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Патент USA US2408753

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2,408,753
Patented on. e, Y1946
"UNITED STATES PATENT OFFICE
Y TREATMENT 0F HYDEocARßoNs
Robert E. Burk, Cleveland Heights, Ohio, assign
or to The Standard Oil Company, Cleveland,
Ohio, a corporation of Ohio
Application June 22, 1943, Serial No. 491,755
s claims. (ol. 26o-_671)
1
This invention relates to the treatment of hy
drocarbon stocks to form alkyl aromatics such
sion of a process in which a single catalyst re
covery system may be used for the isomerization
and both the alkylation processes to separate the
catalyst from the off-gas and make it available
as ethyl benzene and iso-propyl benzene, and also
branched chain aliphatics such as iso-hexanes,
i or reuse.
'
iso-heptanes, and iso-octanes, all of which are Cl
Other objects of the invention will be apparent
valuable for use as >an aviation gasoline base
from „the following description of an illustrative
stock, with lead tetraethyl, or blended vwith other
example which is to be read in connection with
stocks or in ratios other than those of normal
the sheet of drawings forming a part of the speci
recovery.
.
f
,
More particularly, the invention comprises a 10 fication.
The
cracking
and
separation
of
cracked
products
process in which hydrocarbons are
unitary
cracked so as to form an ethylene and propylene
In accordance with the invention, a cracking
containing fraction, an aromatic containing frac
stock is subjected to “drastic” cracking, i. e., a
tion, and a butane and pentane containing frac
high temperature for a relatively short time. The
tion; and the first fraction combined with the
stock may vary from the lower gasoline range to
latter two fractions through appropriate alkyla
the kerosene range, although different stocks will
tion and isomerization and alkylation procedures,
yield somewhat different products, and in differ
ent amounts when cracked, and the stock may
respectively. ’
_
It is an object of the invention to provide a
be selectedl with this in View, The temperature
unitary process for alkylating aromatics and 20 may vary from about 1250° to 1750“ F., depending
(isomerized) aliphatics formed 'inv the same
on the stock, the-cracking time, and the relative y
cracking process-by means of oleñns also formed
amounts of the products wanted. The time may
in said cracking process, so as to utilize a sub
vary from about 0.1 to 0.25 seconds depending on
stantial portionof the hydrocarbons formed in
the stock, the temperature, and the relative
cracking to provide products of the greatest value 25 amounts'of the products wanted. The pressure
may vary from about atmospheric to about 300
pounds per square inch depending on the other
aprocess in which essentially the same catalytic
variables noted above.
material may be used for the isomerization and 30 The stock is fed through an inlet I, to the
both of the alkylations, >and which material com
cracking furnace 2, following which it is imme
for motor fuel purposes.
^
’ ï A further object of the invention isfto provide
prises essentially hydrogen fluoride and boron
trifluoride.
i
'
Still a further object of the invention is the
provision of a process in which the catalyst used
in the- isomerizing and `alkylating is not delete
riously affected by the products of the cracking
operation, and which catalyst can be recovered
l diately quenched with water or oil in the con
duit 3, and fed to the tower 5. If the quench is
oil it is removed at 6 with any other condensate.
' The vapor leaves the tower 5 through a conduit
1 and is subjected to a Water quench as it moves
to the tower 8. The water is removed for the
most part at 9.
The hydrocarbons formed in the cracking op
either or both of the alkylations.
40 eration are fractionated in the tower 8, the major
A An additional object of the invention is the
portion of the gaseous products leaving the top
provision of a process in'which the catalyst used
at I0, where they are compressed by the pump
in one alkylation may be transferred to and used
II and sent to the tower I2, where the C3 and
in the other alkylation before separation of the
lighter hydrocarbons are removed from the top
at I3 asa gas and sent to the supply line I4.
catalyst from the off-gas.
` Still a further object of the invention is to pro
The C4 and heavier hydrocarbons are removed
vide a> process oi great flexibility in which the ~ from the tower 8 through the conduit I5 and sent
olei’ins may be used selectively for alkylating
to the tower I8 by the conduit I1. Any C4 and
either the aromatics or the iso-paraiiins, i. e., the
heavier hydrocarbons separated in the tower I2
ethylene may be reacted with the aromatics and 50 may be added at I6 and sent to the tower I8.
the prcpylene with the iso-parafûns, or the ethyl
The tower I8 serves to separate the Ce and
ene reacted with the iso-parañlns and the pro
heavier hydrocarbons from the Cs and lighter
pylene with the aromatics, or in which both ole
hydrocarbons. The Ce and heavier hydrocarbons
ñns may be reacted with both the aromatics and
are removed at I9, and the C5 and lighter hydro
iso-parafiins. f
55 carbons are sent to the tower 20 where any re
. 'A further object of the invention is the provi
continuously andreused in the isomerization and
3
2,408,758
4
maining C3 and lighter hydrocarbons are sepa
further cracked, dealkylated or otherwise used or
rated as a gas and added to the supply I4. The
disposed of.
C4 and C5 hydrocarbons may be separated in the
The amg/lation of aromatz‘cs
The benzene and/or toluene is then subjected
to alkylation. Both may be alkylated together,
particularly if they are separated as a single
fraction, or each may be alkyl'ated separately.
