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Патент USA US2124606

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2,124,606
Patented July 26,
; UNITED‘ STATES ‘PATENT OFFICE
2,124,808
I
I
.rnooass roa narmmc man. on)
Johannes Arnoldus Buchel and Reyerus Nicolaas
Jan Saal, Amsterdam, Netherlands, assignors to
Shell Development Company, San Francisco,
Calif., a corporation of Delaware
No Drawing. Application November 6, 1933, Se
rial No. 896,910. In the Netherlands July 23,’
1928 ‘
" 5 Claims.
(on. 196-13)
‘ This invention relates to extraction methods of
re?ning mineral oils, and is particularly con
cerned with methods for extracting such oils by
means of a selective solvent in the presence of
5 benzol or an equivalent auxiliary solvent.
It has been known in the art that crude pe
troleum .oils, lubricating, transformer and spin
dle oils, kerosenes, heavy or light naphthas, etc.,
from relatively volatile liquids chemically or
physically related to benzol (such as aromatic '
hydrocarbons) ,- and which usually are miscible
in all proportions with the main solvent and the.
oil being treated, the invention is not intended
to be limited to such solvents. Other substances,
such as ether and chloroform. were found to
possess the property of improving extraction
can be separated into groups-‘of components by ~characteristics of various liquids which‘ may be
used as the main solvents, and these relatively 10
10 extraction with suitable selective solvents. A volatile liquids ‘are to be considered as equivaé
large number of such solvents are available for
lents of benzol for the purpose of this, specifica
the purpose. The present invention is particu
tion and the appended claims.
larly (but not exclusively) directed to an im
It will be understood, therefore, that the pres
provement in, methods of extracting mineral oils
15
with furfural or acetone, which improvement is ent invention is to include within its scope the
analogous to the one claimed for SO: in Patent extraction processes employing a selective sol
No. 1,945,516, which issued upon our copending ,vent (which may be a\single substance or a
application, Serial No. 379,310, filed July 18, 1929, mixture of suitable substances) and wherein ex
traction is carried out in the presence of an
of which this is a continuation in part.
,
The invention is‘ based on the discovery that auxiliary solvent having an action similar to that
20
the extraction characteristics ‘of ‘substantially of benzol, i. e. causing an increase in the efii
any solvent which is capable of separating a’ ciency of separating a mineral oil into its com
mineral oil into two- component groups—one ponents, which may be the naphthenic and
more soluble therein than the other-can be‘ para?inic portions of the oil.
Generally speaking,'the e?iciency of extrac 25
markedly modi?ed by introducing, for example
tion
is determined by the solvent power and the
into the extraction mixture, a quantity of benzol
or other suitable substance, such as toluol and/or selectivity of the solvent (or solvent mixture)
30
other aromatics, or ether, or chloroform, which ~ with regard- to the components of the mixture
will hereafter be referred tov as, the auxiliary ' being extracted. The efficiency maybe meas 30
ured by and compared with ‘the relative yields
‘solvent.
I
The type of selective solvents whose effective—
ness as the extracting agents in re?ning mineral
oils can be improved by practicing this inven
tion is illustrated by liquid S02, furfural, and
acetone. These speci?c examples represent,
of the ra?lnate of- the desired purity in cases
where the mass or volume of the main or selvecf '
tive solvent is kept constant.
If the extraction e?iciency is to be compared
in cases where the relative yield is ?xed, whilst 35
however, only typical solvents of a large number . also the mass or volume of the main or selective of known selective solvents capable of separating solvent. is kept constant, then the quality of the
mineral oils into aromatic and non-aromatic raf?nate may be taken as the measure of the
components (sometimes referred to as naph
The e?lciency of the various extractions mayv
thenic and parafilnic or as non-para?inic and
para?inic), which. solvents are intended to be also be measured by comparing ‘the extent to
‘which the solvent is conserved, if the same raf
within the scope of this invention.
Likewise, the auxiliary solvents, whose 'pres-, nnate is made with orwithout the use of the
ence in the extraction mixtures improves the auxiliary solvents described in this speci?cation. ,
eiilciency.
45 _ efficacy of extraction, are merely represented by
benzol, and aromatic hydrocarbons, in
general, '
‘
'
'
By applying this inventio , i. e. by using a
main- solvent in the presence of an auxiliary sol
or by ether, or by chloroform, or their mixtures, vent, it becomes possible therefore in extracting
but may be selected fromv a number of other ?uid hydrocarbon oils to improve the quality and/or
substances which produce the desired effect, and a quantity of the ra?inate and/or to conserve the 50
which can be relatively easily separated from the main solvent.
