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Патент USA US2405660

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Allg. 1.3, 1945."
N_ F_ |_|NN
Filed Oct. 17, 1942
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2 Sheets-Sheet l
Filed oct. 17,1942
2 sheets-sheet 2
Patented Aug. 13, 1946
Norman F. Linn, Mountainside, N. J., assignor to
Standard Oil Development Company, a corpo
ration of Delaware
Application October 17, 1942, Serial No. 462,323
3 Claims.
(Cl. 26o-673.5)
The-present invention is directed toward the
fraction is withdrawn through line 5, condensed
in a cooler ‘I and thence discharged through line
8 into a naphtha storage Vessel l0.
production of automotive fuel and, more par
ticularly, it relates to a method of improving a
hydrocarbon oil boiling in the naphtha and/or
The bottoms from distillation zone 3 and boil
gas oil range, particularly as regards octane
number, which naphtha or gas oi1 is of the
Fischer type. By “Fischer” type naphtha or gas
and Hz in the presence of a known suitable cat
ing say from 440-650o F. are Withdrawn through
line I5, condensed in a cooler Il, thence dis
charged through line I9 into a gas oil storage
vessel 20.
The overhead fraction and the gas oil bottoms
alyst and under known conditions of tempera
10 from the distillation zone 3 are treated as will
oil, I refer to hydrocarbons synthesized from CO
ture, pressure, etc.`
As is generally known, hydrocarbons may be
“Fischer” synthesized in the presence of suitable
be lmore fully explained hereinafter. At the out
set it is explained that the- naphtha is sub
jected to reforming in the presence of hydrogen,
catalysts such as iron, nickel or cobalt either
While the gas oil is cracked. ` The reforming op
alone or deposited on a carrier such as kieselguhr 16. eration results in the production of aromatics
or kaolin. This may be promoted and stabilized
which may be solventl extracted to recover, for
by alkalies and manganese and copper. These
example, toluene with a degree of purity suit
products, however, have a very low octane num
able for nitration.. The gas oil cracking also re
_ber since they are largely composed of normal
sults in the production of an automotive fuel
parafñns. Broadly speaking, my invention com 20 of high octane number, together with toluene of
prises improving the octane rating of such a
a high degree of purity.
hydrocarbon oil by subjecting it to a combined
Continuing the description of the process
hydroforming, solvent extracting and catalytic
shown in the drawings, the naphtha in storage
cracking operation. It is also concerned with
vessel I0 is 'Withdrawn through a line 35 and
the production of substantially pure aromatics, 25 thence discharged into a heater 32, which may
e. g. toluene of so-calledl “nitration grade’.’ by
«be a furnace or other suitable heating means,
subjecting selected fractions to a combination of
Where _it is heated to reaction conditions, thence
processes which will be more Vcompletely described
below. By “hydroforming” I mean to imply an
l discharged through line 35 into a reactor «45 >con
taining a _catalyst ofthe type previously indi
operation in which the treated oil is subjected 30 cated. Hydrogen from 50 is Withdrawn through
to elevated temperatures, say of¥ the order of
900-1000° F. and pressures of 10D-400 lbs. per
line 52, heated in a ñred coil or other heating
means `53, and thence discharged through line
square inch and in the presence of a catalyst,
55 into reactor 40 so it is present with the oil
chromia or molybdena- alone or supported on
undergoing treatment. vWith respect to operat
activated alumina, orother VI group oxide or a 35 ing conditions, the following give good results:
mixture of sulñdes, such as nickel and tungsten
sulñdes, and also employed in the presence of
added hydrogen. The hydroforming operation
is, for the most part, one of dehydrogenation
With the formation of aromatics and oleñns from 40
paraiiins, accompanied also by some cyclization
of paraiiins, aromatization, isomerization and
cracking of parafûns, but the operation generally
is conducted under conditions such that there
is a minimum changein the boiling range of 45
the _charging oil.
In the accompanying drawings, vIl have indi
cated diagrammatically a flow plan illustrating
a preferred modification of my invention.
Temperature _____ __ S50-1000’ F., with tempera
tures of from about 925
950° F. preferred.
