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Патент USA US2404080

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July 16, 1946.
`
AT, B_ MccULLoCH
> .
2,404,680
CATALYTIC CONVERSION PROCESS
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QM .ä ßZâá/ÁZINVENTOR.
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ATTORNEY.
July 106, 1946-
.'r. B. MccuLLocH
'
. 2,404,080
CATALYTIC CONVERSION PROCESS
Filed oct. 15. 1943
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ATTORNEY,
July 16,1946.
2,404,080
T. B. MccuLLocH
cATALYTIc CONVERSION PRocEss
Filed oct. >15, 1945.
|50
A
3 sheets-sheet 's
Alkym'fionReac‘lor
MAakcei-dUp
lsomerîz«ionReactor
SApceindt
..._
ßg-fáWINI/ENTUR.
BY
I
ATTORNEY.
`
2,404,080
Patented July 16, 1946
UNITED STATES PATENT OFFICE
2,404,080
CATALYTIC CONVERSION PROCESS
Thomas B. McCulloch, Baytown, Tex., assignor to
Standard Oil Development Company, a corpo- ‘
ration of Delaware
Application october 15, 194.3,V serial No. 506,327
9 Claims.
(Cl. 260-683.4)
2
1
The present invention relates to a method for
changing the structural configuration of a par
500° F. The invention also contemplates the
isomerization of mixtures of normal parafûns oc
añin hydrocarbon. More particularly the inven
curring in the gasoline boiling ranges. One spe
cific feature of the present invention is the isom
tion is concerned with the isomerization of par
affin hydrocarbons and the utilization of the re
‘ erization of normal paranîns to isoparaf?ns and
the alkylation of the isomerized product with ole
ñns utilizing as the catalyst for the alkylation
reaction the catalyst withdrawn from the isom
sulting isoparaffin hydrocarbons in the alkylation
of oleñns. In its more speciñc aspects the in
vention is concerned with the isomerization of
normal parafñns to isoparaflins in the presence
of sulfuric acid at elevated temperatures followed
by the alkylation of the isomerized product with
oleñns, in the presence of the catalyst withdrawn
from the isomerization reaction.
It is well known in the prior art to isomerize ‘
normal parañins to isoparañìns utilizing an alu
minum halide in the presence of a hydrogen hal
ide as the catalyst. It is also known to isomerize
isoparafûns in the presence of aluminum halides
and hydrogen halides and then to utilize the cat
alyst from the isomerization stage to alkylate the
isomerízed product with olefins in an alkylation
stage. This latter process, however, has disad
vantages in that aluminum halides and hydrogen
erization reaction.
'
`
When carrying on the isomerization reaction
of the present invention, the normal paraffin is
contacted with concentrated sulfuric acid of a
strength between 90 and 100 per cent H2SO4. It
is preferable that the hydrocarbon be in the va-~
15
por phase when it is brought into contact with
the sulfuric acid, but liquid phase may also be
employed. When the hydrocarbon is in the liq
quid phase during the contacting step it is nec
essary that super atmospheric pressure be em
20 ployed to maintain the hydrocarbon in liquid form
at the temperatures speciñed.
'
In isomerizing normal parainns to isoparaf
ñns in the presence of concentrated sulfuric acid,
the amount ofv acid contacted with the hydrocar
themselves to recovery and reutilization in the 25 bon should be at least equal to the volume of
halides are expensive and do not readily lend .
process.
hydrocarbon charged. `In general, however, it is
preferred to employ an excess of hot sulfuric acid.
