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Nov. 5, 1946.
I
~
)Aj FARKAs ErAL
PROCESS FOÉ OXIIDATION
_ Filed Aug. 16, 1‘943
SWQLOUDAÄÈ
2,410,642"
2,410,642~A
Patented> Nov.> 5, v1946
UNITED STATES) PATENT ori-fics*
2,410,642
_
`
‘
Paocnss Foa OXIDATION ~
„ Adalbert Farkas andmhur F. stanley, Jr., Lang
Beach, Calif., asslgnors to Union (lil‘Company- ,
_ of California, Los Angeles, Calif., a corporation'
of California
Application August 16l 1943, Serial No. 498.775
l 13 Claims. 4(Cl. 260-593)
1
,
'Í‘his invention relates to partial oxidation prod- ñ
2>
.
the partial oxidation products being removed con
tinuously by processes involving fractional dis
ucts and methods of producing such products
from hydrocarbons or hydrocarbon oils, such as
tillation, extractive distillation, azeotropic 'dis
petroleum `and petroleum fractions. The inven
tion_also relates to alcohols and/or ketones and
tomethods of producing such alcohols and/or
ketones from non-aromatic cyclic hydrocarbons.
The invention also relates to polyvalent metal
salts of phosphate. esters of the partial oxida
tion of hydrocarbons or hydrocarbon'fract-ions 10
and to lubricating oil compositions containing
tlllation, solvent extraction or adsorption from the .
slightly oxidized hydrocarbon or. hydrocarbon
fraction at such a rate that only minor propor->
tions of these primary oxidation products are
further oxidized, thus permitting the production
of relatively high yields oi’ partial oxidation prod
ucts.
-
'
»
'
'v
ì
The invention' also comprises separating the
products of‘ partial oxidation into substantially
An object of the present invention is to further
the progress in preparing oxygenated hydrocar
cohols or ketones by relatively simple processes
these metarsalts.
,
`
pure compounds or into fractions comprising al- _
involving physical and/or chemical treatments,
l , bon derivatives from hydrocarbons or hydrocar
the particular method employed in a, given case
depending upon the character andthe complexity `
of the oxygenated products to be separated,
bon fractions, using' in this case a method which
limits the extent of oxidation thereby limiting
the number and complexity of oxygenated prod
ucts thus allowing the more ready segregation
of the oxygenated -derivatives into pure com
pounds.
The invention further comprises converting
20 said partial oxidation products into lubricating
-
oil addition agents 'and blending >said addition
agents with lubricating oil to produce lubricating
Another object of the invention is to prepare
from a single hydrocarbon or from a given hydro
oil compositions having improved iilm strength,
carbon fraction, such as a relatively narrow boil
anticorrosion and detergency characteristics.
ing range hydrocarbon fractionI prepared from 25
Alcohols and ketones having five or more car
petroleum, cyclic and/or acyclic alcohols and ke
bon atoms per molecule are particularly valuable'
tones with a minimum production of .the more
highly oxidized products, such as aldehydes, acids,
products. ` The ketones are used in fthe'synthesis
of chemicals and perfumes, as solvents for lac»
hydroxy acids etc., and ultimate oxidation prod
quers, gums, resins, nitrocellulose, etc., and for
30 the production of alcohols. The alcohols‘have
ucts such as water and carbon dioxide.
A further object of the invention is to provide
use in perfumes, as antifoaming agents, as sol- .
a method fgr producing alcohols and/or ketones.
in substantial quantities from hydrocarbons.
A further object of our invention is to ‘prepare
cyclic and/or acyclic alcohols and ketones hav 35,
vents for dyestuffs, oils, waxes, gums, resins, etc.,
in the production of esters, acids, etc., as emulsi
fying agents, and in textile iìnishing compositions.
ing ñve or more carbon atoms per molecule from
Also alcohols produced by our oxidation process
may be reacted with phosphorus pentasulflde to
non-aromatic cyclic hydrocarbons, whether used
form the corresponding dialkyl thiophosphates
alone or mixed with acyclic or aromatic hydro
and the products of this reaction may then be
carbons boiling at or near the same temperature
reacted with metals or metal oxides to form the
as the non-aromatic cyclic hydrocarbons, by a 40 corresponding metallic salts of the dialkylthio
phosphates and/or dicycloalkylthiophosphates
process involving oxidation with oxygen, air, or
other oxygen-containing gas.
and these compounds are excellent lubricating oil
A particular object of our invention is to pre
additives.y When blended with mineral lubricat
pare a lubricating oil addition agent and to pre
ing oils in amounts in the order of from about
pare a lubricating oil composition comprising a 45 0.1% to about 10% or more the metal dialkyl-_
thiophosphates impart high film strength to the
major proportion of a lubricating oil and a minor
proportion of an addition agent, said addition
oil, they improve the stability of they oil toward
agent being a polyvalent metal salt ofthe reac- „
oxidation, reduce bearing corrosion in an enginev
and, when used in conjunction with other addi
tion product of phosphorus pentasulñde or phos
phorus pentoxide and the cyclic and/or acyclic 50 tives having detergency characteristics, ,they
markedly increase the detergency of the -lubri
alcohols produced by partial oxidation of hydro
cating oil blends containing the latter additives.
carbons.
Such other additives, which may be employed in
Other objects, features and advantages of our
amounts in the order of from about 0.1%‘to about
invention will be apparent to those skilled in
the art as the description'thereof proceeds and 55 5.0% of the finished lubricating oil composition,
from the examples submitted herein.
The invention comprises oxidizing a hydrocar
bon or a relatively narrow boiling range hydro
may be oil-soluble polyvalent metal soaps of vari
ous carboxylic acids, such as phenylated carbox
ylic acids, e. g., calcium phenyl stearate and mag
nesium phenylstearate, chlorinated and phenylat
carbonA fraction in the liquid phase and under con
ditions such that only partial oxidation occurs, 6.0 ed îatty acids, e. g., calcium dichlorophenylstea
2,410,642
.
<3
\
rate and zinc dichlorophenylstearate; oil-soluble
polyvalent metal salts of oil-soluble petroleum
. '4
one of these metals to» form the corresponding
polyvalent metal salt of the dialkyl or dlcyclo
sulfonic acids, such as the calcium salts of the
Y alkyl phosphates.
oil soluble sulfonic acids prepared by treating
Alcohols which are useful for the above pur
petroleum oils, such as lubricating oil, with strong Cl poses are in general difficult and costly to pro
sulfuric acid. Other oil-soluble polyvalent metal
duce, their preparation requiring the use of ex
salts of these acids may also be used, such as
pensive chemical processes.
those in which the metals may be strontium,
We find that we
may produce alcohols, both cyclic and acycllc,
barium, magnesium, zinc, manganese, aluminum,
containing ñve or more carbon atoms per mole
10 cule by a relatively inexpensive and simple proc
and lead.
i
Lubricating oils which may be blended with our
css involving partial oxidation of certain hydro
organic phosphate addition agent, or with our
carbons or hydrocarbon fractions, separating the
agent together with one of the above disclosed
products of partial oxidation from the unoxidized
‘ other additives having detergency characteristics,"
hydrocarbon and subsequently segregating the
include al1 mineral lubricating oils because we 15 partial oxidation products into fractions consist
:dnd that the valuable characteristics of our ad'
ing primarily of alcohols- and ketones. The
dition agent are imparted to all mineral lubricat
ketones, if desired, may be subsequently converted
ing oils. We prefer to employ treated oils such
into the corresponding alcohols as indicated here
as acid reñned `Westem lubricating oils, highly
inbelow.
solvent reñned Western lubricating oils or We may 20
In carrying out the production of partial oxi
use Eastern lubricating oils such as Pennsylvania
dation products according to the principles of our
oils.