Alternatively, only one may be alkylated; for
example, the toluene may be withdrawn and
used for making explosives and only the benzene
alkylated. The alkylation is carried out in the
tower 2i, the C5 hydrocarbons being sent to the
supply line 22, The C4 hydrocarbons are removed
at 23 and if desired the butadiene may be sepa
rated at 24, the butadiene removed at 25 and the
remaining C4 hydrocarbons sent to the supply
line 25.
-
If desired, the C5 and higher hydrocarbons
may be returned by adjusting the valves 21 andl
28, and sent to a separate cracking furnace 0p
erated at about 20° to 50° F. higher than the
temperature of the furnace 2L forfur-ther crack
ing. The products from this- second' cracking
presence of hydrogen fiuoride as the essential
catalyst promoted‘by a minor proportion of boron
. 7
furnace may be fractionated in the manner de'
triiluoride.v
For illustrative purposes, it may be assumed
that, the benzene is to be alkylated. Benzene is
fed through conduit 42 to the aromatic alkylator
432. ri‘he valve 44 is opened and the valve 45 is
scribed and the C5, C4 and lighter' hydrocarbons
added to the respective supply lines 22, 26 and i4,
The C5 and higher hydrocarbons are fed to the
supply line Z 9.
20 closed. The mixture containing ethylene and
lint accordance with anillustrative example, the
propylenerisv admitted to the alkylator 43 through
cracking stock: may be a heavy naphtha, i. e., a
pipe- 46., The catalyst. is. admitted through the
major portion boiling within. the range of 300 to
conduit 471, valve 48 and conduit 49. Since the
450.“ F. The cracking temperature may be 1380°
propylene. is more reactive they conditions may be
to 1650" E, the time of cracking about 0.175
adjusted' sov that only thev propylene will react
second and' the pressure about 5 pounds per
square inch. Such a cracking operation will pro.
and the.I product formed Will. be primarily iso
propyl benzene (cumene). This is removed at
âlßfandY returned at» 5| for fractionation so that
the alkylate ends as one of the Wanted products
Weight per cent on~ feed
Ethylene __________________________ __ 17 to 23 30 in theY storage. 4l). The amount of benzene in
the alkylator 43A generally is in excess of the
Propylene __________________________ __ 27 to 33
stoichiometric amount of propylene to be reacted,
Butadiene _________________________ __ 4 to 9
and` the unreacted benzene may be recycled
Butylenes __________ __ ______________ __
3 to 7
through the conduit 50, fractionated and re
Butanes ___________________________ __ 7 to 9
, turned: to the alkylating zone through conduits
Pentanes __________________________ __ 4 to 6
34` and`42’. The unreacted ethylene. and the
Benzene ____________________________ __ 7 to 13
catalyst are» removed from the alkylator at 52.
Toluene _________________________ __’__ 3 to 5
Xylenes
2 to 4
Valves 54, 51 and 58a are closed and- valves- 53,
duce products of about` the following amounts:
58- andY 58, are open so- that ethylene and the
The ethylene and prop-ylenel are fed into the 40 catalyst passte the conduit 59 to be used in the
supply line t4, and to a suitableV gas holder Ma,
alkylation of isopara-fñns to bel described later.
from' which they may be withdrawn and used in
The olefin containing gas and the benzene may
the a'lkylation processes to- be described. The C4
befed tov the alkylator 43, concurrent, counter
and'v C5 hydrocarbons are sent to their respective
current or both;V Under the preferred conditions
storage tanks 35 and Si. If desired the frac
the. aromatic will be in the liquid phase and the
t-icnator 2i may be omitted» and> the C4 and C5
catalyst and olefin in the gaseous phase. How
hydrocarbons treated as a single> fraction and
ever, all ofthe componentsñ may be in the vapor
lsent to-a common storage tank.
phase’or inY the liquid» phase, depending primarily
The Cs and higher fraction contains a sub
on the. temperature andpressure of the opera
stantialV amount of benzene (C5), toluene (C1) 50 tion. In- a vapor phase operation, the tempera
and xylenes (Ca). This fraction is fed from the
ture` of the reaction, under the preferred condi
supply line 29 tothe fractionator 52. Provision
tions, is above the boiling point of hydrogen
is also` made for augmenting the supply of ben
fluoride atv the pressure used» (671° F. at atmos
zene or other a-romatics which may be admitted
pheric.
pressure-l, for example, within the range
through the valve 35;
F., preferably 90° to- 150° F. In a
The fractionator 52 preferably separates the
liquid; phase operatiom the temperature would
benzene and toluene; the former is sent through
13e-«25m 140° F.
pipe 34 to a storage supply 35 and the latter
The pressure mayA bef varied over a wide range,
throughl pipe 36A to storage supply 37. If desired,
but under the other conditionsv preferred a pres
sure» of atmospheric to 25o" pounds per sq. in.
pressure is; utilized. Under the preferred condi
tions the pressure.> should below enough to per
the benzene and toluene may be separated as a
single fraction and sent to a common storage
supply. The Xylenes and heavier aromatics are
removedY from the bottom- of the fractionator 32
and sent to a fractionatorv 38. If desired, the
toluene may be separated with the Xylenes and
heavier aromatics. The fractionator 38 sepa
mit the“ hydrogen fluoride catalyst to be gaseous
except for such as may bev dissolved inv the ben
f zene in the. liquidY phase'atßthe temperature used.