The prior art also teaches the isomerization of
The preferred ratios of hot sulfuric acid to hydro
selected isoparafñns to other isoparañ?ins in the
carbon charge will range from about 2:1 to about
presence of hydrogen fluoride and concentrated
5:1.
sulfuric acid. These latter processes have the ob
Since hot sulfuric acid is a powerful oxidizing
jection of being limited to the isomerization of
agent, it is preferred to employ relatively short
one iso-compound to another of similar structure.
contact times between the hot acid catalyst and
Prior to the present invention mention has
the hydrocarbons. As stated above, it is pre
been made in the literature of the isomerization
eiîect of sulfuric acid in alkylation reactions. In 35 ferred that the hydrocarbon contacted with the
sulfuric acid be in the vapor phase, and under
all of these previous investigations the isomeriza
such conditions contact times of less than 15 min
tion noted was the isomerization of one branched
utes, and usually less than one minute, are most
chain compound to another of more or less
satisfactory. When the hydrocarbon is main
branched nature. In all of these earlier investi
gations the sulfuric acid employed as the cata 40 tained in a liquid phase, contact times of up to 60
minutes between the sulfuric acid catalyst and
lytic agent was utilized at relatively low temper
the hydrocarbon may be used.
atures. However, isomerization of normal paraf
Since hot sulfuric acid is corrosive toward steel
ñns to the corresponding isoparañìns in the pres
and steel alloys, it is desirable to inhibit hot sul
ence of sulfuric acid was heretofore unreported.
In the present invention normal parafñns are 45 furic acid against steel and steel alloys by intro
ducing and maintaining in the hot acid catalyst
isomerized to isoparañins with concentrated sul
an inhibitor of corrosion. It is well known in
furic acid as the catalyst at temperatures sub
the piokling industry when using sulfuric acid as
stantially above that employed heretofore in the
a pickling agent to utilize inhibitors of corrosion,
isomerization of isoparañìns to more or less
branched chain hydrocarbons. In its broadest 50 and similar inhibitors may be used in the prac
tice of the present invention.
aspects the invention contemplates theisomeriza
When it is undesirable to use corrosion inhib
tion of normally gaseous or normally liquid nor
itors as a precaution against destruction of me
mal paraffins to the corresponding isoparanins
employing concentrated sulfuric acid at temper
tallic equipment, ceramic reactors and handling
atures in the range from about 300° F. to about 55 lines and other auxiliary equipment may be uti
3
2,404,080
4
lized. Construction of such equipment does not
present any particular problems.
The present invention will be better understood
by reference to the drawings in which:
drawn from the system for further treatment
as desired by opening valve 26 located in line 2l.
When acid is withdrawn from the system, it will
Figure 2 is a flow diagram of another embodi
ment for practicing the present invention in which
the product and the catalyst from the isomeriza
acid supply source not shown.
be necessary to introduce a like amount of fresh
Figure l is a flow diagram of one embodiment UI acid to maintain the acid catalyst at maximum
of the present invention utilizing 'not sulfuric acid
eñìciency. Provision is therefore made for in
as the catalyst;
troduction 0f fresh strong acid by opening Valve
28 located in line 29 connecting line 22 with an
\
Since the isomerized hydrocarbon product sep
tion stage are cooled and then charged to an
arated from the acid in settler 20 may still con
tain residual acidity, provision is made for re
alkylation stage wherein olefins are alkylated
with the ísomerized product; and
Figure 3 is a flow diagram of still another em
bodiment in which the product and the catalyst '
from the isomerization stage are cooled, the isom
erized product and oleiins being charged directly
moval of acid >bodies by washing the hydrocarbon
with an alkaline reagent. lTherefore the hydro
carbon phase from settler 20 discharges there
from by line v3i?, an alkaline reagent is added
thereto by line 3| and these components pass into
mixer 32. The mixture of alkaline reagent and
hydrocarbon discharges from mixer 32 by way of
line 33 into Second settler 3d, which is of suiñcient
to an alkylation reactor with recycling of la por
tion oi“ the acid catalyst from the alkylation re
actor back to the isomerization reactor.
