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Sept. 10, 1946.
c. s. LYNCH ETAL
2,407,311
CHEMICAL PROCESS
Filed March 6, 1943
v CATA I_VST
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Pra/VP.
2,407,3111
¿UNITED STATES PATENT OFFICE
Patented'sept. 10, 1946
CHEMICAL PROCESS
Charles S. Lynch, Plainfield, and Howard G.
Codet, Mountainsìde, N. J .„ assignors to Stand
ard Oil Development Company, a corporation of
Delaware
Application March 6, 1943, Serial No. 478,184
9 Claims. (Cl. .E60-683.4)4
2
1
The present invention relates to improvements
in the art of. producing aviation gasoline and,
Referring to the drawing, I is a reactor, Car
rying a pressure gauge 20, preferably consisting
more particularly, it relates to a method of pro
of a cylindrical shell or case, packed With a suit
such that, when it is'leaded with 4 cc. of lead
from the system. However, during the early
phases of the operation all of the AlCls which
able packing material such as Raschig rings R,
ducing 2,3 dimethyibutane by aikylanng emmene f
and 5 is a settling zone into which reaction prod
with isobutane. In the application of Ralph M.
Hill and Charles l-I. Watkins, Serial No. 472,192, ' ucts pass from the top-of the reactor. In the
.settler 5, entrained catalyst material, i. e. the
filed January 13, 1943, there is described a meth
AlCl; hydrocarbon complex collects at the bot
od of alkylating ethylene with a catalyst compris
tom and may be withdrawn thro-ugh line 2I. Of
ing an aluminum chloride-hydrocarbon complex
to yield 2,3 dimethylbutane, a substance which>` 10 course, other portions of the AlCls complex which
venter 5 may gravitate back into I. But 2| pro
when used as a fuel in an internal combustion
engine, has a rich mixture performance rating ' vides a method of withdrawing spent catalyst
tetraethyl per gallon, itis superior to pure iso
octane plus 6 cc. of leadtetraethyl per gallon. . In 15 enters Zone 5> gravitates or drains back into re
action zone _I and itis only after the process is
theçaforesaid application, all of the aluminum
chloride was addedr at >the begnning of there
oil-stream fora relatively long period .of time
>( 100 hours >ormore) that Spent catalyst is With
drawn through line' 2 I, in the ordinaryfmethod of
operating; However, v.if the tower should become
ñlled with catalyst and then flowed into Zone 5
(thuseontaminating the productstream I5) be
fore the time period stated, obviously the valve in
action and after an induction period, the catalyst '
vcomprising the said aluminum' chloride-hydro
carbon complex was formed whereupon the'
octane number of the ICs fraction greatly im
proved. However, this induction period required
forty hours before the octane number of the Ce
fraction (containing the 2,3 dimethylbutane) kat
tained an octane number ciA over 90 as deter
mined bythe A. S. T. M. method.
'
. line 2I'shou1d‘be opened to draw oiT catalyst.
25 The product is withdrawn through line I0 and
a portion of this material containing in addition
to the desired 2,3 dimethylbutane, unreacted iso
butane is ‘recycled Via line II and pump' I2 to re
v
We have now discovered a method forirnprov
ing the operation described in the saidapplica- '
tion of Ralph- M. -Hill and Charles
Watkins, , actor I. The remainder of the product is con
and in its essence our invention involves'supply 30 V'ducted through’line I5 to distillation, washing
and purificationvequipment adapted to yield a
ing fresh aluminum chloride to the'> circulating
pure product; " The isobutane yremoved from the
stream of reactants and recycled product inin
product during finishingis ‘recycled to the reactor
crernental portions rather ythan adding the total
Ithruî the hydrocarbonfeed‘line 2 for further use
quantity at thebeginning. By thus proceeding,
inv the process. The method of zpurifying the
we greatly reduce the' induction vperiod requiredl
Lproduct
is omitted for purposes of simplicity of
to form the'catalytically active _aluminum ehlof.
ride-hydrocarbon complex.