_
‘ '
material being treated, for example by distilla
tion, and have no detrimentaleii'ect on the re
, 'ilned products.
-
It should be noted that, while it may be pref
erable sometimes to select the auxiliary solvents
The method of this invention also provides-a
means for improving mineral ,oils having rela
tivelyv low contents. of naphthenic (aromatic)
components, which contents it is vdi?icult or im
,2
2,124,608
possible to reduce still further by extraction
withv
the main solvent alone.
The improved qualities of the ra?inate may
ity of the ramnate, ve. 3. its anti-knock property,
in case of the extraction of relatively heavy hy-“
be controlled, e. g. by determining the'viscosity drocarbons withthe aid of benml as auxiliaryv
index, the no or refractive index, or the stability.
In order to demonstrate the effectiveness of
against oxidation. All these properties are de
solvent.’
‘
-
'
.
c
,
5
thet new process the following example may be set
pendent on the ratio- between aromatics (non
paramns) and the para?ins.
A number of samples of a lubricating oil hav
The increased extraction eihciency of the mixed ' ing viscosity index '—59 (indicating that the oil
solvent process, as compared with the e?icien'cyu had arelatively high content of aromatics or a~
of the corresponding'single solvent process,’ is low content of para?lnic hydrocarbons) were
'10
apparently due to the favourable effect of the
thoroughly contacted with various quantities of
furfural,‘ and of furfural-benzoi, of furfurale
non-para?inic and para?inic components of the . chloroform,
‘and of furfural-etherj mixtures; in
oil in the extract and ra?lnate phases; in other each case the‘ ra?inate (upper) layers‘ were sep
15
words, the content of the components‘ preferen
arated, and the'viscosity and retracting indices
tially soluble in the selective solvent as compared of solvent-free'portions (raiilnates). were deter
with that in the rafiinate phase-is increased in mined.‘ The following table contains the perti
the presence of the auxiliary solvent, vso that y
. “mixed solvent on the distribution ratios of the
nent data:
20 when a mixed solvent is used it becomes possible
>
,
-
'
-
20
sometimes, under suitable temperature condi
tions, to produce from'an oil a greater quantity
Y
‘I , of the raiiinate, which is richer in paraiiinic com
ponents than it would have been possible to ob;
a?“
30
tain if only themain solvent were used.
.
.
,
‘
-
1
—
. Oil
Furiural ' Benzol
05%”
Ether
parts’
parts ,_ parts,
parts
‘parts
'
»
Ra?inate
" 2°
'
viscosity
0
index
‘
'25
From the natureof the auxiliary solvents it ,i '
100-_
may beseen that their‘additionrto the mainsol~
ntreated oil‘
150
150
vvent would normally"pro_d_uce .a solvent mixture _ . - 100
100.
with av greater solvent ‘power for the oilz'than; ‘100,
that'of the main solventso thatuthe selectivity
*belimpaired. Although this'is not necessarily a
.
1. 5115
_ .. . .. . . _
. _ _ _-
+11 ‘
1.5100
+21
1. 5082
+31
.150
1.5125
' +11
100
300
l. 5120
+16
300 I
1.5081‘
.+25
1. 5058
. +33
100
_______ ._
+3
- +7
-100
300 '
100 ‘
35 ful in increasing the extraction e?iciency so far > ,
—59 '
1.5160
1.5136
150
150’
1100
disadvantageas a’main solvent, with an auxil
iary solvent added thereto in any case will be use-,v
.... _-
150
100 »
of the solvent-and the yield‘ of theramnatemay '
1.5366
None
, 50
31!!
100
_300
100
, 300 '
100 -
1.5034'
_
+5; '
1.5120
+1
1. 5032
300, v
________ --
-
30
'
I
+37’
1. 6060
‘ +30
asv the quality’ of the ra?lnate is concerned, it isv
possible ‘to improve this impaired selectivity by .
suitably lowering. the, temperature of extraction
with they resultantadditional increase inthe e?l
35
These- results showtthat the presence of an .
auxiliary solvent,,such‘ as vbenzol, or chloroform,
or ether, causesa-marked improvement in the
ciency of extraction so far as eg the yield of
refined, product; the results also demonstrate
‘that .non-para?inic components are extracted in‘
the raf?nate is concerned. ; Ingeneral, the ex
traction temperature is so selectedyas to create
optimum conditions. from .‘the view points of
40
preference to, para?inic‘ components when fur-,
fural-benzol mixture is used instead of furfural
economy, yield, purity of the ‘products, etc. = v
alone,
The operating details of putting the invention
-
._
'
>
v'
.
