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Патент USA US2404897

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vJuly 30, 1§46„
`
Y
v
w, N, AXE'
-
\ _2,404,897
ALKYLATIO'N PRocEss
Filed Nov.' 24, 41942
ATTORNEYS
2,404,897
Patented July 30, 1946
UNIT-ED "STATES PATENT ¿OFFICE
:ALKYLATION PROCESS
“îWilliam‘ Nelson Axe, . Bartlesville, Okla., _ assignor
tto ‘Phillips Petroleum Company, a corporation
Application November 24, 1942,2‘Serial No.î466,‘7.62
2
t have been found‘inadequate whenappliedtoiso
This invention relates to the synthesis of high
octane-number isoparan‘lnic hydrocarbons Ífrom
lower molecular weight isoparañins andethylene.
More specifically, thisinvention Vrelates .tothe
paraiiin-ethylene reactions.
‘
,Insofar astheîprior-,artis concernedaanhydrous
aluminum-chloride activated -With hydrogen chlo
ride - appears 4to '~ be .the . best catalyst . described »as
alkylation of low-boilingisoparafûns with ethyl- .
applicable `to >alkylation rWith -ethylene and lits
enequnder moderate -conditions of temperature
higher homologues. However, ythere are =. certain
and pressure in` the presence of -a novel alkylation
valid objectionsito the-.use„of 4this catalyst com
bination -among which ythere 4may `be mentioned;
isomerization- of> theÍ isoparai’linsy and auto destruc
catalyst. Inone specific modiñcation‘this inven
tion relates to an improvedprocess ,for the» utiliza
tion Íof ethylene-in the falkylationof isoparafñns .1,0 tivewalkylation `forming high boiling .products
suc-has isobutane to,;produce-isoparan^in fractions
of :exceptional V-value as :component-s of 4,aviation
fuel.
‘The `introduction ' of lalkyl groups 'into . the . ben
zene .ring‘ in the `presence fof the @various Friedel
Crafts `type catalysts is'a’classic‘reaction'in or
ganic chemistry. More ¢recently alkylation, in
volving‘isoparaftinsand oleñns, has been -extended
tothe ñeld of aliphatiochemistry as a 4result of
sludge materials. Thus with oleñns-aboveethyl
ene in the homologous series attempts to .mini
L15 mize these undesirablecharacteristics have .been
madehy 'operating `ai‘rtemperatures `below .32° F.
Even «with .the ,less lreactive ethylene, `a lack- of
specificity »at .room-temperature Ioperation lhas
been reported lor .the >allcylation of `butano with
ethylenefinlthathexanes so .produced amounted
.toonlya minor proportion ofthe total .alkylate
andthe.difisopropylfraction made up- only. a-still
smallerzpen cent .of the total alkylate.
_'It is `.the `object <cf` the _present .invention to
N) TA providea `process 'for >the alkylation of isoparañ‘lns
the demands for saturated hydrocarbon stocks
of high octanerating in" thema-nui acture‘of: avia
tion gasoline. Even `more recently :recognition
of the importance of tthefso-.called “rich-mixture
rating” of aviation fuelszhasagiven addedlimpetus
to the Asynthesis of specific hydrocarbon types.
Thus itihas been` foundîthat .certain gasolinas of
requisite octane-rating .are deficient `in perform
ance `*under conditions involving‘the high ',fuel
air ratios »often »demanded yin rmilitary air-'craft 30
operation.
-Alkylated Aaromatic ' v*hydrocarbons
have Ybeen found `to `improve ¿the rich-mixture
in general, vand ,isobutane in particular, .with
ethylene employingan improved catalyst-,capable
ofpperating with .a .lhigh degree of specificity
undcroperating conditions conveniently attained
in industrial practice. The specific action 'of my
novel catalyst will .be illustrated '.by >subsequent
.data showing the ‘.:total alkylate to have an iso
>characteristics of high-octane gasoline, `but tbe
hexanecontent 4ranging from `50.tc 80 volume per
cause of »their low volatilityîthequantity o'fsuch
cent With pure `di-isopropyl comprising 93 to 95
additives that >can'be incorporated `into the‘blend 35 .per cent ofthe isohexane fraction. Other ob
is necessarily limited. -On the `other hand, the
jectsand advantages will be apparent `from .the
isoparafñn, 2,3»rdimethylbutane ‘ihereinafter :re
accompanying disclosure and discussion.
