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Патент USA US2136767

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2,l36,767
_ Patented Nov. 15, 1938
PATENT or
~ ,UNITED STATES‘
‘car ‘
' 2,136,767 .
‘METHOD OF REFINING MINERAL OILS BY
MEANS OF AROMATIC. FLUORINE GOM
POUNDS '
Ernst 'I’erres, Berlin, Germany, and Josef Moos,
New York, and Hans Ramser, Long Island City, >
N. Y., assignors to Edeleanu Gesellschaft
m. b. H., a corporation of Germany
No Drawing. Application October 25, 1937,
.
Serial No. 170,973
16 Claims.
This invention ‘relates to the refining of hydro
.
(Cl. 196-13)
especially aliphatic, solvents with respect to_ the
solvent power and selectivity.
carbon olls and more particularly to solvent ex
It is our invention to have discovered that ?u
traction and solvent dewaxin'g of mineral oil by '
__ means 0! organic ?uorine compounds, and this orine exerts exactly the opposite e?’ect of either ‘
chlorine or bromine. For example, para?uoro- 5
,1 application is a continuation in part of'appli
cation Serial No. 23,130, ?led May 23, 1935, for ' aniline and 2.4 di?uoroaniline are more selective
and less powerful solvents than either chloro
Method of re?ning lubricating oils.
This invention contemplates the separation of
para?ine type hydrocarbons from non-para?inic
1° ones by solvent extraction and further the separa
tion of solid hydrocarbons, or wax, from those
which are liquid at low temperatures, by the use
of suitable ?uorinated solvents, and for the pur
pose of, producing high quality lubricatingoils or
low pour point.
In our copending applications Serial Nos. 22,914
and 23,130, we have disclosed‘that certain liquid
or lique?ed organic ?uorine compounds are ‘es
pecially advantageous for dewaxing and that oth
20 ers have special advantages in solvent extraction ‘
of mineral oils.
aniline or aniline.
,
,
This particular action of ?uorinemakes it pos
sible to change the selectivity and solvent power 10
of selective solvents at will. The substitution of
one or more hydrogen atoms in a selective sol
vent by ?uorine increases the selectivity of the
solvent. At the same time, non-selective solvents
may be made selective by the introduction of ?u 15
orine. For example, propane is known to dis—
solve mineral ‘oil entirely at temperatures of from
about +50 to +150” F., except for asphaltenes.
It exerts no distinctive solvent action on low vis
cosity index and on high viscosity index com
pounds, dissolving both with equal facility. If,
In continuation of this experimental work a
large number of aliphatic and aromatic ?uorine
‘_ cind other halogen containing compounds were
'—-’ prepared and‘their behavior and‘ suitability in
however, two or more hydrogen atoms of propane
are substituted by ?uorine the resultant com
solvent re?ning and solvent dewaxlng of mineral
oils were'investigated and became known. Also
certain rules as to the in?uence of the introduc
tion of chlorine and/or bromine into certain ali
acteristics of selective solvents; they preferably
dissolve the aromatic, hydroaromatic and unsat
urated hydrocarbons leaving undissolved the par
3" phatic and aromatic hydrocarbons on ‘they one.
hand and that of the introduction of one or more
?uorine atoms on the other hand became appar
ent as will be noted from the description of our
invention.
35
'
>
The respective selective solvent action of, for
example, phenol and aniline is ‘well known. It
20
pounds, 1, 2, di?uoropropane, l, 3 di?uoropropane
and 1,2, 3 tri?uoropropane--have all the char
25
a?lnic type or high viscosity index compounds. '
Anisol (CHa—-O—-CcH5) and ortho?uoro anisol 30
(CH3—-O—-C6H4F) are corresponding examples in
the aromatic series of hydrocarbons, anisol being
a non-selective solvent and ortho?uoro anisol be
ing selective. ortho?uoro anisol is particularly 35
adapted for the refining of mineral oils and for
the production of high quality lubricating oils as
is also known, that, if one or more chlorine atoms‘ will be shown later on by way of examples. }
are introduced into the phenyl radical, the sol
vent power of the chlorinated compounds, chloro
10 phenol and chloro-aniline, is“‘much greater than
that of ‘phenol and aniline. Solvent power‘ of a
. ‘selective solvent is generally measured by rela
tiouships between amount of selective solvent
used and quality of ra?lnate obtained. For ex
" ' ample, generally one volume of para-chloro
The number of ?uorine atoms which must be
introduced into a non~selectivesolvent in order
to make it selective we ?nd will depend to a large 40
extent on the character and size of the molecule
of the organic solvent. Methane and ethane may
in some respects be considered selective and
therefore the substitution of one hydrogen by ?u
orine produces the highly selective solvents meth 45
phenol will produce a like amount of re?ned oil
yl?uoride (CI-13F) and ethyl?uoride (C2H5F) ;
of the same quality as twovolumes of phenol
will produce; The more powerful a selective sol
whereas‘ it is found that the'corresponding chlo- '
rent is the less satisfactory is usually‘its selectiv
'10 ity, that is, its ability to dissolve only the low vis
cosity‘ index hydrocarbons of mineral oil and to
rine derivatives CHaCl and U2H5Cl are non-selec
tive. In cases 01' a large organic radical, for in,
stance, propyl (C3H1), the introduction of one 50'
leave undissolved all the high viscosity index com
?uorineatom is not su?lcient to produce selec
tivity. Proply?uoride (Cal-11F‘) is still non-selec
pounds, for example;
tive.