It is pointed out " ' `explanation and because the invention resides in
other features of our process.
that as in the process described in the aforesaid
The recycled material in line I I may be passed
application of I-Iill et al.,'the catalyst isv formed'
by the interaction between isoparaflinic, oleñnic 40 via pipe I‘I through fresh AlCla container I8 and
thence through rpipes I9 and `22 into .the reactor.
hydrocarbons and AlCls.v
Meanwhile,` fresh feed containing ethylenev and
An object of our invention‘therefore is to alkyl- ’
isobutaneis
dischargedintorhe reactor I through
ate mono-oleñns7 particularly ethylene or propy1
pipe 2. The ratio of isobutane to ethylene -in the
ene, with isoparaiiins such as isobutane, and the`Á ` fresh feedmay be'relatively low, say .4 mols of
like in the presence of ya catalytically active alu- ’
isobutane tov 3 of ethylene. However, by employ- ,
minum . chloride-hydrocarbon complex under '
ing a high'recycle ratio, say from l0 to'lGD v01.
conditions such that the induction period neces
-umes >of liquid inr recycle line II to one volume of
'liquid feed in line và, a high internal ratiol of iso
to olefin is maintained in reactor I. This
promotes the _formation of an alkylateof desired 50 ‘butane
internal ratio Aof isoparaflin to oleiinmayarnount
high quality, isgreatly reduced.
.
- ‘
sary for the formation of a catalytically active;
raluminum chloride-hydrocarbon complex, whichv `
:fromj 10 to 100 or more mols of isoparaiiinper
Another object of ourinvention‘is to ,scoper
mol of olefin.
ate the .alkylationfof ethylene with isobutane as "
-to enable the process to functíonf'continuously. '
Other and further objects of our invention Will
appear from the following more detailed descrip
n
'We consider the crux of our invention to reside ,
DI in the manner of operating the process with re
spect to the addition of AlCla from a reservoir I8.l
»We 'start :the‘operation ‘by first -filling-,the reactor
with `liquid isobutane, satura-ting the isobutane
I1n the accompanying »drawing we have .shown a
Ewith¿ethylene at the operating pressure, and then
Vflow plan illustratingapreferred modi-flcationvof
60 feeding i-sobutanè -and ¿ethylene from '2 into the'
our invention..
. ’
.»
tion'and
claims.
'
l
>
,
'
y
.
2,407,311
3
4
reactor I. >During the iirst phase of the opera
tions nearly all of the material recovered from
the top of the reactor is recycled by way of pipes-
ber, namely an octane number of 94 as deter
mined by the A. S. T. M. (American Society for
Testing Materials) some time between the 5th
II, IT, reservoir IS and pipes I9 and 22 to the re
actor I. In. passing thro-ugh the reservoir I8
fresh A1Cl3 is absorbed or acquired by the ñowing '
and 8th hour so that from at least the 8th hour
until the end of the operation the octane number
r.
of the Cs fraction was considerably above 90.
We set forth below the result of a second run
stream of reactants. After that, the recycle
stream passes into the reactor and after about 8
which we made, including operating conditions
and an inspection of the product. In this run,
hours of thus operating a product having an oc
tane number above 90 A. S. T. M. is removed
all of the AlCla was added at the start of the op
eration, and it will be noted that the product dis
continuously from line vI5 for puriñcation.
Further describing our method of operating the
tribution as well as the yields were low due to
excessive cracking, no doubt, as evidenced by the
system, we» have proceeded as follows:
1.8 lbs. of aluminum chloride was placed in the
large amounts of low molecular Weight hydro
receptacle I8 in four aliquot portions of 0.45 lb.
each during the first eight hours of operation.
carbons.
Also the octane number was low up to
21-24 hours.
Table II.--Ethylene alkylation
2.5 lbs. AlCla charged
tower at start.
Promoter: ethyl chlo ride.
'
Pressure: 275 lbs. sq. in.
Temp.: 105-110° F.
?
n
Feed: 27 mole C2H4/hr.; iso C4/C2=mol ratio 3/1 (in fresh feed).
Hours of operation ____________ __ 5-8
270
260
272
256
245
140
___
__
40
39
31
46
34
43
24
52
14
62
11
64
8
64
5
52
__
16
17
16
17
18
18
20
26
265° F.-|-(Cu-l-) ____________ __
5
6
7
7
6
7
8
17
Ca _____________________________ __
85. 7
85.6
89. 1
91. 9
92. 5
93.6
_____
Net percent alk. on Cz
_. 269
-F. (C5)_
11G-165° F. (Cs) ____ __
165-265o F. (C1-CSL---
ASTM o
129
No.:
C11-Cs _________________________ __
0.45 lb. of aluminum chloride was placed in re
ceptacle I8 and the recycle stock passed through
the receptacle containing the aluminum chloride.
