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Патент USA US3083164

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March 26, 1963
.1.J. GERslc ET AL
` 3,083,154
DEwAxING AND DEOILING PRocEss
Filed Sept. 29, 1960
km.
mm.
2 Sheets-Shea?l 1
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QN
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/nl/enfars
.Ja/7n J Gers/'e
Lawrence 5. /Ve/san
Norman L. Ma/a/raff
Harry Z' l/an Harn
¿gy/WML@rfa; y
United States Patent O ” lCe
l
3,0ä3,154
DEWAXING AND DEGILING PRÜCESS
.lohn J. Gersic, Elmhurst, Norman L. Malakoff, Brooklyn,
Lawrence B. Neison, Garden City, and Harry T. Van
Horn, Franklin Square, NX., assignors to Soeony
Mobil Gil Company, Inc., a corporation of New York
Filed Sept. 29, 1960, Ser. No. 59,280
â Claims. (Cl. 208-31)
3,083,154
Patented Mar. 26, 1963
2
particles. These patents teach avoiding small particles
at all costs as they are said to be diti‘icult to remove
and may tind their way into the solvent-oil fraction and
increase to an undesirable level the pour point of the re
sulting oil.
Another method for separating wax-containing mate
rials is disclosed in the following patents: U.S. 2,301,965;
2,302,428; 2,302,432; and 2,302,433. The method dis
closed in »these patents commences by conventionally
This invention relates to an improved process and
apparatus for separating wax from a wax~oil mixture.
The invention can `be sapplied -to the deoiling of wax con
taining variable amounts of oil or the dewaxing of oil
containing variable amounts of wax. The invention re
lates particularly to an improved technique for obtain
ing directly from a waxy oil an oil of satisfactory or ac
ceptable pour point as well as a wax of low oil content in
precipitating wax `crystals from a solvent chosen because
of special properties of gravity, Visco-sity, interfacial ten
sion and oil solvent power. Such a solvent is diflicult to
obtain and is generally formed as a mixture of individual
solvents as described in U.S. Patent No. 2,301,965. 'Ihe
conventional wax crystals obtained separate from the oil
solvent mixture due to the difference of gravity between
a single operation. ln a broad sense, however, the inven
the wax and the special solvent. The crystals are then
forced .through a nozzle into a countercurrent stream of
tion involves lthe ‘separation of high pour point materials
from a liquid or semi-liquid material to improve fluidity
of the material.
A large amount of oil is processed in petroleum refin
procedure is much more efiicient than the usual method
of washing wax by spraying solvent onto a wax cake
deoiling solvent. Patent No. 2,302,432 states that this
deposited on a filter.
eries to make commercially acceptable lubricating oils
U.S. Patent No. 2,254,597 discloses a method of sep-`
for internal combustion engines, machinery and other
arating paraíiin wax from oil which is dependent upon
lubricating purposes. The lubricating oil stocks generally 25 apparatus features. The charge material is injected into
contain commingled with the oil differing amounts of wax.
Unfortunately, this Wax sets up 4at low temperature inter
fering with the liowability of the oil and hence must be
removed to insure that the lubricating oil will have ade
quate pour, i.e., to insure that Ithe oil will iiow at a low
an acetone or acetone-benzol solvent and the wax is
separated from the oil by a disclosed apparatus combina
tion. The slurry of' wax crystals, solvent and oil is fed
into a ‘shell filter with a filter and take-off line at the upper
end. As rthe shell lil-ls the filter retains the crystals and
the oil-solvent passes through .the wax cake and ñlter andA
out the »take-oft line. When the filtration is complete the
has been to gradually cool the waxy oil cornrningled with
position ofthe shell is reversed, bringing the take-off line
a suitable solvent having solvent power for the oil but
to the bottom. Air is then pumped into the shell through
limited solvent power for the wax. Wax crystals are 35 a hollow trunnion disp-lacing the liquid contents through
formed Iin the mixture and then the mixture is passed
the filtering medium leaving behind a wax filter cake.
through Aa rotary drum filter to remove the wax, form
Wash solvent is then introduced into the shell and flows
ing a wax cake on the filter. Frequently the oil must
through the filter cake. Steam is then admitted to the
be remixed with additional solvent, cooled and refil 40 tank, after the cake has been blown to remove the acetone,
temperature.
The general refining procedure followed in the past
tered several times to eñect a satisfactory removal of
the wax and provide ‘an oil of acceptable pour point.
Furthermore, the wax scraped from the filter -is found
the wax filter cake melted and removed. _The use of
benzol in the solvent complicates the blowing procedure
as it is not as readily evaporated as acetone. Benzol is
to have a substantial amount of oil, such as 30-40%
not desirable in wax.
by weight. The wax is therefore collected in a stor 45
We have found that a vastly improved result can be
age tank »and from time to time the apparatus is used
obtained by spraying the waxy oil or oily wax into and
only to remove oil lfrom the accumulated wax. This
beneath a bath of cold solvent under conditions whichk
separate wax treatment severely limits the capacity of
cause the charge to be distributed in the- solvent as
the filtering apparatus to produce the premium product,
separate discrete particles of a carefully controlled size.
lubricating oil, reduces the eliiciency of the operation and 50 Waxy oil is sprayed above the pour point and the oily
also increases the loss of solvent.
wax is sprayed above its melting point. These small
Other methods have been proposed for the separation
of wax and oil.