<
.
It is known that bromine will act in a similar
-‘- manner to chlorine when introduced into organic,
Only the introduction‘ of more than one
?uorine atom produces the desired selectivity
which we ?nd in (11- and tri-?uoropropane. 55
2
2, 186,767
Likewise, we ?nd the same to be true in the case
of more complex aliphatic compounds. N-bu
tyl?uoride, n-‘amyl?uoride, n-hexyl?uoride and
n-heptyi?uoride are all non-selective, and much
more than one ?uorine atom would have to be
introduced to establish selectivity.
In the case of non-selective aliphatic com
pounds which already contain other halogen than
?uorine, correspondingly more ?uorine must be
10 added because of the antagonistic eifect of chlo
rine and/or bromine. For example, di-bromo
mono-?uoro-ethane, CzI-IaBrzF, was found to be
non-selective,
whereas
oil. was extracted with 100% plus 2X75% by
volume of monobromo-di-fluoro-ethane at 77° F.
by the multiple batch method. After each agi
tating the ra?inate and extract phases were allowed to stratify and were thereupon separated.
The solvent was removed from both phases by
distillation under diminished pressure and the
re?ned oil, after clay treatment at 450° F. with
10% by weight of activated clay, showed the fol
lowing speci?cations in comparison with the un- 10
. treated distillate:
mono-bromo-di?uorq
Untreated
ethane, CzHaBrFa, showed excellent characteris
15 tics as a selective'solvent. (See example 1 be
low). As a general rule, aliphatic halogenated
solvents must contain at least as many, and pref
erably more ?uorine atoms than chlorine and bro
mine atoms'together in order to be selective for
20 extracting low from high viscosity index hydro
carbons, or for separating para?lnic and non
para?inic hydrocarbon groups.v
In order to substantiate further the ‘above
statement the following ?uorine and- ?uorine plus
other halogen containing aliphatic hydrocarbons,
designated as Class A, were synthesized and tested
and were found to be selective with bothiow and
high boiling mineral oil fractions.
Class A.-—Selective ?uorine and ?uorine plus
80
other halogen containing aliphatic solvents.
Methyl?uoride __________ _.
CHaF
Methylene?uoride _______ _. CHaFz
Fluoroform _____________ __ CHF;
Carbontetra?uoride__-_____ CF4
distillate ‘
Rama“
v
15
_ Yield percent by volume ................ ..
°A. P. I _________________ __
Vis. at 100° F ___________ __
Vis. at 210°
100
64. l
23.2
1287
27.5
811
-
92
70
Viscosity index _______________________ __
78
95
Carbon residue __________________________ _ .
1. 9
0. 6
20
Also non-selective aromatic‘ hydrocarbons and
their derivatives may be made selective by the
introduction of one or more‘ ?uorine atoms. It 25
was explained above that the amount of ?uorine
which is necessary to produce selectivity in ali
phatic-halogen-free-hydrocarbons will largely
depend on the size of the aliphatic radical. Mon
o?uoropropane is not selective in distinction.to
di- and tri?uoropropane. This characteristic is
even more evident in case of aromatic hydrocar
bons because of the high solvency eifectpf the
benzol ring. For example monoiluorobenzoL-
0
r
Col-15F, metadi?uorobenzol, in-C8H4F2, and 1,2,4 3"
Mono - chloro - monoiluoro
methane _____ _;. _______ _.
r
"
tri?uorobenzol, CsHaFa, are not selective, neither
is the highly ?uorinated meta-?uoro-tri?uoro
toluol, m-‘CsH4F(CF3), in which fluorine substi
OHaClF
Mono - bromo - mono?uoro
methane____' ________ __‘_. CHzBl‘F
tution was made in the benzol ring as well as in
Mono - 0 hi 0 r o - difluoro
the side chain.
