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Патент USA US3083256

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MarCh 26, 1963
Filed DSG. 7, 1959
2 Sheets-Sheet 1
March 26, 1963
Filed Dec. 7, 1959
2 Sheets-Sheet 2
Patented Mar. 26, lgëâ
Arthur R. Goldsby, Chappaqua, and Howard H. Gross,
Pleasantville, NY., assignors to Texaco Development
Corporation, New York, N.Y., a corporation of Dela
Filed Dec. 7, 1959, Ser. No. 857,717
4 Claims. (Cl. 26th-683.46)
action zone wherein the reaction proceeds without the
addition of further oleñnic material or the mixing of
unconsumed intermediate fractions with the product dis
charged from the reaction zone. Progressive reaction
of the intermediate reaction product is effected by pass
ing emulsion, the hydrocarbon portion of which contains
a high proportion of isoparafíinic material, in a single
pass through an elongated reaction zone, for example, a
tubular, pipe or coil reactor. As the reaction mixture
10 passes through the elongated Zone, the intermediate prod
uct continues to react With the isobutane present effect
presence of an alkylation catalyst and more particularly
ing a continuous decrease or diminution of the unreacted
to such an alkylation process wherein at least a part of
or incompletely reacted material. Advantageously, tur
the aforesaid reaction is effected in once through linear
bulent flow conditions are maintained in the elongated
liow in an elongated reaction zone whereby intermediate 15 reaction zone by employing high linear velocities thereby
This invention is directed to a method of reacting ole
lin based alkylatable material and isoparaiiin in the
reaction products are effectively converted to alkylate.
Alkylation of oleiinic materials with isoparaiîins is ern
maintaining intense mixing and intimate contact of the
reactants and catalyst. Although high turbulence is
ployed extensively for the production of high octane
achieved, back-mixing of reaction products with incom
number fuels. The alkylation reaction is effected in the
pletely reacted feed material is substantially avoided by
liquid phase in the presence of a liquid catalyst. The al 20 virtue of the single pass lineal flow employed.
kylation reaction is directed to the production of a maxi
In the catalytic alkylation of olefins with isoparaflins,
mum yield of high product quality alkylate with mini
a preponderance if isoparañin (typically about 60 to 8O
mum catalyst consumption by maintaining desirable oper
volume per cent or more of the hydrocarbons in the
ating conditions including conditions of intimate mixing,
reaction mixture) over olefin material and hydrocarbon
low temperature, and high ratio of isoparañin to oleñn. 25 diluents is used to direct the reaction towards production
Intimate contact of the reactants and catalyst is effected
of the most value aviation or automotive fuels. Conse
by intensive mixing forming an emulsion of liquid hydro
f quently a large quantity of isoparañin must be recovered
carbon and catalyst. The alkylation reaction temperature
and recycled for reuse in the process. Isobutane is gen
is desirably maintained within a range of about 35 to 75°
erally used as the isoparafiin for the manufacture of avia
F. It is necessary to refrigerate the reactants and reaction 30 tion or motor fuels although other isoparaffins, for exam
mixture to maintain a desirable reaction temperature
since a large amount of heat is liberated as the heat of
reaction of the olefin and isoparafìin. Mixing is typically
obtained by rapid circulation of the reaction mixture
ple isopentane, may be employed.
The alkylatable material for reacting with isoparafñn
is olefin-based, that is, it is generally an oleñnic hydro
carbon itself such as propylene, butylene or the like, but
by means of pumps as in pump and tank systems or by 35 it also can be an alkyl sulfate (as obtained for example
means of impeilers or jets in internal circulating systems.
in a so-called “two stage” process wherein an oleñnic
Refrigeration may be provided by autorefrigeration, efflu
hydrocarbon is absorbed in sulfuric acid as a first stage in
ent refrigeration or external refrigeration as is well known
the alkylation operation).
in the art. In all of these systems, an emulsion of the
In catalytic alkylation, the mol ratio of isoparafñn to
reaction mixture is formed and circulated in the reaction 40 olefin-based material supplied to the alkylation zone is
zone. Reactant hydrocarbons and catalyst are continu
maintained »substantially in excess of 1 to 1, and prefer
ously added to the reaction mixture, and a portion of
ably within the range of about 4 to about 2O to 1. The
the emulsion is continuously withdrawn. The emulsion
catalyst to liquid hydrocarbon volume ratio is maintained
which is withdrawn is separated into catalyst and hydro
the range of about 0.5 to 1 to about 5 to 1 and
carbon phases; the catalyst phase is recycled and alkylate 45 preferably within the range of about l to 1 to about 3 to 1.
product is recovered from the hydrocarbon phase.