This was continued for a period of two hours,
whereupon a second 0.45 lb. portion of aluminum
chloride was added to receptacle I8. This proce
dure was repeated at the sixth and eighth hours
until all of the 1.8 lbs. of aluminum chloride was
85. 6
73.8
_ _ _ _ _
_ _ _ __
_ _ _ _ _
_ _ _ ._
product and the yield.
To recapitulate, our present invention relates to
a continuous method of alkylating ethylene with
isobutane to form substantial quantities of 2,3
No» more aluminum chloride was added
after _that until at the 54th hour whereupon an
other 0.22 lb. of aluminum chloride was added to
receptacle IS. The addition of aluminum chlo
69.8
We wish to point out that best results are ob
tained by maintaining a high recycle ratio. That
is to say from 10 to 100 volumes of the product
is recycled via line I0 and pump I2 to the reactor
per volume of fresh feed (ethylene plus isobu
tane), in line 2. The purpose of this high recycle
ratio is to maintain a high ratio of isoparaiiin to
oleñn in the reactor for it has been foundthat
this high ratio improves both the quality of the
In other words, at the beginning of the operation
added.
13-16 21 -24 29-32 37>40 45-48 53-56 65~68
¿lo
dimethybutane which is a very valuable blending
agent in the manufacture of aviation fuels. We
have found it advantageous to add the catalyst
to the system in incremental portions rather
ride continued at the 66th, '78th,‘90th, 102nd, and
114th hours until a total of 3.1 lbs. of aluminum
chloride had been added. A temperature of 105°
F. and a pressure of 275 lbs. per square inch gauge
was maintained within the reactor.
than to add the catalyst at o-ne time for we re
duce the number of hours necessary for the cata
~ As a result of the ope-ration, we set forth be
lyst to attain maximum activity. In other words,
where the catalyst is formed in situ by interaction
low thedata obtained as a result of the continu
ous run:
Table I.--Ethylene'z'sobutane aZlcyZatz'onf--contínuous tower
Catalyst: A1013 (l).
Promoter: C1HßOl(2)/.
/
Mol ratio: liso C4/C2=3.0 (in fresh feed).
Pressure: 2751bs./sq. in.
Hours of operation..
__ 5-8 9-12 17-20 29-32 33-36 41-44 49-52 57-60
_- 105
106
104
100
10
10
7.5
7.5
187
208
222
sumed (cumulative)___' _________________ __ 197
220
242
262
4.12
6. 76
2. 3
3. 8
3
66
23
8
4
67
21
8
2
71
20
7
____
94. 5
C2H4mols/hr,.»__-______
__
98
7. 5
94
7. 5
90
7. 5
101
7. 5
230
227
221
219
263
7. 59
4.2
265
8. 98
5.0
61-64 73-76 81-84 93-96 105-108 117-120
105
104
-108
108
107
108
7. 5
7. 5
7. 5
7. 0
7. 0
7. 0
Wt. per cent (J5-talk. on 02H4 fed (cumu
lativ
_________________________________ __
220
223
224
229
230
233
282
14. 6
6.4
280
16. 1
6.6
282
18. 5
6.8
280
20. 8
7.1
280
23. 2
7.4
61
Wt. per cent CVI-slk. on 02H4 fed c011
Yield gal. alk. (cumulative) ____________
__1 54
.
Yield gal. alk/lb. A1013 (cum
Vol. per cent alk.:
3
70
3 Y
70
10
60
2
61
21
2O
22
28
6
Y 7
8
9
14
18
7
1l
65 `
14
62
18
18
6
6
ASTM oct. No _____________________ _.Í ss. 2
1 Iso C4=isobutane
It isobvious from the above data that the frac
tion of the product which is the most important
fraction, namely the C6 fraction or that fraction
boiling from 11G-165° F., had a high octaneV num 75
between the aluminum chloride and hydrocarbon,
as is the case in the present process, we have
found that there is an induction period during
which the alkylate` formed, particularly the Cs
2,407,311'
3. 'I‘he method set forth in claim 1 in which a
ratio of at least 100 mols of isoparafûn per mol of
olefin is maintained in the reaction zone.
