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Патент USA US2285727

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June 9, 1942.
v_ |_ KOMAREWSKY
v2,285,727
TREATMENT 0F GASOLINE
Filed Jan. .'50,> 1959
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2,285,721
estema June 9, 1942
UNITED STATES PATENT oFFlcE
TREATMENT 0F GAS OLINE .Y ‘
Vasili I. Komarewsky,` Chicago, Ill., assignor to
Universal Oil Products Company, Chlcago,'lll.,
a corporation of Delaware ,
,
Y
Application January 30, 1939, Serial No. 253,603
(C1. 196-49)
17 Claims.
This invention relates particularly to the treat
ment of gasolines of inferior knock-rating to im
' step to further treatment with catalysts effective
in dehydrogenating and producingfcyclic com
pounds from the parailln hydrocarbons.
prove them in this respect and is specially con- 1
cerned with a catalytic treating process for ac
complishing this object.
'
It is within the scope of the invention to em
5 ploy different catalysts in the two stages or to
employ the same catalyst with the temperature
and other conditions so that the dehydrogena
tion 'of the naphthenes is brought about in the
primary stage withv substantially no eñect ¿on
While the'proces's to be disclosed is primarilyl
adapted to the treatment of straight-run gaso
line's produced by the simple distillation of crude
oils, it may be also applied under suitably modi
ñed conditions of operation to cracked gasolines 10 aliphatic hydrocarbonswhile the -said aliphatic
hydrocarbons are dehydrogenated and cyclicized
in conjunction with the cracking process to in
in the second stage under moreïsevere conditions
crease the overall e?ñciency thereof.
’
"i
of operation in regard to temperature and time‘of
Apart from the small amounts of contami
contact. This point will be developedfin later
nating compounds containingV sulfur, nitrogen,
and oxygen which are present in varying amounts 15
in straight-run gasolines, extensive analyses for
The process of the present invention -is to some
extent based on thefact that the conditions and
hydrocarbon groups have shown that straight
catalysts best » employed for dehydrogenating
run gasolines consist essentially of mixtures of
6-carbon atom naphthene hydrocarbons and var_i
naphthenes are sharply differentiated from those
ous parañin hydrocarbons in varying proportions. 20 which are best for dehydrogenating and cycliciz
‘ ing straight chain hydrocarbons. Whereas cata-ï
'I'he group analyses thus far madel do not gom
pletely distinguish between naphthenes of 5, 6, ~ lytic reforming processes are known for improv
ing the antiknock value of gasolines inferior in
and 'l carbon atoms inthe ring orbetween par
this respect, substantially all of‘these processes
amn hydrocarbons of normal or branched chain
structure, _but for the purpose of the present de 25 operate in a single stage with a‘selected catalyst
under average conditions which are foundgby
scription of a 'process applicable to improving
the knock rating of these gasolines, they may be ~
trial to produce the best overall results but usually
considered as consisting of varying proportions
not the 'optimum for the treatment of the vdii
examples.
v of cyclo-hexane and its alkylated derivatives on
'
f Y
'
ferent hydrocarbon groups separately. . For ex
the one hand and the various normal paraiiln 30 ample, cyclo-hexane and other naphthenes are
hydrocarbons ranging from approximately 5 to
readily- dehydrogenated to benzol and its al
12 carbon atoms to the molecule on the other
kylated derivativesy by contacting >their vapors
with nickel or other members of the iron group
It is a known fact that in general the more
at temperatures of the order of 250-300’ C. 'I'hese
35
highly unsaturated compounds of a given mo
conditons, however, are usually without material
lecular structure have a higher antiknockyalue
efl’ect upon paraiiin hydrocarbons of gasoline boil
hand.
.
'
'
than the saturated compounds. VIt is further
ing range and if conditions oi' increasing severity
are employed'with the same catalysts, the par
generally higher antiknock value than straight
aiilns show a greater tendency to -sui’ñer carbon
chain compounds of asimilar >number of `carbon 40 to-carbon splitting and the formation of unde
known in general that cyclic compounds have a
atoms unless the latter are of a branchedchain
or isomeric structure. 'I'he process of the pres
ent invention utilizes both of these facts in con
verting in the most selective and generally ad
vantageous manner substantial proportions of
the naphthene content of gasolines into aromatics
and substantial proportions of the paraffin con
tent into oleflns and aromatics as will be herein
after more fully disclosed.
