Year: 1899

page_text: A communication from abroad by GEORGE FREDERICK CULMER, and GEORGE
C. K. CULMER, Manufacturers, both of 153, Madison. Street, Chicago,
Illinois, U.S.A.
I, WILLIAM LLOYD WISE, of 46, Lincoln's Inn Fields, in the County of
London, Consulting Engineer and Chartered Patent Agent, do hereby declare
the nature of this invention and in what manner the same is to be performed to
be particularly described and ascertained in and by the following statement:-
:-
In the preparation of asphaltic cements, for example, employed in paving,
roofing, or for other purposes, it is usual to admix say 80% of refined Trinidad
asphalt with 20% of the oil residuum from petroleum distillation. The residuuni
is heated to 2500-300°F., and the refined asphalt added thereto, melting gradu-
ally in the menstruum. The mixture is maintained at the, stated temperature
for some 6 to 8 hours and during this period air is injected into the mass in
quantities chiefly as an aid in disengaging the asphalt proper from its intimate
association with the earthy sediments retained thereby, and also to ensure the
intimate admixture of the separated asphalt with the residuum solvent. Inci-
dentally, the air injected acts to drive off the water and such minor portion of
the hydro-carbons as may freely volatilize under the prescribed conditions.
the end of the treatment, the residuum has become thoroughly amalgamated
with the refined asphalt producing an homogeneous compound into which pul-
verized limestone and sand can be admixed, as in usual preparation of paving
materials.
At

page_text: του απ
run into an open kettle loosely covered by a hood of size sufficient to catch the
escaping vapours and deliver them to a suitable exit. The kettle is heated by
direct fire. When the temperature of the residuum attains, e.g. 380°F., (which
may require some 8 hours heating to effect) the batch can be advantageously
held at such point during treatment.
While this preliminary heating is in progress, the residuum expands in the
kettle and foams markedly giving off a notable quantity for the most part of
watery vapors. Gradually, the batch becomes quiescent, and at 380°F., may
have lost some 400lbs. in weight.
Into the hot quiescent batch at 380°F., air is now injected by a perforated
pipe suitably branched and located near the bottom of the kettle to distribute
the oxidizing agent evenly throughout the liquid. The air pipe is connected
externally with a force-pump or other source of supply.
Treatment by air-blast may extend over a period, e.g., of 40 hours divided
roughly into a first stage of about 32 hours duration and a second or final stage
for some 8 hours beyond. The volume of air injected varies as the treatment
proceeds, the inflow per hour ranging from 6500 to 5000 cubic feet during the
first stage, and from 4000 to 3000 cubic feet during the second.
Under the influence of the air, the batch gradually thickens, its notable pro-
gress in this respect marking the close of the first stage; eventually the
operator is obliged to lessen the blast. An increase in the internal heat of the
batch is also observed. To maintain the mass at even temperatures e.g. 380°F.—
which may often prove desirable, the air blast can be diminished temporarily
(at times) although it suffices generally to check the fire instead.
11 1