The time; i‘n‘which'; the’reacti'on occurs will de
pend;upon the sizeof. the reacting vessel, and the
rate and nature ofv the. flowA of. materials through
it. Under the preferred', conditions' the time of
rates the> wanted aromatics- generally the Cs, C9
and Cio aromatics, such as Xylenes, ethyl benzene,
iso-propyl benzene, ethyl methyl benzene, di
ethyl' benzene, methyl iso-propyl benzene, etc.,
and they are removed through the conduit 39 and
sent to storage 4d. The C7 hydrocarbons may be
included in the wanted products depending on the
operation of theV fractionators 32» and 38. The
heavier alkylate is removed at llïlï and may be 75
reactiomiszvery shortfand is of' an order of from
one-ñfth minute: to fifteen minutes, a time of
from .20y to4300‘seconds being entirely satisfactory.
`
The catalyst-used in the’ process, as` mentioned
previously, is hydrogen fluoride promotedy by~ a
minor proportionv of boron triiluoridel. . The
2,408,753
5
amount >of boron triñuoridemay vary from a
trace u'p to 50 mol per cent.- Large amountsof
upon the partial pressure ofthe boron fluoride
and the temperature. This may be increased, if
desired, by the pump 64a in the conduit 64 and
boron trifluoride are not required.
the boron trifluoride admitted. through the valve.
, .
>-.The amountofthe catalyst employed is Vnot
critical except that a suflicient amount must be
employed under
toper
mit
the
reaction
pletion -desired. Larger amounts permit ,shorter
times of reaction Aand corresponding alterations
The isomerization is accomplished by .thor
oughly mixing the liquid catalyst and the butane
for thelrequired length of time, following which
~ the mixture is transferred to a separator 62 in
in temperature and pressure and give »better
yields. Under the conditions ofthe process it is
preferred to employ the minimum amount that
will achieve the desired Ycompleteness of the re
action. In general the amount will vary from 15
about 2 to 50%, an amount of the order of about
4 to 15% is preferred.
.
which the hydrocarbons separate as an upperV
layer and the catalyst separates as a lower layer.-
Generally, the stratification may be accomplishedV
by settling, but centrifuging or other separating
techniques may be employed.
,
.
The lower catalyst layer (which may be an
emulsion of catalyst and hydrocarbon) is with
drawn inthe conduit 63h and returned through
' The ymol ratio of olefin to benzene may be about
1 m01 of olefin to 1 to 8 mols of benzene, but the
the conduit 64b to the isomerizer 6I where it malr
be reused. In this way it will be apparent that
higher ratios are'preferred and the excess ben-y 20 large quantities of fresh catalyst are notl re
quired, but such as `may be necessary can be ad
Vzene is then recycled.
f
VLAS a specific example, in which a propylene and
mitted through the valves E5 and 65a. If the
ethylene containing gas is fed to the alkylator,
lower layer builds up with hydrocarbons, par
and benzene is the aromatic to be alkylated, the
ticularly unsaturates which may form a complex
reaction may be carried out at a temperature of
with thecatalyst, a portion of the lower layer
110° F. The contact time of the propylene and
may -be withdrawn, the catalyst removed there
the benzene may be 35 seconds, the pressure may
from by heating, and the catalyst returned to the
be 100 pounds per square inch. The amount of
conduit 4l on any of the zones in which it’ is
catalyst (hydrogen fluoride with a trace of boron
triñuoride) may be about 14% based on the ben 30
The upper layer containing substantial portions
zene >inthe reactor. The amounts of propylene
of iso-butane iswithdrawn from the separator 62
and benzene may be 0.66 and 7.21 pounds per
through the conduit 6B, and transferred .to the
hour, respectively, the mol ratio of benzene to
fractionator 61 in which the iso-butane is removed
propylene being about 5.9> to 1.0. Under these
at the top and transferred through the conduit
conditions the iso-propyl benzene formed is about 35 68 to the iso-paraffin alkylator 69. The n-butane
not isomerized is withdrawn from the fractionator
"1.03 pounds per hour.
~
4--While in the above examples benzene is de
61 by means of the conduit 10 and returned to
scribed as the aromatic to be alkylated, toluene
the isomerizer 6I through the conduit 64b.
may be treated under the same conditions. If
Provision is also made to admit an additional
toluene is alkylated instead of benzene the prod 40 quantity of normal butane through the valve 12
uct will be primarily methyl iso-propyl benzene;
if ‘the amount obtained in the cracking process
if both benzene and toluene are alkylated to
is not suñ‘lclent to utilize all of the olefin formed
used.
gether, both iso-propyl benzene and methyl iso
propyl benzene will be formed as the primary
products.
Y
»
The isomerization of paramns
The n-butane and n-pentane in the storages
-3I and 30 are isomerized to form iso-butane and
iso-pentanes. These may be isomerized together
¿or separately. However, they can be isomerized separately with facility because of the simplicity
of recycling the unisomerized fraction. For i1
during cracking.
.
