Патент USA US2383768

Patented Aug. 28, 1945
2,383,768
.UNlTEi) s'rATss PATENT. orrics .
CALCIUM NAPHTHENATE 1N HYDRDOAB
.
BON EXTRACTION
Mar-inns Buis, Ellesmere Port, and Leonard Bel
chetr, Ince, near Chester, England, assignors to
Shell Development Company, _San Francisco,
Calif” a corporation of Delaware
No Drawing. Application June 28, 1944,
Serial No. 542,808
7 Claims.
(01. ice-1s)
>
i a
amount is required to produce a given sett
This , invention involves an ‘improved liquid
liquid solvent extraction process for hydrocar
time, than if acids of higher acid number had'_
bons. More particularly, it deals with a method
for increasing the rate of separation or the liquid
been used. As a rule, oil suspended in the solvent
separates much more slowly than solvent sus
pended inch, and if too great an amount of cal-lv
hydrocarbons from the solvent by carryins out
cium naphthenates is used, it will have'the’ effect
the extraction in the presence 0! a small amount
of calcium naphthenate.
- of inverting the emulsion tendency, thereby in- ,
,
creasing the stability of hydrccarbonin solvent‘
Liquid, solvent extraction processes comprise
contacting a liquid mixture to be extracted with a
emulsions and defeating the purpose of this in
liquid selective solvent for one oi the components 10 vention. Generally, suitable amounts of calcium
naphthenates range between about .01% and 1%
of that mixture either in a mixer and settler or
and preferably between .02 and 15% by weight of ,
countercurrently through a vessel such as‘ a
packed tower. The solvent is not completely
the hydrocarbon in the mixture. ~
_ The’ calcium naphthenate may be derived from
miscible with the mixture under the conditions
of the extraction, so that two liquid phases are 15 any suitable source. It is most easily produced
by simply neutralizing ngphthenic acids with,
formed which are separated and the solvent in
either or both of these phases is then removed and
lime.
,
The calcium naphthenate-may be added con
may be re-cycled for contact with more of the
une'xtracted mixture;
tinuously 'or intermittently either to the hydroe
,
Previously, wax suppressors such as aluminum 20 carbons or to the solvent, or to both.
and magnesium stearates and palmitates and,
magnesium and lead naphthenates have been used
In the course of the extraction,‘ mcst'of the
'naphthenate goes into the extract phase from
which it may be recovered, and, if desired, be re
turned to the extraction zone. A small portion
in processes for the liquid solvent extraction of
hydrocarbon oils containing waxes, but calcium
naphthenate was not suggested for such processes 25 may remain in the raiilnate.
because it is not a wax suppressor as will be seen
‘
Depending on the use of the ra?lnate oil or ex
from Example VI below.
tract oil or both, it may be necessary to remove
It is the primary purpose of this invention to ' ‘ all or part of the naphthenate therefrom, if such
- improve the separation time, or settling time, be
removal has not occurred as a result of removal
tween the solvent and hydrocarbon phases pro-. 80 of the solvent from the respective phases. - Re- ,
duced in such liquid solvent extraction processes. >
moval can normally be achieved by means such
_as distillation, the naphthenate remaining in the;
irrespective of whether the hydrocarbon does or
does not contain wax.
‘
residue: or acidification and distillation, in which, ‘
'
This invention, as previously stated, comprises 4
case the naphthenic acid may distill overhead: or
carrying out the liquid solvent extraction of a
hydrocarbon mixture in the presence. or a small
clay treatment; the naphthenate being retained
amount of calcium naphthenate in order to reduce the time of separation of the hydrocarbon
Insome cases, the presence of the napthenate
by the clay; etc.
‘
‘,
.
. in the extracted oil may be decidedly beneficial.
Thus, in lubricants-it acts as a detergent, in spray
As a result of the greater rate of separation the 40 oils vit causes increased deposition of toxic agent:
throughput through a given equipment can’ nor
in asphalts (which may have been blended with
mally be increased considerably since settling rate
extract oil containing it) Alt improves the adhe
is usually the limiting factor. Or else for a given,
sion toward mineral aggregates.
throughput the yield and/or quality of the‘ prod
Any hydrocarbon mixture which may be ex
ucts may be improved due to reduced carryover.
tracted in theliquid phase with a liquid selective
solvent may have its separation improved by the
' In an extraction tower the number of theoretical
extraction stages may increase materially for a ' process of this invention, particularly those mix
given feed rate because of ‘a reduced tendency to
tures derived from petroleum including gasolines,
carry finely suspended droplets in the wrong di- ' kerosenes, spray oils, gas oils‘,- Diesel fuels, lubri
and solvent phases,
'
rection.
