vent, Zueitina 56
4.5-14 Accumulative Weight Loss, half filled, 1/4" vent, Tia Juana 57
4.5-15 Evaporation Rate, half filled, 1/4" vent, Tia Juana 58
4. 5-16 Accumulative Weight Loss, half filled, 1/4" vent, #6 Fuel Oil 59
4.5-17 Evaporation Rate, half filled, 1/4" vent, #6 Fuel Oil 60
4.7-1 Acclimatizing Aquaria 69
4.7-2 Toxicity Test Aquaria 69
4. 7-3 Test Fish - Cyprinodon variegatus 69
4.7-4 Toxicity of Emulsifiers, 1-1751 73
4.7-5 Toxicity of Emulsifiers, 1-1752 73
4.7-6 Toxicity of Zueitina Emulsions, with 1-1751 75
4.7-7 Toxicity of Zueitina Emulsions, with 1-1752 75
4.7-8 Toxicity of Tia Juana Emulsions, with 1-1751 77
4. 7-9 Toxicity of Tia Juana Emulsions, with 1-1752 77
4.7-10 Toxicity of #6 Fuel Oil Emulsions, with 1-1751 79
4. 7-11 Toxicity of #6 Fuel Oil Emulsions, with 1-1752 79
4.9-1 Oil Distillation Curves 86
5-1 Bench Scale Emulsification System, Schematic 88
5-2 Bench Scale Emulsification System, Photograph 89
5-3A "Emulsion Seed" Pre-mix Unit, Bench Scale Unit 89
5-3B Flat-Plate Homogenizer, Bench Scale Unit 91
5-3C Column Blender, Bench Scale Unit 91
5-4 Mixer Motor Air Pressure, Oil & Seed Inlet Pressure, Zueitina
Crude 96
5-5 Measured Flow Rate, Zueitina Crude 96
5-6 Room & Emulsion Discharge Temperatures, Zueitina Crude 96
5-7 Blender Air Motor Speed, Zueitina Crude 96
5-8 Mixer Motor Air Pressure, Oil & Seed Inlet Pressure Tia
Juana Crude 98
5-9 Measured Flow Rate, Tia Juana Crude, Run No. 1 98
5-10 Room & Emulsion Discharge Temperature, Tia Juana Crude, Run
No. 1 98
5-11 Blender Air Motor Speed, Tia Juana Crude, Run No. 1 98
5-12 Mixer Motor Air Pressure, Oil & Seed Inlet Pressure, Tia Juana
Crude, Run No. 2 100
5-13 Measured Flow Rate, Tia Juana Crude, Run No. 2 100
viii
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LIST OF FIGURES CONTINUED:
Figure Title Page
5-14 Room & Emulsion Discharge Temperatures, Tia Juana
Crude, Run No. 2 100
5-15 Blender Air Motor Speed, Tia Juana Crude, Run No. 2 100
5-16 Mixer Motor Air Pressure, Oil & Seed Inlet Pressure,
Tia Juana Crude, Run No. 3 102
5-17 Measured Flow Rate, Tia Juana Crude, Run No. 3 102
5-18 Room & Emulsion Discharge Temperatures, Tia Juana,
Run No. 3 102
5-19 Mixer Motor Air Pressure, Oil & Seed Inlet Pressure, #6
Fuel Oil 104
5-20 Measured Flow Rate, #6 Fuel Oil 104
5-21 Room & Emulsion Discharge Temperatures, #6 Fuel Oil 104
5-22 Blender Air Motor Speed, #6 Fuel Oil 104
5-23 Mixer Motor Air Pressure, Oil & Seed Inlet Pressure, #2
Diesel Fuel 106
5-24 Measured Flow Rate, #2 Diesel Fuel 106
5-25 Room & Emulsion Discharge Temperatures, #2 Diesel Fuel 106
5-26 Blender Air Motor Speed, #2 Diesel Fuel 106
6-1 Plan View - Basic 100 BPM Emulsification Unit 109
6-2 Elevation - Basic 100 BPM Emulsification Unit no
6-3 Single Unit Crude Oil Emulsification System 114
6-4 Multi-Unit Crude Oil Emulsification System 116
7.2-1 Overall Cost Estimation 125
II-l Flat-Plate Homogenizer Drawings 161
ix
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LIST OF TABLES
Table Title
4.3-1 Emulsion Stability as Indicated by Yield Values 20
4.4-1 Time Stability of 1% Dispersed Emulsion 35
4.4-2 Time Stability of 0.1% Dispersed Emulsion 40
4.6-1 Comparison - Flash Points 62
4.6-2 Comparison - Vapor Pressures 63
4.6-3 Oil & Emulsion Flow Properties 64
4.6-4 Rupture Tests - Influx of Sea Water 65
4.6-5 Rupture Tests - Spill Rate 65
4.7-1 Analysis of Synthetic Sea Water 70
4.7-2 Toxicity of Emulsifiers 72
4.7-3 Toxicity of Zueitina Emulsions 74
4.7-4 Toxicity of Tia Juana Emulsions 76
4.7-5 Toxicity of #6 Fuel Oil Emulsions 78
4.7-6 Summary of Ninety-Six Hour TL5Q Values 80
4.8-1 Emulsion Separation Following Atomization 83
4.9-1 Oil Characteristics 85
5-1 "Emulsion Seed" Rates for 2 to 5 Gallons Per Minute 92
5-2 Blender Inlet Oil Rates for 2 to 5 Gallons Per Minute 93
5-3 Run with Zueitina Crude, Emulsification Pilot Model Data 95
5-4 Run No. 1 with Tia Juana Crude, Emulsification Pilot Model
Data 97
5-5 Run No. 2 with Tia Juana Crude, Emulsification Pilot Model
Data 99
5-6 Run No. 3 with Tia Juana Crude, Emulsification Pilot Model
Data 101
5-7 Run with #6 Fuel Oil, Emulsification Pilot Model Data 103
5-8 Run with #2 Diesel Fuel, Emulsification Pilot Model Data 105
6-1 Basic 100 BPM Emulsification Unit Parts List 111
6-2 Basic 100 BPM Emulsification Unit Oil Flow Rates 112
6-3 Time Required to Load a Tanker with 100 BPM Units 115
7.2-1 Basic 100 BPM Emulsification Unit Cost Estimate 119
7.2-2 Emulsification Unit Costs of Operation 120
7.2-3 Schedule of Emulsifier Costs 122
7.3-1 Summary of Costs and Potential Cost Reductions - Range 124
1-1 Evaporation Rate, Half Filled, Open, Zueitina Crude 133
1-2 Evaporation Rate, Half Filled, Open, Zueitina Crude with 1-1751134
1-3 Evaporation Rate, Half Filled, Open, Zueitina Crude with 1-1752 135
1-4 Evaporation Rate, Half Filled, Open, Zueitina Crude with 1-1752 136
1-5 Evaporation Rate, Half Filled, Open Tia Juana Crude 137
1-6 Evaporation Rate, Half Filled, Open, Tia Juana Crude with
1-1751 - 138
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LIST OF TABLES CONTINUED:
Table
1-7
1-8
1-9
1-10
1-11
1-12
1-13
1-14
1-15
1-16
1-17
1-18
1-19
1-20
1-21
1-22
1-23
1-24
1-25
1-26
1-27
Title
Page
Evaporation
1-1752
Evaporation
Evaporation
Evaporation
Evaporation
Evaporation
with 1-1751
Evaporation
with 1-1752
Evaporation
Evaporation
with 1-1751
Evaporation
with 1-1752
Evaporation
Evaporation
1-1751
Evaporation
1-1752
Evaporation
Evaporation
Evaporation
Evaporation
Evaporation
Evaporation
Evaporation
Evaporation
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
Rate,
half
half
half
half
half
half
half
half
half
half
half
half
half
full
full
full
full
full
full
full
full
filled
filled
filled
filled
filled
filled
filled
filled
filled
filled
filled
filled
filled
dish,
dish,
dish,
dish,
dish,
dish,
dish,
dish,
, open
, open
, open
, open
, 1/4"
, V4"
, 1/4"
, 1/4"
, 1/4"
, 1/4"
, V4"
, 1/4"
, 1/4"
open,
open,
open,
open,
open,
open,
open,
open,
, Tia Juana Crude with
, #6 Fuel Oil
, #6 Fuel Oil withI-1751
, #6 Fuel Oil with I- 1752
vent, Zueitina Crude
vent, Zueitina Crude
vent, Zueitina Crude
vent, Tia Juana Crude
vent, Tia Juana Crude
vent, Tia Juana Crude
vent, #6 Fuel Oil
vent, #6 Fuel Oil with
vent, #6 Fuel Oil with
Zueitina Crude
Zueitina Crude with 1-1751
Zueitina Crude with 1-1752
Tia Juana Crude
Tia Juana Crude with 1-1751
Tia Juana Crude with 1-1752
#6 Fuel Oil with I- 1751
#6 Fuel Oil with 1-1752
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
xi
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1. CONCLUSIONS
This report covers the ultrasonic emulsification of oils for tanker transportation
as a pollution preventive concept. Tests performed show that this is no longer
just a concept, but with reasonable refinement, isapractical method. This oil
spill preventive method is a fail-safe method because no decision is required
when disaster impends.
Crude oils have been emulsified by a continuous flow-through process with 97%
oil as the inner phase. The continuous and outer phase of the emulsion is 2.5%
water and 0.5% chemical emulsifiers. Briefly, the ultrasonic emulsification
technique is as follows: (1) an emulsion seed is created by passing oil, water
and emulsifier through an ultrasonic homogenizer, (2) the emulsion seed is 70%
oil and 30% water (and emulsifier), (3) the seed (10%) is blended with raw oil
(90%) for the final emulsion.
1.
Data from the laboratory emulsification unit show that full size units for tanker
loadings are practical. A 100 barrel per minute module unit was designed for
single or multi-unit applications. Skid base size is 10 ft. x 27 1/2 ft. with a
27 ft. 7 in. blending column at one end.
2.
A flat plate ultrasonic transducer was developed during the course of this study.
This device has application in high rate, continuous, emulsification process.
3.
The emulsions studied are stable in a quiescent state at temperatures from 25° F
to 140° F. Gentle agitation as provided by simulated ship motion improves emul-
sion stability.
4.
Emulsion dispersion tests, in sea water with one percent emulsions, show only
trace amounts of free oil after twenty-four hours. We conclude that if an emulsion
were spilled at sea, no oil slick would form. Test conditions were more exacting
than those at sea. In reality, the emulsion would be spread out so far and become
so diluted in only a few hours that before break-back could occur, oil droplets would
be spread too far apart to form an oil slick.
-1-
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5.
Our toxicity tests on fish determined that emulsions of heavy oils are less toxic
than those of light oils. This is in line with published literature and data. Also,
comparing emulsion toxicities with reported oil toxicities, in confined spaces,
the emulsion is more toxic than the oil. This is believed to be due to the fact
that the fish were in more intimate contact with the emulsion. It is reasonable
to believe that emulsions released at sea will be dispersed by wind, tide and
ocean currents and rapidly diluted below the toxic level.
The toxicity tests were static tests and not flow-through. The tests are discussed
in detail elsewhere in the report.
6.
In an open system there was a tenfold reduction in evaporation rates due to emul-
sification. The evaporation rates for the three emulsions in a partially open
system (vented) are the same as for non-emulsions. In a transportation or nor-
mal handling situation, emulsification does not reduce loss due to evaporation.
However, in the case of a spill at sea, the tenfold reduction (open system) is of
significance. This reduced rate would have a safety value in the immediate vi-
cinity of a spill (reduced fire hazard).
7.
Emulsification significantly improves the safety of the transportation and han-
dling of liquid hydrocarbons. Two things are changed: (1) fire hazard is re-
duced and (2) spill rate is reduced. The Zueitina crude had a flash point of 42°F
and after emulsification it was raised to 84°F. The flash point of the Tia Juana
crude was raised from 64°F to 96°F. In addition, the emulsified oil, due to the
higher conductivity of the water, has a lowered static electrical charge potential.
All these factors reduce the chance of fire and explosion and, due to the slower
burning rate of emulsion, provide more time for control in case there is a fire.
This reduced fire hazard could reduce insurance rates.
The formation of tank bottoms and sediment build-up on the walls of compart-
ments will be reduced or eliminated. Pollution of ocean environments by oil
slicks resulting from tank cleaning or ballast discharge could virtually be elimi-
nated.
The chemical and physical character of the two crudes and the fuel oil tested
-2-
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were not altered by emulsification. About seventy-five percent of the water
soluble salts contained in the oils were removed as a result of the emulsi-
fication and demulsification process. This upgrading could be a cost offset
in the case of high salt content crudes.
10.
Means and cost to break emulsions as used in this study were based on work
of others. Means to break-back are: (1) atomization, (2) chemicals, (3)
pumps and (4) combinations of the foregoing.
11.
The study suggests that emulsified # 6 Fuel Oil can be used as ship fuel
without break-back. This would be an improvement in safety due to less
chance of fire in case of accident or other uncontrolled occurrences. Also
there would be less tank cleaning required and thereby, a reduction in
ocean pollution.
12.
Economic analyses indicate emulsification costs are about 20 cents per
barrel without any consideration for demulsification or possible cost
offsets. Modifications of the procedure itself hold potential for reduc-
tions in process costs.
-3-
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2. RECOMMENDATIONS
Results of this feasibility study show that the ultrasonic emulsification concept
for the transportation and handling of oil is reasonable. The mechanics of emul-
sification and the character of the emulsions have been well defined. Overall
economics are not as well defined, but from data available,appear reasonable.
For a complete and more realistic appraisal of the concept, two factors that re-
quire refinement are emulsifier costs and break-back costs. The study per-
mitted the evaluation of only two emulsifiers and as a necessity they were select-
ed strictly on performance. Break-back techniques were not within the scope of
this study.
Results of tests performed on the emulsions strongly suggest use of emulsified
oil as ship fuel. About the only thing required to finalize this concept would be
some actual burner tests. Two of the advantages would be: safety and elimina-
tion of sediment in tanks. The reduction and/or elimination of fuel tank bottoms
has one obvious pollution abatement aspect, the elimination of dumping. We
recommend that action be taken on this concept with the proper Marine and Trans
portation Authorities.
During the course of this feasibility study a flat plate transducer was developed.
This device has application in the ultrasonic emulsion seed process for oils.
The disclosure was made in the second monthly progress report (9 September
1969). Patent proceedings should be initiated for the U.S. Government by the
F.W.P.C.A.
fri view of the results obtained in this study, we believe that justification exists
for further investigations and refinements of economics. Listed are our recom-
mendations for further definition of the concept.
1. Optimize emulsifiers as to concentrations and cost. Determine
reuse characteristics.
2. Develop low cost break-back technique.
3. Evaluate economic offsets and safety features.
4. Evaluate desalting as a result of this complete process.
5. Evaluate emulsified fuel oil as a ship fuel.
6. Upgrade economics based on items 1 through 5.
7. Actual dispersion tests at sea after satisfactory completion of above
items.
-4-
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8. Toxicity tests on optimum emulsifiers and emulsions at the FWPCA
Marine Laboratory. These tests, if needed, should be on a flow-
through basis that takes into account continual dispersion.
9. Construction and demonstration of emulsification and demulsification
unit. This should be after all other work is completed.
Some discussion of factors for investigation follows:
Optimize Emulsifiers
The chemical cost is the greatest single cost in this ultrasonic emulsification
process. A reduction in this cost will greatly enhance the economics of the
process. Additional investigations are needed to develop: (1) a group of low
cost emulsifiers with reasonable stability (2) emulsifiers that can be used at
minimum concentrations (less than 0.5%), (3) emulsifiers that can be reclaimed
and reused (4) better overall economics.
Emulsion Break-Back
The emulsions studied were broken by chemical demulsifiers and no investiga-
tions were made of other techniques. The total economics can be greatly im-
proved by the elimination of Hemulsifier chemicals. A low cost and practical
break-back technique that is compatible with the rest of the concept is needed.
Prior work by others indicates that emulsions can be broken mechanically.
Shearing action can rupture the outer phase of emulsions and this is one of the
reasons we believe that pumps should be studied.
The investigation should include evaluation of pumps, pumps with nozzels or
jets, heat and restricted use of chemicals. Also, the use of ultrasonic equip-
ment should be tested in combination with above as well as singly. Economics
developed will apply to the total process or concept.
Economic and Safety Offsets
Certain features of the emulsification concept suggest other advantages. These
features should be investigated to better define their values. Briefly these are:
(1) tanker maintenance, including bottom sediments and corrosion, (2) safety
due to electrostatic charge reduction, lowered flash points, reduced burn rates
and reduced evaporation, (3) desalting of oils, and (4) use of emulsions as a
ship fuel.
Desalting
This study has shown that some product up-grading is accomplished as an end
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result of the ultrasonic emulsification process. Water soluble materials were
removed from the three oils tested. The reduction in water soluble materials
was in the order of 75 to
The three oils tested were not high salt content oils. The Zueitina Crude con-
tained about 28 pounds of water soluble salts/1000 bbls. of oil when received in
our laboratory. After ultrasonic emulsification using 30 bbls. water/1000 bbls.
oil in the process and subsequent chemical break-back the crude contained only
7 pounds of water solubles per 1000 bbls. of oil. This is an indicated reduction
of about 75%. Thirty barrels of water can carry about 3000 pounds of salt in
solution. Test results on the Tia Juana Crude and the #6 Fuel Oil were similar.
As explanation, the fresh water used to make the emulsion is mixed very tho-
roughly with the oil during the emulsification process. The water dissolves salt
crystals and also mixes with brine present in the oil. When the emulsion is bro-
ken back, the water contains the salt in solution. All these data indicate the high
salt content crudes can be effectively desalted as a side benefit of this ultrasonic
process.
We recommend that work be done to determine the desalting characteristics of
the ultrasonic emulsified oil handling concept including disposition of the re-
covered brine. The disposal will depend on several things: (1) facilities at the
terminal, (2) emulsifier content, and (3) reuse of water and emulsifier. ft will
not create a pollution problem. The investigation should be made on several
crudes with high salt content. Also, an economic investigation should be made
to determine the value of desalting process. This study will provide economic
data to offset some of the costs of the ultrasonic process.
Dispersion Tests at Sea
We recommend that dispersion tests be performed at sea. Several spill tests
of about one barrel each should be made with emulsified oils and with raw oils
for comparisons. The data to be gathered would provide information for dis-
persion rates, emulsion or oil concentrations at various distances with respect
to time and flammability of the spill at different time intervals. These tests
should be made under varying sea conditions ranging from calm to high. At
least one test should be made on a large lake to simulate a spill in a bay area.
These tests must be made in a controlled area and after emulsifiers have been
optimized.
-6-
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3. INTRODUCTION
3.1 Problem Background
In recent years the threat of oil pollution of the waterways, seas and beaches has
increased with the rapidly increasing volume of oil and oil products which is
transported in barges and tankers. As the number of petroleum product laden
vessels and the waterborne traffic increases there is increased danger of oil
spillage due to collision, accidental grounding, or other breakage.
Compounding this danger of large scale oil spillage is the ever increasing size of
tankers. In 1945 a world fleet of 1,911 tankers could carry 24 million tons of oil
and oil products, and the largest supertanker was rated 23,000 deadweight tons.
In 1956, the world's fleet had grown to 2,778 tankers with a total capacity of 45
million tons, and the largest supertanker had a capacity of 45,000 deadweight
tons. By 1966 the number of tankers was 3,524, and their combined capacity was
103 million deadweight tons. The largest supertanker in 1966 had a capacity of
210,000 deadweight tons. There are now many 210,000-deadweight-ton tankers,2
several 312,000-deadweight-ton tankers in service or under construction and even
larger ones (500,000 to 1,000,000 deadweight tons) are being planned. 3>4,5
Oil tankers account for about 40 percent of the worlds ocean going traffic, and
carry about half of the worlds total ocean tonnage.
Barges are also increasing in size and number. With the rapid expansion of off-
shore production, tank barges have grown larger than the average World War II
tanker. Tank barges with a capacity of 20,000 tons are in operation and 30,000
ton barges are planned. In 1967 there were 2,781 tank barges with a net cargo
capacity of 5,120,029 tons.6
In 1967 about 173 million tons of crude oil and petroleum products were trans-
ported on the 25,380 miles of inland waterways. Crude oil and petroleum pro-
ducts accounted for 35 percent of the total inland waterway tonnage. About 72
percent of the inland waterway tonnage is transported by barges.
As more supertankers are being placed into service each year the probability of
catastrophic oil spills is consequently increased. One of the most dramatic
examples of such catastrophic oil spills is the grounding of the Torrey Canyon
off the southwest coast of England on March 18, 1967. The Torrey Canyon was
a 127,000-ton displacement tanker loaded with 118,000 tons (900,000 barrels)
of Kuwait crude oil. About 13,000 tons of the oil spilled by the Torrey Canyon
7
was washed onto the Cornish beaches.
It is not possible to predict where or when the next major spill will occur. How-
ever, on the average, tankers will be involved in one major oil spill and more
than 100 minor accidents per year. Since most of these accidents are results
-7-
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of human error, it will not be possible to completely eliminate tanker accidents.
In addition to the oil spills resulting from tanker and barge accidents are the
many unknown negligent spills resulting from handling errors, vessel leaks and
illegal discharge of bilge washings. Estimates of the yearly addition of oil to the
sea range from one million to 100 million tons.
Present technology does not make it possible to accurately predict the behavior
of specific oil spills. However, studies of previous oil spills permit some
generalizations about the behavioral characteristics of an oil slick. Upon mak-
ing contact with the water an oil spill rapidly spreads in a constantly thinning
layer. The water soluble portion of the oil dissolves into the liquid hydrosphere
and the lighter fractions evaporate into the atmosphere. In some instances a
portion of the oil will adhere to particulate matter and sink. The remaining oil
will be subjected to oxidation and bacterial decompositon. Bacteria tend to de-
compose only the straight-chain, moderate molecular weight hydrocarbon frac-
tions. The heavy molecular weight, branched-chain fractions will sink, once
they are freed of the lighter fractions. These heavy fractions form a tarry mass
on the ocean floor or at a subsurface depth in the ocean, and are attacked by
anaerobic bacteria.8 The net result, with time, is essentially complete degra-
dation of the spilled oil.
An oil slick is a navigational hazard to sea traffic, a killer of sea birds and a
toxic pollutant of marine life. Crude oil and many of the petroleum products
cannot be treated as a single pollutant but must be considered as a collection of
many substances with different properties and toxicities. Knowledge of the ac-
tual toxicity of oil to marine life is limited. Most toxic are the low-boiling point,
saturated hydrocarbons and the aromatic hydrocarbons (benzene, toluene, xy-
lene). The concentrations of the various hydrocarbon fractions toxic to the many
species of marine life are not known. The most easily observed victims of an
oil spill are the marine birds. Very few birds survive contact with an oil slick.
The high death rate may be the result of one or a combination of many factors,
which include toxicity and increased susceptibility to diseases due to a weakened
physical state caused by feather matting, flying difficulties, loss of buoyancy,
etc.
Methods of treating oil spills are numerous and vary widely in efficiency. Oil
slick treating methods may be classified into two general categories: 1) contain- ,
ment and recovery and 2) dispersion and forced precipitation. Preference is
and should be given to containment and recovery methods,if they are feasible.
Often, however, the most feasible method of removing an oil slick is by disper-
sion or forced precipitation.
The methods grouped under containment and recovery include booming, skim-
ming, adsorbing and burning. Booming consists of various methods of fencing
the oil spill, the most common being a mechanical, hydrodynamic barrier.
The barrier is hydrodynamically designed to maintain an upright orientation
-8-
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with predetermined portions above and below the water line. Booms which have
been used range in degree of sophistication from carefully designed structures to
fire hoses. Also, worthy of mention is the air bubble-curtain barrier which, when
deployed, generates a continuous flow of air bubbles to the surface. The resul-
tant surface tension and turbulence act as a retaining wall to an oil spill. Che-
mical booming is accomplished by adding a gelling agent to the peripheral oil of
a slick. The gelled oil then acts as a barrier to prevent further oil spread.
Skimming is accomplished by pumps with buoyed suctions or by rotating drums
which are preferentially oil wet. These drums mount to a recovery vessel which
plies the slick collecting the spilled oil.
Adsorbing and recovery are accomplished by spreading the adsorbent over the oil
slick and subsequent pick-up of the oil soaked material. Straw and sawdust are
often used for this process due to their ready availability.
Burning is seldom attempted because the slick must be ignited immediately after
spillage to realize any degree of success. Selective burning of the lighter oil
fractions, rapid transfer of heat to the water, and the limited supply of oxygen
to the center of the slick are all factors which impede sustained burning of an
oil slick.
The major disadvantage of all the containment and recovery methods is their
greatly reduced efficiency in the presence of any wave action. The advantage of
containment and recovery methods is the removal of the oil from the water,
thereby eliminating pollution.
Dispersion and forced precipitation methods leave the oil in the water but dilute
it to such an extent that its harmful effects are greatly reduced or nullified. To
accomplish dispersion, a surfactant, often in a solvent carrier, is sprayed over
the oil spill. The surface is agitated to emulsify the oil, which is thereby dis-
persed in the water. Forced precipitation is accomplished by dispensing adsor-
bents, such as treated sand .or chalk, over the spill. The oil is adsorbed and
sinks with these materials.
The major objection to dispersion and forced precipitation is that the oil remains
as a pollutant in the water. When dispersion is chosen as the treatment method,
a large volume of emulsifying agent, often nearly equal to the volume of oil being
dispersed, is required. In many instances the emulsifier and its carrier sol-
vent have been more toxic to marine life than the spilled oil. When forced pre -
cipitation is chosen, a portion of the oil carried to the bottom by the adsorbents
is often later released and will reappear on the surface of the water.
There are several advantages to dispersion and forced precipitation methods of
treating oil spills. These methods are effective in the presence of wave action
and are aided by the wave action imparted in rough seas. Often one of these
-9-
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methods offers the quickest and/or most economical means of treating an oil
slick.
3.2 Case History - Summary of Torrey Canyon Catastrophe
A dramatic example of a catastrophic oil spill was provided by grounding of the
Torrey Canyon near Land's End, off the southwest coast of England, on March
18, 1967. The Torrey Canyon was a 127,000-ton displacement tanker loaded
with 118,000 tons (approximately 900,000 barrels) of Kuwait crude oil. Of the
initial 30,000 tons of oil spilled onto the water, 13,000 tons were washed onto
the Cornish beaches. '
Immediately after the spill, 2,500 tons (500,000 gallons) of detergents were
sprayed on the oil slick in an attempt to emulsify and disperse the oil before it
got to the beaches. Despite this action nearly half of the initial spill was spread
over the beaches. To clean this 13,000 tons of oil from the beaches, 10,000
tons (two million gallons) of detergent were used. A fleet of 42 ships was used
to dispense the total 12,500 tons of detergent. A major problem encountered as
a result of using emulsifiers was the formation of a water-in-oil emulsion rather
than the desired oil-in-water emulsion. The French estimate that by the time the
emulsified oil reached their coast the mass had increased to as much as 600,000
tons ^ as a result of the sea water dispersed within the oil. This emulsion be-
haved quite differently from a normal oil slick. It was a sticky mass which
floated as a thick mat on the water and coated everything it contacted. Rather
than remain on the surface of the beach as oil normally does, this emulsion
penetrated the sand to a depth of as much as 12 inches.