'
Y
As has been mentioned previously, the isomer
ization preferably is carried out under suñicient
pressure to maintain the butane and the catalyst
in .the liquid phase at the isomerizing tempera
ture employed. This pressure is preferably ac
complished by utilizing relatively high partial
pressures of boron trifluoride and this partial
pressure may be from 25 up .to 550 pounds per
square inch. Since the catalytic activity ofthe
catalyst depends in part upon the amount of
lustrative purposes, it may be assumed that the ` boron triiluoride, the activity may be controlled
butane is to be isomerized separately. It is re
by regulating the partial pressure of the boron
‘moved from the storage 3l and fed through a
trifluoride. The amount of catalyst 'used may
vconduit 60 to an isomerizer B I. YCatalyst from the
vary depending upon the speed of the reaction
>conduit 41 may be admitted through the valve
desired; in general, from 25 to 100 volume per
Í62a and conduit 63. A pump 63a may be included
cent of the catalyst based on the hydrocarbon
»in the conduit 63 to place the catalyst under pres
60 is preferred. TheY temperature may vary from a
The
liquefied
catalyst
>sure and liquefy the same.
relatively low figure, for example, --25o F. up to
»is collected inthe receiver 1I. Above the liquid
215° F. Higher temperatures, however, not only
trifluoride
under
pressure.
fwill be gaseous boron
require increased pressure to maintain the liquid
The liquid catalyst is admitted to the isomerizer
phase but also tend to undesirable cracking. The
‘5I through valve 65. The isomerization is car
lengthl of time to which the hydrocarbon is sub
ried out preferably w'th the catalyst in the liquid
jected to the isomerizing catalyst may vary de
phase, that is, with liquefied hydrogen fluoride
pending upon the extent of isomerization desired
.containing boron trifluoride dissolved therein.
in a single pass. Inasmuch as provision is made
:This is accomplished by employing a temperature
for recycling, it may be more eiiicient to carry
for the isomerization below the boiling point of
out the reaction for shorter periods accompanied
70
the hydrogen fluoride at the pressure employed,
by greater recycling; a period of from 15 minutes
or in other words, a pressure at least as great as
to 3 hours is preferred.
l
Áthe vapor pressure of the hydrogen fluoride at the
It should also be understood that the tem
temperature of the isomerization. Boron fluoride n perature, pressure, amount of catalyst, amount of
l is dissolved in the liquefied hydrogen fluoride used
~-as the catalyst and the amount .dissolved depends
lboron triñuoride and .the time of treatment are
2,4083753;
more or less. interrelated' and that any one vari.
ableshould be. selected and adjustedv with refer
ence to the others for the most enîcient opera
tion. This consideration, however, goes only to
eiliciency and yields and not operability and,
therefore, may be adjusted by those skilled in
the: art in. view of .the descríption'herein.
As an illustrative example', n-butane may be
subjected tothe catalytic' action of 50 volume
per cent' of liquid'v hydrogen iluoride in which is
dissolved'> boron trifluoride in an amount as ,to
8
builds up‘too muchl in the form. off a catalyst
hydrocarbon complex, a> portion. may be with
drawn and the catalyst removedz therefrom. by
heating and' the catalyst returned .to the con
duit 't1Í or any of the zones utilizing the catalyst..
The upperV layer containing the alkylated
products is withdrawn from the separator 'I6
through a conduit 'I3 and transferred to the
fra'ctionator 19". The'alkylated products are-sep
arated at the bottom of the fractionator through
a. conduit 80 and sentito storage.v Since the
amount of iso-butaneused preferably exceeds the
amount stoichiometrically required; for reaction
withA oleñns. provision.> is made for recyling the
excess iso-butane through the conduit. 8l tothe
27 per cent iso-butane.
alkylator 69.
The above process- has. been described particu
The butano fraction in the storage. 3 I' alsomay
larly with reference to the isomerization of> bu
contain
butylenes, and if so, these may alkylate
.tane but it may be carried- out in the same way
with theÍ iso-butano in the isomerizer 6l.. Provi
with pentane. In this event pentane is with
drawn. from storage 30 and treated in the> same 20 sion is made for withdrawing such alkylates. at
the bottom of the fractionator ‘61- through the
manner as previously described.
conduit 82 and transferring them through the
If .the butano and pentane have not been sepa
conduit lliV where they are separated with the
rated. by a fractionator such as shown at 2'I so
wanted alkylated- productsr in the conduit 80.
the normal hydrocarbon for isomerization is a
The alkylation reaction preferably should be
mixture, or if it is desired to isomerize both the
carried out with an excess of the. iso-parañìn to
butane and pentane simultaneously by withdraw
promote complete utilization of. the oleñn and
ing from both the storages 30 and 3|, .this :can
repress» polymerization thereof. In. general, the
also be accomplished in Ithe same manner de
mol. ratioy of oleñn to iso-paraíñn should be 1:2
scribed previously. Under such circumstances,
however, it is desirable tov utilize an additional 30 to 12. The pressure should be sufûcient to main
tain the isobutane and the catalyst inthe liquid
fractionator .to separate the: iso-butane and iso
phase.
This may be accomplished preferably by
pentane from the normal butane and, normal
employing
a relatively high partial pressure of
pentane after isomerizationso that both of .the
boron triiluoride. The temperature. may vary
unisornerized, normal hydrocarbons may be re
from _30° up to 160° F. In general, thetemper
turnedthrough. the conduit 'lll> for further isom
ature and partial. pressure of boron trifiuoride- in
erization.
provide a partial pressure ofA boron triñuoride of
300' pounds per square. inch'. Isomerization may
be carried on for two hours at a temperature of
122° E'. The producty is found to contain about
the alkylation zone- aret lower than in the isomer
ization» zone. This suggestsy thatV the pump ‘I4
may
be omitted and the pressure in the supply
The- iso-parafñns isomerizedì in> the manner" de 110
li maintained at that desired in the alkylation.