_
eating oils, etc.
'
The amount of calcium naphthenate required
' to increase the separation time depends upon
several factors, namely: the type of solvent em
ployed in the process: the type of mixture to be
separated in theprocess; the components in the
mixture which a?ect emulsibility; the molecular
‘ weight and the acid equivalent of the calcium
naphthe'nate: etc. an example, if the naph
thenic acids» have a low acid number. a greater
_
~
Some suitable liquid selective solvents which
may be employed in the separation of hydrocar
bon mixtures are: phenol, cresylic acids, alkyl
55
phenol mixtures, aniline, alkyl aniiines, diphenyl
amine, ditolyl amines. carbitols (diethylene
glycol monoethers) such as methyl, ethyl, propyl
carbitols, chlorinated dialkyl others such as beta
beta dichlor-ethyl ether, nitrobenzene, nitro
toluene. nitroxylenes. na'ohthois a'lkvl 'nanhthn‘le
2.
2,383,768
benzophenone, phenyl tolyl ketone, diphenylene
sulfolane
ketone, alkyl phthalates such as dimethyl phthal
ate, alkyl salicylates such as methyl salicylate,
benzyl alcohol, benz chlorides, i. e., benzyl, benzal,
benzo-chlorides, benzonitrile, diphenyl oxide, sub
and the settling times were determined -
for diiferent contents of calcium naphthenate as
shown in the following table:
CY
Percent by wt. calcium nspbthenate
stituted diphenyl oxide which may contain amino,
Settling time
calculated on the oil
in minutes
nitro, hydroxy, etc., radicals; ditolyl oxide, sub
stituted ditolyl oxides which may contain amino,
nitro,- hydroxy, etc, radicals, hydroxy pyridine,
nitro pyridine, chlorinated pyridines, substituted 10 I 11.:
quinolines, isoquinoline, chlorinated quinoline,
such as hydroxy quinoline, S-nitroquinoline,
qulnaldine, beta-alpha picoline, alpha picoline,
re?nery N-bases, tetrahydrofurfuryl alcohol, fur»
EXAMPLE IV
Two samples of a Mid-Continent dewaxed dis~
tillate (250 S. U. vis. at 100° F.) were contacted
furyl alcohol, furfural, monoglycerol ethers such '
with 150% by wt. phenols and 250% by wt. pro
as l-methoxy glycerol, 2-methoxy glycerol, 1
pane in a glass bomb at a temperature of 95° F.
to simulate conditions present in a DuoSol ex_
ethoxy-glycerol, 2-ethoxy glycerol, l-propoxy
glycerol, 2-propoxy glycerol, l-isopropoxy glycerol,
traction process.
2-isopropoxy glycerol, glycerol diethers such as
1,2-dimethoxy glycerol, 1,3-dimethoxy glycerol,
1,2-diethoxy glycerol, 1,3-diethoxy glycerol, 1,2
dipropoxy glycerol, 1,3-dipropoxy glycerol, 1,2-di
isopropoxy glycerol, 1,3-di-isopropoxy glycerol,
taln 33% by wt.-of calcium naphthenate in the
distillate. It was found that the separation times
between the solvent and the oil were 22 seconds
and 14 seconds respectively. The resulting phases
mixed diglycerol ether such as 1~ethoxy, 2-meth
oxy glycerol, l-methoxy, 3=propoxy glycerol, 1
ethoxy, z-isopropoxy glycerol, antimony trichlo
ride, crotonaldehyde, acrolein (Foster-Wheeler
solvents), various suli’ones—sulfolanes, 2-sul~
folenes, sulfoxides, aliphatic suliones, etc.
The following examples illustrate the effective 30
ness of this invention:
One of the samples contained
no calcium naphthenate and the other did con
were then, tested to determine the content of the
phenol in each phase, and it was found that the
sample containing the calcium naphthenate had
less phenol in the ra?inate than the other sample,
as seen by the following table:
Phenol contents,
C‘
percent w.
Exmu I
Several samples of a Colon waxy distillate
lubricating oil were extracted with furfural in 35
the presence of different amounts of calcium.
naphthenate and in the absence of calcium naph
thenate. The in?uence of the concentration of
the calcium naphthenate having a relatively
high molecular weight and an acid value equiva 40
lent to 115 mgs. of KOH per gm. on such extrac
tion mixtures is shown in the table below:
Ra?‘lnate
Extract
{1) No calcium naphthenate ______________ ..