invention, the hydrocarbon or narrow boiling
' The alcohols which may be prepared by the
range hydrocarbon fraction to be oxidized is
partial oxidation of hydrocarbons and which may
blown with oxygen, air, or other gas containing
'be employed to produce >desirable lubricating oil 25 free oxygen until the proportion of hydrocarbon
additives when treated in the above manner in
molecules oxidized is about 0.1% to about 10%
‘ clude the cycloaliphatic alcohols containing from
or preferably about 0.5% to about 5.0% of the
. ilve to about twelve carbon atoms and preferably
total molecules present and the concentration of
seven to ten carbon atoms per molecule and the
oxygenated molecules is thereafter maintained at
acyclic aliphatic alcohols containing from seven 30 an approximately constant value by continuously
to about eighteen carbon atoms and preferably
withdrawing portions of the slightly oxidized hy
eight to fourteen car-bon atoms per molecule.
drocarbon material present in the oxidation ves
The lubricating 'oil additives may be prepared ' sel, separating the oxygenated molecules from the
by heating and agltating a mixture of 4 gram
unoxidized hydrocarbon material, as by frac
moles of the alcohol with 1 gram mole of phos 35 tional distìllation, and returning the latter mate
phorus pentasulfide at a temperature of 250° F.
rial to the oxidation unit together with sufficient
to 300° F. until the PzSs is completely dissolved,
additional feed to maintain an approximately
indicating that it has reacted completely with the
constant level in this vessel. The volatile mate
alcohol and the product of this reaction is main
rials, such as any oxygenated degradation prod
tained at the same temperature and agitated wtih 40 ucts, pass out of the unit with spent air or other
one gram mole of an oxide of one of the polyvalent
gaseous oxidizing medium. This operation in
metals disclosed hereinabove or with one gram
volving the separation of oxidation products from
atom of the polyv‘alent metal itself to form the
unoxidized hydrocarbons can be considered to be
metal salt of the thiophosphate ester. The first
a stripping operation.
reaction results in the formation of relatively
Although we may treat any hydrocarbon or
large proportions of the dialkyl or dicycloalkyl
narrow boiling hydrocarbon fraction We prefer
thiophosphates represented by the following for
to employ a non-aromatic cyclic hydrocarbon, or
mula in which R represents the hydrocarbon
a narrow boiling range hydrocarbon fraction,
radical of the alcohol:
containing at least one non-aromatic cyclic hy
drocarbon. Thus, hydrocarbons which may be
¿in
..
s=r-on
used as feed include cyclopentane or any of the
\on
mono, di, tri, tetra, or pente. alkylcyclopentanes,
such as methylcyclopentane, dimethylcyclopen
It is known vthat other acid thiophosphate esters
are produced by the above reaction but their pres- >
ence in the reaction mixture apparently does not
degrade the quality of lubricating oil additives
prepared from this mixture. Formulas for `the
other esters which are present in the reaction
product of an alcohol and phosphorus penta
sulñde in `relatively small proportions are:
tane, methylethylcyclopentane, etc.; cyclohexane
or any of the mono, di, tri, tetra, penta, or hexa
alkylcyclohexanes, such as methylcyclohexane,
dimethylcyclohexane, diethylcyclohexane, etc.;
naphthenyl cyclopentanes or cyclohexanes con
taining one or more naphthenyl groups, such as
bicyclopentane, bicyclohexane and alkyl substi
tuted bicyclopentanes and bicyclohexanes, such
as methylbicyclopentane and methylbicyclohex
ane; hydro aromatics, such as decahydronaph
thalene and alkyl substituted hydroaromatics,
Mixtures
of two or more of the above disclosed naphthene
hydrocarbons may be employed as feed if desired
when such mixtures have boiling ranges not wider
than about 50° F. and preferably not Wider than
I moles of an aliphatic or cycloaliphatic alcohol 70 about 10° F. Also hydrocarbon fractions contain
may be reacted with one mole of phosphorus
ing at least one of the above disclosed naphthene
Phosphorus pentoxide may be used in place of
the phosphorus pentasulñde in the production of
lubricating oil addition agents and in this case
the oxyphosphate esters are formed. Thus 4
pentoxide to produce the corresponding dialkyl
or dicycloalkyl phosphates. These phosphate
esters may then be reacted with one of the above
65 such as methyldecahydronaphthalene.
hydrocarbons together with non-naphthenic hy
drocarbons, such as for example, paraiiins or ole
fins or aromatics, or mixtures of these non-nanh
'
2,410,842 '
our invention; lSuch >fractions should have a boil
' logs of these compoundspthe alkenyl cycloali
. -ing range not wider ,than about 50° F. and >prei'
erably notwider than about 10° F;
cyclopentanol, ethenylcyclohexanol, ethenylcy
phatic alcohols and ketones, such as ethenyl
' Other hydrocarbons which may desirably be
clopentanone and ethenylcyclohexanone and the '
treated'by our _process include the> cycloolenn
higher homologs of these compounds. such as
hydrocarbons- and the naphthene hydrocarbons
the isomeric methylethenylcyclohexanols, meth
containing oleflnie substituents,` narrow boiling
ylethenylcyclohexanones, ethylpropenylcyclopen
range mixtures of the oleilnic cyclic hydrocar
bons or narrow boiling range fractions contain
tanol, etc. The aliphatic alcohols and ketones
>which may be produced by our process include
A ing one or more of these oleflnic cyclic hydro
pentanol, pentanone, the various isomeric meth
yl- -and ethyl-pentanols and pentanones, hex
anol `and hexanone, the isomeric methyl-, ethyl-,
propyl-, and isopropyl- hexanols and-hexanones;
carbons. Thus we may employ cyclopentene and
cyclopentadiene and the mono, di, tri, etc., alkyl
cyclopentenes and cyclopentadienes; cyclohexene
and cyclohexadiene andthe mono, di, tri, etc.,
dialkylpentanols, pentanones, hexanols, and hex
' alkyl cyclohexenes and cyclohexadienes; mix 15 anones and higher >homologs of these com
' tures of these hydrocarbons when such mixtures
pounds such as trimethylhexanol, dimethyleth
have boiling ranges not wider than about 50° F.
and preferably not wider than about 10° F.; hy
ylhexanone, etc. Oleflnic alcohols and ketones
which may be> produced include hexenol and hex
enone; the various isomeric methyl-, ethyl-, etc.,
drocarbon fractions containing one or more of
the above mentioned cyclooleflns or cyclodiole
20
fins together with one or more dissimilar hydro
. carbons, such as parafilns. naphthenes, oleflns
Aand aromatics; alkenyl -substituted cyclopentanes
and cyclohexanes, such as ethenylcyclopentane,
ethenylcyclohexane,
etc.; - allienyl
hexenols and hexenones; heptenol, heptenone
and the various alkyl substituted heptenols and
heptenones; higher molecular weight oleñnlc
alcohols and ketones including octenol, octenone,
nonenol, nonenone, decanol, decanone, and the
substituted 25 alkyl substituted derivatives of these alcohols
and ketones, such as the various isomeric meth
mono, di, tri, etc., alkyl cyclopentanes and cyclo
hexanes, such as methylethenylcyclopentane, di
methylethenylcyclohexane, etc.; mixtures of such
alkenyl substituted cyclopentanes, cyclohexanes,
yl-octenols, methylnonenones, methyl-ethylnon
enols, etc.
The above disclosed alcohols may be used sin
alkyl cyclopentanes and alkyl cyclohexanes; and 30 gly or mixtures of two or more of these alcohols
hydrocarbon fractions containing at least one
' may be reacted with phosphorus pentasulñde or
of the alkenyl derivatives, such mixtures or frac
phosphorus pentoxide and the resulting reac
tions having relatively narrow boiling ranges as
tion product reacted with a polyvalent metal or
specified hereinabove for mixtures or fractionsmetal oxide to produce Aa. desirable lubricating
35 oil addition agent. Moreover, the ketones listed
suitable for treatment in our process.