. The following example further illustrates some - 45
into practice, such as temperatures, pressures,
5 etc. may vary in different cases, depending upon . of the effects of vextraction vtemperature upon
speci?c properties of the substances used in each the e?‘lciency of extraction when a motor oil having a viscosity index -.5 is extracted. .
case, or may be controlled by some otherconsid- ,
'50
eration. For example with a so-called batch
extraction the auxiliary solvent may. berhixed
with "the oil undergoing'treatment either before,
'
. v
-
>
‘
Fur- Ben- Chloro-
Tempera
fural
ture of ex-
zol
parts parts
or'at thetime the oilis contacted with the main '
. solvent; the wholeor a part of 'the'auxiliary'sol
55 vent maybe mixed vwith the main solvent prior ,
to contacting it with the oil. -
i
on
parts
*
_
.
form
parts
'
‘
.
100 ' '
tinuous countercurrent manner, i. e. passing the
’ with the oil being extracted through a mixing
h settlin'gzone and adding atleast a portion of the“ I
"iscosity
index
. 66
64
65
67
34
41
, 29
61
100
15
64
39
65
29
72
.
,
80
72
- 100
100
60 main solvent'countercurrently to and in contact
.
yield’.
100
50
Ra?‘inate
traction ‘'0. Percent
.
100
100
,
-It_ is ., preferable, althoughnot. necessary, to
I operatethe process of this invention in ya con
-
21 '
24 '
55
35
45
,
35
60
"These data demonstrate that the yield and'the
auxiliary solvent to the-oil-ma'in solvent mixture ‘degree of re?nement of the 'ra?inate' may be con
at apoint, or points, valong the mixing-settling » trolled at will by regulating the extraction tem- ,
1
65' zone, and preferably at, such a place, where suchv
"perature and- the relative‘ quantity and the com¢
~ :‘-"an addition of the auxiliary'solvent would be position of the mixed" solvent, and the selective
most effective. The extract and ra?inate phases‘
' are separated, usually by gravity, and the-main
and auxiliarysolvents or the main solvent only" z'
-
1:715
solvent can be__'conserved, when used with an
auxiliary solvent for producing the railinate hav
ing a ?xed viscosity index. a
are then'removed from each of the phases'by '
Similar results ‘may be obtained when extract
vdistillation ‘(both solvents beingremoved together ' ing mineral oils with other selective solvents,
or in separate fstagesy'or by‘ some other suitable ' such as acetone, ‘in the presence of an auxiliary
‘means. The separated solvents'may be- contin
- olvent of the type of benzol, chloroform or ether,
ually
inthereused.
raf?nateThe
if this
auxiliary
solventsolvent
improvesthe
may: bequalleft 1. e. either a somewhat polar or more often a non
polar solvent, but whose action is manifested in
v
.
2,124,606
the extraction processes through an increase in
the extraction efficiency.
A series of extractions similar to those demon
strating the use of furfural-auxiliary solvent mix
tures were‘carried out using acetone as the main
solvent. The results are tabulated below.
'
Railinate
on ?g; Benzol ,ggggg,
parts] parts parts parts an
1.”
Temp.
Yield, of ex
percent tracéion
100
400
1'
.8719
1. 4194
sbt 50
100
300
100
.8703
1.4790
(10 60
—20
100
240
120 ....... .- .8713
1.4789
do 60
~20
100
300 ...... __
100
.8707
20
1.4787
~20
The original oil extracted with acetone was-an
Edeleanu ra?inate having d2o=.8765 and n§’-,°=
1.4820.
7
I
The particular feature of the extractions with
20 acetone and acetone-auxiliary solvent mixtures
was that while the ?rst extraction could be car”
ried out at about 20° C., the last three extractions
required temperatures of about -20° C. in order
to produce either about the same or better yield
of the raf?nate than obtained with acetone alone.
As indicated by gravities and refractive indexes
3
ously diluted. On the other hand, oil which may
be regarded as being viscous at ordinary‘tem
peratures (say, over 80 seconds at 100° F.~Say
bolt universal) would become easy iiowing- at
" '
the slightly elevated temperatures of extraction
with furfural, for example, or some other selec
tive solvent, so thattheir dilution for thenpur
pose of reducing the viscosity would be unnec-I >
essary. The use of auxiliary solvents in these
cases would serve only the purpose of improving 10
the extraction e?iciency through the e?’ec't of
such solvents on the distribution of the com
ponents being extractedbetween the extract and
ra?inate phases, no dilution being necessary.