These methods fare not now currently
accepted or in use because of operational difiiculties in
adapting the methods to commercial practice. For in
stance, a process land apparatus for dewaxing and treat
particles, having a size range of about 5-100 microns,
are rapidly cooled rby the solvent and the oil is removed
from the wax particles by the solvent. In dewaxing, the
mixture is passed to a standard filter, perhaps after pas»
ing oils is disclosed in the United States Patents Nos.
sage through a cooler, and is filtered to provide a wax of
very low oil content as well as an oil of acceptable pour
2,137,549; 2,194,968; 2,218,518; 2,218,519; and 2,218,520.
point. Ot course, the invention Yalso contemplates and
All of these patents describe a process 'of discharging a
is used advantageously to remove oil from a wax con
wax-oil mixture into cold solvent to form strings, ribbons, 60 taining a substantial volume of oil.
buttons or flakes. A leaching process is then used to re
The improvements which this invention shows over
move the oil from the wax matrix which requires from
known dewaxing »and deoiling methods are:
fifteen minutes -to two hours for completion, depending
(l) Utility requirements for heating and refrigeration
upon the wax mass. This is a long period of time and
are lower.
not consistent with usual refinery operation. The dif
fusion of oil away from the wax surface through the sol
losses during treating and recovery.
(2) Less solvent is needed. This reduces solvent>
vent is the time rate controlling step. This is a slow
(3) An improvement in the rate of filtration of wax
process and .accounts for the considerable length of time
from oil. This increase in the speed of processing may
needed for leaching »to be completed. Aside from the
be considerable, as is shown in the data, and has the
considerable length of time needed to deoil the wax great 70 effect of increasing processing capacity without capital
care is called for in all of the above patents to prevent
investment for additional equipment.
a breaking up of these large wax masses into smaller
(4) In dewaxing, produces a wax with a lower oil
3
-
content than is now made by one stage of dewaxing.
This wax requires less processing to I‘oe refined to a sale
able product than wax produced by the present methods.
(5) In deoiling, produces a finished wax with less
processing and a higher yield than conventional processes.
The object of this invention is to provide an improved
method and means lfor deoiling wax and dewaxing oil.
A further object of this invention is to provide in a
single operation the separation of wax and oil to produce
directly oil of acceptable pour point and wax of low
enough oil content for use without further oil reduction.
A further object of this invention is to provide a means
of increasing the capacity of existing dcoiiing and de
waxing equipment.
d
the conduit 35, Chiller 35 to be passed either through
conduit 37 to ñlter Z6 or conduit 33 to filter 39 or both.
The wash from either or both ñlters enters the collection
tank di) through the conduits 4l, 42, and 43. The Wash
solvent can be transferred through conduit 44, pump 45
and conduit d6 for recirculation through the conduit 19.
This solvent canalso be recirculated through -the' conduit
47 -or through the conduit e8. Fresh solvent or recircu
lated wash solvent can be introduced into the charge
tank l2 by conduit 5l. to cut back the charge stock with
solvent.
The filtrate from filter 26, iilter 39 or both passes
through conduit 52, conduit 53 or both respectively into
' conduit 54 and then to filtrate tank 55. From the filtrate
These and other objects of the invention will be more 15 tank the ñltrate is pumped by pump 56 -to solvent re
covery and oil storage, not shown.
clearly disclosed in the following detailed description of
The filter 3% is used in the event of the need for repulp
the invention which is to be read in coniunction with at
ing of the wax from lilter 26. This wax is mechanically
tached iigures.
.
mixed with solvent, passed through chiller 49 and con
FIGURE 1 shows a schematic arrangement of dewax
ing and deoiling equipment illustrating the invention. 20 duit 50 and then onto tilter 39. With this exception the
process with repulping is exactly the same as the process
P_{GURES 2 and 3 show, respectively, a vertical sec
tion and a horizontal section of a low pressure atomizing
nozzle of a type useful in the practice of the invention.
FIGURE 4 shows a vertical section of a low pressure
nozzle useful in forming droplets in the practice oi the
invention.
without repulping, previously described.
v
An essential feature of this invention is `the formation of
Wax-oil particles in the presence of a suitable solvent
which is at a temperature below the melting point of
the Wax a suiîicient amount -to precipitate the wax as solid
.
FIGURE 5 shows a pneumatic atomizing nozzle useful
Vin forming droplets in the practice of the invention.
FIGURE 6 shows a hypodermic needle type injection
device. In commercial practice this type device could
be -a small bore tube.
FIGURE 7 shows a solid stream injection device.
Referring now to FIGURE l, the process will be dis
closed in further detail. The charge, either waxy oil
above its pour point or oily wax above its melting point,
is pumped through conduit 1€?` by pump 11 into a charge
tank 12. The charge tank 12 has a heater i3 located
therein to control the temperature of the charge. From
the charge tank the charge is passed through conduit la
by pump 15 and then through the heater-Chiller id and
conduit 17 into the spray chamber 1S.