In the several embodiments described with ref
capacity to provide separation by gravity between
erence to Ythe drawings, it will be assumed for
the hydrocarbon Vand alkaline reagent phases.
purposes or” illustration that normal butane is
The isom-erize‘d product is removed from settler 34
being isomerized to isobutane in the presence of
by 4way of line 35 and then may be submitted to
hot sulfuric acid'oi‘ about 97 per cent concentra 25 distillation for recovery of the isobutane or may
tion at 450° F. It will also be assumed for the
be used as such, or further handled as refining
purpose of illustration that the normalbutane is
practices may dictate,
maintained in the vapor phase during vthe isom
The alkaline reagent phase separated from the
erization reaction.
hydrocarbon phase in settler 311 is recycled by
Referring now to the drawings 'and speciñcally 30 way of lines 36 and pump 3l `to contact additional
to Figure `1, nmneral I I illustrates a charge tank
quantities -‘of isomerized product in line 3Q.
containing normal butane. Normal butane is
In order to maintain the strength of the alka
withdrawn from tank II by pump 'I2 located in
line reagent at an optimum point ‘for removal
line T3 and passes through vap'orizer Ill where
of acidic materials, it'will be necessary >from time
the hydrocarbon is completely vaporized. The 35 to time to withdraw a quantity of the alkaline
vaporized‘hydrocarbons are injected through dis
reagent by opening valve 38 inline 39.
Under
tribution means I5 into isomerization reactor I6
these circumstances it will be necessary to intro
wherein Ythe vaporize‘d hydrocarbons are inti
duce an equivalent amount of fresh alkaline
mately contacted with hot sulfuric acid descend
reagent by opening valve 139 in line 3|.
ing therein ‘and introduced by way of line I7.
40
With respect to the embodiment shown in Fig
The l.hot sulfuric acid discharged into the upper
ure 2, a normal butane feed in charge tank 5i)
portion of isomerization reactor Ilì ñows down
is'introduced by way of line 5i, pump 52, and
wardly therein and contacts the upflowing vapor
line 53, Vaporizer 54 and distributor means 55
ized hydrocarbon. It is understood ‘that isom
into isomerizat'ion reactor 55. As described with
erization reactor I6 may be a packed tower, a 45 relation’to 'the embodiment of Figure lJ isomer
tower equipped with bell caps or any suitable
' ization reactor 56 may be a packed tower, a tower
contacting means whereby intimate contact ybe
equipped with bell cap plates or any equivalent
contacting means whereby contact between va
tween the vaporize'd normal butane and the hot
sulfuric‘acid may be effected.
pors and liquids is eifected. AThe vaporized hydro
Isomerized vproduct leaves isomerization reactor 50 carbons pass upwardly through isomerization
I6 by way of line I8, passes through cooler I9,
reactor ’55 and are contacted with down-flowing
wherein the product and any acid carried over
with the >product is cooled and liquefied, and dis
charges into settler 20 wherein suiìcient resi
dence time is provided for separation between the
hydrocarbon `and acid phases. Line 2| connects
to’s‘ettler 20 for Aremoval of any SO2 resulting
from decomposition of the sulfuric acid catalyst
in isomerization reactor I6.
The -acid separated from the hydrocarbon phase
in settler 2U discharges therefrom by way of line
22 and recycles thereby back to isomerization re
actor IG. Between settler 2D and isomerization
reactor I6, heat must be introduced tothe with
drawn acid and this is effected by providing acid
heater 23. The Vwithdrawn acid from settler 20'
is admixed with acid discharged from reactor I6
by way of line 24 and passes through coil 25 lo
cated in acid heater 23 and >ultimately discharges,
as described before, by way of line I‘I into re
actor I6.
Since, for best results, itis necessary to main
tain the acid strength between 90 per cent and
100vper cent of H2SO4, a portion of the acid dis
charged from settler '20 by way of line 22 is with
hot sulfuric acid introduced thereto by way of
line 5l; the hydrocarbons and hot sulfuric acid
remain in contact for a time suñicient to allow
55 conversion of the normal butane to isobutane.
The ‘hydrocarbons pass upwardly and out of
isomerization reactor 55 by way of line 53, are
cooled and liqueiied on passage through cooler
59 and are discharged into settler .55), which is
60 provided with sufñcient capacity to allow separa
tion by gravity of hydrocarbons from entrained
catalyst carried over therewith. Settler vSi) is
provided with line 5I to lead off anySO2 resulting
from decomposition of the sulfuric vacid at the
65
high temperatures employed in reactor 56.