When an attempted salvage operation was unsuccessful, it was decided to try
in situ burning of the unspilled portion of the Torrey Canyon cargo. In attempts
to ignite and sustain burning of the oil, 160,000 pounds of high explosives
(rockets and bombs), 10,000 gallons of aviation kerosene and 3,000 gallons of
napalm were used.10 In situ burning destroyed 60,000 to 75,000 tons, a little
more than 1/3 of the oil.?
The costs and damages caused by the oil spilled from the Torrey Canyon include
7.2 million dollars paid to the British and French governments, H 0.1 million
dollars set aside for miscellaneous unsettled private claims, the loss of approx-
imately 1.5 million dollars worth of oil, the loss of the supertanker, and an
estimated 30,000 sea birds killed (primarily guillemots and razorbills 12) and
an unknown kill of marine fauna and flora.
3. 3 Problem Definition
The Federal Water Pollution Control Administration, as the principal United
States government agency dealing with water pollution problems, continues to
search for preventive and corrective means of pollution abatement. The basic
-10-
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problem which precipitated this study is the continual pollution of seas, water-
ways and beaches with crude oil and petroleum products spilled from tankers and
barges, as a result of accidents and negligent procedures during normal trans-
port and loading operations and in event of collision or grounding.
3.4 Purpose of Project
This project was proposed as an alternate study in response to Federal Water
Pollution Control Administration, Department of the Interior, Request for Pro-
posal WA-68-141, "Treatment of Oil Wastes", April 18, 1968. An alternate
proposal was made on the assumption that a preventive approach is better than
corrective treatment of oil spillage. It was reasoned that if the oil and oil pro-
ducts were emulsified an an oil-in-water emulsion the cost of emulsification and
the sacrifice of 3 percent (volume required for minimum external phase of emul-
sion) of tanker capacity might not be excessive when compared with the costs and
damages incurred with major oil spills.
An emulsified cargo appeared to offer several advantages over corrective treat-
ment. The most commonly used corrective treatment is to disperse the spilled
oil into the sea using an emulsifying chemical and a jet stream of water. The
volume of emulsifier required to disperse spilled oil often equals the volume of
the oil spill. Predictions were that an emulsified cargo would:
1. Retard spillage, due to the increased viscosity of the cargo,
in the event of normal tanker leakage and minor ruptures.
2. Disperse rapidly into the sea in the event of major spillage,
thus never permitting the formation of an oil slick.
3. Be much less toxic to marine flora and fauna due to the low
concentration of chemical emulsifier (0.5%).
4. Reduce fire hazard because each droplet of oil is encased in
a protective water jacket.
5. Allow increased rate of microbial decomposition and auto-oxidation
as a result of oil dispersion and the resultant increase in oil
surface area exposure.
6. Increase cargo stability.
7. Reduce cargo evaporation losses.
8. Upgrade product quality as a result of desalting when the con-
tinuous phase of the emulsion is removed.
-11-
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9. Provide relief from potential pollution damage claims and penalties.
10. Make possible a reduction in insurance rates.
Therefore, the purpose of this project was to study the feasibility of producing
emulsified oil at a rate comparable with conventional tanker loading rates and to
investigate the economic and ecological advantages and disadvantages of handling
oil in an emulsified state.
3.5 Scope of Project
To investigate blender design parameters and emulsified oil characteristics,
two crude oils and one oil product were chosen. The Zueitina crude oil from
Libya is a high-quality, light oil. The Tia Juana Medium crude oil from Vene-
zuela is representative of the more common medium gravity oils. The #6
Fuel Oil is a very heavy, viscous oil consisting primarily of the residuum from
refinery distillation vats.
Two different emulsifiers were selected on the basis of their compatibility with
sea water and the oils, their cost and availability. These were base neutra-
lized sulfonated nonionics.
Emulsions were prepared in a batch mixer for various tests during the project.
The oils were tested before and after emulsification to determine any product
change which may have been caused by the emulsification/demulsification pro-
cess.
The stability of the emulsions was tested with reference to time and variation of
motion and temperature.
The emulsions and oils were comparatively subjected to various tests to deter-
mine the degree of increased safety imparted by emulsification.
The toxicity of each emulsion and emulsifier was evaluated, using salt water
fish and the procedure specified by "Bioassay Methods for the Evaluation of
Acute Toxicity of Industrial Wastewaters and Other Substances to Fish",
Standard Methods for the Examination of Wate-r and Wastewater^ Twelfth Edi-
tion, American Public Health Association, Inc. This procedure was modified to
be in accord with the draft copy, dated November 18, 1968, of the FWPCA
"Interim Toxicity Procedures".
Ambient temperature evaporation-rate tests were comparatively conducted on
the emulsions and oils.
Emulsification unit design was projected using the data collected while running
-12-
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a bench scale model assembled for this contract. An emulsification unit of 100
barrels-per-minute capacity was chosen as the basic unit.
A conceptual design for a terminal system employing one or more of the basic
emulsification units was developed.
An economics study was made, giving due consideration to the capital and operat-
ing costs of equipment necessary for a typical terminal. Also considered were
chemical costs and economic offsets.
Consideration was given to various methods of breaking the emulsion at its des -
tination.
-13-
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4. SELECTION OF OILS AND PREPARATION AND TESTING OF EMULSIONS
4.1 Selection of Oils
Three oils were selected to provide sampling of a broad range of petroleum
liquids - two imported crude oils and one petroleum product. A light, high
quality crude, the Zueitina (Libyan) crude oil, was chosen to represent the
light crudes and the low boiling point petroleum fractions. The Tia Juana Medium
(Venezuelan) crude was selected to represent the more common medium gravity
crude oils. #6 fuel oil was chosen as the petroleum product because it is widely
used as ship fuel, and with a specific gravity heavier than water, it represents
the extreme of heavy petroleum fractions. Characteristics of these three oils
are given in the "As Received" columns of Table 4.9-1.
4. 2 Preparation of Test Emulsions
Test emulsions were prepared using each of the three oil samples with each of
two chemical emulsifiers for a total of six test emulsions. The six test emul-
sions were prepared in five gallon batches with a three speed, 30 quart Hobart
mixer (Figure 4.2-1).
4.2.1 Selection of Emulsifiers
The inexpensive chemical emulsifier class, sulfonated methyl ethyl amines, nor-
mally used by the contractor for emulsifying oils, are ionic and not compatible
with sea water. Since compatibility with sea water was important, two new
emulsifiers were developed for use during this study.
The selection of emulsifiers for use in this study was primarily governed by com-
patibility with simulated sea water, cost, toxicity and availability. Considering
the above mentioned factors, three emulsifiers were selected and submitted to
the contractor by the developer of these emulsifiers, Electro-Chem Chess Lab-
oratories of Ft. Worth, Texas. Screening tests by the contractor reduced the
number of emulsifiers to two, which were used throughout the study and herein-
after are referred to by their numbers, 1-1751 and 1-1752.
To prepare an emulsion containing 97 percent hydrocarbon as the internal (dis-
persed) phase, it was necessary to select a predominately water soluble material
which had tendencies to inhibit the mobility of the exterior water phase. These
properties could be achieved by the use of nonionic, ethoxylated materials. How-
ever, nonionics usually are not salt water tolerant, so a sulfated or sulfonated
nonionic was chosen. The base neutralized sulfonated nonionics were used to
reduce emulsifier acidity.
Added emulsion stability could be imparted by the addition of a highly polar sur-
factant. This polarity could be achieved through the use of cationic or anionic
-14-
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materials. The requirement for saltwater compatibile, nontoxic materials
directed the use of amine oxides or betaines. Addition of sufficient potassium
chloride to obtain 0.002 molar KC1 in the continuous phase increased the stability
of the finished emulsion.
The several emulsifiers tested were various blends based on the above discus-
sion. The two blends chosen for this study were:
1-1751
N-Alkyl, polyethoxy ammonium sulfate
N-Alkyl, amido tertiary amine oxide
Potassium chloride
Inert solvent
1-1752
N-Alkyl, polyethoxy ammonium sulfate
N-Alkyl, amido tertiary amido sulfobetaine
Potassium chloride
Inert solvent
4.2.2 Emulsification Procedure
The procedure for emulsification used in this study was a two step method,
which first prepares an "emulsion seed", ultrasonically, then gradually blends
the bulk of the dispersed (hydrocarbon liquid) phase into the "emulsion seed" to
produce the desired emulsion. ^ The "emulsion seed" consists of 30 percent
continuous phase (in this project 25 percent water and 5 percent emulsifier)
and 70 percent dispersed phase (one of the three oils used in this study). The
"emulsion seed" was prepared by agitating the constituents to form a coarse
emulsion premix. The premix was then subjected to ultrasonic cavitation
provided by a 500 watt, 20 kilohertz, homogenizer horn. A volume of "emul-
sion seed" (Figure 4.2-2), equivalent to 10 percent of the volume of end pro-
duct emulsion, was poured into the 30 quart bowl of the Hobart mixer (Figure
4.2-1). With the mixer paddle rotating, the remaining 90 percent of the dis-
persed phase was blended into "emulsion seed" to produce the finished emul-
sion (Figure 4. 2-3). The mixer speed was varied from high to low during the
blending operation.
Test emulsions were prepared by the above described batch process to assure
consistent composition for the test emulsions. A continuous flow system em-
ploying the same concept was used for bench-scale determinations covered
under section 5 of this report.
4.2.3 Emulsion Storage
Five gallons of each test emulsion was prepared. Each batch was stored in two
-15-
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Figure 4.2-1
30-Quart Hobart Mixer
Figure 4.2-2
"Emulsion Seed" (x 210)
Figure 4.2-3
Finished Emulsion (x 210)
-16-
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2-gallon jars and six 1-quart jars at 20°C (68° F).
4.3 Emulsion Stability
4.3.1 Method
Long term stability of the emulsions was tested under various conditions for
periods in excess of normal transportation times. The test procedure con-
sisted of periodic visual observation and determination of the yield value of
each emulsion. Stability was tested under the following conditions:
1. Stability during ambient temperature while quiescent.
2. Stability during - 4° C (25° F) while quiescent.
3. Stability during 50-60° C (122-140° F) while quiescent.
4. Stability during repeated freeze/thaw cycles.
5. Stability under simulated ship motion at ambient temperature.
Visual observations consisted of examination of the emulsion to determine the
amount of break-back, stratification and/or changes in physical characteristics.
If no visual changes were observed, the emulsion was considered stable.
Emulsion stability was further evaluated by periodic measurement of yield values
of the emulsions. A cone penetrometer apparatus, (Figure 4.3-1) specified in
ASTM D-217 and modified as recommended for use with emulsified fuels , was
used in these tests. Yield values not significantly different from original values
were considered indicative of emulsion stability. For each test or phase of test
of temperature and motion stability of the emulsion, a one quart glass jar was
filled sufficiently to provide a ten centimeter depth of emulsion. The filled jars
were placed in the desired environment and periodic observations and determina-
tions made.
For tests of stability during ambient temperature while quiescent, the test con-
tainers were placed on a warehouse shelf where the maximum temperature vari-
ation was from 18° to 28°C (64-82° F).
For stability during -4°C (25° F) quiescent tests, the jars were placed in a re-
frigerator and held at -4° t 2°C. Yield values were not determined since tem-
peratures were below the pour point of two of the oils.
To determine the stability of the emulsions in a quiescent, elevated temperature
environment, the test jars were placed in a test chamber where the temperature
was maintained at 50-60° C (122-140°F).
Freeze thaw stability was determined by transferring the test jars between the
refrigerator and the elevated temperature chamber. A residence of two days in
each chamber was allowed during each four day cycle. Yield values were
-17-
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Figure 4.3-1
Cone Penetrometer, Modified
Figure 4.3-2
Motion Apparatus, Modified
-18-
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determined at the end of each of the five cycles.
Stability during simulated ship motion at ambient temperatures was determined
by placing the test jars in a box which was clamped on a Ro-Tap sieve shaker
(Figure 4.3-2) that was geared down to provide a 56 rpm rotation through a cir-
cular pattern with all/4 inch diameter. The ambient temperature of the room
housing the Ro-Tap machine varied from 18 to 28° C (64-82° F). The emulsions
were allowed to relax by undisturbed standing for five days prior to starting the
ship motion stability test. After 20 continuous days of simulated ship motion,
the emulsions were allowed two days of quiescence followed by eight additional
days of resumed ship motion.
4.3.2 Emulsion Stability Data
Table 4.3-1 presents the data collected during the above described stability test-
ing.
Figures 4.3-3 through 4.3-5 are graphic presentations of the yield stability dur-
ing ambient temperature quiescence. Figures 4.3-6 through 4.3-8 are graphic
presentations of emulsion yield stability at 50-60°C (122-140° F) in a quiescent
environment. Figures 4.3-9 through 4.3-11 are graphic presentations of the
emulsion yield stability during five four day freeze/thaw cycles. Figures 4.3-12
through 4. 3-14 are graphic presentations of emulsion stability during simulated
ship motion at ambient temperature.
4.3.3 Discussion of Emulsion Stability
When subjected to a quiescent environment with an ambient temperature of 18 to
28° c (64-82°F) for ninety days, the emulsion remained stable. (Figures 4.3-3
to 4.3-5). The crude oil emulsions sustained a continual, slow relaxation,
which was reflected as a gradual reduction in yield value. The relaxation was
never complete enough to allow phase separation, that is, the formation of free
oil. The#6 Fuel Oil emulsion relaxed less than the crude oil emulsions because
it was made with 0. 8 percent emulsifier rather than 0. 5 percent used to make the
crude oil emulsions. Nixon, Philippoff and Siminski 3 found that the initial yield
and the yield stability increased with increases in the amount of emulsifier used
to form a jet fuel emulsion.
These emulsions were relatively stable in a cold (-4°C), quiescent environment.
Yield value determinations were not made during these tests. However, all six
emulsions were "stiffer" in the chilled state - especially the Zuietina crude and
#6 Fuel Oil emulsions. This increased emulsion stiffness can be attributed pri-
marily to the increase in oil viscosity, reflected by the high pour point of the
oils. These tests were conducted at a temperature considerably below the pour
point of both the Zueitina crude and the #6 Fuel Oil (see Table 4.9-1 for the char-
acteristics of oil samples). The Tia Juana medium crude emulsified with 1-1751
-19-
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TABLE 4. 3-1
EMULSION STABILITY AS INDICATED BY YIELD VALUES
Stability Test
Emulsion Yield Values (dynes/cm2)
Zueitina with Tia Juana with # 6 Fuel Oil with
1-1751 1-1752 1-1751 1-1752 1-1751 1-1752
Initial 600
Ambient Temperature,
1 hour 600
1 day 590
10 days 590
30 days 580
60 days 580
90 days 570
-4°C, Quiescent
1 day Stable
10 days Stable
30 days Stable
60 days Stable
50-60°C, Quiescent
1 day 590
10 days 580
30 days 560
Freeze /Thaw Cycles
1 cycle 580
2 cycles 560
3 cycles 530
4 cycles 500
5 cycles 460
Simulated Ship Motion,
Relaxed 590
1 day 600
5 days 600
10 days 600
20 days 600
30 days 600
500
Quiescent
530
510
500
500
500
490
Stable
Stable
Stable
Stable
500
490
460
(4 days per
500
490
470
450
420
600
600
560
550
540
520
510
Stable
Stable
Trace of
free oil
Broken
560
540
510
cycle)
550
530
500
460
Trace of
free oil
550
550
500
490
470
440
400
Stable
Stable
Stable
Stable
500
480
440
500
480
460
430
400
1,800
1,800
1,800
1 , 800
1,800
1,800
1,750
Stable
Stable
Stable
Stable
1,750
1,700
1,600
1,750
1,750
1,700
1,700
1,650
1,550
1,550
1,550
1,500
1,500
1,500
1,500
Stable
Stable
Stable
Stable
1,500
1,450
1,400
1,500
1,500
1,450
1,450
1,450
Ambient Temperature
510
510
520
520
520
520
560
570
570
570
570
570
500
510
510
510
510
510
1,800
1,800
1,800
1,800
1,800
1,800
1,500
1,500
1,500
1,500
1,500
1,500
-20-
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I
to
FIGURE 4.3-3
STABILITY TO AMBIENT TEMPERATURE QUIESCENCE
ZUEITINA EMULSIONS
Emulsified with I-
Emulsified with 1-1752
Ambient Temperature
(64° - 82°F)
400
60
TIME (days)
105
120
-------
I
to
to
6
U
H
FIGURE 4.3-4
STABILITY TO AMBIENT TEMPERATURE QUIESCENCE
TIA JUANA EMULSIONS
A -Emulsified with 1-1751
D -Emulsified with 1-1752
Ambient Temperature
(64° - 82°F)
450
400
60
TIME (days)
120
-------
FIGURE 4.3-5
STABILITY TO AMBIENT TEMPERATURE QUIESCENCE
#6 FUEL OIL EMULSIONS
IsS
CO
1800
s
o
I
&
1700
1600
1500
1400
A-Emulsified with 1-1751
-Emulsified with 1-1752
,
Ambient Temperature
(64° - 82°F)
60
TIME (days)
120
-------
FIGURE 4.3-6
STABILTIY TO 50° - 60° C QUIESCENCE
ZUEITINA EMULSIONS
i
to
CN
a
u
£
S-
M
S
-Emulsified
-Emulsified
500
450
400
35
40
TIME
-------
to
en
i
FIGURE 4.3-7
STABILITY TO 50° - 60° QUIESCENCE
TIA JUANA EMULSIONS
-Emulsified with I
-Emulsified with I
400
0
10
15 20
TIME (days)
25
30
35
40
-------
FIGURE 4.3-8
STABILITY TO 50° - 60°C QUIESCENCE
# 6 FUEL OIL EMULSIONS
to
CN
6
o
en
w
D
_1
$
3
Pfl
1800
1700
1600
1500
1400
-Emulsified with 1-1751
-Emulsified with 1-1752
20
TIME (days)
30
35
-------
FIGURE 4.3-9
STABILITY TO FREEZE-THAW CYCLES
ZUEITINA EMULSIONS
-J
I
CN
B
o
T3
3
600
550
500
450
400
-Emulsified with 1-1751
-Emulsified with 1-1752
CYCLES (4 days/cycle)
-------
FIGURE 4.3-10
STABILITY TO FREEZE-THAW CYCLES
TIA JUANA EMULSIONS
oo
I
a
CJ
03
CD
a
600
550
500
450
400
A -Emulsified with 1-1751
-Emulsified with 1-1752
CYCLES (4 days/cycle)
-------
to
\o
I
FIGURE 4.3-11
STABILITY TO FREEZE-THAW CYCLES
#6 FUEL OIL EMULSIONS
1800
CS
£
o
CQ
1700
Q
_I
CtJ
1600
1500
1400
A-Emulsified with 1-1751
-Emulsified with 1-1752
CYCLES (4 days/cycle)
-------
FIGURE 4.3-12
SHIP MOTION STABILITY
ZUEITINA EMULSIONS
I
co
o
I
CM
O
w
Ol
H
3
Q
-I
W
i «
>H
600 4
575
550
525
500
20
TIME (days)
35
-------
s
o
w
3
W
FIGURE 4.3-13
SHIP MOTION STABILITY
TIA JUANA EMULSIONS
550
525
500
475
450
A -Emulsified with 1-1751
-Emulsified with 1-1752
Ambient Temperature
(64° - 82°F)
'
1 I ' '
0|-L_]_L_4
J_U.l
_U_J_J
15 20
TIME (days)
35
-------
FIGURE 4.3-14
SHIP MOTION STABILITY
# 6 FUEL OIL EMULSIONS
I
Go
to
I
cs
CO
T3
w
3
w
11
!x
1800A
1700
1600
1500
1400
A -Emulsified with 1-1751
D-Emulsified with 1-1752
Ambient Temperature
(64° - 82°F)
15 20
TIME (days)
-------
was the only emulsion to break and separate into its constituent phases during
these tests.
All six emulsions remained stable throughout 30 days of exposure to elevated
temperature (50-60° C) quiescent (Figures 4.3-6 through 4. 3-8). As expected,
the emulsions relaxed much more rapidly in an elevated temperature environ-
ment that in the ambient temperature environment.
Test emulsions were generally stable to repeated freeze/thaw cycles (Figures
4.3-9 through 4.3-11). The freeze/thaw cycles caused the most rapid rate of
emulsion relaxation observed during emulsion stability testing.
The stability of each emulsion was enhanced by simulated ship motion (Figures
4.3-12 through 4.3-14). The emulsions had higher yield values after five
days of simulated ship motion than after five days of quiescent relaxation. These
higher yields were maintained as long as the simulated ship motion continued.
In conclusion, the emulsion stability determinations revealed satisfactory
stability, in a quiescent environment, over a broad range of temperatures.
Gentle agitation, provided by simulated ship motion, improved emulsion stability.
4.4 Dispersion of Emulsion in Sea Water
4^4.1 Method
To determine the stability of a high concentration of dispersed emulsion such as
would be expected in the immediate vicinity of a major spill, a one percent (by
volume) solution of emulsion in the standard, synthetic sea water (see Section
4.7.3 for a discussion of standard sea water) was placed on the test apparatus
for simulated wave motion (described in Section 4.3.1) for a period of 96 hours.
Each test sample was prepared by adding 5 milliliters of emulsion to 495 milli-
liters of standard sea water in a one quart glass container. Each container was
shaken to achieve complete dispersion of the emulsion. The dispersed emulsion
was then allowed to stand undisturbed for one hour, after which visual observa-
tions were made for any indications of break-out of free oil.
After recording the one hour observations, each sample was placed on the test
unit which provided a constant gentle agitation comparable to that of a. calm sea.
Visual observation of the dispersed emulsions were recorded after 24, 48 and
96 hours of agitation. The visual observations consisted of determining the per-
cent ofthefivemllliliter charge emulsion which was present as free oil, as float-
ing emulsion (as a concentration of emulsion which collected near the surface of
the water, but could be redispersed by stirring or more vigorous agitation than
that provided by the simulated wave motion) and as uniformly dispersed emulsion.
Also recorded were any unusual phenomena.
-33-
-------
The same method, using 0. 5 milliliters of emulsion in 499.5 milliliters of stan-
dard sea water, as described above was used for a 0.1 percent, or 1,000 parts
per million solution. Also considered was the behavior of the emulsion dispersed
at various concentrations for the toxicity determinations (Section 4.7).
4.4.2 Emulsion Dispersion Data
Test results using the one percent dispersion determinations are presented in
Table 4.4-1 and Figures 4. 4-1 through 4. 4-3. Test results with the 0.1 per-
cent determinations are presented in Table 4.4-2 and Figures 4.4-4 through
4.4-6. Observations on emulsion dispersion during toxicity testing were taken
from the laboratory notes and incorporated in Section 4. 4. 3 Discussion of Emul-
sion Dispersion.
4.4.3 Discussion of Emulsion Dispersion
The concentration of dispersed emulsion would be relatively high in the imme-
diate vicinity of a major emulsified oil spill on the open sea. A short distance
(a few inches) from the spilled emulsion, the concentration would be about one
percent or 10,000 parts per million. The concentration would rapidly diminish
to 0.1 percent, or 1, 000 parts per million. This rapid dispersion would result
from the tendency of the minute oil droplets (1 to 10 microns in diameter) to be
released and repelled by the emulsion mass as a result of the surface tension
phenomena encountered when emulsions of the type used in this study are brought
into contact with water. The tendency of the emulsion to disperse would be aided
by wind and wave action.
In the one percent dispersion tests (Table 4.4-1 and Figures 4.4-1 through 4.4-3),
the two crude oil emulsions formed a dispersion within this confined volume, which
was stable and remained uniformly dispersed during one hour of quiescence. One
hour would be sufficient time for the emulsion to be extensively dispersed in a
normal sea environment. The crude oil emulsions displayed remarkable disper-
sion stability in the presence of mild agitation for two days. After 24 hours of
simulated wave motion, less than five percent of the dispersed charge emulsion
had coalesced to form free oil. The remaining 95+ percent was still dispersed
or present as a floating emulsion which could be readily redispersed with a
slightly more intense agitation than that provided by the shake tester. After 48
hours, only 10 percent of the dispersed emulsion had formed as free oil. After
96 hours, 70 to 80 percent of the emulsion was present as free oil.
The one percent solution of #6 Fuel Oil emulsion was much more difficult to dis-
perse and keep dispersed than the crude oil emulsions. After one hour of quies-
cence one-half of the #6 Fuel Oil emulsion was dispersed and the other half was
a floating emulsion which was not easily redispersed. As the emulsion coalesced,
it entrapped considerable free water and formed "balls" on the water surface.
After 96 hours of simulated wave motion, 70 percent of the emulsion was present
-34-
-------
Ctf
TABLE 4.4-1
TIME STABILITY OF 1% DISPERSED EMULSION
TIME
AFTER
START
(hours)
0
1
24
48
96
PORTION OF CHARGE EMULSION (%)
Zueitina Emulsified With
1-1751
FO
0
0
5
30
80
FE
0
0
50
50
10
DE
100
100
45
20
10
1-1752
FO
0
0
tr*
10
70
FE
0
0
40
50
20
DE
100
100
60
40
10
Tia Juana Emulsified With
1-1751
FO
0
0
tr*
10
70
FE
0
0
30
35
25
DE
100
100
70
55
5
1-1752
FO
0
0
5
10
70
FE
0
0
40
40
20
DE
100
100
55
50
10
#6 Fuel Oil Emulsified With
1-1751
FO
0
0
30
60
70
FE
0
50
40
30
30
DE
100
50
30
10
0
1-1752
FO
0
0
20
40
70
FE
0
20
20
30
30
DE
100
80
60
30
tr*
FO = Free Oil
FE = Floating Emulsion
DE = Dispersed Emulsion
tr = trace (less than 1%)
-------
FIGURE 4.4-1
STABILITY OF 1% DISPERSED EMULSION
CO
o
i
2
w
w
o
BJ
u
PH
O
z
9
E-
c^
2
DISPERSED
EMULSION
5 ml emulsion
495 ml sea water
1 24 48
Zueitlna emulsified with
96 1 24 48 96
1-1751 Zueitina emulsified with 1-1752
SHAKE TIME (hours)
-------
100
FIGURE 4.4-2
_TIME STABILITY OF 1% DISPERSED EMULSION
III
111
FREE
OIL
FLOATING
EMULSION
DISPERSED
EMULSION
Test Composition
5 ml emulsion
495 ml sea water
I 24 48
Tia Juana emulsified with
96 1 24 48 96
1-1751 Tia Juana emulsified with 1-1752
SHAKE TIME (hours)
-------
CO
OO
D
s
w
w
o
&
<
£
O
fe
o
2
S
E-
100
90
FIGURE 4.4-3
TIME STABILITY OF 1% DISPERSED EMULSION
FREE
OIL
FLOATING
EMULSION
DISPERSED
EMULSION
Test Composition
5 ml emulsion
495 ml sea water
24 48 96 1 24 48 96
#6 Fuel Oil Emulsified with 1-1751 #6 Fuel Oil Emulsified with 1-1752
SHAKE TIME (hours)
-------
as floating masses of water-in-oil emulsion.