Detail l8 represents one or a group of nozzles, orifices or
capillary Itubes adapted to spray or atomize the charge
into dispersed particles of «a restricted small size. These
nozzles will be disclosed in »more detail hereinafter. The
particles or droplets emerge within la bath of solvent in
chamber 1'8 and are rapidly cooled to solidify the wax
particles. Any of the solvents used in dewaxing or de
oiling by conventional means, such as benzene or tolu
ene-ketone mixtures, propane, or other hydrocarbon sol
vents and chlorinated solvents may be used. The solvent
system that is most Widely used is methyl ethyl ketone
either with toluene or benzene. Solvent temperatures
from ambient to _60° F. have been used successfully.
We have found it convenient to produce the droplets of
the required size by means of a Spray nozzle. Although
other means of dispersion are possible, such as capillary
tubes or orifices, the ease and convenience of spraying
and its easy adaptability to procedures of refinery opera
tion make this method the preferred scheme.
Solvent temperatures from +70° F. to _60° F. have
been used successfully. The primary effect of filter tem
perature is to determine the melting point of the wax pre
cipitated.
In this invention a Wax-oil mixture at a tem
perature such that it will flow is sprayed through a
selected nozzle into the solvent. 'Ihe nature of the wax
and oil components and their relative amounts in the
mixture determine the flow characteristics. It is prefera
ble to spray waxy oils (about 20% Wax) at about 100 to
150° F. and oily waxes (about 20% oil) at about 150 to
oil is rapidly taken up in the solvent. The solvent is
introduced through conduit 19 by the pump 2d into the 50 209° F. Solvent may be added to the wax-oil mixtures to
reduce the temperature necessary for adequate flow.
lheater-chiller 21 and then through the conduit 22 into Y
Nozzle
pressure may also be increased at a given tempera
the spray chamber 18. The heater-Chiller 21 is used
ture to increase flow.
to adjust the solvent temperature to that level below the
The temperature, heat capacity, and amounts of sol~
charge temperature required to provide the rapid solidiñ
vent and wax-oil sprayed determine the final temperature
cation of the Wax in the sprayed droplets.
ot the mixture. The temperature of the mixture may be
The eñluent slurry from the spray chamber is then
adjusted by heating or cooling before filtration. In the
passed through conduit 23 and trim chiller 2d», where
production of oils with a pour point of about +20” F.
the temperature of the slurry is adiusted prior to pas
it is necessary to Íilter the wax-solvent oil mixture at
sage through the conduit 25 and into the rotary drum
ñlter 26. A preferred solvent temperature for waxy oil 60 about -|-5° F. In deoiling waxes ñltration temperatures
and make the oil more available to solvent action.
The
is about ‘L1-40° F. which must then be chilled to +5° F.
to make acceptable (-l-20° F.) pour point oil. When
deoiling an oily wax there is generally no need to trim
chill as these slurries are usually filtered at about 30-40"
F. This will, of course, depend upon the temperature of
the solvent into which the oily wax is sprayed.
The wax from the filter is passed through the conduit
27, heater 28, and conduit 29 into the wax solvent storage .
’ of +20 to +120° F. may be used depending on the type
of wax and the melting point desired. While an initial
solvent temperature as low as _60° F. may be obtained
in the laboratory, the solvent is usually chilled only to
-20° F. for practical reasons. In dewaxing a waxy oil
by spraying one volume- of charge into two volumes of
solvent at -20° F. a iinal temperature of about +40“ F.
is obtained. In order tomake +20° F. pour oil it is
necessary to chill this mixture to +5° F. and lilter. Ad
tank 30. The solvent storage tank 30 contains a heater 70 justing the temperature of the sprayed mixture has no
31 which maintains the wax at a ñowable temperature.
adverse eiîect on the oil or'wax recovered and may con
The wax containing solvent is passed through conduit 32A,
pump 33 and conduit 34» to a solvent recovery and wax
tribute to the improved ñlterability of the crystals.
In this process, it is necessary to form droplets of a
storage unit, not shown.
size range about 5 to l00 microns. These drops are
.Fresh solvent is also introduced into the system through 75 rapidly chilled in the cool solvent to solidify the wax.
3,083,154
5
6
The solidiñcation takes only micro seconds to occur, after
tern of uni-form distribution. Atomization is determined
by pressure and capacity.
A pnueumatic atomizing nozzle illustrative of the type
which the small initial particles agglomerate to a size
that is easily filterable. The oil is washed into the sol
vent. Particles produced under conditions where the
size is smaller than the minimum size have been deoiled
used, is shown in FIGURE 5. In this type of nozzle liquid
and air or gas are mixed externally, that is after leaving
the nozzle. The air is introduced via air inlet 69 and
charge material via liquid inlet '70. -The liquid travels up
past the needle valve 71 and out through the orifice 72
by this process but are too small or iilter at a slower rate.
The ñlterability of this crystal is improved on aging but
the time and special handling necessary for this would
not be consistent with refinery operations. Particles pro
where it is atomized `by the air. The needle valve can
duced under conditions where the size is greater than 10 be adjusted to vary the proportion of Vair to charge at
the maximum are not sufficiently deoiled to justify this
the nozzle. Nozzle unit, FIGURE 5,7supplied1by Spray
operation economically.
