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Патент USA US2110845

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March 8, 1938.
‘ 2,110,845
Original Filed May 23, 1932
4 Sheéts~$heet l
March 8, 1938.
Original Filed May 25, 1932
4 Sheets-Sheet 2
March 8, 1938.
Original Filed May 25,’ 1952
4 Sheets-Sheet 3
3g + a
mum: NRW 2.»?h &R?xQ4
March 8, 1938.
Original Filed May 23, 1952
52 %
4 Sheets-Sheet 4
Patented Mar. 8, 1938
James M. Whiteley, Roselle, and Gustav AlBei
swenger, Elizabeth, N. 1., assignors to Standard
Oil Development Compan a corporation of
Original application my 23, 1932, Serial No. 612,
908. Divided and this application June 10,
1933, Serial No. 675,240
9 Claim. (01. 196-13)
This invention relates to hydrocarbon oils, es
pecially petroleum oils, and more particularly
relates to the treatment of these oils with light
This application is a division of our copending
application Serial Number 612,908 filed on May
23, 1932.
The term light hydrocarbons will be under
stood to mean hydrocarbons or mixtures of hy
10 drocarbons of 1 to 5 carbon atoms in a liquid or
' lique?ed condition.
We have found that light hydrocarbons have,
at high temperatures, say within 50 to 100° F. of
their critical temperature, a marked selective
action on hydrocarbon oils. We have also found
that the selective action of these light hydro
carbons may be varied by changing‘ the tempera
ture at which they are used.
In the present invention the light hydrocarbon
20 solvent may comprise either a .single light hydro
carbon or a mixture of light hydrocarbons and
instead of changing the composition of the sol
vent to vary its selectivity, (in accordance with
the method described by James M. Whiteley in
25 United States Ser. No. 582,501 ?led December 21,
1931) the temperature at which it is used may be
changed and the composition may remain sub
stantially constant.
The present invention therefore comprises the
30 treatment of hydrocarbon oils with light hydro
carbon solvents either once at a constant high
temperature whereby the oil is separated into
two components of dissimilar characteristics, or
repeatedly at a progressively changing high tem
35 perature whereby each component may be sepa
rated further into other components.
The method of carrying out these treatments
- with the‘ light hydrocarbons will be fully under
stood from the followingv description read with
40 reference to the accompanying drawings of
in a series of stages with a solvent of progres
sively increasing temperature.
Referring to Figure 1, numeral l designates a
storage supply tank for oil to be treated. Nu
meral 2 designates a supply tank for light hydro
carbon solvent. Pump 3 draws oil from tank I
and forces it through line 4 into mixer 5, and‘
pump 6 draws solvent from tank 2 and forces it
through line 1 also into mixer 5, wherein oil
and solvent are thoroughly cornmingled. From 10
mixer 5, the thoroughly mixed oil and solvent
?ow [through line 8 into a heating means 9
wherein the mixture is raised to within 50 to
100° F. of the critical temperature of the light
hydrocarbon solvent. Heat may be provided by 15
steam, by heat exchange, or by other means.
From heating means 9 the hot mixture flows
through line I ll into a settling chamber ll pro
vided with insulating means 12 and ?tted with
steam coils l3 whereby the required temperature 20
can be maintained. The oil will ‘separate into
two layers in chamber H, the top layer contain
ing the lighter fractions of the oil and the bot
tom layer the heavier fractions. The top layer is
withdrawn from chamber ll through line H and
is discharged into a still 15 provided with a
steam coil IE or other heating means whereby
the light solvent may be distilled, off of the oil.
The vapors of solvent pass out of still l5 through
line H, are cooled in cooler 18 and the con
densed solvent is returned to solvent supply tank
'2 through line I9 by pump l9a.
The light oil freed from solvent is withdrawn
from still 15 through line 20 and may be passed
to storage or to equipment for further treating.
The bottom layer in separating chamber II
is withdrawn therefrom through line, 2| and
passed into still 22 ?tted with steam coil 23.
The solvent vapors‘ pass out of still 22 through
line 24, pass through cooler 25 and the con
densed solvent is returned to solvent supply tank
2 through line 19.
