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Патент USA US2140574

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Dec. 20, 1938'.
_
c. s. CERF
'
‘
2,140,574
PROCESS OF DESALTING MINERAL‘ OIL
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Filed Aug. 16, 1937
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Patented Dec. 20, 1938
UNITED STATES
mrsm orrica
2,140,574
PROCESS OF DESALTING MINERAL OIL
'
Cedric s. Cerf, Holt, Calif.
Application August 16, 1937, Serial No. 159,222
11 Claims.
This invention relates to the desalting of min
eral oils. The term “mineral oil” is used herein
and in the claims as referring to petroleum hy
drocarbons, as ordinarily produced after the
5 petroleum has been largely separated from any
attendant emulsion.
This invention is not con
cerned with emulsion-breaking, but with the re
moval of those inorganic salts, usually sodium
chloride, calcium chloride and magnesium chlo
10 ride, which gasoline manufacturers have found
such a problem. For a long time the oil industry
was not cognizant of the fact that in a‘day’s oper
ation there would be fed into a still, along with
the crude petroleum, a mass of inorganic salts
15 which could be readily measured in tons. These
materials make their presence known by a high
corrosion rate, by “spotting” of still bottoms, and
by erosion. The mineral oil- to which attention
is directed herein is therefore relatively dry,
20 emulsion-free, but contains an undesirable salt
content, including chlorides.
-
Prior to the ?ling of this application, it ha
been proposed by the Petroleum Rectifying Co.
that mineral oils, of the character dealt with in
'25 this application, be desalted by being contacted
with water to the end that the salts be dissolved
out. To remove the salts e?ectually, it was found
(Cl. 196-4)‘
As I have previously explained, this invention is
concerned with a salt-containing mineral. oil
which is relatively dry by reason of prior treat
ment or because it is so produced.
I have been
able to successfully reduce the salt content in
mineral oils containing a small amount of water.
For example, upon treatment of an emulsi?ed
crude from Section 5, Kern Front, Standard Oil
Company of California, I was able to reduce the
S. and W. (sediment and water) content from 6% 10
to 1% and to reduce the chlorine content to nil.
Referring, for example, to the operation as dia
grammed in the drawing, the incoming oil was
passed into the bottom of a tower 6 wherein a
bed of mineral ?ooded with water was main- l5
tained. This mineral is fully disclosed in my
co-pencling application Ser. No. 69,225, ?led
March 16, 1936, and my co-pending application
with Conrad Ser. No. 131,198 ?led March 16, 1937.
The e?luent from the tower 6 was passed through 20
line 1 into a separator 8 wherein excess water was
drawn off through line 9. To maintain the min
erals water-?ooded, in accordance with the teach
ing of my aforementioned application, water was
introduced through line l0 into the base of the 25
tower, as was needed.
The oil was introduced
into the tower through line I l. The substantially
necessary to re-emulsify the oil.‘ It appears that dry oil passing out. from the separator through
the salt is held in -the oil, often being surrounded 9 line 12 was directed into the base of a tower Ill
30 by wax-like bodies which prevent water from ?lled with‘ crude rock salt. The nearly dry oil 30
gaining access to the salt and removing it by was passed upwardly through the rock salt and.
solution. Thereafter, in accordance with the water was drained o? of the rock salt, as it ac
Petroleum Rectifying Co. process, it was necessary cumulated, through line l6. Outlet I‘! provided
7
to break the petroleum emulsion, thereby includ ‘ for the drawing oif of substantially dry chloride86 ing the cost of‘ a de-emulsi?cation step in the
_ desalting operation.
It is generally the broad object of the present
invention to provide for the desalting of a min
‘ eral oil while obviating emulsi?cation.
40
Another object of the present invention is to
free oil.
~
I claim no novelty in the material per se of
which the bed is composed but may use any water
and oil insoluble solid substance. Thus, the bed 40
provide a new and novel process for desalting of
may be formed of one of the minerals disclosed
a mineral oil.
by Robinson, (Patent 1,974,692) such asyhematite,
_
A further object of the present invention is to
provide a relatively simple process of low operat
45 ing cost which can be effectively used to reduce
the salt content of a mineral oil to the order of
0.001%.
_
‘
.
35
My application Serial No. 69,225 ?led March
16, 1936 contains the following disclosure:
hornblende or garnet, or it may be “of quartz,
glass, iron ?lings, pyrites or hard burned or vit
rifled clay.
The surfaces of these materials af- 45 I
forded by crushing the massive body and screen
ing to suitable size ranges are usually the most
desirable as well as the easiest to prepare, but
The invention includes other objects and fea
tures of advantage, some of which, together with ‘ clay products with or without the additiq'i; of
50 the foregoing, will appear hereinafter wherein oxides may be formed into pellets before or during 50
the present manner of practicing the process of burning and such shaped materials are included
in references to fraginental materials.
this invention will be disclosed.