‘ferred toas `di-isopropyl, lis Ucharacterized .by :its
This application‘is a continuation-impart 'of
goed >rich-mixture rating and» a volatility permit
my. copending application Serial‘No. ‘459,985,.filed
ting v(-:oncentrations»of 10 per'centland higherlin 40 September 28, 1942, in Which‘isbroadly disclosed
ñnishedgasoline blends.
‘
'
the use of my preferred catalyst‘in the alkylation
-`’Except -ifor nearly negligible -quantities 'labori
of isoparaflins With oleñns.
ously Visolated `from> natural gasoline,` ¿li-‘isopropyl
The catalyst composition of ‘this invention .is
is obtained primarily as'aisyntheticfproduct. i The
preparedby treating phosphoric acid of variable
Ymost-convenient `'direct «synthesis fof K hexane thy
Water content with anhydrous boron fluoride until
complete saturation has been realized. With 100
drocarbons 4invnlvesitlie ¿alkylati'on of ßisobutane
with ethylene. Although :the ,alkylationfof ‘iso
per cent phosphoric acid substantially one mol
parai’ñns „in general and isobutane in particular
of boron iiuoride is absorbed per mol of acid While
in the case of aqueous solutions `both the phos
with _oleiins ¿of three or Vmore carbon .atoms is
phoric acid and water absorb boron iiuoride ap
now a Well 4established practice, the utilization
of ethylene `-in reactions of .this type _has Abeen
proximately mol for mol. 'No theories are >ad
extremely difficult. Thus .certain -acid catalysts
vanced as to ‘the chemistry .involved in the cata
lyst preparation, but >it .is `presumed that a ‘type
such as sulfuric and phosphoricacids, Whilerela
tively .quite :elîective ,in alkylation reactions .in
VQlvlng .olefìns «of three lorlmore carbon atoms,
of chemical combination often referred to as a
complexer addition compound'has resulted. "The
2,404,897
3
complex derived from boron fluoride and Water
is usually designated as boron ñuoride hydrate.
Where 100 per cent phosphoric acid is concerned,
the empirical representation of its complex with
boron ñuoride is HsPO4.BFs.
In the same man
ner` catalysts prepared from aqueous phosphoric
acid and boron fluoride would be a mixture of the
following components: H3PO4.BF3 and HzOtBFa.
The boron fluoride-orthophosphoric acid cata
lyst is prepared by adding gaseous boron fluoride
to the acid, or an aqueous solution thereof. The
resulting reaction is exothermic and the rate of
boron fluoride addition is usually controlled to
4
total alkylate. Alternately, if desired, the alkyl
ate may be fractionated to separate traces of high
boiling material and employed directly as a
blending agent in the preparation of high oc
tane aviation fuels.
A specific preferred embodiment of the process
is illustrated in the fiow'diagram which shows
diagrammatically an arrangement >for process
equipment for the continuous alkylation of iso~
butane With ethylene to produce and segregate
products valuable as blending ingredients of av
iation gasoline. Ethylene and isobutane are
withdrawn fromsuitable sources, represented by
gether with external cooling of the addition prod
storage tanks I and 2 and passed by means of
uct and/or products to avoid temperatures much 15 pump 3 to feed tank 4. 'I‘he isobutane-ethylene
above 200° F. Saturation of the acid solution
and completion of the preparation is denoted
usually by escaping boron fluoride fumes or by a
blend is fed to reactor 6 by means of pump E.
Reactor 6 is equipped With means of agitation
such as motor driven agitators, jet mixers, a
constant specific gravity.