In one speciiic 'embodiment the present in
vention comprises a process for improving the
sirably‘large amounts of gases and heavy liquid
v byproducts.
45
As previously intimated, it is within the scope
of the invention to use other catalysts than nickel
or the other members of‘V the iron group in the
first stage and these catalysts may be of'a mixed
character such as, for example, alumina support
ing both nickel and chromium sesquioxide. In
the manipulation of the process with such cata
lysts it is possible to regulate conditions so‘that
substantially only naphthenes are dehydrogenate'd
in the 'primary stage, the temperatures usually
first subjecting the gasoline to contact with cata
employed for thîsbelng of the orderoi 35o-450°
lysts eiïective in dehydrogenating the naphthenesl
and then subjecting the gasoline from the first 55 C. depending upon the percentage of naphthenes
anti-knock value of gasolines which comprises
2 .
2,285,727 ,
hydroxides or carbonates furnish suitable sup
present and the activity of the particular cata
lyst employed.
ports for the catalytic oxides and a catalyst
Ifv catalysts are employed which are primarily
which has given excellent-service consists of
effective in dehydrogenating and cyclicizing the
granular activated alumina supporting minor
parañin and other straight-chain hydrocarbon
compounds present in admixture with naphthenes
proportions (usually 15-20% by weight) of chro
mium sesquioxide. The temperatures employed
in a given gasoline, the conditions employed are
in the second step are preferably somewhat
higher thvan'thos’e employed in' therprimary stage
usually too severe for the simple dehydrogenation
of naphthenes and the catalysts furthering the
of the process and are usually 450° C. or higher,
reactions cf the parafiins are not as speciñc in 10 this combination of temperature and catalyst
being substantially without effect on the aro
their dehydrogenating effect upon naphthenes as
matic hydrocarbons produced from the first
the nickel and other materials mentioned. vThe
present invention comprises therefore the step
stage.V
binations ofcatalysts and conditions specific to
the dehydrogenation of naphthenes and secondly
those catalysts and conditions which tend to cause
dehydrogenation and dehydrocyclization of par
afñns.
'
~
~
For-the dehydrogenation of naphthenes, nickel,
’
'
The accompanyingv drawing is a flow diagram
of the process of vmy invention. The naphtha
wise aromatization of gasolines using first com- ' `
charging VVstock'isV supplied to tne vsystem by way
of line l from which it is Ydirected to the first
dehydrogenating zone indicated by 2 in the draw
» ing.t In this zone the hydrocarbonsare sub
20 jected to> contact with a dehydrogenating cata
cobalt and iron have already been mentioned,
but it is within the scope of the invention toV
lyst under conditions effectivefin the dehydro
employ if desired more expensive materials such
hereinbefore set forth, >the temperature' of the
as the members of the platinum group, including
catalyst in this stage is of the order of 25o-450° C.
genation of naphthenes to form aromatics. . As
platinum, palladium, iridium, osmiurn, etc. In 25 while utilizing suchcatalysts as 'nickel on` sup
porting materials such as kieselguhr or other
the operation of the process, best results“ are
substances ofsiliceous’ ' or alumin'ous character.
usually obtained when these metals are used on
relatively inert granular supports to present a _ The products of this `dehydrogena‘tion’'zone are
removed byway of line 3 and,_if desired, may
larger `catalytic surface due to their extensive
distribution. Various types of supporting mate 30 be directed to a separation zoneY No. 1, ,indicated
by 5 in the drawing.V Inthis separation zone,
rials of a siliceous or alurnîrifous character may
hydrogen together with smaller quantities' of
be
kieselguhr
employed
andasother
carrierssuch
forms of silica,
as, forclays,
example,
and' s
normally gaseous hydrocarbons is removed from
other silicates, alumina, either naturalbr‘pre
pared and other inert materials. In the treat
35
ment of most gasolines with such catalysts, tem
peratures of approximately300° C. are employed
in the first stage, thegasoline being vaporized
the 'system' by wayfofI line 6." If 1desi'red, this
separation vstep may be omittedand the reaction
products from the first dehydrogenation zone in
.this case are directed from line 3 to'iline I which
connects with line l, rsi'ipplying the second dehy
drogenation zoneindicated by B in the drawing.
andpas'sed over a selected and active dehydro
genating metal catalyst at a rate commensurate 40 y In'the second dehydrogenation‘zone the'v par
aillns are Yldehydrocyclici‘z'ed to form aromatic
with obtaining best results in converting the
naphthene ~content into aromatics.v Obviously
hydrocarbons. The temperature in the second
the exact conditions of‘operation will be deter
zone lies within the approximate rlimits of 450
mined by the amount and’character of the naph
l750" C. Effective catalysts in the' second zone
treated.