Catalyst strength is maintained of at least about 88 percent
In the alkylation reaction, it is postulated that the ole
when sulfuric acid is used. A liquid catalyst which is non
ñnic material reacts with the catalyst forming an acid
volatile under alkylation reaction conditions, for example,
ester as an intermediate product and that this intermedi
50 sulfuric acid, is preferred. Sulfuric acid strength is main
ate product then reacts with isoparañän releasing the
tained within the range of about 88 to 95 percent by
catalyst and forming alkylate. Although the alkylation
purging spent acid from the system and by adding make
reaction is rapid and proceeds substantially to comple
up acid of about 98.0 to 99.9 percent purity.
tion in the reaction systems described above wherein
An important part of the isobutane employed in alkyla
reactants are continuously added to circulating emulsion, 55 tion processing is a recycle stream produced by fractional
the acid ester intermediate product is presented in the
distillation of alkylation productsin a deisobutanizing frac
catalyst phase of the emulsion. As a result, a part of the
tional distillation zone, the isobutane being recovered as a
olefin feed, for example, up to about l0 percent of the
distillate Ifraction of high isobutane concentration, for ex
olefin feed, may appear as the acid ester intermediate
ample, about 85 to 95 liquid volume percent isobutane.
product in the emulsion phase which is withdrawn from 60 The higher-boiling alkylate in such distillation zone is re
the reaction Zone in prior art processes. Since the hydro
covered in the liquid bottoms fraction. This liquid bot
carbon fraction rich in isobutane is no longer in intimate
toms fraction may be fractionated in -conventional manner
Contact with the bulk of the acid after coalescence of
to separate light ends and alkylate fractions for use as
the acid in the settler, these intermediate products tend
fuel blending stocks. In the usual deisobutanizing frac
to react further with the catalyst by conjunct polymeriza 65 tional distillation operation, isobutane distillate is returned
tion effecting degradation of the catalyst and the forma-l
to the top of the distilling column as reflux at a high re
tion of hydrocarbons of poor fuel quality.- This un-.
flux ratio, for example 4 to 1, to maintain high isobutane
desirable reaction in the settler is evidenced by a tempera
purity in the distillate.
ture rise which may be as much as 5 to 10° F.
In accordance with the process of this invention at least
70 a part of the alky-lation reaction is effected in a single pass
sion of hydrocarbon reactants and catalyst containing
through an elongated reaction Zone. All the functions re
intermediate reaction products is passed to a finishing re
quired in an alkylation system of forming an emulsion,
In accordance with the process of this invention, emul
absorbing the heat of reaction and providing sufficient
effluent of the finishing reactor is separated into catalyst
and‘hydrocarbon phases. FIGURE 2 illustrates a modi
reaction time may be provided in an elongated reaction
zone. For exampie, intimate mixing effective to for-rn and
maintain an emulsion may be achieved by employing
velocities corresponding to Reynolds numbers above 2000.
Absorption of the heat of reaction may be effected by
externally cooling the reaction zone, yfor example the elon
tication of the method of FEGURE l wherein reactor ef
fluent is separated into hydrocarbon and catalyst phases
and the separated catalyst and added isoparailin are passed
through a finishing reactor.
