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Патент USA US2408187

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Sept. 24, 1946.
H. V. ATWELL ETAL
CATALYTIC CONVERSION OF HYDROCARBONS
lFiled May 18, 1944
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2,408,186
Patented Sept. 24, 1946
2,408,188
UNITED STATES PATENT OFFICE
2,408,186
CATALYTIC CONVERSION OF
- HYDROOARBONS
` VHarold V. Atwell, Beacon, and Howard H. Gross,
Pleasantville, N. Y., assîgnors to The Texas
Company, VVNew York, N. Y., a corporation of
Delaware
Application May 18,Y 1944, Serial N0. 536,088 t
12 claims.
1
This invention relates to the catalytic conver
sion of hydrocarbons and particularly to cata
lytic conversion with a liquid metallic halide
hydrocarbon complextype of catalyst.
The invention involves moving a body of hy
drocarbons undergoing conversion in continuous
liquid phase through a reaction zone while in
direct contact with a liquid 'catalyst moving
(o1. 28o-683.5)
2
The present invention provides a means for
avoiding catalyst migration, as for example in
the isomerization of normal butane.y Thus in
accordance 'with' the present invention the com
plex catalyst containing the highest concentra
tion of aluminum halide is maintained in an in
’ termediate portion of the reaction tower. The
concentration of aluminum halide in the com
plex is maintained relatively low in the hydro
continuous liquid phase. Therñowing fluids are 10 carbon exit portion of the reactiontower so that
maintained at a predetermined 'temperature such
the exit hydrocarbon stream is substantially free
that substantial conversion occurs` during flow
from dissolved aluminum halide.
through the reaction zone.
'
In accordance with the present invention the
through the reaction Zone in dispersed or dis
The invention is applicableto the isomeriza
tion of saturated hydrocarbons by contact with
an aluminum halide-complex catalyst in the
presence of hydrogen halide, the react-ion being
carried out in a reaction tower advantageously
packed with inert contact material such as
make-up aluminum halide is introduced to the
reaction tower at an intermediate point. There
fore` with the upward ilow 0f hydrocarbons the
Valuminum chloride concentrationÍ in the catalyst
' is relatively higher in the'intermediate section of
tageous to employ a ceramic material such as
the reaction tower than it is in either the upper
or lower portion of the reaction tower.
In order to describe the invention in more de
clay or porcelain which is preferentially wetted
tail reference will~now be made to Ytheaccom
Raschig rings and Berl saddles.
It is advan
by the catalyst complex liquid.
panying drawing illustrating a diagram of flow.
In the drawing the numeral I designates a
In accordance with the invention the reaction .
tower is filled with a column of liquid hydro Iv Si reaction tower packed with inert packing ma
terial 2 such as Raschig rings.
carbons moving through the tower in continuous
When operating rthe tower for the isomeriza
liquid phase. The complex catalyst is introducedtion of normal butane a stream of normal butane
to the upper portion of theY tower in a dispersedl
form and descends through‘the column oi hy 30 is drawn from a source not shown through a pipe
3 and conducted through a heater 4 wherein it is
drocarbon liquid over the contact material.
heated to the-temperature in the range about 200
The column of hydrocarbon liquid may rise
to 240° F. or even as high as 300° F. The heated ,
through the tower countercurrently -to Vthe de-„
normal butane is then conducted through a pipe
scending catalyst liquid or in the alternative, the
5 to the lower portion Aof the tower I. The pres
hydrocarbon liquid may descend through the
.35 sure in the tower is vmaintained in the range
tower concurrently with the catalyst liquid.
about 150 to 400 pounds per square inch gauge
One advantage in employing the liquid ,cata
and sui'licient to maintain the normal butane
lyst in dispersed form as contemplated by the
liquefied.