scribed previously are. then. alkylated with. an
Any higher pressure for isomerization can be
olefin. In the following illustrative. example it is
supplied by the pump 64a.. The length of, the
assumed that the n-butane has been i'somerized
reaction may vary from 15 minutes. to. 3 hours
separately and that the iso-butane4 will be. alkyl
but the alkylation may be accomplished in some
Allcylatz’on of iso-butano and/or iso-pedirme
ated separately. The iso-butane coming. from
what shorter time than the isomerization. The
the fra'ctionator 6l is introduced into the. alkyl'
amount of the catalyst may varyy from l0 to 100
ator 69 through the conduit. 63. Inasmuch as
volume per cent depending upon theY speed of
the alkylatíon preferably is carried' out 'm the
the reaction. desired, temperature', and pressure.
liquid. phase, >the catalyst may be introduced in
is preferred to carryl out the' alkylation with
the liquid phasefrom. the receiver ‘Il through. the 50 It
a large amount of hydrogen fluoride and a- small
valve T3. The olefin used> for the alkylation. in
amount of boron `triiluoride or a large amount of
this example is. the ethylene and catalyst con
boron fluoride. and' a small amount of. hydrogen
taining gas left over from. the alkylation of. the
iiuoride..
aromatics, and which. existsy from. the. aromatic
amount of boron tri-fluoride dissolved in
alkylator 43 through conduit 52€ and valves: 53.-, Cn Ul theThe
liquid hydrogen iiuoride depends on the pres
56, 58 and conduit 59. A. pump 'I5 maybe. pro
sure' and temperature andV may be expressed in
vided to liquefy .the hydrogen fluoride and place
terms of its partial- pressure at a given temper
the boron fluoride under the propel' pressure".
ature. The amount of. the catalyst'„ the propor
Since in the illustrative example the propylene
tiony of the twovv ?luorides, the» temperature' and
will have been used inr allrylatingY thearomatics’, 60 time. of the' reaction are morel or less'> interrelat
the> product formed in the alkylation» of> iso-bu
edi andY should be adjusted with referencey to each
tane with the remaining ethylene. will? be the iso
other. These adjustments arey concerned more
meric hexanes.
with efñciency and> yields> than> with operability
The alkylation is accomplished by mixing the
and may bey adjusted by' one skilled in the. art for
iso-butano withV the catalyst> in'. the liquid phase
the: most efñci'en-t operation in> view of the dis.
in the presence of the oleñn; -after'the reaction
closures herein.
has proceeded to the desired extent, the mixture
AS an illustrative example, iso-butano and
is transferred to ythe separator 1S wherev the hy
ethylene. in the' proportion of about 1:0.7 mols
drocarbon and catalyst are separated preferably
may be reacted atv 40° F. for 1% hours in the
by gravity stratiñcati'on. The separa-tedA catalyst 70 presence
of liquid> hydrogen fluoride. inl the
layer (which may be a hydrocarbon-catalyst
amount of 50 vol. percent of the iso-butano and
emulsion) may be returned' through the conduit
an amount of boron. triñuoride to provide apar
"I7 to .the alkylat'or 69 and reused. In this way
tial' pressure of läûîpounds’per. square inch; Con
relatively small amounts of fresh» >catalyst are
version> >t’olabout 60% in the.` gasoline. range is
required from the supply 1|, If the 'catalyst layer 75 obtainedl
The gasolinev contains: about 25% iso
2,408,753
Any pressure may- be used in the absorbing and
desorbing operations.
pentanes, 36 % iso-hexanes and 15% iso-heptanes.
the remainder boiling below 350° F. ' ` ~ The above example has been described utiliz
ing isoLbutane. The process- may be carriedl out
under about the same conditions utilizing iso--
'Alternative procedures
In the examples described heretofore thevpro
pylene isused to alkylate the aromatics,and the
ethylene is utilized to alkylate the iso-lparafñns.
If desired, this procedure may be reversed by
closing valves> 44, »53, 55,~and 58 and opening
pentane. For example, iso-pentane and ethylene
' may
be introduced into the alkylator E9 in the
ratio of about 1:0.4 mols at 40° F. for 11/2 hours
in -the presence of 60 weight per centhydrogen
ñuoride and an amount of boron trifluoride to
provide a partial pressure of 50 pounds per square
inch. TheA yield shows a conversion of about
valves 45, 54, 56, 51 and 58a.
I
In this operation the propylene and ethylene
containing supply in the line I4 is sent through
the open valve 45 to the alkylator 69. The pro
pylene being the more `reactive will be utilized
76%». About 30% is iso-butane which is recycled
for alkylation, about 20% iso-hexanes, about 17%
1.5
to -alkylate the isofbutane and/or iso-pentane.
The catalyst andunreacted ethylene will exit
through the conduit 83, open valves 5l, 56; and
58a,.through the conduit 89, so that the aromatic
gasoline range."
'
‘
'
alkylation is accomplished with the ethylene and
mixture of .iso-butane" and iso»
- Ii" desired a
pentane may be `alkylated together under> about 20 catalyst contained therein which is admitted
through the conduit 89. In this procedure it may
the‘same conditions.
or may not be necessary to admit additional cat
'
Recovery of the catalyst
alyst through the valve 48 depending on the
amount desired with the aromatic alkylation.