44. 4
90. 5
2) 0. 5% calcium nsphthenate ____________ v.
38. 6
91. 5
EXAMPLEV
Three other samples of dewaxed Mid-Continent
lubricating distillate (250 S. U. vis. at 100° F.)
were tested similarly to the samples in Example V
above and more data was obtained as seen in
Percent calcium naphthenste
the following table:
Type emulsion
45 E?eci' of calcium naphthenate on acid-retention
Nil __________________________ . _
Stable oil in iurfurai.
cor-0.03% w/w __________ ..
Coagulation and rapid settling.
_..
3.05 o __________ __
.
Above 0.1% ____________________ _.
Of the rai?nate and extract layers in DuoSol
extraction
Incipient iuriural in oil.
Stable furiuml in oil.
ExAmLn II
50
Two samples of Colon waxy distillate lubri
cating oil were extracted with furfural at differ
ent solvent-to-feed ratios and in the absence
and in the presence of calcium naphthenate to,
obtain a, substantially identical product. As can
be seen from the table below, the presence of
:alcium naphthenate materially reduces the sol
vent-to-feed ratio necessary to obtain the given
V‘. I. (viscosity index) from the same lubricating
:11.
4x200
3X200
1.4674
1. 4682
113
116
0s
97
LLoiwsxy m?‘ .............. _.
I. 1. above rail. alter dewaxing ..... __
EXAMPLE III.
Several samples of an East Texas dewaxed dis
layer
40. 0
37. 5
29. 1
ples IV and V.
from ex-
cent of
Ron
52. O
58. 6
63. 4
92. 0
96. 0
92. 5
Trace
. 004
. 011
tract layer phenol chg.
'
Extract
. 002
. 030
. 090
It was found that the presence of
(within experimental error) on the settling time
or the pour point of the wax containing distillate
_ as seen from the following two tables:
E?‘ect of calcium naphthenate‘on acid settling’
70
1 R. Ll-reirsctive index.
from ra?'.
'
calcium naphthenate had substantially no effect
tillsto
lolvent ratio ________ ..
dish
Percent calcium
covered covery, per
EXAMPLE VI
Several other-‘samples were prepared both with
a waxy and the dewaxed Mid-Continent distillate
lubricating oil (250 SUV at 100° F.) and subjected
to tests similar to those disclosed above in Exam
' to waxy dis
2. L! of waxy rn?
Percent
Percent
Total
phenol re- phenol re- phenol re
covered
0
0. 067
0. 333
0.016% cal
No calcium cium neph
naphthenate thenate added
used
Percent
C8 Ha I?
thanaté) in
rate in DuoSol extraction
Settling time, minutes
Percent Ca naphthenate in
distillate _______________ __
0.0
Dewaxed M-C 250 distillate“ 25
illate lubricating oil were admixed with dimethyl 76 Waxy M-C 25c disti1late____ 27
0.067
20
23
0.33
asas’nes
l?ect or calcium mh?uemte on, your point of
11-0 250 distillate
3
2. The process 0! claimi, wherein said hydro
carbon mixture contains para?in wax; -
3. The process oi claim 1, wherein said lxvdro
Luhricatlnl oil
'
fiu??znsé "15PM
oil
'
Domed 14-0 250 distillate ........ ..
Waxy M-C250distillate ............ ..
'
0. 0
8.};
' a
ase-=
carbon mixture is free irom wax.
5
-
4. The process of claim 1, wherein said hydro
carbon mixture is a lubricating oil.
5. The process of claim 1, wherein said solvent
is iuriural.
' a
6. The process of claim 1, wherein the amount
10 0! calcium naphthenai'e is between about '.02%
and .5% by wt.
We claim as our invention:
1. In a liquid-liquid solvent extraction process
for the separation of a hydrocarbon mixture with
a selective solvent, the improvement comprising
carrying out said extraction in the'presence of
between about .01% and 1% by wt. of calcium
' 'I. In a DuoSol extraction process for the sep- -
aration of a hydrocarbon oil with a mixed solvent
comprising a phenol and propane,‘ theimprove
ment comprising carrying out said extraction in
the presence of .01% and 1% by wt. of calcium
naphthenate, said amount being insumcient'to
cause a stable aolvent-in-hydrocarbon emulsion;
naphthenate in said hydrocarbon mixture, said
amount being insumcient to‘cause a stable sol- 20
vent-in-hydrocarbon emulsion.
MARINUS BUIS.
LEONARD BELCHETZ.