Referring to FiGURE l, a hydrocarbon feed compris
ing oleñnic and paraffinic hydrocarbons, for example, a
lbutylene fraction from catalytic cracking, is introduced
ploying coolant in the shell side of the exchanger. In 10 through line l into contactor 3.v Catalyst, for example,
sulfuric acid in line 4 is isobutane recycle streams in lines
another method of cooling, cold hydrocarbon, for example,
5 and 6 are also passed to contactor 3. The contents
isoparamn reactant, may be introduced at several points
of contactor 3 are circulated rapidly by impeller 7 effect
along the reaction zone. Reaction time is provided by
gated reaction Zone may comprise a number of passes
through the tubes of .a shell and tube heat exchanger em
ing formation of an emulsion of hydrocarbons and cata
the use of a reaction zone of suñicient length, for example,
at a How rate of about 20 feet per second, a reaction time 15 lyst. The emulsion circulated in contactor 3 is cooled
by heat exchange coil 10'. A portion of the circulating
of one minute is provided in a coil 1200 feet in length.
emulsion is withdrawn through line 12 and discharged by
In a preferred embodiment of our process the reactants
pump 13 at high velocity through finishing reactor coil 111.».
are initially contacted in conventional reaction systems
Incompletely reacted oleñn in the form of intermediate
employing circulation of the reaction mixture and a por
tion of the reaction mixture is withdrawn and -ñnished in 20 reaction products present in the acid phase of the emul
sion Withdrawn through line 12 react with the excess of
single pass flow through an elongated reaction zone. For
isobutane present in coil 14.
example, the emulsion is formed and most of the reaction
The eftluent from coil 14 is discharged into settler 15.
is effected in conventional equipment which is adapted
Settler 15 is a quiescent zone wherein hydrocarbon and
to the removal of the heat of reaction, for example, pump
Iand tank, impeller or jet mixed reactors, employing auto 25 acid catalyst phases separate, the lighter hydrocarbon
phase rising to the top as indicated by numeral 16 and
refrigeration, efñuent refrigeration or external refrigera
the heavier acid catalyst phase settling to the bottom as
tion. The amount of reaction occurring in the elongated
indicated by numeral 17. Acid catalyst is withdrawn
finishing reaction zone is relatively small, little heat of
through line 1S and recirculated to the contactor 3
reaction is liberated, and Ithe iinishing reactor may be
operated without encountering excessive temperature rise 30 through line 4. Spent acid is withdrawn through line 20
and make-up acid added through line 211 to maintain the
even though no cooling is provided. In the effluent of the
concentration of the acid in the system at a desired level.
first stage lconventional reaction system, the catalyst con
Hydrocarbon liquid is withdrawn from settler 15 through
tains alkyl acid sulphate within the range of about 0.5 to
line 22 and passed through throttle valve 23 wherein the
4.0 Weight percent. After treatment in the second stage
pressure is reduced effecting concomitant vaporization of
elongated reaction zone in accordance with the process of
a part of the hydrocarbon and chilling of the resultant
this invention, the catalyst contains alkyl acid sulfate with
liquid-vapor mixture. The chilled liquid-vapor mixture is
in the 'range of about 0 to 0.5 weight percent.
discharged through line 24 to cooling coil 10 in contactor
In one embodiment of our invention illustrated in FIG
3 to provide refrigeration and absorption of the lheat lib
URE 2, the emulsion from the primary reaction zone may
be separated into hydrocarbon and catalyst phases and only 40 erated therein. Eñiuent from cooling coil 10 is discharged
through line 25 to vapor separator 3d. Liquid separated
the catalyst phase is passed with additional isoparañ‘in
in separator 30' comprising product alkylate and unre
through an elongated tinishing reaction zone. In this case,
acted isobutane is withdrawn through line 31 to neutrali
it is preferred to employ an accelerated separation tech
zation and fractionation facility 32. Alkylate is discharged
nique, for example centrifugation, for separation of the
through line 33 for use as high octane motor or aviation
catalyst and hydrocarbon »from the primary reaction zone.
fuel. Recovered isobutane from neutralization and frac
The isoparafñn added to the finishing zone may be rapidly
tionation facility 32 is recycled through line 5 to con
emul‘sit'ied with the 4catalyst by the use of turbulent flow
velocities. Emulsion from the finishing zone may be re
turned directly to the primary reaction zone or may be
separated into hydrocarbon and catalyst phases for separa
tion of the alkylate.
An advantage of the process of this invention is that in
termediate reaction products are efiiciently converted to
high quality alkylate.