In the 0.1 percent (1,000 parts per million) dispersion tests (Table 4. 4-2 and
Figures 4.4-4 through 4.4-6) all three emulsions formed stable dispersions.
The Zueitina emulsions formed dispersions which were stable for two days of
motion testing, and showed only slight tendencies to stratify after 96 hours.
The Tia Juana and #6 Fuel Oil emulsions formed stable dispersions for one
day, displayed tendencies toward stratification after the second day, and had
begun to form free oil after 96 hours on the motion tester.
During the 96 hour toxicity tests, the emulsions all remained well dispersed at
all concentrations below 600 parts per million. Above 600 parts per million,
the Tia Juana and #6 Fuel Oil emulsion dispersions had tendencies to stratify
after 48 hours, thus allowing portions of the emulsions to float to the surface.
In the case of the dispersed Tia Juana emulsion, this floating emulsion was
easily redispersed by additional hand stirring with a glass rod. The dispersed
#6 Fuel Oil emulsions developed a trace of free oil, which would not redisperse,
on the water surface. After 96 hours, free oil was present as a uniform thin
film. There was no "balling" or coalescence of the #6 Fuel Oil emulsion as was
observed in the dispersion tests.
As the emulsion disperses, the emulsifier, which is primarily hydrophilic, is
diluted with water and freed from the oil droplets. As the emulsifier is lost,
the droplets become widely separated so that there is little tendency to coalesce,
even with no emulsifier remaining. For example, assume a spill, creating a
mass of emulsified oil, from which emulsion is being dispersed at a rate of
10,000 barrels per day. Further assume an ocean current of one knot, and
that the plume of contaminated water downstream widens at an angle of 10 de-
grees from the center line and deepens to 250 feet. If the dispersal of one
element of emulsion is followed as it is carried away, in one hour the oil con-
centration will be down to 0.7 milligrams per liter. Thus, it appears likely
that, as emulsifier is lost, the droplets will become too widely dispersed to
agglomerate. No slick should form under these conditions.
In summary, the dispersed emulsions each displayed a high degree of stability.
All data indicate that the emulsions would be so completely dispersed by natural
sea forces that the minute droplets of oil would not coalesce to form an oil
slick, even though the emulsifiers had been lost due to dilution by sea water.
Indications are that the spilled emulsion would be dispersed within a day's time,
to a concentration well below the presently accepted 100 parts per million for
oily waste waters. At concentrations below 100 parts per million, the oil
droplets are so completely dispersed that droplets coalescence would rarely
occur.
4. 5 Evaporation Rate Tests
-39-
-------
TABLE 4.4-2
TIME STABILITY OF 0. 1% DISPERSED EMULSION
TIME
AFTER
START
(hours)
0
1
24
48
96
PORTION OF CHARGE EMULSION (%)
Zueitina Emulsified With Tia Juana Emulsified With #6 Fuel Oil Emulsified With
1-1751
FO
0
0
0
0
0
FE
0
0
0
0
5
DE
100
100
100
100
95
1-1752
FO
0
0
0
0
0
FE
0
0
0
0
5
DE
100
100
100
100
95
1-1751
FO
0
0
0
0
tr*
FE
0
0
5
15
25
DE
100
100
95
85
75
1-1752
FO
0
0
0
0
5
FE
0
0
5
20
30
DE
100
100
95
80
65
1-1751
FO
0
0
0
tr*
10
FE
0
10
20
35
40
DE
100
90
80
65
50
1-1752
FO
0
0
0
0
5
FE
0
10
20
40
50
DE
100
90
80
60
45
FO = Free Oil
FE = Floating Emulsion
DE - Dispersed Emulsion
'tr = trace (less than 1%)
-------
2
O
HH
CO
w
9
ei
-------
100
90
80
8
§ 70
CO
FIGURE 4.4-5
TIME STABILITY OF 0.1% DISPERSED EMULSION
H
60
50 ^
40
a 30
txt
2 20
10
0
I
"
l"A
V % %
&%/&
'
I
m
1
FREE
OIL
FLOATING
OIL
DISPERSED
EMULSION
Test Composition
0.5 ml emulsion
500 ml sea water
24
48
96
24
48
96
Tia Juana emulsified with 1-1751 Tia Juana emulsified with 1-1752
SHAKE TIME (hours)
-------
00
i
W
w
o
U
fo
O
z
o
8
100
90
80
70
60
50
40
30
20
10
0
FIGURE 4.4-6
TIME STABILITY OF 0.1% DISPERSED EMULSION
::: ::;
::: : ::
' * »* *
in
in
1
vv
i
1
i
^
XX
^
^
^
^
i>: / V-V
^> i '*
^^ !
oo .
^ ^ $
^ ^ ^
in
i
1
i
i
Pi!
'.,
!
FREE
m °IL
X FLOATING
::: OIL
rX;
V/ DISPERSED
^J EMULSION
Test Composition
0.5 ml emulsion
500 ml sea water
1 24 48 96 1 24 48 96
#6 fuel oil emulsified with 1-1751 #6 fuel oil emulsified with 1-1752
SHAKE TIME (hours)
-------
4.5.1 Method
The contractor's concept of the factors involved in the evaporation of these
emulsions is described as follows:
1. Encapsulating water jacket loses water and ruptures.
2. Free oil thus released loses light fractions.
3. Protective layer of heavy fractions forms.
4. Cycle of rupture and loss of material repeats at a
reduced rate.
Under closed conditions, the vapor phase above the emulsion would reach a
state of equilibrium with the liquid phase. In this study, losses of material from
various vented systems would be more representative of conditions expected,
therefore, the following procedure was selected.
To measure evaporation loss, an amount of emulsion was placed in a 3. 8 inch
diameter petri dish (61 cm^ surface area) 1/2 inch in height and weighed. Peri-
odic weighings were recorded to determine weight loss. Determinations were
obtained for the following three sets of conditions:
1. A full open dish.
2. A half filled open dish.
3. A half filled dish covered with 1/4 inch vented cover.
The dishes were weighed on two analytical balances (Figure 4.5-1).
Figure 4.5-1 Analytical Balances with Petri Dishes being Weighed
-44-
-------
w
CO
O
O
FIGURE 4.5-2
ACCUMULATIVE WEIGHT LOSS
ZUEITINA CRUDE OIL & EMULSION
O-Zueitina Crude Oil
A-Zueitina Emulsified with/I-1751
D-ZueJtina Emulsified with/I-1752
Full, open dish
1,000
10,000
ELAPSED TIME (minutes)
-------
*«
CO
T3
cs
w
-Q
O
H
O
0,
FIGURE 4.5-3
EVAPORATION RATE
ZUEITINA CRUDE OIL & EMULSION
O- Zueitina Crude Oil
A- Zueitina Emulsified with/I-1751
D- Zueitina Emulsified with/1-1752
Full, open dish
100
ELAPSED TIME (minutes)
1,000
10,000
-------
FIGURE 4.5-4
ACCUMULATIVE WEIGHT LOSS
#6 FUEL OIL & EMULSION
CN
4-1
w
o
-I
h
X
o
O-#6 Fuel Oil
A- #6 Emulsified with/I-1751
D- #6 Emulsified with/I-1752
Full, open dish
,0001
1,000
10,000
ELAPSED TIME (minutes)
-------
J
*
00
I
a
CO
§
g
W
FIGURE 4. 5-5
EVAPORATION RATE
#6 FUEL OIL & EMULSION
O-#6 Fuel Oil
-#6 Emulsified with/I-1751
Q- #6 Emulsified with/I-1752
Full, open dish
100
ELAPSED TIME (minutes)
1,000
10,000
-------
FIGURE 4.5-6
ACCUMULATIVE WEIGHT LOSS
ZUEITINA CRUDE OIL & EMULSION
CN
CO
O
O
O- Zueitina Crude Oil
A- Zueitina Emulsified with/I-1751
Q- Zueitina Emulsified with/I-1752
Half filled, open dish
,001
100
ELAPSED TIME (minutes)
1,000
10,000
-------
en
o
I
cd
o
CO
s
<
>
W
FIGURE 4.5-7
EVAPORATION RATE
ZUEITINA CRUDE OIL & EMULSION
O - Zueitina Crude Oil
A- Zueitina Emulsified with/I-1751
D - Zueitina Emulsified with/I-1752
Half filled, open dish
100 1,000
ELAPSED TIME (minutes)
10,000
-------
FIGURE 4. 5-8
ACCUMULATIVE WEIGHT LOSS
TIA JUANA CRUDE OIL & EMULSION
co
CO
O
Q
»l
W
j. , : : i !. I;: |'.:
O- Tia Juana Crude Oil
A- Tia Juana Emulsified with/I-1751
U- Tia Juana Emulsified with/I-1752
Half filled, open dish
0001
100
ELAPSED TIME (minutes)
1,000
10,000
-------
ctf
*O
CN
4, £
V JS
W
FIGURE 4.5-9
EVAPORATION RATE
TIA JUANA CRUDE OIL & EMULSION
O- Tia Juana Crude Oil
A- Tia Juana Emulsified with/I-1751
D- Tia Juana Emulsified with/I-1752
Half filled, open dish
100
ELAPSED TIME (minutes)
1,000
10,000
-------
en
co
i
FIGURE 4.5-10
ACCUMULATIVE WEIGHT LOSS
#6 FUEL OIL & EMULSION
CN
CO
.Q
CO
CO
O
O-#6 Fuel Oil
Emulsified with/I-1751
- #6 Emulsified with/I-1752
Half filled, open dish
,001
,0001
100
ELAPSED TIME (minutes)
1,000
10,000
-------
on
FIGURE 4. 5-11
EVAPORATION RATE
#6 FUEL OIL & EMULSION
rt
o
to
2
O
§
w
#6'Fuel Oil
#6'Emulsified with/I-1751
#6 Emulsified v/ith/I-1752
Half filled, open dish
.001
,0001
100
ELAPSED TIME (minutes)
1,000
10,000
-------
O1
en
w
£1
C-
w
CO
O
_1
H
3G
O
FIGURE 4. 5-12
ACCUMULATIVE WEIGHT LOSS
ZUEITINA CRUDE OIL & EMULSION
.- '; . ' L:_'_j ;.L_J_4. ; -J.-,'-__.___U :__[
J-l
. i i i : ; : ; i . ; . ; i . ; : :
O- Zueitina Crude Oil
A- Zueitina Emulsified with/I-1751
- Zueitina Emulsified with/I-1752
Half filled, 1/4" vent
,0001
100
ELAPSED TIME (minutes)
1,000
10,000
-------
en
CN
4-1
<*-!
CO
-Q
Z
o
O
P-I
<
>
w
FIGURE 4.5-13
EVAPORATION RATE
ZUEITINA CRUDE OIL & EMULSION
Q- Zueitina- Crude Oil
- Zueitina Emulsified with/I-1751
Q- Zueitina Emulsified with/I-1752
Half filled, 1/4" vent
001
100
ELAPSED TIME (minutes)
1,000
10,000
-------
cs
\
w
o
FIGURE 4. 5-14
ACCUMULATIVE WEIGHT LOSS
TIA JUANA CRUDE OIL & EMULSION
0.1
.01
,001
,0001
O- Tia Juana Crude Oil
A- Tia Juana Emulsified v/ith/I-1751
D- Tia Juana Emulsified with/I-1752
Half full, 1/4" vent
100
ELAPSED TIME (minutest
1,000
10,000
-------
OO
I
FIGURE 4.5-15
EVAPORATION RATE
TIA JUANA CRUDE OIL & EMULSION
1.0
O- Tia Juana Crude Oil
A- Ti,a Juana Emulsified with/I-1751
D- Tia Juana Emulsified with/I-1752
Half filled, 1/4" vent
100 1,000
ELAPSED TIME (minutes)
10/000
-------
Cfl
FIGURE 4. 5-16
ACCUMULATIVE WEIGHT LOSS
#6 FUEL OIL & EMULSION
.001
en
-Q
CO
CO
O
K-J
h
E
.00001
O- #6 Fuel Oil
A- #6 Emulsified with/I-1751
#6 Emulsified with/I-1752
Half filled, 1/4" vent
,0001
1,000
ELAPSED TIME (minutes)
10,000
-------
o\
o
FIGURE 4. 5-17
EVAPORATION RATE
#6 FUEL OIL & EMULSION
Z
O
O
P-.
<
w
O- #6 Fuel Oil
A- #6.Emulsified with/I-1751
D- #6.Emulsified with/I-1752
Half filled, 1/4" vent
.001
,0001
100 1,000
ELAPSED TIME (minutes)
10,000
-------
4. 5.2 Evaporation Rate Data
All data are presented in Tables 1-1 through 1-27 (Appendix I). Data for con-
ditions of "full, open dish" are shown on Figures 4.5-2 through 4.5-5. Data
for conditions of "half filled, open dish" are shown on Figures 4.5-6 through
4.5-11. Data for "half filled, 1/4 inch vented cover" are shown on Figures
4.5-12 through 4.5-17.
4.5.3 Discussion of Evaporation Rates
The filled, open dish, evaporation rate data (presented graphically in Figures
4.5-2 through 4. 5-5) show that evaporation of the Zueitina crude oil is reduced
by a factor of 10 when the oil is emulsified. The half filled, open dish data
(Figures 4. 5-6 through 4.5-11) show a reduction factor of 5 for the Zueitina
emulsions compared to the free oil. The difference between the filled dish and
the half filled dish is accountable to the evaporation rate of the free oil. The
emulsions, whether in a filled or half filled dish, evaporated at about the same
rate. However, the free oil evaporated from the half filled dish at half its
rate of evaporation from the filled dish. The half filled, open dish of Tia Juana
medium emulsions had an initial evaporation rate one-tenth that of the free crude
oil. Within one hour of exposure to the atmosphere the evaporation rate of the
free oil was only five times as great as that of the emulsions.
The #6 Fuel Oil emulsions showed a reversal of trend. The free oil initially evap-
orated at a rate approximately one-tenth that of the emulsions. This reversal
may, in part, be explained by the extremely low vapor pressure of the #6 Fuel
Oil. The vapor pressure of the #6 Fuel Oil at 100° F was less than the vapor
pressure of water under the same conditions.
The rate of evaporation in the vented dish was quite different than in the open
dish. In the half filled one fourth inch vent covered dish evaporation rate tests,
data (Figures 4.5-12 through 4.5-17) indicate a rate of evaporation for the emul-
sions which is comparable to the rate for the free oil. This was the case for all
three oils and the emulsions. For the Zueitina crude and emulsion, the evapo-
ration rate for both emulsions and the free oil was approximately one-tenth the
rate of the open dish emulsions. The evaporation rate of free oil and emulsions
in the vented dish was approximately one one hundredth the evaporation rate of
the free oil in the open dish.
The vented dish evaporation rate tests indicate that no significant reduction in
cargo evaporation loss can be expected as a result of emulsification. However,
in the event of an exposed spill the evaporation rate would be substantially re-
duced with a corresponding reduction in hazard to sea craft in the vicinity of a
spill.
Additionally, the ligher fractions of the petroleum would be retained by the emulsion
-61-
-------
until dispersion had widely separated the oil droplets. The retention of the
light fractions would tend to prevent formation of the thick, sticky mass which
so often appears a few days after a large oil spill.
4.6 Increased Safety
One major hazard of hydrocarbon transportation is fire. This hazard can be
minimized or eliminated by thickening the petroleum crudes or products to be
carried. Emulsification is one of the best approaches from both technical and
practical standpoints for thickening such materials. Laboratory tests have been
developed for measuring the characteristics of hydrocarbons that contribute to
fire hazards. For this study, two tests were selected: (1) Flash point deter-
mination and (2) Vapor pressure determination.
4.6.1 Flash Point Determinations
4.6.1.1 Method
Flash point determinations were performed in accordance with STANDARD
METHOD OF TEST FOR FLASH POINT BY MEANS OF THE PENSKY-MARTENS
CLOSED TESTER (ASTM designation: D 93). Of two standard accepted methods
for flash point determinations, the Pensky-Marten Procedure is used for the less
volatile and more viscous petroleum products and is considered superior for
flash point determinations of emulsions.
4.6.1.2 Flash Point Data
Comparison of flash point determinations for the various test samples are shown
in Table 4.6-1. Included are data for the sample "as received" as well as data
for the emulsions (two emulsifiers).
TABLE 4.6-1
COMPARISON-FLASH POINTS
(Pensky-Martens Method)
As Received Emulsified
Crude or Product (°F) Emulsifier (°F) Change (° F)
Zueitina 42
Tia Juana 64
#6 Fuel Oil 220
1-1751
1-1752
1-1751
1-1752
1-1751
1-1752
84
82
96
92
240
240
+ 42
+ 40
+ 32
+ 28
+ 20
+ 20
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4.6.2 Vapor Pressure Determinations
4.6.2.1 Method
Reid vapor pressure determinations for this study were performed in accordance
with STANDARD METHOD OF TEST FOR VAPOR PRESSURE OF PETROLEUM
PRODUCTS (ASTM Designation D 323).
4.6.2.2 Vapor Pressure Data
Comparisons of vapor pressures are shown in Table 4.6-2. Vapor pressures
were determined for the samples "as received" as well as the samples in their
emulsified form (two emulsifiers).
TABLE 4.6-2
COMPARISON-VAPOR PRESSURES
(Reid Method)
Pressure at 100° F
As Received Emulsified
Crude or Product (psia) Emulsifier (psia) Change (%)
Zueitina 8.2 1-1751 4.2 -49
1-1752 4.8 -41
Tiajuana 4.2 1-1751 2.1 -50
1-1752 2.3 -45
#6 Fuel Oil 0.4 1-1751 0.1 -75
1-1752 0.1 -75
4.6.3 Rupture_Leakage Tests
4.6.3.1 Method
Yield value is a standard test to measure the reluctance of emulsion type mate-
rial to flow through holes or ruptures. Viscosity is typically used to compare flow
characteristics of Newtonian fluids. In this study, yield values were determined
by the modified ASTM D 217 method and viscosities were measured by ASTM D 445
(Ostwald modification).
In addition, qualitative tests to determine rates of water influx from the sea
environment and spill rate to the atmosphere were performed. Procedures for
these tests were as follows:
-63-
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Water Influx - consisted of puncturing a 2 7/8 inch diameter by 5 inch high can
with a chisel to form a 1 inch by 1/4 inch rupture, 1/8 inch from the bottom of
the can. The can was filled to a 4 inch level with 500 ml of emulsion or oil and
placed in a fish acclimatizing tank filled with 20° C (68° F) synthetic sea water.
Water agitation was created by intermittent hand stirring with an 8 inch square
board in a plunger motion, up and down, to create waves. After two hours in
the tank, the rupture was covered, the can removed and the influxed sea water
drained into a graduated cylinder and the amount of water measured.
Spill rate - used the same ruptured can as described above. The spillage rate
was recorded in ml/sec as the material was allowed to drain from the container,
filled to a liquid level of 4 inches, into a graduated cylinder under atmospheric
conditions.
4.6.3.2 Rupture Leakage Data
Table 4. 6-3 gives the flow properties of the oils and emulsions as indicated by
viscosity and yield values. Table 4.6-4 presents the influx of s©a water
tests results and Table 4.6-5 gives the spill rate of the oils and emulsions.
TABLE 4.6-3
OIL AND EMULSION FLOW PROPERTIES
As Received Emulsified
Crude or Product Viscosity Emulsifier Yield Value
(cp) (dynes
Zueitina 3.4 1-1751 600
1-1752 500
Tiajuana 26.0 1-1751 600
1-1752 550
#6 Fuel Oil 2490 1-1751 1800
1-1752 1550
-64-
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TABLE 4.6-4
RUPTURE TESTS-INFLUX OF SEA WATER
Crude or Product
Zueltina
Tia Juana
#6 Fuel Oil
As Received
Emulsified
Emulsifier Influx
(ml)
109
101
64
1-1751
1-1752
1-1751
1-1752
1-1751
1-1752
(ml)
15
21
16
17
0.5
1.0
Crude or Product
Zueitina
Tia Juana
#6 Fuel Oil
TABLE 4.6-5
RUPTURE TESTS-SPILL RATE
As Received
Emulsified
Emulsifier Spill
(ml/sec)
230
170
0.8
1-1751
1-1752
1-1751
1-1752
1-1751
1-1752
(ml/sec
0.5
0.4
0.4
0.4
0.0
0.0
4.6.4 Discussion of Increased Safety
Problems of safety in transportation of petroleum crudes and products closely
parallel the problems of handling fuels. Considerable work has been done in
this field to change characteristics of fuels to improve safety. Emulsification
of fuels leads most other developments in this problem area as a possible so-
lution.
The relative flammability of various materials is typically used to measure the
-65-
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danger involved. Rates of vaporization, flash points, and time required for
materials to begin to burn are considerations in determining relative flammability.
Emulsions reduce the rate at which combustible vapors are released from the
hydrocarbon phase. The two laboratory tests selected to measure improvements
in reduction of flammability for this study were flash point and vapor pressure.
The flash point of a material is determined through the exposure of the material
to a flame under controlled conditions. The flash point is recorded as the temp-
erature read on a thermometer submerged in the test material at the time the
flame application causes a distinct flash in a measuring cup. Flash points are
compared in Table 4.6-1. It can be seen that the high gravity Zueitina crude has
a much lower flash point than the Tia Juana Medium gravity crude which in turn
is substantially less than the #6 Fuel Oil. Increases in flash point represent im-
proved conditions from the standpoint of safety. The necessity for improvement
is much greater for low flash point petroleum crudes which represent a much
more hazardous material to transport.
Vapor pressure is a measure of the tendency of a liquid to vaporize. Explo-
sions of vapors , caused by the vaporization of hydrocarbon materials, is one
of the hazards in transporting and handling hydrocarbon materials. Rates of
vaporization represent a second approach to determining the relative flammability
of various materials. A comparison of vapor pressures for the various test
materials is shown in Table 4.6-2. Substantial reductions in vapor pressure
were achieved through the emulsified forms for all of the test samples used in
this study. This is contrary to what would be expected thermodynamically for
the vapor pressure of two immiscible phases in equilibrium. It must be con-
cluded that the emulsions lost vapor so slowly that equilibrium was not obtained
during the Reid vapor test. These results are in agreement with published data
on the Reid vapor pressure of fuel emulsions.
Flow properties of emulsions differ greatly from those of the raw forms of the
material itself. Emulsions of the type prepared and tested in this study can be
moved through conventional piping, yet will resist flow out of a hole or rupture
in a containing vessel. A comparison of apparent viscosity for the raw material
with penetrometer yield values for the emulsified form is shown in Table 4. 6-3.
Results are typical for emulsions prepared with the type emulsifiers used in this
study. Emulsions with stiffer textures can be obtained with different emulsifiers;
however, emulsifier optimums were beyond the scope of the present study.
There are numerous other considerations and laboratory tests, not performed in
this study, to measure improvement in safety of emulsified liquid hydrocarbons
compared to the free oil. Burning rate is often considered. Emulsions will al-
ways start to burn at a slower rate, and this additional short time available at
the start of a catastrophe often permits control. Flame propagation is another
consideration in determining relative flammability. This test measures the speed
at which flame moves along a path under controlled conditions. Flame propagation
-66-
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times are substantially increased for hydrocarbon liquids in emulsified form .thus
again allowing additional time at a critical point. Formation of ignitable mixtures
on impact of vessels is also severly slowed for emulsified combustible liquids as
compared with free oils.
In loading and unloading liquid hydrocarbons, static charge build-up is an always
potentially serious hazard. Emulsions are so much more conductive than free
oils that the static hazard becomes negligible.
Fire hazards aboard vessels at sea and at docks are serious problems. A recent
Associated Press news release points up the frequency of such fires. Within a
two week period, three of the world's largest ships suffered explosions and fire . v
These were the Norwegian-King Haakon VII - 220,000 tons, the British Mactra-
205,000 tons, and the British Marpessa - 207,000 tons.
Emulsification significantly improves the safety of transporting and handling liquid
hydrocarbons. Such an improvement should result in substantial reduction of in-
surance rates.
4. 7 Toxicity
4.7.1 Method
The procedure used in this study was one furnished in draft form by the Federal
Water Pollution Control Administration, dated Novemver 18, 1968. The method
was provided only as an "interim guide" to be used until standard procedures had
been developed and endorsed by Federal Water Pollution Control Administration
(FWPCA). The procedure is a comparative bioassay performed in accordance
with the procedure contained in Standard Methods for the Examination of Water
and Waste Water, 12th Edition, modified to insure the comparability of the data
from different test laboratories.
4.7.2 Test Apparatus
A specially insulated test laboratory was constructed with a thermostatically con-
trolled air conditioning system to maintain the required temperature control. Two
fifty gallon glass tanks were used for acclimatizing the test specimens (Figure
4.7-1). Both were located in the test laboratory to assure the required constant
temperature conditions for acclimatization.
Fish were exposed to the test emulsions and emulsifiers in five gallon glass test
aquaria (Figure 4.7-2). One gallon fish bowls were used for the exploratory tests
to determine the ranges of treating concentrations for the actual test determinations.
Requirements for liquid re-aeration were limited to the acclimatizing tanks. Aera-
tion was achieved through constantly supplied compressed air filtered through a
-67-
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five micron cartridge filter followed by a 0.5 micron membrane filter.
The proper level of agitation in the test containers was provided by a bank of
magnetic stirring bars. All magnets were rotated by pulleys driven by the same
electrical drive motor and gear box, thus assuring the same rate of agitation in
each test container.
4.7.3 Test Fish and Experimental Water
Fish selected for this salt water test were Cyprinodon variegatus (Figure 4.7-3).
This species is one of those acceptable for the Gulf Coast salt water environmental
studies. All test fish were obtained from a single location near Houston, Texas.