Although, asis indicated hereinabove, we may
above may be reduced to the corresponding alco
treat a hydrocarbon mixture or fraction com
hols and these alcohols may then be employed
prising‘at least one non-aromatic cyclic hydro
as above indicated in the production of lubricat
carbon together with paraflìn, olefin and aro
ing oil addition agents.
matic hydrocarbons boiling at or near the boil 40
Hydrocarbons or hydrocarbon fractions such
ing point of the non-aromatic cyclic hydrocar
bon, it is preferable to remove substantially all
of the aromatic hydrocarbons before carrying out
as those specified hereinabove may be oxidized in
the liquid phase by blowing or otherwise con
tacting them'with oxygen, air or other oxygen
said treatment. _ Methods for separating and/or
containing gaseous mixture. The liquid hydro
removing the aromatic hydrocarbons from such
mixtures include azeotropic distillation, solvent
extraction, extractive distillation and, in the case
of hydrocarbon 'fractions which do not contain
cycloolefln hydrocarbons, sulfuric acid treatment
carbon is maintained at a temperature and a
pressure high enough to cause oxidation to oc
cur. We Ymay oxidize at temperatures in the
order of from about 100° F. to about 500° F.
although We prefer to carry out the treatment
may b'e employed.
at temperatures in the order of `from about 200°
F. to about 350" F. Pressures in the order of
from about normal atmospheric io; :ssure to
about 300 pounds per square inch gage may be
employed, although we prefer to effect the oxida
tion at gage pressures in the order of from about
50 to about 150 pounds per square inch. The
temperature and pressure selected for oxidation
will vary with the compound being treated and
in general the temperature used will be as low as
can be successfully employed to cause the oxida
tion reaction to proceed at an economical rate.
This general rule is followed because it is found
that the use of lower temperatures reduces the
amount of secondary oxidation products for a
The methods of effecting ^
azeotropic distillation, extractive distillation and
solvent extraction and the azeotrope formers or
solvents which may be employed are disclosed
hereinbelow.
Alcohols and ketones which may be produced
by our process include the cycloaliphatic and
alkylcycloaliphatic alcohols and ketones, such as
cyclopentanol and cyclohexanol, and cyclopen
tanone and cyclohexanone; the various iso
meric methyl-, ethyl-, propyl-, isopropyl-, butyl-,
etc., cyclopentanols, cyclohexanols, cyclopenta
nones and cyclohexanones; the various isomeric
dimethyl-, methy1ethy1-, methylpropyl-, methyl
isopropy1-, methylbutyl-, diethyl-, etc., cyclopen
tanols, cyclohexanols, cyclopentanones and cy
cl'ohexanones and higher molecular weight ho
mologs of these alkylcycloaliphatic alcohols and
ketones. Other products include the cycloole
flnic alcohols and ketones, such as cyclopentenol,
cyclohexenol, cyclopentenone and cyclohexe
none; the various mono, di, tri, etc., alkyl sub
stituted cycloolefinic alcohols and ketones, such
as for example, the various isomeric methylcyclo
pentenols, methylcyclohexenols, methylcyclopen
tenones, methylcyclohexenones and higher homo- >
given quantity production .of primary oxidation
products and also reduces the proportion of oxy
genated degradation products and polymeriza
tion and/or condensation products. These latter
products are defined, for the purpose of this in
vention, as those products which may contain
oxygen or not, which have been produced during
the oxidation and which contain fewer carbon
atoms per molecule than the hydrocarbon stock
being oxidized. Moreover, the pressures em
ployed will vary with the particular hydrocarbon
2,410,842
being treated and with the temperature. In gen
eral it> is‘desirable that the pressure be great l
enough to prevent the ready volatilization‘ o'f the
hydrocarbon stock being oxidized, thus'minlmiz
ing the required condenser and coolerv capacity
required .to strip liquid products from the exhaust
gasegjeaving the »oxidizen
f j
-
'drawn from the bottom of the oxidizer through
line A, the rate o! flow being controlled by valve
5, and passed ,to fractionating column 6 contain
ing >packing material or plates or other means of
aiding fractionation and having a reboiler 1 to
supply the heat required for fractionation. Col
' umn 6, together with its essential appurtenances
We may carry out the oxidation without the
constitutes the stripping section and this section
iid of oxidation catalysts since, in general, liquid
and its operation 'may be varied as indicated
phase oxidation of hydrocarbons of the types dis 10 hereinbelow. In those cases in which fractional
closed hereinabove occurs readily in the'absence
distillation is employed as the means of effecting
of catalysts.l However, we may employ catalysts
the separation of oxygenated molecules, i. e.,
to increase the rate of oxidation, to permit the
products of partial oxidation, from unoxidizedl
use of lower temperatures and/orl pressures which
hydrocarbon molecules and oxygenated degra
would otherwise be required, or to direct the
dation products which boil at temperatures atl or
course of the oxidation reaction. Solid catalysts
below the boiling point or boiling point range
which are supported in the oxidation vessel are
of the hydrocarbon -feed. column 6 is maintained
desirable since they do not complicate the sepa
at .any desirable pressure between about 29 inches
ration of partial oxidation products from unoxi
of mercury vacuum and 300 pounds per square
dized hydrocarbons and are not removed from 20 inch. gage. In these cases, the products of par-the oxidation vessel along with portions of the
' tial oxidation are removed from the bottom of
partially oxidized hydrocarbon charge which are
column B through valved outlet( 8 and the unoxi
withdrawn and treated for the removal of partial
dized hydrocarbon materials, together with deg
oxidation products. Catalysts which-are useful
radation products, pass as vapors from the top
in our process include those oxidation catalysts 25 of the column through line 8 and condenser I 0
comprising metals of the series having atomic
where the vapors are condensed and the con
numbers 20 to 3o, inclusive, i. e., calcium, scandi
densate passes into reñux drum II. A portion
um, titanium, vanadium, chromium, manganese,
of this liquid is returned as reflux to the top of
iron, cobalt, nickel, copper, and zinc as Well as
column 6 through line I2, the rate oi.’y flow
the metals magnesium, aluminum, molybdenum, 30 through this line being controlled by valve I3.
silver, tin, tantalum, cerium, neodymium, plat
Valved line I4 carries liquid products -from reflux
inum, thorium, and uranium. By the term oxi
drum Il to pump I5 and thence to the oxida
dation catalysts comprising metals we also in
'tion column I. New feed enters the system
tend to include compounds of these metals such
through valved line I6 leading into line I4. Ex-4
as oxides and salts, such as the chlorides, bro 35 haust gases and vapors leaving the oxidation
mides, iodides, nitrates, sulfates, sulñtes, phos
vessel through line 3 are passed through con
phates, phosphites, Vanadates, titanates, chro
mates, bichromates, molybdates, tungstates,
denser I'I into separator I8 from which the un
condensed gases escape through line I9 and pres
uranates, etc. These metals, metal oxides or
sure control valve 2U. The liquid in this separa
salts maybe used as such or they .may be dis 40 tor separates into two phases, an aqueous phase
~ tended on or impregnated in supports, said sup- '
ports being materials such as pumice, silica gel,
koalin, kieselguhr, fuller’s earth, alumina, mag
nesia, asbestos ñber, etc. Also, combinations of
two or more of the above metals, metal oxides,
or salts may be used as the catalyst.' In some
instances it is desirable to employ a soluble or
containing low molecular weight fatty acids, al- '
dehydes and other preferentially water-soluble
oxygenated products and a hydrocarbon phasey
containing in addition tor unoxidlzed hydrocar
bons, oxygenat'ed degradation products which are
preferentially soluble in the hydrocarbon phase.