'I‘he catalyst carried into the fractionator 19
with the hydrocarbon layer from the separator . The products leave the aromatic alkylator
iso-heptanes, about 10% >iso-'octanes and 19%
higher products, _most of which are nwithin lthe
16 isl removed at thetop of the fractionator 19
through conduit 52 whichvwill containthe sat
through Vthe conduit 83 togetherwith unreacted
uratedgases and the catalyst which will be sent
gases, such as C1 toCs saturates and any small
` throughrvalve 54, conduit 85 and the catalyst will
be absorbed and desorbed in the absorber 84 and
desorber 88, respectively. In this operation the
amount of unreacted oleiins.. In the illustrativo
¿example valves‘54 and 5_1 are’ closed,_valve `E55 is
open so that the catalyst is sent to an absorber
iso-paraii‘ins`V alkylated withy the propylene will
84»-through the conduit 8,5. The absorber may be
have a slightly higher molecular weight.v For
.a packed column or bubble -plate column» The
example, if iso-butane is alkylated with propyl
absorbent ifs-introduced as a liquid into the top
ene the product will consist primarily of isomeric
of the absorber 84 by meansof- a conduit 85a.
heptanes,'such as'2,2l,3-trimethyl butane. _The
35
The catalyst is absorbed by or forms a loose
product formed in the alkylation of the aro
chemical combination with theV absorbent and is
removed through the conduit 8B. Any> saturat
matics will be primarily ethyl benzene.
'Additional alternative procedures' r
ed C1 toACa hydrocarbons in theïsupplyl line I4 v
.whichhavebeen carried throughthe alkylators
~ -
43 and 69, after the catalyst .has been extracted
therefrom, exit as the oir-gas in conduit-»81 land
If desired, both valves 44 and 45 may be opened
and the mixture of ethylene and propylene >fed
to both ofthe alkylation zones. 'I‘he alkylation
may be used as fuel or for other purposes >`de
in each zone may be suiiiciently vigorous to re-.
e
act both the propylene and ethylene in each zone
. The `absorbent charged with the catalyst and
removed through the conduit86 is ßsent to a de
that the products exiting through the conduits
:45 so
52 and 83 contain nothing but the saturated gases
-sorber 88 where the catalyst is removed, and sent
through conduit 44Í| Vfor use inthe isornerizing> or
and catalyst. ~ In this event, valves 53 and 51 are
either of the alkylating reactions. The denuded
ça)'r_>sorbe'nt is returned through the conduit 85a
catalyst from both alkylators is sent tothe ab-v
ypending upon the composition therein.
Ito the absorber 84.r
,
.
Y
Y
.
¿
»
~
closed, valves 54 and 55„are opened so that the
sorber
84.
.
,
„
Si.
„
IIt, willbe apparentin view -of theabove de
scription that'the process is `extremely flexible
in the mode of operation andthe productsto be
obtained. In.- general, the -manneriny which the
g
_ The absorbent for- separating the catalyst from
_the gas may beanyv'of a large -enumber of com
«pounds which form a complexwithor otherwise
>absorb hydrogen" fluoride and, boron triiluoride..`
Hv`¿IElXa‘rnples are dihydroxyiluobcric acid; substi
tuted `and unsubstituted- diarylketones, such as
process is operated will depend upon„thecha’ráv
racteristicsof theY wanted products,. the »mehrer
beuzßphenone.. amines,
isofparañins are to be blended either together or
iniwhichthe alkylated aromatics and alkylated
basic >nitrogen-.heterocy- .
clic.- compounds, and other nitrogenous basic _com
separately for products ofhigh anti-knock gaso-A
pounds suchwas, diphenylamine, `coal tar bases,
and chlorinated amines; certain aromatic ,hydro 1,60
line.
.
‘
l
~
~
,
~carbf‘ms,l ethers such as anisole `anddiphenyl
ether; 'and certain metal fluorides. The temper
The process has the additional advantage in
that a singlecatalyst may be used for both isom
erization and alkylation reactions» and maybe
¿ature-under; which they absorption operation is
continuously reused and recycled through the
4carried out will depend upon the absorbent used
various zones depending on the relative 'require
.and -the g, pressure .conditions maintained Vand is
ments of each.
.such as to secure a desirable or maximum absorp-> l
tion.` ` When benzophenone is the absorbent-_~ a
`ten’iperature;from"near the melting pointoi’ `the .
.benzophenone up »to 300511'. may be used,v pref
erably 160 to 210° F; . The >desorbing may be ac‘
,complished `at a higher temperature at-which the
complex is destroyed _at least ïto some extent to
i'reeîthe catalyst in theïvapor form. In the case
`oi'fbenzophenone _a temperature within the range
2010300 to 530° F: may .bei used -for desorption.
The process has the advantage of utilizing sub-.
stantially all of the useful products of the vcrack
ing to form highly desirable final products. In
general, the cracking may be conducted'so` that
the ,proportion of the aromatics and aliphatics
to be isomerized and/or alkylated maywcorre-,~
spond. stoichiometrically with the oleflns formed
by cracking and to be used in the alkylation proc
.15
esses.
.