Relatively light aromatic extracts, such as those 15
boiling within gasoline or kerosene ranges, which
can be later removed‘ from the products of ex
traction, may be used with advantage ‘as equiva- >
lents of benzol in extracting the oils which are '
not viscous at the extraction temperature. We. claim as our invention:
3
‘
-
1. In an extraction process for re?ning hydro
carbon oils, the steps of bringinga liquid hydro
carbon oil into contact with a selective solvent‘
for- non-para?inic hydrocarbons, in the presence 25
of an auxiliary solvent selected from the group
consisting of: benz'ol and toluol, under conditions
of the ra?inates the process of this invention con
causing the formation of liquid extract and raf
stitutes a decided improvement of the known _ finate phases, and separating the said phases.
process using only acetone as a solvent.
\ 2. In an extraction process for separating a 30
It has‘ been also found that various mixtures of mineral hydrocarbon oil into two component
selective solvents, such, for example, as liquid groups, the steps of contacting a liquid mineral
SOz-furfural, can be successfully used for ex
hydrocarbon oil with furfural in the presence of- v
tracting mineral oils in the presence of either the , toluol under conditions causing the formation of
35
While it is practical and may be desirable in liquid ra?inate and extract phases, and separat
individual auxiliary solvents or their mixtures.
some cases to carry out the extraction of mineral
ing said phases.
7,
. '
' 3. In‘ an extractionprocess for separating a
oils ,by means of the main and auxiliary solvents hydrocarbon oil into portions having different
at such temperatures, at which the auxiliary sol
degrees of paramnicity, thesteps of bringing a
vent is. only partially‘ soluble in either the main .liquid hydrocarbon oil into contact with furfural
40 solvent or theoil being extracted, or in both, it,
in the presence of an auxiliary solvent selected
should be noted that the extraction process of .from
the group consisting of: benzol and toluol,‘ F I
this invention may be operated at the tempera
tures at which the auxiliary solvent becomes under conditions causing the formation of liquid
miscible in all proportions with either the main, ra?‘lnate and extract phases, and separating the
45 1. e. selective, solvent or the oil, or both.
said phases.
'
‘
-
'
.
4. In an extraction process for separating a
The main solvents used in this extraction proc
oil into portions having different
ess to separate a mineral oil into two component ' hydrocarbon
degrees of para?lnicity, the steps of bringing a
groups as defined, have the common characteris
tic that, like liquid S02, acetone or 'furfural, at
50 the extraction temperature they are completely
miscible only with the non-para?lnic component
group. With the para?inic component group
they are miscible only to a limited extent. Ex
amples of- such like selective solvents are: nitro
55
methane, propionltrile, dimethyl sulphate. di
methyl sulphite, methyl formate and several
alcohols or esters at suitable temperatures.
, With reference to what has been stated above
in respect to the auxiliary solvents, it deserves
60 notice that the particular effect of auxiliary sol
' vents on the extraction efficiency is independent
of the ‘phenomenon of dilution of the mixture
being extracted, whichv dilution may or may not
take place, depending upon viscosities of the
66 liquids involved. Therefore, the process is e?ec
tive not only with oils which may be viscous at
extraction temperatures, but also with oils which
are-easy ?owing or non-viscous at such tempera
tures. For example, when liquid S0: is used as
70 selective solvent, the extraction temperatures are
relatively low, so that certain viscous‘ oils may
have to be diluted with light solvents, while less
viscous oils can be extracted without being previ
liquid hydrocarbon oil into contact with acetone
in the presence of an auxiliary solvent selected
from the group consisting of: benzol and toluol,
under conditions causing the formation of liquid -
ramnate and‘extract phases, and separating the
said phases.
5. In an extraction process for separating a
hydrocarbon oil into portions having di?erent
degrees of para?lnicity, the steps of contacting a
stream of liquid hydrocarbon ' oil countercur
rently with a ‘stream of a. selective solvent fornon
para?inic hydrocarbons under . conditions-caus
ing the formation of liquid ramnate and
phases in the presence of an auxiliary ‘solvent
selected from the group consisting of: bensoland
toluol, a portion'oniy of said auxiliary solvent
being initially introduccdinto the oounter?ow
ing streams with the fresh ‘selective ‘solvent, and
another portion being
._ into“ said
streams at a point spaced from the'pointof in
troduction of the selective solventin the-‘direc
tion of the point of introduction "offthe'initial "'9
oil, and separating said phases. ' ~
JOHANNES ARNOLDUB
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