`
recirculation pump, or the like, and line 3@ may
The presence of boron fluoride hydrate in the 20 be used, when necessary, to drain they reactor.
catalyst composition is not essential to the catal
Provision is also made for removal of the heat of
ysis of the isobutane-ethylene reaction although
reaction by conventional design. An emulsion
it may co-operate and/or promote the activity of
of hydrocarbonv and catalyst is continuously
the H3PO4.BF3 complex. On the other hand
Withdrawn from the reactor to catalyst sepa~relatively large percentages of the hydrate do 25 rator
'I. Becausey of the relatively high specific
not interfere with this reaction as may be the
gravity of the catalyst, separation by gravity is
case where alkylation of the higher molecular
rapidly effected vand a portion of the catalyst
weight oleñns are concerned. Since the polymer
phase is drawn 01T into tank 8 and a portion is
izing activity of the hydrate is well known high
through line I2 for recovery of boron
percentages are to be avoided with oleflns such 30 discarded
fluoride. Make-up catalyst is provided by the
as the butylenes. However, with regard to ethyl
introduction of boron fluoride from line I3 and
ene alkylation a wider latitude is possible since
partially saturated acid delivered from the
ethylene exhibits a much greater resistance to
washer I4 by line I5. Maintenance of a catalyst
polymerization.
The phosphoric acid employed may be in con 35 phase completely saturated with boron fluoride
is the function of tank B. From tank 8 the catl
centrated form, ranging from the 85 per cent
alyst
is delivered to tank 9, from which itis
acid of commercial grade up to about 100 per
pumped backthrough line IU by pump. Il, 'into
cent or more of HaPOr; or aqueous solutions con
reactor 6. If desired, a portion'of the catalyst
taining as little as 20-40 per cent H3PO4 may be
may be directly recycled from separator 'i through
employed. For most applications the moderately 40 line
32.
'
`
concentrated to concentrated acid is ordinarily
Eiliuent hydrocarbon is passed from Vseparator
preferred for several reasons: (1) a considerable
'I into washer I4 where intimate contacting with
economy in boron fluoride consumption per vol
phosphoric
acid, introduced through line i5, re
unie or per unit weight of catalyst is effected;
(2) less boron fluoride is carried away with the 45’ moves the last traces of boron fluoride. The acid
in the Washer also serves as the feed for the prepr
eiiluent hydrocarbon; (3) the production of a less
aration of fresh catalyst. An auxiliary Water
corrosive catalyst; (4) a better recovery of boron
washer
or a clay tower, not shown, may be em»
ñuoride from spent catalyst by convenient means.
ployed immediately following the acid Wash to
The unique action of aqueous phosphoric acid
remove any entrained acid. The hydrocarbon
in the preparation of my preferred catalyst is 50 stream then is passed through line I'I into esta»
demonstrated by the fact that other mineral acids
bilizer I8 where the isobutane is taken overhead
such as'sulfuric acid and hydrochloric acid fail
and returned to storage via line I9. Any uncon
to result in catalysts of comparable activity even
densed gases such as ethylene or ethane, etc.,
though the quantity of boron fluoride hydrate
may be separated and vented either from the
may be appreciable. This is especially true of
stabilizer through line/39 or from auxiliary gas
sulfuric acid which appears to have an inhibiting
stripping equipment (not- shown).- The stabi
effect on the catalytic activity of boron fluoride
lized total alkylate is passed through line 26 into
complex compounds.
the fractionating column 2| where a Vpentane
I have discovered that the alkylation of iso
fraction is removed as an overhead fraction and
butane with ethylene to produce a high yield of
passed to storage throughline 22. The kettle
di-isopropyl is smoothly and eñîciently promoted
by catalysts which comprise saturated solutions
of boron fluoride in ortho phosphoric acid of
variable Water content. While the alkylation
process can be carried out under a Wide range of
mild conditions it often comprises the contacting
of controlled molar proportions of isobutane and
ethylene with the liquid catalyst under condi~
product, now comprising hexanes and heavier,
is charged to fractionator 24 through line 23 and
isohexanes, of which di-ísopropyl is the major
component, are taken overhead leaving heptane
and heavier as the kettle product to be charged
to fractionator 2l. A naphtha fraction in the
gasoline range and of good octane number and
lead response constitutes` the overhead product.
