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Патент USA US2409387

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v15, 1941s.v
Filed larch 11, 1942
v #87.
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Patented Oct. 15, 1946
Edward B. Peck, Elizabeth, N.‘ J ., assignor, by
mesne assignments, to Standard Catalytic Com
pany, a corporation of Delaware
Application March 11, 1942, Serial No. 434,206
1 Claim. (01. 196-49)
The present invention relates to improvements
in the manufacture of gasoline and, more partic~
'ularly, ‘it relates to improvements in the produc
tion of aviation gasoline by removing from gas
oline or naphthas low octane fractions by frac
tional distillation and thereafter subjecting the
ed fraction to a two-stage catalytic treatment
to produce aromatics.
A more speci?c object of my present invention
is to separate from a gasoline or naphtha of low
octane number the lowest octane fraction and
to produce from the separated fraction by a
combination of dehydrogenation and aromatiza
tion, toluene under conditions conducive to max
imum yields and minimum coke formation.
low octane fractions removed to a two-stage op
eration, in the ?rst stage of which naphthenes
present in the said low octane fraction are de
A still more speci?c object of my invention is
hydrogenated to form the-' corresponding aro 10
to segregate at least one of the low octane frac
matic derivatives, thence separated ‘from the
tions of a naphtha, to thereafter subject the
para?ins, and in the second stage of which the
fraction to catalytic reforming in the presence of
paraf?nic constituents are aromatized catalyt
hydrogen to aromatize the naphthenes and re
Prior to my invention, it was known that the 15 duce unsaturation by hydrogenating ole?nic hy
drocarbons, to thereafter separate the naph
octane number of a gasoline could be improved
thene conversion products from the unchanged
by removing certain fractions by distillation, and
para?inic constituents, and then to aromatize the
it has been further proposed to hydroform the
said para?in constituents.
low octane number fractions and blend them
back into the gasoline. For example, it has ‘been
subject a fraction of the naphtha or gasoline
proposed heretofore, in order to improve the‘ oc
boiling within the range of from about 180-220°
tane rating of the gasoline and particularly the
and containing naphthenes and heptane par
octane rating as determined by actual road tests,
afn‘ns and ole?ns essentially to a two-stage proc
to separate the intermediate fractions, say those
ess, in the ?rst stage of which the naphthenes
boiling within the range of from ZOO-325° F., and
are converted to aromatics, while the heptanes
to subject these fractions to a catalytic reform‘
are substantially unchanged, and after separa
ing operation in the presence of added hydrogen
tion of the aromatics from the para?ins to con
and thereafter to combine the hydroformed frac
‘ vert the latter to toluene.
tion with the other fractions to produce a gaso
Other and further“ objects of my invention will
line of greatly improved octane rating.
appear from the following more detailed descrip
The present invention as stated. carries out
tion and claim.
the conversion of the low octane fraction of a
My invention will be best understood by setting
gasoline or naphtha in two steps, with intermedi
forth a speci?c example illustrating a preferred
ate separation of reaction products in the ?rst
modi?cation of my invention and also by refer
stage or step. In the ?rst step, the naphthenes
ence to the accompanying drawing in which I
or hydroaromatics are dehydrogenated to aro
have set forth diagrammatically a ?ow plan il
matics while ole?n hydrocarbons are hydrogen
lustrating, apparatus elements in which my im
ated to decrease the unsaturation of the frac
proved process may be carried into practical ef
tion. In other words, my present invention is
carried out particularly with respect to the ?rst 40
Referring in detail to the drawing, an East
step mentioned above under selective hydrogena
Texas virgin gasoline boiling within the range
tion-dehydrogenation so that aromatics are
formed from hydroaromatics, while ole?ns are
hydrogenated. This result may be accomplished
in the presence of a proper catalyst and under
‘proper operating conditions, and I prefer to use
a catalyst composed of a mixed sulphide of nickel
and tungsten (2 mols of NiS and 1 mol of W83).