The acid separated from the hydrocarbons in
settler Se .discharges therefrom by Way of line 62
and recycles to isomerization reactor y5S by way
of line B3 and coil 64 located in acid heater B5,
70 and line 57, as has been described before. The
acid Withdrawn from isomerization reactor 56
alsodischarges into line 63 by line 66 for passage
through coil 64 :for maintenance of temperature
in isomerization reactor 5S and for reutilization
in .the process.
2,404,05'50
5
of line 89 into third settler 90 whereina s_ep-V
aration is ¿made between the hydrocarbon/and
' `A branch line 61 equipped with valve 68 con
nects line 66 with line 62 to allow utilization of
a-portion of the acid withdrawn from isomeriza
tion reactor 56 as a catalyst in alkylation of the
isomerized product, as will be described herein
after. Line 63 is equipped with a Valve 69 for
regulation of flow of acid from settler 60 to
reactor 56.
The acid discharged into line 62 by way of lines
66 and'61 from isomerization reactor 56 may be 10
acid phases. ' Provision is> made for withdrawing
acid from >settler 90 by way of line Sil-_and re»
cycling of a portion of the vwithdrawn acid to
line 1i by opening valve 92 located ,in line 9|.
Since it -will be necessary to maintain the
strength of acid- used in isomerization reactor 56
and in alkylation reactor 10 at an optimum point
for isomerization and alkylation, respectively,> it
will be necessary to withdraw continuously from
routed to’alkylation reactor 19 through line 1I
the system an amount of spent, acid and to intro
by opening valve 12 located therein.
y
duce continuously an equivalent amount of
» The isomerized product separated from the
make-up acid. The spentV acid may be dis
acid carried over therewith in settler 6!)v dis
charges therefrom by way of line 13 and is intro 15 charged from the system by opening Valve 93
located in line 94 and make-up acid may be in
duced in admixture with an alkaline reagent
troduced into the system by opening valve .95
injected into line 1,3 by line 14 into mixer 15
where the alkaline reagent and hydrocarbon
phases are intimately contacted for removal of
residual acidic material resulting from the con
located in line 96 connecting line .62 to an acid
supply s_ource not shown.
20
'
y
.
In some instances it may be desirable to intro
duce make-up acid into vthe system immediately
tact of the hydrocarbon with the hot sulfuric
ahead of alkylation reactor 19 instead `of into
acid catalyst in reactor 56. The mixture of alka
the acid recycled to isomerization reactor 56, `In
line reagent and hydrocarbon discharges from
those particular instances make-up acid may :be
mixer 15 by way of line 16 into a second settler
11 wherein provision is made for separation be 25 introduced into the system from a‘source ,not
shown> by opening valve 99.111 line |00» which
tween isomerized hydrocarbon product and the
connects into line 1 I. It is understood, of course,
alkaline reagent.
that when make-up acid is introduced into'line
The separated alkaline reagent discharges from
1I, rather than into line 62, it will be necessary
settler 11 by way of line 13 and may be recycled
therefrom by pump 19 to line 1d for admixture 30 to withdraw used acid from the process by open-ing valve IGI in line |02., Likewise, the acid
in line 13 with additional quantities of isomer
ized hydrocarbon product.
-
Provision is made for withdrawal from time to
time of amounts of alkaline reagent by opening
Valve 89 located in branch line 8|. When alka
separated in settler-90 from the hydrocarbon
containing alkylated product Will in turn be re
cycled to isomerization reactor 56 by opening
35 valve |03 inline |04.
As conventional in the alkylation art, a por
tion of the acid emulsion discharged from the
bottom of alkylation reactor 90 may be recycled
to the system through line 91 and valve 98 lo
ing valve 3_2 located in line 14.