page_text: Date of Application, 5th June, 1899-Accepted, 8th July, 1899
COMPLETE SPECIFICATION.
Improvements in Asphaltic Fluxes and in the Manufacture thereof.
".
A communication from abroad by GEORGE FREDERICK CULMER, and GEORGE
C. K. CULMER, Manufacturers, both of 153,- Madison. Street, Chicago,
Illinois, U.S.A.
'
I, WILLIAM LLOYD WISE, of 46, Lincoln's Inn Fields, in the-County of
London, Consulting Engineer and Chartered Patent Agent, do hereby declare
the nature of this invention and in what manner the same is to be performed to
be particularly described and ascertained in and by the following statement:-
In the preparation of asphaltic cements, for example, employed in spaving,
roofing, or for other purposes, it is usual to admix say 80% of refined Trinidad
asphalt with 20% of the oil residuum from petroleum distillation. The residuúni
is heated to 2500-300°F., and the refined asphalt added thereto, melting gradu-
ally in the menstruum. The mixture is maintained at the stated temperature
for some 6 to 8 hours and during this period air is injected into the mass in
quantities chiefly as an aid in disengaging, the asphalt proper from its intimate
association with the earthy sediments retained thereby, and also to ensure the
intimate admixture of the separated asphalt with the residuum solvent. Inci-
dentally, the air injected acts to drive off the water and such minor portion of
the hydro-carbons as may freely volatilize under the prescribed conditions. At
the end of the treatment, the residuum has become thoroughly amalgamated
with the refined asphalt producing an homogeneous compound into which pul-
verized limestone and sand can be admixed, as in usual preparation of paving
materials.
The residuum serves in a sense as a solvent for the refined asphalt, markedly
reducing its hardness, but, by reason of the low melting point of the resultant
compound, exposing it always to the risk of becoming soft under the action of
the summer sun. Any material excess in the percentage of the residuum taken,
lowers still further the melting point of the final compound, so that the safety
limit is soon reached. Practically, 20% of residuum addition is about as much
as the refined asphalt can absorb and yet afford an ultimate product acceptable
for paving purposes.
The present invention has for its object, inter alia, to modify considerably
the character of the petroleum 'residuum, the course of treatment being such
that a flux is obtained not differing very widely in specific gravity or volume
from the original residuum, but highly distinctive in its value as an agent to
cut" refined Trinidad asphalt and other materials, as hereinafter specified.
With Trinidad asphalt, for example, the improved flux can be used; say to
the extent of 60-80% to make a paving composition at once firm and elàstic
in winter without being brittle, and yet not liable to become soft on exposure
to the summer sun. The cost of the compound is decidedly cheaper by reason

page_text: of the lessened quantity of refined asphalt taken, this being displaced to advan-
tage by the large increase of the flux addition with a considerable saving in
expense.
<
Residuum of 18°-22° Baume, derived on cracking" crude petroleum is a
Residuum from
suitable material for treatment according to this invention.
the oil district of Lima, Ohio, U.S.A., serves the purpose very well.
Ordinarily, fractional distillation of petroleumi advances through successive
stages until the paraffine and heavy lubricating vapours are driven off, under
partial vacuum, at about from 5500 to 600°F., residuum is the liquid remnant
yet retained in the still. Residuum often varies in density between the limits
above noted, especially if steam be used to clarify it; protracted air exposure
also increases the quantity of water present therein.
An example of the treatment of petroleum residuum according to this inven-
tion will now be described in detail.
1050 gallons (say 7777 lbs.) of petroleum residuum at about 18° Baumé are
run into an open kettle loosely covered by a hood of size sufficient to catch the
escaping vapours and deliver them to a suitable exit. The kettle is heated by
direct fire. When the temperature of the residuum attains, e.g. 380°F., (which
may require some 8 hours heating to effect) the batch can be advantageously
held at such point during treatment.
While this preliminary heating is in progress, the residuum expands in the
kettle and foams markedly giving off a notable quantity for the most part of
watery vapors. Gradually, the batch becomes quiescent, and at 380°F., may
have lost some 400lbs. in weight.
Into the hot quiescent batch at 380°F., air is now injected by a perforated
pipe suitably branched and located near the bottom of the kettle to distribute
the oxidizing agent evenly throughout the liquid. The air pipe is connected
externally with a force-pump or other source of supply.
Treatment by air-blast may extend over a period, e.g., of 40 hours divided
roughly into a first stage of about 32 hours duration and a second or final stage
for some 8 hours beyond. The volume of air injected varies as the treatment
proceeds, the inflow per hour ranging from 6500 to 5000 cubic feet during the
first stage, and from 4000 to 3000 cubic feet during the second.
Under the influence of the air, the batch gradually thickens, its notable pro-
gress in this respect marking the close of the first stage; eventually the
operator is obliged to lessen the blast. An increase in the internal heat of the
batch is also observed. To maintain the mass at even temperatures e.g. 380°F.-
which may often prove desirable, the air blast can be diminished temporarily
(at times) although it suffices generally to check the fire instead.
At the close of a 40 hours' run, during which the batch at 380°F. will have
been exposed to the action of the air, the batch will have lost some 3.5 to 4.0%
by weight.
By extracting bituminous substances with petroleum ether, the amount of
"petroline" is determined; extraction with carbon disulphide determines the
percentage of asphaltine." The following comparative table shows the changes
that take place, as ascertained by actual test of samples taken at the outset of
the air treatment and at various hours thereafter:--

