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A survey of the manufacture of airblown petroleum products from California asphalts

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A SURVEY OF THE MANUFACTURE OF
AIR-BLOWN PETROLEUM PRODUCTS
FROM CALIFORNIA ASPHALTS
A Dissertation
Presented to
the Faculty of the Graduate School
University of Southern California
In Partial Fulfillment
of the Requirements for the Professional Degree
Chemical Engineer
by
Earle William Gard
June 1941
UMI Number: EP41693
All rights reserved
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Dissertation Publishing
UMI EP41693
Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author.
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unauthorized copying under Title 17, United States Code
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789 East Eisenhower Parkway
P.O. Box 1346
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T his thesis} w ritten by
............ EABL..JQAED.....................
u n d e r the d i r e c t i o n o f h X a. F a c u l t y C o m m i t t e e }
a n d a p p r o v e d by a l l its m e m b e r s , has been
presented to a n d accepted by the C o u n c i l on
G r a d u a t e S t u d y a n d Research in p a r t i a l f u l f i l l ­
m e n t o f the re q u ire m e n ts f o r the degree o f
CHEMICAL ENGINEER
Dean
Secretary
D a te
June 4..12.41
Faculty Committee
Chairman
TABLE OF CONTENTS
CHAPTER
PAGE
I.
EARLY HISTORY ...............................
1
II.
METHODS OF M A N U F A C T U R E ......................
4
Shell still control * ......................
4
Air and temperature.............
4
Use of top s t e a m .........................
5
Grading curves and s a m p l e s .............
6
Coking difficulties ......................
7
Oxygen u t i l i z a t i o n ..................... .
8
Blowing t i m e s ......... .. ...............
10
Vertical still control
..................
10
Principal differences between vertical and
shell stills
...........
10
Heating requirements. . . . .
............
12
..........
12
Explosion hazard
. . . . . . .
Correction of specifications by blending
.
F l a s h ...................................
G-A tube still c o n t r o l ....................
13
14
15
Early development and investigation . . . .
15
Comparison of shell and tube stills . . . .
17
G-A improved shell s t i l l ................
19
Circulating u n i t .........
21
Cooling coils
22
.........................
Measurement of f l o w ......................
23
Comparison G-A unit with shell still
24
...
iii
CHAPTER
PAGE
Yield and loss of oil fractions • • • • • •
26
Oxygen utilization
27
...
................
Elimination of coke formation
III.
28
Temperature r a n g e .......................
29
B l e n d i n g ...............................
30
SELECTION OF CHARGE S T O C K S ..................
Method of evaluating materials
Sulfur
IV.
..........
............
...........................
AIR-BLOWN ASPHALT CHARACTERISTICS .
Temperature susceptibility
31
31
32
........
33
................
33
Nature of asphalt.........................
34-
Melting p o i n t .............................
34
Synthetic-blown asphalts
............
35
Character of constituents..................
35
Change in melting point-penetration by mixing
37
Flash point
.........................
37
Ductility.................................
38
W e a t h e r i n g ...........................
39
Photosensitivity
42
B l i s t e r i n g ...............................
44
S t a i n i n g .................................
4?
Compatibility of asphalts..................
47
...
iv
PAGE
CHAPTER
VARIOUS USES OF AIR-BLOWN A S P H A L T S ............
48
......................
48
Asphalt classification
Paving
..................................
48
Roofing...................................
48
Floor materials . .........................
49
Corrosion protection for steels ............
49
Pipe line coatings........................
50
Deck coatings.................
50
Anti-fouling coatings......................
50
Paints and p r i m e r s ........................
50
Waterproofing.............................
50
I n s u l a t i o n ...............................
51
Sewer joint compounds......................
51
Mineral rubber
51
...........................
Specialties . . . . .
......................
51
BIBLIOG R A P H Y .......................
52
A P P E N D I X .........................
59
LIST OF TABLES
TABLE
PAGE
I*
Constituent Relationship......... • • •
36
II*
Weather-Ometer L i v e s ..................
40
III.
Photosensitivity Scale . .............
43
IV,
Comparison of Coatings Used by Various
Roofing Manufacturers . . . . . . . .
60
Analytical Data on Properties of Various
Coatings . . . . . ..................
6l
Change in Percentages and Properties of
Asphaltic Constituents with Air Blowing
62
Oxidized Asphalts - Tests
. . . . . . .
63
Steam-Blown Asphalts - T e s t s .........
64
Bureau of Standards - Thermal Expansion
of Petroleum Asphalts and Fluxes . . .
65
Bureau of Standards - Thermal Properties
of Petroleum Products
........
66
V.
VI.
VII.
VIII,
IX,
X,
LIST OF FIGURES
FIGURE
PAGE
1*
Flow Sheet G-A Asphalt Oxidizing Still . . .
67
2.
Relationship of Melting Point, Penetration,
Ductility, and Tensile Strength of Asphalts
Resynthesized from Edeleanu Treated Extracted
Oils, and Comparison with Refinery Produced
Asphalt .
.......................
68
Blends of Raw Oil and Extracted Bitumen Effect of Oil-Bitumen Ratio on the Melting
Point, Penetration, Ductility and Tensile
Strength of the Blends
................
69
Melting Point-Penetration Relationship of
California Steam-Blown and Air-Blown
.........
Asphalts
70
Thin Film Loss on Heat Test for Various
Coatings . .
.............
71
Changes in Percentage of Oil and Melting
Point of Bitumen Fraction with Air Blowing
of Oreutt Stock
............
72
3.
4»
6*
7*
8.
9*
10*
11*
Grading Curves of Air-Blown Santa Maria
Valley, Santa Fe Springs, and Blended
Coating Asphalts ........................
73
Weather-Ometer Lives and Stain Numbers of
Santa Maria Valley and Santa Fe Springs
Coatings and Coatings from Blends ........
74
Changes in Asphalt Constitution During
Air Blow i ng ...................
75
Grading Curve and Oxygen Utilization on
G-A S t i l l ...............................
76
Relation of Foaming Tendency to Viscosity,
Softening Point, and Time of Air Blowing
.
77
12.
Coke Deposits above Oil L e v e l .............
78
13*
Circulation Ratio - Grading Rate Relationship
79
14*
Process Flow Sheet No. 1 - Vertical Stills
with Tubular Heaters
80
vii
FIGURE
lj*
PAGE
Process Flow Sheet No* 2 - Vertical Stills
with Integral Fireboxes
..............
81
Process Flow Sheet No* 3 - Horizontal Stills
with G-A Agitators
..............
82
17*
Flame Arrest or and Fume Burning System
83
18.
Commercial Installation of G-A Units in
Conventional Shell Stills
........ . .
84
19*
G-A Circulating Pump and Cooling Coils
. .
8?
20.
Grading Curve and Oxygen Consumption on G-A
Unit Operated to Show Rapid Temperature
Increase of Vapors as Compared with Normal
Operation . . . . . .......... . . . . .
86
16.
CHAPTER I
EARLY HISTORY
It has been known for many years that California
crude petroleum contained large amounts of heavy materials
known as asphalt.
For some time this material was practi­
cally worthless on the market in California, since the use
of asphaltic products had not been developed to such a point
that it was economically feasible to use them in the manner
in which they are used today.
Asphalt is produced from these
crudes either by the continuous distillation process, by
solvent extraction, or by the use of the older type shell or
batch process.
Asphalts produced directly from crude by
these processes are generally known as steam-blown asphalts.
This designation is used because they were originally pro­
duced with large amounts of steam passing through the body
of the oil in order to give a lifting effect to the heavier
oils present in the crude, or, in other words, change the
vapor pressure relationship within the still.
These steam-
blown asphalts of varying grades are used as the base stock
in the manufacture of the many types of air-blown or oxidized
asphalts that we now find on the market.
Early investigators knew that petroleum products when
exposed to the sun and air would oxidize, and as early as
2
1865, Gesner observed that organic substances were oxidized
by the air and its action was promoted by a high temperature*
Also hot air was forced through hydrocarbon oil during the
process and in some instances with advantage*
Later, in the
year 1876, W. P. Jenning obtained a patent for the oxidation
of certain petroleum fractions*
done by DeSmedt.
This was followed by work
This work, however, was in connection with
the air-blowing of residual fractions in the presence of
other materials which might be termed catalysts*
This work
was then followed by Schallfs contribution, who found that
paraffinic fractions such as paraffin and vaseline as well
as heavy mineral oils would oxidize rapidly when heated at
elevated temperatures in the presence of air*
The first
commercial work for the production of oxidized asphalts was
performed by F* X* Byerley*
This work was followed by a
large amount of work conducted by Dr Fred Salathe.
It is interesting to note that much of Dr Salathe1s
early work was carried on in California while he was asso­
ciated with the Stewart and Hardison Oil Company at their
Santa Paula Refinery.
This company was the parent company
of Union Oil Company of California so that the pioneering
work on the commercial oxidation of asphaltic fractions was
carried on with California crudes by California talent*
3
Several years elapsed between the early work by the
various investigators before the oxidized asphaltic frac­
tions could find a ready market.
Before proceeding with
the discussion on the manufacture of air-blown asphalts and
the characteristics of the various products, it might be
well to briefly state the difference between air-blown and
steam-blown asphalts.
Both of these materials, although
made from the same source of crude, vary widely in ductility,
melting point, penetration, and solubility in either carbon
bisulfide or eighty-six degree naphtha.
Although there are
many ways in which air-blown and steam-blown asphalts differ
in specification and in use, it can be stated that the prin­
cipal difference in air-blown asphalts over steam-blown
asphalts is that the air-blown material is not as suscep­
tible to temperature changes and for a given penetration,
it will always show a higher melting point than steam-blown
asphalt.
The ductility of air-blown asphalts is always less
than the ductility of steam-blown asphalts of either the
same melting point or same penetration.
CHAPTER II
METHODS OF MANUFACTURE
The earliest method of manufacturing air-blown as­
phalts was to charge asphalt into a shell still, the shell
still having a capacity of from 100 to 300 barrels.
This
shell still was similar to those used for distilling crude
oil for the manufacture of gasoline, kerosene, etc. before
the advent of the more modern continuous distillation type
of unit*
About the only variation that could be found in
this still over the regular crude still unit was the sub­
stitution of a perforated air spider in the bottom of the
still in place of a steam agitation
spider thatwas nearly
always present in the crude unit.
I.
SHELL STILL CONTROL
Air and temperature.
The asphalt charged to the
shell still was gradually heated to a temperature of about
300 or 3?0*F.
At this temperature air, generally between
ten and thirty pounds pressure, was
admitted to the air
spider at a rate of approximately one cubic foot of air per
minute for each barrel of oil in the still.
In other words,
if 200 barrels of oil were charged to the still, the start­
ing oxidation rate would be 200 cubic feet of air per minute.
5
As the temperature of the oil was gradually raised, due to
the fire Tinder the bottom of the shell still, the air became
more effective in oxidizing the oil*
Also, during the oxi­
dation process, the oil itself was heated by the reaction of
the oxygen in the air with the various petroleum fractions
in the asphalt.
This operation was carried on until a temper
ature of about 450° F was obtained.
However, at times the
oxidation was carried on at temperatures as high as ?00 to
525«F.
As the temperature was gradually raised to 500°F, it
was necessary to control the fire and the air in the still,
since the oil in the still after undergoing oxidation would
increase in temperature due to the exothermic heat of reac­
tion caused by the combination of oxygen with the petroleum
fractions.
The oxidation of asphaltic fractions may be
looked upon also as a dehydrogenation operation since the
oxygen in the air combines with a certain amount of hydrogen
in the hydrocarbon molecules to form steam which is condensed
into water in the overhead condensing system.
Use of top steam.
In the old spider or shell still
type of operation, due to the fact that practically no con­
trol except that to be had by regulating the fire and air
could be had on the charge in the still, it was necessary to
watch the operation very closely, since the oil temperature
might quickly get out of hand.
The oil temperature might
6
suddenly increase from 450 or 500°F to as high as 700 or
750°F.
At this temperature it was generally found that the
vapor temperature above the oil in the still also rapidly
increased due to the fact that there was still a large amount
of oxygen in the spent gases that had not been consumed in
going through the body of oil, and the reactions continued
in the vapor*
It can readily be seen that with higher oil
and vapor temperatures in the presence of oxygen a fire
would result*
From past experience it has been known that
fires and explosions were common occurrences in the old
shell still type of operation.