-ing Systems Company as round spray pneumatic atomiz~
FIGURE 2 of the drawings shows a vertical section,
ing l(nozzle, was used successfully in our experimental
taken along line 2-2 of FIGURE 3, of a typical low pres
wor .
`sure atomizing nozzle found useful for the initial me
chanical atomization. The nozzle is composed of a body
60 containing an inlet passage 61, which enters swirl
chamber 62 tangentially so that the material passing into
chamber 6‘2 has a vortical motion. Here, material swirls
15
In place of the atomizing device illustrated yin FIGURES
2, 3, 4 and 5, other `such devices known in the art can be
used. For example, the following can -be mentioned:
impinging jet nozzles, centrifugal or rotating-disc atom
izers, vibrating atomizers, multi-jet atomizers, impact type
around and down, acquiring increasing tangential velocity 20 nozzles, high pressure type atomizing nozzles and other
components. Below the swirl chamber, replaceable orifice
liquid dispersing devices.
- ,
cap 63 is secured to body 60' as shown. Material issues
from the orifice as a hollow conical sheet which atomizes
into a so-called “hollowcone spray.” The diameter of a
A typical nozzle of orifice diameter from 0.020 to
0.075 inch will give the desired particle distribution for
efiicient deoiling with pressures from 10 to 200 p.s.i.g.
typical orifice cap 63 useful herein is 0.0625 inch. This 25 Below l0 p.s.i.g. a particle size will -be obtained such that
nozzle is supplied by Spraying Systems Company, as 1/ S
deoiling is not rapid enough to be consistent with usual
B-l Whirljet nozzle. Particle size and throughput char
refinery operations. If these larger particles are allowed
acteristics of the nozzle can be regulated by varying the
to remain in contact with the solvent for a period of time
nozzle body size which alters the entranceI diameter (or
deoiling will take place. At pressure in the excess of
inlet passage 61) and swirl chamber (62) sizes, and by 30 200 p.s.i.g. the particles formed are eñiciently deoiled
varying the orifice diameter which can be changed in
but of such a small size that even when agglomeration
dependently by substituting orifice caps with different
»takes place the ñlter rate is adversely influenced. If a
more porous -filter medium is used to speed up the filter
also varies throughput.
rate in the above case, wax agglomerates pass through
FIGURE 3 is a horizontal section of the nozzle of 35 into the oil-solvent mixtures which causes the formation
FIGURE 2, taken lalong line 3-3 of FIGURE 2.
of a high pour point oil.
oriñce diameters. Varying the feed pressure to the nozzle
Another low-pressure nozzle used success-fully is the
This nozzle, having a
0.047 inch orifice is supplied by Spraying Systems Com
one illustrated in FIGURE 4.
The data yfrom laboratory tests illustrating the utility
of the invention are found in the following Tables I,
pany as 1/8 GG-2 Fulljet nozzle. The nozzle is com 40 II and III. The data show successful application of the
invention to dewaxing light, heavy and residual raf
posed of a cap 64 which contains the orifice 65. Into
ñnates; oils of +20° F. pour point were obtained and in
this cap, which is removable from the body 66, is inserted
addition a wax superior to that obtained -by conventional
a removable internal vane 67. When charge is introduced
methods. It is noted that the filter rates in accordance
through inlet passage `68 it impinges upon the vane 67
causing the material to assume a swirling 4motion as it 45 with this process are superior to those rates obtained in
issues forth 4from orifice 65 in a full cone spray pat
any other way. The column headings are generally self
TABLE I
Light Distzllafe
Labora
âgírlï'
Conditions
reüneîy
varia
ble
Solvent composition (MEK-toluol) ...................... _.
70/30
Actual
refinery
Spray laboratory
data
Ca. 70/30
70/30
70/30
2.0
2. 0
70/30
Dilution ratio:
Primary
l 0.3
0.5
Secondary
Z 0.6
0. 5
Tertiary
3 0.6
‘ 2.0
Total
1. 5
Wash ratio.-
0.7
Slurry cooling rate, °F.lmin ............................. _-
2. 8
Filtration temp., ° F .................................. __
+3
Equiv. filter speed, minutes per revolution í filter drum.-
2
2. 0
...................... __
3.0
2.0
2.0
21.0
1.0
1` 0
2.0
1.0
.................................. __
+5
+5
Equiv. Submergence, percent ____________________________ ._
+5
+5
1
1
50
50
Vacuum, in. Hg:
Pickup
Wash
`
Percent solvent in cake __________________________________ __
Cake thinknes in
Percent yield:
Wax
Oil-.
Wax:
12. 3
87. 7
Solidification point, ° F ______________________________ -_
Ou Oil, perf-ent
121
0.9
Pour, ° F
Filtration rate, gallons of dewaxed oil per square foot
of filter area per hour ______________________________ __
lAt 120° .F./llä‘7 F;
133
25.0
75.0
2 At 88° F./77° F.
5 At 0° F.
+15
30.0
+20
7. 7
4 Recirculate.
6. 5
10. 6
89. 4
128
0. 64
+20
17. 5
20
20
20
20
80.9
74. 7
12/32
1.6/32
12. 2
87.8
21. 3
78. 7
126
119
1. 98 ...... -_
+20
20.1
+20
15.1
3,083,154
7
_
TABLE II
.
_
.