'supported >on refractory materials-such’as alu
thenes present in whatever gas mixture is being 45 comprise particularly group 5 and group 6 oxides
'
„
’
`
After the aromatization of 'the naphthene con
‘ mina.` GroupV 4 oxides `have'also been used> but
tent, the type of catalyst is changed and the
in general are regarded as less electiveA than
vapors with or without separation of hydrogen
such oxides as those'of vanadium, chromium and
and other reaction products are contacted with 50 molybdenum. The products 4from the second
catalysts which have a dehydrogenating and
dehydrogenation zone"v are directed by way of
line 9 to a`second separation zone indicated by
cyclicizing activity with respect to residual par
añin hydrocarbons. Catalysts of this character
l0 in the drawing. Inthis second separation
zone, hydrogen and normally gaseous. hydro
include generally compounds and particularly
oxides of the elements in the left-hand columns 55 carbons are separated from -,the stabilized gaso
.line which constitutes the product ofthe process.
of groups 4, 5, and 6 of the periodic table, includ
ing titanium, zirconium, cerium, hafniurn,'tho-
It is usually found desirableto rerun the stabi
lized gasoline in order toreduce the "quantityof
rium, vanadium, columbium, tantalum,- chro
mium, molybdenum, tungsten, and uranium.
Such catalysts are readily prepared by deposit
gum formingconstituents present therein. '. `
ing nitrates or other salts or hydroxides of the
elements on miscellaneous supports and’calcin
ing and reducing with hydrogen or‘hydrocarbons
to produce the lower oxides. The optimum percentages of these oxides which are suitable for
.
Thejfollowing example- is given to ¿indicate the
advantages of. thejpresent type fofprocess in .im
proving the antiknock value of vstraight run gaso
lines, although it will be'understood 'that cata
lysts and conditions willbe considerablyV niodiñed
in thecase ofl other gasolineslso that the exam
effecting the desired dehydrogenation and cycli
cizing~of mixtures of paraffin hydrocarbons will
ple `is not intended to4 place'undue limitations y
obviously vary with the amount and character
A Pennsylvania straight run gasoline fraction
boiling between 100 ,and 150° Cfa'ndhavingan
of the paraffin hydrocarbons and the lactivity
of the particular oxide promoter. However, a
on the scope ofthe invention.
.
,
l
octanenumber by the motor method of 43' .was
few trials will determine which is the most effec
tive in a given instance. Granular activated
treated by three'different procedures as follows:
V.aluminas prepared from precipitated aluminum
sistingof reduced nickelon alumina'at atem
(l) vVapors were passed noverjacatalyst con
' perature of 300‘7 C. .and substantially atmospheric
hydroxide by calcination methods or by similar
treatment of some'naturally occurring aluminum 75 pressure. After this treatment, >it was found by
2,285,727
analysis that the percentage of aromatic hydro
carbons was 36.5 and that the octane number
4. A process for the treatment of >gasoline to
„increase the antiknock value thereof which corr
prises subjecting- vapors of said gasoline in a
first stage to contact `with a catalyst containing
has been raised to 51. The gas evolved consisted
of 95% hydrogen.
' 3
-
a metal 'effective in dehydrogenating naph
thenes, and in a second stage to contact with a
After separation of hydrogen the product of
the first stage was passed over an alumina
chromia catalyst at va temperature of 45,09 C.
catalyst containing a metal oxide effective in n
and analyses indicatedrthat the percentage of
dehydrogenating and cyclicizing parafl‘lns.
y
5. A process for the treatment of'straight run
aromatics had been increased to 55 and the
octane number raised to '15.L The gas evolved
in the second stage was 92% hydrogen.