In order to reduce this
fire hazard, it was common practice to use top steam during
the oxidation process.
Steam at low pressure was generally
admitted at one end of the still or along a spider located
in the top of the still for the full length of the unit.
As
the oil temperature was raised to approximately 400°F, top
steam was generally cut into the unit and kept in the unit
until the oxidation had been completed.
Grading curves and samples.
Periodic samples or
grading samples were generally taken about every hour during
oxidation and tested for melting point and penetration.
As
a rule it was desired to run a still so that it would finish
on grade at a predetermined time.
By reviewing a large
number of runs, taking the time-temperature relationship on
7
the various batches, and plotting them against melting point
and penetration, the grading curve was obtained.
This grad­
ing curve was used as a model on subsequent runs for a given
product.
Experience, however, proved that it was almost
impossible to follow a set grading curve with the old type
operation, due to the poor control that was available, such
as changing of heat and air in the still.
Many types of
agitation spiders have been used to eliminate a part of this
difficulty.
Coking difficulties. Air was admitted into the oil
in the still at a plurality of points, and it was found that
large carbon particles or nigger heads formed around each of
the air jets.
In time, these carbon particles, or nigger
heads, finally choked up the air jets, thereby increasing
the length of time required for a given run.
These nigger
heads were generally formed because of the impossibility of
getting rapid oil circulation around the jets by any means
of spider agitation, so that an eddy current formed directly
behind the jets which kept the oil in contact with the air
for too long a period of time.
Since the asphalt was in
contact with the air for too long a time and too much oxygen
was available, the reaction was not stopped at the desired
point, but continued to the formation of carbon rather than
the desired air-blown product.
8
Oxygen utilization.
In analyzing the overhead gases
from the conventional spider still operation it was found
that very little oxygen was used during the oxidation process*
If It is assumed that the air entering the still and coming
out through the spider had an oxygen content of approxi­
mately 21-1/2$, It will he found that the exit gases after
the air has passed through the body of oil in the still
contained from 17 to 21$ of oxygen,thus showing a very
inefficient operation with respect to oxygen utilization*
The air rate in the old stills varied from one to three
cubic feet of air per minute per barrel of oil charged in
the still and was a function of oil temperature, the type
of oil charged, and the time of the run, whether it was
observed in the first, middle, or end of the run.
This
air passing through the spider and then through the body of
the oil created high turbulence in the oil5 and as the air
left the surface of the oil, it carried with it varying
amounts of oil which was thrown against the inside of the
still over the top of the oil*
This oil thrown against the
inside of the still in the vapor space accumulated and then
started to drip back into the bulk of oil within the still
similar to the effect produced by turning a water spray on
a flat horizontal overhead surface*
As this oil in the shell still collected in this
9
manner and dripped back into the still it was constantly in
contact with high temperature gases leaving the unit and
they still contained a large percentage of oxygen.
The oil
thus in contact with the oxygen in the still gases underwent
further oxidation, and the reaction was carried farther than
necessary to produce a satisfactory air-blown product and
actually formed carbon or coke*
During subsequent runs,
additional particles of oil were carried into the vapors,
onto the top of the still, and dripped back over these small
carbonaceous particles until long icicles or carbon stalac­
tites were formed hanging down from the roof of the still.
Many of these stalactites were as long as twelve to eighteen
inches and entirely covered the top of the still.
These
carbon icicles or stalactites periodically broke off and
fell back into the body of the still; and since they were
partially held together by asphaltic material, they were
gradually dispersed in the body of oil.
When the oil was
withdrawn from the still to be used in commercial processes,
it was found to contain a considerable amount of carbon
particles, but less than
If the material had been used
in the manufacture of roofing paper, these carbon particles
would have given a very imperfect type of paper.
10
Blowing times.
On California stocks the average
blowing time for the production of paper saturant material
with a melting point of around 17 5°F and up and with a pene­
tration of 30 or greater was approximately twenty-four to
thirty hours from the time the material was ready to oxidize
until it had been brought to grade.
If it had been desired
to make a high melting point coating, that is, a material
with a melting point of approximately 220*F and a penetra­
tion of from 15 to 25, the time required would have been
extended to thirty-six or as high as forty-five to fifty
hours.
These long times are not a direct function of the
material but more directly a function of the equipment
available for the manufacturing operation.
II.
VERTICAL STILL CONTROL
Principal differences between vertical and shell
stills.
In reviewing the early work that was done by
Dr. Salathe" and others, it was found that there have been
practically no major changes made in asphalt blowing equip­
ment since that time until the past few years.
One of the
first steps taken to improve the blowing operation was the
use of a vertical still instead of the horizontal still just
discussed.
The vertical still has in all respects the same
essential features as the horizontal shell still.
However,
11
the oil body depth has been greatly increased*
It has been
increased from around four or five or perhaps seven feet to
approximately twenty-five or thirty feet.
This greater oil
depth permits the air to be in contact with the oil for a
longer period of time, and thus allows a greater utilization
of the oxygen content of the air.
The same difficulties, however, that have been noted
in the horizontal shell still are also encountered in the
vertical still; that is, plugging of air spiders and the
formation of coke or nigger heads around the spiders and the
formation of large coke icicles on the top of the still.
In
analyzing the results of the vertical still, it will be found
that the running time and cleaning period have been reduced,
but it is yet far from the type of operation desired for the
efficient manufacture of oxidized products.
As noted previously, the horizontal shell still is
fired on the bottom sheet or fire sheet, and only a small
proportion of the still is available for firing.
Since the
oil lays in the still and is not circulated or moved at a
rapid rate over the fire sheet, the heat transfer rate
through the oil is very poor; and several hours, generally
five or six, are taken to heat the still.
occurs unless caution is exercised.
Cracking also
In the vertical still,
however, it is necessary to use a fired heater and heat the
12
charge before it is placed in the vertical still or the
vertical still must be designed in such a way that it gets
heat not only on the bottom, which is a small portion of the
wtill, but also around the sides so that it can be brought
to temperature within a reasonable length of time*
Heating requirements.
In either the horizontal shell
still or the vertical still without the outside firing set
up, it will require in excess of a gallon of oil to heat a
barrel of charge to the desired temperature, that is, around
300°F before air is admitted to the still*
This, of course,
is a rather large amount of oil to be used for heating pur­
poses, but due to the inefficiency of the operation, it has
not been possible to reduce it below this figure*
Explosion hazard.
Care must also be exercised in the
operation of these types of units in order to keep the vapor
line free of oil entrained fractions*
This oil which collects
in the vapor exhaust line also undergoes further oxidation,
and at times this oxidation may be sufficiently rapid to
start a fire in the vapor line and travel back into the body
of the still where a severe explosion will result*
Top steam
in the still, as well as top steam in the vapor line, has a
tendency to reduce this phenomenon; in fact, if sufficient
steam is used, no fire hazard should be encountered*
However,
13
this requires a very large amount of steam, and the steam
must he condensed with the vapors in the vapor condensing
system.
A few brief calculations will show that the great­
est heat ioad in the vapor condensing system is that of the
steam admitted to the system as top steam.
Of course, there
is a certain amount of steam produced as a result of dehydro­
genation which also must be condensed, but this is generally
less than the amount of steam used to suppress the fire hazard.
Correction of specifications by blending. In reviewing
the operation of the horizontal or vertical shell still it
will be noted that very little control can be exercised
during the oxidation process.in order to change the character
of the material undergoing treatment.
Quite often it has
been found that at the end of the run when it is expected
that the product will be on grade, either the melting point
is entirely too high or some other specification is off.
Generally the melting point-penetration relationship is the
crucial guide point, and either the penetration will be too
low for a given melting point or the melting point will have
become too high.
The higher melting point results in a
lower penetration material.
It is then necessary to add a
certain amount, although small, of feed stock to the asphalt
in the still.
This small amount of feed stock must then be
thoroughly agitated with the rest of the oil in the still so
14
that a homogeneous mixture is obtained.
By “cutting back”
or adding this feed stock to the blown stock it is possible
to modify the penetration and melting point relationship to
a certain extent.
Flash.
It is also desirable to have as high a flash
point on the finished product as possible.
It is quite dif­
ficult to get the flash point over 425°F on California
stock5 whereas on asphalts produced from other sources,
those of more paraffinic character, it is easy to obtain
flash points of around 475 to 525°F.
The conventional still
which has been described is notorious for its failure to
produce a satisfactory flash point asphalt; therefore, it
is necessary at the completion of the run, in almost every
case, to use a certain amount of bottom steam.
In other
words, additional steam agitation must be introduced through
the air spiders so that sufficient steam distillation can be
effected in order that the lighter fractions remaining in
the oil can be lifted off by changing the vapor pressure
condition within the still.
These light fractions which
cause low flash points, may have been present originally in
the asphalt charge or they may have been produced during the
oxidation process.
Since the various reactions which take place during
the oxidation of asphalt are not altogether clear, it is not
15
too easy to vary the specification of a given product5 but
it is a well known fact that some light fractions and water
are formed and that a certain amount of polymerization takes
place*
As a rule, however, if the charge material to the
still has a flash point in excess of 425°F and if carefully
controlled operations are carried out, it will be found that
the finished product will have a flash point at least as
good as the charge.
With a reasonable amount of final steam­
ing, the flash point can be held at 42?°F and sometimes
raised to a slightly higher value.
The proper flash point
is essential to meet the underwriter's specifications as
well as to meet the desires of the consumers of the airblown product*
III.
G-A TUBE STILL
Early development and investigation*
Recognizing
the various drawbacks to shell and vertical still opera­
tion, experimental work directed toward the use of more
efficient equipment in the manufacture of air-blown asphalts
was started by Gard and Aldridge before 1926.
Just as
Salathe's and Byerley's work in the late 1800's was the
turning point in the commercial manufacture of air-blown
asphalts, this work has been a contributing factor in
modernizing the air-blowing procedure for the manufacture of
16
air-blown asphalts.
These investigations were directed to
the improvement in the manufacturing procedure both from the
standpoint of improving the shell or vertical still operation
and also from the standpoint of obtaining a substitute
method, such as the use of a pipe still where the petroleum
fractions could undergo oxidation at higher temperatures and
pressures with a maximum efficiency of oxygen utilization.
This work led to the development of the G-A process as well
as equipment for the manufacture of these materials which is
completely detailed in the following.
In the fired heater type of installation, the asphal­
tic fractions undergoing oxidation are held in a surge drum
and suction is taken from the bottom of this drum by a pump
at a pressure of approximately 7? to 1?0 pounds per square
inch.
As the oil leaves the discharge side of the pump,
oxygen or air is admitted into the flowing stream.
The oil
and oxygen, then thoroughly mixed, pass through tubes in a
fired heater maintained at a constant temperature or grad­
ually increasing temperature.
The heater is so arranged that
fire can be maintained in the furnace just as fire is main­
tained in a boiler.
The heat produced by the fire is
effective in raising the temperature of the oil undergoing
oxidation* and after the proper temperature is reached by
the oil undergoing oxidation, the fires can be withdrawn and
17
air circulated around the tubes in the heater by use of
forced draft.
The heater thus becomes a cooler.
The oil
passes out of the tubes of the heater and is then returned
to the original supply tank or bulk supply, at which point
the vapors are released from the oil.
The oil thus brought
back into the bulk supply is made available for recircula­
tion through the fired heater.
This operation continues for
the necessary period of time to obtain a satisfactory product.
The design of the heater can be regulated so that the process
can be either batch or continuous or continuous batch.
However, experience has shown that very few plants have
sufficient capacity to warrant the installation of continuous
asphalt manufacturing facilities.
Therefore, it will be
assumed that this operation is on a batch basis.
Comparison of shell and tube units.
If the operation
is compared with that obtained in the conventional horizontal
or vertical still method, it will be found that the blowing
times are considerably reduced.
Where in the previous units,
the blowing time required for the manufacture of the coating
asphalt may be as high as fifty hours and seldom runs below
thirty hours, in the fired heater installation, it is found
that this time is reduced to approximately six or seven hours.
Again in comparing the oxygen utilization in the G-A type of
unit, it will be found that in the shell still, the oxygen
18
was reduced from 21-1/2$ to 17 or 18$; while in the G-A unit,
the oxygen is reduced to as low as 6 or 7$ during certain
periods of the oxidation operation, and at no time does the
oxygen content increase above approximately 14 or 15$? with
a good average value for the period of the run of around 12$*
This greater oxygen utilization allows for a much shorter
oxidation period.