~
~
,
»
v
_
l
'
2,408,753
11
12
It will be understood >that the description of
hydrocarbon fraction boiling in the »butane
the invention is illustrative of a process and that
the drawing is to facilitate an understanding of
the process. It is not intended to show appara
tus either in form or scale that is necessarily suit
pentane range and comprising a normal par
añ‘inic hydrocarbon, and a C6 and heavier hy
drocarbon fraction containing aromatics; intro
able for practicing the invention. Similarly lno 5 ducing atleast part of the aromatic containing
fraction and the lighter propylene and ethylene
attempt is made to include all of the heaters,
containing fraction into any alkylating zone and
condensers, pumps and other apparatus that may
reacting
the propylene with at least a part of
be necessary, as all of _these features will be ap
parent to one skilled in the art in View of' lthe 10 the aromatic in the presence of a catalyst com#
prising hydrogen fluoride and boron triiiuoride
explanation of the process herein.
c
‘
at
a temperature of 80 to 210° F'., and at .a pres
The invention is capable of many modinca
sure of up to 250 pounds per square inch but
tions in the details of operation, as will be ap
not more than that necessary to maintain the
parent to one skilled in the art, and all „such
catalyst
in the vapor phase,A withdrawing the
modiñcations are to be included as arewithin 15
unreacted ethylene in admixture> with catalyst,
the scope of the following claims.
isomerizing the Vnormal parafûnic hydrocarbon
Y
in the aliphatic containing fraction-at a tem
1. The process which comprises heating hydro
perature of «30° F'. to 215° F. in the presence of
carbons to a relatively high temperature lfor a
short time to form ethylene and propylene,~ C4 20 a catalyst comprising liquid hydrogen ñuoride
in which is dissolved boron >triiluoride under a
and C5 aliphatic Ahydrocarbons, and aromatics,
Iclaim:
partial pressure of 50 to 550 pounds per square
separating Athe C3 and lighter hydrocarbons con
inch, separating the isomer and transferring it
taining propylene and ethylene, an aliphatic frac
to a second alkylation zone, introducing the un
tion selected from the group consisting of C4
hydrocarbons, >C5 hydrocarbons and a mixture 25 reacted ethylene and catalyst withdrawn from
the first alkylation zone into the second alkyla
thereof and comprising a normal parañ‘inic hy
tion zone, alkylating the isomer at a temperature
drocarbon, and a Cs and heavier hydrocarbon
of ~30 to 160°A F. in the presence of liquid hy
fraction containing aromatics; introducing the
drogen fluoride containing dissolved boron' flu
propylene and ethylene containing fraction and
the aromatics into an alkylation zone and re
acting the propylene with at least a part of
the aromatics, isomerizing at least part of the
normal parañinic hydrocarbon in the aliphatic
30
oride under a partial pressure of 50 to 200 pounds
per square inch, transferring Vthe funre'acted prod
ucts of the lighterfraction and catalyst contained
in the same to a recovery zone, separating the
fraction, transferring the ethylene from the iirst
catalyst from the 'unreactedlighter products, and
separating the C3 and lighter hydrocarbons con
fraction boiling inV the butane-pentane range
thereof and comprising a normal parafûnic hy
drocarbon, and a Cs and heavier hydrocarbon
the aromatic containing _fraction and the lighter
alkylation zone and alkylating the isomerized 35 returning the catalyst for reuse. _
6. The process which comprises heating a
hydrocarbon with the ethylene.
heavy naphtha hydrocarbon stock to `a temper
2. A process in accordance with claim 1 in
ature within the range of about 1380 to 1650° F.,
which the »isomerization and both alkylations are
for about 0.175 second to crack .said hydrocarbon
carried out in the presence of a catalyst com
stock and form ethylene and propylene, aliphatic
prising hydrogen fluoride and boron triñuoride.
hydrocarbons in the butane-pentane range, and
3. The process >which comprises heating hy
aromatics, fractionating the products to yield
drocarbons to a relatively high temperature for
a C3 and lighter hydrocarbon fraction containing
a short time to form ethylene and propylene, C4
propylene and ethylene,A an aliphatic hydrocarbon
and C5 aliphatic hydrocarbons, and aromatics,
taining propylene and ethyleneJ an aliphatic 4'5 and comprising a normal paraiiinic hydrocarbon,
and a Cs and heavier hydrocarbon vfraction con
fraction selected from vthe group consisting of
taining aromatics¿introducing at least part of
C4 hydrocarbons, C5 hydrocarbons and a mixture
propylene and ethylene containing vfraction into
fraction containing aromatics, isomerizing at »50 an alkylating zone and reacting the propylene
with at least a part of the aromatic in the pres
least part of the normal parañinic hydrocarbon
ence of a catalyst comprising hydrogen fluoride
in the aliphatic `fraction, introducing _the propyl
and boron triñuoride'at a temperature of 90°
ene and ethylene containing fraction and the
to 150°
‘and at a ypressurenof about‘80 to 150
isomerized hydrocarbon into an alkylatinïg zone,
and alkylating the isomerized hydrocarbon with V55 pounds ‘per square inch, withdrawing the un
reac'ted _ethylene Iin admixture 'With catalyst,
the propylene contained in the lighterwfraction,
isomerizing the normal parafiìnic hydrocarbon in
transferring the unreacted ethylene and intro
the' aliphatic containing fraction at a temper
ducing it and at least part of the aromatics
into a second alkylation zone and alkylating said
aromatics with the ethylene.
4. A process in accordance with claim 3 in
which the isomerization and both alkylations are
carried out in the presence of a catalyst com
prising hydrogen ñuoride and boron triíiuoride.