The aqueous phase is removed throughñ valved
homogeneous catalyst which would be particu- '
outlet 2|. The hydrocarbon phase in separator
lariy active in initiating the oxidation and in
Isvmay be returned directly to column I through
such instances an organic salt of the above dis 50 valved outlet 22, or it may be transferred through
closed metals may be employed. Thus calcium,
valved line 23 to a fractionating column 24 which
magnesium, iron, etc., naphthenatesare active
is heated by means of reboiler 25 and operated
oxidation catalysts. Moreover, we may prefer to
under atmospheric or higher pressures, in which
use an oxidation initiator, such as a peroxide as,
column the liquid product, separated from the
for example, benzoyl peroxide, nitrogen peroxide,
hydrogen peroxide, etc. ,
exhaust gases and vapors from the oxidation col
umn, is fractionated to separate as a bottoms
The treatment of a hydrocarbon or hydrocar
fraction, unoxidized liquid hydrocarbons which
bon mixture for the production of partial oxida
are returned through line 26 and by means of
tion products is desirably carried out in the
pump 21 to the oxidation column and as over
equipment illustrated in the drawing. A column 60 head distillate the oxygenated degradation prod
1, consisting of any type of column or vessel suit
ucts, said distillate being passed/from the top of
able for liquid phase oxidation, which if desired,
column 24 through line 28, condenser 29 and into
may contain packing material, plates or trays,
reñux drum 30, A portion of the condensed
baffles, or other means of increasing the contact
overhead is returned as reñux through line 3|
between the hydrocarbon material and the oxy 65 and valve 32 to fractionating column 24. Oxy
gen or oxygen-containing gas and which is ar
genated degradation products are produced
ranged for heating and cooling, as by means of
through line 33 and control valve 34. A valved Y
steam and Water in internal coils, is maintained
inlet line 35 leading to the top of fractionating
at a pressure between about normal atmospheric
column B may be used as an inlet line for new
pressure and 300 pounds per square inch gage. 70 hydrocarbon feed or, as described hereinbelow,
Oxygen, air or other gas containing free oxygen
may be used as an inlet line for solvent in cases
is introduced through valved inlet 2 and exhaust
in which extractiva distillation is employed to aid
gases and vapors escape'through outlet 3. Par
in the separation of the oxygenated products and
tially oxidized hydrocarbon ’material together
with unoxidized hydrocarbon material is with
unoxidized hydrocarbon material.
‘
Although‘the oxidation equipment illustrated
l
2,410,642
10.4
I ~>in the drawing and .described above shows the use
-
nitro aromatic compounds, such as nitrobenzene,
of fractional distillation as the means of sep
nitrotoluenes, nitroxylenes, etc.; and alkyl ni-_
arating or stripping- the productsof partial oxi
'trites including the normal and isomeric nitrites
from butyl to octylnitrite.
dation from the unoxidized hydrocarbon we may
employ other means of carrying out this sep
The choice of solvent to be employed will gen
erally depend upon the characteristics of the`
hydrocarbon stock being oxidized and upon the
characteristics of the partial oxidation products
being separated since it is preferable that the
l aration, such as those indicated hereinabove.
Thus the fractionating column 6 in the drawing
may be used as an extractive distillation col
umn. In such cases, a solvent which preferen
tially dissolves the oxidized molecules is pumped 10 solver/1t does not form an azeotrope with the
into the top of the column through valved line
unoxidized hydrocarbon stock under the condi
35 and flows downward through the column con
tions of operation and it is preferable that the
tacting the vapors ascending the column and'
solvent have a boiling point at least 50° F. and
extracting therefrom the partially oxidized hy
preferably more than 75° F. above the boiling
drocarbon molecules. The solvent, containing the 15 point of the hydrocarbon stock ’being treated.
products of partial oxidation, is withdrawn as
It is desirable also thatthe boiling point of the
bottoms from column 6 through valved outlet
solvent be sufficiently different from the boiling
8. This mixture is then pumped to a fraction
point or boiling point range of' the partial oxida
ating column (not shown in the drawing) where
tion product that it may be separated therefrom
the partial oxidation products are distilled over 20 by fractional distillation.
head leaving the solvent as bottoms. The bot
The above disclosed solvents may be used to
toms from this column is returned as solvent to
separate'the products of partial oxidation from
the top of column 6.
the unoxidized hydrocarbon by the well known
Solvents which are useful in segregating the
process of solvent extraction in the liquid phase.
products of partial oxidation from the unoxi 25 Such solvent extraction may be carried out batch
dized hydrocarbons in the extractive distillation
wisev or preferably by batch countercurrent or
of the mixture of these two components include
continuous countercurrent extraction. In such
monohydroxy alcohols, such as ethyl, propyl, iso
processes the oxidized products are dissolved by
propyl, and higher molecular weight normal and
the solvent and separated as an extract phase
isomeric alcohols; polyhydroxy alcohols, such as 30 which is subsequently fractionally distilled to
mono-, di-, tri-, tetra-, etc., ethylene glycols;
segregatevthe oxidation products and the sol
the ethers of these ethylene glycols, such as
vent, and the unoxidized hydrocarbons or raf
monomethyl, monoethyl, monobutyl, etc., ethers
iinate phase may be returned to the oxidizer
of mono-, di-, tri--, etc., ethylene glycols; the
directly or after fractionally distilling or other
esters of these ethylene glycols, and the esters 35 wise treating it to remove small quantities of
of the ethers of ethylene glycols, such as for
solvent. In addition to the solvents disclosed
example, the acetate of the monomethyl ether of
above we may employ aqueous solutions of min
ethylene glycol, propylene glycols and the ethers
eral acids such as sulfuric acid, -sulfurous acid,
of propylene glycols; the esters of the ethers of
nitric acid, hydrochloric acid, phosphoric acid,
_ propylene glycols, including propylene glycol and 40 etc., as the solvents to effect the separation of
dipropylene glycol; polyhydroxy alcohols includ-oxidized products from the unoxidized hydro
ing the trihydroxy and tetrahydroxy alcohols,
such as glycerine and erythritol; hydroxy amines
such as ethanolamine, diethanolamine, trieth
anolamine; halohydrines such as glycolchloro
hydrine; amines, such as butylamine, triethyl
. carbons. 'I'he addition of about 2 to 4 volumes of
water to the aqueous mineral acid solution of
alcohols and/or ketones causes the separation of
the alcohols and/or ketones as an upper phase
which is substantially insoluble in the diluted
amine and diamines, suchas ethylenediamine;
aliphatic ketones, such as methylethyl ketone,
\ diethyl ketone, methylisopropyl ketone, etc., di
acetyl and acetonyl acetone; cyclic ketones, such
as cyclopentanone, cyclohexanone, methylcyclo
,hexanone and methylphenyl ketone; phenolic
compounds, such as phenols, naphthols, cresols,
xylenols, thymol, etc.; polyhydric phenols, such
as resorcinol, pyrocatechol, pyrogallol, phloroglu
cinol, etc.; alkylated polyhydric phenols, such as
. l1-met1fiyl-2,
heterocyclic
bered rings
in the ring
as oxolane,
mineral acid phase and whichmay be decanted
’ from the latter phasel For example, 65% sul
furie acid is an excellent selective solvent for
50 -
the primary oxidation products obtained in our
.partial oxidation process.