Another advantage of this invention is 4that catalyst
degradation resulting from. reaction of intermediate prod
ucts in the catalyst separator is avoided.
Another advantage of this process is that a reaction
zone may be fabricated of inexpensive pipe or tubular
factor 3.
`Vapor from separator 30 consisting substantially of iso
butane is withdrawn through line 35 and is condensed by
means of compressor 36 and cooler 37. Condensate in
line 38 is flashed fby passing through throttle valve 39
effecting partial Vaporizatîon and chilling of the conden
sate. Vapor and chilled condensate are passed through
line 40 to condensate accumulator 41. Vapor from ac
cumulator 4t is Withdrawn through line 42 and recycled
through line 35 by compressor 36. Chilled condensate is
withdrawn through line 6 for recycle to the contactor 3.
Referring to FIGURE 2, contactor eñiuent is passed
60 through line 12 directly to separator 15a. Separator 15a
may be a gravity settler or a separator employing an ac
Another advantage of the process of this invention is
celerated separating technique, for example, a centrifuge.
that the catalyst recycle stream before introduction into
Hyrocarbon separated from the contactor etiluent is dis
the primary alkylation zone is prcconditioned by contact
charged through line 22 as shown in FIGURE l. Cata
with a stream of high relative isoparaíiin content as corn
lyst from separator 15a is discharged through line 18a.
pared with other reactants and reaction products.
Isoparañ‘in in line 19 is admixed with the separated cata
Another advantage of the process of this invention is
lyst and the mixture is passed by pump 13a through fin
that intense mixing may be effected by turbulent flow.
ishing reactor 14a. Effluent of finishing reactor 14a is
The accompanying drawings diagrammatically illustrate
discharged through line 4 and returned directly to the
the process of this invention. Although the drawings illus 70 alkylation zone.
trate arrangements of apparatus in which the process of
this invention may «be practiced, it is not intended to limit
the invention to the particular apparatus or material de
scribed. iFIGURE l illustrates Va method in which re
actor leffluent is passed through a finishing reactor and
In the following example flow rates are given in barrels
(42 gallons) of liquid per hour regardless of whether
the stream is in the liquid or vapor state. All composi
tions are given in mol percent.
Fresh feed comprising olelin and isobutane feed streams
is provided at a rate of 63 barrels per hour having the
effecting mixing of said feed and said reaction mixture
following compositions:
Ethane and ethylene ________________________ __
_______________________________ __
Propane _________________________________ __
l15 .8
Isobutane ________________________________ __
Butylenes ________________________________ __
Normal butane ____________________________ __
_________________________________ __
and alkylation of a substantial proportion of said olefin
based alkylatable material, withdrawing a portion of said
reaction mixture as etiluent from said lirst reaction zone,
said eñiuent from said first reaction Zone comprising al
klyation catalyst containing within the range of 0.5 to 4.0
weight percent of alkyl acid sulphate, passing said efduent
from said first reaction zone to a separating zone, sep
arating said eílluent `from said first reaction zone into a
separated hydrocarbon phase and a separated catalyst
phase, adding isoparafñn to said separated catalyst phase,
passing said separated catalyst phase in admixture with
said added isoparatiin in once through lineal ñow through
'The fresh feed is admixed with 84.3 barrels per hour
an elongated reaction zone providing a reaction time of at
of recovered isobutane containing 89 percent isobutane
1.0 minute, discharging the etliuent from said elon
and 152 barrels per hour of condensate containing 80 per
gated reaction zone, said effluent from said elongated re
cent isobutane and charged to an impeller type contactor.
action Zone comprising alkylation catalyst containing with
In addition 299 barrels per hour of sulfuric acid catalyst
in the range of 0 to 0.5 Weight percent of alkyl acid sul
is introduced into the alkylation contactor. The catalyst
phate, recycling at least a portion of said efliuent from
is maintained at a sulfuric acid concentration of about
said elongated reaction zone to said first reaction Zone,90.0 percent sulfuric acid by withdrawing used acid as 20 and
recovering alkylate from said separated liquid hydro
necessary and adding make-up acid of 99.5 percent pur
ity. The hydrocarbon and acid are emulsiñed in the con
2. The process of claim l wherein said first reaction
tactor and the resulting reaction mixture is cooled by
zone is maintained at a temperature within the range of
coils immersed in the contacter. A portion of the emul
35 to 75° F.