The physical structure of the bed proper is a
The drawing accompanying and forming a part
hereof is a diagrammatic representation of the matter of considerable importance. For exam--v
ple, a sand bed is of such ?ne mesh that the chan- 55
process of the present invention. v
2
' 2,140,574
_ nels between the sand grains are extremely nar
row. I have found it is impossible to force any
appreciable quantity of emulsion through these
channels without lifting the sand and bringing
it into suspension. It is also impossible to main
tain a sand bed submerged with water except as
to its upper surface, that is, it is impossible to
keep the narrow pores between the sand grains
?lled with water and at the same time to pass
ll)
emulsion through them. If the water is forced‘
out, the grains become oil wet and nonfunctional
for this purpose.
'
I have found that a bed of the ?neness of sand
can not be kept water-?lled if any considerable
15 quantity of emulsion is to be passed through it.
‘To keep the bed water-?lled and also conductive
to emulsion, the channels must be wide enough
to ‘permit the emulsion to pass the water inside
the channels.
20
-
It is true that if any emulsion is resolved in
_ the bed there will be a supply of water produced
by the resolution, and if the water percentage is
large and' the channels are su?iciently open this
supply might be enough to [keep the bed water'
25 wet. However, a relatively dry emulsion or oil
will displace the water from a sand bed and cause
it to become oil wet. I therefore ?ood the bed
and keep it ?ooded, whether by means of the
resolution water or by means of an added water
30
supply.
In accordance with this invention I do not use
material as fine as beach sand since that is not
suitable. Instead I employ material of a size
such that, when a bed thereof is ?ooded with
35
water, the integrity of the water ‘body ?lling the
interstitial space is maintained. With particles
the size of beach sand, this cannot be secured, oil
?lls the interstices, the ‘solid material becomes
oil wet and useless.
I prefer to use relatively coarse material and
40
I have successfully used material wherein the sizes
were between 7/64 and 1%.; of an inch. With
different materials the coarseness can be varied
and I do not wish to be limited to the sizes speci
?ed since the factor governing the selection as to
45
size is to be sure that the material is always coarse
enough so that the water body in the interstices
is not displaced by oil and the material oil wetted.
In some cases it is desirable to place a layer of
relatively coarse fragments (as for example about
50 1/2 inch) on the foraminous support and to im
pose on this layer successive layers of progres
sively smaller fragments (as for example % inch,
M; inch, 1“; inchand 5/8 inch). The ?nest ma
terial should be appreciably coarser than. ordinary
55
V sand in any case, and always coarse enough to
ensure maintenance of the integrity of the water
in the interstices. The above gradation is sug
gestive only and it is possible to make the entire
bed of fragments of substantially one size,.but
for reasons which will appear a bed so constructed
will have a reduced throughput. Successful re
sults have been secured with a bed of particles
65
of sizes between‘ 7/64 and 1%; of an inch.
In order to resolve the emulsion it is passed up
subjected to a'cleaning process. I therefore in
troduce water, or material carrying a large per
centage of water as an easily resolved emulsion,
in advance, in quantity su?icient to completely
submerge the mineral, and maintain this aqueous
submergence at all times, both while the treat
ment is in progress and during any intermission
between treatments.
The water liberated by the resolution of emul
sion remains vin part suspended in the oil and in
part joins the initial water body, which over?ows
to a corresponding degree and ‘keeps the vessel
?lled with water. It is necessary to bear in mind
in this connection that if the channels through
the mineral body be too narrow, or if the emulsion 15
be too viscous for the width of the channels, the
water liberated by resolution may remain com
pletely suspended in the oil phase. In such case
a gradual entrainment of the original water body
may result, by which it will be in part or entirely 20
carried into the over?ow and replaced by oil, and
to just that extent the bed will becomenonfunc
tional.
If this tendency should manifest itself there are
three remedies available: (1) to reduce the ve 25
locity by lowering the throughput or by rebuilding
theJ bed with larger fragments to afford wider
channels; (2) to reduce the viscosity of the emul
sion, as by predilution or heating; (3) to feed
water continuously while feeding emulsion.
30
The choice between these alternatives for main
taining the integrity of the water body will de
pend on several conditions. First, resolution is
usually accelerated by heating, and to such de
gree that it is economical and pro?table to heat
all except'the lightest emulsions. It is therefore
usually the case that all the heat which the emul
sion will tolerate is already being applied, so that
a further heating effect is not available. The
maximum permissible temperature is in all cases
below the boiling point of water and, unless a
condensing system is provided, is below the tem
perature at which appreciable vaporization losses
are incurred.
.
