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Патент USA US2406086

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Patented Aug. 20, 1946
2,406,086
UNITED "STATES PATENT OFFICE-if f
2,406,086
ALKYLATION 0F ISOPAR'AFFIhTIC
HYDROOARBQNS
_ 7 Carl B.'.Linn,
Riverside, 111., assignor to Universal
Oil Products Company, Chicago‘,.1ll., a corpora
j tion of Delaware‘
1' I “No Drawing. Application September
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Serial No. 502,664
‘
16, 1943,
7 Claims; (Cl. 260-6834)
1
2
This application is a continuation-in-part of
my co-‘p'ending application Serial No. 424,784,
ofehydrogen ?uoride alkylation catalyst by the
addition thereto of a particular non-oxidizing
acid which moderates the action of hydrogen
' ?led December 29, 1941.
This invention relatesto the'treat'ment of iso
?uoride and modifies the reactions involved in
para?inic hydrocarbons, both gaseous and liquid, ‘
to produce therefrom branched chain para?inic
lhydrocarbons of higher molecular weight. In
such: away as to improve the yieldand quality
a more speci?c sense this invention is concerned
_The term isopara?ln is herein used broadly .to
include all alkylatable branched chain para?inic
hydrocarbons. The reactions of the present proc
of the hydrocarbon alkylation product.
with ya novel process for alkylating isopara?inic
‘hydrocarbons, comprising isobutane and rela
tively low-boiling normally liquid isopara?‘ins
10
'
-~
ess are effected under controlled conditions of
temperature and pressure until the ole?ns have
been substantially consumed and a- substantially
duce normally liquid saturated hydrocarbons
saturated hydrocarbon product is formed which
which may be utilized as components of gasoline
‘suitable for use in airplane and automobile en 15 boils within the boiling range of gasoline.
‘gines.
'
Hydrogen cyanide is a Weak volatile‘ acid and
like hydrogen ?uoride it is a liquid at ordinary
These isopara?inic and ole?nic hydrocarbons
temperatures and atmospheric or slightly super~
have been utilized in alkylation reactions in the
‘atmospheric pressures. Hydrogen cyanide has a
presence of hydrogen ?uoride alone or of hydro
gen ?uoride diluted by-relatively small quanti 20 boiling ‘point of 26.5° C. and hydrogen ?uoride
boils at'19.4°»C.‘ The melting points of hydro.
ties of water. The present type of catalyst is a
with normally gaseous or liquid‘ ole?ns to pro
‘marked improvement over previous catalysts con‘
»gen cyanide and hydrogen ?uoride are —1'3.4°
~taining hydrogen ?uoride in that the activityvof
C. andf—-92.3° 0., respectively. Hydrogen» cya
the catalytic material may be controlled more
niche is "soluble in water, alcohol, andether, and
also in‘? hydrogen ?uoride in the. concentrations
which are contemplated in the present-lpro‘cm.
accurately by proper dilution with a substance
which is relatively inert catalytically but which
‘has substantial solubility in-liquid hydrogen ?u
oride.
-
Ordinarily the catalyst employed in my inven
tion may comprise from about O.5~to about 10%
by weight of hydrogen cyanide although larger
In one speci?c embodiment the present inven
tion comprises a process for synthesizing sub '30 quantities may be used in certain cases.‘ Because
stantially saturated hydrocarbons of gasoline
boiling range by alkylating isopara?‘inic hydro
carbons with ole?nic hydrocarbons in the pres
ence of a catalyst comprising essentially a ma
jor proportion of a liquid hydrogen ?uoride and ~"
a relatively minor proportion of hydrogen cy
anide.
'
'
of its toxicity and attendant di?iculties when
employed in high concentrations it is generally
desirable to maintain the hydrogen cyanide con
tent of the catalyst below about 5% by weight.