Pressure _________ _- From 150-400 lbs. per sq. in.
gauge, with about 250 lbs.
pressure preferred. ~
Feed rate of oil-____ From 0.5-2 volumes of oil
per volume of catalyst per
hour on a cold oil basis,
with a feed rate of about
t 1.2 volumes of oil per Vol
um'e of catalyst per hour
Referring tothe drawings fora better under 50 Hydrogen proportion is in the range of from
say 2000-4000 cubic feet per barrel of cold oil.
standing of my invention, a Fischer synthetic
Under these conditions the naphtha undergoes
Ahydrocarbon is introduced'into >_the present Sys
tem through line >l_ and thence distilled in a
fractionator 3 into anv overhead fraction boil-k
reforming, and the reformed products are with
drawn through line 60 and discharged through
Within the- range of fromvlZS-fizeë 1F., which .5_5 a cooler 62. and thence discharged'through line
phase formed in extraction vessel ||5 and this
is Withdrawn through line |69 and discharged
into stripper |52 where the solvent is removed
withdrawn through line l2 and pumped by
by distillation, withdrawn through line |63 and
pump l5 to hydrogen storage vessel 55 for fur
5 pumped by pump |54 into storage vessel I Hl. The
ther use in the process.
substantially solvent-free extract is Withdrawn
The bottoms» from the separation drum 'l5
from stripper |62 through line |15 and discharged
are Withdrawnthrough line 80 and discharged
into.y a fractionating column |15.- The parafûns
into fractionator 85 from which several fractions
still remaining or associated with the toluene cut
are recovered as follows: First, an overhead
621 into a separation drum it. Overhead from
separation drum "i0 a hydrogen-enriched gas is
fraction boiling within the range cf from about 10 .
13G-210° F. and representing about 44 volume'
per cent of the oil in line >853 is withdrawn f
through line 38 and discharged after cooling
into condenser 90 and thencefintoa gasoline
storage vessel |80. The bottoms fraction'repre
senting about 39 volume per cent of the product
are withdrawn through line |85, condensed in
a condenser |32 and thence discharged through
line |83 into paraniníc wash solvent storage |20.
The toluene is recovered from fractionator |75
through line |90 and thence discharged into an
acid treating vessel |92 where it is treated pref
erably with sulfuric acid of polymerizing strength,
fed to the fractionator 55 is Withdrawn'through ~ - such as about 65% by Weight, or it may be treated
with` a polymerizing clay to polymerize the olei'lns
line 55, condensed in a cooler 97 and thence dis- .
charged into line 88 where it mixes with the
to convert them to heavier polymers which may
lighter ends from the iractionator and ñow's
with the latter into gasoline storage vessel |00.
Thus from the reforming omration, the lighter
be separated from the toluene by distillation.
The thus treated material is Withdrawn through
line |95 and discharged into fractionator 28|]
from which lighter ends may be withdrawn
through line 2id, While the heavier polymers are
withdrawn through line 2 | 2. The desired toluene
and heavier ends are recovered as gasoline blend
ing agents.
- ~
Referring again to fractionator 85, a side cut ï
is withdrawn as a side stream through line 265
and delivered into a toluene storage vessel 258.
The toluene in 268 has a degree of purity suii'icient
for making trìnitrotoluene or any other product
representing about 17% of materialcharged to
`85 and boiling within the range of >from about
21d-259° F. is withdrawn as a side stream through
line 55; This " fraction is purified by solvent
treatment, preferably, although other means may
requiring a high degree of purity.
A »
Referring to the heavy bottoms of the original
Fischer product, it will be recalled that these
were collected in storage drum 25. ’This mate
rial is to be subjected to-catalytic cracking and
towards this end it is withdrawn through vline
be employed. Thus, for example, thissfraction
-contains normally not only the toluene, but also
parailins boiling within the range of 21e-250° F.