Size of the fish varied from 13/4 inches to 2 3/4 inches in length with an average
of approximately 2 1/4 inches. All test specimens used in the toxicity determi-
nations met the criteria for fitness. Less than 10 percent died during the four
day period prior to the start of tests.
A standard water was used in order that tests results would be comparable as
instructed in the FWPCA's "interim guide" for toxicity determinations. Stan-
dard sea water was prepared by dissolving "packaged sea salts" in demineralized
water free of any metal ions. An analysis of the test water is shown on Table
4.7-1 of this report. The pH of test water was adjusted in each case to 8. 0 and
controlled to a level not less than 7. 8 during the test.
4.7.4 Test Conditions
The test laboratory temperature was 20° + l°c and was controlled precisely
with a thermostatically controlled air conditioning system. All acclimatizing
vessels and test containers were located in this laboratory.
Depth of liquid in test containers was nine inches.
Dissolved oxygen content was monitored daily throughout the tests. It ranged
from 5 mg/1 to 7 mg/1 at all times. Re-aeration of liquid was not required in
the test containers.
In each actual toxicity test, ten fish were exposed to the test material. Gentle
agitation was provided in the test containers with magnetic stirring bars.
Throughout all tests the rotational speed of the stirring bars was held constant
at 210 rpm.
4.7.5 Procedure
Five exploratory tests were performed prior to each actual test to determine
the proper range of concentrations to be covered in the full scale tests. Results
-68-
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Figure 4.7-2
Toxicity Test Aquaria
Figure 4.7-1
Acclimatizing Aquaria
Figure 4.7-3
Test Fish
Cyprinodon variegatus
-69-
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Table 4.7-1
Analysis of Synthetic Sea Water
Flmld
Formation
source of Sampfe Contract No.
rw. collected Rec: 7-21-69
Countv
Lease
n*r>th
14-12-559
bv
S'ate
M/«II NO
P»rf.
REPORT OF WATER ANALYSIS
"P-538 Specific Gravity
A. OU. pH
8.9
Lab. Number _ _, , . .. __ pii __,
Total Dissolved Solids 19113 Resistivity (Ohmmeters at 689 F.) _ 0.036Q Hydrogen Sulfide ABSENT
DISSOLVED MINERAL ANALYSIS PATTERN
13
10
10
15
20
finjiMiiiin[nii[iMiiiiiijMiijiiiijiiiijMii|ini[MiijiiHjnM|iinjiiMiMii|»i|iiii|iiii|MrYnTTTTTiiiiiijniiiMH|MMiiMi|iiii[iiii[iiiiiiiii|it Q|
1 ' \ / ' 100
Fe |iiiiliiiniiiililii!llll[!lllmiili)ill!iiiliiiiliii!llinliiiillinliiiilinuniiliinliiiiliiTr [liilinilnnlnnliinliHiliinliinlnnlnnlllliliinliniliniln
10 I (Number Below Ion Symbol Indicates meq/Sco/e Unit)
Inn CO,
.10
DISSOLVED SOLIDS ANALYSIS
PRECIPITATED AND SUSPENDED SOLIDS ANALYSIS
Total Solids (Cafe.)
So^'wn1 (C&fr.)
JfOfi (D($SO/V?cO
Barium
Chloride
Su/fate
TOTAL IRON
SOLUBILITY CALCULATIONS
Calcium Carbonate Stability Index
Calcium Sulfate Stability at 95"F
Barium Su/fate Stability at 95° F
Cfmcenfraf/on_
mg/l
19113
6180
0
.
35
722
10400
76
0
1700
at 77° F
meq/l.
meq/l.
meq/f
268-9
0.0
-
1 .7
59.3
293.3
1 .2
0.0
35.4
Cafe. Solubility
Cafe. Solubility
mg/l
Total Undissolved Solids
Oil (Solvent Soluble) . .
Add Solubles
Iron , as
palcitjm . 85
Mafne-siym. ,, as
Suffate . as
Organic f/gn it/on Loss)
Acid Insolubles .
Sand & Clay
Barium Sirffct" fQnan.)
(Qual.)
Scaling Jpnrlenfy
meq/l. Percent Saturation
me<7//. Percent Saturation
REMARKS
The sample consisted of one 1 quart glass jar of water.
-70-
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of these exploratory tests indicated the concentrations used in the final test. All
full scale tests included five concentrations and one control sample.
Test fish were transferred from the acclimatizing tanks to the test vessels with
small mesh, nylon nets. All transfers were made immediately after preparation
of the test dilution. Test fish were not fed for two days prior to the start of full
scale tests, nor during the tests. The number of dead fish was recorded exactly
at the end of 24, 48 and 96 hour test intervals.
4.7.6 Physical and Chemical Determinations
A complete chemical analysis of a representative sample of the synthetic sea
water used for all toxicity determinations is shown in Table 4. 7-1 of this report.
4.7.7 Determination of Median Tolerance Limit and Discussion of Results
The median tolerance limit (TLrQ> is that concentration of the tested material in
a suitable experimental water at which 50 percent of the test fish are able to sur-
vive for a specified period of exposure. Unless exactly half the fish die in a test,
the TLgQ is determined by a straight line drawn between two test points at two
successive concentrations: (1) Where the concentration is lethal to more than
half the fish and (2) Where the concentration is lethal to less than half of the test
fish.
Figures 4.7-4 through 4.7-11 and Tables 4.7-2 through 4.7-5 show results of
the individual toxicity determinations. In each case results of 24 hour, 48 hour,
and 96 hour exposures are shown. In accordance with the FWPCA's "interim
guide", only the 96 hour determinations are discussed.
A summary of the 96 hour determinations is shown on Table 4. 7-6 of this report.
Included are the two emulsifiers alone and each of the three test crude samples
emulsified with each emulsifier.
Results in general agree with prior published material on toxicity. Most authors2
agree that 5 to 10 mg/1 or more of detergents will cause death. Table 4.7-6
shows a TL50 of 9.6 and 14.2 mg/1 of 1-1751 and 1-1752, respectively. Further,
Chadwick^ showed 5 mg/1 of Tricon caused no deaths in 48 hours, in line with
Table 4.7-2. Although the emulsifiers alone were considerably more toxic than
the emulsions, they are present to only 0.5 - 0.8 percent in the emulsions. Taking
this dilution factor into account, the toxicity of the emulsifier present in an emul-
sion is far less than the toxicity of the emulsion. This suggests that the toxicity
of the emulsion comes primarily from the oil rather than the emulsifier. To a
degree, these conditions might have resulted from the difficulty in keeping the
emulsions dispersed in the test liquid. No problem was experienced in keeping
the Zueitina crude dispersed in the test sample; however, the higher concentrations
of the Tia Juana crude was hard to keep dispersed and difficulty was encountered
-71-
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TABLE 4. 7-2
TOXICITY OF EMULSIFIERS
Initial condition - 10 fish per tank
Concentration Number of Dead Fish
(ppm) 24 hoars 48 hours 96 hours
1-1751
18 9 10 -
15 8 10 -
12 4 8 10
9 233
6 000
0 (control) 0 00
1-1752
18 047
15 023
12 013
9 122
6 000
0 (control) 0 00
-72-
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TOXICITY OF EMULSIFIERS
FIGURE 4. 7-4
in
i>
ii
i
O
P
-U
§
O
,r-r; --r_-rinr*:_ ^-.-J3;-. j^-f-J
^tv:~: -_~!Z:^:.-:LV: 1_.: _t5rj
24 hour exposure
48 hour exposure
O 96 hour exposure
10
20 30 40 50 60 70
SURVIVORS (%)
80 90 100
FIGURE 4. 7-5
i
Z
O
E-
2;
w
O
O
24- hour exposure -
58 hour exposure
O 96 hour exposure
0 10 20 30 40 50 60 70 80 90 100
SURVIVORS (%)
-73-
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TABLE 4.7-3
TOXICITY OF ZUEITINA EMULSIONS
Emulsion composition:
0. 5% Emulsifier
2.5% Water
97.0% Zueitina Crude Oil
Initial condition - 10 fish per tank
Concentration Number of Dead Fish
(ppm) 24 hours 48 hours 96 hours
Zueitina emulsified with 1-1751
75 999
60 888
48 666
39 333
33 222
0 (control) 1 11
Zueitina emulsified with 1-1752
75 9 9 10
60 777
48 445
39 222
33 111
0 (control) 1 1 !
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TOXICITY OF ZUEITINA EMULSIONS
FIGURE 4.7-6
I
in
r--
g
u
§
u
[~) 24 hour exposure
48 hour exposure
O 96 hour exposure
0 10 20 30 40 50 60 70
SURVIVORS (%)
80
90 100
FIGURES 4.7-7
a
m
r--
Z
o
p
w
1
u
24-hour exposure
?8 hour exposure
O 96 hour exposure -4-
40 50 60
SURVIVORS (%)
90 100
-75-
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TABLE 4.7-4
TOXICITY OF TIA JUANA EMULSIONS
Emulsion composition:
0.5% Emulsifier
2.5% Water
97. 0% Tia Juana Medium Crude Oil
Initial condition - 10 fish per tank
Concentration Number of Dead Fish
(ppm) 24 hours 48 hours 96 hours
Tia Juana emulsified with 1-1751
480 4 59
360 4 79
240 334
120 222
90 001
0 (control) 0 01
Tia Juana emulsified with 1-1752
600 8 8 10
480 346
360 224
240 ill
120 Oil
0 (control) 0 0 1
-76-
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a
a.
a
1C
§
1
u
TOXICITY OF TIA JUANA EMULSIONS
FIGURE 4.7-8
800
700
600
500
400
^ 300
200
100
0
24 hour exposure
48 hour exposure
96 hour exposure
t-F
0 10 20 30 40 50 60 70 80 90 100
SURVIVORS (5g)
FIGURE 4.7-9
a
-------
TABLE 4.7-5
TOXICITY OF #6 FUEL OIL EMULSIONS
Emulsion composition:
0. 8% Emulsifier
2.2% Water
97.0% #6 Fuel Oil
Initial condition - 10 fish per tank
Concentration Number of Dead Fish
(ppm) 24 hours 48 hours 96 hours
#6 Fuel Oil emulsified with 1-1751
900 7 9 10
800 4 55
700 344
600 222
500 Oil
0 (control) 0 00
#6 Fuel Oil emulsified with 1-1752
900 679
800 445
700 334
600 122
500 000
0 (control) 0 00
-78-
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TOXICITY OF #6 FUEL' OIL EMULSIONS
FIGURE 4. 7-10
2
O
P
W
I
O
24 hour exposure .
A 48 hour exposure
Q 96 hour exposure -
600
550
500
0 10 20 30 40 50 60 70, 80 90 100
SURVIVORS (%)
FIGURE 4.7-J
24 hour exposure --f-p
58 hour exposure
O 96 hour exposure
40 50 60
SURVIVORS (%)
90 100
-79-
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TABLE 4.7-6
SUMMARY OF NINETY-SIX HOUR TL5Q VALUES
Emulsifier or Emulsion T,LSO Concentration
(mg/1)
1-1751 (Emulsifier) 9.6
1-1752 (Emulsifier) 14.2
Zueitina crude with 1-1751 48.0
Zueitina crude with 1-1752 54.0
Tia Juana crude with 1-1751 240
Tia Juana crude with 1-1752 480
#6 Fuel Oil with 1-1751 800
#6 Fuel Oil with 1-1752 800
-80-
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with all concentrations of #6 Fuel Oil. Some free oil was present on the surface
of the test liquid with the three higher Tia Juana concentrations and all of the
#6 Fuel Oil concentrations after 80 hours of testing.
The Zueitina, high API gravity crude, emulsion was substantially more toxic than
the other lower API gravity crude emulsions. These results are in agreement
with results reported by other investigators that lighter hydrocarbon ends are
more soluble in water and contribute to a higher level of toxicity. Thus, Tagatz
found heavier oils substantially less toxic than light oils.
Emulsification may increase the toxicity of oil, when higher concentrations are
present. The level of toxicity found for #6 Fuel Oil,for example, was substan-
tially less than was found for emulsifier #6 FuelOil(2,000 mg/1 vs 800 ppm ).
It may be that oil alone, which tends to stay on the water surface, is less toxic
to fish than oil emulsion dispersed through the water, where it may come into
more intimate contact with the fish.
The mechanism of fish poisoning by oil is not clear. It may be purely a mechani-
cal effect of oil coating the gills. There is some indication that the presence of
detergents increases the absorption of oil constituents by fish. Also, there is
some evidence that the presence of salt reduces the toxicity of detergents.
In summary, the toxicity of the emulsions varies with the oils emulsified. The
lighter, higher API gravity, oils are more toxic than the heavy oils. The emulsi-
fiers apparently dispersed the oils completely and brought the oils into intimate
contact with the fish, thus lowering the TL^Q level below that which might be
expected for oils along. However, in actual sea conditions, the emulsion would
be rapidly dispersed to below the toxic level.
4. 8 Consideration of Break-Back Methods
4.8.1 Introduction
Although quantitative studies of the equipment and cost necessary to break-back
the emulsion when received at the refinery are not a part of this study, some
preliminary tests were made, and certain qualitative comments can be made.
4.8.2 Pumps
Some studies1 indicate that emulsified fuel can be broken back by a high speed
centrifugal pump, or by recirculation through a gear pump. Complete break-
back was obtained at 4, 200 rpm, even with 1.5 percent emulsifier present.
Prior studies on atomization have indicated that an emulsion containing 1.5 per-
cent emulsifier was much more stable than one containing 1.0 percent emulsi-
fier. Since the present study uses 0.5 to 0. 8 percent emulsifier, this would
suggest that these emulsions may break-back under these conditions. Since
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pumps are needed to unload the ship in any case, the only extra cost would be
added pump and power costs due to the high speed. Extrapolation from 3,600
rpm pump charts indicates that 1,600 hp would be required for 400 psi at'100
barrel per minute. This would add approximately 0.2 cents per barrel to the
cost. Separation of external phase from the crude oil in the broken emulsion
should occur in the storage tanks, or might be expedited by use of centrifuges.
4.8.3 Atomization
Bench type tests, flowing through an ultrasonic atomizer indicated that a Tia
Juana emulsion could be broken back to about 80 percent oil, 20 percent emul-
sion (see Table 4. 8.1). However, nearly a day's standing was required to
achieve the separation. Published work1 indicates that atomization of emulsion
at 400 psi with one percent emulsifier persent can give complete emulsion break-
back. With 1.5 percent emulsifier only 95 percent break-back was obtained.
Thus with the 0. 5 percent emulsifier as used in our studies complete break-
back would be expected if results are similar to those found in this published
data. The cost of this operation would be comparable to that for the high speed
pumps discussed in 4.7.2, less than one cent per barrel.
4.8.4 Ultrasonic Break-Back
Ultrasonic treatment of an emulsion tends to break it back approximately to the
"seed" condition - free oil plus an emulsion containing 70 percent oil and 30
percent external (aqueous) phase. A 30 minute ultrasonic batch treatment
followed by one day standing gave 86 percent clear oil and 14 percent emulsion.
Treatment with a 150 watt, 28 kilohertz homogenizer, at a rate of 45 milliliters
per minute, followed by 15 minutes settling gave 86 percent oil and 14 percent
emulsion.
4.8.5 Chemical Break-Back
It is well known that strong, particularly polyionic, electrolytes rapidly agglo-
merate emulsions. Successful use of this method on fuel emulsions has been
reported .
Tests were made with 0.6 percent 11-0521 Electro-Chem demulsifier, and 2.4
percent water mixed with emulsion and allowed to stand one day. Break-back was
complete. The cost of this chemical approach would be much greater than that of
a mechanical approach, if the latter is effective.
4. 8. 6 Re-Use of "Emulsion Seed" or Water Phase
In cases in which tankers do not have a cargo for the return trip, it may well be
economically attractive to carry the external phase (3 percent of the emulsion)
back to a loading dock to be used again, thereby reducing the chemical cost.which
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is the most costly single item in the emulsification operation. An alternative
would be to carry back the "emulsion seed", which would be desirable if dif-
ficulties arise in completely breaking the emulsion. However, the 7.5 percent
of the oil cargo present in the returned "emulsion seed" might represent a pro-
hibitive loss in tanker capacity. The continuous phase of the emulsion alone
represents only a 3 percent loss in cargo capacity, and this would be offset by
reduced ship leakage, reduced volatility and reduced hazards.
4. 8.7 Discussion
Based on published data, the mechanical action of pumps, with return of external
phase for reuse, holds the greatest promise of emulsion break-back. However,
because of differences between oils and emulsifiers any confidence in these pro-
cedures would require tests with the materials of interest.
TABLE 4.8.1
EMULSION SEPARATION FOLLOWING ATOMIZATION
Separation of oil from emulsion when Tia Juana was
flowed through an ultrasonic atomizer, collected in
a graduate and allowed to settle.
Settling Time %Oil % Emulsion
(hours)
0.16 30 70
0.50 60 40
1.00 68 32
24.00 79 21
4. 9 Product Alteration
4.9.1 Method
The maintenance of product intergrity is vital to the economics of this concept
for handling and transporting oil. Standard ASTM tests, used to determine the
basic characteristics of refinery feed stock, have been made on the three test
oils.
Test performed were:
1. Distillation (ASTM D 285)
2. Gravity
3. Viscosity
-83-
-------
These tests were performed on each oil "as received" and repeated on the "re-
claimed oil". The test data shown for "reclaimed oil" represent the conditions
after ultrasonic emulsification and then subsequent chemical demulsification.
The distillation tests, which in effect show the hydrocarbon make up of the oil,
were included to evaluate any changes in the marketable hydrocarbons. The
API gravity, viscosity, vapor pressure, and flash point tests provide additional
definition of basic characteristics.
Water soluble solids and ash content were determined to evaluate the alteration
or removal of substances without process value. Any removal of these materials
represents upgrading of the oil.
4.9.2 Product Alteration Data
Results of product alteration tests are shown on Table 4.9-1 and Figure 4.9-1.
4.9.3 Discussion of Product Alteration^
The distillation tests show no change in the basic character of the three oils. All
"as received" and "reclaimed" temperatures are the same except for five or six,
which are considered within test accuracy. No light or volatile fractions have
been lost as a result of the emulsifi cation/demulsification process.
The API gravity and the viscosity remained the same. These data support the dis-
tillation results. Also, they indicate that no extraneous materials were detected
after reclaiming.
One significant change in each of the three oils did result from the emulsification
demulsification process. The concentration of water soluble solids, including
salt, was reduced. This material was reduced in the Zueitina crude from 80 mg/1
to 20 mg/1 or about 75 percent; in the Tia Juana crude by about 83 percent and in
the #6 Fuel Oil by 94 percent.
The above data also suggest the emulsion particles are very small. Considering
the small volume of water used in the emulsion and the brief contact time during
these tests, there must be intimate mixing to achieve any real solution of salts.
In summary, the oils were not altered in any manner that could be considered
detrimental. There was some upgrading of the oils by removal of various salts.
-84-
-------
TABLE 4.9-1
Characteristic
Distillation
Initial Boll Point (I.E. P.
1% (0F)
10% (°F)
20% (°F)
30% (°F>
40% (°F)
50% (°F)
60% (°F)
70%
F)
End Point (°F)
Gasoline, LB.P. - 378°F (%)
Kerosene, 378 - 487°F (%)
Light Gas Oil, 487°F -End Point (%)
Residue (%)
Gravity (°API at 60°)
Viscosity (cp at 75°F)
Viscosity (cs at 75°F)
Viscosity (Saybolt Univ. at 100°F)
Viscosity (Saybolt Furol at 122°F)
Reid Vapor Pressure (Ibs. at 100°F)
Pour Point (°F)
Flash Point (P.M., °F)
Paraffin (% wt. )
pH of Water Extract
Water Soluble Solids (mg/1)
Sodium Chloride (mg/1)
Water (%)
Sulfur (%)
Hydrogen Sulfide or Mercaptan Oder
Ash (%)
Zueitlna
Crude
(Libya)
As Received
76
80
120
144
196
267
336
428
508
590
660
680
682
33.3
13.8
40.2
10.7
41.8
3.4
4.2
-
8.2
30
42
26
80
4.5
0.0
0.2
Present
0. 006
Reclaimed
79
82
121
145
196
267
336
428
508
590
660
680
684
33.3
13.8
40.2
10.7
41.7
-
4.2
-
7.6
30
44
26
20
1.2
0.1
0.1
Absent
0.004
Tla
Juan a
Medium Crude
As Received
86
110
178
220
296
445
548
610
628
642
-
-
642
15.3
8.8
46.7
29.2
24.3
26.0
28.8
160
4.2
-50
64
15
100
19.1
0.2
1.8
Present
2.75
Reclaimed
85
109
178
220
296
445
548
610
628
642
-
-
642
15.3
8.8
46.7
29.2
24.3
-
28.7
-
4.1
-50
64
15
17
1.8
0.1
1.6
Absent
1.84
No, 6 Fuel Oil
As Received
194
266
425
487
550
602
612
614
614
614~
2.0
3.0
51.7
43.3
8.3
3490
3470
126
0.4
35
220
13
2.0
20
12
1.0
Reclaimed
192
265
424
486
550
602
612
613
614
614
2.0
3.0
51.7
43,3
8.3
-
3450
_
0.4
35
220
13
6.1
1.2
0
0.6
7.41
4.62
-85-
-------
FIGURE 4.9-1
OIL DISTILLATION CURVES
487°F H
o
n
o
cd
o
iJ
0)
I 378°F J
(D
fl
i-l
ii
O
cc
cti
o
0)
M
Oj
iI
iI
ii
l->
tn
r-i
P
Zueitina Crude (Libya)
Tia Juana Medium Crude (Venezuela)
#6 Fuel Oil
100
10 20 30 40 50 60 70 80
Distillate Volume (% of sample)
-86-
-------
5.DESIGN, CONSTRUCTION & OPERATION OF
BENCH SCALE EMULSIFICATION UNIT
5.1 Basis of Design - Prior Work
The design of the bench scale emulsification unit was based on prior work done
with a small system capable of producing about one quart per minute of finished
emulsion, knowledge of emulsification system design and the proprietary emul-
sification method of the contractor. ^
5.2 Design and Construction of Bench Scale Unit
Figure 5-1 is a schematic drawing and Figure 5-2 is a photograph of the labora-
tory pilot model bench scale emulsification system used to determine the feasi-
bility of and design requirements for an emulsification system large enough to
be employed at modern tanker loading facilities. This unit had a maximum emul-
sification capacity of six gallons per minute.
An air compressor was used to supply power for the mechanical blending devices.
A positive displacement pump was used to supply oil at a constant rate from oil
storage (55 gallon drums) to the manifold. The manifold was equipped with
twelve stations, each having an on/off valve and a flow rate control valve. Sta-
tion twelve was connected to the "emulsion seed" premix unit. Seven percent
(by volume of finished emulsion) of oil was metered into the premix chamber
where it was emulsified with a three percent mixture of water and emulsifier.
The premix unit (Figure 5 -3A) was a cylinder four inches deep with a three inch
inside diameter. Two one and three-fourths inch propellers of opposing 30 de-
gree pitch were mounted one inch apart in the middle of a one-fourth inch shaft and
was powered by a small air motor, through a gear train which provided a pro-
peller speed of approximately 1,800 rpm.
The premixed "emulsion seed" was transferred to the ultrasonic homogenizer
with a positive displacement pump. The ultrasonic homogenizer, (Figure 5-3B)
developed and used in this study, was based on a new concept, and differed con-
siderably from the homogenizer normally used by the contractor. For this sys -
tern a 28 kilohertz, 150 watt, flat plate, immersible transducer was modified by
placing a cover plate one -sixteenth of an inch from the transducer plate surface
(see Appendix II for disclosure of invention). The cover plate was tapped at each
end to allow emulsion flow. As the "emulsion seed" flowed across the vibrating
plate, the dispersed oil was broken into uniform droplets of approximately one
micron diameter. Seven volumes of these droplets were dispersed in three
volumes of water and emulsifier to make up the "emulsion seed". The ultrasonic
-87-
-------
I
oo
oo
DISCHARGE
TO DRAIN
S3 SONICS INTERNATIONAL. INC.
FIGURE 5-1 BENCH SCALE EMULSIFICATION SYSTEM SCHEMATIC
-------
Figure 5-2 Bench Scale Emulsifi cation System
Figure 5-3A
"Emulsion Seed" Premix Unit
of Bench Scale System
-89-
-------
homogenizer was powered by a converter designed for a 60 cycle, 110 volt alter-
nating current input.
From the homogenizer the "emulsion seed" was piped to an inlet at the base of
the column blender. The column blender (Figure 5-3C) was a cylinder 24 inches
high with an inside diameter of two and one -half inches. Twelve one and three -
quarters inch diameter propeller blades with 45 degrees pitch were mounted on
a one-quarter inch shaft which extended through the cylinder top to the air motor
power source. The column blender air motor rated at one-half horsepower at
2,000 rpm and 90 psi pressure was driven at speeds of from 2,700 to'3,700 rpm
during the tests. The propeller blades were mounted to provide a pumping action
toward the top of the column. The bulk of the oil (90 percent) was introduced
into the column blender through Manifold Stations 1 through 11, which entered
the column at regular intervals from near the base to near the top of the column.
The flow through Station 1 was about 1 percent of the column effluent, and flow
was progressively increased at each successive station, except Station 11, where
it was decreased from the flow-through Station 10. In the column the oil was
blended into the "emulsion seed" to produce the finished 97 percent oil-in-water
emulsion.
A bypass was added to each of the supply pumps to permit operation of the unit
at various output rates. Calculations were made for output rates from two to
five gallons per minute. Table 5-1 gives the calculated flow rates for the seed
and Table 5-2 gives the calculated flow rates for the oil.
Construction materials were selected on the basis of cost, machinability and
versatility. Clear acrylic was used for the column and the homogenizer cover
plate to provide the advantage of visual observations of the effectiveness of each
piece of equipment. Plastic tubing and nylon fittings were used where possible.
5. 3. Operation of Bench Scale Unit and Data Collection
The emulsification system was operated on a continuous flow basis and was
capable of shutdown and subsequent starting without system cleanup or flushing.
ft was possible to switch from one oil emulsion to another with only a few gallons
of waste emulsion resulting. Once the oil flow rates into the column blender
and the corresponding seed ratios were adjusted, the emulsification unit worked
efficiently. Careful adjustment of the flow rates was essential to prevent carry-
over of free oil. If an excess of oil was introduced during the early blending
stages (through the lower inlets to the column), the column was "flooded" and
normal blending action was inhibited. To maintain proper blender action the
oil had to be fed to each inlet at a rate that would permit nearly complete blend-
ing into the emulsion before the emulsion rose to the next inlet of the column.