In addition, since forced cooling is available, the
temperature can be held at a predetermined point and it is
possible to use larger amounts of air.
Instead of using from
one to three cutic feet of air per minute per barrel of oil
in the still, it is found that from three to eight cubic
feet per minute per barrel of oil undergoing treatment can
be used.
Therefore, with the combination of temperature
control, greater oxygen utilization, and greater oxygen
application rate the running times are reduced to a low
figure.
In fact the running times can be reduced to such a
low figure that it is not possible to satisfactorily test the
material before it has reached grade.
With a unit of this type the heating efficiency is
much greater than in the shell still, since a very large
percentage of the oxidizing equipment is made available for
heating and cooling.
Also the rapid circulation ,of oil
within the tubes gives a high heat transfer rate through the
19
tubes and instead of using a gallon or more of oil per
barrel of oil being heated, it was found that the improved
operation reduced this to less than one-half gallon of oil
per barrel of oil heated.
These quantities are based on
charging oil to the system at about 200°F and raising it
to the oxidation temperature.
Of course, in all of these
units, the oil could be maintained at a high temperature
and then charged to the system at this higher temperature,
thus reducing the heating required.
However, this procedure
is not followed in any of the commercial plants.
G-A improved shell unit.
In order to give a close
comparison of the operation of this improved equipment with
that used by Salathe and Byerley and others even at this
late date, comparative figures will be given on a shell still
that has been converted from an old type operation to the
newer type where all operating conditions are directly under
the operator*s control.
For comparative purposes, a shell still having the
general dimensions of ten feet in diameter and twenty-five
feet in length, will be considered.
As a rule a still of this
type is set in a brick firebox and fires are controlled at
one end of the firebox.
Such a still has one or more vapor
outlets, generally one at each end of the still.
These outlets
may vary in size from eight to twelve or fourteen inches.
The
20
conventional still will have, as previously noted, an air
spider along the bottom of the still for admitting air to
the unit.
In converting this unit over into a G-A (FIGURE 1}
type of operation, it is necessary to remove the air spider
and place a metal plate or baffle across the bottom of the
still.
This baffle extends the full length of the still and
stops about twenty-four inches from one end.
A manhole is
then placed on the top of the still at the opposite end from
the open end of the baffle.
At this point is placed a spec­
ial agitating unit, the agitating unit hanging down into the
still just as a deep well water turbine is suspended in a
water well.
The suction part of this agitating unit extends
below the baffle plate which has already been installed.
This arrangement then permits oil circulation to take place
from the body of oil in the still down to the end of the
still, where the baffle plate is open, and then under the
baffle plate, along the fire sheet of the still to the suction
of the agitating unit.
The oil then passes through the cir­
culating unit and is discharged at the end of the still after
which the oil flows across the still thus establishing cir­
culation.
The circulating unit may be driven by a vertical
electric motor or by any other power means.
However, as a
rule, a vertical electric motor of the hollow shaft type is
desired.
21
Circulating unit.
The circulating unit is designed
from the best type of low lift impeller type of pump.
In
other words, the type that is generally used for raising
water from five to ten feet on large irrigation projects.
This impeller type of pump is placed in the bottom of the
circulating unit.
The straightening vanes are placed
directly above the impeller.
These straightening vanes are
also common to the previously mentioned type of water pump
and are installed for greater efficiency.
On a water pump,
as a rule, the water is pumped up through the column around
the shaft and discharged at the top.
The circulating unit,
however, varies in this respect in that it is a double unit
rather than a single tube unit.
Directly around the drive
shaft is a large pipe, generally six inches in diameter,
used for admitting air into the circulating unit.
Around
this six inch line is another pipe of approximately sixteen
inches in diameter for directing the oil and air from the
circulating unit into one end of the still.
With this
arrangement, it is possible to completely install the unit
or remove it from the still without entering the still, since
the air pipe and discharge pipe of the circulating unit are
all hung together from the manhole in the top of the still.
Also, the straightening vanes are directly connected to the
six inch air pipe.
The straightening vanes instead of being
22
thin as in the ordinary water circulating unit are hollow or
cored in order to permit the air to pass out through them.
Slots are arranged in the straightening vanes to permit the
air to pass out of the slots into the oil as it passes along
the face of the straightening vane.
The circulating unit
therefore circulates the oil at a very rapid rate through
the still, across the fire sheet, and then into the upper
part of the still.
During its passage across the straight­
ening vanes, it comes in contact with low pressure air that
has been admitted to the circulating unit through the six
inch line.
Although the air is in contact only a short time
in this type of operation in comparison with the time it is
in contact in a thirty foot vertical still, or the time in a
horizontal shell still, it has been found that this time is
sufficient due to the proper regulation of oil and air rela­
tionship and the intimacy of contact between the oil and the
air.
Cooling coils.
Directly above the baffle plate which
has been installed across the bottom of the still are installed
vertical cooling coils.
These coils are not large, but are
of sufficient capacity to regulate the temperature of the oil
undergoing treatment.
The top steam line is also connected to the unit to be
used to purge the still of any vapor in case a light type of
23
charge stock is being used*
A steam agitation spider can
also be maintained in the bottom of the still if it is
desired to turn the still over during the time the agitator
is not running.
It can also be used to admit additional
quantities•of steam to the unit in case light charge mater­
ials are used*
In place of using the two vapor outlet lines, it is
generally desired to use just the one and have it located
at the opposite end of the still from which the circulating
unit is located.
Through the cooling coils which have been
placed in a vertical direction or position above the baffle
plate, is circulated a cooling medium, water or oil— oil is
generally preferable in case of failure of a line within the
still.
This circulating oil goes through a cooler to a bulk
supply tank, at which point it is picked up by a circulating
pump and put back through the cooling coil.
The oil circu­
lation rate, through this coil, can be controlled either
automatically or manually— manually appears to be satisfac­
tory since the operation of the unit is not too critical in
this respect.
Measurement of flow.
Flow meters should be located on
the oil circulation lines and on the air and steam lines to
the unit.
With this equipment now installed, the unit is
ready for operation.
By previous experiment, it has been
determined that a certain oil circulation rate should be
used with a given air oxidation rate.
This economical rate
has been determined as being approximately twenty-five
gallons of oil to one cubic foot of air (FIGURE 1).
For
commercial purposes on a still of this size, this data can
be interpreted as calling for a circulating unit with an oil
circulation capacity of approximately 13,000 gallons of oil
per minute.
With this oil circulation rate, air oxidation
rates of from 2 to 5 cubic feet per minute per barrel of oil
in the still can be used without losing efficient operation.
By regulating the amount of oil charged to the still and by
regulating the amount of air used in the still, an infinite '
number of oil-air circulation rates can be obtained.
Comparison G-A unit with shell still.
If it is
assumed that in the conventional type of shell still opera­
tion, approximately one and one-half cubic feet of air per
minute per barrel of oil charged to the still would be used,
it would be found that in making coating asphalts from a
given charge material (and it will not be necessary to dis­
cuss charge specifications at this point), approximately
thirty-five hours are required to bring this material to
grade.
In the G-A type of unit, however, the charge will
consist of exactly the same amount and type of oil, and a
circulating unit with a capacity of 13,000 gallons of oil
2?
circulation per minute will be used#
In place of the one
and one-half cubic feet of air per minute per barrel of oil
charged to the still, three cubic feet, or twice the amount
of air, will be used#
It is impossible to use this larger
amount of air in the conventional still due to an inadequate
temperature control of the oil in the still, and also due to
the inefficient application of the air to the oil#
In the
G-A unit, however, due to the intimacy of contact and the
very rapid circulation of oil within the still itself, it is
found that all of the oil in the still is circulated many
times per hour during the oxidation operation#
On a still this size, the customary charge will run
about 200 barrels of oil#
With the 200 barrels of oil circu­
lating at a rate of 13,000 gallons per minute, which is
equivalent to approximately 20,000 barrels per hour, it is
readily noted that the complete contents of the still are
circulated approximately 100 times per hour#
This circula­
tion rate, or turn-over rate of 100 times per hour, is almost
equal to one and two-third times every minute.
With an oil-
air ratio of twenty-five to one and with an air rate of
three cubic feet of air per minute per barrel of oil in the
still, or a total air applied to the still of 600 cubic feet
per minute, it will be found that the oil undergoing oxidation
will come to grade in about eleven hours instead of thirty-six
26
hours*
This rate can be increased or the time reduced by
increasing the air-blowing rate from three to possibly five
cubic feet of air per minute per barrel of oil in the still.
However, the higher the air rate, the less efficient is the
use of oxygen, but even at the higher rate, there is suffi­
cient oil-air ratio to give the desired oxygen utilization
efficiency*
In practical experience on California stocks, it has
been found that a ten or eleven hour turn-around, or time
consumed in bringing a batch to grade, is about as fast as
is practical due to the time consumed in making the hourly
tests as the man progresses.
It is also found that every
run can be made a duplicate of the former and that they can
all be made to follow a regular grading curve since the con­
trollable factors can be varied at will, and there is no
reason for the operation to get out of control.
If the
temperature on the oil starts to rise too rapidly, it can
easily be checked by increasing the amount of cooling oil
through the cooling coil placed within the body of the oil
within the still.
Yield and loss of oil fractions.
In the conventional
still with the air rates and oxygen consumption efficiency
which has been discussed, it is readily seen that because of the
long time involved in bringing the batch of oil to grade, air
27
distillation of the oil is constantly taking place5 and
experience shows that a considerable amount of the lighter
oxidizable fractions are lifted off overhead and are con­
densed in the overhead condensing system.
This lifting off
of desirable fractions has a direct bearing on the yield,
as well as the characteristics of the asphalt produced.
Yields are thus bound to be considerably lower on the con­
ventional shell still.
In the shell still where yields are
of the order of 65 to 85$, run from 85 to 98$ on the G-A
unit on the same stock.
In the G-A unit, due to the fact that the operating
time has been reduced, it is possible to obtain air-blown
products with higher air-blown characteristics, higher airblown characteristics in one respect meaning a higher
melting point for a given penetration relationship.
Also
with these close controls, it is possible to vary the airblown characteristics with a unit of this type regardless
of the type of charge stock.
Oxygen utilization.
Due to the greater oxygen utili­
zation, it has been found that the oxygen content of the
spent gases from the G-A unit, where run as previously noted,
will average approximately 12.% oxygen.
A large number of
tests conducted over a period of time by independent authori­
ties have shown that vapors of this type will not explode if
28
the oxygen content is maintained at around 10$-— 10# of oxy­
gen with the lean oil vapors present is below the explosion
point*
Also, in view of the fact that the oxidation reaction
produces steam, it is found that even with a slightly higher
oxygen contentin the gas, no explosion hazard is encountered*
Elimination of coke formation*
If the oxygen content
of the spent gases is low, and although a small amount of
oil entrainment remains in the vapors, which deposited on
the upper part of the still, the formation of carbon stalac­
tites, such as found in the conventional spider or shell
still operation, does not exist.
The lack of the formation
of these stalactites is explained as follows:
The oil is
circulated by the circulating unit and is discharged into one
end of the still, therefore, the entire body of the oil is
not in a state of violent agitation.
Since the agitation
has been immeasurably reduced, less oil should be thrown onto
the roof of the still.
Should the oil accumulate on the top
of the still and drip back into the main body of oil, it will
not be converted into carbonaceous material since the oxygen
content of the gases passing over it is entirely too low to
rapidly oxidize it under these conditions.
With the absence
of air spiders in the still, it will be found that coke
deposits are eliminated from the rest of the still*
With the elimination of coke deposits, either in the
29
body of the oil or above the surface of the oil, the clean­
ing time is practically eliminated.
Experience has shown
that units operating over a period of several years will have
to be cleaned probably once in nine to eighteen months.
This,
of course, is a function of the operations which have been
carried on in the unit.
Temperature range. With controls established as in
the G-A type of operation, it is possible to oxidize under
both higher and lower temperatures.
The oxidation conditions
can be varied, and these changes in conditions and time have
a marked effect upon the quality of asphalt produced.
Some
units have been operating consistently over 600°F in tempera­
ture and some of them have been operating on other types of
stock at temperatures as low as 3?0°F.
In spite of this
wide variation in temperature, it is possible to produce
unusual types of asphalt because accurate control is always
maintained.
