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Патент USA US2407396

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Patented Sept. 10, 1946
2,407,390
UNITED; v~_sTATl=.‘.S
PATENT [OFFICE
*
2,407,390 . »
7' -> ;- CHEMICAL PROCESS“ '
Charles
WatRinSQCranford',
.,.a_ssignor'to >
Standard Oil Development _ Company, acor
va199.119.“9.?! 9? Delaware
No Drawing.‘ - Application Apr-1117,1943, g i ‘a
»
.
‘ I‘
‘7
SerialNo.483,'498
~
-W'
7616 91m...‘ <01- new»
I
_The presentinvention relates to improvements
further found that a small amount ofia volatile
in the art of alkylating propylene'with isobutane;
employing aluminum chloride-hydrocarbon com:
halide, suchlas ethyl chloride, hydrogen chloride,
plex catalyst.
ortmethyl chloride, when added to thereaction
mass; improves the performance of catalyst and
'
., The alkylation”, of propylenelwithiisobutanein' 5
1 Since the preparation of the catalyst is an im
thepresence of strong sulfuric acid, sayover90,%
portant featureof my;inventi0n, I shall now de-'
acid concentration. has, not proved satisfactory
scribe in detail theimethod of preparing the‘ same.
becauseof excessive acid consumption.
I charged 1%; lb. of A1013. to a turbo mixer and
I have, discovered ‘a method of alkylating
nropylenewith 'isobutane. and the gist of them .10 then added 69 gram ni‘ols‘of liquefied isobutane
containing ‘51% by volume of ethyl chloride. The
vention residesin 'emploxing aluminumichlcridee
mixture‘was thoroughly agitated. At 70° F., 23
hydrqqarbon. 001111219X catalyst, which; Lheve
is‘otherwise desirable. '
iound _tqpossessg long catalyst life and; toilet
.qepablc pfprbducine good. yields of. alkylat 191.
high quality-
‘
.1; ,5:
.
. .1
.
_i; I
,
. >
.gram mole of propylene were added‘over a period
of‘ 2 hours and .18 minutes while stirring. The
15 stirring was continued for 1A. of an hour following
_.
the addition of the ole?n.
; The maiaoblect 9f. my-inv¢nti9n,.ther9fore. is
The pressure aver
aged-1'10@lbs./sq.-in‘. during the operation. The
to ‘synthesizehydrocarbons, boiling; in the ease
mixture was permitted to remain quiescent to al
low strati?cation and'settling of the material into
1ine,range.,of 209d.- anti-detonationv quality in‘ '
good» yields. from nrbpylene and isobutane. bx
20
9119212111911»
21A? the outset
,
l¢wish~tqpoint
I -7
.,, outthatlhave
.
a lower brown, mobile liquid layer; containing
an Al'Cla hydrocarbon complex and an upper
productv layer (i. e. analkyl'ate, formed by react
discovered thatv a certainaluminum chloride-hy
ing- propylene with isobutane). I repeated the
drocarbon complex formed by contactingrisobu
tane, propylene and aluminum chlorideprovides
an activecatalystforthe allrylation o'i propylene
operation as previously ‘outlined 26 times. except
25 tha' no additional A1013 was-added until the 25th
withisobutane which I have also found remains
active oyerjan extended period of time.“ 'I have
run and‘ as otherwiseindicatedf in the below
V
7
Table I;
'
I_"TABLEIVVV>.
.
,
RrbpyZen'e-kobuiane alkylaiion+3 gallon turbo midrcfi-liqi'ch operaiiqHawlz/st: 22? grams of
.7 -,
;
"
vAZCL: as a hydrocarbon complex-promote”.ethyl chloride
2
H1, 2
3
Run No'IEA7-g', x "
4
5
0 7 '8
9 .10
Prop
v
‘charged, gram mols.
lene
charged,
___
gram
23
~ratio ____ .._.__; ______ -.---.