stantially complete ethylene utilization. The hy 70 The small amount of heavy alkylate is Withdrawn
through line 29 for utilization elsewhere.
drocarbon product mixture is continuously sep
arated from the catalyst and the alkylate is sep
When the illustrated lseparation and concen
arated from unconverted isobutane by means of
tration of di-isopropyl is not desired, the sta
fractional distillation. Subsequent distillation is
bilized, substantially C4.-free alkylatevmay` pass
tions that produce a high degree or even sub1
employed to separate the di-isopropyl from the
through line 3.! to fractionator 21, wherein the
t
_
fascismo?,
A
`
_small amounts of heavy alkylateffmayîïfbe‘fsepa-
Tïïß
‘rature’ and >the.',pressures:desirable inzxsìibseqúent
_hydrocarbons~‘are"separated-fprior’toffractiona- îäñ Often USed- Regardless 0f Operating Conditions
:Ltion of theja-Hçyiatemane-»manner«eeseiibed
gfinßeeneraLjSufñeìent?pressureîshouldßbe applied
_ Although |‘the’ “cata-lystcofr-th'ls ‘- invention *Í'ëdis-
‘m "Offler t0 insure 'il-îqliîd‘flehase‘ Operation i-infthe
_ The_»ifalkylate sr-p'ro'duced ï' from ‘ff-is'obutane wand
_.-ßperabingf conditions; „fwhemisobntaner‘fanœ ethyl- 31’0 »ethylen ' 'by the' iboronl-Tluoridefcatalyst «composi
_;_formance~ ¿_The ¿most important variablesïare;
--ia'll'ï ‘boiling orange'.fofiA¿approximately?0821-350"ÜF.
Contact time, temperature, isoparañin-olelìnra-
`*after *separation ß of ‘f‘excess >L>isolo‘utane.` “Z'I‘he
ntiosantlrhydroearhonecatalyst-î-ratio. :Otherwar- `SI5 ¿ÈÁS‘I‘M‘ e’focïztane I'I’aïtirie-*cif` î ther-’.totalgfalkyiate@may
mames»whiahf'arenargelyf. dependent on the-:mode
«_ tropeuationware:«degreeeof'rdispersion_iofneatalyst
imthëhydmcmbon„Impressum_
_
_
very from about 89.0 to 90.0;for’ìhi‘eher.«Withfa
lead response Such that the addítîoneohliccfiof
j
rtetraethyl leadiis -sufûcientto giveaailoûloctane
I_n general it maybe ‘said that contact times
mumbel‘ 01‘ hîgheï‘_
for ethylene conversioïmust be somewhat longer-51,20 `J‘ractional .distí11ation`_ A,of _ ithe Etotal f_alkylate
"_thanîfori?zhe'highergoleñns «Wherei-the .Contact
t:orsresidence ftimeîinatherreactor is.` short», incom-
from a iiypîßallfrllnlfrevealsrîtheifollowing-«Cûm
ì‘posîtionr
lïiplète:fconversionnof:the‘ethyleneenrayfresult-'even
‘_
vowìthlîa“fullyzactiveacatalystfand- involve;»either
»'¿ÍSODEIIMDC
_
`
_
_
f ,VOL vperscent
_
_¿„.6.5
ë‘loss rorîlrecyclîng"ïof‘the;ethylene. -,--Deñning the225 --fHeXëlIleS
contact time as the following ratio:
A_IéIJeìJtanes
_
c anes
_m
_ `~fil-0
___ ‘ 3.5
_
'
`
Y*16.5
‘iNonanesfarid heavier __________________ _112,5
@may «resultlin älk'ylate ' "dellcient ' in ‘quality
A
‘be‘rmaintainedrinïi-»thef‘reactorwmay'fvaryziwidely 6:, phoric acid to give`1`00"per"c`ent phosphoric aeìd‘
impending@ aheoéliî‘cieney offseontactíngßand »',Whichll-wasuëthenfsaturate'diwith anhydroushoron