The heavy oil remaining in still 22 is with
Figure 1 shows in sectional elevation a type of
drawn therefrom through line 26 and passed to
apparatus suitable for carrying out a single treat
storage or to equipment for further treating.
ment at high temperature,
Referring to Figure 2, numeral 30 designates a
Figure 2 shows in sectional elevation a type of
apparatus suited for a counter-current continu . storage supply tank for oil to be treated. Pump
ous treatment with a solvent of progressively 3| draws oil from tank 30 through line 32. and
forces it through line 33 either into the top of
changing temperature,
‘ '
34 by means of line 35 or into the middle 50
Figure 3 shows in sectional elevation a type of
50 apparatus suited for an intermittent repeated of tower 34 by line 36. If the oil is discharged
into the tower at the top the lighter fraction of
extraction of the oil with a solvent of progres
the oil which separates out leaves the tower im
sively changing temperature, and
medlately and the counter-current extraction is
Figure 4 shows in sectional elevation a type of then carried out only on the heavier fraction of 55
55 apparatus suited for a counter-current treatment
the oil; but if the oil is introduced into the mid
dle of the tower the extraction will be carried
out on both the light and the heavy fractions
of the oil, the former with a solvent of progres
sively decreasing density and the latter with a
solvent of progressively increasing density all as
will be more fully explained below.
Tower 34 is an elongated vertical chamber
which provides for counter-current ?ow of oil
10 and solvent.
It may be packed with contacting
means such as chain, jackstones, lumps of clay,
or suitably designed plates, or may be without
such contacting means. It may be provided with
an insulating coating 31, and with heating means
16 such as steam coils 38 placed at intervals along
its length by means of which the temperature
in the tower may be progressively increased from
bottom to top.
Numeral 38 designates a storage supply tank
20 for the light hydrocarbon solvent. Pump 48
draws solvent from tank 38 through line 4I and
forces it through line 42 into the base of tower
34 into which it may be discharged through a
suitable series of openings'indicated at 43.
In the tower the oil ?ows downwardly in
counter-current relation to the upwardly rising
stream of solvent the temperature of which is
progressively increased as it rises by means of
steam coils 88. The oil is thereby separated into
30 a lighter soluble fraction and a. heavier insoluble
fraction. The former ?ows out of tower 34
through line 44 and discharges into a still 45
wherein the solvent is separated from the oil by
distillation. Vapors of solvent pass out of still 45
35 through line 48, ?ow through cooler 41 wherein
they are condensed, and the recovered solvent is
returned by line ,48, pump 48 and line 58 to sol
vent storage tank 38.
The heavier fraction of the oil passes out of
40 tower 34 through line SI and discharges into still
52 wherein the solvent is removed by distillation.
Vapors of solvent pass out of still 52 through
line 53, flow through cooler 54, and the condensed
solvent returned to solvent supply tank 38 by
4.5 lines 55 and 48, pump 48 and line 58.
Referring to Figure 3, numeral 88 designates a
storage supply tank for oil to be treated. Pump
8| draws oil from tank 88 through line 82 and
forces it through line 83 into a mixing device 84.
50 Numeral 65 designates a solvent supply tank.
Pump 86 withdraws solvent from tank 65 through
line 81 and forces it through line 68 into mixing
device 84 wherein oil and solvent are intimately
The mixture of oil and solvent then ?ows
through line 68 into a heating means ‘I8 where
in the mixture is raised to a temperature within
say 25° F. or less of the critical point of the sol
vent. The heat may be supplied by steam or
60 other hot gases. The heated mixture discharges '
into a settling chamber ‘II ?tted with an insulat
' ing coating 12 and a heating coil ‘I3 wherein the
mass is allowed to stand. The oil separates into
two layers, the top layer containing the lighter
fractions and the bottom layer the heavier.