The normal butane liquid «rises
present. invention is that it permits concurrent
through
the
contact material and provides a
downward-flow of both hydrocarbons and cata 40
continuous :column of hydrocarbon liquid >within
lyst. The aluminum halide-hydrocarbon com
the tower; The yhydrocarbon liquid overñows
plex type of catalyst is relatively more dense than
from
the top .of the tower through a pipe A6 lead
the hydrocarbons usually undergoing treatment.
ing to a fractionating unit 1.
y
Therefore when the complex catalyst is rin con
tinuous phase it is impossible `to operate with 45 f The aluminum chloride-,hydrocarbon >complex
characterized 'by a heat of hydrolysis in the range
downward flow of hydrocarbons undergoing _con
about 280 to 300 calories per gram of complex
`accumulates in the bottom of the tower and is l
'In certain operations up now of hydrocarbons
continuously drawn off through a pipe I0. All
may be preferred, as for example in the’ìtreat
or a portion of this complex is passed through
ment of relatively low molecularweight hydro
a branch pipe IVI-and returned either to the top
carbone such asr butane in which aluminum
of the tower-or to an intermediate point through ,
halide is relatively more soluble thank in higher
branch rpipesAIZV and 13.. Thus the recycled com
version.
'
molecular weight hydrocarbons.
Y
»
Consequently,
catalyst migration is a `problem when treating
relatively low molecular weight hydrocarbons.
plex liquidY maybe returned to the Vvtop of the
tower> and .distribution thereofeñected by meansY
55 of a perforated plate I4. -The dispersed catalyst
2,408,186
3
drops descend through the contact material
forming thin films of catalyst on the contact ma
terial- The catalyst drops eventually trickle to
the botto-m of the tower. In the bottom of the
tower settling space is provided so that stratiñ~
cation between the catalyst and hydrocarbon
liquid occurs forming an interface I5 between the
hydrocahbon liquid and relatively more dense
4
top of the tower becomes enriched in aluminum
halide so that the lean complex in the upper
part of the tower operates to selectively extract
aluminum halide from the hydrocarbons ap.
preaching the top of the to-wer.
In this way
dissolved aluminum halide is removed from the
eiiluent hydrocarbon stream.
The effluent hydrocarbons comprising isobu
tane and unreacted normal butane and, in ad
complex catalyst.
10 dition, a promoter and a small amount of gas
As indicated, provision is made :for introduc
ecus hydrocarbons are conducted through the
ing a promoter such as hydrogen chloride from
pipe Ii to the fractionation unit l’ as previously
a source not shown through a pipe I6.
mentioned. The fractionation unit may com
In commencing the operation of the reaction
prise two or more towers with provision for strip~
tower preformed complex catalyst or the catalyst
ping out the promoter and also for effecting sep
remaining from a preceding operation is used.
aration between i'sobutane and normal butane.
Preformed complex may be prepared by react
Inthe drawing a single tower is shown with
ing aliphatic hydrocarbons with aluminum chlo
provision for removing a gaseous fraction through
ride in the presence of a small amount of pro`
a pipe' 35, a side stream comprising isomerized
moter. The complex catalyst is advantageously
hydrocarbons through a pipe 3% and a residual
free from undissolved solid aluminum chloride. ‘ fraction comprising unreacted hydrocarbons
During continued operation it is desirable to
through a pipe 32.
maintain the activity of the complex catalyst by
Provision may -be made for recycling unreacted
the addition of a small amount of fresh alumi
hydrocarbons and also for recyling the promoter.
num halide which enters into complex formation
If` desired some of the recycled Istreams may
with a small portion of the feed hydrocarbon 'so 25 be used in part to aid in recycling of the used
that some complex is formed in >situ during the
complex through the pipe I I. For this purpose a
stream of isomerized hydrocarbons in vapor form
course of continued operation.
The make-up aluminum halide can be added
may be by-passed through the pipe 33 and passed
as a solution in a portion of the feed stream.
to the pipe II as indicated. In this way the va
Thus a portion of normal butane may be by 30 porized hydrocarbons are used as a gas lift to
passed through a pipe 20 being either heated or
lift the recycled complex through the pipe I I and
cooled during passage through an exchanger 2l
discharge it into the upper sections cf the reac
and then conducted to either one of a plurality of
tion tower.
vessels 22. The vessels 22 contain solid alumi
On the other hand a small portion of the feed
numchloride in lump or granular form. The 35 butane stream may be used to provide the gas
normal butane stream which may be added at
lift, and in such case a portion of the heated bu
about room temperature is conducted- down
tane is by-passed through a pipe 34 and branch
wardly through one of the vessels 22 so that so
35. The promoter may be added or recycled to
lution of aluminum halide in the butane occurs.
the system by way of this lift.
Solution is advantageously effected in the absence 40 A liquid rather than a gaseous lifting medium
may be employed. Thus part of the butane feed
of vadded hydrogen chloride.