As shown in Table 5-2, the inlet flow rate was progressively increased from
the lower to the higher inlets, successively, except for the decrease at Station 11.
-90-
-------
Figure 5-3B Flat-Plate Homogenizer, Bench Scale System
Figure 5-3C
Column Blender
of Bench Scale System
-91-
-------
TABLE 5-1
BENCH SCALE EMULSIFICATION UNIT
"EMULSION SEED1' RATES FOR 2 TO 5 GALLONS PER MINUTE
to
i
EMULSIFIER
WATER
OIL
TOTAL
2 gpm
gal
0.010
0.050
0.140
0.20
in3
2.31
11.55
46.20
46.2
1
0.038
0.189
0.531
0.758
3 gpm
gal
0.015
0.075
0.210
0.30
in3
3.47
17.33
48.51
69.3
1
0.055
0.284
0.793
1.140
4 gpm
gal
0.020
0.100
0.280
0.40
in3
4.62
23.10
64.68
92.40
1
0.076
0.379
1.060
1.515
5 gpm
gal
0.025
0.125
0.350
0.050
in.3
5.77
28.88
80.85
115.50
1
0.095
0.470
1.320
1.900
-------
TABLE 5-2
BENCH SCALE EMULSIFICATION UNIT
BLENDER INLET OIL RATES FOR 2 TO 5 GALLONS PER MINUTE
CO
I
IN
NO.
1
2
3
4
5
6
7
8
9
10
11
12
%
1
2
3
5
7
10
11
12
12
13
14
10
TOTAL
2 gpm
gal
.018
.036
.054
.090
.124
.180
.198
.216
.216
.234
.254
.180
1.800
3
in
4.2
8.4
12.6
15.3
29.4
42.0
46.2
50.4
50.4
54.6
58.8
42.0
414.3
I
.068
.136
.204
.341
.469
.681
.741
.818
.818
.886
.961
.681
6.809
3 gpm
gal
.027
.054
.081
.135
.189
.270
.297
.324
.324
.351
.378
.270
2.700
in^
6.24
12.60
18.70
31.19
44.26
62.37
68.60
74.84
74.84
81.08
87.32
62.37
624.40
1
.102
.204
.307
.511
.715
1.022
1.086
1.226
1.226
1.329
1.430
1.022
10.180
4 gpm
gal
.036
.072
.108
.180
.248
.360
.396
.432
.432
.468
.508
.360
3.600
iti3
8.4
16.8
24.9
41.5
57.3
83.2
91.4
99.8
99.8
108.1
117.4
83.2
831.8
1
.136
.273
.409
.681
.939
1.363
1.496
1.635
1.635
1.771
1.922
1.363
13.620
5 gpm
gal
.045
.090
.135
.225
.315
.450
.495
.540
.540
.585
.630
.450
4.500
ln3
10.5
21.0
31.3
46.4
73.7
104.4
114.8
125.2
125.2
135.7
146.0
104.4
1039.5
1
.170
.341
.511
.852
1.192
1. 703
1.874
2.044
2.044
2.214
2.385
1.703
17.030
-------
The finished emulsion outlet of the column was immediately preceded by the
last oil inlet. Therefore, it was necessary to maintain the oil flow into the top
inlet at a point lower than that of the other upper inlets, to prevent carry-over of
unblended free oil.
Six recorded runs were made. One run was made with Zueitina crude oil, three
runs with Tia Juana Medium crude oil, one run with #6 Fuel Oil and one run with
#2 Diesel Fuel. The following data were collected during each recorded run:
1. Blender Motor Air Pressure
2. Oil Inlet Pressure
3. Seed Met Pressure
4. Blender Motor Speed
5. Ambient Temperature
6. Emulsion Discharge Temperature
7. Blender Outlet Flow Rate
Figures 5-4 through 5-26 and Tables 5-3 through 5-8 give graphic and tabular
presentations of the data collected during these six runs.
5.4 Discussion of Bench Scale Emulsification
The bench scale emulsification unit was designed and operated to provide the
information needed for the conceptual design of the basic 100 barrel per minute
unit. The unit was designed for maximum flow control flexibility to accommo-
date a broad range of oil character is itics and to provide as much basic data as
possible.
The power requirements were determined by monitoring the air motor speed
and the line pressure at the air motor. The air motor was rated one-half
horse-power at 2,000 rpm with 90 psi line pressure. The motor had sufficient
power for blending all the emulsions made during this study.
System pressures and temperatures were monitored to provide data for material
requirements for scale-up.
The system flow rate was monitored to indicate system capabilities and provide
a basis for calculations of the projected economics of constructing and operating
a scale-up.
Demonstration runs were made with #2 Diesel Fuel because it was readily ob -
tained, relatively inexpensive and emulsified readily by the bench scale system
due to its "average" characteristics.
The data presented by Tables 5-3through 5-8 and Figures 5-4 through 5-26 indicate
-94-
-------
TABLE 5-3
EMULSIFICATION PILOT MODEL DATA
TEST RUN - ZUETTINA CRUDE
READING
NO.
1
2
3
4
5
6
7
8
9
10
AIR PRESS
MOTOR
PSI
70
63
61
58
56
53
51
50
48
48
AIR MOTOR
RPM,
3700
3406
3235
3270
3420
3365
3395
3297
3231
3231
MANIFOLD
INLET PRESS
PSI
35
35
35
35
35
35
35
35
35
35
SEED OUTPUT
PRESS
PSI
5
7
7
9
13
13
13
13
13
13
EMULSION
FLOW RATE
LIT/ 'MINUTE
18.0
17.5
16.0
16.0
16.0
16.0
16.0
16.0
16.0
16.0
ROOM
TEMP.
<°F)
71.0
71.0
71.0
71.0
71.0
71.0
71.0
71.0
71.0
71.0
EMULSION
DISCHARGE
" TEMP.fOpi
79
79
79
79
79
79
79
79
79
79
cn
i
-------
u 80
|
w
IK 70 1
D
O
60
a
a
» 50
g 40
w *o
g 30
cn
1 20
0<
s
k t
3 5
^ -a
p c
> <
L <
D C
) <
i^
;
3 [
) o
^
>-C
) f
fr<
5 (
S- i
i^- <
) C
V C
1 f
> C
V f
1 (
>rr
t
-\
f
TIME-MINUTES
FIGURE 5-4 MIXER AIR MOTOR PRESSURE, OIL 81 SEED OUTPUT PRESSURE ZUEITINA CRUDE
0123*56 7
TIME-MINUTES
FIGURE 5-5 MEASURED FLOW RATE, ZUEITINA CRUDE
90
60
40
in
o,
> ^
> <
^
J c
> (:
> 6
) C
> <
j ,-
i)
TIME-MINUTES
FIGURE 5-6 ROOM tl EMULSION DISCHARGE TEMPERATURES ZUEITINA CRUDE
01234
FIGURE 5-7 ZUEITINA CRUDE, BLENDER AIR MOTOR SPEED
5 6 7 8 9 10 11 12 13 14 15
TIME-MINUTES
-------
TABLE 5 -4
EMULSIFICATION PILOT MODEL DATA
TEST RUN NO. 1 - TIA JUANA MEDIUM CRUDE
READING
NO.
1
2
3
4
5
AIR PRESS
MOTOR
(psi)
70
60
59
54
54
AIR MOTOR
SPEED
(rpm)
3700
3678
3540
2998
MANIFOLD
INLET PRESS
(psi)
34.0
33.0
33.0
33.0
33.0
SEED OUTPUT
PRESS
(psi)
8
7
9
10
6
EMULSION
FLOW RATE
(1/min)
7.20
7.00
6.80
ROOM
TEMP.
(OF)
75.5
75.5
75.5
75.5
75.5
EMULSION
DISCHARGE
TEMP. (UF)
80.0
80.0
80.0
80.0
80.0
-------
PRESSURE - POUNDS PER SQUARE INCH
t KJ C*> ib. C/i ^ -J 00 *O
3, OOOOOOOOO
X.
3
r
k
[
D
> -
^n
r
i >.
^-
i
)
^-' ._
^
r
s
T
>
'
-^
r
~c
^
i
|»
/\ - Motor Air Pressure
D - Oil Inlet Pressure
O - Seed Inlet Pressure
0123
7 8 9 10 11 12 13 14 15
TIME-; MINUTES
S 6 7 8 9 10 11 12 13 14 15
TIME - MINUTES
FIGURE 5-8 MIXER MOTOR AIR PRESSURE, OIL & SEED INPUT PRESSURE, SUN NO. 1, TIA JUANA CRUDE
0123
FIGURE 5-9 MEASURED FLO* RATE, RUN NO. 1, TIA JUANA CRUDE
CO
i
80(
i
70
60
50
40
30
20
1
"
"*
A
?
i
O - Emulsion Dischar, e
Temperature
/^ - Room Temperature
0 123 45 6 7 S 9 10 11 12 13 14 15
TIME-MINUTES
FIGURE 5-IO ROOM 8. EMULSION DISCHARGE TEMPERATURES, RUN NO. 1, T1AJUANA CRUDE
5000
MOTOR SPEED - RPM
1 1 1 1 1 1 I i
(j
~~*
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
TIME-MINUTES
FIGURE 5-11 TIA JUANA CRUDE, RUN NO. 1. BLENDER AIR MOTOR SPEED
-------
TABLE 5-5
EMULSIFICATION PILOT MODEL DATA
TEST RUN NO. 2 - TIA JUANA MEDIUM CRUDE
READING
NO.
1
2
3
4
5
6
7
8
9
10
AIR PRESS
MOTOR
psi
70
62
60
59
57
54
52
50
50
48
AIR MOTOR
SPEED
rpm
3350^
3250
3300
3400
3350
3400
3200
3180
3150
MANIFOLD
INLET PRESS
psi
32
32
32
32
32
32
32
32
32
32
SEED OUTPUT
PRESS
psi
5
4
5
6
6
5
5
5
5
5
EMULSION
FLOW RATE
1/min.
7
7
7
7
7
7
7
7
7
7
ROOM
TEMP.
1°F)
80°
80°
80°
80°
80°
80°
80°
800
80°
80°
EMULSION
DISCHARGE
TEMP. (°F)
72°
72°
72°
72°
72°
72°
72°
72°
72°
72°
VO
I
-------
90
80
70'
60
50
40
f
20
10
<
N
i f
^
V*
^ i
s «
*~-
f
1 f
H
^
\
1 F
> <
1 f
> C
~z
\ r
) C
i
i
>
^ - Motor AirLPressure
D ' Oil Inlet Pressure
O - Seed Inlet Pressure
0 0 1 2 3 4 5678 9 10 11 12 13 14 15
TIME-MINUTES
FIGURE 5-12 MIXER MOTOR AIR PRESSURE, OIL 5 SEED INLET PRESSURES, RUN NO. 2, TIA JUANA CRUDE
12 345 678 9 10 11 12 13 14 15
TIME -MINUTES
FIGURE 5-13 MEASURED FLOlV RATE, RUN NO. 2, TIA JUANA CRUDE
O
o
I
90
31*
70'
60
50
40
30
20
10
>i f
\
O ~ HmulsionXHscharge
Temperature
A. '- Room Temperature
0 1234 5 6 7 8 9 10 11 12 13 14 15
TIME-MINUTES
FIGURE 5~I4 ROOM & EMULSION DISCHARGE TEMPERATURES, RUN NO. 2, TIA JUANA CRUDE
w 3500
1 234 56 7 8 9 10 11 12 13 14
TIME-MINUTES
FIGURE 5-15 RUN NO. 2, TIA JUANA CRUDE, BLENDER AIR MOTOR SPEED
-------
TABLE 5-6
EMULSIFICATION PILOT MODEL DATA
TEST RUN NO. 3 - TIA JUANA MEDIUM CRUDE
READING
NO.
1
2
3
4
5
AIR PRESS
MOTOR
PjsL
68
65
64
60
AIR MOTOR
SPEED
rpm_
MANIFOLD
INLET PRESS
psi
35.0
34.0
33.0
33.0
33.0
SEED OUTPUT
PRESS
psi
5
4
3
4
5
EMULSION
FLOW RATE
1/min.
7.20
7.00
7.00
7.00
7.00
ROOM
TEMP.
(OF)
74.0
74.0
74.0
74.0
74.0
EMULSION
DISCHARGE
TEMP. (°F)
7800
78.0
78.0
78.0
7-8.0
I
H-'
O
-------
S
A - Motor Air Pressure
H] - Oil Inlet Pressure
O - SeeJ Inlet Pressure
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
TIME-MINUTES
FIGURE 5-16 MIXER MOTOR AIR PRESSURE, OIL & SEED INLET PRESSURE, RUN *3, TIA JUANA CRUDE
OO©&
3 4 5 6 7 8 9 ID 11 12 13 14 15 16
TIME-MINUTES
FIGURE 5-17 MEASURED FLOW RATE, RUN *3, TIA JUANA CRUDE
O
to
I
90
80(
I
70
60
50
40
30
20
\ ,
> <
^
O - EmulsioirDiscUartfe
Temperature
A - Room Temperature
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
TIME -MINUTES
FIGURE 5-18 ROOM & EMULSION DISCHARGE TEMPERATURES, RUN *3, TIA JUANA CRUDE
-------
TABLE 5-7
EMULSIFICATION PILOT MODEL DATA
TEST RUN - NO. 6 FUEL OIL
READING
NO.
1
2
3
4
5
6
7
8
9
10
11
12
13
AIR PRESS
MOTOR
PSI
65
64
65
64
60
58
56
54
50
49
47
45
43
AIR MOTOR
RPM
3164
2792
2569
2649
2716
2687
2643
2508
2419
2280
2398
2358
2456
MANIFOLD
INLET PRESS
PSI
56.0
56.0
56.0
56.0
56.0
56.0
56.0
56.0
56.0
56.0
56.0
56.0
56.0
SEED OUTPUT
PRESS
PSI
11
6
12
6
7
8
9
11
9
5
7
10
8
EMULSION
FLOW RATE
LITERS/MBS!
3.0
3.0
3.0
3.0
ROOM
TEMP.
(°F)
75
75
75
75
75
75
75
75
75
75
75
75
75
EMULSION
DISCHARGE
TEMP. (u^;
84
85
87
87
87
87
87
87
87
87
87
87
87
o
CO
I
-------
I
I"
O
I
O - Air Motor Pressure
- Oil Inlet Pressure
- Seed Inlet Pressure
FIGURE 5-19 MIXER MOTOR AIR PRESSURE, OIL & SEED INPUT PRESSURES *6 FUEL OIL
O - Emulsidri Temp.
D - Room Temperature
12 34 56 7 8 9 10 11 12 13 14 15
TIME-MINUTES
FIGURE 5-21 ROOM Si EMULSION DISCHARGE TEMPERATURES *6 FUEL OIL
2500
2000
1500
1000
23456789
TIME-MINUTES
1C 11 12 13 14
FIGURE 5~20 MEASURED FLOW BATE #^ FUEL OIL
2345 6789
TIME-MINUTES
.FIGURE 5-22 NO. 6 FUEL OIL, BLENDER AIR MOTOR SPEED
10 11 12 13 14 15
-------
TABLE 5-8
EMULSIFICATION PILOT MODEL DATA
TEST RUN - NO. 2 DIESEL FUEL
READING
NO.
1
2
3
4
5
6
7
8
9
10
11
12
AIR PRESS
MOTOR
PSI
46
44
42
41
40
39
38
37
36
35
35
34
AIR MOTOR
RPM:
2956
2857
2673
2696
2685
2673
2639
2544
2568
2565
2538
2543
MANIFOLD
INLET PRESS
PSI
41
41
41
41
43
45
45
45
45
45
45
45
SEED OUTPUT
PRESS
PSI
2-0
1.0
5.0
5.0
5.0
5.0
5.0
5.0
4.0
4.0
4.0
3.5
EMULSION
FLOW RATE
LITERS/MIN
15.00
9.23
9.23
9.23
9.23
9.23
9.23
9.16
9.23
9.23
8.57
8.57
ROOM
TEMP.
(OF)
74
74
74
74
74
74
74
74
74
74
74
74
EMULSION
DISCHARGE
TEMP. (°F)
78
78
78
78
,78
78
78
78
78
78
78
78
o
en
-------
60
^\ - Motor Air Pressure
L-J - Oil Inlet Pressure
O - Seed Inlet Pressure
* 567 8 9 10 11 12 13 14 15
TIME -MINUTES
FIGURE 5-23 RUN NO. i, *2 DIESEL FUEL
O - Emulsion-Disc. Temp,
- Room Temperature
4 56 78 9 10 11
TIME-MINUTES
FIGURE 5-25 RUN *1. NO. 2 DIESEL FUEL
12 13 14 15
18
16
<
a 14
s
| 12
m 10
b
1 .
2
0
0
4500
4000
3500
, 3000(
Q
w
S 2500
K
° 2000
i
1500
1000
500
\
\
\
\
«
3 0
) C
) «
) 0
) (
) <
) C
5 f
>-^
i
TIME-MINUTES
.FIGURE 5-26 RUN NO. 1, »2 DIESEL FUEL
-------
that the operation of the emulsification system was consistent for a broad range
of oil characteristics. The only significant variation was the flow rate through
the blender. The highest flow rate (slightly over 6 gal/min) was obtained with
#2 Diesel Fuel during a nonrecorded run. The Zueitina crude oil could be run at
nearly the same rate. The flow rate of the viscous #6 Fuel Oil was the lowest at
0.8 gpm.
-107-
-------
6. SYSTEM CONCEPTUAL DESIGN
6.1 Emulsification Unit Scale-up to Basic 100-Barrels-Per-Minute Unit
Based on the performance of the bench scale emulsification system, a basic unit
capable of producing 100 BPM of emulsion was designed. Figure 6-1 is a plan
view and Figure 6-2 an elevation of the basic 100 BPM emulsification unit.
Table 6-1 is the parts list for the 100 BPM unit. The basic 100 BPM unit was de-
signed as a complete, skid mounted unit capable of being placed on line as a
single unit or in parallel as a module of a multi-unit system. The 100 BPM emul-
sification unit was designed to operate in the same manner as the bench scale unit
described in Section 5.
The oil, treated water and emulsifier are each piped into the emulsification unit
through inlets on the left end of the skid. Oil flows through the inlet at the rate
of 97 percent of the emulsion discharge flow rate. As the oil enters the line to
the inlet manifold, 7 percent is diverted to the seed premix unit through a flow
control valve. The remaining 90 percent is distributed by the inlet manifold at
the rates shown in Table 6 -2. The treated water enters the oil line to the premix
unit through a flow control valve at the inlet. The emulsifier inlet is connected
to metering pumps which inject the emulsifier into the water stream prior to its
connection to the premix oil stream. The combined stream of oil, water and
emulsifier then flows through the premix unit where a coarse oil-in-water emul-
sion is formed. The premixed emulsion then passes over the flat plate, ultra-
sonic homogenizer where intense cavitation ruptures the coarse emulsion to form
a fine, uniform "emulsion seed". The finished "emulsion seed" is pumped from
the ultrasonic homogenizer through a check valve to the base inlet of the blending
column where the bulk of the oil is blended into the "emulsion seed" to provide
the finished 97 percent oil-in-water emulsion.
The basic 100 BPM emulsification unit is 27'-l" long by 27'-7" high and is mounted
on a 10' by 23'-2" skid. The unit weight is approximately ten tons.
Manual gate valves are specified for use in the unit, but no problem would be en-
countered in converting to remote control or programmed automatic valves. The
system lends itself to complete automation.
The blender column is powered by a 75 hp electric motor, the premix column by
a 5 hp motor and the "emulsion seed" column by a 15 hp motor. The homogeni-
zer is a 100 hp unit.
6.2 Concept of Complete Emulsification System
The basic 100 BPM emulsification unit was designed for use in a single unit system
-108-
-------
O RAW OIL
^o ^^
' INLET
EMULSIFIER
INLET
FLOW
CONTROL
VALVE
TREATED \
WATER
INLET
§
SEED AND RAW
OIL BLENDING
COLUMN
EMULSIFIER
METERING
PUMPS
FLOW
CONTROL
VALVES
EMULSION
DISCHARGE
ULTRASONIC
SEED EMULSIFIER
UNIT
CONTROL
HOUSE
SEED
PREMIX
UNIT
CHECK
VALVE
FLOW CONTROL
VALVE
PLAN VIEW- 100 BPM EMULSIFICATION UNIT
-------
BLENDING COLUMN
MIXER SHAFT
DRIVE MOTOR-.
O
\
RAW OIL
INLET '
ELEWION100 BPM EMULSIFICAT1ON UNIT
-------
TABLE 6-1
BASIC 100 BFM EMULSIFI CATION UNIT PARTS LIST
ITEM
'NO.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
QUANTITY
REQUIRED
1
4
4
5
1
1
1
4
4
5
2
1
1
1
1
1
1
1
1
8
21 i i
DESCRIPTION
7505780 Rockwell Control Valve
'2" MDL 780 Rockwell Control Val.
3" MDL 780 Rockwell Control Val.
4" MDL 780 Rockwell Control Val.
702 Rockwell Check Value
12" Gate Valve 150 psi
6" Gate Valve 150 psi
2" Gate Valve 150 psi
3" Gate Valve 150 psi
4" Gate Valve 150 psi
10" Gate Valve 150 psi
6" Swing Check Valve
4x3 Centrifugal Pump & Motor
In Line Mixer
Emulsion Metering Pumps
Blending Column
Ultrasonic Transducer (assembly)
Skid
Control House
Ultrasonic Generator
12" MDL 702 Rockwell Control Valve
WEIGHT,
EACH
(pounds)
175
60
96
135
200
653
179
40
64
107
475
172
615
940
900
5,050
1,500
5,000
800
200
175
WEIGHT
TOTAL
(pounds)
175
240
384
675
200
653
179
160
256
535
950
172
615
940
900
5,050
1,500
5,000
800
1,600
175
TOTAL 21,159
-------
TABLE 6-2
BASIC 100 BPM EMULSIFICATION UNIT
OIL FLOW RATE INTO BLENDING COLUMN
INLET
NO.
1
2
3
4
5
6
7
8
9
10
11
12
% of 90 BPM
FLOW THRU INLET
1
2
3
5
7
10
11
12
12
13
14
10
FLOW RATE
(bbl/mia) (gal /m in)
0.9
1.8
2.7
4.2
6.3
8.4
9.9
11.2
12.0
12.4
12.1
8.1
37.8
75.6
113.4
176.4
264.6
352.8
415.8
470.4
504.2
520.8
508.2
340,0
-------
or for parallel installation as required to meet the demands of a multi-unit
system. Figure 6-3 is a schematic of a single unit crude oil emulsification sys-
tem. The system consists of the basic 100 BPM emulsification unit, an oil
storage battery (a pipe line could replace the oil storage battery), a water sto-
rage tank (a water supply line could be used) and an emulsifier storage tank. A
means of transferring the stored liquids to the emulsification unit is also re -
quired. The pressure in the unit forces the oil into the ship without further
pumping.
Figure 6-4 is a schematic drawing of a multi-unit emulsification system. Each
of the basic 100 BPM units is represented by a block labeled "emulsification
unit".
These units are parallel manifolded to the tanker loading lines on the discharge
side and to the oil, water and emulsifier supply systems on the inlet side.
IE a large volume of one petroleum product was handled at a terminal facility,
several units would be placed on site. If the peak demand at such a terminal
was 600 BPM, six units would be employed as shown in Figure 6-4.
Table 6 -3 gives the required loading time for barges and tankers with cargo
capacities from 1,000 through 200,000 tons, relative to the number of emulsifi-
cation units, for one through seven 100 BPM units. For example, if a tanker
with a capacity of 110,000 tons (approximately the size of the Torrey Canyon)
used six units to accomplish onloading, approximately 23 hours would be re-
quired. If the same tanker was allowed 36 hours for onloading, only four units
would be required.
6. 3 Placement of Emulsification System
A visit to typical Gulf Coast terminals revealed that there is insufficient dock-
side space to allow installation of one or more emulsification units. It would be
necessary to install the emulsification units where space was available and pipe
the finished emulsion to the dock.
One or more of the emulsification units could be mounted on a barge for use at
offshore terminals and offshore production facilities.
Placement of the emulsification units is not critical. If necessary they could be
located away from the loading terminal, or they could be on the tanker deck.
-113-
-------
SEED 4
RAW OIL
BLENDING
COLUMN
ULTRASONIC
SEED EMULSIFIER
UNIT
FIGURE 6-3 SINGLE UNIT CRUDE OIL EMULSIFICATION SYSTEM
-------
TABLE 6-3 TIME REQUIRED TO T.OAD A TANKER WITH 100 BPM rJNITS
TANKER CAPACITY
1000 TONS
1
2
3
4
5
6
7
8
9
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
ISO
190
200
i 1000 B3LS
7.5
15.0
22.5
30.0
37.5
45.0
52.5
60.0
67.5
75.0
150.0
225.0
300.0
375.0
450.0
525.0
600.0
675.0
750.0
825.0
900.0
975.0
I, 050. 0
1,125,0
1,200.0
1,275,0
1, 350. 0
1,425.0
1,500.0
1 UNIT
HOURS
1.25
2.50
3.75
5.00
6.25
7.50
8.75
10.00
11.25
12.50
25.00
37.50
50.00
62.50
75.00
87.50
100.00
112.50
125.00
137.50
150.00
162.50
175.00
137.50
200.00
212.50
225.00
237.50
250. 00
2 UNITS
HOURS
4. 38
5.00
5.62
6.25
12.50
18.75
25.00
31.25
37.50
43.75
50.00
56.25
62.50
68.75
75.00
81.25
87.50
93'. 75
100.00
106.25
112.50
118.75
125. 00
3 UNITS
HOURS
4.10
-8.20
12.30
16.40
20.50
25.00
29.10
33.20
37.30
41.40
45.50
50.00
54.10
58.20
62.30
66.40
70.50
75.00
79.10
83.20
4 UNITS
HOURS
6.15
9.36
12.30
15.62
18.45
21.86
25.00
28.70
31.15
34.22
37.30
40. 37
43.45
46.52
50.00
53.70
56.15
59.22
62.30
5 UNITS
HOURS
7.50
10.00
12.30
15.00
17.30
20.00
22.30
25.00
27.30
30.00
32.30
35.00
37.30
40.00
42.30
45.00
47.30
50.00
6 UNITS
HOURS
6.15
8.20
10.41
12.50
14.58
16.66
18.75
20.83
22.91
25.00
27. 08
29.16
31.25
33. 33
35.41
37.50
39.58
41.66
7 UNITS
HOURS
7.15
8.91
10.70
12.50
14.28
16.06
17.85
19.63
21.41
23.20
25.00
26.78
28.56
30. 35
32.13
33.91
35.70
-------
0
1
UNIT
UNIT
UNIT
UNIT
UNIT
UNIT
n SONK:S INTERNATIONAL. INC.
