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Патент USA US2411054

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Nov. 12, 1946. _
E. `|--. PEVERE
2,41 1,054
CATALYTIC CONVERSION OF HYDROCARBONS
Filed April 15. 1942
ERNEST E PEyERE
IN VENTOR
Patented Nov. 12, y1946
2,411,054
UNI-TED STA-ras PATENT OFFICE
2,411,054
CATALYTIC CONVERSION 0F
HYDROCARBONS
Ernest F. Pevere, Beacon, N. Y., assigner to The
Texas Company, New York, N. Y., a «corpora-
..
tion of Delaware
Application April 15, 1942, Serial No. 439,048
2 Claims.
(Cl. 26o-683.5) ` .
This invention relates to the catalytic conver
sion of hydrocarbons for the production of hydro
carbons suitable in the manufacture of gasoline.
More particularly, the invention relates to the
catalytic conversion of relatively low boiling sat
urated hydrocarbons to produce hydrocarbons of 5
zone and is thereby consumed in the production
of valuable hydrocarbon products rather than
entering into reaction with the catalyst to form
complex. At any rate under such conditions a
definite promoting effect is realized.
Moreover, the conversion reaction can be car
ried out at lower temperatures than prevail in
the ordinary isomerization reaction. In addition
hydrocarbons, such as saturated relatively low
boiling hydrocarbons derived from a petroleum 10 the character of the product is diiîerent. For
example, when isomerizing normal butanle by the
source, to the action of a conversion catalyst' in
highly branched chain character.
The invention contemplates subjecting feed
action of aluminum chloride and hydrogen chlo- '
a reaction zone under conditions such that isom
ride at a temperature of about 120° F. in the pres
erization constitutes the principal reactionI and
ence of a small amount of ethylene and in ac
eiTecting the reaction in the presence of a small .
amount of olefinic hydrocarbon in such a way as 15 cordance with the method of this invention, the
product contains very lsubstantial amounts 0f
to substantially promote the lsomerization reac
tion.
. neohexane and methylpentanes.
'
The following experiments comprise batch liq--
More specifically the invention contemplates
uid phase experiments in which normal butane
eiîecting the reaction so that a relatively small
amount of low boiling oleñn, inthe presence of 20' was converted by the action of aluminum chloride
and hydrogen halide at a temperature of about
isoparafiin hydrocarbon,` is maintained in the
isomerization reaction, the isoparañin advanta
geously being present in substantial amount rela
tive to the olefin at and subsequent to the initial
contact between the feed hydrocarbon and the 25
conversion catalyst. Advantageously' both iso
parañin and oleiin are maintained present
150° F. In each experiment anhydrous aluminum
chloride, hydrogen chloride and some hydrocar
bon were charged to a reaction .vessel provided
with a stirrer and means for heating the vessel.
The stirrer was then started and the tempera
ture adjusted to the desired point, lfollowing l
which hydrocarbon feed was added slowly over
a period of 1 hour, the mixture being stirred for
It has been found that by carrying out the
conversion in the foregoing manner and particu 30 30 minutes afuter completion of the addition of
the hydrocarbon. Thereafter, the reaction mix
larly at temperatures lower than normally used
ture was drawn off and the hydrocarbon product
in isomerization, the hydrocarbon reaction prod
separated into gaseous and liquid fractions, re
uct obtained contains a materially greater pro
spectively.
The gaseous fraction comprised essen
portion of isomerized` feed hydrocarbons than
when the reaction is carried out in the substan .35 tially isobutane, normal butane and lighter hy
drocarbons, while the liquid fraction comprised
tial absence of olefin hydrocarbon. The reason
normally
liquid hydrocarbons free from butanes.
for this is not clearly understood, but neverthe
The following tabulation compares the amount
less the existence of a substantial promoting
of catalyst, hydrocarbon charge, and hydrocarbon
effect through having both oleñn and isoparamn
present at least during the initial contact between 40 product in parts by weight. 'I'he composition of
the gas and liquid fractions of the product is
iced hydrocarbon and catalyst appears to be sub
shown in per cent by weight.
throughout the entire reaction.
stantiated by examples which will be describedA
hereinafter.