' We may Vemploy azeotropic distillation to sep
arate the unoxidized hydrocarbons from the prod
ucts of oxidation using'fractionating column 6
55 in the drawing as the azeotroping column. This
method is desirably employed in those cases in
`which the products of oxidation boil at or near
the boiling point of the hydrocarbon being oxi
3-dihydroxy benzene, etc.; saturated
compoundsl having'ñve or six mem
in which at least one of the atoms
dized. The compound selected as the azeotrope
is oxygen, nitrogen or sulfur, such 60 former forms a minimum boiling point azeotrope
thiolane, dioxolane, dioxane, oxane,
with the unoxidized hydrocarbons and thus facil
piperidine, morpholine, dithiane, etc.; derivatives
itates the'separation of said hydrocarbons from
of such iive and six membered heterocyclic ring
the oxidation products. Azeotrope formers which `
compounds, such as N-ethylpyrolidine, tetra
may be employed may be selected from the list
hydrofurfuryl alcohol, dibutanol, N-ethylipiperi
dine, N-methylmorpholine, N-phenylmorpholine,
etc.; nitroparaiîins, such as nitromethane, nitro
ethane, 1,2-dinitropropane, nitrobutanes, nitro
pentanes, etc.; nitro alcohols, such as 2-nitro-1
ethanol, 2.- and 3-nitro-1’-propanol, etc., the nitro
derivatives of unsaturated aliphatic hydrocar
bons, such as nitroethylene and nitropropylene;
the halogenated derivatives of the aforemen
, tioned nitroparaiiìns and nitroalcohols, such as
chloronitromethane, 1-chloro-1-nitroethane, etc.,
65 of solvents disclosed hereinabove for use in ex
tractive distillation processes. In »selecting the
particular azeotrope former to use in a speciñc
~ case it is important that the boiling point of the
solvent used as azeotrope former is not more than
50° F. and preferably not ,more than about 20°
F. above the boiling point of the hydrocarbon
being oxidized.
'
In carrying out the azeotropic distillation the
azeotrope former is mixed ,with the feed to the
lfractionating column 6 in line 4 in a sumcient
2,410,642
l11
12'
quantity to distill overhead all of the unoxidized _
gen forming a cycloaliphatic alcohol. In the sec-J
hydrocarbon together with said azeotrope former
ond reaction the oxygen atom replaces the ter
leaving the oxidized products as bottoms. sub
tiary hydrogen and in this case the ring, breaks
stantially free of unoxidized hydrocarbon and
at position I, the tertiary hydrogen atom shifting
azeotrope former. The overhead distillate or 5 to the end carbon atom of the carbon chain and
azeotrope is withdrawn from‘reilex drum Il,
the reaction results in the formation of an acyclic
through line Il and valved line” to an azeotrope
aliphatic ketone.
.
former recovery unit where the azeotrope former
Other types of ketones which may be produced
is separated, as by solvent extraction, from the
by partial oxidation and which may be present
unoxidized hydrocarbon. The separated unoxi
in the oxidized product together> with the alco
’ dized hydrocarbon is' returned to the oxidizer
-hols and ketones of _the types noted above are
through valved inlet I6 to line I4, and pump I 5.
the cycloaliphatic ketones. These compounds are
We may also use an adsorption process for
produced by the reaction between one molecule
the removal of partial oxidation products from
of oxygen and one molecule of the hydrocarbon
the mixture of unoxidized ‘and oxidized hydro
and this type of reaction may be represented by
carbons withdrawn from the oxidation vessel.
the following equation:
In this case the product withdrawn from the oxi
0*(
dizer through. line 4 is contacted with a solid ad
Hs
H
sorbent, such as activated charcoal, or a min- ,
eral adsorbent, such as silica gel, alumina, full
er’s earth, bentonite, etc., in a percolator. In
/C\
20
such a system the oxidized molecules are adsorbed
and the unoxidized hydrocarbon after removal
of the oxidized products is discharged from the
percolator and returned to the oxidizer for fur 25
ther treatment. Two percolators containing an
adsorbent are connected in parallel so that one
may be used for adsorbing oxidation products
while the spent adsorbent in the other percolator
is being treated for the recovery of adsorbed prod
ucts -and otherwise regenerated. 'Regeneration
of the spent adsorbent may be accomplished by a
steam stripping operation in which steam or su
perheated steam is blown through the percolator,
after first draining all of the unoxidized hydro
carbon from the unit, and the steam containing
the oxidation products is condensed and cooled
and passed through a separator vessel where the
aqueous phase is separated from the oxidation
products.
.The crude partialoxidation product, which may
be stripped from its mixture with unoxidized
hydrocarbon leaving the bottom of the oxidizer
by any of the above mentioned processes, con
HxC
CH: + o
Ha
¿Hx
C
I
--»
_ /C\
HxC ~. CH:
Hdl)
¿Hr
`
+ Eo
i
C
H:
Hz
Cyclohexane
Cyolohexanone
In .this case one atom of oxygen replaces the
two hydrogen atoms attached to one of the car
-bon atoms forming a, cyclic ketone and the thus
>freed hydrogen atoms combine with the second
30 ` oxygen atom to form water.
The proportion of alcohol to ketone in a given
partial'oxidation product will depend upon the K
particular hydrocarbon being oxidized, the cat
alyst employed, and upon the temperature and
' pressure maintained in the oxidizer and may
therefore be varied Within certain limits by
changing the hydrocarbon feed and/or the con
ditions of treatment. Thus the controlled par
tial oxidation of methylcyclohexane at relatively
low pressures and temperatures results in the
production of approximately equal quantities of
methylcyclohexanol and 2-heptanon'e, whereas
the oxidation of 1,3-dimethylcyclopentane under
similar conditions of temperature and. pressure
sists primarily of molecules having the same 45 results in the formation of large proportions of
number of carbon atoms as the parent hydro
5-methylhexanone-2 and relatively small propor
carbon and containing one atom of oxygen. This
tions of 1,3-dimethylcyclopentanol.
product comprises alcohols, ketones, or mixtures
In those instances in which alcohols are the
of alcohols and ketones, which may be produced
desired products and mixtures of alcohols and
by a primary oxidation reaction involving only 50 ketones
are obtained as products of partial oxi
the addition of one atom of oxygen per mole
dation
the
ketones may be reduced to the corre
cule. Thus, for example, the partial oxidation
sponding alcohols. This reduction may be car
of methylcyclohexane proceeds in the manner
ried out on the mixture of alcohols and ketones
illustrated by the following equations:
and in this instance the resulting alcohols would
ont /H
/G\CH:
HxC
l
è
B1G
/ Ha
HIC
è
/C\CH:
En \ / Ha
C
Hz
Ha
Methylcyclohexane
l-methylcyclohexanol
H
'
/C\om
mè
\C/
,
+ 360: _»
C
on,
mc
`on\, /on
0||y
drogenating organic compounds, such as hydro
genation with gaseous hydrogen over a nickel,
65 copper, or platinum catalyst.
»l
`
¿E + M0; --» CHz-C-CHs-UHf-CHz-CHz-CE:
i
allontanano
Hf
55 be a mixture of cyclic and acyclic alcohols, or
the crude product may iirst be separated into a
ketone fraction and an alcohol fraction by frac
tional distillation or by a chemical .treatment as
indicated hereinbelow and »the ketone fraction
60 subsequently reduced to the corresponding 9.100
hol. The reduction may be .carried out by any
of the well known processes for reducingl or hy
"
Methylcyclo
hexane
In the iirst reaction the oxygen atom enters
the molecule at the tertiary carbon atom and the
tertiary hydrogen atom attaches itself to the oxy
-
`
-This segregation of the partial oxidation prod
ucts into a fraction consisting primarily of al
cohols and a second fraction consisting Apri
marily of ketones may be eiîected in any con
70 venient manner. In some instances it is possible
to accomplish this separation by fractional dis- ’
tillation.
Thus, for example, when oxidizing
methylcyclohexane the products of partial oxida
tion comprise l-methylcyclohexanol which boils
75 at about 315° F, and 2-heptanone which boils
2,410,642
13
_
at 302° F. These compounds can be separated
by careful fractional distillation. Improved sep
aration by fractional distillation may often be
realized by carrying out the distillation at re
"
14
fractionating column and was condensed and re
turned to the oxidizer for further oxidation and
oxidized products were removed as bottoms from
the fractionating column, said oxidized products
duced pressures, i. e., under a-vacuum, or at 5 being further treated as described hereinbelow.
pressures greater than atmospheric pressure be- y
cause the vapor pressures of the alcohol and ke
tone components do not change to the same ex
tent with changes in distillation pressureÍ and
thus the spread between the boiling points of
the two components usually becomes greater with
changes in pressure, often allowing separation of
components which boil at the same temperature
under ordinary atmospheric pressures.