Power requirements. A unit, as just outlined, using
the oil circulation rate discussed, will require a horse
power of approximately thirty-four on the motor driving the
circulating unit.
Although this horse power appears rather
high, it is more than compensated for by the reduced horse
power needed for air injection because low air pressure is
30
used in a unit of this type, whereas in a spider still
operation, air pressures of ten to thirty pounds are common*
Blending *
From the blending standpoint, a unit of
this type also has considerable merit since a blending oil
can be admitted through the air injection vanes and be
immediately blended with the remaining amount of oil in the
still due to the rapid circulation caused by the circulating
unit*
CHAPTER III
SELECTION OF CHARGE STOCKS
Method of evaluating materials.
Now that modern
equipment is available for the production of the highest
quality asphalt from a given stock, the next factor is the
determination of the type of stock to be used*
The
California stocks are notoriously deficient in heavy inter­
mediate fractions which some of the Eastern types of stock
contain.
These are the heavier intermediate, high flash
fractions or lube oil fractions which oxidize to give the
desired improved asphaltic product*
Therefore, it is im­
portant to obtain a charge material which has a sufficient
amount of these fractions available for oxidation; and if
the stock does not have a sufficient amount of these frac­
tions available, it will be necessary to make a synthetic
blend— a blend containing an increased amount of these frac­
tions available for oxidation*
Not only must the stock be
available which contains those fractions oxidizing readily,
but also the heavy oil fractions apparently highly resis­
tant to oxidation in combination with the proper percentage
of bitumen fractions*
There are many fractions available to the refiner
which could be used for modifying the charge materials
fractions, such as those taken from strictly asphaltic type
crudes, fractions taken from the mixed base crude, fractions
32
taken from the more paraffinic types of crude, waxy distil­
lates from which the wax has been removed, fractions taken
from solvent extraction processes, such as phenol extracts
and Edeleanu extracts#
As a rule, however, the thing work­
ing against a blend of this type is the cost of the raw
material.
One of the most important factors that the asphalt
manufacturer must remember is the availability of a charge
material of sufficiently low cost so that the finished
material will not be too high priced to be competitive.
Various methods of analysis can be used in separating
the charge stocks into its component fractions, such as the
oils and the asphaltenes, bitumens and resins, and other
fractions desirable in the stock, and vary these fractions
in order to obtain a charge material having proper
charac teri stic s•
Sulfur.
One of the important points which has not
been discussed is the amount of sulfur available in the
various feed stocks as sulfur does have a direct bearing on
the quality of the asphalts produced. As a rule the greater
the sulfur content of the charge, the better the quality of
the asphalt produced.
Sulfur can be added during oxidation
to produce an improved asphalt.
California crudes with
sulfur contents of around 3 to 5% produce the better asphalts*
CHAPTER IV
AIR-BLOWN ASPHALT CHARACTERISTICS
Temperature susceptibility.
As previously stated,
the three important specifications for air-blown asphalts
are melting point, penetration, and flash.
Of course, there
is also ductility, but ductility as a rule is relatively low.
The controlling factors are melting point and penetration
assuming that a ductility of at least two or three centi­
meters is obtainable and that flash points meeting specifi­
cations above 425°F are available.
In penetration, an
asphalt having a good temperature susceptibility is desired.
In other words, penetration of the asphalt should not vary
widely over a wide range of temperatures, and the one which
varies the least will have the better penetration or tempera­
ture susceptibility.
Steam-blown asphalts, in contrast with air-blown
asphalts, will have a very poor temperature susceptibility,
penetration running extremely high at the high temperatures
and very low at the low temperatures.
Since penetration in
air-blown asphalts is a function of the oil content of the
asphalt and also a function of the heavy oil content, it is
found that the best penetration susceptibility can be obtained
in an asphalt having a greater proportion of the proper type
of heavy oil fractions present, provided that the other
34
fractions in the asphalt are approximately the same*
Nature of asphalt.
It might he simpler to understand
this subject, if the constituents of asphalt are reviewed,
and if it is realized that air-blown asphalts and asphalts
in general are a complicated mixture of oil, bitumens,
asphaltenes, etc*
It is believed that the words neolloidal
solution”, although not exactly correct, might more nearly
define the nature of the asphalt.
When these points are
stressed, and it is realized that this is not a true solu­
tion, it can be understood how it is possible to vary the
melting point-penetration-ductility relationship*
Melting point. Melting point, after the type of
asphalt production and selection of the proper type of
charge stock are determined, is a function of the dispersion
of the various materials in the asphalt*
This can readily
be demonstrated by adding to an asphalt of a given melting
point, a certain amount of finely powdered slate or other
inert material, and then testing the melting point after the
addition of the finely divided material.
The addition of this
finely divided material invariahly raises the melting point
and yet the basic asphalt fractions used before the finely
divided slate or other material was added have not in any way
been changed.
35
Synthetic-Blown Asphalts.
It is possible to produce
asphalts having air-blown characteristics by the blending of
materials which have not been air-blown, such as taking
steam-blown asphalts apart as far as the various constituents
are concerned, and then back-blending some of these fractions
with fractions from other steam-blown asphalts which have
been taken apart in a similar manner.
By changing the
molecular weight of the various constituents in the oil and
by changing the paraffinicity of the oil, an asphalt having
air-blown characteristics can be easily obtained.
In the
air-blowing operation, a procedure is used which gives these
results merely by oxidation.
This can be summarized by
stating that in the air-blowing process, the resins are
actually converted by dehydrogenation and polymerization to
form asphaltene fractions which asphaltenes are increased in
molecular weight by a somewhat similar operation.
Character of constituents.
The heavy oils as previously
referred to are also dehydrogenated and polymerized to form
resins.
The light oils in the charge material are lost by
distillation and that is why it is important that the feed
stock be of such a characteristic that a minimum loss is
obtained during the oxidizing operation.
The longer the time
required to oxidize, the greater the loss of these light
fractions.
Then, of course, since oxygen is used, certain of
36
the petroleum fractions form oxygenated compounds.
Therefore,
a proper feed stock should be such that upon oxidation the
relationship of resin to asphaltene should be low, the paraffinicity of the oil in the charge stock should be high,
molecular weight of the asphaltene formed should be high, and
the content of the undistilled oil should be high.
The tabu­
lation noted below will give a comparison of some of these
factors as applied to the various types of crude.
TABLE I
CONSTITUENT RELATIONSHIP
Crude Source
Resin to
Asphalt
Ratio
Content of
Par aff InUndi stillable ici ty of
Oil
Oil
Mol.Wt.
Asphal­
tene s
Midcontinent
medium
very high
very high
low
L.A. Basin
medium
medium
med. high
low
Santa Maria
low
very low
very low
very high
Colombian
medium
high
medium
medium
Venezuelan
medium
medium
low
medium
Mexican
low
medium low
low
high
Talso
low
medium
med.low
high
Poso Creek
high
medium
low
low
Orcutt
low
med. low
med. low
medium high
From this table, it is noted that all of the oils
possess a considerable amount of the desirable characteristics.
37
However, it is easy to see that the preferable asphalts
would be a combination rather than any particular one.
Change in melting point-penetration by mixing.
The
handling of asphalts quite often has a direct bearing on the
melting point of the asphalt, and the working of the asphalt
with gear pumps should be avoided if it is hoped to maintain
a high melting point material.
For example, an asphalt
having a melting point of in excess of 220°F and a penetra­
tion of twenty-eight, when thoroughly worked through a gear
pump, showed a melting point of only 175° F and a penetration
of thirty-three.
This is a condition often encountered in
the handling of asphalt, and invariably a drop in melting
point is accompanied by an increase in penetration.
Flash point.
As previously noted, in the manufacture
of air-blown asphalts, it is desirable to obtain as high a
flash point as possible.
The minimum flash point is con­
trolled by the Fire Underwriters and is 410°F by the PenskyMartens test or 437°F by the Cleveland open'cup.
Practically
all Pacific Coast asphalts are notoriously low in flash as
compared with Eastern stocks; and Pacific Coast roofing
manufacturers have been confronted with this phenomena and
have had to overcome it by adjusting their manufacturing
procedure.
38
The California crudes, as a general rule, having the
higher bitumen content generally have the lower flash point.
This can be called a function of the crude because if it is
desired to obtain a certain viscosity feed stock for the
blowing operations and a material is selected which is high
in bitumen content, it must have sufficient low boiling oils
to meet the viscosity requirement.
Therefore, the flash
points are generally low on this type of stock.
If these
light oil fractions are removed from the crude having the
high bitumen content and are replaced with high flash or
high boiling oils, this difficulty can be overcome.
Ductility.
Although the ductility, as previously
mentioned, is one of the specification factors in the purch­
ase or manufacture of air-blown asphalts, it has lost the
importance that it formerly had, since practically all good
air-blown asphalts now have ductilities in excess of two
centimeters.
At one time it was the desire of most of the
roofers and manufacturers of asphalt to have as high a duc­
tility as possible.
This ruling was probably fallacious
because it is now known that the most desirable asphalt is
one with a low wax content, since the addition of wax to the
asphalt does "shorten11 the asphalt or make it what is termed
"cheesy".
With the wax removed or kept at a minimum, however,
there is no difficulty in obtaining ductilities of two, three,
or perhaps five.
39
Weathering.
One of the new specifications which has
been applied to air-blown asphalts is weathering life, a test
established to determine that the name implies— its weather­
ing life under alternate weather conditions.
There are
several ways of obtaining weathering life, and practically
all the more accelerated tests are now being used since the
weathering life has become an important factor in testing
and buying asphalt.
Although the weathering life of an asphalt is taking
on more and more importance each day, it is regretable that
no standardized procedure has been worked out which is a
solution to this problem.
There are several standard pro­
cedures of testing the weathering life of an asphalt, but
they are difficult to duplicate in the various laboratories,
and it is hoped that this problem can be settled before too
many more years elapse.
Table 2 noted in the following,
details the weatherometer life, as tested by one method of a
typical coating produced from crudes from various sources.
40
TABLE II
WEATHER- OMETER LIVES
Weather-Ometer
Cycles___
Coating Source
Santa Maria Valley
Gato Ridge
Midcontinent
Oklahoma
Kansas
Illinois
Mexican
Colombian
Venezuelan
Orcut t
Santa Fe Springs
Poso Creek
105
105
105
95
90
80
75
60
55
30
30
From this table it will be noted that crudes of the
best weathering lives are Santa Maria Valley and Gato Ridge
as well as Midcontinent,
The Santa Maria Valley and Gato
Ridge crudes are notorious as high sulfur crudes, and those
of the poorest weathering life are those from Santa Fe Springs
which is a mixed base crude and Poso Creek which is a naphthenic and low sulfur California crude.
In examining the panels on a weatherometer, it is
noticed that the weathering life is determined by the failure
of the surface on the panel.
Surface failure is noted by
cracks formed which indicate that the asphalt has lost its
usefulness.
This is probably a function of the escape of the
oil from the asphalt, and the light oils that are in the
asphalt will escape more readily than the heavy oils*
41
Possibly one of the reasons why the Midcontinent type
of asphalt is very good is that it has a reasonable content
of high boiling point oil*
This also probably applies to the
Santa Maria and Gato Ridge type of asphalts because the oils
which can be removed or extracted from the asphalts of this
source are generally the heavy type of oil which do not
escape to the atmosphere in service.
As previously noted,
it has been possible to produce from California crude, by
one method or another, a synthetic charge stock that would
produce air-blown asphalts having weatherometer lives far in
excess of those obtained from the blowing of one or more
crudes.
One of the important points to be remembered in the
manufacture of an asphalt is the selection of the proper
operating temperature so that when the asphalt is produced
meeting the melting point-penetration specification, its
characteristics have not been sufficiently changed to impair
its weathering life.
It is possible to change the blowing temperature on a
given stock from around 450 to 475,500, or 525°F and drop the
weatherometer cycle from perhaps ninety or seventy-five down
to as low as thirty.
This is a direct function of the
operating conditions selected for the manufacture of the
asphalt.
If the proper equipment is available for the manu­
facture of asphalt so that operating conditions can be varied,
42
then the finest grade of asphalt should be producible from a
selected material.
Photosensitivity.
In recent years another new test
has been developed in addition to weathering life which is
the photosensitivity of an asphalt.
This test has not been
standardized to the point where its value can actually be
measured satisfactorily.