Isobutane is the isopara?in commonly subject
ed to alkylation although higher molecular
‘Weight isopara?ins also react with ole?ns under
similar or modi?ed conditions of operation to
‘By the addition of hydrogen cyanide to sub;
produce branched chain para?ins of higher boil
stantially anhydrous hydrogen ?uoride, the or
dinarily vigorous reaction of hydrogen ?uoride 40 ing point than the isopara?ins charged to the
process. However, as the higher 'molecular
on catalytic condensation reactions among hy
weight isopara?ins such as isopentane, isohex
drocarbons is moderated to the extent that reac
tions of alkylation occur in preference to other
ane, etc. are themselves Valuable constituents of
gasoline, they are consequently used less com
-'less desirable reactions. Alkylation is essen
tially a complex reaction since the simple union 45 monly as charging stocks for the alkylation proc
ess than is isobutane. Mono-ole?nsv and partic
‘:of isopara?inic and ole?nic molecules to give the
ularly those containing from 3 to about 16 car
Isa-called primary reaction product is accompan
bon atoms per molecule are utilizable for alkyl
ied by many side reactions, among which are de
rating isopara?lns in the presence'of- hydrogen
composition or cracking reactions and isomeri
tzation, which can, under certain conditions, 50 ?uoride and a diluen't'or spacing agent, although
‘the common ole?n-containing charging stocks
achange a substantial proportion of’ the primary
are often limited to hydrocarbon fractions con
1 product such as iso-octanes into a mixture of
‘lower? and higher boiling hydrocarbons fre.
'quently-of; lower antiknock value. Accordingly,
taining ethylene; propene, and butenes. Normal
ipara?ins frequently present in hydrocarbon frac
;the present invention deals with the ‘modi?cation 55 tions containing propene and butenes dilute the '
reacting hydrocarbons but are separable ‘from the '
‘
2,406,086
' ' jalkylationrproducts by distillation.
good products from the standpoint of high anti
knock gasoline are produced usually by maintain
Thus pro‘
fpane and normal butane may be removed from
ing at alltimes in the reaction zone a molar
excess of isoparaf?n to ole?n. The presence of
such an excess of isopara?ins, generally at least
‘the alkylation product while an isopara?in such "
also separated from the2
5 as isobutane, which is
. reactionproduct, is recycled to further alkylation
.Vtreatmentj.
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2lmo1ecular proportions‘ ofisoparai?nrper molec
iiularcproportiont of ole?n,»tends to minimize un
desirable polymerization reactions. The mixture
'
In order "to flavor the alkylation reaction rather
polymerization, ’ the hydrocarbon ‘ ' of alkylation products and catalyst composite is
‘ charging stock including the isopara?in and"!10 removedperiodically from thebatch type process
. added ole?n-containing fraction may be com.
: 1 and i‘separated ‘into a hydrocarbon layer and a
§ mingled with recycled isoparaf?n so that‘thejratioi
vcatalyst layer, the latter being returned, to the
1 of isopara?in to ole?n in the total hydrocarbon 1' . reaction zone :for further use while the hydrocar
1 mixture charged to the alkylation zonenis zap-,1 ibonlirlayertx' '.;fractionally distilled to separate
f proximately 5:1. In some4ca'ses-l'this ratio may i‘
therefrom the? gasoline fraction and the excess
10f the isopara?inloriginally charged to the proc
1 the exact'ratio being somewhathependentupon. » 4 ess.v IThe'exce'ss' isopara?in may be reacted fur-V
‘
be as low as about 2:1 or as high as 10:1, or more, i
the particular isoparaf?n and'blé?n or olefin!‘
containing mixture charged.
Alkylation reaction temperatures
ther ‘with an ole?n in a subsequent alkylation .»
' treatment'in the alkylation zone of the process.
7' between ~
It is usually preferable to carry out the alkylaa .