page_text: "
**
the functions of a flux for bituminous matter. The higher its percentage of
asphaltine, the higher, it is thought, will be the melting point of the resultant -
mixture obtained, if the flux be applied as an agent to cut" rich bitumens
such as Gilsonite, Wurtzelite, Uintaite, or the poorer sorts, such as refined.
Trinidad asphalt.
The details given thus far relate, as was stated, to a sample batch of residuum..
Its approximate weight in the crude was 7777 lbs.; at the outset of the air treat-
ment on reaching 380°F. after 8 hours heating, the weight was 7387 lbs., and,
at the close of the treatment 40 hours later, was some 7103 lbs. For the first 32
hours of the blowing operation, the average air supply per minute was about
100 cubic feet to the 1000 gallons.
If the flux thus derived be accepted, for convenience of comparison, as a
standard" grade, it is plain that with a temperature above 380°F., a harder
flux will be produced and below such temperature a softer. Hence, at the
higher range, the air blast need be used for less time to afford a "standard"
yield, and, at the lower range, the blast must persist longer. Again, at the
lower range, for example, by increasing the volume of air supply it is thought
that the period of treatment may be lessened, doubling the blast may nearly
halve the time.
As the foregoing table shows, the 32-hour flux differs markedly from the
16-hour variety, but more closely resembles the 40-hour sort. In many instances,
the 32-hour flux is on the whole to be preferred; an increase of temperature
and of air volume during the blast may reduce the period of treatment necessary
to obtain such quality of the flux say to 16 hours.
It is not requisite to keep the batch at an even temperature during the blast,
although the results are more certain, especially in the hands of unskilled work-
men, if this occurs. Indeed, the blast can be turned on before the batch has
attained the desired degree of heat, but this must be at the risk of undue
"foaming" particularly in the earlier stages.
When the flux is to be prepared as a separate marketable product, capable
of a variety of uses, the residuum can be treated alone. Yet it is entirely feasible
to combine therewith, refined Trinidad asphalt, for example say 50% of each-
and carry this mixture through the preliminary heating, and through the subse-
quent air blast treatment, when the purpose is to obtain a pavement compo-
sition suited for union with lime-stone powder and sand, as in usual practice.
But such procedure demands larger kettles or boilers and is more cumbrous;
certainly, the high percentage of residuum present will enable the Trinidad
asphalt to scour itself free from the associated earthy sediments more quickly.
While the air-blast stirs the mass to aid the scouring, yet, when the air is shut
off to clear the liquid of the sediments, this must be at risk of "scorching" the
asphalt which lies nearest the walls of the kettle, unless the heat be compara-
tively low.
Once the sediments are cleared, the temperature can be raised and the air be
injected in proper volume suited for the formation of the flux, just as if no
asphalt were present. The period of oxidizing treatment may extend over from
16 to 32 hours, dependent upon conditions already stated. On the whole, it is
better to prepare the flux separately in avoidance of the complexities and
possible injuries which the asphalt ingredient may ineur.
Heavy crude oils such as are found in California, U.S.A., and other like
natural oils may be used without preliminary distillation as a substitute for the
residuum. The air blasting will proceed under much the same conditions, but
the escape of watery and light oil vapors will entail a much larger loss in the
weight of the derived flux than if residuum were employed.
With the temperature constant, it is obvious that the longer the air treatment
persists, the higher becomes the "asphaltine" content of the flux, and, in con-
sequence, the higher its melting point. Variations occur in keeping with the
uses to which the product is to be applied.