The bottom layer is withdrawn from settling
chamber ‘II throughv line ‘I4. It passes to a
second mixing device 15 wherein it may be com
18 and discharges into a second settling chamber
‘I8 provided like the ?rst one with an insulating
coating 88 and a heating coil 8|. After standing
with the two layers separate, the bottom layer
is withdrawn through line 82 and subjected again
to another extraction. This time with a solvent
of still lower temperature. Additional solvent
is supplied through line 83 and the oil and solvent
pass through mixing device 84, line 88, heating
means 88 and line 81 into a third settling cham 10
ber 88, provided with insulating coating 88 and
heating coil 88. A
rd separation occurs and
the bottom layer m y be withdrawn and sub
Jected to as many further extractions with sol
vent at progressively lower temperatures as 15
If settling chamber 88 is taken as the last
chamber, the bottom layer will be withdrawn
therefrom through line 8| and discharged into
a still 82 wherein the solvent may be separated 20
from the oil by distillation. Solvent vapors pass
out of the still through line 83, ?ow through
cooler 84, and the condensed solvent returns to
solvent supply tank 68 through lines 95 and 88.
The heavy oil remaining in the still is withdrawn 25
therefrom through line 81.
The top layers are withdrawn from the sev
eral settling chambers through lines 88 and dis
charge into stills 88 wherein the solvent is sep
arated from the oil by distillation. Solvent 30
vapors pass out of stills 89 through lines I88,
and ?ow through coolers IN. The condensed sol
vent then returns to solvent supply tank 85
through lines I82, I83, and 86. The light oil
remaining in stills 89 is withdrawn therefrom 35
through lines I84. The several fractions of light
oil so obtained may be blended in any desired
proportions, or may be maintained separate and
worked up into several different light oil frac
tions. It will be understood that in place of 40
using a separate still for the top layer from each
settling chamber, a single still into which the
top layers from all the settling chambers dis
charge may be used. Any other arrangement
of stills may be made.
Referring to Figure 4 which illustrates a type
of apparatus for carrying out a counter-current
treatment of both the lighter and heavier frac
tions in a series of stages, the apparatus is in
general similar to that shown in Figure 3 with
these exceptions; the bottom layer formed in the
?rst settler instead of being forwarded to the
second mixer and-settler is removed through line
II8; the top layer formed in the first settler is
withdrawn‘through line III and passed to the
second mixer and settler; the bottom layers
from the second and third settlers are'withdrawn
through lines H2 and H3 respectively, and intro
duced into the mixers ahead of the ?rst and
second settlers respectively. In other words, the
bottom layers are continuously withdrawn and
returned to the next preceding stage instead of
5 being forwarded to the next succeeding stage as
in Figure 3, and the top layer in each settler is
forwarded to the next succeeding stage instead
of being removed as in Figure 3.
' The top layer from the ?nal settler is removed
through line I“ and passed into a still wherein
mingled with additional solvent supplied thereto ' the oil is separated from the solvent. In this
70 through line ‘I8. The mixed oil and solvent then method of operation the ?nal top layer com
flow through line ‘I8 to a heating means 11 where
prises an oil of greatly improved color over the
in the mixture is heated, this time to a tempera
original oil. It should be noted that in this meth
ture somewhat lower, say 10 to 15° F. lower, than od of operation the temperature is progressively
it was heated prior to entering the ?rst settling increased from stage to stage instead of progres
75 chamber. Theheated mixture ?ows through line sively decreased as is the case in treating the
bottom layer ‘in successive stages as in Figure 3.
In other respects the apparatus in Figure 4 may
be substantially similar to that in Figure 3, allow
ing for obvious modifications.
In the operation of our process the principal
variable factors are the type of material selected
as the feed oil, the kindoi light hydrocarbon sol
vent, the proportion of solvent to oil, the temper
ature at which the treatment is carried out and
the pressure maintained.
In general, our process is applicable to any type
of heavy hydrocarbon material, whether obtained
from petroleum oil or its products of distillation
or cracking, or from the products of the destruc
tive > distillation or hydrogenation of petroleum
oils, coals, tars, pitches, shales, lignites, bitumens
tane, the temperature necessary to obtain the
same selectivity as exhibited by propane alone at
a particular temperature must be near or above
the critical temperature of propane but below the
critical temperature of butane. For example, a
heavy bottoms oil obtained from a Ranger crude
is treated with 8 volumes of propane per volume
of oil at a temperature of'about 158° F. and an
80% yield of an oil having a Saybolt viscosity at
210° F. of 114 secondsand a, color (Robinson) of 10
2% (dilute) is obtained. When a solvent com
prising 8 parts of propane to 1 part of butane is
used it is necessary to treat at a temperature of
180° F. in order to obtain the same yield of the
same quality oil.