It was probably originated for the
purpose of determining the characteristics of asphalts after
certain types of fillers had been put into the asphalt.
The
test panel is exposed to light whereupon the asphalts form a
thin surface coating of oxidized materials.
By immersing
the exposed asphalt panel in warm water, the degree of oxi­
dation can be shown by the color changes.
If the asphalt
has oxidized sufficiently, it takes on a yellow appearance—
this yellow appearance being termed ,!rust,f.
The length of
exposure necessary to develop this rust is an indication of
its degree of photosensitivity.
The various asphalts might
be grouped roughly as follows in the order of their sensi­
tivity, the most sensitive asphalt being listed firsts
4-3
TABLE III
PHOTOSENSITIVITY SCALE
1
2
3
A
5
6
7
8
9
Gato Ridge
Santa Maria Valley
Mexican
Orcut t
Talc o
Venezuelan
Santa Fe Springs
Midcontinent
San Joaquin Valley
It can readily be noted by comparing this photosensi­
tivity scale and the weatherometer cycles (table II) that
photosensitivity and weatherometer life do not necessarily
correspond.
Therefore, no great importance is placed on the
photosensitivity test at present except in the case of a few
roofing manufacturers.
However, one thing which should be pointed out is that
as the asphalt oxidizes and forms this so-called rust which
is a water soluble type of material, quite often when airblown asphalts are incorporated in roofing paper, it is found
that the asphalt roofing paper will oxidize and the yellowish
rust material will be picked up by fog or rain and carried off
down the side of the building or into the downspout.
These
same asphalts are those very sensitive as far as the photo­
sensitivity test is concerned.
If an asphalt has been
produced in an unsatisfactory manner, it is possible that
these oil-soluble, water-soluble fractions would be of an
44
acidic nature and in the long run might be detrimental to
water spouts or tin roofs located at some other point of the
building.
They, therefore, should be avoided.
Although it is not known exactly what properties of
asphalt are supposed to influence the photosensitivity, some
authorities believe that the sulfur content is one of the
influencing factors*
The presence of photo-reactive sulfur
compounds affect this to some extent.
The presence of rela­
tively light oils also has something to do with photosensi­
tivity as well as the tendency of the oils to exude to the
asphalt coating.
There is no doubt that certain fractions
can be added back to the asphalt in order to retard this
tendency to give trouble and thus improve the photosensitivity
of the asphalt.
Blistering.
The blistering of asphalt roofing has been
quite a troublesome problem for years and probably the least
understood of the properties of asphalt.
Small blisters form
in the asphalt roofing, and under the blisters may be found
small pockets of water or of air.
These small blisters upon
heating and expansion of the air or water, break and thus in
time cause the asphalt roofing to disintegrate.
There is a
decided difference of opinion between the various asphalt
manufacturers and roofing manufacturers as to what causes the
blistering.
Some believe that blistering is caused, to a
45
certain extent, by the type of granules that are used in the
manufacture of roofing paper, others feel that it is a
function of the type of material in the original asphalt*
The melting point of the asphalt apparently has
nothing or very little to do with the tendency of the asphalt
to blister.
As previously stated, the cause of blistering
is not known, but some of the factors which prevent blister­
ing may again be repeated:
the amount and type of filling
in the asphalt, the wettability, the humidity, the location
in which the asphalt is used, surface tension, effect of oxi­
dation, and weathering.
In spite of the cause of these
difficulties, asphalts can be produced which will be almost
completely free of blistering troubles.
Staining.
Staining of oxidized asphalts, particularly
as applied to roofing asphalts as this is where the majority
of the air-blown asphalts are used, might be classed as
follows:
staining due to photosensivity, oxidation of light
oils, and oxidation of fractions forming materials which stain.
In preparing a large number of asphalts and asphalt roofings,
it can be stated that the asphalts and coatings containing
the highest oil content probably show the greatest staining,
since the exudation of oil from asphalt has a bearing on the
staining, it is desirable to have this exudation kept at a
minimum.
In addition, in storing asphalt roofing in rolls,
46
the asphalts exude a certain amount of material which causes
the paper to stick in the rolls and thus not only damages
the rolls hut makes the roofing appear very unsightly.
The tendency of the roofing to exude these oils or
these fractions is dependent to a certain extent on the
temperature of the location at which it is applied.
It is
common practice for companies expecting to use their asphalts
in high temperatures to blow them to a higher melting point,
perhaps ten or fifteen degrees higher than is ordinarily used
in the remaining part of the country.
Although some asphalts
have a very high tendency to exude these fractions, this is
no indication that the asphalt itself is not a durable
asphalt.
In fact, some of the most durable asphalts have a
strong tendency to exude.
In California the less durable
asphalts, those generally produced from the low sulfur bearing
crude, also exude; but the results of the exudation of these
low sulfur bearing California crudes are more serious than
the exudation experienced with some of the higher quality
asphalts of the high sulfur bearing crudes or some of the
Eastern crudes.
The tendency of an asphalt to exude also,
like some of the other deficiencies recently mentioned, can
be rectified by proper blending of the charge stock and by
the proper manufacture of the asphalt from blended or syn­
thetic charged stock.
47
Compatibility of Asphalts.
One of the problems that
must be given serious consideration by every asphalt user is
whether the material purchased currently will blend satis­
factorily or be compatible with the material purchased in
the future.
In the manufacture of roofing paper, both
saturant and coating asphalts are used; and if the two are
not compatible and mutually solvent, considerable difficulty
may be experienced.
An asphalt made from one source of crude
quite often will give difficulty in both manufacture and In
the finished roofing when that particular asphalt is blended
with a material produced from another crude source.
It is,
therefore, quite essential to determine whether or not the
asphalts are compatible before they are used.
CHAPTER V
VARIOUS USES OP AIR-BLOWN ASPHALTS
With the installation of proper air blowing facili­
ties and by the careful choice of blowing stocks and
operating controls, it is possible to produce a wide
variety of air-blown products*
The following classification
lists some of the more important products.
Specifications
for these materials are generally varied in minor detail by
the manufacturer.
I.
Paving.
ASPHALT CLASSIFICATION
These asphalts are produced from steam-blown
asphalts and are only slightly air-blown in order to change
their characteristics sufficiently to meet the various paving
specifications.
Roofing.
Roofing papers are manufactured from a
composition material, consisting generally of rag and hair
felt which have been thoroughly saturated in what is called
**saturant asphalt11.
These asphalts have a melting point of
approximately 160 to 180°F.
After the roofing paper has been
thoroughly saturated, a final coating of "coating asphalt11
is applied.
210 to 230°F.
This asphalt will vary in melting point from
Various types of granules, such as, ground
49
brick, slate, stone, etc. are placed on the coating asphalt
while it is still soft.
Patching asphalt is also produced
from materials of this general nature to be used in the
repair of asphalt roofs which have been in service.
Floor materials. Asphalt floors are generally of two
types, the first being the asphalt tile which is similar in
appearance and wearing quality to linoleum and second being
an asphaltic mastic which is generally placed over wood or
concrete floors and is an air-blown asphalt with a certain
percentage of filler added.
The type of filler, such as
rock dust, etc. is varied depending upon the manufacture and
specification involved.
Corrosion protection for steels.
Air-blown asphalts
of various specifications are used for the protection of
steels.
In the protecting of pipe lines or steel to be used
under corrosive conditions, an asphalt primer is first applied
to the clean surface of the steel.
These asphalts are of a
non-filled type and have a low melting point.
Following the
application of the primer, the steel is coated with a material
called lfpipe dip11.
This is also generally a non-filled
asphalt but of a higher melting point than the primer.
In
the case of buried pipe lines or steel to be placed underground,
it might be desirable to apply a coat of armor coat enamel.
50
This material is a filled enamel and is applied to give a
wearing resistance to the coating.
Pine line coatings.
In special cases where a heavy
pipe line protection is desirable, a final coating of asphal­
tic material from one-half to over an inch may be applied.
These coatings are of the filled type and are again applied
primarily to resist abrasion due to the movement of either
the pipe or the ground.
Deck coatings. Certain grades of air-blown asphalt
diluted with a volatile thinner may be used for the coating
of ship!s decks.
This material may also be applied hot, and
the thinner can be eliminated under these conditions.
Anti-fouling coatings.
The application of the
proper grade of air-blown asphalt over various types of
anti-fouling paints has been very effective in decreasing
the marine growth on ship bottoms.
Paints and primers.
A large variety of paints and
primers are manufactured from the various grades of air-blown
asphalt.
The asphalts used in these products are generally
varied in specification by the manufacturer concerned.
Waterproofing.
Air-blown asphalts of medium melting
point have been found to be very effective for the coating of
51
tanks, reservoirs, concrete floors, and foundations to
reduce water seepage through the concrete.
Insulation.
Asphalts have good electrical resistance
characteristics and certain types have been found effective
for the sealing of outdoor electrical fixtures.
Sewer .joint compounds.
Filled airblown asphalts
properly compounded make excellent materials for the sealing
of either concrete or tile sewer joints.
Mineral rubber.
The higher air-blown asphalts,
generally from 250 to 300°F, are effectively used as
plasticizers in the manufacture of various types of commercial
rubber goods.
Specialties.
There is a large list of special
asphalt products which may be produced, such as storage
battery sealing compound, binder for briquettes, clay
pigeons, etc.
BIBLIOGRAPHY
52
A.
BOOKS
Abrahams, Herbert, Asphalts and Allied Substances.
New York: D. Van Nostrand Company, Inc., 1929*
Cross, Roy, Handbook of Petroleum Asphalt and Natural Gas
Bulletin No. 2^7 Kansas City, Missouri: Kansas City
Testing Laboratory-, 1928.
Day, D. T., Handbook of the Petroleum Industry. Volumes I
and II. New York: John Wiley and Sons, Inc., 1922.
Engler, C., and Hofer, H*, Das Erdol, Volume VI. Leipzig,
Germany: S. Herzol Publishing Company, 1925*
Gurwitsch, Leo. Petroleum Technology. (Moore, Harold,
translator). New York: D. Van Nostrand Company,
Inc., 1934*
Hamor, W. A., and Padgett, E. W . , The Technical Examination
of Crude Petroleum and Petroleum Products. New York:
Mb Graw-Hill Book Company, Inc., 1920.
Holde, D., and Mueller, Edward, translator, Examination of
Hydrocarbon Oils. New York: John Wiley and Sons, Inc.,
1915.
Richardson, Clifford, The Modern Asphalt Pavement.
New York: John Wiley and Sons, Inc.," 1908’.
B.
PERIODICAL ARTICLES
Bencowitz, I., and Boc, E. S., (Texas Gulf Sulfur Company),
’’Change of Penetration with Temperature of Various
Asphalts,11 Industrial and Engineering Chemistry. 8*3,
January, 193^.
Holland, Charles J., ftThe Manufacture, Packaging and Shipping
of Oxidized Asphalts,” (six articles), The Petroleum
Engineer. February-July, 1935*
Holmes, A., Collins, J. 0., and Child, W. C., (Standard Oil
Company of New Jersey), ‘’Measuring the Susceptibility
of Asphalts to Temperature Changes,*1 Industrial and
Engineering Chemistry. Analytical Edition,~B:2,
March l5, 1935*
53
Kay, Emby, (Skelly Oil Company), 11Availability of Domestic
Asphalts for Highway Construction in U. S.,11 The Oil
and Gas Journal, December 1939*
Nellensteyn, F. J. (Technical University of Delft, Holland),
"The Composition of Asphalt,11 Weekblad, 1923.
Nelson, W. L., (professor of Petroleum Refining, University
of Tulsa), "Evaluation of Asphalt Bearing Stocks,"
Petroleum Engineer, March, .1933*
Taylor, F. M« H., "The Manufacture of Asphalt from Cracking
Process Residues," The Industrial Chemist, December, 1932.
Thurston, Robert R., and Knowles, Edwin C,(The TexasCompany),
N. Y.}, "Oxygen Absorption Tests on Asphalt Constituents,"
28:1, January, 193&* Industrial and Engineering
Chemistry.
C.
UNPUBLISHED MATERIAL
Bray, Ulric B., Beckwith, L. B., and Barnes, C. D.,
"Air-Blown Asphalt Investigations," Research and
Development Department Report No. 501, Union Oil Company
of California, August 8, 1935*
Carr, D. E., "Production of Coating Asphalts," Research
and Development Department, Union Oil Company of
California, A pril 30, 1939*
Carr, D. E., and Scott, F. S., "Paving Type Asphalts from
Santa Maria Valley and San Joaquin Valley Crudes,"
Research and Development Department Report No. 570,
Union Oil Company of California, January, 1940.