about 0° and about 50° C. are preferred, although 20 =tion; reaction on? a continuous basis - by: withdraw
satisfactory results {maybe obtained at tempera
ing fromthe ialkylationreactor amixtureof ex- ‘
turesaslow as about -30° and as high as about
cess unreacted isopara?ins; and: admixedenormal' '
+100? 0. when reacting isoparaf?ns with ole?ns
para?ins, an alkylate of. gasoline boiling :ran‘ge,
in the presence of a mixturesof hydrogen ?uoride ‘
higher boiling hydrocarbons;v and. catalyst-com
posite, said i-mixture {being withdrawn atzsubstan
tially the. same rate-as thatat which-vitheq-tresh
‘andia diluent 1or spacing agent v.asherein *de-‘
scribed. As additional means of regulation of the
‘upper limits of temperature, ther-proportionsyo-f
hydrogen fluoride and diluentmay be'varied; to
and recycled hydrocarbon . - charging ~ stocls. and
.produce ' good results :provided. they are co-ordi
~‘natedproperly‘ with the reaction temperature and‘
rate‘ of charge of theisoparaf?n and ole?n hydro
30
‘mixture of fresh andv recycledcatalystgare sup
plied to the alkgylation-reactor. In iorderlto-zkeep
low the competing olefin :polymerizationreaction,
the molar ratio of isoparaf?ns».to-ple?nsiQZ-the
alkylating zone. is"kepthighithroughoutthe entire
carbons. Forinstance, the reaction of isobutane
lwith propene may require {moresevere conditions
such as a somewhat~ higher temperature‘ or a cat- '
~alyst containing-a higher proportion'oi hydrogen
vfluoride. todiluent than- that used vfor catalyzing
reaction; The ratio of. isoparaffin-to- ole?n issub
jectto . some variation - and is affected consider
35 ably by the method of introducing the ole?n
containing fraction andby the efliciency; oimix
ling. =As theiprocess-is' usually operated; sulii-cient
.the reaction ‘of isobutanewith the more reactive
isobutene. *Superatmospheric pressure; generally
'of'the reactants and catalyst lay-vaporization and,
when desirable, to maintainthe ‘hydrocarbons
and catalyst in substantially liquidmstate' or to
effect liquefaction of alportion of the'reaction
mixture..__
;
j
i-X- »
pressure’ is=maintained1 'upon'. thereaction ;
:not in” excess of about 20. atmospheres,» is employed
' to assist the reactioniandto *preventundue "loss
turev to keep: a» substantial; proportion ther'eo__f__ n
liquid- state.
The Y‘ exactv pressure necessary ;de
bends bothrunon thecomposition o-fgthe reaction
mixture-and‘ the‘ temperaturepemployed. v‘The
used- in Pt-hie. "pI‘Q¢ess'..-c0nSiSl$S
< alk-ylation Y reactori
45 quite: often; of ’ a; coil or tower provided withrbaiiies,
Yorifice<plates,.aorv othermixing‘;devicesioria-vessel
‘y
W hilegin most cases the actiyity'hoif. the‘ialklylat
ing composite employed-is due principally -to_ the
‘provided with aistirreriorotherimechanicalimeans
of agitation although any method may herein
hydrogenr?uoridait is recognized'thatthe hy
ployed' which; satisfactorily-1 effects‘ {intimate con
drogen cyanide .iadded theretomay at times; exert 5" -tact of ‘the reacting- hydrocarbons:and-‘mixture
a de?nite chemical in?uence uponitherreactions uoiicatalyst-and. spacing-r agent employed; 7 ‘
other than merely moderating the B?BQtaDf'tHG
The following'examplje isgiven toindicate'f 11'6
hydrogen fluoride.- It is alsoevident thatzthe
sults obtainablerby the ;use of theipresentrprocess,
selection of any particulandiluentcrap xtureof
- although :ity is . not rintended ‘ to: limit the seopezof
V
.diluents for use qwith; hydrogen}
?uoride; ~_is~-'de
termined largely'by solubility relations; the; ease
of alkylating the; isoparaf?nlc hydrocarbonsin
volyed, the general operating conditions, andv the
“matter of economy-in the cost'of. the reagents,
55 the inventionw-in exact correspondence;~;with the ,
example.
.
V,
..
A mixture of 143 grams of substantiallyoarrhy
drous hydrogen ?uqrideand?grams»of'hydrogen v .
cyanide :is; placed: in- ‘an autoclave iofriapproxir
' The process of the present-invention is carried
-mately 2000 ‘ a-cc. ~ capacity equipped ~~witht a ipres
out- in either batch or continuous types oto-pera .60 sure-sealed - stirring device; iThe autoclave-11s
tion. In a simple ‘batch.’ tyne ’process. an~;~iso.
para?in to be. alkylated} such- as isobntane, .is
'maintained: at approximately <50‘?