'
,
w
40
However, in certain phenylethers, for.example,-.
anisol, CcHs—O-—CH3, and phenetol
methane _____________ __ CHCIF:
-Mono - 0 hi 0 r o - tri?uoro
methane ______________ ... CClF:
Ethylfiuoride ____________ _. CzHsF
45
sym. Di?uoroethane _____ __ CH2F-—CH2F
which per se are not selective, selectivity could be
produced by ?uorination in meta position to the
sym. Monobromo-mono-?u
methoxy~and ethoxy group respectively. The
corresponding para-derivatives, however, are not
oroethane _____________ _. CHaBr-CHW
2,-monobromo-1, di?uoro
so
ethane _______________ __ CH2Br—CHFg
Mono - chloro - tri?uoroeth-
selective.
-
?uorine solvents as Class B.
ane __________________ __ CHClF-CHFz
Di?uoro-di-chioro-ethane-. CzHzClzF:
'I‘ri?uoro-di-chloroethane_. CzHClaFa
o-fluoroanisol ____________ .._ 0-CcH4(OCI-I3)F
o-?uorophenetol __________ _. o-CaHdOCzHQF
Tetra?uoro - di - chloroeth
55
p-?uoroaniline ___________ __ D-CsH4(NH2)F
ane __________________ __ C2Cl2F4
55
2,4, nitro-di?uorobenzol____. 2,4 CcH3(N0z)F2
ethane _______________ __ CC'IF2—_CH;
2,4, di?uoro-aniline____r____. 2,4- CcH3(NH2)F2
'
Tri?uoro-m-toluidine___‘___. m-CcHdNH?CF:
yl?uoroform) _________ __ CFa-CH:
1,2 di?uoropropane ______ __ CH2F—CHF—CH3
1,3 di?uoropropane______ _. CH2F—CH2—-CH2F
Tri?uoro-m-cresoi‘. _______ _. m-CoH4(OH)CFa
1,2,3vtri?uoropropane ____ _. CH2F—CHF—'CHzF'
excellent re?ning e?ect of this class of ?uorinat
ed aromatic hydrocarbon derivatives when used
as selective solvents.
oropropane ___________ __ CH=Br—CHF-CH;
1,3 mono-bromo-mono-?u
oropropane ___________ __ ~CHaBr—CH-z—CI-IQF
Allyl?uoride ____________ __ CH:=CH—CH2F
60
The following examples are illustrative of the .
1,2 mono - bromo-mononu
‘
The eillcacy of z-monobromo-l-di?uoroeth
we as a selective solvent and as one member of
the above cited Class A will 'now be shown by way
. of speci?c example.
Example 1
75
'
m-nitro-tri - ?uorotoluol ___. m-Csm (N01) (CFa)
1,1,1 'monochloro-di-?uoro
1,1,1 tri?uoroethane (met -
,
The following table lists the selective aromatic
A mixed base, dewaxed' Mid-Continent motor
Example 2
65
A motor oil from Mid-Continent crude was
extracted with 100+ 50 Vol.% orthofluoroanisolr
0-CaH4 (OCHa) F, at —3‘’ F. In each of the two
batches the oil and solvent were properly agitated 70
at the mentioned temperature, the layers were
separated from each other after stratification
- was completed and the solvent was thereupon
recovered by distillation. The properties of the
re?ned oil, after contacting with 10% clay at 450° 75
4
2, 186,767
course limited in that phase separation must
not occur at the dewaxing temperature. In gen
eral we employ from 15 to 35 Vol. % solvent
of Classes A or B and from 85 to 65 Vol. % of
Classes C or D for dewaxing treatment. The de
?uorine containing lique?ed aromatic hydrocar
waxing treatment may either precede or follow
temperature as to produce a separation into two
bon derivative, as a selective solvent, in admix
ture with an organic auxiliary solvent of the
class which is miscible in any proportion with
the selective solvent but not with the oil, at such
the extraction treatment by suitably adjusting ‘phases respectively containing relatively par
the proportions of the selective'and non-selective , a?inic and non-para?lnic constituents, separating
solvents and the temperatures of extraction and
10 dewaxing to avoid-phase separation during the the phases from each other, and recovering the
solvents therefrom.
dewaxing treatment and to avoid precipitation of
5. A method of re?ning a mineral oil compris
wax during the extraction treatment.
ing extracting the oil with a predominantly ?u
_ In the claims the term "selective solvent" is orine containing lique?ed aromatic hydrocarbon
applied to such liquids and lique?ed gases as derivative, as a selective solvent, in admixture
15 have a preferential solvent action for certain with
an organic auxiliary solvent of the class
constituents of ‘mineral oils only, such as the
non-para?lnic or aromatic, hydroaromatic and
unsaturated constituents, for example, as con
trasted with the para?inic group of constituents.
which are insoluble in the selective solvent; the
latter having a higher viscosity index and a high
er A. P. I. gravity than the former, and being
substantially free from oxidizable and gummy
substances which are so undesirable in lubri
cating oils.