"tl-le‘ratex of’ '?lowï‘throughlthei reaction zone. \--«With
iîílu'o?ide. " The oalkyl'ation .treaction «maw-»carried
*reasonably '-'goo'd La'git'ati'on-anratio :of aboutfz'four
'-'vblumesof hv‘dreoa?oonß‘per volumeeof-f'eatalyst
r:“o'1`1t~=as»fï»a f_‘continuons‘eproeess‘;under"z250~ îpoun'ds
A~fea-gerpressm'e. 'rheiliydrocarbon :_phasefnn the
vi-is‘usually>ìa'deq-u-e‘nze,‘~‘although higherrorf-lowerfra- 57o reactor amounted to four volumes per volume
ßiOS may be employed Withoutimßlbefialïîïämiïto
“öf‘ficatalystoan'cl’ tneeavera‘geatimerof:lcontactïwas
the quality of the hydrocarbon product.
iadjustedríátzn35fiminutes.
reaotionßptemper
*Pressures' are Lac‘liosen‘in laccordance*with the
:iatureß-‘wasì’held‘iat.x100-106°:.F.rä.thro11ghout the
"'reactionweqnirements asL determined byfthef’com-
@reaction ¿The ‘.-rfmalsstabilizedralkylatef;hadden
position" óf -"the ìfeed " stoèk,` *the reaction- itemper- ’17 5 overall I l(boiling range rofeßo :_toë1340°;\'€E‘_qfandf~fwas
2,404,897
' 7
substantially completely saturated. A di-iso
propyl concentrate of 92.5 ASTM octane number
Feedcomposition:
Isobutane____per cent by'weight.~
,
.. „'
-made up 50 per cent of the total alkylate.
Example II
.f V84.15
vEthylene ___________ __`_____do_____
15.85
Mol ratio,` isobutane/ethylene__-__
2.56:1
Hydrocarbon/catalyst, volume ratio in
The preparation of dl-isopropyl was carried
out by the continuous alkylation of isobutane
with ethylene in the presence of a catalyst pre
-
reactor _________________________ __
2.5: 1
Contact. time _____________ __minutes..V
30
Temperature range ____________ __° F-- 120-130
. pared by saturating 85 per cent phosphoric acid
Pressure ____________________ __p. s. i--
l ‘225
with boron iiuoride. The catalyst contained v53 10
The stabilized alkylate showed an overall boil
per cent by weight of boron fluoride which cor
responds to a mol for mol reaction between the
boron fluoride and phosphoric acid and water,
ing range of 8O to 350° F. Octane-number rat
ings by the ASTM method with 0.0 and 1.0 cc.
of tetraethyl lead were 90.0 vand 100.0, respec
respectively. Substantially complete conversion
of the ethylene was realized under the following 15
lreaction conditions:
Hydrocarbon feed:
'
Isobutane____per cent Iby weight“A
87.7
Ethylene ________________ __do_..-_
12.3
Mol ratio, isobutane/ethylene____~
344:1
zone ____________________ _s
2.5:1
'
.Y ,
urating 85 per cent commercial phosphoric acid ,
`
205
with boron iiuoride. The continuous operation
described in the previous example was followed
25 in this instance.
The di-isopropy1 concentrate distillingjbetween
135-139° F. comprised 53 volume per cent of the
total alkylate.
`
The catalyst for this run was prepared by sat
Contact time _____________ __minutes__
40
Temperature range _____________ __° F__ 120-125
Pressure ___________________ __p. s. i."