‘of a liquid. mixture containing:2rmolecularrvpro
brought to the alkylating temperatureewithinithe
portions? of isobutane and: 1t moleculan-proportion
approximate range speci?ed and in the; presence
‘of normal- butene is 1 introduced: continuously:-: to _
.of the necessary amount of catalystimixture and .165' the autoclaveover:afperiodi-or li5jhourssa‘fter
alkylation is- effected by the gradual introduction
of an ole?n, or preferably of an ole?n-isopar
a?in mixture, under- the surface of the liquid
i which the stirring [is continuedforran: additional
“time-of 0;5ihour.V
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The, resultant: mixture. ofreaction- products; is
lwhichyfis stir-red mechanically-‘to ef?ect intimate 70
_ contact between the catalyst ‘and the; reacting
_;
drocarbons and; to prevent isettlingrjofgther-catalyst
separated into ~ a hydrocarbonilayer an'dra heavier
.which is heavier‘ than the, liquidtihydrocarbon
while the;v vhydrocarbon layer. is jractionallm'dis
tilled: to :. separate: from: higher boiling; alkylation
.. mixture.
Alkylationamay be-'allowed-toprogress
.lto different stages of reaction, ‘ In-the case ofithe
' :;.a1'ky1ation of .isobutane by propane: or vbutenes.»-
catalyst Jaye-r. . The :used: catalyst :is'returnedcito
the autoclave for use. in. another alkylatiomrun
products lithe l'unreacted': isobutane anduz small
2,406,086
amounts of hydrogen ?uoride which generally
dissolve in the hydrocarbon layer. The recovered
isobutane is used in another alkylation run while
the higher boiling hydrocarbons are washed with
water and caustic soda solution, then dried and
distilled to separate therefrom a substantially
saturated fraction of gasoline boiling range con
taining a high proportion of branched chain
6
Y
'
tacting an isopara?inic, hydrocarbon With an ole
?nic hydrocarbon at a temperature of from about
—30° C. to about 100° C. in the presence of a
catalyst comprising essentially a major propor
tion of liquid hydrogen ?uoride and a relativelyv
minor proportion of hydrogen cyanide.
5. An alkylation process which comprises con
tacting an isopara?inic hydrocarbon with an ole
From 1000 cc. of the isobutane-norm'al butene 10 ?nic hydrocarbon in the presence of a catalyst
comprising essentially a major proportion of
mixture there is obtained approximately v3'70
liquid hydrogen ?uoride‘ and a relatively minor
grams of normally liquid paraf?nic hydrocarbons
proportion of hydrogen cyanide at a temperature
containing 90% by volume of 300° F. end point
of ‘from about -30° C. to about 100° C.’ and under
aviation gasoline with an A. S. T. M. octane num
ber of 92.5.
‘
sufficient pressure to maintain a substantial pro
octanes.
'
I claim as my invention:
.
15 portion of the reacting hydrocarbons and catalyst
in the liquid state.
6.‘ An alkylation process which comprises con
tacting a molar excess of an isoparat?nic hydro
carbon with an ole?nic hydrocarbon in the
1. An alkylation process which comprises re
acting an isopara?in with an ole?n in the
presence of a liquid
"
hydrogen ?uoride catalyst to
which’ has been added a minor proportion of
20 presence of a catalyst comprising essentially a
hydrogen cyanide.
major proportion of liquid hydrogen ?uoride and
2. A process for synthesizing substantially
a relatively minor proportion of hydrogen cyanide
saturated hydrocarbons of gasoline boiling range
at a temperature of from about —30° C. to about
which comprises alkylating an isopara?inic hy
100° C. and under suf?cient pressure. to maintainv
drocarbon With an ole?nic hydrocarbon in the
presence of a catalyst consisting of a major pro 25 a substantial portion of the reacting hydrocan
bons and catalyst in the liquid phase. .
portion of liquid hydrogen ?uoride and a minor
proportion of hydrogen cyanide.
I
3. The process of claim 1 wherein said hydro
gen cyanide comprises from about 0.5 to about
10% by Weight of the catalyst.
4. An alkylation process which comprises con
7. An alkylation process which comprises re
acting isobutane with a mono-ole?n in the
presence of a liquid hydrogen ?uoride catalyst
30 containing a minor proportion of hydrogen
.
cyanide.
CARL B. LINN.
.
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