Similarly when using a solvent comprising
ethane and propane, higher temperatures are
necessary than if ethane alone is used in order to
and the like. Our process is also applicable to
synthetic hydrocarbon oils, waxes or resins, pre
obtain the same selectivity in each case.
pared for example by condensation or polymer
The pressure in our process should in general 20
be ' maintained su?i‘cientiy high to retain the
the temperatures at which the extraction is car
hydrocarbons in liquid phase at the temper
ried out, most of the normally solid hydrocarbons’ light
ature of working, but preferably not substantially
are above their melting points and therefore have greater than the equilibrium vapor pressure of
substantially the ,same solubility characteristics the liquid at that temperature. This pressure
25. as oils. Our process is particularly adapted, how
will be between say slightly above atmospheric
ever, to the fractionation, purification and de
and 50 or more atmospheres depending upon the
colorization of petroleum oils, especially the lu
particular components of the solvent and the
bricating fractions thereof.
temperature at which the treatment is carried
The type of light hydrocarbons that may be out.
If the solvent comprises a mixture of light_ 30
used as the solvent in our process comprise gen
hydrocarbons, the pressure necessary will be close
erally hydrocarbons of 1 to 5 carbon atoms or to the equilibrium vapor pressure of the lightest
mixtures of any 2 or more of such hydrocarbons.
Thus methane, ethane, propane, butane, pentane, component of the solvent which is present in sub
ethylene, propylene, butylene, amylene, and
isomers of these may be used. The presence of
small quantities oi'higher molecular weight hy
drocarbons is not especially harmful but in gen
eral it is desirable. to avoid the presence of these
higher hydrocarbons. Ethane, propane and bu—
tane, or mixtures of ethane and propane or pro
pane and butane arev particularly satisfactory
solvents for our purposes. The gases obtained in
the cracking of petroleum distillates and in the
stabilization of gasolines are generally rich in the
lighter hydrocarbons such as ethane, propane
and butane and they furnish a convenient and
readily available source of the solvent hydrocar
The proportion of solvent to oil may be varied
within wide limits, but between 3 and 15 volumes
of solvent per ‘volume of oil is satisfactory for
most purposes. Between 8 and 12 volumes of sol
vent per volume of oil'is an especially suitable
stantial amount.
The type of operation indicated in Figure 1,
that is, a single extraction with solvent at a high
temperature is especially adapted for obtaining
from a heavy oil a fractionv of better quality with
respect to viscosity temperature characteristics
and gravity. It is also adapted for separating a 40
heavy lubricating fraction into a lighter fraction
and a heavier fraction, both of which fractions
differ in characteristics from the original oil.
The types of operation indicated by- Figures 2,
3, and 4, that is, counter-current or repeated in
termittent extraction, are especially adapted for
decolorizing and highly purifying heavy petro
leum oil fractions and obtaining therefrom vain
able lubricating 0115. By means of the successive
treatment with solvent of progressively changing
density it is possible to extract from the oil solid
impurities which could not be removed in a single
extraction. In the case of intermittent extrac
tion it is possible to obtaina plurality of oil frac
of dissimilar characteristics, and these may ,
The temperatures employed in the operation of, tions
be blended in any proportions to obtain blended
the process in general range from the critical oils of any desired characteristic. It is also
temperature to 10, 50, 100, 125° F. or more below
by intermittent extraction to obtain in
the critical temperature of the particular light possible
the last steps oils of extremely high viscosities,
hydrocarbon selected as the solvent. Thus for say from 1000 to 5000 seconds Saybolt viscosity 60
60 propane which has a critical temperature of
about 212° F., temperature may be decreased
progressively from say 200° F. to 175 to 150 to 100
to 75° F., and so on, the density and consequently
the selectivity thereof increasing and decreasing
65 respectively with the decreasing ‘temperature.