Chemical methods of separation, wherein a 15
chemical reagent is caused to react, or form an
addition compound with one of the components
of the mixture, may also be employed. For ex
ample, the _product of partial oxidation may be
Exhaust gases and vapors leavingthe top of the
oxidation column were passed through a con
denser and into a separator. The condensed
liquid being returned directly to the oxidizer and
the uncondensed gases, consisting primarily of
spent air, were vented -to the atmosphere.
'I'he oxygenated product obtained as bottoms
from the fractionating column consisted pri
marily of a mixture of equal parts by weight of 1
methylcyclohexanol and 2-heptanone. A portion
of\ this mixture was extracted with a saturated
aqueous sodium bisulñte solution to separate the
2-heptanone, as an addition product with the
sodium bisulñte, from the l-methylcyclohexanol.
washed with a. concentrated aqueous solution of 20 The extracted cyclohexanol was ~' subsequently
sodium bisulfìte which forms an addition product
fractionally distilled at reduced pressure to pro
with the ketone. The alcohol which is unaffected
duce a substantially pure 1-methylcyclohexanol
by this treatment may then be decanted from the
as a heart cut boiling between 160° F. and 166°
aqueous solution of the ketone addition compound
F. at 22 mm. of mercury pressure. The bisulfite
and then decomposed as by warming with alkalis,
addition product with the ketone was decomposed
such as dilute sodium hydroxide or with an acid,
by treatment with dilute sulfuric acid, the freed
such as dilute sulfuric acid, releasing the ketone
ketone was separated by decantation from the
which may be decanted from the remaining
aqueou's layer, washed with additional quantities
aqueous phase. The alcohol and the ketone may
of water and ñnally fractionally distilled to
be further puriñed by fractional distillation.
30 produce a heart cut boiling between 300° F. and
In those cases in which more than one alcohol
304° F. at normal atmospheric pressure and con
and/or more than one ketone is formed- >by the
sisting substantially of pure Z-heptanone. 'I'his l
oxidation reaction, as for example, when the hy
latter fraction was reduced to the correspond
drocarbon feed to the oxidizer contains more
ing alcohol„ 2-heptanol, by hydrogenation over
than one naphthene hydrocarbon, the ketones
35 a nickel catalyst at 300° F. and 400 pounds per
may be separated from the alcohols, as .indicated
above, and the separated components may then
be fractionally distilled to separate individual al
square inch pressure for a period of 4 hours.
i
A second portion of the oxygenated product
obtained as bottoms from the fractionating col
cohols and/or ketones in those cases in which the
umn and comprising a mixture of 1-methylcyclo
boiling points of the individual alcohols and ke 40 hexanol and Z-heptanone was hydrogenated in
tones are suiliciently far apart to allow such sep
the manner indicated above for hydrogenating
aration to be made. However, in many instances
the separated Z-heptanone. The product com
it is not essential that the alcohol component be
prised a mixture of l-methylcyclohexanol and 2
separated into individual compounds since mix
heptanol.
tures of alcohols such as are produced in our
process are entirely satisfactory for most of the
uses indicated hereinabove. Moreover, mixtures
of ketones of similar' types may be reduced to
,
»
'
-
To illustrate one use of the alcohols prepared
as above, to 457 grams of the l-methylcyclo
hexanol, the Z-heptanol, or the mixture of these
alcohols, is added 222 grams of powdered phos
the corresponding-alcohols and the .thus produced ,
phorus pentasulñde and the mixture is agitated
mixture of alcohols may be employed without fur 50 and heated to 275° F. for a period of three hours
ther separation.
-
The following speciñc examples further illus
trate the invention.
at which time the phosphorus pentasulfide has
completely dissolved. To the resulting solution
is added 82 grams of zinc oxide and the agitating
and heating is continued for an additional four
55 hours at which time the product is filtered hot
Methylcyclohexane was pumped into the oxida
(275° F.) to remove small amounts of unreacted
tion column, heated to a temperature of 250° F.
zinc oxide._ This product may be added to an
and maintained at a pressure of about 90 pounds
SAE 30 highly solvent refined Western lubricating
per square inch gage. Air was introduced at
oil having Saybolt Universal viscosities of 540
the bottom of the vessel at the rate of 65 cubic 60 seconds at 100° F. and 64 seconds at 210° F. and
feet per barrel of methylcyclohexane per minute
a Viscosity index (Dean and Davis System) of 90,
for a period of about 20 minutes until analysis
in the ratio of about 1 part by weight of the zinc
of the> oxidation charge showed the presence of
salt to 99 parts of the lubricating oll and the
one atom of combined oxygen per 200 molecules
resulting mixture heated to about 250° F. and
of methylcyclohexane. At this time fresh feed 65 agitated until the zinc salt is dissolved and thor
was started into the oxidizer at a rate such that
oughly mixed in the oil to produce a lubricating
the liquid level in the oxidizer remained constant
oil composition which is a particularly desirable
throughout the operations described below. Par
lubricant for internal combustion engines. wThis
tially oxidized methylcyclohexane was removed
lubricating oil composition possesses improved
from the bottom of the column and transferred 70 nlm strength, anti-corrosion and detergency to a fractionating column maintained at normal
characteristics. Also, 1 part of the above de
atmospheric pressure and a temperature such that
scribed zinc salt may be blended in a similar man
«the temperature in the vapor line leading from
ner with 1 part of the calcium salt of oil-soluble
the top of the column was 212.5° F. Unoxidized
-petroleum sulfonic acids produced by treating
methylcyclohexane distilled overhead from this 75 petroleum with strong sulfuric acid and 98 parts
i Example I
\’
‘
L
.
2,410,642 '
>
1s
16
,
of the above mentioned highly'solvent reñned
Western lubricating oil to produce a lubricating
_ oil composition having high ñlm strength and
_ anti-"corrosion ~characteristics and particularly
high detergency characteristics. `
‘
{
Example II
l
A naphthenic fraction of petroleum boiling be
tween 192° F. and 198° F. .prepared by careful
fractionation of a straight run gasoline derived
from a highly naphthenic crude oil and con
taining about 50% by volume oi’ a mixture of
l dimethylcyclopentanes was charged to the oxida
/
i tated and heated to 275° F. for three hours. To
this product is then added 82 grams of zinc oxide
and the heating and agitating continued for an
.additional four hours at which time the hot'
product is filtered to remove any unreacted zinc
oxide. 'I'he resulting zinc salt may be blended
v with the lubricating oil described in Example I
in the ratio of about 1 part of the zinc salt to
99 parts of the lubricating oil, or 1 part of the
10 zinísalt may-be blended with 1 part of a calcium
salt of oil-soluble petroleum sulfonic acids and
98 parts of the same lubricating oil to produce
lubricating oil compositions having high film
strengths, anti-corrosion and detergency char
tion column, heated to 250° F. and maintained
at a pressure of 60 pounds; per square inch gage. 15 acteristics which are desirable features of lubri
Air was introduced into the oxidation column at
cants for internal combustion engines and par
a. point near the bottom of the column at the rate
ticularly Diesel engines. In each of the above in
of 65 cubic feet per barrel of charge per minute
stances the blending may be accomplished by
and exhaust gases and vapors were led from the
heating to about 250° F. and agitating the ingre
top of the column through a condenser and into 20 dients until the added salts are completely dis
a separator from which condensed liquid ñowed
solved and mixed in the lubricating oil.