gasoline to increase the antiknock value thereof
(2) A catalyst was prepared which contained
both nickel and chromium oxide on alumina and
thevapors of the gasoline fraction were passed
15'
over this catalyst vat a temperaturer of 450° C. to
simulate a one-stage reforming operation.~ This
treatment produced an aromatic vcontent of 45%
which comprises subjecting vapors of said gaso
line in a first stage to contact with la catalyst
containing a metal effective indehydrogenating
naphthenes,4 and in a second stage to contact
with a catalyst containing a metal oxide `effec
_tive in dehydrogenating and cyclicizing paraflins.
evolved contained 85% hydrogen. rIt will be seen
6. A process for the treatment of cracked gas
'oline to increase the antiknock value thereof
which comprises subjecting the vapors of said
by this test that poorer results were obtainedbyg
combining the catalyst and using a single se
lyst containing a metal effective in dehydrogen
lected temperature for _the reforming operation.
ating naphthenes, and in a second stage to con
and raised the octane number to 65. The gas
gasoline in a first stage to contact with a cata
tact with a catalyst containing a metal oxide
(3) Using `an .alumina-chromia-nickel cata
effective in dehydrogenating and cyclicizing
lyst, the vaporized gasoline fraction was treated
at 405° C. to increase the aromatic contentl to
parafìlns.
_
-
7. A process for'the treatment of ' gasoline to
increase the antiknocky value thereof which com
prises subjecting vapors of said gasoline in a
first stage to contact at a temperature of the
45% and raise the octane number to 57, the gas
evolved consisting of 94% hydrogen. In the sec
ond stage the products were passed over the same
catalyst at 450° C., the yield of products consist
ing of 60% aromatics and having a 75 octane 30 order of Z50-350° C. with a catalyst containing
a metal eiîective'in dehydrogenating naphthenes,
Vnumber, and the gas evolved consisting of 91%
and in a second stageto contact at a tempera
hydrogen.
ture of the order of 45o-750° C. with a catalyst
It will _be seen from the immediately preceding
containing a metal oxide effective-in dehydro
data that better results were obtained with an
"alumina-chromia-nickel catalyst when the aro- '
matization of the gasoline was conducted in two
stages as in section (3) since the octane number
obtained was 75 whereas that obtained in the
single-stage treatment under section (2) was
only 65.
genating and cyclicizing paramns.l `
8. A process for the treatment of straight run
gasoline tó> increase the antiknock value thereof
which comprises subjecting vapors of .said gaso
line vin a first stage to contactA at a temperature
40 of the order of 25o-350° C. with a catalyst con
taining naphthenic and aliphatic hydrocarbons
taining a metal effective in dehydrogenating
naphthenes, and in a second stage to contact at
a temperature ofthe order of 45o-750° C. with
to increase the antiknock value thereof which
a catalyst containing a metal oxide eñective in
I claim as my. invention:
1. A process for the treatment of gasoline con--
comprises subjecting vapors of said gasoline in 45 dehydrogenating and cyclicizing parafllns.
9. A process for the treatment of cracked
a first stage to contact at a temperature of the
gasoline to increase the antiknock value thereof
order of 250-450° C. with a catalyst effective in
which comprises subjecting the >vapors 4of said
dehydrogenating naphthenic A hydrocarbons and
cracked gasoline in a first stage to contact at a
in a second stage to contact at a temperature
within the range of 45m-750° C. with a catalyst 50 temperature of- the order of 25o-350° C. with a
effective in dehydrogenating and cyclicizing ali
phatic hydrocarbons.
‘
'
2. A process for the treatment of straight run
Agasoline containing naphthenic and aliphatic
catalyst containing a metal effective in dehydro
genating naphthenes, and in a second stage to
contact at a temperature of the order of 450-750"
C.' with a catalyst containing a metal oxide
effective in dehydrogenating >and cyclicizing
hydrocarbons to increase the antiknock value 55 _ parafllns.
thereof which comprises subjecting vapors of
10. A process for the treatment of gasoline to
increase the antiknock value thereof which com
prises subjecting the vapors of said gasoline in a
lyst efïectivé- Ain dehydrogenating naphthenic
first stage to contact at-“a temperature of the
60
hydrocarbons and in a second stage to contact
said gasoline in a first stage to contact at a tem
perature of the order of Z50-450° C. with a cata
at a temperature within the range of 45,0-'750°
C. with a catalyst effective in dehydrogenating
and cyclicizing aliphatic hydrocarbons.