Ragatz, E. G., Wilson, E. A., and Campbell, J. A.,
"Production of Air-Blown Asphalts with G-A Agitator,
Union Oil Companyfs Oleum Refinery," Development
Department Report No. 82, Union Oil Company of
California, March, 1937*
Ragatz, E. G., Wilson, E. A., and Campbell, J. A., "Operation
G-A Agitators, Los Angeles Refinery," Development
Department Report No. 105, Union Oil-Company of
California, July, 1938.
54
D.
UNITED STATES PATENTS
178,061
Jenney, W. P., "Improvement in Obtaining a Resinous
Substance from Purified Sludge Oil," May 30, 1876.
178,154
Jenney, W. P., "Improvement in Resinous Substances,"
May 30, 1876.
236,995
De Smedt, E. J*, "Bituminous Cement," Jan. 25, 1881.
239,466
De Smedt, E. J., "Insulating or Non-conducting
Bituminous Compounds for Electrical Purposes,"
Mar. 29, 1881.
452,763
Frederick Salathe, "Composition of Matter,"
May 19, 1891.
524,130
Byerley, F. X., "Manufacture of Asphalt, etc., from
Petroleum,""Aug. 7, 1894.
635.429
Culmer, G. F., and Culmer, G. C. K., "Process of
Making Asphaltic Fluxes," October 24, 1899*
635.430
Culmer, G. F., and Culmer, G. C. K., "Asphaltic
Flux," Oct. 24, 1899.
1,430,538
Culmer, H. H., "Hydrocarbon Product and Process of
Making Same," Oct. 3, 1922.
1,709,874
Peterkin, et al, "Distillation of Oils,"
Apr. 23, 1929.
1,715,069
Kirschbraun, "Process for Making Asphaltic
Products," May 28, 1929*
1,718,679
Black, et al, "Apparatus for Oxidizing Hydrocarbon
Oils," June 25, 1929.
1,735,503
Kirschbraun, "Process for Making Asphalt,"
Nov. 12, 1929.
1,745,155
Faber, et al, "Asphalt and Road Oil and Process for
Producing Same," Jan. 28, 1930*
1,766,446
Miller, "Apparatus for Treating Asphaltic Oils for
the Production of Asphalt," June 24, 1940.
1,774,756> MacLachlan, “Process in the Art of Manufacturing
Asphalt by Oxidizing Heavy Petroleum Hydrocarbons
Sept, 2, 1930.
1,782,186, Abson, “Asphaltic Material and Process for
Manufacture, “ Nov, 18, 1930.
1,842,10?, Loomis, “Method of Making Asphalt,“ Jan, 19, 1932
1,865,081, Chappel, “Process of Oxidizing Oils," June 28,
1932.
1,881,753) Loebel, “Process for the Manufacture of Asphalt,“
Oct. 11,-1932.
1,883,745, Beardsley, et al, “Process for Converting Oils
and Simultaneously Recovering Asphalt,“
Oct. 18, 1932.
1,886,380, Dowlen, “Method of Oxidizing Asphaltic Oils,11
Nov. 8, 1932.
1 ,889,365, Loebel, “Process for the Manufacture of Asphalt,“
Nov. 29, 1932.
1,889,697, Pullar, “Process for Producing Asphalt,"
Nov. 29, 1932.
1,891,890, Keith, “Method of Making Asphalt," Dec. 20, 1932.
1,902,305, Kirschbraun, “Method of Producing Asphalt,"
Mar. 21, 1933*
1,911,114, Gard, et al, "Process and Apparatus for Producing
Asphalt, May 23, 1933*
1,912,667, Swerissen, “Blowing Asphalt," June 6, 1933*
1,942,656, McNeil, “Asphalt from Blown Petroleum Residuums,"
Jan. 9, 1934.
1,948,296, Haylett, “Method for Producing Asphalt,
Feb. 20, 1934.
1,950,900, McConnell, "Process and Means for Producing
Asphalt," Mar. 13, 1934.
1,953,333, Black, et al, “Process for the Manufacture of
Asphaltic Products, Apr. 3, 1934.
1,953534*5} Gard, "Process for the Manufacture of Asphaltic
Products,11 Apr. 3, 1934.
1?953j346, Gard, "Process and Apparatus for Manufacture of
Asphaltic Products,11 Apr. 3 , 1934.
1,973,294, Mutter, "Method of and Apparatus for Treating
Hydrocarbons," Sept. 11, 1934.
1 j97535633 Tijimstr^, "Process for Treating Hydrocarbons,"
Oct. 2, 1934.
I*979,676, Douthett, "Method of Treating Bitumen,"
Oct. 6, 1934.
1,982,920, Me Connell, "Process for Making Asphalt,"
Dec. 4, 1934.
1 ,988,715, Bray, et al, "Asphalt and Method for Producing
Same," Jan. 22, 1935*
1 ,988,766, Aldridge, "Process and Apparatus for Producing
Asphalt," Jan. 22, 1935*
1,990,466, Allan, "Production of Asphaltic Products from
Aromatic Extracts of Mineral Oils," Feb. 12, 1935*
1,993,532, Skowronski, "Asphalt and Process of Preparing
Same," Mar. 5, 1935.
1,999,018, Gard, et al, "Oxidized Asphalt," Apr. 23, 1935*
2,002,670, Me Connell, "Process of Making Asphalt,"
May 28, 1935.
2,004,210, Morrell, "Method of Producing Asphalt,"
June 11, 1935.
2,010,423, Wells, "Method of Manufacturing Asphalt and
product Thereof," Aug. 6, 1935*
2,024,096, Engler, et al, "Manufacture of Asphalt,"
Dec. 10, 1935.
2,026,039, Hoover, "Treatment of Asphalt to Remove Unsaturated
Compounds Therefrom," Dec. 31, 1935.
2,026,073, Swerissen, "Method of Treating Mineral Oil Residues,
Dec. 31, 1935.
2,028,922, "Process of Making Asphalt," Jan. 28, 1936, (Rose).
2,029,288, Bray, "Petroleum Resin," Feb. 4, 1936.
2,029,290, Bray, et al, "Asphalts and Method for Producing
Same," Feb. 4, 1936.
2,029,504, Ragatz, "Method for Producing Oxidized Asphalts,"
Feb. 4, 1936.
2,032,546, McNeil, et al, "Asphalt Oxidation System,"
Mar. 3, 1936.
2,046,081, McNeil, "Process for Manufacturing Asphaltic
Products," June 30, 1936.
2,055,459, GutzwilXer, "Process for Making Asphalt,"
Sept. 22, 1936.
2,057,265, Ringgenberg, "Asphalt Manufacture,11 Oct. 13, 1936
2 ,062,366, Mack, "Asphalts of Low Susceptibility to
Temperature Change," Dec. 1, 1936.
2,067,264, Ebberts, "Process of Making Bituminous Materials,
Jan. 12, 1937.
2,068,845, Collins, "Process of Manufacturing Hard Bitumi­
nous Materials," Jan. 26, 1937*
2,069,620, Nevitt, "Method for Manufacturing Residual Oils
of High Asphaltic Content," Feb. 2, 1937*
2,073,088, Anderson, et al, "Preparation of High Grade
Asphalts," Mar. 9, 1937*
2,085,992, Nelson, "Manufacture of Asphalt," July 6, 1937*
2,093,450, Jacobsohn, "Method of Producing Bodies of
Bituminous or Tarry Material," Sept. 21, 1937*
2,099,434, Culbertson, "Process for Treating Hydrocarbons,"
Nov. 16, 1937.
2,099,448, McNeil, "Asphalt Oxidation," Nov. 16, 1937*
2,120,376, Shipp, et al, "Manufacture of Asphalts,"
June 14, 1930.
2,121,437, McConnell, "Process of Making Asphalt,"
June 21, 1938.
58
2,122,764. Wallis, et al, "Product of Blown Asphalt,11
July 5> 1938.
2,148,869, McConnell, "Manufacture of Asphalt," Feb. 28,
1939.
2,154,746, Held, "Manufacture of Asphalt,". Apr. 18, 1939*
2,170,496, Gard, et al, “Process and Apparatus for Interfac­
ing Fluids," Aug. 22, 1939*
2,172,821, Subkow, "Process for Preparing Oxidized Asphalt,"
Sept. 12,. 1939.
2,179?208, Burk, et al, "Manufacture of Improved Asphalts,"
Nov. 7, 1939.
2,179,988, Whitacre, "Preparation of Asphalt," Nov. 14, 1939*
2,200,914, Burk, et al, "Manufacture of Improved Asphalt,"
May 14, 1940.
2,201,396, Fryar, "Asphalt and Process for Producing the
Same," May 21, 1940.
2,203,081, Daigle, "Asphaltic Product and Method of
Producing Same," June 6, 1940.
2,205,089, Gard, et al, Process for Mixing Fluids,"
June 18, 1940.
2,215,074, Shipp, et al, "Manufacture of Asphalts,"
Sept. 17, 1940.
2,220,714, Hersberger, "Production of Asphalt," Nov. 4, 1940.
2,222,347j Gard, et al, "Process for Producing Asphalt,"
Nov. 19, 1940.
2,223,776, Anderson, "Asphalt Preparation," Dec. 3> 1940.
APPENDIX
TABLE IV
COMPARISON OP COATINGS USED BY VARIOUS
ROOFING MANUFACTURERS
Sample
No.
Probable
Composi­
tion
Duct. Flash
Barber Photosensitivity Weather
ometer
Stain
Hours to Form
Penetration at at
Point
M.P. 32°F 77°F 115°F 77°F COC PM. Number Lt.Rust Hvy.Rust Cycles
15 ‘
31*
3 .0
-
425
1.4
-
11
17
41
-
-
435
2.0
8
32
100
7
14
25
2.1
-
450
-
8
12
105
228 11
S.O.
19
(Probably Coalinga)
30
-
-
455
5.0
Should be low
28
D-6899-■1 Gato
213
T
E-39-2
Gato
222
B-9577
Gato
214
E-38-4
80
E-8351
Probably 221
Torrance
12
20
34
1*3
445
-
-
High
35
B-3643
Torrance 225
14
23
35
1.1
-
440
-
High
27
C-8799
Typical 216
Santa Maria
10
16
34
4.2
-
435
1.0
8
12
110
C-8799
Typical
Orcutt
12
19
38
2.8
460
-
2.5
12
24
55
215
61
TABLE V
ANALYTICAL DATA ON PROPERTIES OF VARIOUS COATINGS
Vis­
cosity
Blowing Stock
Sample
M.P.
Duct. Flash
Penetration at . at
•F
J'f //~r quo r-w cap cola oa-
Santa Uarla Valley (SMV-1 3 0 )
C1794-C1
217
10
17
Poso Creek
A9302-1
232
14
Gato Ridge
B9577-A
214
Midcontinent (Illinois)
D3066-2
Santa Fe Springs (vac.still feed)
Orcutt
Bar- WeatherFurol Sul­ ber
ometer
sec.at fur Stain Life In
Cycles
VIA
34
3 .8
4 3 5 410 99.9 99.8 60.C 180
17
23
1.0
440 430
7
14
25
2.2
228
14
25
38
2.4
C8776-C1
226
22
33
50
1.3
-
430 99.9
-
C8767 -I6
226
13
22
35
2.6
-
4 3 5 99.9
-
70 .
72.0
-
-
-
450 99.8
570 510
-
-
-
57.0
-
r
5.42 l.C
3 4 .3
35.4
30.3
95
2 6 .6
22.7
50.8
16.9
(9,500)
-
2.48
4.5
90
33.9
35.4-
30.7
22.3
-
297
1035
142
6
18
3100
167
7
16
1380
126 ®
0.888 40
(9,500) 1204
177®
0.838 80 115
37.3
23.2
(2,400)
392
80
0.845 71 105
278
0
2
1090
23.5
40.3
19.3
(5,100)
702
104®
0.871 50 75
205
3
7
1550
_
4.02
3.0
60
37.4
21.1
39.5
20.5
(4,800)
612
97®
O .8 6 3 71
90
201
2
4
-
5.62
2.0
90
32-5
23.4
44.1
16.7
(9,300)
917
117
0.891 30
25
133
5
27
_
_
27.8
35.9
36.3
17.7
(9,300)
888
112.6 O .8 8 3 29
25
194
2
9
.