The hydrocarbon separated from the alkaline 40 cated therein. It will be apparent from the
foregoing embodiment that it is possible to em
reagent in settler 11 discharges therefrom by
ploy the catalyst from the isomerization reactor
Way of line 83 and is introduced thereby into
for alkylation of the isomerized product. >It
separator 64, which, for purposes of illustration,
wil1 be `further apparent that such a system,
may be a distillation tower. In separator 84
wherein a cheap reagent like sulfuric acid is
provision is made for separation of isobutane
utilized, embodies a considerable economic ad
from unreacted normal butane. This is con
line reagent is withdrawn from the system by
line 8l, it will be necessary to introduce an equiv
alent amount of fresh alkaline reagent by open
veniently done by adjustment of temperature and
vantage over the conventional art.
„
-
With reference to the third embodiment `of
pressure conditions by heating means 85 whereby
the present invention shown in Figure 3, a nor
a fraction consisting essentially of isobutane is
removed overhead through line 86> for handling 50 mal butane fraction from natural gasolineor any
other petroleum source is introduced into the
as will be described further. The unreacted
system from tank III) by way of lines III, IIZ
normal butane discharges from separator 84 by
and pump H3 located therein. The normal
way of line 53 for re-introduction into isomeriza
butane passing through line II2 is vaporized in
tion reactor 56 along with fresh feed from tank
55 Vaporizer IM and is introduced through dis-V
50.
tributing means II5 into isomerization reactor
The isobutane `taken overhead from separator
H6. In isomerization reactor II6 the vaporized
84 through line 86 is admixed with olefins intro
hydrocarbons flow upwardly therein and contact
duced therein by way of line 61 and the mixture
down-flowing hot concentrated sulfuric acid in
is discharged into line 1| carrying sulfuric acid
from isomerization reactor 56 and settler 60. 60 troduced >into the upper portion of isomerization
reactor H6 by way of line H1. Isomerization
Prior to contact between the mixture of oleñns
reactor IE6 is similar to the isomerization re
and isobutane with the sulfuric acid, the acid is
actors described with respect to Figures 1 and' 2.
passed through cooler 88 whereby its temperature
In isomerization reactor II6 temperature and
is reduced to optimum alkylation temperatures.
The cooled mixture of oleñns, isobutane, and 65 other conditions are adjusted for conversion of
the normal butane to the isobutane as described
acid discharges by way of line 1I into alkylation
reactor 10 wherein temperature, pressure and
The product from isomerization reactor II6_,
other conditions are maintained suitable for
consisting of isobutane and unreacted normal
alkylation of the isobutane withr the oleiins.
The alkylation stage in the present invention 70 butane, discharges therefrom by way of line ~I I8
and passesthrough cooler I I9 which reduces the
is conventional to the alkylation art and details
temperature of the hydrocarbon mixture and any
of its operation will not be gone into herein.
entrained acid catalyst to a temperature opti
The effluent from the alkylation reactor con
mum
for alkylation of the isobutane with lolefin
taining alkylate, unreacted hydrocarbon, and en
trained acid catalyst discharges therefrom by way 75 in thepresence -of sulfuric acid. -This'temper-V
hereinbefore..
>
.
-
2,404,080
7 .
ature 'will generally be in the range of about
`35" to '7?0'” F. The `cooled reacted' hydrocarbon
|44 in line |45 connecting to a source of acid
mixture rcontaining entrained acid discharges by
way lof line H8, in admixture with oleñns intron
duced by way of line |20 and acid Yinjected by
Way of line |2|, into alkyl'ation reactor |22
wherein alkylation between the oleñns andv iso
parañins is effected as will be described further.
Hot acid introduced into isomerization reactor
|||i- vby way of line ||1 fiowsrdownwardly therein 10
contacting the tip-flowing vaporized hydrocar
bons, introduced through distributing means I I5.
The hot acid flows out of reactor ||6 'by way of
line |23 and at least a part of this acid discharges
into line |24, which connects to heating coil |251
located in acid heater |26, wherein the tempera
ture of the acid discharged from the isomeriza
tion reactor and later stages of the process is
adjusted for optimum isomerization of the nor
mal -butane to isobutane.