After separation of the aromatics and hydro
genated ole?ns by distillation and/or solvent ex
tractions, the normal paraf?nic residue is aroma
tized. The aromatized can be carried out using
chromic oxide catalyst supported on activated
of from about ‘YO-300° F. and having an octane
number as determined by the A. S. T; M. method
-' of 60, is charged to the system through line I,
thence heated in a furnace 3 to‘vaporization
temperatures, thence withdrawn through line 4
and discharged into a fractionating column 6.
An overhead fraction and a bottoms fraction
are recovered through lines 8 and Hi, respec
tively, and these fractions are combined and col
lected in a receiving drum l2. This product in
the example given will have an octane number of
about 70. An intermediate fraction: boiling from
alumina or some other suitable catalyst.
ISO-220° F. is withdrawn from the fi‘actionator
through line M. This fraction withdrawn from
the system through line I4 contains ‘naphthenes
and. normal heptane, together with some ole?n's,
although the amount of the latter is ‘rather lim
, The main object of my present invention
therefore is to distill a gasoline or naphtha of
low octane number to separate out the lowest
octane fractions, to leave a residue of greatly ‘im
proved octane rating, and to subject the separat
This material is discharged into a second fur
nace 16 where it is heated to a temperature of
lyst, which catalyst is nickel tungsten sul?de.
It will be understood that numerous modi?ca
tions of my invention may be made by those
:skilled in the art without departing ‘from the
“spirit thereof. The fra‘cticn separated through
line H, for example, from fractionator 6 may
In order to saturate any ole?ns present in the
have a different boiling range from that herein
hydrocarbons charged to reaction vessel 20, hy
ibefore set forth, namely, from 180-220° F., that is
drogen from some source is also discharged into
to say, it may be a hexane or an octane fraction
about 800-950" F..and thence discharged through
line [8 ‘into a reaction ‘vessel 20 containing cata
and, if so, of course the aromatic product pro
the reactor 20 through lines'22 vand .18, the amount
of hydrogen being such that it exerts a ‘partial '10 duced would be benzene or one of the xylenes.
Alsoythe original charging stock may have a dif
pressure of 50-80% of the total pressure. The
ferent boiling range from that hereinbefore set
pressure prevailing within reactor '20 is of the
forth, although preferably it is a fraction boiling
order of 750-1000 lbs/sq. in., and the feed rate
within the gasoline range. Furthermore, also it
is of the order of about 0.5 volume of ‘oil per
volume of reactor per vhour. Under the condi 15 should be pointed out that the charging oil de
livered .to the system through .line I may be a
tions stated, the naphthenes are dehydrogenated
cracked stock, that-is to say, it may be a gasoline
to form toluene, while the ‘para?ins ‘present .in
fraction produced by thermally or catalytically
the'ly'apors are substantially unchanged. Reac
.cracking gas oil and, if so, it may contain con
tion ‘products are withdrawn overhead from re
=a'ctor"2ll ‘through ‘line 26 and discharged ‘into a 20 .siderable quantitiesoi ole?ns which means that
‘the amount of hydrogen employed in reactor .20
second ‘fractionator ‘28. From fractionator 28,
should be sumcient to saturate ‘the ole?ns. If it
the ‘toluene formed is Withdrawn through line 30.
:is acracked gasoline, particularly if it :is .a cata
The overhead product consisting essentially of
lytically cracked gasoline, the removal of the
heptane is withdrawn‘through line 32, thence dis
charged ‘into a third heater 34 where it is heated 125 lowest octane fractions may produce a residual
product of very high octane rating, namely, an
‘to a=temperatureoffrom about 900-1050°
‘a ‘temperature-of about 960° ‘F. being preferred,
aviation gasoline or a base stock which may be
blended with relatively small quantities, say
and at this temperature the heptane is with
"drawn through line~36 and-discharged into a sec
15-20% by volume, of alklated isobutane or
other .alkylates, to produce a high quality 'avia
ondreactor ?ll-containing a catalyst such as chro
:tion gasoline. Also, itshould be pointed out that
mium oxide supported on activated alumina, the
in the dehydrogenation of naphthenes carried out
portions being approximately 9 ‘parts by weight
of alumina per 1 ‘part of chromium oxide. In
.in reactor 20, I may use mixtures of sul?des of
stead of using chromium'oxide, molybdenum ox
the III and V group elements of the periodic
‘ide maybe used.