sion is withdrawn from the contactor as a stream of 571 25
barrels per hour. The acid phase of the emulsion con
tains about 0.91 weight percent alkyl acid sulfate. The
3. The process of claim 2 wherein Said temperature
is maintained by evaporating a part of said reaction mix
emulsion is pumped at a velocity of about 4.5 feet per
4. In an alkylation process wherein olefin-based alkyl
second through a reaction coil consisting of 266 feet of 6
inch diameter tubing and discharged directly into a sep 30 atable material and isoparañin are reacted in the presence
of a sulfuric acid alkylation catalyst in a reaction zone
arator. The alkyl acid sulfate content of the emulsion
a reaction mixture comprising an emulsion
discharged to the separator is 0.2 weight percent.
of reactants, diluents, and catalyst, the contents of said
Acid catalyst is withdrawn from the settler and recycled
reaction zone are subjected to mixing whereby the reac
to the contacter. Liquid hydrocarbon from the settler
mixture is maintained of substantially uniform corn
is passed through a pressure reduction valve effecting par
tial vaporization and chilling o-f resultant liquid and vapor
and the chilled liquid vapor mixture is passed in indirect
position throughout said reaction zone, feed comprising
said olefin-based alkylatable material, said isoparañ’in, and
said alkylation catalyst is continuously introduced into
heat exchange with the contents of the reaction zone.
said reaction zone, and eñiluent comprising a part o-f said
Eñluent from the cooling coils is discharged into a liquid
vapor separator from which is withdrawn 139 barrels 40 reaction mixture is Withdrawn from said reaction zone,
the improvement which comprises passing said effluent
per hour of liquid comprising crude alkylate and unre
from said reaction zone to a separating Zone effecting
acted hydrocarbons. The crude alkylate mixture is neu
separation of said eñluent from said reaction zone into
tralized and is then fractionated in admixture with 38.0
a catalyst phase containing within the range of 0.5 to 4.0
barrels per hour of an extraneous butane stream com
prising about 55.9 percent normal butane and 38.0 per 45 weight percent alkyl acid sulfate and a hydrocarbon phase,
adding isoparafïin to said separated catalyst phase, plass
cent isobutane to separate 48.2 barrels per hour of alkyl
ing said catalyst phase in admixture ,with said added iso
ate, 25.5 barrels per hour of normal butane and 84.3 bar
parafñn through an elongated supplementary reaction zone
rels per hour of recovered isobutane which is recycled to
in lineal once through 4llow at a velocity effective to pro
the alkylation contactor. Vapor from the refrigeration
coils is condensed, depropanized, and autorefrigerated to 50 duce turbulent tiow for a time of at least about 1.() minute
reducing the alkyl acid sulfate content of said catalyst
produce a recycle stream of 152 lbarrels per hour of chilled
phase to within the range of 0 to 0.5 `Weight percent, pass
isobutane condensate.
ing at least a portion of the effluent from said supplemen
Obviously many modifications and variations of the
tary reaction zone to said reaction zone, and recovering
invention as hereinbefore set forth may be made Without
departing from the spirit and scope thereof and only such
limitations should be imposed as are indicated in the
appended claims.
We claim:
l. In an alkylation process wherein olefin-based alkyl
ata-ble material and isoparaliin are reacted in the presence 60
of a sulfuric acid alkylation catalyst, the improvement
which comprises: introducing yfeed comprising said ole
fin-based alkylatable material, said isoparañïin, and said
alkylation catalyst into a ñrst reaction zone, circulating
the reaction mixture in said »first reaction zone thereby 05
alkylate from said hydrocarbon phase.
References Cited in the ñle of this patent
Holm et al. _________ ___ June 10, 1941
Goldsby _____________ __ Feb. 3, 1942
Stahly et al ___________ __ June 22, 1943
Mrstik ______________ __ Nov. 18, 1952
Rollrnan ____________ __ Sept. 13, 1955
Longwell ____________ __ May 6, 1958
Owen ________________ __ Oct. 7, 1958
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