In the isomerization of normal paraffin hydro
carbons with a, metallic halide catalyst it has 45
been found desirable heretofore to remove oleñns
from the feed to the reaction zone since under
Catalyst:
ordinary conditions oleiins, if present, appear to
Reaction temperature, ° F .............. __
Hydrocarbon
charge:
A
_.
cause catalyst deterioration and result in a sub
Normal butano _______ ._
stantial decrease in the yield of isomerized hy 50
Ethylene .............. _.
drocarbons per unit of catalyst employed.
Mols of butano per mol oi ethylene. _ _
'
The present invention, however, involves hav
ing a substantial amount of isoparañin present
with the oleñn during the initial contact between
the feed hydrocarbon and the catalyst anf
throughout substantially the entire reaction.
Advantageously the isoparañ'in is present in sub
stantial molar excess over the olefin. It appears
C
»
Aluminum chloride .................... ._
Hydrogen chloride ......... _-
B
_..
Isobutanc ............ _i
110
10l
1li)
110
lll
l0
15o
»15o
150
540
53D
392
0
0
_
0
26
25
__
0
10, 0
V8, 3
Mols ol isobutane per mol of lethylene ____ _ _
Hydrocarbon product: (las fraction ......... _ _
0
530
0
50o
0_ 8
404
Composition oi gas fraction:
Percent lighter than isobutane..
Percent isobutane ............ __
Percent normal butanc ....... _.
_.
_.
Percent isopentane and heavier _________ _.
4l
0. l
0. 5
l. 8
11.0
87. 5
19. 4
76. 0
42. 1
5l. 9
1. 4
4. 1
4, 2
charged ................................... _ _
10. 2
18. (l
32. 9
Liquid fraction ________________________ _; _ _ ___
None
Yield ol- isobutane, basis normal butane
Percent yield of liquid fraction basis ethylene- ...... __
40|
5S
154A
252
that .under these conditions the olefin is utilized
in alkylatlng isoparamns present in the reaction 60
In experiment A the hydrocarbon charge. con
3
carbon'atoms as well as light naphtha fractions I’
boiling in the range up to about 150 to 170° F.,
for the purpose of converting normal and»
branched chain saturated hydrocarbons into
slsted lsolely of normal butane. In experiment B
ethylene and normal butane was introduced con
tinuously throughout the ,entire run. In ex
periment C isobutane was present initially in
the reactor and ethylene and normal butane
were introduced continuously throughout the
entire
run.
_
.
branched and more highly branched chain
saturated hydrocarbons. In addition it is con
templated that other types of hydrocarbons such
as relatively low boiling naphthene hydrocar
»
In experiment A it will be observed that under
bons may be isomerized.
'
the conditions employed, the -yield of isobutane
Other normally gaseous olefins may be em
amounted „to 10.2% by weight of the normal 10 ployed besides ethylene, for example propylene,
butane charged. However, in experiment B with
butylenes, amylenes, and mixtures thereof, al
a small amount of ethylene present the yield of
though the lower molecular weight olefins are
isobutane obtained amounted to 18.0% by weight
preferred. The proportion of olefin charged to
of the normal butane charged. On the other
the reaction may range from about 0.5 to as
hand, in experiment C where a small amount of 15 much as 10% and advantageously not exceeding
lsobutane was initially present along with the
about 5% by volume of the total feed tothe
ethylene the‘conversion of normal butane to iso
reaction.
butane was nearly doubled. l The results in ex
The >isoparaiîiin introduced to the reaction ad- I
periments Band C calculated on the basis of 100
pounds of normal butane charged may be tabu 20 vantageously comprises a relatively low boiling
isoparaiiin _such as isobutane or isopentane. It
lated as follows:
may be obtained from an extraneous source or
may be separated from the reaction product and
recycled to the reaction zone. The isoparafiin is
maintained in the reaction in the ratio of from
25 about 1 to 10 mols of isoparamn per mol of ole
hai-ge:
Normal butane. _ _
Ethylene_____...._
l*.
Isobutane ..................................... _.
Products:
v
71.
Normal butane _________________________ __
Isobutane .............................. ._
_
18.
.
ñn. As indicated in experiment'C good results
oaums:
l were obtained with- a ratio of nearly 1.