and a minor amount of oleiins also boiling within
this range, although the' presence of hydrogenf
_tends to saturate oleñns formed in reactor Ml,
350, discharged into a suitable fired coil or other
heating means 3|0 where it is heated to cracking
temperatures, say from S25-925° F. and thence
tion is to producej paraf?ns andaromatics. »As
withdrawn through line 3|2 and discharged into
i indicated, these paraiiins in the vboiling range of
from 210-250° F. may be removed',y for instance, 40 a catalytic cracking reactor 325 where it contacts
a cracking catalyst such as an acid treated mont
>by cracking them to products -which’will boil
morillonite clay or a synthetic cracking catalyst
lower` than the toluene so that after- cracking,
so that the final result of the reforming opera
the toluene maybeseparated kby simple distilla
tion. In the drawings, however, I have shown
¿solvent treating employing SO2 as the selectiveV
'~ consisting vof silica :and alumina or silica and
Normally good results are obtained by operating
‘ solvent >forthe aromatics. Toward _this end, the
« ata temperature of 875° F; andat a relatively low
^- pressure and permitting Ycontact- between the
- catalyst and- oil vapors at-reaction temperatures
¿_ of from 15-25 seconds or more. Under these
` SO2 is withdrawn from lthe source ilßland» dis
chargedl intothe top of solvent extraction Vessel
| |5 Where it flows-countercurrently to the hydro
' carbon oil fraction entering from 55. f Asa fur
A- conditions the gas oil undergoes cracking to form
>ther aid to the process, a paraftlnicwash solvent
-catalytically cracked gasoline in good yields there
of» amounting to 35-40‘70. The cracked products
~ such aspentane isV withdrawnffrom the storage
>vessel |25- andv discharged-through line z$22 into
solvent extraction tower H5» ofcourse, in sol
"Vent -extraction tower ||5 the usual» formation
‘ are withdrawn through line 335 and discharged
' into fractionating column 335. ' Unconverted gas
is withdrawn from fractionator 335 through line
34B and thence discharged into storage Vessel 20
for further treatment. However, a portion vof this
- oil is Awithdrawn continuously through liney342,
Yparticularly as it becomes’increasingly refrac
tory, and the thus Withdrawn oil may be used’for
. of raffinate and extract phases takes place. 4The
raffinate phase is withdrawn through line |30
and discharged into a stripping tower |35.
_ rañinate is stripped to remove the SO2 which is
withdrawn through line |45 and pumped by pump
|1i2 to storage vessel lill. The bottoms from
stripper |35 are withdrawn through line |45 and
discharged into fractionating column |41. The
overhead fraction comprising the paraiiinic wash
vsolvent is Withdrawn _from the fractionator |47
»through line |49, condensed in condenser |55,
vthence pumped backv through line |5| to the
paraf?n storage .|2ll.. >The bottoms from frac
magnesia. The catalysts,- as Well as cracking con
ditions for this operation are known to the art.
a ‘heating oil or for some other purpose.
normally gaseous constituents are Withdrawn
i overhead from fractionator 335 through line 358.
f 4`These gases contain butylene, isobutylene, normal
butano and isobutane and they maybe processed
`in means not illustrated to form by alkylation
branchV k'chainV hydrocarbons boiling Within the
gasoline range, or they may be'converted to syn
'discharged into line |51 leading to gasoline stor-` 70 'thetic rubber intermediates suchY as butadiene,
or otherwise-rdisposedof.v
_' " q
age vessel |55. The bottoms Withdrawn `from
«A 'fraction boiling within the rangeïolB` from
Yfractionator Ml through line |55 maybe dis
charged through line |55 to- either the reforming
"100e-40|lf’F. is withdrawn from fractionator 335
tionator |41 are Withdrawn through line |55 and
lzone 4i) or the 'cracking zone 320.
~I ’
" ' As previouslyindicated, there is"an"'e'Xtract
`throughiine~360 and discharged into a'fractîon
ating 'column‘ 310. ~ AThe product entering 310 is
divided preferably into three fractions as follows:
first, an overhead fraction containing the lighter
ends which is withdrawn through line 380 and
condensed in a cooler 38| and thence discharged
there will come a time when it is necessary to
regenerate the catalyst in the reactionk zones.
This may be accomplished, after discontinuing
the flow of oil to the reaction Zones, by treating
.the catalyst with an oxygen-containing gas, such
into stream 88 where it flows with the overhead
from the reforming operation into gasoline stor
as air, or air diluted with fiue gas, at tempera
tures elevated sufficiently to cause burning o-f the
age vessel Iûû. The bottoms from fractionator
310 may be withdrawn .through line 390, con
fouling deposits. This procedure is well known
densed in cooler 39| and also discharged into
in the art. Where the catalyst in powdered form
gasoline storage vessel |00. Finally, an interme 10 moves in and out of the reactors, it may be re
generated in separate regeneration zones and
diate cut boiling from 21o-250° F. and represent
ing about 10% of the material discharged into
thus render the operation continuous.