Valve |40 is provided in line |23 forv regulating
the flow of discharged acid from isomerization
reactor ||5` by way of line |23. The reason for
providing valve |48 is to allow circulation of a
storage not shown. Similar to the embodiment
of Figure 1 the spent acid will be withdrawn from
the acid stream recycling to the isomerization
reactor H6. The acid may be discharged from
the system by opening valve |46 in line |41.
In some instances it may be desirable to return
a part of the acid utilized in the alkylation re
action to the isomerization system.
Therefore,
provision is made for introduction of the acid
withdrawnfrom settler |30 by line |33 into iso
merization reactor by opening Valve |31 located
in line |24, which connects to isomerization re
actor |||i by way of heating coil |25 and line
| |1. The presence of a small quantity of alkyla
tion acid may be beneficial in the isomerization
reaction, since the alkylation acid contains small
quantities of the alkyl sulfates. It has been ob
served, inisomerization of parafiìn hydrocarbons
with sulfuric acid, that the acid becomes colored
on use and the theory has been advanced that
the isomerization proceeds through the forma
tion of the intermediate oleñn. This would sug
gest the formation of alkyl sulfates. Therefore,
portion of the discharged acid to the alkylation 25 it is within the scope of this invention to add
reactor system through line I2|. This is accom
extraneous alkyl sulfates to the isomerization
plished by opening valve |21 located in line |2|
acid.
so that the hot acid may pass through cooler
The hydrocarbon phase separated from the
|128 for reduction of temperature of the hot acid
acid in settler |30 is withdrawn therefrom by line
to the proper alkylation temperature whereby the
|38, which connects to separator |39. It will be
acid then admixes with the isomerized product in
understood, of course, that acidic bodies remain
line || 8 as has been previously described.
ing in the hydrocarbon phase may be removed by
`The mixture of isobutane, normal butane, ole
treatment with an alkaline reagent. For pur
ilns and acid discharges into alkylation reactor
poses of illustration separator |39 will be con
|22. The conditions maintained in alkylation re
a sidered to be one or more distillation zones. In
actor |22 are conventional in the alkylation art
separator |39 temperature and pressure condi
and will not be described further herein. It is
tions of the hydrocarbon introduced thereto by
suñicient to say that best conditions selected to
line |38 are adjusted by heating means |40 to
give optimum alkylation between the isobutane
allow separation of an isoparaf‘rin fraction, a nor
and the oleiins are maintained therein.
40' mal butane fraction, and an alkylate fraction.
`Acid catalyst in an emulsified statewith hy
The isoparafñn fraction, in general, vin‘ll com
drocarbons is» withdrawn from alkylation reactor
prise a minor portion of the stream which was
|22 by Way of line |’3I for recycling toreactor
introduced into separator |39 by way of line |38.
|22 through lines |32 and |"2`| connecting to line
Since most of the isobutane resulting from isom
From alkylation reactor |22 a mixture of
> erization of the normal butane in isomerization
alkylate, unreacted hydrocarbons and entrained
acid is discharged by way of line |29 into settler
|30.
||8.
tion reactor |22, the remaining isobutane fraction
will discharge from separator |30 by way of line.
In settler |30 sufficient residence time is a1
lowed Ifor gravity separation between the hydro- ‘ -
carbon and acid phases. After separation is ac
complished, the acid is withdrawn Jfrom settler
|30 by Way of line |33 which connects to line |32.
and which allows recycling of the acid to the
alkylation reactor. From time to time it will be =
necessary to withdraw from the system ar portion
of the acid discharged 'from settler v|30 to main
tain the acid in the isomerization reactor and in
the alkylation reactor at av strength optimum for
the reactions. In these instances an amount of
the spent acid is withdrawn from the system by
opening valve |34.
When spent acid isdischarged from the system
it will vbe necessary to add an equivalent amount
of make-up acid for maintenance of optimum
acid strength. This is accomplished by >opening
valve |35 located in line |36 connecting to »line
|24.