8
scale _experiments using optimum laboratoryconditions.
Heavy Dim-„ate
Table iIV provides data showing the results of deoiling a
Vvariety of waxes. The data in Table IV is arranged ac
cording to the MBK/toluene ratio used. Examples are
Conditions`
Labora-
Actual
variables
data.
torynsing minery
Tammy
'
.
spray labora.
tory
.
5 also included which show that other solvents also are ap~
plicable, as are other starting materials. In all cases
a significant reduction :in oil content of the starting mate
_
_
_
_
_
_
"""" ’5‘“‘“-“
Laboratory Actual
âlîlllërrä?ïïââätî’Fïfxîïo“
Conditions
Equiv. tllter speed,V minutes per
revolution of ñlter
drum. ___
Equiv. submerëence,
percent..
'
3
______ __
2
50 ______ __ _
Vmë‘fëë?pî'nuÉL ____________ __
Wash ______________________ __
'
Cake thickness, in _____________ __
Y
1%?, ______ __
‘
50
50
20
20
~
29.
70.4e
2o
~
.
73.2
90.5 20 Duutiîm who'
1%2
i952
3o.
69.82
87.8
12. 2
139
'
140
"“
Èîllîent cnmposltion """""" “
Pom. o F __________________ __
putrâtiou ,am gallons of ¿Q_
+
waxed oil per square foot oi
ílïter area per hour ........ _-
133
146 25
50,50
20
3. 0
3~ 8
2l Ü
'
-~
o _________ __
tra ion
emp.,
_____' ______________ __
50/50
50/50
Eqiuiv. iiìílîtler sàneed, minutes per revolu
'i' D
+20
+25
Equiv. submergenee, percent ........... _.
1. 8
i
4. 2
2. s
Vacuum» m- g
$21511’ ----------------------------- -
2
2- 0
1an/50
cooltmg tangy; E_/mm
'
50/50
ra
:ao/5o
--
W hTOttíaI
e“ ary___________ __
es
so/sn
`
änmaâ'y ---------------------------- --
o
âolidläe?refîtàon polnt, F_____-_
_
27.
73.0o
tory
_
suivent composition (MEE-ionico _____ -_
T6603; ary
i
data
Variables
Percent yield:
Wax:
gar
----------------------.......................
___-_
_-
Spray
refinery labora
reúne/TY
2
20
Percent solvent 1n rake
~
using
t on o
ter
rum ____________________ __
30 Percent soÑen't‘Ín-cal-r-el-
_
Cake thickness, in ...................... _
Percent yield‘:
'
_
explanatory.
.
Wax ________________________________ __
23.0
Laboratory sprayv dataA is data obtained
Wax: """"""""""""""""" “‘
by Spraying in the laboratory on a bench scale. Actual
äeäidiñrcâxtrilîß peint. ° F ------------ --
149
¿Gg
¿SÉ
reîìnerilf data is data _obtained on commercial refinery 35 âqìveàgäâmpûsmon _____ _»_ _____________ __
501150
,5o/'50
50/‘50
Pour, o F ___________________________ __
Filtration me gallons of dewaxed on
+20
+25
+20
persquarefoot otñiterarea pcrhoim
1.3
1.3
1.6
'
«
e
.
i
-
1
¿V3X o1 sepeäanon equipm nt Laboratory data using re
eryl varia es and laboratory data refer to bench scale
1
experiments using conditions 1n one case as close as pos-
'7‘0
_
sible to reñnery conditions and in the latter case to bench
Table 1V
Deofling
[Spraying into solvent at lower than ambient temperature]
Wax
MER/TOL Prim.
dil.
Pâgu-
Repinp
ûlte‘r
Repulp . temp.,
œm'p
ratio
° F.
Wash
Wash ratio
Yieiri,
temp.,
Oil,
° F.
Pene. s011511., percent
percent @77° F.
°
.
Weight
'° F.'
Ketone scale ________________ __
Dlstìllate pêtrolatum ....... _.
Residual pet-rolatum ________ -_
70/30 mixture:
Residual(ä .............. ._
an
70/30
60/40
50/50
50/50
8:1
6:1
6:1
6:1
30
40
40
30
30
4()
40
5
2:1, 1:1. 1:1
2:1
1:1, 2:1
1:1
50/50
2:1
30
50/50
6:1
30
'
.-.__
_
30
40
40
5
0. 06
Nil
0. 74
0 20
3 1
5
3:1
5
17. 5
17. 5
19. 0
21. 0
131
153
159
163
75
23
30
53
1:1
5
1:1
5
2.09
25.5
161
44
1.86
31.0
156
54
'
Dlstillato petrolatums__..
Charge stocks:
Ketonc scale
_
Dist-ìllate petrolatuln_-__Residual petrolatum
f
‘
_
'
70/30 mixture residual and
distillate petrolatums.
Y
70l30
7.911
(iD/40
6:1
50/50
7.3:1
50/50
6. 4:1
70/30 Mixture:
_
_ . _ -_
7.5
12. 7
58. 0
195. .5
...... _.
167. 5
126
...... __
167
154
Y
30
Y
2:1.3:1
«
30
1 6 l,1,6:1,1.6:1
30
0 05
______ __
38
3. 2:1, 3.211
38
1.8:1,2:1.2:1
37
1 2
______________ __
'
an
Distîlla'cepctrolatums.