The pressure prevailing in reactor 49 is about
It should be noted that one of the ‘major ad
1 ‘atmosphere gauge pressure, and the material
vantages of my present invention resides in the
feature that less coke is produced in my two-stage
is fed to the reactor vat a rate of about 0.5 vol
ume of oil per volume of reactor per hour on a
process, since I treat the materials under condi
cold oil basis. The reaction products contain 40 tions which are less conducive to coke formation.
i. -.e., by treating naphthenes and para?ins sepa~
ing toluene are Withdrawn through line 42 and dis
charged into a fractionator 44 from which tolu
ene‘may be recovered through line 46. The over—
head fraction is Withdrawn, through line 68 and
recycled to line 32 for ‘further treatment in re
actor '40. The toluene ‘collected through lines 30
and 46 is discharged into equipment (not shown)
matter inherent in my invention, except that
.It is .my intention to claim all of the subject
pm. 9i' excluded by the terms of the appended claim.
What I claim is:
The method of treating a hydrocarbon oil
cracked stock containing ole?ns, naphthenes and
paraf?ns and boiling substantially within the
‘to re?ne and purify the same and to produce a
‘product of any desired degree of purity. The
"actual ‘puri?cation of this product is well known
’to the prior‘art and need not be described in de
‘It will '-‘be appreciated ‘that in both reactors
‘20 and-'40, it ‘will be necessary periodically to dis
continue the operation to regenerate the cata
lyst in‘ said reactors since, due to the reaction,
‘carbonaceous deposits are formed on ‘the said
catalyst. The method of regenerating the cata
lyst most commonly employed is that wherein it
gasoline range, to produce separately aromatic
compounds and a gasoline of substantially higher
knock .rating than said cracked stock, which com
prises vaporizing said cracked stock, passing the
vapors through a fractionating zone, removing a
‘light fraction, an intermediate hexane to octane
fraction, and .a heavy fraction, said light frac
tion and said heavy fraction containing com
pounds having relatively high anti-knock value
as compared with said intermediate fraction,
is vtreated ‘with an oxygen containing gas under 6 0 combining said light fraction and said heavy
such conditions of temperature and pressure as
‘fraction ‘to form gasoline, passing said interme
to burn the carbonaceous deposits formed there—
diate fraction through a heating coil and thence
on. This regeneration .method'isalso well known
‘into a hydrogenation ‘zone in which naphthenes
‘to the art. It should be pointed out that in
_'are converted into aromatic compounds and ole
stead of using :stationary beds of :catalyst inre (3 ° ?ns are saturated, thereby forming a product con
actors '20 and 40, a powdered catalyst may be
:used and the catalyst may be suspended in ‘the
sisting vprincipally of aromatic compounds and
'paraf?ns of 6 to 8 ‘carbon atoms "per molecule,
reaction vapors by means already known, during
separating the aromatic compounds and the 6 to
the reaction period and thereafter separating
8 carbon atom paraf?ns, passing the 6 to 8 car
‘catalyst from the reaction vproducts and return
0 bon atom parafiins through a heating ‘coil and
ing the catalyst to the reaction zone. vIn other.
thence into a zone where they are converted into
Words, any prior known method .of eiiecting con
a product composed mainly of aromatics, ‘and
tact between catalyst and reactants under reac
combining the aromatics produced by the two
tion conditions may be used in my improved
‘conversion stages 'hereinbefore recited.
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