FIGURE 6-4 MULTI-UNIT CRUDE OIL EMULSIFICATION SYSTEM
-------
7. ECONOMICS OF EMULSIFIGATION PROCESS
7.1 Introduction
Considerable effort was spent in this study in attempts to obtain representative
numbers necessary for a complete economic analysis. Estimates of capital
costs for the equipment and operating cost for the total system are relatively
good. Chemical emulsifier costs are not exact since costs vary with composi-
tion. Optimums of emulsifiers were beyond the scope of this study. All of the
numbers required to assess "cost offsets" were not available, primarily be-
cause of the competitive nature of those phases of the business and vagueness of
numbers available in some cases.
From the standpoint of economics, it would be desirable to have the additional
cost of a system to emulsify oil for transportation not exceed the savings that
would result from its use. However, under present conditions with our Country's
all-out efforts to eliminate pollution problems, it is difficult to fix dollar magni-
tudes on incentives for control of oil spills. To the degree these factors become
significant, the total economic picture is not seen from the cost estimates de-
veloped in this report.
Tankers vary in size so much that "typical" or "average" are meaningless as
tanker capacity descriptions. The World Wide Tanker Nominal Scale indicates
a "standard vessel" for rate calculations for 1969 would be as follows:
Summer deadweight 19,500 tons
Summer draft laden in salt water 30T 60"
Average service speed 14 knots
Fuel consumption at sea 28 tons per day
Fuel consumption in port 5 tons per day
Port time allowance 96 hours
Fixed time element $1»800 per day
Brokerage $2,500
The trend in tanker size is rapidly toward the super tankers. These huge vessels,
100,000 deadweight tons and larger, now constitute less than 10 percent of the
world's tanker fleet, but are projected to represent 50 percent by 1975. Two
sizes have been selected as examples for this section of the report: 1) 20,000
tons (approximate "standard vessel") and 2) 200,000 tons (representative of
super tanker).
7.2 Cost of Emulsified System for Oil Transportation
7.2.1 Loading Rate Considerations
-117-
-------
Tanker rental rates are high, even when in port for loading. World Wide Tanker
Nominal Scale, a schedule intended as a standard reference by which rates for
all voyages and market levels can be prepared, fixes demurrages for a 100,000
summer deadweight ton tanker is $13,200 per day. Laytime allowances for load-
ing and discharging are set at 72 hours. From this it is seen that loading rates
become important in selecting size of units for the conceptual design. Processing
rates, available through single unit or multiple unit stations, must be comparable
to conventional loading rates of present facilities. The basic unit selected for the
concept presented in this study is capable of operating at 100 BPM or 144,000 BPD.
A loading timetable for units of this size is shown in Table 6.3. In Table 6.3,
"Tons" are long tons and equal to 2,240 pounds or 7.5 barrels.
7.2.2 Capital Costs of Equipment
The concept presented in this study contemplates a system which uses the present
lines, pumps and docking facilities with the addition of multiple skid mounted
emulsification units to be located on or near the present docks. The emulsion,
when formed, would flow through conventional loading lines in the usual "plug
flow" of slippery gelled materials. Costs per single 100 BPM unit are outlined
on Table 7.2-1. Outlined costs total $84,000 per unit, however, with a con-
tingency for unidentified miscellaneous costs, the full cost of a single unit is
estimated at $100,000.
7.2.3 Operating Costs of System
Estimates of operating costs for the system are shown on Table 7.2-2. Since
several of the cost items included vary with the number of units at a location and
the volume handled for a period of time, two sample cases were used to deter-
mine costs per barrel:
Case I - 20,000 ton tanker with 1 - 100 BPM unit operating 60 percent
of time and 1 - 100 BPM unit on stand-by.
Case II - 200,000 ton tanker with 6 - 100 BPM units operating 80 percent of
time with 1 - 100 BPM unit on stand-by.
Estimates of costs range from 1.58 cents per barrel for Case II to 4. 32 cents per
barrel for Case I. These numbers are the operating costs for the emulsification
units only and are exclusive of chemical and break-back costs.
7.2.4 Cost of Chemical Emulsifier
Costs of chemicals used in the experimental portions of this study would be pro-
hibitive (estimates range from $0. 37 to $0.50 per pound or $0.67 to $0. 92 per
barrel processed) for a full scale operation. However, optimums of cost and
performance of emulsifier were beyond the scope of this study. In large volumes,
-118-
-------
TABLE 7.2-1
BASIC 100 BPM EMULSIF1CATION UNIT COST ESTIMATE
ITEM
NO.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
QUANTITY
REQUIRED
1
4
4
5
1
1
1
4
4
5
2
1
1
1
1
1
1
i
i
8
1
1
DESCRIPTION
7505780 Rockwell Control Valve
'2" MDL 780 Rockwell Control Val.
3" MDL 780 Rockwell Control Val.
4" MDL 780 Rockwell Control Val.
702 Rockwell Check Value
12" Gate Valve 150 psi
6" Gate Valve 150 psi
2" Gate Valve 150 psi
3" Gate Valve 150 psi
4" Gate Valve 150 psi
10" Gate Valve 150 psi
6" Swing Check Valve
4x5 Centrifugal Pump & Motor
In Line Mixer
Emulsion Metering Pumps
Blending Column
Ultrasonic Transducer (assembly)
Skid
Control House
Ultrasonic Generator
12" MDL 702 Rockwell Control Valve
Manufacture and Assembly Estimate
COST
EACH x
(dollars)
'681.00
367.00
456.00
598.00
2,481.00
540.00
136.50
47.70
62.60
86.00
390.00
137.00
1,381.00
1,922.00
3,198.00
9,270.00
4,000.00
1,440.00
1,200.00
4,200.00
2,073.00
13,900.00
COST
TOTAL
(dollars)
681.00
1,468.00
1,824.00
2,996.00
2,481.00
540.00
136.50
190. SO
250.40
430.00
780.00
137.00
1,381.00
1,922.00
3, 198,00
9,270.00
4,000.00
1,440.00
1,200.00
4,200.00
2,073.00
13,900.00
TOTAL: 83,848.00
-------
TABLE 7.2-2
EMULSIFICATION UNIT COSTS OF OPERATION
Item
* Labor
* Equipment Amortization
(10 yr.)
Interest on Investment
(20% on balance)
Maintenance
Power
Taxes
Case I
20,000 ton tanker
1-100 BPM Units
(M$/Yr) ft/bfol)
70
20
20
2
14
1
2.90
0.64
0.64
0.06
0.05
0.03
Case II
200,000 ton tanker
6-100 BPM Units
(M$/Yr) (tf/hbl)
170
70
70
12
84
6
0.90
0.29
0.29
0.05
0.03
0.02
Total
147
4.32
462
1.58
Use Factor
Terminal Handling Rate
(Million barrels per year)
Costs (tf/bbl)
0.6
31
4.32
0.8
245
1.58
Case I - Labor at $5/Hr. plus 125 percent overhead for 3 shifts per day.
Case II - Assumes increase in labor proportional to square root increase
of capital.
Assumes basic unit costs of 100 M $ each. Case I includes 1 unit in use
60 percent of time and 1 unit on "stand-by". Case II includes 6 units in
use 80 percent of time and 1 unit on "stand-by".
-120-
-------
chemicals of the same class as those used in this study should be obtained for
about $0.12 per pound or $0.22 per barrel of oil processed. A cost schedule
covering a reasonable range of chemical costs for varying tanker capacities is
shown on Table 7.2-3.
A volume of water equal to about 2.5 percent of the tanker capacity will be re-
quired for processing; however, water costs will be negligible in relation to
other costs of the operation.
Emulsions must be broken-back when the refinery is reached. Regular chemical
demulsifiers would cost about the same as above, or double the chemical costs
for the emulsification/demulsification process.
While these costs appear prohibitive, discussions with chemical suppliers indi-
cate reductions in costs could likely be achieved through development efforts
on chemicals for the specific purpose, particularly when considering the poten-
tial volumes that would be used.
7.2.5 Possible Gains Offsetting Emulsification Costs
The primary purpose of emulsification would be to reduce potential pollution
hazards by spills during emergencies. There would be other possible advan-
tages :
(a) Fire hazards would be greatly reduced because the emulsion is not an
insulator as is oil, and therefore would not build up static charges.
Insurance rates should be reduced because of lower hazards.
(b) Any salt present in the crude would go into the water phase. In some
cases this would desalt the crude to a level that would not require
farther treating at the refinery, thus reducing costs up to 5 cents per
barrel.
(c) Evaporation rates would be lowered, lessening light fraction loss dur-
ing transit at sea.
(d) The high viscosity of the emulsion would greatly reduce leakage from
the ship through normal small holes and ruptures.
(e) The rapid dispersion of the emulsion in the sea would favor rapid
bacterial degradation without damage to sea life or beaches.
7.2.6 Possible Procedure Modifications
It has been our experience that ultrasonic treatment will break an emulsion
back to about 90 percent free oil and 10 percent "emulsion seed , the latter
-121-
-------
TABLE 7.2-3
SCHEDULE OF EMULSIFIER COSTS
TANKER CAPACITY
1000 TONS
1
2
3
4
5
6
7
8
9
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
1000 BBLS
7.5
15.0
22.5
30.0
37.5
45.0
52.5
60.0
67.5
75.0
150.0
225.0
300.0
375.0
450.0
525.0
600.0
675.0
750.0
825.0
900.0
975.0
1,050.0
1,125.0
1,200.0
1,275.0
1,350.0
1,425,0
1,500.0
EMULSIFIER
POUNDS
13,782
27,565
41,348
55,131
68,914
82,696
96,479
110,262
124,045
137,828
275,656
413,484
551,313
689,141
826,969
964,797
1,102,626
1,240,454
1,378,282
1,516,110
1,653,939
1,791,767
1,929,595
2,067,423
2,205,252
2,343,080
2,480,908
2,618,736
2,756,565
COST OF EMULSIFIER FOR GIVEN TANKER CAPACITY
6<£/lb
(lltf/bbl)
$ 826
1,653
2,480
3,307
4,134
4,961
5,788
6,615
7,442
8,269
16,539
24,809
33,078
41,348
49,618
57,887
66,157
74,427
82,696
90,966
99,236
107 , 506
115,775
124,045
132,315
140,584
148,854
157,124
165,393
9^/lb
(16^/bbl)
$1,240
2,480
3,721
4,961
6,202
7,442
8,683
9,923
11,164
12 , 404
24,809
37,213
49,618
62,022
74,427
86,831
99,236
111,640
124,045
136,449
148,854
161,259
173,663
186,068
198,472
210,877
223,281
235,686
248,090
120/lb
(22^/bbl)
$ 1,653
3,307
4,961
6,615
8,269*
9,923
11,577
13,231
14,885
16,539
33,078
49,618
66,157
82,696
99,236
115,775
132,315
148,854
165,393
181,933
198,472
215,012
231,551
248,090
264,630
281,169
297,708
314,248
330,787
15tf/lb
(27^/bbl)
$ 2,067
4,134
6,202
8,269
10,337
12,404
14,471
16,539
18,606
20,674
41,348
62,022
82,696
103,371
124,045
144,719
165,393
186,068
206,742
227,416
248,090
268,765
289,439
310,113
330,787
351,462
372 , 136
392,810
413,484
180/lb
(33^/bbl)
$ 2,480
4,961
7,442
9,923
12,404
14,885
17 , 366
19,847
22,328
24,809
49,618
74,427
99,236
124,045
148,854
173,663
198,472
223,281
248,090
272,899
297,709
322,518
347,327
372,136
396,945
421,754
446,563
471,372
496,181
21£/lb
(38^/bbl)
$ 2,894
5,788
8,683
11,577
14,471
17 , 366
20,260
23,155
26,049
28,943
57,887
86,831
115,775
144,719
173,663
202,607
231,551
260,495
289,439
318,383
347 , 327
376,271
405,214
434, 158
463,102
492,046
520,990
549,934
578,878
240/lb
(44<£/bbl)
$ 3,307
6,615
9,923
13,231
16,539
19,847
23,154
26,462
29,770
33,078
66,157
99,236
132,315
165,393
198,472
231,551
264,630
297,708
330,787
363,866
396,945
430,024
463, 102
496,181
529,260
562,339
595,417
628,496
661,575
-------
consisting of about 30 percent aqueous phase and 70 percent oil. If this opera-
tion were installed at the refinery, the 90 percent oil being sent to the refinery
and the 10 percent "emulsion seed" being returned with the ship for use with the
next oil cargo, the chemical cost would be reduced to capital cost and makeup-
but the ship's capacity would be reduced by 7 percent because of the returned '
oil.
There is indication from the literature that some emulsions can be completely
broken back by mechanical means as mentioned in Section 4. 8 of this report.
If this were possible at a cost similar to the equipment operation cost for emul-
sification, the picture would be much more attractive.
Estimates of savings for both the above discussed modifications in procedure are
included in Table 7.2-4.
7.3 Discussion of Economics of Emulsification Process
Estimates of the economic loss caused by oil spills ranges from 5 to 10 cents
per barrel of oil shipped. Emulsification prior to shipment would offer the
advantage of causing oil spilled gradually or by catastrophe to become widely
dispersed in the sea. It would follow sea currents along shore or seaward in-
stead of following the wind which frequently carries it ashore. Further, as it
became increasingly diluted with sea water, it would soon reach the non-toxic
level, and would readily be degraded by bacteria.
Estimates of costs for the emulsification/demulsification process for transport-
ing oils are summarized on Table 7.3-1. It can be seen that total processing
costs range from about 20 to 83 cents per barrel, without consideration of cost
offsets. Cost offsets could reduce these numbers from 5 to 15 cents per barrel.
Modifications of the procedure itself could provide additional savings up to near-
ly 4 cents per barrel. Due to the variation in costs of, and the alternates avail-
able in estimating overall costs, a nomograph is included with an example cal-
culation on Figure 7.2-1 of this report.
-123-
-------
TABLE 7.3-1
jiUMMARY OF COSTS AND POTENTIAL COST REDUCTIONS - RANGE
I. Summary of Costs
Item
a) Operating Costs of System
b) Chemical (Emulsifler) Costs
c) Emulsion Break -Back Costs
d) Cargo Capacity Reduction (3% Volume)
Total
II. Potential Cost Reductions - Through Cost Offsets
to
I
Item
a) Hazard Cost - Insurance and Clean Up
b) Crude Upgrading - Desalting
c) Reduced Leakage and Cargo Evaporation
Practical Range
Low (<£/bbl.) High (
-------
FIGURE 7.2-1
OVERALL COST ESTIMATION
12 345678
Put cost of equipment operations
(Table 7.2-2) in scale (1), run
vertical line to curve represent-
ing chemical cost (2), (If seed or
emulsifier is recovered and used
over, cost is chemical make-up
cost per barrel per trip). From
intersection of vertical line with
curve, run line to curve j(3),
giving demulsification and cargo
reduction cost. Drop line to curve
(4) giving offsetting gains, and
from intersection draw horizontal
line to (5), "overall net cost of
emulsification."
Dotted line represents 4<£/bbl
operating and equipment cost to
make emulsion, 6g5/bbl net
chemical cost (270/bbl used 3
times), with 13<£ demulsification
and cargo reduction charge, 5<£
benefit for desalting, insurance
reduction, etc. , giving an over-
all net cost of 21^/bbl.
-125-
-------
8. ACKNOWLEDGEMENTS
Many of the Sonics International, Inc. staff were asked for their advice or
assistance during this study. Their support was invaluable and greatly appre-
ciated.
Mr. M. G. Langhorne, Hunt Oil Company assisted in the procurement of foreign
oils, and in providing handling and shipping information.
Mr. A.R. Thomassen and his employer, Sun Oil Company, were very coopera-
tive in packaging and shipping, on short notice, four drums of Zueitina crude
oil. Without their assistance, the study would have been delayed during its first
few weeks.
Mr. G.O. Wheeler, Jr., Mr. W. B. Halladay and Mr. John G. Miller of Atlantic
Richfield Company, are due thanks for their efforts in obtaining and shipping
samples (four drums of each) of the Tia Juana medium crude and the #6 fuel oil.
Atlantic Richfield Company furnished these samples at no cost to the project.
Mr. R. G. Dulaney of Atlantic Pipe Line Company provided information on nor-
mal terminal operation.
Mr. Jack Frost of Ashland Chemical Company in Ashland, Kentucky, was kind
enough to review the concept contemplated in this study, and give his thoughts
and some of his employer's experience with their dispersant-Ridzlik.
Special thanks are due Mr. Glen White and his employer, Electro-Chem Lab-
oratories, Inc. of Fort Worth, Texas, for their work to develop and supply the
emulsifiers used in this study.
-126-
-------
9. LIST OF PUBLICATIONS CRITICAL TO STUDY
Listed below are key references selected to provide a thorough understanding of
the concept of handling crude oil and petroleum products in an emulsified state
to reduce pollution and other hazards of an oil slick resulting from a catastro-
phe or negligence during the normal operation of tankers on the seas and water -
ways. Also included are key references to provide background knowledge of the
problems and incidents which precipitated the search for methods to control oil
pollution of the seas and waterways. For a more complete coverage of the liter-
ature, the reader is referred to the reference subsection of each section in the
text of this report.
1. Battelle Memorial Institute, Pacific Northwest Laboratories, Oil Spillage
Study; Literature Search and Critical to Control and Prevent Damage, Novem-
ber 20, 1967.
2. Benyon, L.R., The "Torrey Canyon" Incident, A review of Events, The
British Petroleum Company, Ltd., September, 1967.
3. Nixon, James, Waldimer, Philippoff and Siminski, Vincent]., Optimization
of Nonoqueous Fuel Emulsions, USAAVLABS Technical Report 69-26, May,
1969.
4. Sherman, Philip, et. al, Emulsion Science, Academic Press, London and
New York, 1968.
5. Urban, C.M., Bowden, J.N. and Gray, J.T., Emulsified Fuels Gharacteris-
tics and Requirements (USAAVLABS Technical Report 69-24), U.S. Army
Aviation Material Laboratories, Fort Eustis, Virginia, March, 1969.
-127-
-------
10. GLOSSARY
1. API - American Petroleum Institute
2. ASTM - American Society of Testing Materials
3. bbl - barrel
4. bpm - barrels per minute
5, °C - degrees centigrade
6. continuous phase - the phase or liquid which forms the matrix
in which the droplets (dispersed phase) are
suspended
7. dispersed phase - the liquid which is present in the form of finely
divided droplets
8. dwt - dead weight tons
9. displacement - state of being displaced
10. emulsion - a very fine dispersion of one liquid in another with which
it is immiscible
11. °F - degrees Fahrenheit
12. gal - gallon, 3.78 liters
13. gpm - gallon per minute
14. hp - horsepower, 745 watts
15. in3 - cubic inches
16. KHz - kilohertz
17. 1 - liter
18. ml - milliliter
19. mg/1 - milligram per liter
20. ppm - parts per million
21. psi - pounds per square inch
-128-
-------
22. % - percent
23. rpm - revolutions per minute
24. seed emulsion - dispersed phase distributed as colloidal particles
in the continous phase by ultrasonic means
25. surfactant - surfacting agent, wetting"agent
26. TLgQ = TL - median toxic limit to toxic materials
27. ton - 2, 240 pounds (approximated as 7.5 barrels, 42 gallons each)
-129-
-------
REFERENCES
INTRODUCTION
Section 3.5
1. "Tankers Move the Oil That Moves the World", Fortune, p. 85, Septem-
ber 1, 1967.
2. "Shell's Fleet of 200,000 - Tonners", Shipbuilding and Shipping Record,
September 14, 1967.
3. "The 500,000 Ton dw Tanker", Shipbuilding and Shipping Record, January
6, 1967. ~
4. "Tankers of 500,000 Deadweight, Feasibility Study by Lloyd's Register of
Shipping", Shipping World and Shipbuilder.
5. Parker, T.J., "Approximate Hull Dimensions for 500,000 and 1,000,000
Deadweight Tankers", Shipping World and Shipbuilder, June, 1967.
6. The American Waterways Operators, Inc., 1967 Inland Waterborne Com-
mergejjtatistics, pp. 1, 2, 5, April, 1969.
7. Smith, J. W. , The "Torrey Canyon" Disaster, paper given at the annual
meeting of British Association for the Advancement of Science, Leeds,
England, September 6, 1967.
8. Zo Bell, C.E., "The Occurrence, Effects, and Fate of Oil Polluting the
Sea", fat. Jour. Air Water Poll., vol. 7, pp. 173-198, 1963.
9. Battelle Memorial Institute, Oil Spillage Study; Literature Search and
Critical Evaluation for Selection of Promising Techniques to Control and
Prevent Damage, pp. 4-28 and 4-29, November 20, 1967.
10. "The Torrey Canyon", report presented to Parliament by the Secretary of
State. London, England, Cmmd. 3246, April, 1967.
11. "Torrey Canyon Settlement Made", Abilene, Texas, Reporter-News,
November 12, 1969.
12. Bourne, W.R.P., Parrack, J.D. and Potts, G.R., "Birds Killed in the
Torrey Canyon Disaster", Nature, vol. 215, pp. 1123-1125, 1967.
-130-
-------
REFERENCES CONTINUED:
SELECTION OF OILS AND PREPARATION AND TESTING OF EMULSIONS
Section 4.2
1. Patent applied for, Method for Forming Emulsions and Products Thereof.
Section 4.3
1. American Society for Testing Materials, Book of A.S.T.M. Standards,
PartS, A.S.T.M. Designation: D217.
2. Urban, C.M., Bowden, J.N. and Gray, J.T. , Emulsified Fuels Char -
acteristics and Requirements, USAAV LABS Technical Report 69-24,
pp. 4-7, 64-74, March, 1969.
3. Nixon, James, Waldimer, Philippoff and Siminski, Vincent J., Opti-
mization of Nonaqueous Fuel Emulsions, USAAV LABS Technical Re-
port 69-26, pp. 65-93, May, 1969.
Section 4.7
1. American Public Health Association, Inc. , Standard Methods for the
Examination of Water and Wastewater, Twelfth Edition, pp. 546-566,
1965.
2. "Oil Spillage Study and Literature Search and Critical Evaluation for
Selection of Promising Techniques to Control and Prevent Damage",
Pacific Northwest Laboratories of Battelle Memorial Institute, p. 6-8.
3. Loc cit, p 6-11
4. Loc cit, p 6-6
5. Loc cit, p 6-10
6. Loc cit, p 6-12 and 6-13
7. Loc cit, p 6-6 and 6-7, "Bunder Oil"
8. See Table 4.7-6, of this Report
Section 4.8
1. USAAV LABS Technical Report 67-62, 1967.
-131-
-------
APPENDIX I
-132-
-------
TABLE 1-1
HATE FH0M LAb0KAT0KY
CKUDE:
DEI-Th
F IEK: i\i0N£
3F FILL: HALF
T I iyi E I M wT DISH
MINUTES DAYS
DISH AKEA* CMt2
INITIAL SA'^LE wT
CUMULATIVE WT L0SS
^S >* 0/0^*2 L
GtfS:
61
30
5455
KATE 0F wT L0SS
i*iIC/\'0-OJS L8S
/CMtg /FT'fg
/SEC /DAr
0
1
2
3
b
6
10
20
30:
60
1 20
240
360
500
1 470
0
0
0
0
0
0
.01
.01
.02
.04
.08
. 17
.25
.35
1 .02
64
64
64
64
63
63
63
63
62
62
61
60
59
58
57
.276
. 16
.099
.022
.88
619
.599
. 193
898
.241
318
.007
.095
.57
-283
0
.096
.179
.256
. 396
.439
.679
1 . 06 5
1 -36
2.037
2.96
4.271
5. 183
5. 70S
6.995
1 .
g.
4.
6.
7.
1 1
1 7
22
33
48
70
84
93
1 1
607
93^.
197
525
525
. 13
.79
.62
.39
. 53
.02
.97
.57
4. 7
3>291E-
6
8
1
1
m
3
4
6
.01 1E-
. 597E-
. 33 /L-
. 541 E-
0228
. 644E-
. 634E-
.641 £-
0994
1 434
1 741
1917
2349
3
3
3
2
2
2
2
2
26.78
22.13
21 .04
19.4
16.6 7
15.03
11.09
8.06
5.964
4.203
2.935
2.077
1 .025
363
4. 739
3.917
3.724
3*433
2-9b
2-66
1 .963
1 .427
1 .059
. 7439
.5283
.3675
.1613
.0642
-133-
-------
TABLE 1-2
EVAP0KATI0N KATE FK0t"i LAB0KAT0XT DISH
r\ uiyc. .
MULSIF
Ei-Tri £
ENfl'lLP
1 M t
iNUTEi
0
1
2
3
5
6
10
20
30
60
120
226
41 1
567
1 1 10
£. UC- i 1 1
'I EH : 1
IF FILL
il I0N:
I f\
; DArs
0
0
0
0
0
0
.01
.01
.02
.04
.08
- 16
,29
.39
.77
t Vfn
751
. : HALF
J tvT OlSh
--SAMPLE
) Cu H M ! .- o
64.2642
64.242
64.225
64-21 3
64. IS
64. 1 7
64.136
64.09
64.07
64.003b
6 3. 92 b 6
6 3 . d 1 4 1
63.681 7
63. 602 1
63.31 34
l C UM
GRAMS
0
0^22
.0392
.0512
0842
.09^2
. I2b2
. 1742
- 1942
.2604
.3386
.4501
.Db25
.6621
.9 bOB
u i on HK
I N i T I AL
ULATIVE
364
. 643
.339
1 . 3«
1 b44
2. 102
2 .656
3. 1«4
4.269
5.551
7.379
9.S49
10.65
1 5.59
SLHi L,MT'tt
'fiT LOSS
7 . 455E-4
1 .31611-3
1 . 719E-3
2 .02&E-3
3«1 63£-~ '3
4.30bE-3
b.(35E-3
6. 522 E- 3
8- 745E-3
1 . 137E-2
1 -b!2E-2
] .956E-2
2.223E-2
3. 193E-2
KATE 3F
6 « U 6 6
* 64 b
3.279
4. 506
2. 732
2.322
1 .257
.546
.603
. 356
.287
. 196
. 1 39
145
61
td t c' 1 /2
A'T L0SS
S L a S
/Fit?