7
Normally liquid fraction ....................... __
In no
case, however, should the isoparaflin exceed about
30
Reference may be had to the accompanying
»The liquid fractions obtained in experiments B
and C comprised hydrocarbons boiling over the
range about 85 to 175° F. and consisted mainly of
pentanes and hexanes.
The following additional experiments afford a
" 50% by volume of the normal paraffin undergoing '
conversion in the reaction zone.
' drawing comprising a. flow diagram illustrating
_ one mode of practicing the invention in a con
35 tinuous flow operation.
A hydrocarbon such as a normal paraffin hy
drocarbon or mixture consisting. essentially or , "
normal paraffin hydrocarbons is drawn from a
source not shown through a pipe I and conducted'`
comparison of the yield and product character
when reducing the reaction temperature from
150 to about 120° F. These experiments were
carried out in a similar manner to that described 40 to a heater 2 wherein it is heated to the reaction
above.
temperature. Oleñn may lloe present in the feed
~
in the requisite amount or may be'added sepa- '
D
Catalyst:
»
Aluminum chloride ............... _ _~_ ________ __
Hydrogen chloride ....... _ _
_
_
Reaction temperature. ° F___._
Hydrocarbon charge:
_
110
110
30
rately as mentioned later. The heated feed hy
drocarbon or hydrocarbon mixture is conducted
45 from the heater through a pipe 3 ~to a conversion
unit 4 wherein it is subjected to the action of the
15
150
conversion catalyst.
120
_
331
'257
85
80
50 ' The reacted, together with unreacted, hydro
Ethylene _________________________ _ _
32
25
Mols oi butane per mol oi ethylene.
6. 3
6. 2
_ ___
l. 1
1.1
Hydrocarbon product: Gas fraction ________________ __
310
250
through a pipe 5 and advantageously introduced
5. 7
to a fractionator 6.
Mols of isobutane per mol of ethylene_
carbons are drawn'off from the conversion unit '
_
Composition of gas fraction:
Percent lighter than isobutane _________________ __
1.7
Percentl isobutane _____________________________ . _
Percent normal butane ________ _ .
Percent isopentene and heavier _________ _ _
43. 5
53.1
Yield ol isobutane, basis normal butane charg d
-
For example, a suitable _
conversion catalyst comprises aluminum chloride
activated with hydrogen halide.
`
Normal butane _________________________________ ._
Isobutane ..................... _ _
E
Liquid fraction ____________________________ _ _
Percent yield oi liquid fraction basis ethylene...
`
1.7
36. 7
55. 4
2. 2
3i . l
23. 3
67
40
210
160
The hydrocarbons' are ad
vantageously scrubbed upon removal from the
55 conversion unit to remove entrained catalyst and
promoter.
`
.
_'
The fractionator 6 may Ibe operated so as to
y separate the hydrocarbon mixture into any de
The liquid `fraction from experiment D was
sired number of fractions or may be operated so
analyzed and found lto comprise hydrocarbons 60 as to remove only gaseous constituents, the de
boiling over the range about 86 to 145° F. and
gasiiled hydrocarbons passing to a separate frac
~about 60% of this fraction comprised isopentane,
the remainder being largely mixed hexanes.
The liquid product from experiment E was
analyzed and found to comprise hydrocarbons 65
tionator fol` further treatment. However, as in
dicated in the drawing the fractionator 6 may be
operated so as to remove overhead a gas frac
tion through a pipe ‘l and branch pipe 6.
Since this gaseous >fraction removed through
the pipe 'l may comprise substantial amounts of
30% of the liquid comprised isopentane, about
vhydrogen chloride or other gaseous agents used
14% comprised neohexane and about 12% com
in the reaction it is usually desirable to recycle
prlsed a mixture of 2-, and 3-methylpentanes.
While normal butane was charged in the fore 70 the gaseous material to the conversion reaction.
boiling over the range about 86 to 196° F. About
going experiments it is, of course, contemplated
that the invention has application to the conver
sion of other parafñn hydrocarbons having from
. In such case the recycled mat/arial is returned
through a, pipe 0.
A side stream comprising isomerized hydrocar
bons may be drawn off through a pipe I0 and
about 4 to about 11 carbon atoms per molecule
and in particular hydrocarbons of about 4 to 6 75 cooler Ii while a heavier fraction may be drawn
2,411,054
off in liquid form from the bottom of the frac-a
tionator through a pipe I2.