'
Resolution is also accelerated by increase in
the velocity of emulsion ?ow- through the chans 45
nels between the fragments, the limit to this in
crease being the point where turbulence sets in
and tends to produce reemulsi?cation.
The ac
celeration of resolution with increasing velocity
follows from the nature of the treatment, the
effect of resolution being produced by the‘ actual
contact of the dispersed water particles with the
water-wet solid surfaces. These particles, dis
persed and suspended in the oil phase, arebrought
into such contact by their inertia, which causes
them to move in straight lines out of the narrow
streams of oil asthese streams are de?ected from
straight lines in passing through tortuous chan
nels. Such an inertia effect is afunction of ve
locity and while no numerical limits can be set,
because of the extreme diversity in particle size,
gravity difference and ?uid friction, it will be
found with any given emulsion that the rate of
resolution at very low velocities is extremely 65
small, that the rate increases rapidly- as the ve
the emulsion stream is introduced the vessel ' locity increases, and that resolution ceases when
should be ?lled with water to a level su?iciently the velocity of turbulence is reached.
high to cover the mineral. It is not sui?cient to
Widening the channels by the use of larger
70 merely wet the material with water as the oil fragments reduces velocity for any given through
phase of many emulsions will displace a water put rate and therefore reduces the tendency to 70
?lm if allowed to remain in contact with it, the ward entrainment of water. However, it also re
effect of mass action reversing the normal selec
duces the rate of resolution and is equivalent to
tivity of the solid surface. Once oil wet, the solid or requires a reduction of throughput. This is
surface
is
thereafter
inactive
until
it
has
been
75
intrinsically undesirable although in some cases it 75
wardly through this fragmental bed, but before
,
.
2,140,574.
3
flow that ordinarily a petroleum emulsion would
is useful to reduce ebullition of gas from oils hav
This objection does
re-form. However, because of the presence of
not apply to the step of feeding water along with
the water-?ooded mineral, emulsion formation
the emulsion, as only such supply is required as
does not occur and instead the oil is so agitated
ing a high vapor pressure.
and contacted with the water, scrubbed with the
will balance the usually slow rate of entrainment,
and the addition of this‘small proportion of water
will usually be found to increase rather than to
diminish the rate of resolution, due to the increase
in velocity.
water, that sodium chloride and other water- .
soluble salts therein are effectively eliminated,
particularly the chloride content.
It may be said that the addition of '
ter.
1
I have successfully operated the mineral bed
with water from which chlorides have been
water will seldom be required if the emulsion un
der treatment contains a large proportion of wa
eliminated, and also with aconcentrated brine.
‘ The action in this respect is hard to explain,
The purpose served in using progressively
smaller fragments in the upper layers of the min
15 eral bed is to increase the velocity asthe emulsion
is progressively resolved. Resolution consists es_
sentially in agglomerating ?ne water particles into
larger drops, and as this e?ect progresses the
number of particles suspended in the oil phase
becomes smaller and their spacing greater, re
quiring an increased inertia effect to bring a unit
number of particles into contact with the solid
surfaces. The same effect may be produced,
though in a less desirable manner, by progresi
25 sively decreasing the cross sectional area of the
bed in the direction of flow, thus accelerating the
flow of the emulsion stream as a whole.
In no case should the channels through the
because I have secured successful results with
both treatments. Possibly different explanations
apply in each instance. While the preferred
process is that disclosed, i. e., using both the
water-?ooded mineral bed and the rock salt
column, either can be used, and I have‘ success
fully desalted oils using the water-?ooded min
eral bed and utilizing the rock salt tower sep 20
arately. In place of rock salt, any other inor
ganic material of a water-soluble and highly
ionizable nature can be employed.
I claim:
1. A process for desalting a substantially dry 25
emulsion free mineral ‘oil comprising passing‘
said substantially dry emulsion free oil upwardly
through a stationary bed of rock salt while main
,
bed be narrow enough or the velocity of ‘the liquid taining said bed dry.
2. A process for desaltinga substantially dry 30
high enough to cause the mineral to be lifted from
emulsion free mineral oil containing only about
its position or brought into any degree of suspen
1% of water comprising passing said oil in the
sion to any substantial extent. In order to pro
duce the desired effect of resolution without loss presence of only said 1% of water upwardly
of mineral agent and without oil wetting the agent through a stationary bed of rock salt and~draining
separated water off said bed.
35
35 the mineral bed should be ?xed and permanent
3. A process for desalting a substantially dry
in position.