page_text: Fluxes obtained by blowing the batch for a given number of hours, say
at 380°F., will impart a medium melting point to the final compound obtained
on admixture of the resultant flux with the selected base; if the flux be obtained
e.g. at 300°F., the melting point will, it is thought, be relatively low. On the
contrary, if the batch be blown at a higher degree, e.g. 450°F., the melting
point will be also advanced.
Working at 450°F. demands an increased injection of air, particularly if
continued for any considerable period, the object being to detain in an oxidized
state such of the constituents as might otherwise pass off in material diminution
of the volume of the batch. Should the heat he excessive, the mass will destruc-
tively distil, losing perhaps one-half of its weight and leaving a pitch behind.
All such excess is to be avoided.
Asphaltic fluxes made in accordance with the invention are black and semi-
solid at ordinary temperatures; under sufficient heat they fuse readily to a
limpid liquid. After dehydration-i.e., after expulsion of the water generally
present as an adulterant of the market article-the primary petroleum residuum
varies but slightly in specific gravity from the derived flux, the notable differ-
ences between them appearing instead to be due to the remarkable change in
the relative content of asphaltine and petroline respectively. These changes
are to be attributed to the air-blast treatment. As a consequence, the flux can
be admixed with the selected base in far greater quantity and still establish a
melting point for the compound even higher than if a less quantity of crude
residuum were taken instead. For the preparation of pavement compositions,
this characteristic of the flux is of significant value.
But it has other important uses besides. For instance, Uintaite or Uintahite
is a native mineral consisting of nearly pure bitumen; its melting point is
about 244°F. Adding 50% Uintaite to 50% of hot liquid asphaltic flux which
has been subjected to air blast say for 40 hours, produces a compound melting
at 260°F. and capable of excellent use for lining the sides and bottoms of water
reservoirs. 30% of Uintaite or Uintahite and 70% of asphaltic flux produced
by air blast treatment at 380°F. for 24 hours affords a roofing compound melting
at 170° to 190°F. 30% of Uintaite or Uintahite with 70% of asphaltic flux
produced by air blast treatment at 500°F. for 72 hours yields a dip suitable for
coating iron or other metal pipes, the dip melting at about 270°F., and being
used as a bath in the usual tank at, e.g., from 400° to 450°F.
Examples like the foregoing indicate the wide range of use of these asphaltic
fluxes under varying conditions, and exhibit the relatively high percentage of
the flux that can be safely taken at low cost to utilize the valuable qualities of
the pure bitumen. Fluxes according to this invention are of equal advantage
in dealing with other sorts of bituminous base, whether native or artificial, and
in melted state can act as a solvent to "cut" Gilsonite, Elaterite, Wurtzelite, or
Wurtzilite, and asphalt or analogous gums or materials.
The base to be 66
"
eut can be added in the flux kettle while blowing proceeds
or, better still, at the close of the air treatment or on re-heating the flux at some
subsequent occasion. Several sorts of base can be admixed at once with the
same flux.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed, I declare that what
I claim is;
-
1. The manufacture of asphaltic fluxes by dehydrating petroleum residuum
and by copious injection of air while maintaining the mass at comparatively low
temperature, thereupon transforming the charge so that its contents of asphal-
tine is increased and its petroleum is decreased, the volume and specific gravity
of the de-hydrated residuum being essentially preserved in avoidance of destructive
distillation and the consequent formation of pitch, substantially as described.
2. A black semi-solid asphaltic flux devoid of pitch and consisting of de-

page_text: hydrated and oxidized petroleum residuum nearly like the original residuum in
volume and specific gravity, but markedly higher in its content of asphaltine
and lower in its petroline than the residuum from which it was derived, sub-
stantially as described.
W. LLOYD WISE,
46, Lincoln's Inn Fields, London, W.C.,
Chartered Patent Agent.