By “predominantly ?uorine containing” as ap
plied to a solvent, we mean that the substance
contains fluorine in su?lcient quantity to over
come the e?ect of the presence of other halogens
or organic radicals tending to increase the sol‘
vent power of the substance, such as to give the
substance the properties of the selected solvent
as above de?ned. The term “lique?ed” means
that the substance referred to is used in the liquid
state, whether normally liquid or not.
Reference is made to our companion applica
tion, Ser. No. 170,974, ?led contemporaneously
herewith, wherein the 'method of re?ning mineral
oils with a selective solvent including organic
?uorine compounds is broadly claimed.
‘
We claim the following as our invention: '
spectively containing relatively para?lnic and
constituents, separating the 2.
_ non-parai?nic
phases from each other, and recovering the sol
vents therefrom.
_
‘6. A method of dewaxing a mineral 011 com
prising dissolving the oil in a mixture of a lique
?ed predominantly ?uorine containing aromatic
hydrocarbon derivative and an auxiliary solvent
of the class which is miscible in any proportion
with both the oil and said ?uorinated aromatic
hydrocarbon derivative, the ?uorinated aromatic
hydrocarbon derivative and auxiliary solvent 'be 31
ing present in such proportions as not to produce
a separation into two liquid layers at the dewax
ing temperature, cooling the mixture to below
the desired pour point, removing the precipitated
wax therefrom, and recovering the solvents from
the dewaxed oil solution and from the wax.
7. A method of dewaxing a_ mineral oil com
prising dissolving the oil in a mixture of a lique
?ed predominantly ?uorine containing aromatic
hydrocarbonderivative and an auxiliary solvent
1 of the class of benzol and its homologues miscible
1. A‘ method of re?ning a mineral oil com
- .prising extracting the oil‘with a predominantly
?uorine containing lique?ed aromatic hydrocar
bon compound at such temperature as to pro
duce a separation “into two phases respectively
containing relatively para?inic and non-par
aivilnic constituents, separating the phases from
each other, and recovering the selective solvent
therefrom.
which is miscible in any proportion with the oil
but not with the selective solvent, at a tempera
ture to produce a separation into two phases re
"
2. A method of re?ning a mineral oil com
prising extracting the oil with a predominantly
?uorine containing lique?ed aromatic hydrocar
bon derivative, as a selective solvent, inv'admix
ture with an auxiliary solvent at such tempera
ture as to produce a separation into two phases
respectively containing relatively para?lnic and
non-para?lnic constituents, separating the
‘phases from each other, and recovering the se
with both the oil and said ?uorinated aromatic
hydrocarbon derivative, the ?uorinated aromatic
hydrocarbon derivative and auxiliary solvent be~
ing present in such proportions as not to pro
duce a separation into two liquid- layers at the
dewaxing temperature, cooling the mixture to be
low the desired pour point, removing the precipi
tated wax therefrom and recovering the solvents
from the dewaxed oil solution and from the wax.
8. A method of dewaxing a mineral oil com
prising dissolving the oil in a mixture of a lique
?ed ?uorine containing aromatic hydrocarbon
derivative and an auxiliary solvent of the class
which ‘is miscible in any proportion with the oil 55
but not with said ?uorinated aromatic hydro
carbon derivative, the ?uorinated aromatic hy
drocarbon derivative and auxiliary solvent being
present in such proportions as not to produce a
lective solvent and the auxiliary solvent there-‘ separation into two liquid layers at the dewaxing
rom.