2.5
110
37.3
22.9
39.8
17.9
(6,300)
740
103.5 O.8 8 3 41
50
151
2
11
.
_
_
.
.
_
_
_
.
.
_
460 450
-
25
0.872 35
994
19.8
-
2.5
2870
36.1
460
41
9
1
42.9
4 6 0 4 5 0 99.9
21
3
0
55
2.2
13
145
148
20
3-0
215
-it
15
2.2
32
0.5
0.893 25
Asphaltenes,
[ mol.wt.
3.0
40
20
VJ
3.90
19
11
VGC
Tests on
Ln__
0 .8 0
19
7
105®
Pour
Pt.
150
12
228
769
30
12
E6035-C1
(7,200)
-
225
SMV 7 pen. • 40* SUV 80 viscosity
lubricating distillate
E6016-C1
16.7
5.72
225
5 3 .3
42.6
0.97
E1009-C1
455 445 _
24.8
-
E39-1
SUV 7 pen. ♦ 40* Poso Creek SAE
50 lubricating distillate
3 2 .6
130*P 2I0*F
18.4 (17,000) 1368
Gato P.ldge (now type)
-
77*F
nesina
Tests on Oil
Viscosity,Saybolt
90
Santa Marla Valley and 30* Santa
Fe Springs
-
3.0
1 10
Grav.
•API
• at
60"F .
Vacuum Distillation of Oil Fractions
stillation
Dlst^Bott^
See vacuum distillation data below:
Max. Temp
O.H. •?
Sample No.
C1794-C1
B9577-A
D3066-2
C8767-16
E1009-C1
6
0
0
0
0
33
22
0
20
20
58
52
17
60
60
-
-
72
62
39
71
71
sec. at
210*P
680
873
645
690
658
646
346
728
728
611
VGC
0.888
0.886
0.835
0.872
0.876
2250
62
TABLE VI
CHANGE IN PERCENTAGES AND PROPERTIES
OF ASPHALTIC CONSTITUENTS WITH AIR BLOWING
Santa Maria
Valley
Blowing Stock
Viscosity, S.F. sec. at 122°F
210°F
% by weight:
Asphaitenes
Resins
Oils
130
19.4
29.0
51.6
Tests on oil
Viscosity, S.F. sec. at 210°F
60.5
0.892
Viscosity-gravity constant
Tests on resin
Melting point, °F
135
Penetration at 77°F
17
32°F
3
Asphaitenes
]
Molecular weight
1600
Oil lost by distillation
during blowing, % by wt.
15
Coating asphalt
Sample No<
C-1794-C1
Melting point. °F
217
Penetration at 77°F
17
fo by weight:
Asphaitenes
Resins
Oils
42.6
24.8
32.6
Tests on oil
Viscosity, S.F. sec. at 210°F 105
Viscosity-gravity constant
0.893
Tests on resin
Melting point, °F
145
Penetration at 77°F
9
32°F
3
Asphaitenes
Molecular weight
2870
a.
b.
c.
Poso
Creek
Santa Fe
Springs
185
-
30
2.2a
26.7a
71. la
3.7
19.6
76.7
56a
0.879a
86
O.81
158
1
0
900
IOC
A-9302
232
17
I80b
1
0
1000
10°
C-8776-C1
226
33
30.3
35.4
34.3
37.3
19*8
42.9
148
0.872
80
0.8^
297
1
0
278
2
0
1035
1090
Estimated from data on heavier residuum.
187°F m.p. resins, insoluble in butane plus
4.6% of l65°F m.p. resins, soluble in butane.
Approximate
TABLE VII
OXIDIZED ASPHALTS
Grade
M.P.
Pen.
1A
IB
1C
2A
2B
2C
Pipe dip
Mineral rubber
Battery seal
190
170A
170B
215-240
185-210
170-185
155-170
148-165
140-155
5-10
10-15
15-20
20-30
25-35
30-40
Abbreviations;
M.P.
Pen.
Sp.Gr.
Ductility
Flash, P.M.
Flash, C.O.C
L.O.H.
B.I.H.
CS2 .
CCI4
Max.
MLn.
Sp.Gr. Duct. Flash L.O.H. B.I.P. CS2 CC14 Stocked in
approx. min. P.M. max.
max.
min. min.
min.
1.060
1.047
1.040
1.034
1.030
0
1.0
2.0
4.0
5.0
7*0
2.0
1.026
190-200 30-40
1.025
293-320 3-6 1.0-1.05
210-220 50-60
1.025 2.0
185-195 18-22
1.047 3*0
1.034 5.0
165-175 25-30
e
145-155 30-40
1.026 10.0
420
420
420
420
"420
420
420
0.7
0.7
0.7
0.7
0.7
0.7
20
20
20
20
20
20
99.7
99.7
99.7
99.7
99.7
99.7
-
mm
-
-
-
-
475
425
425
-
-
-
1.0
1.0
1.0
20
20
20
-
425
99.8
-
-
99.6 Wood bbls.
tt
99.6 it
tt
tt
99.6
11
tt
99.6
tt
99.6 11
tt
tt
99.6
-
-
it
tt
Steel drums
it
tt
99.0 Wood bbls.
it
99.0 H
tt
it
99.0
Ball and ring melting point, °F ASTM D 26-36
Penetration at 77°F, 100 grams, 5 sec.. ASTM D5-25*
Specific gravity at 60°F, Union Oil Company method.
Ductility at 77°F; cm., ASTM D113-32T.
Flash point, Pensky-Martens closedcup, °F, ASTM D93-22<
Flash point, Cleveland open cup, °F,ASTM.D92-33*
% loss on heating 50 grams 5 hrs. at 325°F ASTM D92-33*
% reduction in penetration at 77°F after heating.
$ soluble in carbon disulfide ASTM D4-27*
% soluble in carbon tetrachloride ASTM D165-27.
maximum or "not more than",
minimum or "not less than".
ON
u>
TABLE VIII
STEAM-BLOWN ASPHALTS
Grade
M.P*
Pen*
A 260-280
A 220-260
A 200-220
B 170-200
B 150-190
C 10-20
c 20-30
C 30-40
D 40-50
D 50-60
D 60-70
D 70-80
D 80-90
E 90-110
E 110-130
E 130-150
E 150-200
E 200-250
260-280
220-260
200-220
170-200
150-190
130-155
125t 135
120-130
115-125
110-120
110-120
110-120
105-115
105-115
100-110
100-110
95-105
95-105
0
0
0-3
0-5
5-10
10-20
20-30
30-40
40—50
50-60
60-70
70-80
80-90
90-110
110-130
130-150
150-200
200-250
Sp.Gr* Duct. Flash
approx. min. P-M
min.
1.125
1.110
1.095
1.090
1.080
1.055
1.035
1.026
1.024
1.023
1.022
1.021
1.020
1.019
1.018
1.016
1.014
1.010
0
0
0
0
0
10
100
100
100
100
100
100
100
100
100
100
100
100
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
600
450
450
L*0*H* R.I*P. CCl^
max.
max.
0.1
0.1
0.1
0.1
0.1
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.3
mm
mm
-
-
25
30
30
30
30
-
-
90.0
90.0
90.0
90.0
90.0
96.0
99.?
99.5
99.?
99.?
99.?
99.?
99.?
99.?
99.?
99.?
99.?
99.?
Stocked in
Wood bbls
rt
it
tt
tt
tt
tt
tt
tt
tt
n
tt
tt
tt
tt
tt
tt
tt
tt
it
tt
tt
tt
it
tt
tt
tt
tt
tt
n
Note 1. E grade asphalt is seldom sold in barrels*
Note 2. Other steam-blown asphalts than the above can be produced if necessary.
Abbreviations:
M.P*
Ball and ring melting point, °F, ASTM D26-36*
Pen.
Penetration at 77°F, 100 grams, ? sec* ASTM D?-2?.
Sp.Gr*
Specific gravity at 60°F, Uni6n Oil Company method.
Duct.
Ductility at 77°F; cm., ASTM D113-32T.
Flash, P-M
Flash point, Pensky-Maftens closed cup, °F, ASTM D93-22.
Flash, C.O.C. Flash point, Cleveland open cup, °F, ASTM D93-22.
^
L.O.H*
% loss on heating 50 gms. 5 hrs. at 32?°F,'ASTM D6-33*
R.I*P.
% reduction in penetration at 77°F after heating
cs2 $ soluble in carbon disulfide ASTM D4-27; CC14 % soluble in carbon tetra. ASTM D165-27
TABLE IX
BUREAU
1.
OP S T A N D A R D S
T H E R M A L E X P A N S IO N O F P E T R O L E U M A S P H A L T S A N D F L U X E S
Values of V . / V t given ill Table 1 represent volumes at GO’ F. occupied by a unit volume at Indicated tem peratures, t F.
Fo r example. 1 gallon of petroleum asphalt measured at 350' F. w ill have a volume of 0.9051 gallon at Go K. T able 1 is
sim ila r in form to the corresponding table given in N atio n a l Standard Petroleum O il Tables. It. S. C ircular No. 151. and
to the abridged volume correction table given in the supplement to C ircular No. 151. In fact. T able 1 m ight well be con­
sidered as an addition to th a t supplem ent: th a t Is, aa group 0 for the grav ity range (• to 15 A IM
Th e data given In Table 1 were calculated from the equation.
V t - V *,( 1 + A ( t — GO>+ Bt t — GO
i
using A — 0.000341 and B - 0.0000001. which is equivalent to the follow ing:
T e m p eratu re range in °F . M ean coefficient of expansion
60
60
60
60
Kanlslflsd Asphalt
to
to
to
to
150
250
350
450
0.00035
.001)36
.00037
.0003S
70 to 212
.00026
These are average values based on unpublished m easurements made at the Bureau of Standards on 25 samples w ithin
the tem perature range 32" to 176° F.. and tw o samples w ith in the range 60“ to 400° F. These coefficients ami the expan­
sions, (V „ /V t> — 1, obtained from T a b le 1 apply to petroleum asphalts and fluxes In general w ith an estim ated uccuracj
of 5 per cent, which is equivalent to the fo llow ing percentage accuracy in the relative volumes. V», Vt. for various tempera
ture ranges: 0.1 per cent, 0° to 100°; 0.2 per cent. 100° to 200°: 0.4 per cent, 200“ to 300°; 0.6 per cent. 300“ to 400 ; and
0.8 per cent, 400° to 500° F.
Products containing wax. gas bubbles, or nonbitum lnous m aterials have expansions which differ front those given by
T able 1 in proportion to the am ount present.
Th e experim ental data obtained by:
Observer
M a te ria l
Reference
Zeitfuchs
Rossbacher
C alifo rn ia A sphalt
Petroleum Reslduums
1ml. Eng. Chent.. 17. p.
Ind. Eng. Chent.. 7, p.
1280;
1925
577: 1015
agree w ith the expansions <VW/ V t) — 1 given by T able 1 to about 5 per cent. These constitute the only data found in tin
lite ra tu re on this class of petroleum products.
Exam ple— I f the volume of a given q u an tity of petroleum asphalt Is 10..000 gallons at 35(1“ F.. what is its volume et
60° F.? Calculate from the value given in T a b le 1 as follows:
V„ :
10.000 X 0.9031
9031 gallons at 60
F.
W here necessary to convert to a ton basis, the follow ing equivalents should be utilized
GRADE
"A " and
'
"C ”
7‘D ~
"E"
Cut back MC-2. 3. 4. 5
R C 27.U 4
MC-T
_ R (' 1
A ir blowu asphalt
Hoad O il 30-40/80 ( SC-1)
40-60/80
~
50-60/80 (S C -lA t
~
60-70/80 { SC-21
70-80/80 (S C -3-S C -4)
80/80
85~80
-- —
_ _
G A LL O N S
PER TO N
P E N E T R A T IO N
-pp7g0~95~80
EanLslfl»d Asphalt
““
05
ln-40
40-90
90-250
221
23n
232
253
215
2 I5
250
25o
25.5
^
251
251
219
211
212
5-40
—
~
.
"
...
"
”
~
~ 239
237
240
TABLE X
T H E R M A L PROPERTIES OF PETRO LEU M PRODUCTS
Table 1.— Thermal expansion of petroleum asphalts and fluxes.