4. A continuous method for alkylating ethylene
fraction, is of inferior quality particularly as re
gards octane rating. We have found that we
may reduce the induction period very substan
tially by adding the catalyst in incremental por
tions rather than by adding to the system all of
the catalyst intended to be used in one _total
>with isobutane which comprises mixing ethylene
with isobutane in a reaction zone containing an
inert contact material, withdrawing a mixture of
quantity.
it is obvious that two or more receptacles I8
unreacted ethylene and isobutane from said re
action zone, recycling the mixture through a
that is to say, while one of the receptacles I8 is
» of the process for an induction period suiñciently
In order to operate our process continuously,
should be provided and these may be operated in lO catalyst charging zone containing AlCls and
thence to a reaction zone, maintaining the cir
parallel so that the hydrocarbon recycle in line
culatory system indicated during the early phases
I I may be alternately fed through the receptacles,
being recharged with catalyst, the other may be
on the onstream operation thus maintaining co-n
tinuity of operation.
long to permit the formation of AlCla hydrocar
15 bon complex by interreaction of said AlCla and
’
As to operating conditions in the reaction zone
said hydrocarbons, simultaneously feeding iso
butane and ethylene to said reaction, during said
induction period, withdrawing a portion of the
the temperature may vary froml 90° to 175° F. with
' stream leaving the reaction zone as product fol
100° to 110° F. preferred, the pressure may vary
from 100 to 1000 lbs. per square inch gauge with 20 lowing the induction period, recycling the re
mainder of the said stream through the catalyst
200 to 400 lbs. preferred, and we use from 0.04
charging zone to the reaction zone, and periodi
lb. to 0.08 lb. of AlCla per gallon of alkylate pro
cally adding fresh AlCl3 to said catalyst charging
duced in the system.
zone.
By an analogous method we may alkylate ethyl
5. The method of claim 4 in which the volume
ene, propylene, butylene and other mono-oleñns 25 ratio of recycled stream to total volume of fresh
with isobutane or some other isopar‘anin such as
feed isobutane and oleñn is from 10 to 100 to 1.
isopentane.
‘
6. The method of claim 4 in which the induc
Many modifications of our invention will read
tion period is from 5 to 8 hours.
ily suggest themselves to those> who are familiar
7. The method specified in claim 4 in whicha
30
with this art.
>
temperature of from 100° to 110° F. is maintained
What we claim is:
' in the reaction zone.
1. In the process of continuously alkylating
8. The method speciñed in claim 4 in which the
ethylene with an isoparafiin, the improvement
_reaction is carried out at temperatures within the
which comprises forcing a mixture containing
isoparañin and ethylene through a catalyst charg-V
ing zone containing aluminum'chloride and which
can be recharged therewith from time to time
whereupon a portion of said aluminum chloride
is absorbed in the said mixture, forcing the mix
ture containing the aluminum chloride into a 40
reaction zone, permitting the ethylene, isoparaiiin
and aluminum chloride to remainrin contact with
each other for a suñicient period of time to form
a catalytically active aluminum Vchloride-hydro
carbon complex, thereafter” continuing 'the flow
of isoparaii'in and ethylene through the catalyst
charging zone and through the reaction Zone,
range of from 90-175° F.
9. VIn the continuous alkylation of ethylene with
isobutane, the improve-ment which comprises pro- ~
Viding `a body of AlCls in a catalyst charging zone,
feeding isobutane and ethylene to a reaction
Zone, withdrawing a recycle stream containing
unreacted ethyleneand isobutane- from said re
action zone, flowing said recycle stream through
said body of AlClaA in the» catalyst charging zone
to said reaction zone for a period of 5 to 8 hours
until the reaction product shows an octane num
ber above 90, then withdrawing the reaction prod
uct, and adding A1013 in aliquot proportions from
time to time by directing the recycle stream
maintaining the reaction zone at elevated tem
through the catalyst charging Zone and thereby
peratures and pressures during the process and 50 maintaining the octane numbervof the product
A vwithdrawing from the reaction zone a product
continuously above 90.
¿
containing a Ce fraction of high octane number.
2. The method set forth in claim 1 in which
fresh aluminum chloride is added to the catalyst
charging zone at spaced intervals of time.
55
CHARLES S. LYNCH.
HOWARD G. GODET.
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