-
The di-isopropyl concentrate dlstilling between
135-139° F. amounted to 50 volume per cent of
the total alkylate. The octane rating of the'clear
concentrate wasv 92.5 by the ASTM'nn'ethod.">
Example V
Hydrocarbon/catalyst, volume ratio inv
reaction
tively.
Feed composition:
The refractive index of this
fraction (ND20, 1.3746) and the ASTM octane
number (93.1) indicate a di-isopropyl content 30
Vof more than 95 per cent.
l Example III
The operating conditions were
as follows:
1"
_
y
Isobutane_____per cent-by weight“
92.5
Ethylene ______________ _`_-_do____
Mol ratio, isobutane/ethylene__’_..__
7.5
, 6.0:1
Hydrocarbon/catalyst, volume ratio in
l
reactor „___1 _____________________ __
lThe catalyst 'described in Example II was em
ployed in this operation. The general alkyla
tion procedure involved the liquid-phase intro
2.5:1
Contact time ______________ __minutesl25
'I‘emperature range ____________ _Ã__V°.F__ 115-120
Pressure ____________________ __p. s. i__
`
`
200
action was carried out as a semi-continuous
An isoheXane fraction boiling between 13S-139°
E'. amounted to 75 percent by volume ofthe total
alkylate. The ASTM octane rating of the-di
process »"With mechanical agitation being em
isopropyl concentrate was found to be 92.7.
ployed in contacting the hydrocarbon feedV and
While the foregoing disclosure and exemplary
operations have served to describe Vthe invention
and speciñc applications thereof, it will be obvi
duction of the isobutane-ethylene feed int'o a
metal reactor containing the catalyst. The re
catalyst.
The eiiiuent from »the reactor was re
cycledV to the reactor along with make-up
' ethylene.
Reaction conditions were maintained A
Within the following limits: l
,
ous that many modiiications are possiblewithin
4.7 : 1
the scope of the broad disclosure. Thus, While
alkylation of isobutane has been emphasizedwith'
suitable process modifications, the alkylation of
isopentane may be similarly accomplished in the
presence of the catalyst compositions described.
In large scale commercial operations the ethylene
feed to the process is preferably of relatively high
Contact time ____________ _.nminutes“
34
Temperature range _____________ __° F.- 110-120
Pressure ___________________ __p. s. i-200
inert material. However, a dilute ethylene stream
may be utilized, with the inert impurities (usually
Initial hydrocarbon feed:
Isobutane____per cent by Weight__
' Ethylene
`
`
do
Mol ratio, isobutane/ethylene_____
89.0
11.0
3.91:1
Hydrocarbon/catalyst, volume ratio Yin
reactor __` _______ __'_' _________ __'-__„
'
A completely saturated total alkylate was pro
duced having a gravity of 76.6° API. A di
purity to avoid the handling and separationkof
' ethane and/or propane) being separated and re
turned, if desired, to the facilities producing the
ethylene for further conversion. The isobutane
isopropyl concentrate distilling between 134
will generally be obtained from such associated
140" F. and constituting 5_3 volume per cent of
operations as segregation from reiinery or natural
the total alkylate was recovered by fractionation 60 gasoline C4 fractions, normal butane isomeriza
from a still of 20 to 25 theoretical plates. The
octane rating of the concentrate was found to
be 92.9 ASTM.`
n
`
Example
IV
.
The catalyst for this run was prepared by
vsaturating 50 per cent phosphoric acid with boron
fluoride. The absorbed boron fluoride amounted
to about 2.2 parts by Weight for each part of
acid.
'
The hydrocarbon feed was introduced con
tinuously into the reactor containing the catalyst
in a once through operation. Substantially
complete conversion of ethylene was vrealized.
under the following operatingconditions:
tion processes, and the like. The amount-of
normal butane in Ithe isobutane feed to thel proc
ess may vary appreciably, and provisions Aare
usually madeA to maintain suitablylow concen
` tration thereof, even with indicated isobutane re
cycle. The same considerations apply to vother
isoparaiiin reactants. These and other modiñca
tions and adaptations 4of lthe present process will
be obvious to one skilled in the art and suitable
I conditions for any particular case may be readily
determined by trial.