'
10.9
30. 2
-1.-.
_. _ _ _
'
Distillate petrolatum_____
Residual(i ___________ -_
-__
-
'
Refinery
Ketone
data:
scale ____________ __
`
2:1, 3 1
3 ' 1, 2 1
3:1
3:1
Y
Y
133
79
37
-
50 .................... -_
1 3:1
50 ______ __
22132
170
42
164
43
Y
____ .-._
1. 2:1
...... _.
0. 6:1
...... __
2 5
30
3,os3,1 54
l0
TABLE V
E?‘ect of MEK/Toluol Ratio on Oil Content and Yield
Filter
Primary te mper
dilution
ature,
Solvent ratio MEK/toluol
Wash re
pulp tern
Repulp 2
perature
° F.
Oil,
per
cent
Pene
tration
at 77°
Yield,
percent
° Fß
Ketone scale wax: l“
_
_
__
_ne
__
„mw
0.
0"
O..uSl___„te___
0_
üßWüim
Vdit5ne719_mYeo005sm
C_
__
n
u
os1_.
_
__
_
X___
Íl.___ 0____.v0_.__
____
53d___ k1
„
_____
1„
m
_lw
__
_
_
__
_„_____ ___
_l____0____0.___
_
_
__
Wm
___
«ma
_b__
Y.5__
___
__
_____
m.
_._
5"___
n
0
HCAP eGtCa.Eu@
1 Properties of starting waxes:
_____
___. _
.___ _____ _
_
_. ___ _
__ _.___
43 3
2.13
6428 1lnr“ 13406
M.P. ° F.
678529130
Penetra
Oil
tion at
content,
percent
77° F.
317960
ß Ketone scale wa_\:._____-__________________-__
a t e S l â c k .a
ed HCermmYe ommmuYVaX-_____________________-__..___
w
2 Notation (3 : 1)2 indicates that the re pulp operation was repeated twice using 3 volumes oí solvent to l volume of original charge.
(3:1)3 indicates 3 repulp stages.
3 The indicated Wash ratio was used íollowin g each filtration.
4 Solvent saturated with water at the indicat ed temperature used.
5 The last three examples show the versatility of ou r process with different starting crude waxes and solvents.
FIGURE 6 shows a simp le iiui introduction device
made in the form of a hypodermic needle. These needles
can be prepared in a variety of diameters and atiord a
the strainer 78 and exits from the orifice 77. The ma
terial which issues from the orifice is in the form of a
solid stream which subsequently breaks up into particles.
simpliñed method of adjusting oriñce diameter to vary de 55 Such a nozzle is supplied by Spraying Systems Company
oiling and dewaxing efliciency. The charge material en
as l/4 TT00O4-0° sol id stream nozzle. A typical oriiice
ters the inlet 73 and issues from the end of the hollow
diameter fou-nd acceptable for use in practicing this in,
needle 74 in a fine stream which then breaks up into par
vention is 0.046 inch and this oriñce utilizes `a 50 mesh
ticles.
screen as the strainer.
Hypodermie needles are sold commercially by
number index which refers to needle diameter. Needle 60
While this invention has particular application to the
numbers and the corresponding .diameters used success
removal of wax from waxy oil or the separation of oil
fully in practicing this invention were as follows:
of oily wax, i t can be applied to the removal of high
pour materials from various carrier liquids. The solvent
can be c-onsidered broadly to be a medium having solvent
No. 13__________________________________ 0.072"
No. l5__________________________________ 0.057” 65 power for the liquid and little or no solubility for the
high pour or solid material at the temperature at which
No. 17__________________________________ 0.0453”
the materials are separated. For example, expe rlments
No. 19
0.0359”
have been successfully made using water and an emulsi?ler
No. 22____ 0.0253"
as the solvent and substantial amounts of oil were re
70 moved by this solvent from a crude wax. For example,
FIGURE 7 shows another nozzle used successfully in
using an amomc emu lsiiier the oil content of a ketone
laboratory spray experiments demonstrating the practice
scale wax was lowered from 12% by wei ht to 4% by
of the invention. This nozzle is composed of a body 75,
a cap 76 which holds ythe orifice insert 77 and an internal
weight. The results of laboratory tests using water with
various surfactants as the solvent medium and ketone
strainer 78. The liquid enters at inlet 79, passes through 75 scale wax as the starting material are shown in Table VT.
3,083,154.
11
TABLE V1
Spray Deoz'rlíng Using Water
KETONE SCALE WAX*
Filter
Emulsifier system
1° dil
Temp.,
temlp., Repulp
°
.
° F.