\
3. A method of re?ning a mineral oil compris
ing extracting the oil with a predominantly ?u
temperature, cooling the mixture to below the
desired pour point, removing the precipitated
wax therefrom, and recovering the solvents from
orine containing lique?ed aromatic hydrocarbon
the dewaxed oil solution and from the wax.
derivative, as a selective solvent, in admixture
with an organic auxiliary solvent of the class
which is miscible in any proportion with~the oil
9. A method of producing lubricating oils of
high viscosity index and low pour point com
and with, the selective solvent, at such tempera
ture as to produce a separation into two phases
respectively containing relatively para?inic and
non-para?inic constituents, separating the
phases from each, other, and recovering ‘the sol
vents therefrom. I
'
,
'
4. A‘ method of ‘re?ning a mineral oil com
prising extracting the, oil with aapredomina‘ntly
prising extracting the oil with a selective solvent U
including a lique?ed predominantly ?uorine con- .
taining aromatic hydrocarbon derivative, asv a '
selective solvent, adding to the ra?inate phase so
obtained before recovery of the solvent there-v
from, further amounts of said selective solvent
and an auxiliary solvent of the class which ‘is
miscible in any'proportion with the oil, said sol? '
vents being added in such proportion as noti'tof'ls
5
‘ 2,136,767
produce a separation into two liquid layers at the
dewaxing temperature, cooling the mixture to
below the'desired pour point and removing the
wax therefrom.
,
'
10. A method of producing lubricating oils of
high viscosity index and low pour point compris—
ing extracting, the oil with a selective solvent in
‘ cluding a lique?ed predominantly ?uorine con
taining aromatic hydrocarbon derivative, adding
10 to the ra?inate phase so obtained before recov
ery of the solvent therefrom, further amounts of
the selective solvent and an auxiliary solvent of
the. class of benzol and its homologues, said SO11‘
»vents being added in such proportions as not to
15 produce a separation into two liquid layers at the
dewaxing temperature, cooling the mixture to
below the desired pour point and removing the
wax therefrom.
'11. A method of producing lubricating oils of
20 high- viscosity index and low pour point compris
ing extracting the oil with a selective solvent in
two liquid layers at the dewaxing temperature,
cooling the mixture to below the desired pour
point and removing the wax therefrom.
13. A method of producing lubricating oils of
high viscosity index and low pour point compris~
ing dewaxing the oil in accordance with the
method of claim 6, adding to the dewaxed oil
‘solution so obtained, before recovering the sol
vents therefrom, a further amount‘ of the lique
?ed predominant fluorine containing aromatic 10
hydrocarbon derivative. to produce a separation
into two phases respectively containing relatively
para?inic and non-para?inic constituents, and
separating the phases from each other.
14. A method of producing lubricating oils of 15
high viscosity index and low pour pointcompris
ing dewaxing the oil in accordance’ with the
method of claim 8, adding to the dewaxed oil solu
tion so obtained, before recovery of the'solvents
therefrom, a further amount of the lique?ed
predominantly ?uorine containing aromatic hy
cluding a lique?ed predominantly ?uorine-con
taining aromatic hydrocarbon derivative in the
two phases respectively containing relatively par
presence of an auxiliary solvent of the‘ class of
aifinic and non-paraf?nic constituents, and sep
arating the phases from each other.
benzol and its homologues, adding to the ra?i
nate phase so obtained before recovery of the sol
vent therefrom, further amounts of the selective
solvent and auxiliary solvent, said solvents being
drocarbon derivative to produce a separation into ‘
25
15. A method of dewaxing a mineral oil com
prising dissolving the oil in from one to ten vol
umes of. a solvent containing a non-selective
?uorinated aromatic hydrocarbon derivative, the
amount of fluorine therein contained in the pro 30
temperature, cooling the mixture to below the portions used being insu?icient to cause a sepa
desired pour point and removing the wax there- > ration of the solution into two liquid layers at the
added in such proportions as not to produce a
30 separation into two ‘liquid layers at the dewaxing
from.
-
,
12. A method of producing lubricating oils of
85 high viscosity index and low pour point com
prising extracting the oil with a selective solvent
including a lique?ed predominantly ?uorine con
taining aromatic hydrocarbon derivative in the
dewaxing temperature, cooling the mixture to
about the desired pour point, removing the pre
cipitated wax therefrom, and recovering the sol 35
vent from the dewaxed oil solution and from the
Wax.
.
16. The method of ‘dewaxing mineral oils de
presence of an auxiliary solvent which is'miscible scribed in claim 15 wherein the solvent consists
with the oil, adding to the rai?nate phase so ob-v exclusively of non-selective
hydrocarbon derivatives.
tained before recovery of solvent therefrom, fur
ther amounts of the selective solvent and auxil
iary solvent, said solvents being added in such
proportions as not to produce. separation into
?uorinated aromatic
_ '
ERNST TERRES.
'JOSEF MOOS.
HANS RAMSER.
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