"i'gtamimols
Propylene addition
.....‘.L.'
ra
Totalalkylata
yield,W
.60—.1l0‘.’ Facut
"
"
p,
____
(C|),,.vol.-'
‘~
‘
H01),
___.
vol.
-
___
'
'
13
' 8 , 10 10
10
.>
.
.1
_
..
.
2168
2
1916 1816.18.10
.4
~'
'
~
~
39 35 30
,
'
‘11.10 12
'
’
-
~'
1
,9
226
-
9 v 9
.
' 5
~ __ _._-_
-'
13
20
___-
5 ___.
__-.,_
10
9
' 3 - 9
.
s
:7;v
-
~
~
___
___
1s
3
9‘ 10 10 1O
8
___
8
-
8
8
~
>
j,‘
'
-
w
1
)3;
.
2>1.,0,0
-
'1
1‘
0,2
s;q-~2- '310 ~ 3
~>
-
'
1
~
y
.
,
.
.
a
'
20,00200
‘a - ,2
2
1 ‘1
4 ‘9
9
~
21
5
4
2
I
71» - 70
<75 60
_;;
4
69
66-
57 60 45 43 25
>
519’
3
,
1'
12‘ 12 1,1119 ,13 11
8 i’ ll
71 65
7 '14» 312 v'17
2
s
22
31 60
i
_1
4
9
7
1
14}‘28{ is 1413 14}61 1a 1o
\' 9
27 23,32 36
41 26 32
‘
'(60-266" F; cut) ____ -.'.'.' 84.2 ___ ___ 82.0
82.1 ___ '._-183.3 185.5184.5184.2 "186.3 ____X86._3.--189.5 ___ ___
.;._ ___ _-'_ ___- -.-
___.
Nil _ Nil -
‘Nil -;._
1.600 cos. of 2656 F.+ bottoms from previous runs added to reactor in this run.
' L15 gmaHCl added in Run 21 (cquivale t to approx. 0.05 lb. HOl/gal. alkylate).
l 75 p. s. i. H. imposed on reactor.
50.505
39 ___ _;_
'
-_._-
ct.No.
BromlneNo.(60-266°F.cut). Nil
5 (3) 0.50.5
60... ___’ ___ ___
-
9 10
_
8
0.2
39
234 ,229212 _ 240 214’ 225191 215212211 219152 156220183
~9 _4
9
71 70 70 71 70*150‘72‘72
Tr. 0.2
40
,
31145 56 r 77
1214 16 _14 11.9
l0 l0
p
-
10" > 10
,
.
1
.~~
141618
-
4
*
,12 1913
47 _4138
,
___.
,
r6715
_
"
"
'69. »90 70
. ,
"
.»
i
13 17 l1
.M.
.
0.2
'
3
'11 12 11 » 99 .9’ 9 9 9
,LS.
'
___
l
f
.
"
210-265°F.-c
___ ___
1
50W'49';_,__70 .40 >, 91
0.5 ,0.2
___.
229 241252254 250 239 218 ‘224
'.
___;_‘_-..‘.‘. ______ _'__'__
"
___ ___
___.
.
_
.
‘-165—210°F.cut(C1),‘vol.
--
39
8 10
‘ l0 ' 10 10 13
%'(bas‘ed on ole?n)-.
,
___
0.2
;__
-
‘
3 ___
___. 1.0 0.5
___
~
-Isobutane/ptopylene
mo s..'-2Z_.'.__;_"____‘-‘_____
mol
~1’roductdlstribution:
5
69.-- ___
1,
11. :12 ;_13.' >15 1.5. '16 ‘~17, '18 19 *20 21 22 28 24 25 26
Reactiontemp.,°F;._.'___‘-_ v71 71 725 70 70 72, 70 71 69 . 70
EtQl vol.%,on/,C1
Iso-
.
-
-
'
-| 25 31115.0! A1011‘ dded w reactor in addition to the zzi'gms. originally.‘ '
' 10 :ms. of A101; added to reactor in addition to tho227 amsioriglnally
..