As was previously stated, the S. and W. content emulsion free mineral oil comprising passing said
substantially dry emulsion free oil upwardly
of the incoming mineral oil was 6%. That pass
ing out through line I‘! carried only 1%. The through a substantially dry stationary mass of
salt crystals, and draining separated water off 40
40 incoming oil contained 0.04% of ash but this was
reduced in the oil passing out through line I‘! adjacent the bottom of said mass.
to 0.026%. The oil passing through line l2 con
4. A process for desalting a mineral 011 com
tained only 3% S. and W. while the ash content prising passing said oil through a mineral bed‘
had been reduced to 0.033%. The treatment in maintained ?ooded with water, separating out
only the mineral bed was effective to reduce the free water to provide dry emulsion free oil and 45
chlorine content to zero, but an appreciable cal
then passing the dry emulsion free oil through i
cium and sodium oxide content still remained in a substantially dry mass of‘ salt crystals.
the oil, amounting to 12.5% on the basis of ash. '
5. A process for desalting a mineral oil com
Passage through the rock salt reduced the sodium prising contacting the oil with water under con
oxide content to zero.
ditions normally tending to emulsion formation
50
In a similar operation, treating a crude oil for ' but in the presence of a material effective to re 50
the Lion Oil Company of Arkansas, the oil in its solve an emulsionof said oil and water, and sep
arating the oil from said water to provide sub
“wet” condition contained0.0097% sodium chlo
ride. The oil passing through line 12 had a salt stantially dry emulsion free oil and passing the
content of 0.00594%, while that passing out of so water-treated substantially dry emulsion free 55
line H was reduced to 0.001451%. The other salts oil through a dry salt bed. _
present of a deleterious nature were similarly re
duced.
I have also been able to successfully desalt the
oils utilizing rock salt alone, and upon the afore
mentioned oil from the Lion Oil Company the
same wet oil was introduced through line l2, with
out previous treatment by the mineral. Passage
through the rock salt bed alone reduced the salt
content to 0.00105% and the other salts were like
wise reduced.
,
The treatment accorded the oil in the water
?ooded mineral bed, I have determined upon
study in glass, is such that although normally one
would expect an emulsion to re-form, such is not
apparently the case because of the presence of
the mineral which, as I explain in my co-pending
application, is effective to resolve a petroleum
emulsion. Therefore, I can successfully contact
75 the dry oil with water under such conditions of
6. A process for desalting a mineral oil com
prising contacting the oil with water carrying
a relatively high salt concentration under con
ditions normally tending to emulsion formation 60
but in the presence of a material effective to re
solve an emulsion of said oil and water, and sep
arating the oil from said water to provide sub
stantially dry emulsion free oil and passing the
so water-treated substantially dry emulsion free 65
oilthrough a dry salt bed.
7. A process for reducing the salt content of a
substantially dry emulsion free mineral oil to
the order of 0.001% comprising contacting said
oil containing an undesirably high-salt content 70
with a relatively dry mass of an inorganic water
soluble highly ionizable material e. g. sodium
chloride, removing said oil from the material and
separating from said material any water liberated
from said oil.
75
4
25,140,574
8. A process for reducing the salt content of a
substantially dry emulsion free mineral oil .to
the order of 0.001% comprising contacting said
oil containing an undesirably high salt content
with a relatively dry mass of an inorganic water
soluble highly ionizable material e. g. sodium
chloride.
_
9. A process for desalting mineral oil compris
ing passing substantially water- and emulsion
oil through a substantially dry rocl: salt mass,
and maintaining said rock salt mass substantia1—
ly-dry.
11. A method 'of treating an'oil-water' emul- ‘
sion to rid the oil of emulsion'and salt compris
ing a treating the emulsion by passing-said emul
sion upwardly at a velocity belowthat of turbu
lent flow through a porous bed of fragmental,
solid, insoluble material in which the fragments
10 ‘free mineral oil through a substantially dry mass ' are so large that the integrity of a Water body
10
of rock salt.
?lling the interstitial space in said bed is main- ‘
10. .A method of treating an oil-water emulsion
to rid the oil of emulsion and salt comprising
treating the emulsion by passing said emulsion
tainable,v the fragments comprising said beds in
cluding those of a size between %4 and 1%‘;
of an inch, continuously maintaining interstitial ’
15 upwardly through 'a porous bed of fragm'ental,” space in said bed substantially ?lled with water
15
solid, insoluble material in which the fragments
are so large that the integrity of a water body
?lling the interstitial space in said bed is main
tainable, continuously maintaining interstitial
20 space in said bed substantially ?lled with water
and the bed water flooded, permitting the so
treated emulsion to ‘stand and separating o?
water to provide substantially dry emulsion-free
‘ oil, passing said substantially dry emulsion-free
and the bed water flooded, permitting the so
treated emulsion to stand and separating off
water to provide substantially dry emulsion-‘free
oil, passing said substantially dry emulsion-free
oil through a ‘substantially dry rock salt mass, 20
and maintaining said rock salt'mass substantial
1y dry.
CEDRIC S. CERF.
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