5. The process which comprises heating a hy
ature of 65° to 160°
in the’presence of a
60 catalyst comprising 25’ to 100 volume per cent
liquid hydrogen fluoride (based on rthe hydro
carbon) in which is dissolved boron trifiuoride
under a partial pressure of 150 to 350 pounds
per square inch, separating the isomer andtran's
65 ferring it >to a second alkylation zone, introduc
drocarbon stock boiling in the gasoline-kerosene
ing the unreacted ethylene and catalyst With
aliphatic hydrocarbons in the butane-pentane
range, and aromatics, fractionating the products
in' thepresence of liquid hydrogenñuoride con
taining dissolved .boron fluoride under a partial
drawn from the ñ'rst alkylation zone' into the
range to a temperature Within the range of about
second alkylation zone, the isomer being stoi
1250c to 1'750°
for a time within the range of
chiometrically in excess of the ethylene, alkylat
about 0.1 to 0.25 second to crack said hydro
carbon stock and form ethylene and propylene, 70 ing the’ isomer at a temperature of 10°v to 105° F.
to yield a C3 and lighter hydrocarbon fraction
containing propylene and ethylene, an aliphatic
pressure of 50 to 200- 'pounds per square inch,
recycling the unreacted' isomer, @withdrawing the
75 alkylated products," transferring the unreacted
, 2,408,753
products of the lighter fraction and catalyst con
tained in the same and contacting them with
14
8. The process which comprises heating a
Y 13
heavy naphtha hydrocarbon stock to a tempera
ture within the range of about 1380 to 1650° F.,
an absorbent, desorbing the catalyst from the
for a time Within the range of about 0.1 to 0.25
absorbent, and returning the catalyst; for reuse.
second to crack said hydrocarbon stock and form
Ul
'7. The process which comprises heating a hy
ethylene and propylene, aliphatic hydrocarbons
drocarbon stock boiling in the gasoline-kerosene
range to a temperature within the range of about
-1250° to 1750° F., for a time within the range of
about 0.1 to 0.25 second to crack said hydrocar
bon stock and form ethylene and propylene, ali
phatic hydrocarbons in the butane-pentane
in the butane-pentane range, and aromatics,
fractionating the products to yield a C3 and
lighter hydrocarbon fraction containing propyl
ene and ethylene, an aliphatic hydrocarbon frac
tion boiling in the butane-pentane range and
comprising a normal parañinic hydrocarbon, and
range, and aromatics, fractionating the products
a Ce and heavier hydrocarbon fraction contain
to yield a Cs and lighter hydrocarbon fraction
ing aromatics; isomerizing the normal parañinic
containing propylene and ethylene, an aliphatic 15 hydrocarbon in the aliphatic containing fraction
hydrocarbon fraction boiling in the butane-pen
tane range and comprising a normal parailìnic
hydrocarbon, and a Ce and heavier hydrocarbon
at a temperature of -5° F. to 160° F. in the pres
ence of a catalyst comprising 25 to 100 volume
per cent liquid hydrogen fluoride (based on the
hydrocarbon) in which is dissolved boron trifluo
ride under a partial pressure of 150 to 350 pounds
20
containing fraction at a temperature of _30° F.
per square inch, separating the isomer and trans
to 215° F. in ythe presence of a catalyst compris
ferring it to an alkylation zone, transferring the
ing liquid hydrogen iiuoride in which is dissolved
lighter ethylene and propylene containing frac
boron trifluoride and under a partial pressure of
tion to the alkylation zone and reacting the pro
50 to 550 pounds per square inch, separating the
pylene and at least part of the isomer at a tem
25
isomer and transferring it to an alkylation zone,
perature of +10“ to 110° F., in the presence of
fraction containing aromatics; isomerizing the
normal parañinic hydrocarbon in the aliphatic
transferring the lighter ethylene and propylene
liquid hydrogen fluoride containing dissolved
containing fraction to the alkylation zone and
reacting the propylene and at least part of the
boronfluoride under a partial pressure of boron
trifluoride of 50 to 200 pounds per square inch,
isomer at a temperature of -30 to 160° F. in the
recycling the unreacted isomer, withdrawing the
30
presence of liquid hydrogen fluoride >containing alkylated products, withdrawing the unreacted
dissolved boron ñuoride under a partial pressure
ethylene in admixture with any catalyst, intro
of boron trifluoride of 50 to 200 pounds per
ducing at least part of the aromatic containing
square inch, withdrawing the unreacted ethylene
fraction and the withdrawn ethylene and catalyst
in admixture with any catalyst, introducing at
35 into a second alkylating zone, and reacting the
least part of the aromatic containing fraction
ethylene with at least a part of the aromatic in
and the withdrawn ethylene and catalyst into a
the presence of a catalyst comprising hydrogen
second alkylating zone, and reacting the ethylene
with at least a part of the aromatic in the pres
ence of a catalyst comprising hydrogen fluoride
40
and boron ‘.trifluoride at a temperature of 80 to
210° F., and at a pressure up to 250 pounds per
square inch, but not more than that which will
fluoride and boron triñuoride at a temperature
of 90° to 150° F., and at a pressure of 80 to 150
pounds per square inch, withdrawing the unre
acted products of the lighter fraction and cata
lyst from the second alkylation zone and con
tacting them with an absorbent, desorbing the
maintain the catalyst in the vapor phase, With
catalyst from the absorbent, and returning the
drawing the unreacted products of the lighter 45 catalyst for reuse.
ROBERT E. BURK. ~
fraction and catalyst from the secondì alkylating .
zone, separating the catalyst from the unreacted
lighter products, and'returning the catalyst for
reuse.
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