The resulting solution is conducted through a
may be used as the liquid lifting medium. In such
pipe 23 to the intermediate portion of the re
case the butane so used may also contain dis~
action tower l. The solution may be introduced 45 solved aluminum chloride required for maintain
at one or more succeeding points as indicated.
ing catalyst activity. This latter arrangement is
The proportion of butane by«passed through
advantageously employed when recycling the
the Vessels 22 may amount to l0 to 30 per cent
complex to an intermediate portion of the re
action tower. 'I‘he stream of butane containing
of the tota-l butane feed passing to the reaction
tower. The amount of' butane passed through
the vessels 22 and the temperature of solution
may be varied, however, depending upon the
amount of aluminum halide vwhich must be added
in order to maintain the complex catalyst at the
predetermined level of activity.
In isomerizing normal butane a complex cata
lyst having a heat of hydrolysis of about 390 to
330 calories per gram of complex is quite ef
fective.
However, in the operation of tower I as just
described the complex catalyst in the intermedi~ 60
ate section of the tower will have a heat of hy«
drolysis of about 330 to 340 calories per gram of
complex while the activity in the terminal sec
tion's will be relatively lower. For example, the
complex being drawn off through the pipe IFI
may have a heat of hydrolysis of about 289 while
the complex near the top of the contact material
will have a heat of hydrolysis of about 30€).
The fresh feed hydrocarbons entering at the 70
bottom of the tower effect a stripping action upon
the complex so that free aluminum halide is
washed from the descending complex and carried
upwardly into the tower. Thus the complex be
ing drawn off is relatively lean in aluminum hal
ide. This lean complex when returned to the
dissolved aluminum halide is conducted from pipe
23 through pipe 43 which communicates with
pipe 34.
Instead of discharging directly into the tower,
the complex may be lifted into an elevated re
ceiver 40 from which it gravitates through a pipe
4I and pipe I2 into the top of the reactor. The
lifting agent may thus separate from the complex
in the receiver Ml and be discharged therefrom
through a pipe 42.
In the foregoing description upf-low of feed
butane through the tower has been described. It
is contemplated, however, that downfiow may
be employed.
Where downflowA of feed hydrocarbons is em
ployed the feed stream may be passed through the
pipe 34 and pipe 35 (shown in broken line)
through which it is passed to the top of the tower,
In this case the product stream is continualliÍ
drawn off from the lower portion of the tower
through pipe 31 (shown in broken line) and con
ducted to the fractionating unit 1 as indicated.
While aluminum chloride has been specifically
mentioned it is intended that other Friedel-Crafts
type metallic halides such as aluminum bromide
and zirconium chloride, etc. may be employed.
27,408, 186 `
If 5
Likewise the promoter may comprise 'other hydro'
gen halides.V
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ide which comprises maintaining in a reaction
'
tower an elongated column of feed hydrocarbon
It is Valso contemplated that other saturated
hydrocarbons besides normal "butan‘e’ may v»be
in continuous liquid'phase, continuously supply
isomerized.r Individual hydrocarbons boiling
suchV that the hydrocarbon liquid rises through
ing fresh' feed yto theY lower portion of the 'tower
within the gasoline'range may be charged or
mixtures thereof. Preferably the feed hydrocar
the towerV while undergoing'conversion therein,
continuously 'introducing 4complex catalystY toi the
>bons are substantially free from'aromatic-and
upper portion of the tower: causing zthe intro
duced» complex to descend` in dispersed'liquid
olefinic constituents although in `isomerizin'g‘nor
mally liquid saturatedr gasoline ' hydrocarbons 10 phase through the hydrocarbon liquid body, with'
such as pentane it may be desirable to add a small
drawing used complex' fromthe ybottom of the
amount of low boiling aromatic hydrocarbons
tower, `recycling withdrawn complex to the upper
portion of the ’tower maintaining thercounter
currently flowing liquids Within the tower ata
temperature'suñîciently elevated to effect isom
such as benzene and toluene for the purpose of ï
inhibiting cracking and other side reactions. I The
amount of aromatic hydrocarbons added is inthe
range about .l to .5 per centand preferably'not
in excess of l per cent by weight of the feed hy#
drocarbon undergoing conversion.
i
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erizationof the isomerized hydrocarbons, with
drawing hydrocarbons Vsubstantiallyl free from
'
aluminum halide from the top of the tower and
4Isomerization has been speciiically described.
introducing a small amount of aluminum halide t
However, it is contemplated that the invention is
to the tower at anl intervening point between, and
applicable to eifecting other’eonversion reactions
removed substantially from, thepoints ofused
complex withdrawal and isomer'izedîhydrocarbon
such as the alkylation of oleñns Vwith isoparaiiins
by contact with an aluminum halide-hydrocarbon
complex catalyst.