' by gravity back into the .oxidizer and uncondensed
The foregoing description and examples are
gases were allowed to escape to the atmosphere.
not to be taken as in any way limiting but
The air blowing was continued for a period oi’
merely illustrative of our invention /for many
approximately 20 minutes at which time analysis 25 variations may be made by those skilled in the
of the liquid in the oxidizer indicated the presence
art without departing from the spirit or scope
of approximately 0.5% of molecules containing
of the following claims.
oxygen. At this time fresh feed was pumped into
We claim:
»the oxidizer at such a rate that the liquid level
l. A process for the treatment of a saturated
>in the column remained constant throughout the 30 cyclic hydrocarbon to produce substantially only
following operations. The slightly oxidized hy
those partial oxidation products containing the
drocarbon fraction was withdrawn from the bot
tom of the oxidizer and transferred to a fraction
same number of carbon atoms per molecule as
said saturated cyclic hydrocarbon and contain
ing one atom of oxygen per molecule, comprising
ating column maintained at normal atmospheric
pressure and at a temperature such that the vapor 35 contacting said saturated cyclic hydrocarbon in
leaving the top of the column had a temperature
the liquid phase in an oxidation vessel with a gas
of 198° F. This overhead vapor consisting of un
containing free oxygen at temperatures between
oxidized hydrocarbon material was condensed,
about 200° F. and about 350° F. and at pressures
part of the condensate being returned to the frac
between about 50 pounds and about 300 pounds
tionating column as reñux and part of it being 40 per square inch gage until between about 0.1%
pumped back into the oxidizer along with the new
and about 10% of the molecules are oxidized,
hydrocarbon feed referred to above.
thereafter maintaining said proportion of oxi
Products of partial oxidation were withdrawn
dized molecules by withdrawing partially oxidized
asbottoms from the fractionating column, and
liquid from said oxidation vessel, passing said par
transferred to a second fractionating column 45 tially oxidized liquid to a fractionating column
from which a fraction boiling between about
wherein unoxidized hydrocarbon is vaporized and
284° F. and 302° F. was produced as a side cut.
This fraction, which amounted to about 50% by ‘
volume of the oxidized fraction obtained as bot
toms from the ~ilrst vfractionating column com~ 50
prised a mixture of aliphatic ketones having seven ,_
carbon _atoms per molecule. The overhead from
the second fractionating column contained lower
boiling alcohols and ketones, i. e., having fewer
distilled, withdrawing unvaporized partial oxida
tion products containing one atom of oxygen per
molecule from the bottom of said fractionating
column, condensing said vaporized unoxidized
hydrocarbon and returning the condensed vapor
ized unoxidized hydrocarbon together with addi
tional quantities of saturated cyclic hydrocarbon
.to said oxidation vessel, passing exhaust gases
than seven carbon atoms per molecule, and the 55 and vapors from said oxidation vessel through a
bottoms from this column contained a mixture
condenser and into a separator from which un
of dimethylcyclopentanols and higher molecular
condensed gases are exhausted and> returning
’ weight alcohols and ketones together with oxy
condensed hydrocarbon from said separator to
genated polymerization products. `
The mixture of aliphatic ketones boiling be
said oxidation vessel.
60
' tween about 284° F. and 302° F. lwas reduced
to a mixture of the corresponding alcohols by
liquid phase hydrogenation with gaseons hydro
'
2. A process .for the treatment of a saturated
cyclic hydrocarbon to produce substantially only
those partial oxidation products containing the
same number of carbon atoms per molecule as
gen over a nickel catalyst at 300° F. and 400
said saturatedv cyclic hydrocarbon and contain
pounds per square inch gage for a period of 65 ing one atom of oxygen per molecule, comprising
four hours. The hydrogenated product was _frac
tionally ,distilled and the mixture of alcohols
contacting said saturated cyclic hydrocarbon in
the liquid phase in an oxidation vessel with a gas
containing free oxygen at temperatures between
293° F. and 311° F. The yield of alcohols
about 100° F. and about 500° F. and at pressures
amounted to about 90% by volume of thè mix 70 between about 50 pounds _and about 300 pounds
ture of ketones.
'
per square inch gage until between about 0.1%
To illustrate one of the uses of the mixture
and about 10% of the molecules are oxidized,
of alcohols prepared as indicated above, to 465
thereafter maintaining said proportion of oxi
grams of the alcohols is added> 222 grams of
dized molecules by withdrawing partially oxi
phosphorus pentasulflde and the mixture is agi 75 dized liquid from said oxidation vessel, passing
obtained as a heart cut boiling between about .
2,410,642
said partially oxidized liquid to a fractionating.
column wherein unoxidized >hydrocarbon is va
porized and distilled, withdrawing unvaporized
partial oxidation products'containing one atom
of oxygen per molecule from the bottom of said
fractionating column, condensing said vapor
izedwunoxidized hydrocarbon and returning the
condensed vaporized unoxidized hydrocarbon to
gether with additional’quantities of saturated
cyclic hydrocarbon to saidoxidation vessel, pass
ing exhaust gases and vapors from said oxida
tion vessel through a condenser and into a sep
arator from which uncondensed gases are ex
v
heptanoneare obtained'as distillation bottoms.
condensing said vaporized vmethylcyclohexane
and returning the condensed methylcyclohexane -
together with a sufficient quantityïof additionalmethylcyclohexane feed to maintain an approxi- -
mately constant liquid level in said oxidation ves
sel, constantly passing exhaust gases and vapors
from said oxidation vessel through a condenser
and into a separator- from which uncondensed
gases are .exhausted and from which condensed ‘
hydrocarbon liquid comprising methylcyclohex
ane is returned tosaid oxidation vessel.
-
6._A` method of producing l-methylcyclohex
anol and Z-heptanoi, comprising contacting/
hausted, passing a condensed hydrocarbon phase
_from said separator to a fractionating column 15 methylcyclohexane in the liquid phase inÄ an
wherein oxygenated degradation products are4 oxidation vessel and in the absence of oxidation
vaporized and distilled leaving unoxidized hy
catalyst with a gas containing free oxygen at
drocarbon as distillation bottoms and returning
temperatures between about 200° F. and about
said bottoms to said oxidation vessel.
350° F. and at pressures between about 50 pounds
3. A process for the treatment of a naphthene 20 and 150 pounds per’square inch gage until be
hydrocarbon to produce partial oxidation pro
tween about 0.1% and 10.0% of the molecules
ducts containing the same number of carbon
are oxidized, thereafter maintaining said propor
atoms per molecule as said naphthene hydrocar
tion of oxidized molecules by withdrawing par
bon and containing one atom of oxygen per mol
tially oxidized liquid from said oxidation ves
ecule, comprising contacting said naphthene hy
sel, passing said liquid to a fractionating co1
drocarbon in the liquid phase in an 'oxidation ves
sel with aggas containing free oxygen at tem
peratures between about 200° F. and about 350°
F. and at pressures between about 50 pounds and
about 150 pounds per square inch gage until be 30
v tween about 0.1% .and 10.0% of the molecules
are oxidized. thereafter maintaining said pro
portion of oxidized molecules by withdrawing
partially oxidized liquid from said oxidation ves
sel, passing said liquid to a fractionating col
umn in whichunoxidized hydrocarbon is vapor
ized and distilled and partial oxidation products
containing one> atom of oxygen per molecule are
umn in which unoxidized methylcyclohexane is
vaporized and distilled and from which partial
oxidation products comprising l-methylcycldhex- ~
anol and z-heptanone are obtained as distillation
bottoms, condensing said vaporized'methylcyclo
hexane and returning the condensed methyl
cyclohexane together with a sufficient quantity
of additional methylcyclohexane feed to main
tain an approximately constant liquid level in
said oxidation vessel, constantly passing exhaust
gases and vapors from said oxidation vessel
through a condenser and into a separator from
which uncondensed gases are exhausted and from
obtained as distillation bottoms, condensing said
vaporized' unoxidized hydrocarbon and return
`which condensed hydrocarbon liquid comprising
ing the condensed vaporized unoxidized hydro
tion vessel, hydrogenating said> partial oxidationn
products 'comprising l-methylcyclohexanol and
carbon together with a sufficient quantity of said
naphthene hydrocarbon to maintain an approxi
mately .constant liquid level in said oxidation
vessel, passing exhaust gases and vapors from
said oxidation vessel through a condenser and
into a separator from which uncondensed gases _v
are exhausted, passing a condensed hydrocar-v
bon phase from said separator to a fractionat
ing column wherein oxygenated degradation
products are vaporized and distilledI leaving un
oxidized hydrocarbon<as distillation bottoms and
methylcyclohexane is returned to said oxida
2-heptanone to produce a mixture comprising 1-'methylcyclohexanol and 2-heptanol.