-order of Z50-350° C. with a reduced nickel cata
lyst effective 'in dehydrogenating naphthenes,
and in a second stage to contact at a tempera
ture of the order of 450~750° C. with a catalyst
3. A process for vthe treatment of cracked gas
containing a metal oxide effective in dehydro
oline containing naphthenic and aliphatic hy 65 genating and cyclicizing parai‘llns.
drocarbons to increase the antiknock value
thereof which comprises subjecting vapors of
11.- A‘process for the treatment of gasoline to
increase the antiknock value thereof which com
prises subjecting the vapors of said gasoline in
70 a first stage to contact at a temperature of the
catalyst effective in dehydrogenating naphthenic
order of 25o-350° C. with a reduced nickel ca* hydrocarbons and in a second stage to contact
lyst eñective- in dehydrogenating naphthenes,v
at a temperature within the range of 45o-'750°
and ln a second stage to contact at a tempera
C. with a catalyst effective in dehydrogenating
ture of the order of 450-750°7C. with a catalyst
said gasoline in a first stage to contact at a
temperature of the order of 250-450° C. with a
and cyclicizing aliphaticl hydrocarbons.
.
consisting essentially of granular activated alu
,
2,285,787
15. A process for »increasing the anti-knockl
mina- supporting chromium sesquioxide effec
4
value of gasoline distillate: containing naph
tive in dehydrogenating and cycliciaing paraiiins.
thenic and aliphatic hydrocarbons which com-i
prises contacting the distillate with a dehydroà.
12. A process for the treatment of gasoline `to n
increase the antiknock value thereof which com- »
prises subjecting the vapors of said gasoline in
a ñrst stage to contact at a'tcmperature of the
order of 250-350 C. with a reduced nickel cata
genating catalyst under dehydrogenating oon
mina' supporting vanadium sesquioxide effective
in dehydrogenating and cyclicizing paramns.
value of gasoline distillates containing naph
ditions'selective for the conversion'of naphthenes`
to aromatics, and thereafter subjecting the thus
partially aromaticized distillate to catalytic de
lyst eiïective in dehvdrogenatingl , naphthenes,
hydrocyclization to produce further quantities
and in a second stage to contact at a tempera
ture of the order of 450-750° C. with a catalyst 10 of aroinatics- from the aliphatic hydrocarbons.
16. A process for increasing the anti-knock
consisting essentially of granular activated alu
thenic and aliphatic hydrocarbons which com
prises contacting the distillate with a dehydro
genating `cataLvst under dehydrogenating condi
tions .selective for the conversion of naphthenes
to aromatica, and thereafter subjecting the thus
partially aromaticized distillate to further con
tact with dehydrogenatingcatalyst under con
lyst effective in dehydrogenating naphthenes,
andA in a second stage to contact at a tempera 20 dltions selective for the dehydrocyclization of
13. A process for .the treatment of gasoline to
increase the antiknock value thereof which com -15
prises subjecting the vapors of saidgasoline in
a ñrst stage to contact at a temperature of the
order of 25o-350° C. with a reduced nickel cata-V
ture of the order of 450-'150’ C. with a catalyst
' . aliphatics into aromatica.
1'7. A process for increasing the anti-knock
consisting essentially of granular activated alu
mina supporting molybdenum sesquioxide effec
tive in dehydrogenating and cyclicizing paraiiins.
value of~ gasoline distillates containing naph
increase the antiknock value thereof which com
genating catalyst under dehydrogenating condi
tions selective for the conversion of naphthenes
thenic and aliphatic hydrocarbons which com
14. A process for thertreatment of gasoline to 25 prises contacting the distillate with a dehydro
prises ‘subjecting the vapors of said gasoline in
a _first stage to contact at a temperaturel of the
order of 35o-450° C. with a composite catalyst
comprising essentially arelatively inert mate
v rial supporting chromium sesquioxide and re
duced nickel to dehydrogenate naphthenes and.
to aromatica, and thereafter subjecting the thus
partially aromaticized distillate to further con
30 tact with an additional quantity of said dehy
drogenating catalyst under conditions selective
for the dehydrocyclization of aliphatics .into
aromatica.
in a second stage to contact with a separate por
tion of the same catalyst at a temperature of
the order of 45o-'7509 C. t0 dehydrogenßte and 35 _
cyclicize aliphatic hydrocarbons,
VASILI I. KOMAREWSKY.
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