I claim:
-
1. A process for the alkylation of a low-boiling
isoparaflin with ethylene, which comprises react
ing such an isoparaffin with ethylene in an al
2,404,897
i
9
kylation zone under alkylation conditions in the
presence of an alkylation catalyst comprising
an addition compound resulting from the com
bination of an acid of phosphorus with boron
trifluoride, separating effluents of said alkylation
into a catalyst phase and a hydrocarbon phase,
10
tions with a liquid catalyst comprising essentially
an addition compound resulting from saturating
with boron trifluoride an acid of phosphorus, in
timately admixing hydrocarbons eiiluent from
said alkylation zone With an acid of phosphorus
to remove minor` quantities of boron trifluoride
associated therewith, separating the resulting ac
contacting said hydrocarbon phase with a liquid
id of phosphorus-containing mixture from said
acid of phosphorus to remove nonhydrocarbon
hydrocarbons and adding to said mixture addi
>impurities including boron triiluoride, removing
tional quantities of boron trifluoride to effect
said liquid acid of phosphorus from said hydro 10 substantially complete saturation thereof, and
carbon phase and admixing same With at least a
passing the resulting material to said alkylation
portion of said catalyst phase, adding boron tri
zone as catalyst.
i
iiuoride to the resulting mixture, passing the re
4. In a process for reacting a low-boiling iso
sultant catalytic material to said alkylation zone,
parañin hydrocarbon with a low-boiling olefin
and subsequently separating from the resulting 15 hydrocarbon by contacting in an alkylation zone
puriñed hydrocarbon phase paraffin hydrocar
a mixture comprising such hydrocarbons, and
bons produced in said alkylation.
containing a molar excess of said isoparaiñn, un
2. A process for reacting isobutane with ethyl
der alkylation conditions With a liquid catalyst
ene, which comprises contacting in an alkylation
comprising essentially an addition compound re
zone a mixture comprising said hydrocarbons, 2.0 sulting from saturating orthophosphoric acid with
and containing a molar excess of isobutane, under
boron trifluoride, the improvement which com
alkylation conditions with a liquid catalyst com
prises intimately admixing hydrocarbons eiiiuent
prising essentially an addition compound result
from said alkylation zone with a liquid ortho
ing from saturating with boron trifluoride aque
phosphoric acid to remove minor quantities of
25
ous orthophosphorio acid containing about 85
boron triñuoride associated therewith, separating
per cent by Weight of orthophosphoric acid, inti
the resulting mixture of liquid orthophosphoric
mately admixing hydrocarbons effluent from said
acid and removed boron trifluoride from said hy
alkylation zone with aqueous orthophosphoric
drocarbons and adding to said mixture addi
acid to remove minor quantities of boron triflu
tional quantities of boron trifluoride to effect sub
oride associated therewith, separating the result 30 stantially complete saturation thereof, and pass
ing orthophosphoric acid-containing mixture
effect substantially complete saturation thereof,
ing the resulting material to said alkylation zone
asY at least a portion of the catalyst employed
therein.
5. The process of claim 3 in which said low
and passing the resulting material to said alkyla- -
boiling isoparafûn is isobutane, said low-boiling
tion zone as catalyst.
olefin is ethylene, and said liquid catalyst com
prises essentíally an addition compound result
ing from saturating with boron trifluoride aque
ous orthophosphoric acid containing about 85
from hydrocarbons so treated, adding to said mix
ture additional quantities of boron trifluoride to
3. A process for reacting a low-boiling isopar
añîn hydrocarbon with a 'low-boiling oleñn hy
drocarbon, which comprises contacting in an a1
kylation Zone a mixture comprising such hydro
carbons, and containing a molar excess of said
low-boiling isoparaflin, under alkylation condi
40
per cent by weight of orthophosphoric acid.
WILLIAM NELSON AXE.
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