For butane and‘ pentane the temperatures of op
eration will be correspondingly higher and may
be readily determined from the critical tempera
ture of ‘each.
when using solvents comprising mixtures of
two or more light hydrocarbons, temperatures
higher than those used with the lighter of the
‘two or more hydrocarbons alone are generally re
quired in order to obtainthe same selectivity.
75 Thus when using a mixture of propane and hu
at 210° F. Oils of these high viscosities cannot
ordinarily be obtained by the usual fractionating
means due to the fact that they decompose or
break down at the temperatures necessary to va
porize them even when distilled under high vacu
um. Moreover, all of the several fractions into
which the heavy oil is separated by our process
are characterized by much greater stability to
heat and oxidation than fractions obtained by
Prior to treatment according .to this process,
the oils may be subjected to preliminary puri
fication treatments. Thus oils initially rich in
asphaltic bodies may ?rst be treated to remove a
substantial portion of these materials.
One 75
9,1 10,845
method of removing asphaltic bodies which is
especially convenient in connection with the pres
ent process is to treat the oil with lique?ed hy
drocarbons such as propane or propane and
ethane at normal temperatures, say around 50 to
100° F.
In this way the asphaltic bodies are
thrown out of the oil in a hard, granular sub
stantially oil-free condition and the remaining
oil is already in solution in the light hydrocarbon
10 used in the high temperature treatment of the
process herein described. Other methods of re
moving asphalt may of course be used.
light hydrocarbon.
The light hydrocarbon comprises pro
pane and is used in the proportion of 8 volumes
of propane to 1 volume of oil. The pressures
maintained at each temperature are substantial
ly the saturated vapor pressures of propane at
those temperatures:
15 gestion, acid and clay treatment and so forth
either preceding or following subjection to the
Y.e1. vare‘
50051 y (as
o noi in *
sq. in
The oils may also be subjected to hydrogena
tion, phenol extraction, aluminum chloride di
The oil used is the same
Ranger residuum as was used in the above ex
80 ............... _-
light hydrocarbon solvent treatment. Dewaxing
210 F.
Percent Seconds
21. 5
2 4
21. 3
l9. 7
also may precede or follow the solvent treating.
and any suitable method of dewaxing may be‘
20 used.
Following the puri?cation of the material in
accordance with the method outlined above, and
before removing the solvent therefrom, a still fur
ther puri?cation may be conveniently and advan
This invention is not limited by any theories 20
of its mechanism nor by any details or data which
have been given merely for purposes of illustra
25 tageously effected by ?ltering the ?ux while still
herent in the invention.
at the high treating-temperature through a bed
of adsorptive material such as clay, charcoal and
the like. Filtration of the oil or other hydrocar
bon material while in hot light hydrocarbon so
30 lution-_ proceeds at an extremely rapid rate and
substantially larger yields of oil per ton of clay
are obtained than can be obtained by ?ltration in
naphtha solution. The extent of the additional
‘puri?cation moreover is substantial, and the oils
35 filtered in this manner are comparable in purity.
' Y and color to oils obtained only after repeated
“subjection to other methods of puri?cation.
1" It will be understood of course that the hydro-v
carbon material may be filtered through the solid
adsorptive media while in hot light hydrocarbon
solution without a preliminary puri?cation such
as described above. This would be particularly
advantageous if the initial material contains only
a relatively small amount of colored or normally
45 solid bodies.
As an illustration of the type of operation
shown in Figure 1, a heavy dark-colored residu
um obtained from a Ranger crude is ?rst partialq
ly puri?ed by treatment with propane at 80° F.
50 By this treatment a large proportion of the as
phaltic material is precipitated from the residu
um. The partially puri?ed oil then has the
following characteristics:
5 4,
tion, but is limited only in and by the following
claims in which we wish to claim all novelty in
We claim:
1. The method of treating heavy hydrocarbon
oils which comprises ?owing a stream of such oil '
counter-current to and in intimate contact with
a stream of a light hydrocarbon solvent the tem
perature of which is progressively increased in
the direction of its flow from a temperature sub
stantially above the wax separation temperature
to a temperature near the critical temperature
of the solvent, removing a stream of oil and sol
vent and recovering the oil therefrom.