fractionator 310 is Withdrawn as a side stream
Another ramification of my process as herein
through line 400, and this may be discharged into
described involves -including the reproportionat
ing of xylenes, formed during the reforming, with
line 99 to recover with the product from the re
benzene in the presence of a suitable catalyst
forming operation, its toluene content, in a man
such as AlCla whereby additional quantities of
ner which has already been described.
toluene may be produced. The details of this
In an alternate modification, the intermediate
cut boiling from 210-250° F. which is withdrawn
process are generally known in the prior art.
from fractionator 310y through line 400 Vmay-be 20
What I claim is:
discharged into line |58 for ultimate reforming
l. A method of producing toluene of high pur
in zone G0 or passed through lines> |56 and 305
ity from a hydrocarbon product obtained by the
to coil 3|û and thereafter cracked.
hydrogenation of carbon monoxide which com
prises fractionating the said hydrocarbon product
Many modifications of the invention as above
set forth may be made without departing from 25 into a naphtha fraction and a gas oil fraction,
submitting the latter to a cracking treatment at
the spirit thereof. I have shown solvent extract
ing a toluene fraction with liquid sulfur dioxide.
a temperature of the order o_f S25-925° F. in the
presence of a catalyst suitable for promoting the
Instead of using this method, I may use another
cracking of aliphatic hydrocarbons, recovering a
solvent such as phenol, in which operation the
vapors to be extracted are treated with liquefied 30 fraction boiling at about 210° to about 250° F.
anhydrous phenol. This process or the process
from the product of said cracking treatment, com
of extracting the liquid SO2 do not form per se
bining such fraction With the naphtha fraction
the gist of my invention and any known method
obtained in the fractionation of the product of
for recovering toluene by solvent extraction may
the hydrogenation of carbon monoxide, subject
be employed. If the solvent is SO2 the tempera 35 ing the combined `fractions to a reforming treat
ture maintained in the extraction zone I I5 should
ment at a temperature of the order of S50-1000“
be from O to --60° F. or lower.
The flow of SO2
F. and under a pressure of the order of 1GO-400
with respect to the hydrocarbon should be from
lbs/sq. in. in the presence of hydrogen and a
1-3 parts by Weight of SO2 per weight of hydro
catalyst comprising an oxide of a group VI metal,
carbons and the volume of paraffinic wash sol 40 recovering from the product of said treatment a
vent, for example, pentane from |20 should be
fraction boiling at about 210° to about 250° F.
from 1/2 to 11/2 volumes of the wash solvent per
and treating such fraction to selectively separate
volume of liquid consisting of SO2 and the hydro
therefrom its aromatic content.
carbon in the extractor ||5.v Of course, it will
2. A process according to claim 1 in which the
be appreciated that in reactors 40 and 320 the 45 aromatic content of the fraction produced in the
reactions therein taking place result in the dep
reforming treatment is separated therefrom by
osition of cokey or tarry deposits on the catalyst
extraction with a solvent, followed by treatment
and these operations must be interrupted inter
of the extract phase with a parañinic hydrocar
mittently to remove these deposits since they de
bon solvent lighter than the parafìnic hydro
activate the catalyst. This can be accomplished 50 carbon remaining in said extract phase to dis
in known manner by burning off the tarry or
place the latter, and distillation toÍ remove the
cokey deposits with an oxygen-containing gas.
said lighter parafñnic hydrocarbon solvent from
In the foregoing disclosure, I have described
the aromatic hydrocarbon product.
my process in terms of fixed or stationary beds
3. A'process according to claim 1 in which the
of catalyst. My process may be carried out using
aromatic content of the fraction produced in the
a suitable powdered catalyst suspended in the
reforming treatment is separated therefrom by
reaction vapors in the several reaction Zones.
extraction with a solvent, followed by treatment
Thus, the reforming and/or cracking operations
of the extract phase with pentane to displace the
may be carried out by flowing the vapors to be
parafiinic hydrocarbon remaining in said extract
cracked or reformed through a zone where they
phase, and distillation to remove the pentane
contact a ñuidized powdered catalyst which is
from the aromatic hydrocarbon product.
suspended in said vapors.
Also, of course, in the operationsl described
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