.
ì
7. A process as in‘claim 6 wherein said partial
oxidation product obtained as distillation bot- ~
toms comprising 1-methylcyclohexanol‘and 2
heptanone is separated into a fraction compris
ing 1-methylcyclohexanol and another fraction
comprising 2-hexanone and said fraction coni
prising 2-hexanone is hydrogenated'to produce 2
returning said last named distillation bottoms to
8. A\process for the 'treatment of dimethyl
cyclopentane to produce partial oxidation prod
4. A process as in claim 3.wherein said partial 55 ucts having at least ñve carbon atoms per mole
said oxidation vessel.
I
oxidation products containing one atom of oxy
gen per molecule comprise alcohols and ketones
containing at least ñve carbon atoms per mol
ecule.
5. A process for the treatment of methylcyclo
hexane to produce l-methylcyclohexanol and 2
heptanone, comprising contacting said methyl
cyclohexane in the liquid phase in- an oxidation
culev and containing one atom of oxygen per mole
cule comprising contacting said dimethylcyclo- r
pentane in the liquid phase in an oxidation vessel
with a gas containing free oXygen at temperatures
between about 200° F. and about 350° F. and at
pressures between about 50 pounds and 150
pounds per square inch gage until about 0.1%
and about 10.0% of the molecules are oxidized,
vessel with a gas containing free oxygen at tem
thereafter maintaining said proportion of oxidized
peratures between about 200° F. and about 350° 65 molecules by withdrawing partially oxidized liq
F. and at pressures between about 50 pounds
uid from said oxidation vessel, passing said liquid ^
and `150 pounds per square inch gage until between
to a fractionating column in which unoxidized
about 0.1% and about 10.0% of the molecules are
dimethylcyclopentane is vaporized and distilled
oxidized, thereafter maintaining said proportion
and from which said partial oxidation products
of oxidized molecules by withdrawing partially
having at least ñve carbon atoms per molecule
oxidized liquid from said oxidation vessel, pass
and containing one atom of oxygen per molecule
ing said liquid to a fractionating column in which
are obtained as distillation bottoms, .condensing
unoxidized methylcyclohexane is vaporized and
said vaporized dimethylcyclopentane and return
distilled- and from which partial oxidation prod
ing the condensed dimethylcyclopentane together
ucts comprising l-methylcyclohexanol and 2 75 with a sufûcient quantity of additional dimethyl
e
t
>r19
2,410,649
.
1
` cyclopentane feed »to maintain an approximately
after maintainingÍ said proportion of oxidized
constant liquid level 1in ‘said oxidation vessel, con
stantly passing exhaust gases and vapors from
molecules-by withdrawing partially oxidized 1iq_-
said oxidation vessel through a condenser and ~
into a separator from which uncondensed gases
are exhausted and from which condensed hy
drocarbon liquid
comprising
dimethylcyclo
pentane is returned to saidoxidation vessel.
i
9. A method for the treatment of a dimethyl
' cyclopentane fraction of petroleum boiling be
tween about 192° F. and 193° F. to produce ke
tones and alcohols having seven carbon atoms
uid fromsaid oxidation vessel, passing said liq- ~
uid to afI iractionating column .in which un
, oxidized hydrocarbons are vaporized and dis
tilled and from which partial oxidation products
are obtained as distillation bottoms, condensing
said vaporized hydrocarbons and returning the
= condensed hydrocarbons to said oxidation vessel
together with a suñiclent quantity of said neph
thenic fraction of petroleum to me'ntain an ap
proximately constant liquid level in. said oxida
per molecule comprising contacting said dimethyl
tion vessel, fractionally distilling! said partial
cyclopentane fraction in the liquid phase in an
oxidation products obtained as distillation bot
oxidation vessel and in the> absence of added 15 toms to _separate therefrom a fraction boiling be
oxidation catalyst with a gas containing' free
tween about 284° F. and about 302° F. compris
oxygen at temperatures between about 200° F.
ing said aliphatic ketones having seven carbon
and about 350° F._ and at pressures between about
atoms per molecule.
50 pounds and\150 pounds per square inch gage
13. A method of producing aliphatic alcohols
until between about 0.1% and 10.0% of the mole 20 having seven carbon atoms per molecule com
cules are oxidized, thereafter maintaining said
prising airblowing a naphthenic fraction of pe
proportion of oxidized molecules »by withdrawing
troleum boiling between about 192° F. and 198° F.
'partially oxidized liquid from said oxidation ves
and containing dimethylcyclopentane in the
sel, passing said liquid to a fractionating colunm
absence of oxidation catalyst in an oxidation ves
in which unoxidized dimethylcyclopentane frac 25 sel at a temperature of about 250° F. and a pres
tion is vaporized and distilled and from which,
sure of about 60 pounds per square inch gage until
partial oxidation products comprising ketones»
between about 0.1% and 10.0% of the molecules
and alcohols having seven carbon 'atoms per
are oxidized, thereafter maintaining said pro
portion of oxidized molecules by withdrawing par
densing said vaporized dimethylcyclopentane 30 tially oxidized liquid from said oxidation vessel,
fraction and returning the condensate to said
passing said liquid to a fractionating column in
molecule are obtained as distillation bottoms, con
oxidation vessel together with a suilicient quan
which unoxidized hydrocarbons are vaporized and
tity of additional dimethylcyclopentane fractionv
distilled and from which partial oxidation prod
to lmaintain an approximately constant liquid
ucts are obtained as distillation bottoms, con
level in said oxidation vessel, constantly passing 35 densing said vaporized hydrocarbons and return
exhaust gases and vapors from said oxidation
ing the condensed hydrocarbons to said oxida
vessel through a condenser and into a separator
tion vessel together with a suiñclent'quantity of
said naphthenic fraction of petroleum to main
from which uncondensed gases are exhausted
tain an approximately constant liquid level in
and the condensed unoxidized_,dimethy1cyclo-
pentane fraction is returned' to said oxidation 40 said oxidation vessel, separately fractionally dis
tilling said partial oxidation products obtained as
~
distillation bottoms to separate a fraction boil
10. Aprocess as in claim 9 wherein said ketones
ing between about 284° F. and 302° F. compris
are aliphatic ketones.
ing a mixture of aliphatic ketones having seven
11. A process’as in claim ì9 wherein said al
45 carbon atoms per molecule hydrogenating said
cohols are saturated cyclic alcohols.
mixture ofraliphatic ketones with gaseous hy
12. A method for producing aliphatic ketones
vessel.
having seven carbon atoms per molecule com
drogen at about 300° F. and at a pressure of
about 400 pounds per square inch gage in the
prising airblowing a naphthenic fraction of, pe
presence of a nickel catalyst to produce a mixture
troleum boiling between about 192° F. and 198°
F. and containing dimethylcyclopentane in the 50 of alcohols containing ~seven carbon atoms per
molecule.
.
absence of oxidation catalyst at a. temperature
of about 250° F. and at a pressure of about 60
pounds per square inch gage until about 0.1%
and 10.0% of the molecules are oxidized, there
ADALBERT FARKAS.
ARTHUR F.v STRIBLEY, Ja.
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