N11l
.-__ ___
___.
-_-_ ___ ___
2,407,390
4
3
In the foregoing runs, it will be noted from the
table that during the ?rst seven runs the'amount“
of ethyl chloride 'was unchanged at 5%, but
I claim:
I
1. Process of alkylating propylene with iso~
butane which comprises contacting the propylene
with an excess of isobutane in the presence of a
thereafter it was varied, and from the data, it is
liquid aluminum chloride-hydrocarbon complex
clear that about 0.2% to 0.5% is optimum. This
Also, the tem- . ' as the alkylating catalyst formed by contacting
for an extended period of time aluminum chloride
perature was varied up to 150° F. (Run 24) , but
the data indicates that best resultsare'obtainable 'i ' with isobi-itanev and propylene.
2-, ‘The~.metjhodj-set forth in claim 1 in which
at about ‘70° F. The desired'icut orv‘fraction- was,
the alkylation process is carried out at a tem
of course, the C7 fraction and the undesired frac
?gure was veri?ed in other runs.
peraturejwithin the range of about 50-1500 F.
tion (or one of‘them) was the, C150 fraction, It
.
will be noted that after the 17th run, the ClOiI'?Cr:
tion increased, showing that the catalyst was los-_
ing selectivity. The addition of A1013 caused in
crease in the amount of C1 hydrocarbons from
31% tol60%.
,
»
from 0.001'¢5-% by-weight-of- hydrogen chloride
‘
Theforegoing runs. weref‘depletion” runs, to
determine among other things, how. longa time
would elapse before it wouldv be necessaryto add
A1013. Subsequent test runs, usingabout 5.1%.
AlCl3 by. weight present as hydrocarboncompl'ex
based» on; the’ isobutane is employed as a- pro
moter.
20
~ -'1
on the isobutane is-employed asv a‘ promoter. _
6. Theprocess of claimv 1 in iwhicli-fr'om 01.01
to 10% by weight-of methyl chloridebasedon
the isobutane is employed as a promoter.
'7._ The method-set-forth in claim ‘11m which
the liquid-‘aluminum chloride-hydrocarbon com
Table II below shows this in six runs:
-TABLE II
Propylene-,isobutdne aZIcyZation—-AZCZ3-hydro_cgr
hon complex catalystéreaction temperature,‘
7 70° F.—,-batch operation
-
5. The process set forth in claimv liin- which
from.0.01~ to 10% by» weight of ethyl'chloride-based
based on total- hydrocarbons, gave-best results.
‘
The process set forth in claim 1, in which
a promoteris used which is one of the class con
' sisting of alkyl halides and HCl.
4. The process set forth in claim 1 in which
plex catalyst is prepared in- situ- under'ireacti'on
conditions using the ole?n and isoparaf?nzwhich
; '
are to be alkylated in contacting relationship with
[E?ect of catalyst/hydrocarbon weight ratio]
30
the aluminum chloride.
,
' e
‘8: The method'ofI-claim 1 performed-in" the
‘Wt. %'AIC13
presence of from 0.2 to 0.5% ethylrchloridebased
0.5-1.1
on the isobutane, a-t-temperatures oflfrom'70i’
to 90° R, under‘ superatmo'spheric pressure: and
as 15.1. 20,
Total alkylate yield, wt. % (based on
olefin ______________________________ -.
:1v
Product distributi0n,vo1.%:
‘
60-
180-149
'
0‘? F.cut _________________________ __
0
‘
'
242
.
during contact times of from 1/2 to 1% hours.
265
9. The-method :of claim 1 in which thepreS
"
l
7
37
2
10
21
25'
61
20
10. The method of claim 1 performedrcone
11
tinuouslyl by adding’ AlCl; to the reactants so as
5
11
to maintain an A1013 hydrocarbon complex to
3
6
g
sure ranges from ‘75120250 lbs. /sq';i>n~.'