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removal and suflicient in amount to maintain said
l
The activity of the complex catalyst used tmay 25
be varied depending upon the type of conversion
reaction being carried out but usually the alu
Y
>Obviously many modifications and variations
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the complex catalyst within thereaction tower is
acterized by having a heat of hydrolysis within
.
the range 200 to 400 small calories per gram of 30
complex catalyst.
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The reaction temperatures @employed -may
\
3.-'The process-'according to claim 2 in -:which
characterized by ' having a heat f of hydrolysis
'minum halide-hydrocarbon complex will be char
range from 0 to about 300 to 350° F.
predetermined'activity,
within the range 280 to 330 calories per gram of
complex.
4. The processaccording to claim 2 in which
the complex catalyst of greatest activity is main
tained within the intermediate portion 4of the
reaction tower.
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5. A conti'nuousprocess for converting `hydro'
of the invention, as hereinbefore set forth, may 35 carbons by contact `with a liquid Friedel-Crafts
be made without departing vfrom the spirit and
metallic vhalide-hydrocarbon complex catalyst in
scope thereof, and therefore only such rlimita
the presence of hydrogen halide by continuous
tions should be imposed as are indicated inthe
countercurrent now of hydrocarbons and catalyst
' appended claims.
through a reactiontower which comprises" intro
We claim:
'
.
l
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'
l. In aV continuous process for converting hy
drocarbons bythe action of an aluminum halide
hydrocarbon complex catalyst of, predetermined
activity inthe presence of hydrogen halide,` the
steps which comprise maintaining a reaction
tower substantially lìlled with a column of feed
hydrocarbon in continuous liquid phase, said
tower being -packed with inert contact material,
continuously introducing feed hydrocarbon to the
40 ducing a stream of feed hydrocarbon to the lower
portion of an elongated reaction tower, intro
ducing a stream of complex catalyst to the upper
_portion of vsaid tower, moving the hydrocarbons
upwardly through the tower in continuous,y liquid
phase ,and in direct contact with downwardly
ilowing complex catalyst in dispersed liquid phase
yand in the presence of hydrogen halide at atem
perature in the range from 0 to about 350° F.
such that substantial conversion of hydrocarbons
lower portion of the tower such that feed hydro 50 occurs, continuously discharging a stream con
carbon rises through the tower while undergoing
taining converted hydrocarbons from the upper
catalytic conversion, continuously introducing
complex catalyst liquid to the upper portion of>
the tower, moving the catalyst in dispersed phase
downwardly through the tower, continuously '
withdrawing used complex from the bottom of`
the tower, recycling withdrawn complex to the
upper portion of the tower, introducing a small
amount of fresh aluminum halide to the tower at
an intervening point between, and removed sub
stantially from, the points of used catalyst with
drawal from, and return to, the tower and suñi
cient to maintain the concentration of aluminum
halide in the complex relatively greater in the in
tervening portion than in the upper and lower
portions of the tower, maintaining the reaction
tower at elevated -temperature sufficient to effect
said conversion, and continuously removing from
the upper portion of the tower, hydrocarbon
products of reaction substantially free from alu
minum halide.
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2. A continuous process for isomerizing satu
rated hydrocarbons by the' action of aluminum
halide-hydrocarbon complex of predetermined
catalyst activity in the presence of hydrogen hal
`portion of the tower, said hydrocarbons being
substantially free from dissolved metallic halide,
continuously discharging a stream of used com
plex of relatively low metallic halide concentra
tion from the bottom portion of said tower, re
cycling discharged complex to the upper portion
of the tower, introducing metallic halide to said
tower atan intervening point between, and'sub
stantially removed from, ,the points of converted
hydrocarbon and used catalyst discharges and
regulatingthe rate of said metallic halide intro
‘duction such that the concentration of metallic
halide in the complex catalyst in said intervening
portion is substantially greater than in the com
l plex in the terminal portions of said tower.
6. The process according to claim YV5v in which
the metallic halide is’aluminum halide.