If desired the liquid fraction drawn olf through
the pipe I2 may be passed through a branch pipe
I3 for introduction to another fractionator I 4
6
between hydrocarbon‘and catalyst phases occurs,
the catalyst phase being >returned all or in part
to the reaction zone, while the hydrocarbon
phase is passed all or in part to the fractionating
zone or subsequent treating zone, that portion
wherein the hydrocarbons are subjected to fur
not so disposed of being returned to the reaction
ther fractionation. In this instance an over
zone.
head fraction may be removed through a, pipe I5
The reaction may be carried out in the presence
and a cooler. I6 while a liquid fraction may be
of extraneous agents such as hydrogen for the
drawn off from the bottom of the fractionator
purpose of controlling or modifying the reaction.
through a pipe Il.
Various metallic halide _catalysts may be em
Any portion, of either or both of the fractions
ployed such as aluminum chloride, aluminum
removed through the coolers lI and I8, may be
bromide, zirconium chloride, beryllium chloride,
recycled to the conversion unit.
titanium tetrachloride, stannic tetrachloride, an
For example, when charging a feed Ahydrocar
timony chloride, or mixtures of halides such as
bon consisting of normal butane the product
AlC13-SbCl3,
AlCla-NaCl, etc.
fraction removed from the cooler II may consist
Suitable promoters other than hydrogen chlo-r y '
essentially of isobutane, while the product frac
ride may be hydrogen bromide, hydrogen iodide,
tion removed from the cooler I6 may comprise
essentially unreacted normalbutane. The unre 20 carbon tetrachloride, alkyl, aryl or acyl halides or
any substance which is capable of liberating halo
acted normal butane is advantageously recycled
gen ‘halide `after coming into contact with the
all or in part to the conversion unit together with
metallic halide catalyst. Chlorine, bromine and
a small amount of isobutane which may be ob
iodine may be injected for purposes of promoting
tained from the stream drawn off from the cooler
Il. However, it is contemplated that the frac 25 the reaction. Alkyl halide formed by chlorina
’ tionation operations may be conducted so that
the normal butane stream drawn oiî from the
cooler I6 contains a small but sufficient amount
of isoparaflin to supply the isoparañin required in
the conversion unit.
The recycled hydrocarbons may be returned
through a pipe 20 communicating with the pipe
3 previously mentioned, or communicating by
means of a branch pipe 2I with the pipe I pre
viously mentioned.
Oleiln hydrocarbon obtained from an extra
tion of a portion of the feed hydrocarbon to the
reaction may be utilized as the promoter.
Other catalysts or promoters besides those spe
clñcally mentioned above may be employed since
it is contemplated that the process of this inven
30 tion is applicable to the conversion of hydrocar
bons by the action of any suitable catalyst where
in isomerization constitutes the principal reac
tion.
With an aluminum halide-hydrogen halide cat
35
alyst, such as aluminum chloride activated with
hydrogen chloride, the temperature maintained
in the reaction zone is preferably somewhat lower
advantageously commingled with the recycled'
than that employed when eiîecting isomerizatlon
hydrocarbons. On the other hand, it may be
injected directly with the feed hydrocarbon o_r 40 in the usual manner and in the absence of olefin.
On the other hand, the temperature is somewhat
may be _injected‘dlrectly to the conversion unit
. neous source is `conducted through a pipe 22 and
above the range employed in the conventional al
kylation reaction with this type of catalyst. For
example, `:'Jhen isomerizing normal butane in the
which is rich in normal parafllnl
Isoparafiln from an extraneous source and 45 presence of ethylene in accordance with this in
vention the reaction temperature may range from
which may be necessary in the early stages of
about 100 to 175° F. When isomerizing normal
the operation may be introduced through a pipe
23.
'
pentane the temperatures may range from about
75 `to 125° F.