6:1
65 ______________ ._
D0.“ ...................... __
6:1
65
8 l
Nonionic 3 in charge __________ _-
‘
Antonie 4 and tap water ....... __
8:1
8:1
MP., Yield,
° F.
percent
Wax
1 1:1
30
8.9
128
3:1
75
11:1
30
8.6
128
89. 0
f
1:1
65
65
2:1
65
6. 9
127
S6. 4
1 1:1
30
7. 1
127
90. 4
5 7
129
S0. 6
4. 2
130
81. 7
3:1
2:1
1:1
2:1
85
S5
Y 3 :1
l 1:1
30
2:1
1:1
90
3:1
2:1
l 1:1
90
30
2:1
1:1
90
2:1
90
l 1:1
30
8:1
85
3
Anionie ë and tap water _______ __
per-
2:1
65
90
Anionic 4 and tap Watcr.____--._
Oil,
° F.
cent
Nonionic 2 in tap Water _______ _-
D0.2 ...................... __
Temp.,
Wash
Y
100
Q0
100
Q0
3:1
93. 6
'
1 Last wash ls acetone at 30° F. Acetonc is used to displace as much of the Water as possible from the iilter
cake prior to processing the Wax.
2 Triton X-lGO. i
3 Triton X-45.
’i Ammonium oleate surfactant formed by interaction oí ammonium hydroxide in water and oleic acid in
charge.
e Ammonium stearato surfactant formed by interaction of ammonium hydroxide in Water and stearic acid
in charge.
‘See the following table:
Property of starting wax
NLP., ° F. Oil, percent
'Ketone scale wm: ______________________ __
125
12. 6
It is noted from Table VI that when anionic surfactants
were used, the active ingredients for the formation of the
anionic were split between the water and the charge.
the crude oil whereas the distillate yfraction could be left
in the crude oil and sold with the oil.
Thus, when the surfactant was ammonium oleate, am
in place of the distillate fraction and the methyl ethyl
monium hydroxide was added to the Water intoY which
Vhetone. A liqueñed petroleum gas may be used as the
the charge containing oleic acid was sprayed.
There are many other materials which can be used
solvent, or a crude may be topped to provide a distillate
In this '
and the residual oil sprayed into the tops, or a waxy crude
Way the surfactant is formed at the time of spraying and
is more effective in emulsifying the liberated oil. When 40 can be sprayed into a crude of low wax content. The ad
vantage of each of these “solvents” is that only a filtration
just one non-ionic was used it was dissolved in the appro
is required to remove the high pour waxy or wax-like ma
priate medium. Triton X-lÜO (trade name) was added
terials and the “solvent” can remain with the dewaxed
to the water and Triton X-45 (trade name) to the charge.
crude, thus eliminating the need for distillation. The re
The Tritons are branded products available commercially
from Rohm and Haas Company and are alkyl aryl poly 45 sults of laboratory tests using methyl ethyl ketone and
Sovasol No. 5 (trade name -Íor «distillate petroleum frac
ether alcohols. Depending upon chain length, they are
tion) are shown in Table VII as follows:
either water- or oil-soluble materials.
TABLE VII
Removal of High Pour Materials From Crude by Spray
Processing
.
Crude
TYP@
oGray..
API
Esquina-Venezuela-- Naphthenic-para11`i1:dc_-~
Do
_____r‘n
Guario-Venezuela___- Intermediate paratlinic.-
Solvent
Filter
Chg.
Crude
D11. 1° temp., Wash Temp., temp„1 yield,
M, L.;
° F.
° F
° F.
Wax
oil
percent content,
percent
Wax
Wax
M. P., yield,
° F.
percent
40.7
MEX ______ __
3:1
50
1:1
50
80
83.1
9.1
145
40.7
Solvaêol no-"
3:1
0
1:1
O
80
91.5
26.2
133
7.9
44.4
Is ...... _-
3:1
50
1:1
50
80
79.3
17.2
132
16.3
20.0
l The charge temperature is the temperature ofthe crude at the time of spraying.
Some oil fields produce a heavy crude such as Guario,
Esquina and Mata. These crudes, because of high pour
waxy or wax-like materials, are not easily pumped or
handled. It is, therefore, desirable to remove the high
pour material from these crudes as the crude oil is re
moved from the ground so that the oil may be more
conveniently handled in transit to the refinery. VThe sepa
ration required is a simple separation without the necessity
Although this invention has heen described with pre
ferred embodiments, it is to be understood that modifica`
tions and variations may be used; without departing from
the spirit and scope of the invention, as those skilled in
the art will readily understand. Such variations and modi
a‘ications are considered within the purview of the attached
claims.
We claim:
.
i
1. A process vfor separating Wax and oil which com
V‘for highly emcient separation. Experiments were success
fully completed using both Sovasol `#5, trade name of 70 prises providing the wax-oil mixture at a ñowable tem
perature, maintaining a liquid solvent bath at a »tempera
Socony Mobil Oil Company, Ine., a light petroleum dis
ture below the solidiñcation temperature of the Wax in
tillate fraction having good solvent power for oil, and
said wax-oil mixture, conducting the mixture in ñowable
methyl ethyl ketone. The ketone gave a better quantita
form to beneath the surface of the bath of solvent, spray
tive separation than the petroleum distillate fraction.
'l'he ketone would have to be distilled, however, from 75 ing the wax-oil mixture into said bath so as to emerge
13
3,083,154
therein as particles or droplets of a size about 5-100
microns, separating the wax particles from ythe solvent and
oil and separating oil »from said solvent whereby a Wax
of low oil content and an oil of acceptable pour point is
produced.