2. Method according to claim 1 in which the ‘
initial temperature is from 75 to 125° F. below
the critical temperature of the light hydrocarbon
solvent and the ?nal temperature is within 10 to
50° F. of the critical temperature of the solvent.
3.' Method according to claim 1 in which the
light hydrocarbon solvent comprises a hydrocar
bon of 3 carbon atoms.
4. Method according to claim 1 in which the
light hydrocarbon solvent comprises hydrocar 45
bons of 2 and 3 carbon atoms.
5. The method of purifying and decolorizing a
lubricating oil fraction of petroleum which com
prises causing a stream of the oil to flow in coun
ter-current relation to and in intimate contact
with a stream of alight hydrocarbon solvent com
prising propane, progressively increasing the tem
Gravity, A. P. I ______________ __degrees__ 22.5
55 Saybolt viscosity @ 210° F____ __seconds__ 133.4
Conradson carbon ____________________ __
Color, Robinson _____________ __(dilute) __
This oil is then diluted with 8 volumes of pro
60 pane and the mixture heated to 183° F. where
upon two layers form. After allowing the mixture
to stand at this same temperature the two layers
are separated and the propane distilled oil from
each. The two oil fractions so obtained have the
following characteristics:
perature of the solvent in the direction of its flow
from a point about 100° F. below to a point with
in a few degrees of the critical temperature of
propane, removing a stream of oil and solvent,
and recovering the oil therefrom.
6. In the process of fractionating heavy min
eral oils by means of light hydrocarbons such as 60
ethane, propane and butane at temperatures
within about 50° F. of the critical temperature of
the light hydrocarbon, the method which com
prises eifecting separation at temperatures suc
cessively increasing from about 50° F. below the
critical temperature of said light hydrocarbon to
Top layer
Bottom layer
temperatures near said critical temperature. '
7. The method of treating a heavy hydrocarbon
Gravity, A. P. L...
.. 24.6°_.
Saybolt viscosity @ 210° F ________ _- 105.5 seconds.. 229 seconds.
Conradson carbon ................. _-
Color Robinson ......... __
l.98.___ ...... ..
_- 3%(d1luie)___.
Yield ............................. _.
68% _________ __
Very dark.
The following table illustrates the e?ect of
75 varying the temperature on the selectivity of the
oil which comprises diluting the oil with several
volumes of a lique?ed normally gaseous hydro 70
carbon, heating the mixture to a temperature
about 50° F. below the critical temperature of the
lique?ed hydrocarbon at which the oil is caused
to separate into two liquid fractions, separating,
the two fractions, subjecting the lighter of the
two fractions to treatment with additional lique
?ed hydrocarbons in a series of stages at tem
peratures increasing to near the critical temper
ature of the lique?ed hydrocarbon in the last
stage, returning the heavier fraction from each
stage to the next preceding‘ stage, and removing
the lique?ed hydrocarbon from the lighter frac
tion obtained in the last stage.
. 8. The method of treating a heavy asphalt con
10 taining hydrocarbon oil which comprises diluting
the oil with several volumes of a lique?ed nor
mally gaseous hydrocarbon, heating the mixture '
to a temperature about 50° F. below the critical
temperature of the lique?ed hydrocarbon, remov
15 ing the heavy asphalt-containing layer thereby
caused to precipitate, heating the remaining solu
tion to a temperature about 10° F. higher than
that at which the asphalt-containing layer was
caused to separate whereby the oil is separated
into a soluble liquid’ fraction and an insoluble
liquid fraction, subjecting the soluble fraction to
treatment with additional lique?ed hydrocarbon
in a series of successive stages at increasing tem
perature, the temperature in the-last stage being
close to the critical temperature of the lique?ed ‘
hydrocarbon, removing the insoluble fraction
from each stage and returning it to the next pre
ceding stage, and recovering oil from the soluble 10
fraction obtained in the last stage.
9.' Process according to claim 8 in which pres
sure is maintained throughout the treatment
sufficient to retain the lique?ed hydrocarbon in
liquid phase.
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