Temp.
1
!
i
|
!
:\ ,00- T !
Yt
i
Yso
Yt
Temp.
t°F.
0
2
4
6
8
1.0205
1.0198
1.0191
1.0185
1.0178
100
102
104
106
108
0.9864
.9857
.9S50
.9844
.9837
200
202
204
206
208
0.9527
.952.0
.9513
.9506
.9500
300
302
304
306
30S
0.9195
.9188
.9181
.9175
.9168
400
* 402
404
406
408
0.8869
.8863
.8856
. 8850
. 8843
10
12
110
112
114
116
118
.9830
.9823
.9816
.9810
.9803
210
212
214
216
218
.9493
.9486
.9480
.9473
.9466
310
312
314
316
318
.9162
.9155
.9149
.9142
.9135
410
412
414
416
418
.8837
.8831
.8824
.8818
.8811
■
18
1.0171
1.0164
1.0157
1.0150
1.0143
20
22
24
26
28
1.0137
1.0130
1.0123
1.0116
1.0109
120
122
124
126
128
.9796
.9789
.9783
.9776
.9769
220
222
224
226
228
.9460
.9453
.9446
.9440
.9433
320
322
324
326
328
.9129
.9122
.9116
.9109
.9103
420
422
424
426
428
.8805
.8799
.8792
. 8786
.8779
1
1
30
32
34
36
38
1.0102
1.0095
1.0089
1.0082
1.0075
130
132
134
136
138
.9762
.9755
.9749
.9742
.9735
230
232
234
236
238
.9426
.9420
.9413
.9406
.9400
330
332
334
336
338
.9096
.9090
. 9083
.9077
.9070
430
432
434
436
438
.8773
. 8767
.8760
. 8754
. 8747
40
42
44
46
48
1.0068
1.0061
1.0054
1.0048
1.0041
140
142
144
146
148
.9728
.9722
.9715
.9708
.9701
240
242
244
246
248
.9393
.9386
.9380
.9373
.9367
340
342
344
346
348
.9064
.9057
.9051
.9044
.9038
440
442
444
446
448
.8741
.8735
.8728
. 8722
.8716
50
52
54
56
58
1.0034
1.0027
1.0020
1.0014
1.0007
150
152
154
156
158
.9695
.9688
.9681
.9674
.9668
250
252
254
256
258
.9360
.9353
.9347
.9340
.9333
350
352
354
356
358
.9031
.9025
.9018
.9012
.9005
450
452
454
456
458
.8709
.8703
.8697
.8690
.8684
ij
60
62
64
66
68
1.0000
.9993
.9986
.9980
.9973
160
162
164
166
168
.9661
.9654
.9647
.9641
.9634
260
262
•264
266
268
.9327
.9320
.9313
.9307
.9300
360
362
364
366
368
.8999
.8992
. 8986
.8979
.8973
460
462
464
466
468
.8678
.8671
.8665
.8659
. 8652
ij
70
72
74
76
78
.9966
.9959
.9952
.9945
.9939
170
172
174
176
178
.9627
.9620
9614
.9607
.9600
270
272
274
276
278
.9294
.9287
.9280
.9274
.9267
370
372
374
376
378
.8966
.8960
.8953
.8947
.8940
470
472
474
476
478
.8646
. 8640
.8633
. 8627
.8621
80
82
84
86
88
.9932
.9925
.9918
.9912
.9905
180
182
184
186
188
.9594
.9587
.9580
.9573
. 9567
280
282
284
286
288
.9260
.9254
.9247
.9241
. 9234
380
382
384
386
388
.8934
. 8927
.8921
.8914
. 8908
480
482
484
486
488
.8614
.8608
.8602
. 8595
.8589
90
92
94
96
98
100
.9898
.9891
.9884
.9878
.9871
.9864
190
192
194
196
198
200
.9560
.9553
.9547
.9540
.9533
.9527
290
292
294
296
298
300
.9228
.9221
.9214
.9208
.9201
.9195
390
392
394
396
398
400
.8901
.8895
.8888
.8882
.8876
. 8869
490
492
494
496
498
.500
. 8583
. 8577
.8570
j
. 8564
. 8558
.8552 ' 1
t°F.
1
4
16
Yao
Yt
Temp.
t°F.
Yao
Vt
Temp.
t°F.
\ 00
Yt
Temp.
t°F.
I
J
H
!
|
1
1
'
,
!|
!'
!|
1
!|
||
i|
:
Air @ s Y n
and of a Pa/e ofi/A Cu. Ft Pen M m .
P er
■do H P . W e a t h e r P r o o f / V f o / o r - 4 - 4 - 0
f j> o u b /e E n e / o s e d V a p o r P r o o f T y p e )
3 h /. o f S / i / / C fn a rg e
„r
O r ific e
Mpk
M e te rF
V o /f
60
C y c /e .
--->4~
V a p o rs
O u /^
2 5 Lo"
S-teom T ra p
' C o o fin<y C o i t t y i / / b e r e p a i r e d
E a ff/e
a /o n q S o //o m \
/o
re m o v e
P e a * fro m
Abe
tr./ ’/1 /
Idsphej/-/- W ^ - r p
s-r
o f S/i/l
do p/ve C/rot/- J
/a d/on o f S t/// and better / 2 S 3 d a . p e r fvt/n- p e r
B h /. o f S ■/■/// C ~/?ar<ye /fecr/ Transfer fro m
C/re Sor.
FIGURE 1
G -A
F L O W
S H E E F
A S P H A L T O X /D /Z /N G
S T /L L
AJ& »IWXIi
.•;'a141'jfPsfl7n
<QMP<
NGTH OFAPP
: pr d d d :e d
Refinery R m
IESEND
wwrvar
laigti <JL-2z!g
Oil
*239
t
1L
L15JL9112
X
:i
B
FIGURE 2
»Uhi:r'»Ui:'ii
BBii::i'ib<
l:F'i BribilfBHI/i»'Bi>Hrihi:H^u:’
i'
Ubi
inT:-i.
^j«^i
i»:ii
*'’i
iiibbai:iub
"i:iubIiiTT::>
ii'Bi: HjwiiVBV
:/»
Br
:iB
Br«
hi
«
U^LMiLWi'^L'-m^FiMttknB'UJWB^'PVWW^iL'W'
‘■'B^Vi --UW > Bl’MBM Ji^B'-'i*
6?
I
FIGURE
3
/ «•
++f
H
d
K
46
SO
54
X
62£6
Per Cent Oil In Blend by Weight
3
70
54
se
£2
Per Cent Oil In Blend by Weight
oe
ir n ilia ;
H
S
if
4:
Jes.
H
p
hilM
1
3
m
±
3d
E
tt
H
fflgnpy
-i
ry^rrTiT:^
p p
=
III IIIIII I III
m m
I
m
iin:r:m ,r.rr» •rt:n
-t
li^CUL
rrprr
ir.r.r
f
FIGURE
10
O
6
8
10
12
74
2
Time In hours from start of air
: /2:
t*
•zMixzaeiaas-
22
it
m
SOFTENIM
FIGURE 12
Coke D eposits
ABOVE
OI L L E V E L
X
L/no/ox D/st
B e p a r a tir
rranf/b*£>/ac.
Cona/anser Boxes .
E a c h B o x 2 ~6 "Co//s c/ear
thro.' 7bta/ CO//-curface
6 0 0 ^ S f .f f .
Each St///- ‘/••S'//£>/a. ana/
P0Ettt/gh
■
E a c h C oo//ng C o i/- £ * tO //n e a /
f t / ' E “p / p e i n / 2 r e t - t i c * /
p a s s e s m r/th a ? // t u b e s / a
onep/a/7e.
C/rc. O H
Coo/er-Eto/t
2 " p /p e .
/tec/roo/crting //eater 7 0 0 &?E-
WBanhs-EOti/6c*-*/'£>/*
E / r & b a k IW/'atti 6 C "
//poo A t eh /U r M e t
BOb/h
3/Ops.i
L
C /r c . 0 /7
£2/r>£> g<tn cy
Storage
L/re fortieat/ny
//£> bbi. Cep.
a Co/c/ Sf/// -
% /i/g h M e / t i n g
E s p h o /h s
B A S E S O E D E S I G N :/■ CJia/ g/ng s t o o p ten>/oeratLre i/OO “p
2 ' C h a rg/ nf r a t e t h r o ’h e a t e r / S O b/h. t o 3 S O *E7~emp.
3 ~A spha/t rec/roc/at/on pa t e t h r u ‘h e a t e r 3 O C b / h
*f~Coincic/enta/. ope/atic/is
[a) C h a r g e thru’o n e /ieatsr
(A) Efec/r co/ate rtcpha/t thru' o t h e r H e a t e r
(cl E t o H u c e a s p n a / t
5 -Each batch = 2 6 0 bb/. - O n e t o p oo pa/, tianh c a r +’/&%,
of f/ni&hctt aspha/f.
C h a r g e M'eater-7 7 0 s,?.ft •
ft b a n h s - S C ti/Sm* S " & , +
f c m p Capac/h/
E /n c b o k w/eth!/ ' 7 2 *
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A - s p h o /t
E re c t.
S,SOO M/S hi/hr A/et
S te a n
r / G U R E 14PROCESS PLOW SREET A/91
l/ERTICAL ST/LLS W/TH
TUBULAR HEATERS
Ur.o/ox
81
.st/i/afe.
S e p U r l;
-
^ f t.D ia . / O f t / f a A
Condenser 3oxes
£ach boa Z~b" Coifs e/ear
thru.' 7otai co/i<surfac e.
600 JSg.fi
m
ffdme Arrester
fi/rne 3urner-
£acb -s////'9.3 ftD/a and
AO ft fiph
S a c d C o o //n g C O ih Z A O
iineaift /fi"p ipe in /J2
u e r f /c a //o a s d e s r v iib a / /
fdbe^s /n one p/ane
Circ.O H
coo/er -AdO
fi.2wp/pe
ft
V- >&
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PO bb.'. Cop,
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Aspha/ts
3 A S £ 5 O F D£SI6N:~
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d
„■ ...g£
(b i A /n or yST-u a b.-.-w
: a ~r . <Ui*e .-/s p n < t , r .
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of finished aspha/f.
*-V
A s p b a /r
S ro d .
C i/a r p , rig
S / oc/ t
F I G U R E 15
PROCESS FLOW SHEET N° 2
VERTICAL STILLS WITH
INTEGRAL FIREBOXES
S ue! & as
C o n d e n s e r B oxes
Each Box -2 'i"Co)k
c/ear fhrv‘
.Tito/
cof/surface 600
Sf.f >f
L /n o /o x D i e t
S e p a ra to r
6D/a /O'///&/?
C/rc.- O f/ C o o /e r
f/yo f t 2 "E/pe
EZam e
Arrester
B ra n ^ ib fe ^
D/sc
f u m e Burner
1^-*
B O b /h
7o S/opo
SQpsj.
E a c h S t / / / - Z 2 f f £?/'*.
rS O f f L o rp.
Each coo/i'ng co// 26/0 Z/nea/
ZZ Z'Zi"pipe in /£ Po^'/z. out*/
passes yv/t/> a// tz/bas in
one p/ane.
C /'r c . O ff S / p
f/O b b f . C a p .
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yV
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T i
T
yv
i
y'</t
fi/qh Me/tinf
Aspha/ts
E A S E S O S DLS/O/V:-
f-Charp/nfrataESOl/fi
B u m p Cn/jac/fy
2'Co/nc/a/entaZ oparations
/S O b /h e a c h
(a j C h a r g e
(b J A /r o r s f e a / n b/ow
(c)Eropuce asphe/f
yV
*3-O ne b a t c h - 2 6 0 p b /. - One ZO/OD g a /. r a n A c a r r / o f t
o f f in is h e d a s p h a /t
Aspha/Z
Bnid.
C h a tc f/n #
S to c A
Stean?
r i G U R E /6
* PROCESS FLOW SHEET A/S3
HORIZONTAL STILLS WtTH
G-A AGITATORS
/ o '•
Afr
FIGURE 17
FLAME ARRESTOR AND FUME BURNING SYSTEM
84
FIGURE
COMMERCIAL INSTALLATION OF G-A UNITS
IN CONVENTIONAL SHELL STILLS
FIGURE
19
G-A CIRCULATING PUi.IP AND COOLING COILS
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