3 .074
.822 1
. 5603
.7979
.4636
.<*! 1
.2224
.0967
. 1067
.063
0509
.0346
.0247
.0257
-134-
-------
TABLE 1-3
EVAP0RATI0N RATE KK0tf LAB0KAT0RY DISH
CRUDE: /1UE1TINA
EMULSIrlER: 1752
DEPTH 0F FILL: HALF
VENTILATI0N: 0PEN
DISH AREA, GMT2 61
INITIAL SAniPi-E wT* GMS: 25.2705
E
i N WT DISH
+SAMPLE
MINUTES DAYS GRAINS
COPULATIVE
GRAtfS
RATE 0r
LCJS/FT.T2 /C>nt2
/SEC
L0SS
LBS
0
1
2
3
5
6
10
20
30
60
126
240
3b6
702
0
0
0
0
0
0
.01
.01
-02
04
.09
. 1 7
.27
.49
btt
56
bb
58
58
58
58
58
t>y
bb
58
58
58
58
.966
.95
.934
.921
.892
.878
.841
.787
. 755
.71 78
.681 1
.6383
.524
361
0
.01 6
.032
.045
.074
.088
. 125
.179
;21 1
.2482
.2849
. 32 7 7
.4^2
.605
.262
.525
. 738
1=213
1 . 443
2.049
2.934
3-459
4.069
4.67
5.372
7 .246
9.918
5.
1 .
1 .
2 .
2 .
4-
6 .
7 -
8.
9 «
.0
i .
2.
373E-
075E-
51 1E-
485E-
955E-
198E-
01 1E-
086E-
33sE-
567E-
1 1
464E-
4
3
3
3
3
3
3
3
3
3
2
032E-2
4.
4.
3-
3-
3-
2.
1 .
« b
372
372
bb2
962
b25
527
475
74
339
. 1
. 1
-2
. 1
52
03
14
41
. 7 7 3 7
. 7737
. 62«6
. 70 12
. 6 7 7
. 4473
.261 1
. 1 547
.06
-0269
.0182
--379
. 0249
-135-
-------
TABLE 1-4
iaiM /\ATE FK0M LAd0KAT0HY DISn
CKUDE: ZUEITiNA 01 Sh AKEA, O>t2 61
EMULblFIEK: 1752 INITIAL SA--VLE *'T , G^b: 27.122
DEPTH 0F FILL: HALF
VtiMTlLAT10N:
i I t»i £ IN IA/T LJibtt CUMULATIVE wl L.0SS KATE 0K 'A'T LOSS
+ SAKIHLE MlCr^-CsMS Lbb
MINUTES DAYS UrtA.yiS GncAiMS iMG/C/it^ LH5/KT»2 /C-v;t2 /FTt2
/SLC
0
1
2
3
b
7
10
20
30
60
104
1 560
0
0
0
0
0
0
.01
.01
.02
04
.07
i .Ob
68.395
68 383
68 .365
6b.352
58.335
68-318
66.299
63.23
68 . 1 71
68-035
67.889
66.208
0
012
03
043
10.06
077
096
. 165
.224
.36
506
2.187
- 197
.492
. 705
164.9
1 .262
1 .574
2.705
3.672
5.902
8.295
35.85
4 0 3 E - 4
1 .007E-3
1 .444E-3
.3378
2 . 586E-3
3.224E-3
5. 541 E-3
7. 522 E-3
1 .209E-2
1 .699E-2
7.344E-2
3.279
4.918
3.552
1 3 6b .
- 1364.
1.73
1 .8b5
1.612
1 .239
.907
.31 5
. b803
.3704
.62 06
242.2
-24 I .4
. 3063
.3337
. 28 53
.2192
. 1 60 b
.0558
-136-
-------
TABLE 1-5
EVAP0KATI0N HATE FR0M LAB0RAT0Rr DISH
CRUDE: TIA JUANA
EMULSIFIER: N0NE
DEPTH 0F FILL: HALF
VENTILATION: 0HEN
TIME
I N WT DISH
+SAMHLE
MINUTES DAYS GRAMS GRAMS
DISH AREA, CMt2
INITIAL SAMPLE WT* GMS:
CUMULATIVE WT L0SS
61
42.7578
KATE 0F WT L0SS
MICR0-GMS LBS
MG/CMt2 LBS/FTT2 /CMt2 /KT»2
/SEC /DAY
0
1
2
3
5
6
10
20
30
60
120
273
335
1320
4320
15840
36000
0
0
0
0
0
0
.01
.01
.02
.04
.08
.19
.23
.92
3
1 1
25
81 .89
81 .86
81 .832
81 .808
81 .755
81 .728
8 1 . 62
81 -482
81 .359
81 .0195
80.55
79.962
7.9.763
78. 1321
76.7459
75.298
74.418
0
.03
.058
.082
. 135
. 162
.27
.408
.531
.8705
1 .34
1 .928
2.127
3.7579
5. 1441
6.592
7.472
.492
.951
1 .344
2.213
2.656
4.426
6.689
8.705
14.27
21 .97
31 .61
34.87
61 .61
84.33
108.1
122.5
1 .007E-3
1 .948E-3
2.754E-3
4.534E-3
5.44E-3
9.Q67E-3
.0137
1 .783E-2
2. 923E-2
.045
6.475E-2
7. 143E-2
. 1262
.1727
.2214
.2509
8. 197
7.65
6.557
7.24
7.377
7.377
3.77
3.361
3.092
2. 138
U05
877
.452
.126
.034
.012
1 .451
1 .354
1.161
1 .282
1 .306
1 .306
.6673
. 5948
.5472
.3784
1 8 58
. 1552
.0801
.0223
.0061
.0021
-137-
-------
TABLE 1-6
EVAP0KATI0N HATE FR0M LA80KAT0KY DISM
L.I%UUL. 11H iJUHWH
EMULSIFIEK: 1751
DErTH 0F FILL: HALF
VENTILATI0N: 0HEN
TIME IN WT DISH
+SAMFLE
i^INUTES DAVS GHAMS
0
1
2
3
5
7
10
20
30
60
120
240
1000
2000
3960
9840
15960
34260
0
0
0
0
0
0
.01
.01
.02
.04
.08
. 17
.69
1 .39
2.75
6.83
1 1 .08
23.79
61 .705
61 .696
61 .691
60.686
61 .6755
61 .6655
61 .652
61 .6156
61 .584
61 .505
61 .383
61.19
60.42
60.078
59.37
58.492
57.673
56.5278
UlSrt AKEA, CMT2 61
INITIAL SAMPLE WT, GMS: 26.2585
CUMULATIVE WT L0SS HATE 0F WT L0SS
GHAMS MG/CM*2 LBS/FTT2 /CMt2 /FTf2
/SEC /DAY
0
.009
014
1 .019
.0295
.0395
.053
.0894
. 121
.2
.322
.515
1 .285
1 .627
2.335
3.21 3
4.032
5. 1772
. 148
.23
16. 71
.484
.648
.869
1 .466
1 .984.
3.279
5.279
8.443
21 .07
26.67
38.28
b2.67
66. 1
84.87
3.022E-4
4. 70 IE- 4
3.422E-2
9.907E-4
1 . 326E-3
1 .78E-3
3-002E-3
4.063E-3
6.716E-3
1 .081E-2
1 .729E-2
4.31 5E-2
5.464E-2
7-841E-2
.1079
. 1354
. 1 739
2.459
1 .366
274. 6
- 135.2
1 .366
1 .23
.995
.863
.719
. 556
.439
.277
.093
.099
.041
.037
.017
.4352
.2418
48-6
-23.92
-2418
.2176
. 176
. 1 528
.1273
.0983
.0778
.049
.0165
.0175
.0072
.0065
.003
-138-
-------
TABLE 1-7
EVAP0KAT10N RATE FK0Kt LAB0HAT0Kf Di Sri
TIA JUANA
EMULSIFIEK: 1752
DEPTH 0F FILL: HALF
VENTILATI0N: 0PEN
TIME
IN WT DISH
+SAMPLE
MINUTES DAYS GKAMS GRAXiS
DlSn AREA, Ci*M2
INITIAL SAMPLE vVT
CUMULATIVE wT L0SS
GHi S :
61
32.0191
KATE 0F wT L0SS
1ICK0-GMS L'dS
LBS/KTt2
/SEC
/DAV
o
1
2
3
5
7
10
20
30
60
120
900
4140
8220
1 5960
0
0
0
0
0
0
.01
.01
.02
.04
.08
.63
2. -88
5.71
1 1 .08
67.
67.
67.
67.
67.
67.
67.
67.
66.
66-
66.
65.
64.
63.
61
127
1 19
1 12
106
094
0335
069
035
997
96
763
887
51 1
634
.855
0
»
*
*
1
2
3
008
01 5
021
033
-0435
058
092
1 3
167
364
.24
.616
.493
5.272
. 131
.246
. 344
. 541
.713
.951
1 . 508
2-131
2 . 738
5-967
20.33
42-89
57-26
86.43
2.
*'
7.
1 .
1 .
1 .
3.
4.
5.
1 .
4.
8.
. 1
. 1
68 7 1.
037E
052E
108E
46 1 E
94bE
09E-
366E
608E
222E
164E
785E
173
77
-4
-A
- 4
-3
-3
-3
3
- 3
-3
-2
-2
-2
2.186
1.913
1 .639
1 .639
1.434
1 .321
.929
1 .038
. 337
.897
. 307
.116
.059
.063
.3869
. 33t55
.290 1
.2901
.2539
.2337
« 1 644
.1838
.0596
. 1588
.0543
.0205
-0104
.0111
37020 25.71 60.634 6.493 106.4
.218
.016
.0028
-139-
-------
TABLE 1-8
EVAP0RATI0N RATE FR0M LAB0RAT0R* DJSH
0IL
CRUDE: N0.6 FUEL
EMULSIFIER: N0NE
DEPTH 0F FILL: HALF
VENTILATI0N: 0PEN
DISH AREA, GMt2
INITIAL SAMPLE
GMS:
61
37.
408
TIME
I N
WT DISH CUMULATIV
+SAMPLE
MINUTES
0
1
2
3
5
7
10 ,
20
30
60
120
1560
4080
10080
16000
DAYS
0
0
o
0
0
0
.01
01
.02
.04
.08
1.08
2.83
7
11.11
GRAMS
68.538
68.538
68.538
68.538
68-5375
68-537
68.5365
68.5363
68.5358
68.5323
68 . 52 58
68.4492
68.342
68.191
67.923
GRAMS
0
0
0
0
.OOOb
.001
.0015
.0017
.0022
.0057
.0122
.0888
.196
347
.615
MG/C
0
0
0
.008
.016
025
.028
.036
.093
.2
1 .456
3.213
5.689
10.08
WT L0SS HATE 0F WT L0SS
MICK0-GMS LBS
'2 LBS/FTT2 XCMT2 /FTt2
/SEC /DAr
0
0
5.037E-5
5.709E-5
7.388E-5
1.914E-4
4.097E-4
2.982E-3
6.582E-3
1.165E-2
2.065E-2
0
0
0 0
1.679E-5 .068
3.3b8'E-i> .068
.046
.005
.014
.032
03
.015
.012
.007
.012
0
0
0
.0121
-0121
.OOel
.001
.0024
.0056
.0052
.0'026
.0021
.0012
.0022
-------
TABLE 1-9
EVAP0RATI0N RATE FK0M LAB0RAT0RY DISH
DISH AREA* CMt2 61
INITIAL SAMPLE WT* GMS: 37.8312
CRUDE: N0.6 FUEL 0IL
EMULSIFIER: 1751
DEPTH 0F FILL: HALF
VENTILATI0N: 0PEN
TIME IN WT DISH
+SAMPLE
MINUTES DAYS GKAMS GRAMS MG/CMt2 LBS/FTt2
CUMULATIVE WT L0SS
RATE 0F wT L0SS
MICK0-GMS LBS
/DAY
/SEC
0
1
2
3
5
7
10
20
30
60
120
240
390
1440
3120
7200
1 5960
36030
0
0
0
0
0
0
.01
.01
.02
04
.08
.17
.27
1
2.17
5
1 1 .08
25>02
71 .745
71 .743
71 .742
7 .741
7 .7395
7 .736
7 .7315
7 .717
7 .704
71 .6725
7 1 . 62 5
71 .562
71 .497
71 .338
71.161
70.89
70.594
70.2906
0
.002
.003
.004
.0055
.009
.0135
.028
.041
.0725
.12
.183
.248
-407
.584
.855
1 . 151
1 .4544
.033
.049
.066
.09
. 148
.221
.459
.672
1 .189
1 .967
3.
4.066
6.672
9.574
14-02
18.87
23.84
6.716E-5
1 .007E-4
1 . 343E-4
1 .847E-4
3.022E-4
4.534E-4
9.403E-4
1 .37 7 £-3
2.435E-3
4.03E-3
6. 145E-3
8.328E-3
1 .367E-2
1 .961E-2
2.B71E-2
3-S65E-2
4 864E-2
.546
.273
.273
.205
.478
.41
.396
.355
.2ri?
.216
. 143
.118
.041
.029
.018
.009
004
.0967
0484
0484
.0363
.0846
.0725
»0701
.0629
0508
.0333
.0254
.021
.0073
.0051
.0032
.0016
0007
-141-
-------
TABLE 1-10
EVAP0RATI0N RATE FR3i'
CKUDE: N0.6 FUEL OIL
EtfULSIFlER: 1752
DEPTH 0F FILL: HALF
VENTILATI0N: 0PEN
TIME
LA80RAT0KV DISri
I N WT DISH
+SAMPLE
MINUTES DAYS GRAMS GRAMS
DISH AREM, CMt2
INITIAL SAMPLE WT*
CUMULATIVE WT L0SS
GMSJ
61
42.7542
HATE 0F WT L0SS
rtlCfta-GMS LBS
MG/CMT2 LBS/FT»2 /GMtg /F7t2
/SEC /DAY
0
1
2
3
5
7
10
20
30
60
120
240
360
1400
2880
0
0
0
0
0
0
.01
.01
.02
.04
.08
. 1 7
.25
.97
2
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
.572
.57
.569
.567
.563
56
.555
.541
.524
.497
.457
.397
.37
. 165
.07
0
.002
.003
.005
.009
.012
.01 7
.031
.048
.075
.115
. 175
.202
.407
.50,2
*
*
1
1
2
3
6
8
033
049
082
3 48
197
279
508
787
23
.885
.869
.311
.672
.23
6.
1 .
1 .
3.
4.
5.
1 .
1.
2.
3.
716E-5
007E-4
679E-4
022E-4
03E-4
709E-4
041E-3
612E-3
519E-3
862E-3
5>877E-3
6.
1 .
1 .
783E-3
367E-2
686E-2
.546
.273
.546
.546
.41
.455
383
.464
.246
.182
.137
.061
.054
018
.0967
.0484
.0967
.0967
.0725
.0806
0677
.0822
.0435
.0322
.0242
.0109
.0095
.0031
17280 12
70.51
1 .062
17.41
3.566E-2
01 1
0019
-142-
-------
TABLE 1-11
EVAP0RATI0N RATE FH0M LAB0RAT0HY DISH
DISH AREA, CMT2
INITIAL SAMPLE WT, GMS:
61
31.7295
CRUDE: ZUEITINA
EMULSIFIER: N0NE
DEPTH 0F FILL: HALF
VENTILATI0N: 1/4 INCH VENT
TIME IN WT DISH CUMULATIVE WT L0SS RATE 0F WT L0SS
+ SAMPLE MICR0-GMS LBS
MINUTES DAYS GRAMS GRAMS MG/CMt2 LBS/FT*2 /CMt2 /FTt2
/SEC /DAY
0
1
2
3
5
7
10
.20
30
60
120
240
360
780
1 470
4320
8640
16000
0
0
0
0
0
0
.01
.01
.02
.04
.08
.17
.25
.54
1 .02
3
6
11.11
97. 169
97. 164
97. 1603
97.156
97. 1494
97.143
97.132
97.105
97.068
96.996
96.836
96.546
96*415
96.0297
95.57
94.475
93.4466
92.216
0
.005
.0087
.013
.0196
.026
.037
.064
. 101
. 173
333
.623
.754
1 1393
1 .599
2.694
3.7224
4.953
.082
. 143
.213
.321
.426
.607
1 .049
1 .656
2.836
5.459
10.21
12.36
18.68
26.21
44.16
61.02
81 .2
1 .679E-4
2.922E-4
4.366E-4
6.582E-4
8.731E-4
1.243E-3
2.149E-3
3.392E-3
5. 8 IE- 3
1 . 1 18E-2
2.092E-2
2.532E-2
3.826E-2
.0537
9.047E-2
.125
.1663
1 .366
1 .01 1
1. 175
.902
.874
1.002
.738
I .01 I
.656
.729
.66
.298
.251
. 182
. 105
.065
.046
.2418
. 1789
.2079
. 1596
. 1547
. 1773
. 1306
. 1789
. 1 161
. 129
. 1 1 69
0528
.0444
.0322
.6186
.0115
.0081
-143-
-------
TABLE 1-12
EVAP0RATI0N RATE FR0M LAB0RAT0RY DISH
CKUDE: ZUEITINA
EMULSIFIER: 1751
DEPTH 0F FILL: HALF
VENTILAT10N: I/A INCH
DISH AREA,
INITIAL SAMPLE
WT, GMS:
61
24,
6865
VENT
TIME
I N
WT DISH
CUMULATIVE WT L0SS
+ SAMPLE
MINUTES
0
1
2
3
5
7
10
20
30
60
120
240
600
1 140
2520
5460
10080
16000
DAYS
0
0
0
0
0
0
.01
.01
.02
04
.08
.17
.42
.79
1 .75
3.79
7
11.11
GRAMS
94.879
94.876
94.874
94.871
94.866
94.861
94.854
94.832
94.807
94.75
94.652
94.495
94.2079
92.903
92.858
91 .823
90.6286
89-4978
GRAMS
0
003
005
008
.013
.018
.025
.047
.072
.129
.227
.384
.671 1
1.976
2.021
3.056
4.2504
5 38 1 2
MG/CMt£
049
.082
. 131
.213
.295
.41
.77
1 .18
2.1 15
3.721
6.295
1 1 .
32.39
33.13
50.1
69.68
88«22
i LBS/FTT2
1 .Q07E-4
1 .679E-4
2.687E-4
4.366E-4
6.045E-4
8-395E-4
1 .578E-3
2.418E-3
4.332E-3
7.623E-3
.0129
2.254E-2
6.636E-2
6.787E-2
.1026
.1427
.1807
RATE 0F WT L0SS
MICR0-GMS LBS
/CM*2
/SEC
.82
.546
.82
.683
.683
.638
.601
.683
.519
.446
.357
.218
.66
.009
.096
.071
.052
/FTT2
/DAY
.1451
.0967
. 1451
. 1209
>1209
. 1 128
. !064
. 1209
.0919
.079
.0633
.0386
.1 169
.0016
.01 7
.0125
.0092
-144-
-------
TABLE 1-13
EVAP0RATI0N RATE FR0M LAB0RAT0RY DISH
CRUDE: ZUEITINA
EMULSIFIER: 1752
DEPTH 0F FILL: HALF
VENTILATI0N: 1/4 INCH VENT
DISH AREA, Oit2 61
INITIAL SAMPLE WT, GMS: 26.325
TIME IN WT DISH CUMULATIVE WT L0SS RATE 0F WT L0SS
+SAMPLE MICK0-GMS LBS
MINUTES DAYS GRAtMS GRAMS iMG/CMr2 LBS/FTt2 /CMt2 /FTt2
/SEC /DAY
0
1
2
3
5
7
13
20
30
60
120
600
1080
1860
5520
10080
16000
0
0
0
0
0
0
01
.01
.02
.04
08
.42
75
1 .29
3.83
7
11.11
95*797
95.792
95.789
95.785
95.778
95.W75
95.755
95.735
95.705
9S.644.
95.527
95.085
94.525
93.885
92.709
91 .551
90.0688
0
.005
008
.012
.019
.022
.042
.062
.092
.153
.27
712
1 .272
1 .912
3.088
4«246
5.7282
.082
. 131
.197
>31 1
.361
.689
1 .016
1 .508
2.508
4.426
1 1 .67
20.85
31 .34
50.62
69.61
93.9
1 .679E-4
2.687E-4
4.03E-4
6>38E-4
7.388E-4
1 .41E-3
2.082E-3
3.09E-3
5. 138E-3
9.067E-3
2.391E-2
4.272E-2
6.421E-2
. 1037
.1426
. 1924
1 .366
.82
1 .093
.956
.41
.91 1
.781
.82
.556
.533
.252
.319
.224
.088
.069
.068
.2418
.1451
. 1934
. 1693
.0725
. 1612
.1382
.1451
.0983
.0943
.0445
.0564
.0397
.0155
.0123
.0121
-145-
-------
TABLE 1-14
EVAP0RATI0N KATE FR0M LAB0RAT0RY DISH
CRUDE: TIA JUANA
EMULSIFIER: N0NE
DEPTH 0F FILL: HALF
VENTILATI0N: 1/4 INCH
DISH AREA, CMt2
INITIAL SAMPLE WT, CMS:
61
19.9708
VENT
TIME
I Nf . WT DISH
+SAMPLE
CUMULATIVE WT L0SS
MINUTES DAYS GRAMS GRAMS MG/CMt2 LBS/FTT2
RATE 0F WT L0SS
MICR0-GMS LBS
/SEC
/DAY
0
1
2
3
-5 .-...
V^
40
20 ;
30
60
"120
240
1000
2640
6960
0
0
0
6
0
0
*
*
- - . : *
'"'%
*
*
1
4
01
01
02
04
08
17
69
.83
S3
92.
92.
92.
92.
92.
92.
92.
92-
92.
92.
92.
92.
91
91.
90.
418
415
413
4105
406
402
394
3753
358
313
237
126
755
436
993
0
.003
.005
0075
.012
016
.024
0427
.06
.105
.181
.292
.663
.982
1.425
»
.
*
»
*
*
1
2
4
1
1
049
082
123
197
262
393
7
984
.721
.967
.787
0.87
6.1
23.36
1
1
2
4
5
8
1
2
3
6
9
2
3
4
.Q07E-4
679E-4
.519E-4
.03E-4
373E-4
.Q6E-4
434E-3
015E-3
. 526E-3
078E-3
.806E-3
.2S6E-2
.298E-2
.785E-2
.82
.546
683
.615
.546
.729
.51 1
.473
.41
.346
.253
. 133
.053
.028
. 1451
.0967
- 1209
. 1088
.0967
. 129
.0904
.0837
.0725
.0613
.0447
.0236
.0094
.005
16000 11*11 90-6652 L7528 28.73 5-886E-2 .01
0018
-146-
-------
TABLE 1-15
EVAP0RATI0INJ RATE FR0M LAti0RAT0RT DISH
CRUDE: TIA JUANA
EMULSIFIER: 1751
DEPTH 0F FILL: HALF
VENTILATI0N: IXA INCH VENT
DISn AREA* C«*2 61
INITIAL SAMPLE wT* CtfS: 29.511
TIME IN WT DISH CUMULATIVE wT L0SS RATE 0F >,-T L0SS
+SAMPLE MICR0-GMS LBS
MINUTES DAYS GRAtfS GRAMS MG/O1t2 LBS/FTt2 /Civ/t2 /FT*2
/SEC /DA5f
0
1
2
3
5
7
10
20
30
60
120
240
400
742
1440
4320
8640
16000
0
0
0
0
0
0
.01
.01
.02
.04
.08
.17
.28
.52
1
3
6
11.11
94.744
94.74
94.736
94.732
94.731
94.729
94.725
94.714
94.701
94.675
94-622
94.515
94.46
94.23
93.95
93.203
92.621
91 .9507
0
004
.008
.012
.013
.015
.019
.03
043
.069
.122
.229
.284
.51 4
.794
1 .541
2. 123
8. 7933
.066
. 131
. 197
.213
.246
.31 1
.492
. 70 5
1 .131
2.