14
oily wax into the lbath of solvent so as to emerge therein
as particles or droplets of a size about 5-100 microns,
maintaining the droplets in said bath of solvent for 4said oil
-for a time period ranging about l to 10 minutes, to sub
stantially »free the wax of oil, filtering the wax from the
2. The method of separating wax from an oil in which
mixture and separating the oil and solvent.
it is commingled which comprises providing said oil at a
'6. The method of substantially reducing the wax con
ñowable temperature, cooling a stream of liquid `solvent
tent of a waxy oil which comprises heating said waxy oil
to a temperature below `the melting point of the wax, c011
to a temperature above the melting point of the wax,
ducting the oil in ñowable form to beneath -the surface 10 maintaining a bath of liquid solvent medium at a tempera
of the stream of liquid solvent and then spraying the oil
ture below the solidiñcation temperature of the wax, as
into the stream of liquid solvent so as to emerge therein
measured after said waxy oil is commingled with the sol
as particles or droplets of a size about 5~l00 microns,
vent medium, conducting the waxy -oil in ño-wable form
maintaining the solvent and oil particles in contact for
to beneath the surface of said bath of solvent and then
a period of time suñicient to solidify the wax and ldissolve 15 spraying the waxy oil into the bath of solvent so as to
the oil exuded from the solidiiied wax particles in said
emerge therein as particles or `droplets of a size about
solvent, passing the wax particles and commingled oil-sol
5-100 microns, maintaining the droplets in said bath of
vent through a rilter, under conditions to separate a low
solvent medium for a period of time suiïicient to substan
oil content wax and an `oil-solvent mixture free of wax
tially free the oil of wax, separating the wax from the
particles, separating solvent yfrom said oil-solvent mixture 20 oil and solvent medium and separating the solvent me
to provide an oil of a pour point not greater than about
dium from the oil, whereby an oil of low pour point is
+20° F.
3. The method of substantially reducing the oil content
directly prepared.
emerge therein as particles or droplets of a size about
the oily wax into the bath of solvent so as to emerge
therein as particles or droplets of a size about 5-100
7. The method of substantially reducing the wax con
of an oily wax which comprises providing said oily wax
tent of a waxy oil which comprises heating said waxy oil
at a ilowable temperature, maintaining a bath of liquid 25 to a temperature above the melting point of the wax, main
solvent medium at a temperature below the solidiiication
taining a -bath of liquid solvent for said oil at a tempera
temperature of the wax, as measured after said oily wax
ture below the solidiiication temperature of the wax, as
is commingled with the solvent medium, conducting the
measured after said waxy oil is commingled with the
oily wax in flowable form to beneath the surface of the
solvent, conducting the waxy oil in ilowable Iform to be
bath of solvent and then spraying the oily wax into the 30 neath the surface of the bath of solvent and then spray
bath of solvent so as to emerge therein as particles or
ing the waxy oil into the bath of solvent so »as to emerge
droplets of a size about 5-100 microns, maintaining the
therein as particles or droplets of a size about 5-100
droplets in said bath of solvent medium yfor a period of
microns, maintaining the droplets in said bath of solvent
time sufficient to substantially free the wax of oil and
for a period of time sutñcient to substantially -free the wax
separating the wax from the oil and solvent, thereby -pro 35 of oil, separating the wax from the oil and solvent, and
ducing a wax of substantially reduced oil content.
separating the solvent from the oil, whereby an oil of
4. The method of substantially reducing the oil content
low pour point is produced.
of an oily Wax which comprises heating said oily wax to
8. The method of substantially reducing the wax con
a temperature above the melting point of the wax, main
tent
of a waxy oil which comprises heating said waxy oil
taining a bath of liquid solvent for said oil at a tempera 40 to a temperature above the mel-ting point of the wax,
ture below the solidiñcation temperature of the wax, as
maintaining a bath of liquid solvent for said oil at a tem
measured after said oily wax is commingled with the sol`
perature below the solidification temperature of the Wax,
vent, conducting the oily wax in llowable form to beneath
as measured after said waxy oil is commingled with the
the surface of the bath of solvent medium and then spray
45 solvent, conducting the waxy oil in ilowable form to be
ing the oily wax into the bath of solvent medium so as to
neath the surface of the bath of solvent and then spraying
5-100 microns, maintaining the droplets in said bath of
solvent for a period of time suñicient to substantially free
microns, maintaining the droplets in said bath of solvent
the wax of oil and separating the wax 'from the oil and 50 'for said oil for a -time period ranging about l »to 10 min
solvent, thereby producing a wax of substantially reduced
utes, to substantially -free the wax of oil, filtering the
oil content,
wax from the mixture, separating the solvent from the oil,
5. The method of substantially reducing the oil content
whereby an oil of accepta-ble pour point is directly pro
duced.
of an oily wax which comprises heating said oily wax to
a temperature above the melting point of the wax, main 55
References Cited in the file of this patent
taining a bath of liquid solvent for said oil at a tempera
ture below the solidiiication temperature of the wax, as
UNITED STATES PATENTS
measured after said oily wax is commingled with the sol
2,116,144
Dickinson _____________ __ May 3, 1938
vent, conducting the oily wax in ñowable form to beneath
2,301,965
Mauro et al. _________ __ Nov. 17, 1942
the surface of the bath of `solvent and then spraying the
2,370,453
Dons et al. __________ __ Feb. 27, 1945
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