Similar to the embodiment described with rrela
tion to Figure I, it is ’within the sco-pe of the
present invention to yintroduce make-up acid into
'the system so that the fresh Yacid contacts the
i-sopara'iiîn and olefins in alkylation reactor |22.
reactor H6 will have been consumed in alkyla
icl and maybe recycled to the alkylation re
actor or may be further used as desired. The
unreacted normal butane discharged with iso
b'utane from isomerization reactor H5 will be
recovered by line |42 for recycling to the isom
erization reactor. Line |42 connects into line
i |2 whereby the feed is introduced into isomeriza
tion reactor H6.
Alkylate, suitable for inclusion in 100 octane
number aviation fue-ls, is withdrawn from sep
arator |35' .by way of line |43 for further treat
ment and handling. rThe alkylate withdrawn by
way of line M3 may be distilled for separation of
light and heavy allrylates and caustic washed
prior to introduction of light blending agents and
tetra-ethyl lead.
While the present invention has been vdescribed
and illustrated by the isomerization of normal
but-ane and the alkylation of the resulting iso
butane, it is to lbe clearly understood that other
normal parafñnsr such as normal pentane, normal
heptane., `normal hexane and the like, may com
prise the charge stock of the present process.
The Ynature and objects of the present‘invention
`having been completely illustrated andidescri'bed,
In this particular instance the make-up acid will’
what I Wish to claim as new and useful and to
be introduced into the system by opening valve 'I CR secure by Letters Patent is:
2,404,080
9
l. The isomerization of normal parañins to
isoparaiiins comprising the steps of contacting a
normal paraiiin hydrocarbon' with sulfuric acid
maintained at a temperature in the range oi 300°
to 500° F. to cause the isomerization of the nor
mal parair’in hydrocarbon and subsequently sep
arating the resulting isomerized hydrocarbon.
2. A process in accordance with claim 1 in
which the normal parañin hydrocarbon is main
tained in the Vapor phase.
3. A process for converting a normal pararûn
hydrocarbon to an isoparaiìn hydrocarbon which
comprises the steps of contacting a normal par
afíin hydrocarbon in the vapor phase with sul
furic acid at a temperature of between 300° and
500° F. in an isomerization Zone, removing any
10
sulfuric acid at a temperature of between 300°
and 500°
separating isomerized hydrocarbon
product from the hot acid catalyst, cooling the
hydrocarbon product and adding oleíins thereto,
cooling the acid catalyst and mixing it with the
hydrocarbon phase containing oleñns and main
taining the mixture under conditions to cause
alkylation of the oleñns and subsequently re
covering an alkylate of high octane number.
'7. A :process in accordance with claim 6 in
which the normal parañin hydrocarbon is normal
butano and the added oleñns are butylenes.
8. A method for producing alkylate which com
prises contacting a normal paraffin in vapor phase
With sulfuric acid in an isomerization zone at a
temperature of between 300° and 500° F. to cause
isomerization of the normal paraii‘in, separating
eliluent including an acid yphase and the hydro
the resulting isomerized hydrocarbon product
carbon phase from the isomerization Zone, cool
from the acid, mixing oleñns With the hydrocar
ing the effluent and separating it into a hydrocar
bon product, cooling the acid and adding it there
bon phase and an acid phase, heating the sep 20 to and maintaining the mixture under conditions
arated acid phase and recycling the reheated acid
to cause alkylation oi hydrocarbons present there
to the isomerization stage and removing acidic
in, separating a hydrocarbon phase containing
constituents from the hydrocarbon phase.
alkylate from an acid phase, recovering isopar
A process in accordance With claim 3 in
aii'lns, normal paraiñns and alkylate from the hy
which the paraffin hydrocarbon is normal butane. 25 drocarbon phase and recycling at least a portion
5. A process in accordance With claim 3 in
of the acid phase to the isomerization zone.
which the normal paraflin hydrocarbon is normal
9. A process in accordance with claim 8 in
pentane.
which the normal parafiin is vaporized normal
6. In the production of high octane number
fuels the steps of isomerizing a normal parafûn 30 butane.
THOMAS B. MCCULLOCH.
hydrocarbon by contacting it in vapor phase with
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