3.754
4.656
8.426
13.02
25.26
34.8
45.79
1 .343E-4
2.687E-4
4.03E-4
4-366E-4
5.037E-4
6.38E-4
1 .007E-3
1 .444E-3
2.31 7E-3
4.097E-3
7.69E-3
9.537E-3
1 .726E-2
2.666E-2
5. 175E-2
7. 129E-2
.0938
1 .093
1 .093
I .093
. 137
.273
364
.301
.355
.237
.241
244
.094
. 184
. 1 1
.071
.037
.025
. 1934
. 1 934
. 1934
.0242
.0484
.0645
.0532
.0629
.0419
.0427
.0431
.01 66
.0325
.0194
.0125
.0065
.0044
-147-
-------
EVAr>0«ATI0N RATE FR0M
TABLE 1-16
LAB0RAT0RY DISH
CRUDE: TiA JUANA
EMULSIFIEK: 1752
DEPTH 0F FILL: HALF
VENTILATI0N: I/A INCH VENT
DISH AREA, CMt2
INITIAL SAMPLE l
CMS:
61
29.^02
TIME
I N
WT DISH
-» SAMPLE
MINUTES DAYS GRAMS GRAMS
CUMULATIVE WT L0SS
MG/CM*2
RATE 0F WT L0SS
fiICK0-GMS LBS
'/SEC
/DAY
0
1
2
3
5
7
10
20
30
60
120
240
796
1 140
4020
8640
16000
0
0
0
0
0
0
.01
.01
.02
.04
.08
. 17
.55
.79
2.79
6
11.11
101 .491
101 .48
101 .475
101 .473
101 .471
101 .467
101 .464
101 .455
101 .436
101 .416
101 .355
101.3
101 109
100.781
99-984
99.391
98.952
0
'-.Oil
.016
.018
02
.024
.027
.036
.055
.075
. 136
.191
.382
.71
1 .507
2. 1
2.539
.18
.262
.295
.328
.393
.443
.59
.902
1 .23
2.23
3- 131
6.262
1 1 .64
24.71
34.43
41 ,62
3.694E-4
5.373E-4
6.045E-4
6.716E-4
8.06E-4
9.067E-4
1 .209E-3
1 .847E-3
2.519E-3
4.567E-3
6-414E-3
1 .283E-2
2.384E-2
5.061E-2
7.052E-2
8.526E-2
3.005
1.366
.546
.273
.546
.273
246
.519
.182
.278
.125
.094
.261
.076
.035
.016
. 5319
.2418
.0967
.0484
.0967
.0484
.0435
.0919
.0322
.0492
.0222
.0166
.0461
.0134
.0062
.0029
148-
-------
TABLE 1-17
EVAP0RATI0N KATE FR0tf LAB0RAT0RY DISH
CRUDE: N0.6 FUEL 0IL
EMULSIFIER: N0NE
DEPTH 0F FILL: HALF
VENTILAT10N: I/A INCH \yENT
DISH AREA* CM f2 61
INITIAL SAMPLE WT.. CMS: 35.7328
TIMt IN WT DISH CUMULATIVE NT L0SS RATE 0F WT L0SS
+SAMPLE MICR0-6MS LBS
MINUTES DAYS GHAMS GRAiMS MG/CM»2 LBS/FTt2 /O)T2 /FT'r2
/SEC /DAY
0
1
2
3
5
7
10
20
30
60
120
360
1380
5760
1 6000
0
0
0
0
0
0
.01
.01
.02
.04
OS
.25
.96
A
11.11
103.955
103.955
103.954
103.953
103.953
103.952
103.952
103.951
103.95
103.948
103.943
103.935
103.916
103.853
103-796
0
0
.001
.002
.002
.003
-003
.004
.005
.007
.012
.02
.039
.102
.1 59
0
016
.033
033
.049
.049
066
.082
.115
.197
.328
.639
1 .672
2.607
0
3.358E-5
6.716E-5
6.716E-5
1 .007E-4
1 .007E-4
1 .343E-4
1 .679E-4
2-351E-4
4.03E-4
6.716E-4
1-.31-E-3
3.425E-3
5.339E-3
0
273
.273
0
. 137
0
.027
.027
018
023
009
.005
004
.002
0
.0484
.0484
0
.0242
0
.0048
.0048
.0032
.004
.0016
.0009
.0007
.0003
-149
-------
EVAP0KATI0N KATE FK0M
CRUDE: N0.6 FUEL 0IL
EMULSIFIES: 1751
DEPTH 0F FILL: HALF
VENTILATI0N: 1/4 INCH VENT
DISH AREA, CMT2
SAMPLE
61
CMS: 30.3945
TIME
IN WT DISH
-i- SAMPLE
CUMULATIVE WT L0SS
KATE 0F
T L0SS
LBS
0
1
2
3
5
7
10
20
30
60
120
240
360
1440
5760
0
0
0
0
0
0
01
.01
.02
04
.08
17
25
1
4
97.241
97.241
97.2408
97.2406
97.24
97.2395
97.2385
97. .235
97.232
97.2239
97.215
97.205
97. 1915
97.162
97.033
0
o
0002
0004
.001
001 5
.0025
.006
009
.0171
.026
036
.0495
.079
.208
003
-007
016
025
041
098
1 48
.28
.426
59
81 1
1 .295
3.41
0
6.716E-6
1 -343E-5
3.358E-5
5.037E-5
8.395E-5
2.01 5E-4
3.022E-4
5.742E-4
8.731E-4
1 .209E-3
1 .662E-3
2..653E-3
6.985E-3
0
055
.055
082
068
.091
.096
.082
074
.041
023
031
.007
.008
0
0097
.0097
0145
0121
-0161
0169
.0145
0131
.0072
.004
.0054
0013
0014
16000 11.11 96.8452 .3958 6.489 1.329E-2
>005
0009
-150-
-------
KATE
TABLE 1-19
?) LAB0rtAT0KY DliJM
CKUDE: N0.6 FUEL 0IL
ErtULSIFiER: 1752
DEPT« 0F FILL: HALF
VENT1LATI0N: 1/4 IMCri VENT
DiSn AKEA., Ctvft2 61
INITIAL SAMPLE WT* CMS: 43.752
7 I
WT DISH
CUMULATIVE WT L0SS RATE 0F WT L0SS
MICR0-GMS LBS
MINUTES DAYS GHAMS GHAMS c)G/C'Vt2 LBS/FTtg /CHt2 /FTt2
/SEC /DA*
0
1
2
3
5
7
10
20
30
60
120
240
480
1 440
5760
0
0
0
0
0
0
.01
.01
.02
.04
.08
. 17
.33
1
4
1 10.297
1 10.296
1 10.296
1 10.295
1 10.295
1 10.294
1 10.293
1 10.29
1 10-2b6
1 10.28
1 10.265
1 10.245
1 10.206
110.113
109.87
0
.001
.001
.002
.002
.003
.004
.007
.01 1
.01 7
.032
.052
.091
.184
.427
.016
.016
.033
.033
.049
.066
.115
. 18
.279
.525
.852
1 .492
3-016
7.
3-358E-5
3.358E-5
6.716E-5
6.716E-5
1 .007E-4
1 .343E-4
2.3S1E-4
3.694E-4
5-709E-4
1 .075E-3
1 .746E-3
3-056E-3
6. 179E-3
1 .434E-2
.273
0
.273
0
. 137
.091
.082
. 109
.055
.068
.046
.044
.026
.01 5
.0484
0
.0484
0
.0242
-0161
.0145
.0193
.0097
.0121
.0061
.0079
.0047
.0027
11460 7.96 109.765
532
8.721
1.787E-2 .005
0009
-151-
-------
TABLE 1-20
EVAH0RATI0N RATE FK0M LAB0RAT0KY DISH
CRUDE: ZUEITINA
EMULSIFIER: N0NE
DEPTH 0F FILL: FULL
VENTILATI0N: 0PEN
DISH AREA, CM»2
INITIAL SAMPLE WT*
CMS:
61
77.649
TIME I N WT DISH
+SAMPLE
MINUTES DAYS GRAMS GRAMS
CUMULATIVE WT L0SS
Me/CMT2 LBS/FTT2
RATE 0F WT L0SS
MICR0-G.MS LBS
/SEC
/DAY
0
1
2
3
5
6
10
20
30
60
120
180
0
0
0
0
0
0
.01
.01
.02
.04
.08
. 13
1 13.413
1 13.21
1 13.04
1 12.882
1 12.585
1 12.301
1 1 1 .99
1 1 1 .2
1 10.625
109.329
107 .02
106.53
0
.203
.373
.531
.828
1.112
1 .423
2.21 3
2.788
4.084
6.393
6.883
3.328
6.1 15
8.705
13.57
18-23
23.33
36.28
45.71
66.95
104.8
1 12.8
6.817E-3
1 -253E-2
1 . 78-3E-2
2. 781 £-2
3.734E-2
4.779E-2
7.432E-2
9.363E-2
.1371
.2147
.231 1
55.46
46.45
43.17
40.57
77.6
21 =24
21 .59
15.71
1
1 1 .8
10.52
2.231
9.817
8.221
7.641
7. 181
13.73
3.76
3.82
2.781
2.089
1 .861
.3949
-152-
-------
TABLE 1-21
EVMP0RATI0N RATE FROM LAB0RAT0RY DISri
CRUDE: ZUEITINA
ErtULSIFIER: 1751
DEPTH 0F FILL: FULL
VENTILATI0N: 0PEN
TIME IN WT DISH
+SAMPLE
tMINUTES DAYS bRA^S
DISH MREA, CMt2 61
INITIAL SAMPLE WT> CMS: 70.3912
CUMULATIVE wT L0SS
MG/Cr»lt2 LBS/FTT2
RATE 0F WT L0SS
MICR0-GMS LBS
/CM*2 /FTt2
/SEC /DAY
0
1
2
3
5
6
10
20
30
60
120
240
490
1065
1820
2950
6130
14220
0
0
0
0
0
0
.01
.01
.02
.04
.08
.17
.34
.74
1 .26
2.05
4.26
9.88
106.675
106.657
106.633
106.62
106.6
106.591
106.567
106-532
106.51
106.471
106.415
106.265
106.204
105.977
105.271
104.586
102.386
100.515
0
.018
-042
.055
.075
.084
. 108
.143
. 165
.204
.26
41
.471
.698
1 .404
2.089
4.289
6. 16
.295
.689
.902
1 .23
1 .377
1.77
2.344
2.705
3.344
4.262
6.721
7.721
1 1 .44
23.02 '
34.25
70.31
101 .
6.045E-4
1 . 41E-3
1 .847E-3
2.519E-3
2.821E-3
3-627E-3
4.802E-3
5.541E-3
6.851E-3
8-731E-3
1 .377E-2
1.582E-2
2.344E-2
4.71 5E-2
7.015E-2
. 144
.2069
4.918
6.557
3. 552
2.732
2.459
1 .639
.956
.601
.355
.255
.342
.067
. 108
.255
. 166
. 189
.063
.8704
1.161
. 6286
.4836
.4352
.2901
. 1693
. 1064
.0629
.0451
..0604
.01 18
.0191
.'0452
.0293
.0335
.01 12
36000 25
95.629 11.046 181.jl
3709
.061
0108
-1S3-
-------
EVAP0KATI0N RATE
TABLE 1-22
FK0M LAB0RAT0RY DISH
CRUDE: ZUEITINA
EMULSIFIED: 1752
DEPTH 0F FILL: FULL
VENTILATI0N: 0PEN
TIME
I N WT DISH
+SAHPLE
MINUTES DAYS GHAMS GRAMS
DISH AREA, CMt2
INITIAL SAMPLE WT,
CUMULATIVE WT L0SS
CM S :
61
76.6614
RATE 0F WT L0SS
MICR0-GMS LBS
MG/CMt2 LBS/FTT2 /CM*2 /FTt2
/SEC /DAY
0
i
2
3
5
6
10
20
30
60
120
240
360
1 176
1796
0
0
0
0
0
0
.01
.01
.02
.04
.08
.17
.25
.82
1 .25
1 12.385
1 12.365
1 12.348
1 12.331
1 12.304
1 12.294
1 12.265
1 12.215
1 12.185
1 12.15
1 12.121
1 12.07
111 .738
1 11 .597
1 1 1 .215
0
.02
.037
.054
.081
.091
.12
.1 7
.2
.235
.264
.31 5
.647
.788
1 .17
.328
.607
.885
1 .328
1 . 492
1 .967
2.787
3.279
3.852
4.328
5. 164
10.61
12.92
19. 18
6.716E-4
1 .243E-3
1 .813E-3
2.72E-3
3.056E-3
4.03E-3
5.709E-3
6.716E-3
7.892E-3
8.866E-3
1 .058E-2
2. 173E-2
2.646E-2
3.929E-2
5.464
4.645
4.645
3.689
2.732
1 .981
f. 366
.82
.319
. 132
.116
.756
.047
. 168
.9671
.8221
.8221
.6528
.4836
3506
.2418
. 1451
.0564.
.0234
.0206
. 1338
.0084
.0298
-154-
-------
TABLE 1-23
EVAP0RATI0N RATE FR0M LAB0RAT0KY DISH
CRUDE: TIA JUANA
EMULSIFIER: N0NE
DEPTH 0F FILL: FULL
VENTILATI0N: 0PEN
DISH AREA, CMt2 61
INITIAL SAMPLE WT, CMS: 72.438
T I M E
I N WT DISH
-(SAMPLE
CUMULATIVE WT L0SS
RATE 0F WT L0SS
MICK0-GMS LBS
INUTES
0
1
2
3
5
6
10
20
30
120
240
360
DAYS
0
0
0
0
0
0
.01
.01
.02
.08
.17
.25
GRAMS
109.121
109-075
109.042
109.001
108.942
108.91
108.802
108.6
108.442
108.185
107.35
107.12
GRAMS
0
.046
.079
.12
. 179
.21 1
.319
.521
.679
.936
1 . 771
2.001
MG/CMt2
.754
1 .295
1 .967
2.934
3.459
5.23
8.541
11.13
1 5.34
29.03
32.8
LBS/FTt2
1 .545E-3
2.653E-3
4.Q3E-3
6.01 IE.,3
7.086£%S
1 .071E-2
.0175
.0228
3. 143E-2
5.947E-2
.0672
/SEC
12.57
9.016
1 1 .2
8-06
8.743!
7.377
5.519
4.317
.78
1 .901
.524
/FTt2
/DAY
2.224
1 .596
1 .983
1 .427
1 .547
1 .,306
.9768
-764
.1381
. 3365
.0927
-185-
-------
TABLE 1-24
EVAPORATION KATE FK0M LAB0RAT0RY DISH
CRUDE: TIA JUANA
EMULSIFIEK: 1751
DEPTH 0F FILL: FULL
VENTILATI0N: 0PEN
DISH AREA, CMt2 61
INITIAL SAMPLE WT, CMS: 85.086
TIME IN WT DISH CUMULATIVE WT L0SS
+ SAMPLE
MINUTES DAYS GRAMS GRArtS MG/CM'2 L8S/FTt2
0
1
^
3
5
7
10
20
30
60
120
240
0
0
0
0
0
0
.01
.01
.02
.04
-OS
. 17
1 18.89
1 18.881
1 18.875
1 18.871
1 18.86
1 18.851
1 18.837
118.8
1 18.767
1 18.691
1 18.575
1 18.365
0
009
.01 5
.019
.03
.039
.053
09
.123
. 199
.315
.525
. 1 48
.246
.31 1
.492
.639
.869
1 .475
2.01 6
3.262
5. 164
8.607
3.022E-4
5.037E-4
6.38E-4
1 .007E-3
1 .31E-3
1 -78E-3
3.022E-3
4. 131E-3
6.683E-3
1 ..058E-2
1 .763E-2
RATE 0F WT L0SS
MICH0-GMS LBS
/CMT2 /FT* 2
/SEC /DA1T
2^459
1 -639
1 .093
1.503
1.23
1.27^
1.011
.902
.692
.528
.478
.4352
.29 1
.1934
.266
.21 76
.2257
. 1 789
. 1596
. 1225
-0935
.0846
1090
76
1 17.7
1 .19
19.51
3-996E-2 .214
.0378
-156-
-------
EVAP0RATI0N KATE
TABLE 1-25
FK0i*5 LAB0KAT0KV 01 Sri
CRUDE: TIA JUAN A
EtfULSIFlErt: 1752
DEPTH 0F FILL: FULL
VENT1LATI0N: 0PEN
TIME
DISM AKEA, Ctft2 61
INITIAL SAMPLE WT* CtfS: 83*304
CUMULATIVE WT L0SS
IN WT DISH
-(SAMPLE
MINUTES DAYS GRAMS GRAMS HG/CM»2 LBS/FTT2 /Cl*it2
/SEC
KATE 0F WT L0SS
MICK0-GMS LBS
/DAY
0
1
2
3
5
7
10
20
30
60
120
287
420
1440
3120
7200
14500
36000
0
0
0
0
0
0
.01
01
.02
.04
.08
.2
.29
1
2.17
5
10.07
25
1 11 .225
1 1 1 .218
1 1 1 .212
1 1 1 .205
1 1 1 .196
111. 186
1 1 1 .173
1 1 1 . 135
111.101
1 1 1 .025
1 10.907
1 10.605
1 1 0 . 32 1
109.628
108.8.75
107.542
105.312
102.602
0
.007
.013
.02
.029
.039
.052
.09
.124
.2
.318
.62
.904
1 .597
2.35
3.683
5.913
8.623
.115
.213
328
.475
.639
.852
1 .475
2-033
3.279
5.213
10.16
14.82
26. 18
38.53
60.38
96.93
141 .4
2.351E-4
4.366E-4
6.716E-4
9.739E-4
1 .31E-3
1 .746E-3
3.022E-3
4. 1 64E-3
6.716E-3
1 .068E-2
2.082E-2
3.036E-2
5.363E-2
7.892E-2
.1237
. 1986
2896
1 .913
1 .639
1 .913
1 .23
1 .366
1 . 184
1 .038
.929
.692
.537
.494
.583
. 186
.122
.089
.083
.034
.3385
.2901
. 338 5
.2176
.2418
.2095
. 1838
. 1 644
. 1225
. 095 1
.0874
. 1033
.0329
.0217
.0158
.0148
.0061
-157-
-------
TABLE 1-26
EVAPORATION RATE FR0M LABORATORY DISH
OIL
CRUDE: N0.6 FUEL
EMULSIFIER: 1751
DEPTH 0F FILL: FULL
VENTILATION: OPEN
TIME
DISH AREA, CMtg
INITIAL SAMPLE WT*
CMS:
61
96.765
I N WT DISH
+SAMPLE
MINUTES DAYS GRAMS GRAMS
CUMULATIVE WT LOSS
MG/CMt2 LBS/FTt2
RATE 0F WT L0SS
MICR0-GMS LBS
/SEC
/DAY
0
1
2
3
5
7
10
20
30
60
120
240
360
2880
6960
16000
36000
0
0
0
0
0
0
.01
.01
.02
.04
.08
.17
.25
2
4.83
11.11
25
131 .437
131 .437
131 .436
131 .435
131 .432
131 .429
1 3 1 42 5
131 .409
131.4
131 .364
1 31 .312
131 .239
131 .081
130.896
130-514
129.8
129.035
0
0
.001
.002
.005
.008
012
.028
.037
.073
.125
.198
.356
.541
.923
1 -637
2.402
0
.016
033
.082
. 131
.197
.459
.607
1 . 197
2.049
3.246
5.836
8.869
15.13
26.84
39.38
0
3.358E-5
6.716E-5
1 .679E-4
2.687E-4
4.03E-4
9.403E-4
1 .243E-3
2.451E-3
4.198E-3
6.649E-3
1 . 196E-2
1 .817E-2
.031
5.497E-2
8.066E-2
0
.273
.273
41
41
364
.437
.246
.328
.237
. 166
.36
.02
.026
.022
.01
0
.0484
.0484
.0725
.0725
.0645
.0774
.04,35
.058
.0419
.0294
.0637
.0036
.0045
.0038
.0018
-158-
-------
TABLE 1-27
EVAP0RATI0N RATE FR0« LABORATORY DISH
CRUDE: N0.6 FUEL 0IL
EflULSIFIER: 1752
DEPTH 0F FILL: FULL
VENTILATI0NJ 0PEN
TIME
DISH AREA* CMt2 6i
INITIAL SAMPLE WT, CMS: 100.11
I N WT DISH
+SAMPLE
MINUTES DAYS GRAMS GRAMS
CUMULATIVE WT L0SS
L3S/FT*2
RATE 0F WT L0SS
MICR0-GMS LBS
/SEC
/DAY
0
1
2
3
5
7
10
20
30
60
120
240
360
1400
1680
7200
1 7280
0
0
0
0
0
0
.01
01
.02
.0-4
OS
.17
.25
.97
1 .31
5
12
1 33
133
133
133
133
133
133
133
133
33
33
33
33
32
32
132
131
. 185
.181
. 181
.178
. 174
. 169
.162
. 151
. 145
.115
.096
.062
.035
.775
.65
.365
.8*65
0.
.004
.004
.007
.01 1
.016
.023
.034
.04
07
.089
. 123
.15
.41
.535
.82
1 .32
«
»
«
»
*
1
1
2
2
6
8
1
2
066
066
1 15
18
262
377
557
656
.148
.459
.016
.459
.721
.77
3.44
1 .64
1
1
2
3
5
7
1
1
2
2
4
5
1
1
2
4
.343E-
.343E-
351E-
.694E-
.373E-
. 724E-
. I 42E-
343E-
.351E-
.989E-
131E-
.037E-
377E-
797E-
.7S4E-
4
A
4
4
4
A
3
3
3
3
3
3
2
2
2
..433E-2
1 .093
0
.32
. 546
« 6d3
. 6 3S
.301
. 1 6^
.273
.087
.077
.061
.068
.071
.015
.014
. 1934
O
.1451
.0967
. 1209
- 1 32«
-0538
.029
. 0484
.01 53
.0137
.0109
.0121
.0126
.0026
.0024
-159-
-------
APPENDIX II
-160-
-------
O O Q Q 0 O Q
Q 0 Q Q Q Q O
SONICS INTERNATIONAL, INC.
i| 7101' CARPENTER FREEWAY, DALLAS, TEXAS 75247
DATE: 9-9-^,9
APPROVED BY:
DRAWN BY
JKG
REVISED
FLAT PLATE HOMOGENIZER DRAWINGS
(DISCLOSURE")
FIGURE II-1
DRAWING NUMBER
-------
LEGEND
FIGURES
I. a) FIGURE 1 - Schematic of process
b) FIGURE 2 - Top view of Item 6 in Figure 1
c) FIGURE 3 - Cross section of Figure 2 @ 3-3
NUMBERS
II. 2) Tank or vessel (open or closed)
A) Pump
6) Ultrasonic transducer
8) Blender (or mixer motor)
9) Material being mixed or blended w/that from
10) Blending (or mixing) chamber
11) Ultrasonic generator
12) Face plate (steel, aluminum or plastic)
14) Gasket
16) Fitting
17) Fitting
18) Fitting
20) Transducer case
22) Transducers
23) Transducer plate
-162-
-------
LETTERS
III. A) Distance between fitting #16 and #23 (transducer plate-this distance
may be varied)
B) Distance between #12 face plate and #23 (transducer plate-this distance
may also be varied).
-163-
-------
OPERATION
A mixture of materials - properties of which prevent them from being mixed
ordinarily - such as oil and water - are pumped from vessel (#2), by pump (#4),
through ultrasonic transducer (#6)* which homogenizes the two (or more) liquids
by irradiation with ultrasonic waves. From (#6), the liquid flows to (#10), blend-
ing (or mixing) vessel where it is mixed with material from (#9). The product
of the two leaves (#10).
* This is the heart of the process. Flowing the liquid between two flat plates
gives a uniform homogenization of the liquids and at a much greater quantity
(or flow rate) than possible by other means available at this time.
-164-
-------
BIBLOGRAPHIC: Sonics International, Inc. Ultrasonic Emulsificatlon of Oil Tanker Carm
FWPCA Publication No. 15080 DJQ 04/70. ^
ABSTRACT: As a pollution preventive concept, the ultrasonic emulslfication of oil for marine
transportation has been tested for feasibility . Two crude oils and a common fuel oil were
emulsified and tested. The emulsions are characterized as stable, dispersible in sea
water, not unduly toxic and with reduced fire hazard potentials. This laboratory study
shows that oil emulsions can he created by ultrasonics in a continuous process at tanker
loading rates. Limited economic evaluation shows the concept to be meritorious and
reasonable.
PURPOSE OF PROJECT: The purpose of this project was to study the feasibility of pro-
ducing emulsified oil at a rate comparable with conventional tanker loading rates and
to investigate the economic and ecological factors.
SCOPE OF PROJECT: To determine blender design parameters and emulsified oil
characteristics, two crude oils and one fuel oil were chosen. A Libyan light oil, a
Venezuelan oil and #6 Fuel Oil were used. Only two emulsifiers were used and they
were base-neutralized sulfonated nonlonics. These are compatible with sea water and
of low toxicity. The emulsions tested were oil-in-water. Oil was the internal phase
and 97% of the total. Water and chemical was the external phase and 3% of the total.
1 The tests on the emulsions were to determine: stability under simulated transportation
, conditions, dispersibilltry in eea water, toxicity to fish, and product alteration. Included
were tests with safety aspects: evaporation rates, flash points, vapor pressures and
rupture leak tests. An economic study was made which shows emuls if i cation costs of
about 20 cents per barrel without considering possible offsets or side benefits.
This report was submitted In fulfillment of Contract 14-12-559 between the Federal
Water Pollution Control Administration and Sonics International, Inc.
r
BIBLOGRAPHIC: Sonics International. Inc. Ultrasonic Em unification of Oil Tanker Cargo
FWPCA Publication No. 15080 DJQ 04/70,
1 ABSTRACT: As a pollution preventive concept, the ultrasonic emulslfication of oil for marine
transportation has been tested for feasibility. Two crude oils and a common fuel oil were
1 emulsified and tested. The emulsions are characterized as stable, dispersible in sea
water, not unduly toxic and with reduced fire hazard potentials. This laboratory study
shows that oil emulsions can be created by ultrasonics in a continuous process at tanker
loading rates. Limited economic evaluation shows the concept to be meritorious and
' reasonable.
PURPOSE OF PROJECT: The purpose of this project was to study the feasibility of pro-
ducing emulsified oil at a rate comparable with conventional tanker loading rates and
to investigate the economic and ecological factors.
SCOPE OF PROJECT: To determine blender design parameters and emulsified oil
characteristics, two crude oils and one fuel oil were chosen. A Libyan light oil, a
Venezuelan oil and #6 Fuel Oil were used. Only two emulsifiers were used and they
I were base -neutralized sulfonated nonlonics. These are compatible with sea water and
of low toxicity. The emulsions tested were all-in-water. Oil was the internal phase
] and 97% of the total. Water and chemical was the external phase and 3% of the total.
The tests on the emulsions were to determine: stability under simulated transportation
conditions, dispersibillty in sea water, toxicity to fish, and product alteration. Included
were tests with safety aspects: evaporation rates, flash points, vapor pressures and
rupture leak tests. An economic study was made which shows emulslfication costs of
about 20 cents per barrel without considering possible offsets or side benefits.
This report was submitted in fulfillment of Contract 14-12-559 between the Federal
Water Pollution Control Administration and Sonics International, Inc.
BIBLOGRAPHIC: Sonics International, Inc. Ultrasonic Emulslfication of Oil Tanker Cargo
FWPCA Publication No. 15080 DJQ 04/70.
ABSTRACT: As a pollution preventive concept, the ultrasonic emuls if Ication of oil for marine
transportation has been tested for feasibility. Two crude oils and a common fuel oil were
emulsified and tested. The emulsions are characterized as stable, dispersible in sea
water, not unduly toxic and with reduced fire hazard potentials. This laboratory study
shows that oil emulsions can be created by ultrasonics in a continuous process at tanker
loading rates. Limited economic evaluation shows the concept to be meritorious and
reasonable .
PURPOSE OF PROJECT: The purpose of this project was to study the feasibility of pro-
ducing emulsified oil at a rate comparable with conventional tanker loading rates and
to investigate the economic and ecological factors.
SCOPE OF PROJECT: To determine blender design parameters and emulsified oil
characteristics, two crude oils and one fuel oil were chosen. A Libyan light oil, a
Venezuelan oil and #6 Fuel Oil were used. Only two emulsifiers were used and they
were base-neutralized sulfonated nonionics. These are compatible with sea water and
of low toxicity. The emulsions tested were oil -fn -water. Oil was the internal phase
and 97% of the total. Water and chemical was the external phase and 3% of the total.
The tests on the emulsions were to determine: stability under simulated transportation
conditions, dispersibility in sea water, toxicity to fish, and product alteration. Included
were tests with safety aspects: evaporation rates, flash points, vapor pressures and
rupture leak tests. An economic study was made which shows emulslfication coats of
about 20 cents per barrel without considering possible offsets or side benefits.
This report was submitted in fulfillment of Contract 14-12-559 between the Federal
Water Pollution Control Administration and Sonics International, Inc.
1
ACCESSION NO: 1
KEY WORDS:
Continuous Process
Petroleum
1
Toxicity |
Tanker
i
Water Pollution ,
Ult
Emulsion Stability .
Safety 1
Transportation
j
Em unification
Dispersion
i
Flammabillty
Spills
H
ACCESSION NO:
KEY WORDS: .
Continuous Process '
1
Petroleum
Toxicity 1
Tanker |
|
Water Pollution |
|
Ultrasonics
Emulsion Stability '
1
Safety |
|
Transportation .
1
Em unification
Dispersion
Flamm ability
Spills
ACCESSION NO:
KEY WORDS:
Continuous Process
Petroleum
Toxicity
Tanker
Water Pollution
Ultrasonics
Emulsion Stability
Safety
Transportation
Em unification
Dispersion
Flammabillty
Spills
------- |