Makeup catalyst and promoter may be passed
The use of high promoter concentration facili
to the conversion unit from a source not shown 50
through a pipe 24.
f
tates Yemploying low temperatures such‘that the
reaction may be carried out at even lower tem
The conversion unit may be of any conven
peratures, as for example 0° F,
\
tional type depending upon the type of conver
whichever is desired. It may be injected in a,
stream whlchis rich in isoparañin, or in a stream
The feed hydrocarbon may be treated to remove
be employed in either solid or liquid form al 55 objectionable compounds such as sulfur com
though the liquid form is usually preferred. In
pounds and aromatic constituents, the presence
of which is undesired when employing a catalyst
such case the catalyst may comprise a solid cat
such as aluminum halide.
alyst dissolved or suspended in a liquid carrier
such as hydrocarbon or metallic halide-hydrocar
The process of promoting the isomerization of a
bon complex. For example, an eiïective catalyst
normal parañîn hydrocarbon, such as normal bu~
comprises solid aluminum halide dissolved or sus
tane, to the corresponding isoparaiiin in the pres
sion operation employed. Thus, the catalyst may
pended in aluminum halide-hydrocarbon corn-`
plex.
ence of an aluminum halide catalyst `and a hy
drogen halide promoter at temperatures within
The conversion unit may comprise a vessel con
the range of about 75 to 250° F., by adding to
taining a substantially stationary body of fluid 65 the normal parañin charge a small proportion of
catalyst through which the hydrocarbons under
an oleñn and also a small proportion of an iso
going treatment rise merely by difference in den
parafhn, the'oleñn amounting to from a fraction
sity. On the other hand, the reaction vessel may
or 1% to about 5% by volume of the total hydro
be of the agitated type, such >agitation being im
carbon feed, and the isoparañin amounting to at
parted either by mechanical stirring means or by 70 least the molar equivalent of the oleiìn but not
_ rapid circulation of hydrocarbon or catalyst mix
exceeding about 10% by volume of the normal
ture through the reaction zone.
paraflin undergoing conversion in the reaction
with the agitated type of apparatus it is usual;
zone, is disclosed and claimed in the copending
1y desirable to provide adequate settling space or
co-owned application of Eugene E. Sensei, Serial
auxiliary settling chambers wherein separation 75 No. 606,446, :tiled July 21, 1945, as a continuation
n
2,411,054 "
in-'part of the copending application, Serial No.
; to isobutane constitutes the principal reaction _
liquid branched- ,
and the production of normally
_
chain paraffin hydrocarbons higher boiling than
Obviously many modifications and variations f n-butane constitutes a substantial but minor re
of the invention, as hereinbefore set forth, may
action, removing hydrocarbon reaction products
be made without departing from the spirit and
from
said reaction zone, _separating isobutane>
scope ythereof and, therefore, only such iimitations
from said removed products as a principal final
439,031, iiled April 15e 1942. _
should be imposed as are indicated in the lap
pended claims.
'
-
_
product oi' the process, separating a normally
` liquid fraction consisting essentially of said
higher boiling branched-chain paraffin hydrocar
1. The method for catalytically converting nor 10 bons as a substantial but minor final'product,l
mal butane to more valuable saturated hydrocar
also separating from said products an interme- ,`
bons, which comprises forming a hydrocarbon
diate fraction consisting essentially of uncon
feed mixture consisting mainly of normal butane - verted normal butane with a minor proportion
and containing minor` proportions of isobutane
of isobutane, and recycling' said intermediate i
‘
I
claim:
_
..
~
and a normally gaseous olefin, the olefin being
' present in about 0.5 to not in excess of about 10 _
volume per cent of the total hydrocarbon feed
mixture, and the isobutane being present in' from
fraction to the reaction zone, the amount of nor
mal butane thereby converted into isobutane and
recovered as such in the final product being sub
stantially greater than when the conversion is
1 -to 10 mois per mol of olefin but not exceeding
effected underthe same conditions with a feed.
'an amount which provides about 50% by volume 20 consisting of normal butane and free from said
butane
undergoing
on `the basiisl of the _ normal
isobutane and' oleñn.
thesaid
` conversion in the reaction zoner passing
feed mixture to said reaction zone v
hydrocarbon
,2. The method according to claim 1, wherein _
the normally gaseous olefin is ethylene, and the
and contacting the same- therein in liquid phase
normally liquid product; contains substantial
with- an aluminum halide catalyst and a hydro 25 amounts of neohexane and methylpentanes. `
gen halide promoter under conditions including
a temperature within the range of about -100 to
175° F., whereby isomerization of normal butane
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