.
63'
'
‘ ‘
total hydrocarbons; weight percentage of about 5,
1 A1013 present as a hydrocarbon complex. Percentage based'on
total hydrocarbons.
adding the reactants continuously and'withdrawe
ing product continuously.
The above runs‘ show that 0.5% AlCrla produce
11. In the process, of, alkylating an? ole?n with
a virtually inactive catalyst; while’ 20%‘ is an; “an excess: of isoparaf?n in the presence of an
aluminum chloride-hydrocarbon complex cata
lyst the improvement which comprises contacting
aluminum chloride with isobutane and propylene
amount causing the formation of- too great 2.‘
quantity of light ends. Further, runs showed
that from 3 to ‘7% A1013 gave goodresults.
My process may be operated" continuously; and"
for a period of" time suf?cient to form a liquid
aluminum chloride-hydrocarbon complex catalyst
the'ibest procedure is to ?ow the isobutane and
propylene feeds through a vessel or receptacle
containing the A1613. For-,‘ipor 5 hours, when=the
process is started, the AlCls-hydrocarbon co'm-‘
plex is formed and after that induction period,
the process isoperated'to maintain the optimum
conditions indicated in the preceding tables.‘ As to contact times, good, results are achieved by
' and‘ contacting‘ propylene'with an'excess of'iso
butane in the, presence of said catalyst;
12. In the’ process ‘of alkylating anole?nwith
an excess of an isoparaf?n in the presencedofyan
aluminum chloride-hydrocarbon complex catalyst
the improvement which comprisesmixingf. alumi
- num chloride with lique?ed isobutane; agitating
permitting thereactants to contact each other‘
the mixture until the‘temperature‘reaches I about
and the catalyst for a period of from about 1/3
709R, admixing propylene to themixture; agitat
hour to 1%, hours., Also, while the isobutane 60 7 ing the mixture for a timesui?c'ientjtoconvert the
should be in excess over the propylene in the re.
action mass, the mo] ratio of isobutane to pro
pylene may vary from 2 to 10. mols of. isobutanev
per mol of propylene,
The best temperature
range in the reaction zone is from about ‘70° to' 65
90?’, although temperatures from 50° to 150°‘may1
be used, and the preferred pressure range there
in is from '75 to 250 lbs/sq. in. gauge. With re
spect‘ to the activation, HCl may be used. in
amounts from 0.001 to 5% based onv the isobutane.
From 0.1 to 10% ethyl chloride or methyl‘ chloride
may be used for a like purpose.
aluminum chloride into, aliquid' aluminum) chlor
ide-hydrocarbon complex, allowing._the,,mixture_to
stratify and contacting the lower.- liquid; _, layer
comprising said liquid. aluminum’.chlorideqhydro
carbon complex with additional'arnountspf,pro
pylene andiexcessisobutane.
>~
" 1
7
~'
13. The process set forth in claim;1,2.-,-in.»whlch
an excess of isob-utane based on theipnopylene
addedismixed with the aluminum. chloride.
14. The process set forth in-claim' 12 ing-Which
the isobutane ismixed with the aluminurnjchlo
ride . in the presence of .aapromoter; selected .from
Numerous modi?cations of my invention fall-i ’
ing within the spirit thereof may be made by,
thevclass consisting, of alkylihalides'a-nd hydljQgen
those familiar with this art.
751
chloride,
..
.
v.
_
H
2,407,390
5
15. The process set forth in claim 12 in which
the alkylation is carried out in the presence of
about 3-7% by weight of aluminum chloride based
on hydrocarbons, said aluminum chloride being
16. The process set forth in claim 11 in which
isobutane and propylene are contacted with alu
minum chloride for about 4-5 hours to form said
liquid aluminum chloride-hydrocarbon complex
c present in the form of a liquid aluminum chloride 5 catalyst.
hydrocarbon complex catalyst.
CHARLES H. WATKINS.
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