7. A continuous process for isomerizing satu
` rated hydrocarbons by contact with an aluminum
halide-hydrocarbon complex catalyst inthe pres
ence of hydrogen halide lby continuous counter
current flow of hydrocarbons Áand catalyst
through a reaction tower which comprises intro
ducing a stream of feed hydrocarbon to the lower
2,408,186
7
portion of an elongated reaction tower, introduc
ing a stream of complex catalyst to the upper
portion ofV said tower, moving the hydrocarbons
upwardly through the tower in continuous liquid
phase and in direct contact with downwardly ñow»
ing complex catalyst in dispersed liquid phase
and in the presence of hydrogen halide at an ele
vated temperature in the range up to about
350° F. such that substantial isomerization of
hydrocarbons occurs, continuously discharging a
8
portion of the» tower, introducing a small amount
of aluminum halide to the tower at an interven
ing point between, @and substantially removed
from, -the point-s of used complex withdrawal from,
andA return to, the tower and sufñcient to main
tain the concentration of aluminum halide in the
complex relatively greater in the intervening
portion than in the upper and lower portions of
the tower, maintaining the reaction tower at a
temperature sufficient to effect said conversion,
and continuously removing from the upper por
tion of the tower hydrocarbon products cf re
action substantially free from aluminum halide.
10. In the catalyst conversion of hydrocarbons
minum halide, continuously discharging a stream
by
the action of Friedel-Crafts metallic halide
of used complex of relatively low aluminum halide 15 hydrocarbon complex catalyst of predetermined
concentration from the bottom portion of the
activity in the presence cf hydrogen halide, the
tower, recycling discharged complex to the upper
steps comprising continuously moving a body of
portion of the tower, introducing aluminum halide
feed hydrocarbon in continuous liquid phase up
to said tower at an intervening point between
wardly through a vertical reaction zonel continu
and substantially removed from, the points of
ously moving downwardly through the reaction
stream containing isomerized hydrocarbons from
the upper portion of said tower, said hydrocar
bonsî being substantially free from dissolved alu
isomerized hydrocarbon and used catalyst dis
charge, Iand regulating the rate of said aluminum
halide introduction such that the concentration
zone complex catalyst in dispersed liquid phase,
causing the hydrocarbon body andthe catalyst
to ilow in direct countercurrent contact with each
other through the reaction zone, maintaining
vening portion is substantially greater than in the 25 both fluids at. reaction temperature during flow
complex in the terminal portions of said tower.
through the reaction Zone such that substantial
8. The process according to claim 7 in which
conversion of hydrocarbons occurs, continuously
the heat of hydrolysis of the complex in the in
supplying fresh feed hydrocarbon to the lower
termediate section of the tower is about 340 calo
portion of the reaction zone to provide said body
ries and in the upper portion of the tower >about 30 of hydrocarbons flowing therethrough, continu
280 calories whilethat in the bottom portion of
ously withdrawing converted hydrocarbons from
the tower is about 300 calories.
the upper portion of the reaction Zone, introduc
9. A continuous process for converting hydro
ing a small amount of metallic halide to the re
carbons by the action of an aluminum halide
action zone at an intervening point between .the
hydrocarbon complex catalyst of predetermined . points of converted hydrocarbon withdrawal and
activity in the presence of hydrogen halide which
feed hydrocarbon introduction vto the reaction
comprises maintaining in a reaction tower an
zone, and regulating the amount of metallic halide
elongated column of feed hydrocarbon in con
so introduced such that the concentration of me
tinuous liquid phase, continuously supplying
tallic halide in the complex is relatively greater
fresh feed hydrocarbon to the lower portion of 40 in. the intervening portion of the reaction zone
the tower such that the hydrocarbon liquid rises
than, in the upper and lower portions thereof.
through the tower while undergoing conversion
11. The method according to claim 10 in which
therein, continuously introducing complex catathe metallic halide is aluminum halide.
lyst to the upper portion of the tower, causing
l2. The method according to claim 10 in which
the introduced complex to descend in dispersed 45 the metallic halide is aluminum chloride.
liquid phase through the hydrocarbon liquid body,
HAROLD V. ATWELL.
withdrawing used complex from the bottom of the
HOWARD H. GROSS.
tower, recycling withdrawn complex to the upper
of aluminum halide in the complex in said inter~
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