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Патент USA US2408174

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Sept. Í245 1946.
`2,408,l 73
M. P. MATusz'AK
Filed nay 2s, 1945
Patented sept. 24, 1946
y Maryan I’. Matuszak, Bartlesville, Okla., assigner
to Phillips Petroleum Company, a corporation
y of Delaware
Y ` Application May 26,1943, seria1ïNo.~4s's,547 ,
25 Claims.
This invention relates -to treatment of aro
matic hydrocarbon materials and'more -partic
ularlyrto the removalof organic ñuorine com
pounds Vand other undesirablelcompounds from
` such materials by 'treatment with liquid hydro
iluoric acid. Thisv invention is a continuation
in-part of my'copending application, Serial No.
395,282, 'filed May 26, 1941, now UnitedStates
. Patent 2,320,629, issued June l, 1943.
' In the synthesis of aromatic hydrocarbons by
(Cl. 26o-671) n
'Í acid from aromatic hydrocarbon materials is
eil‘ected `by contacting the material in liquid
phase with liquid anhydrous hydroñuoric acid
at a suitable temperature, vwhich may be between
, aboutÍ .-100° and about 3506i', dependingy some
‘ the*> particular'materîal, but which
` what
Vusually is 'optimally between about 20° >and 100°l
F., separating the hydroñuoric acid extract from
the hydrocarbonrmaterial, and yfreeing the treat
ed hydrocarbon material from a smallpropor
processes inwhich duerme-containing catalysts
' tion of `dissolved hydrofluoric acid. The hydro--
are used, small proportions of organic fluorine
containing Icy-products are formed. Among such
processes, one of the most important is the alkyl
ation of aromatic hydrocarbons, such as ben
zene, toluene, and the like, with alkylating
it should be at least` several times this amount.
agents, such as oleñns, polar alkyl compounds',
and the like, in the presence of catalysts com
prising oneor vmore of such fluorine compounds
iiuoric acid should .be used in suiîflcientV amounty
to form a distinctliquid acid phase; preferably
The amount needed may vary with the content
ofñuorine-containing by-products, but the min
imum'amount for any particular case may be
readily found by trial; an amount between 20
and 100 per cent by volume of the hydrocarbon
as-hydroñuoric acid, boron fluoride, and the like. 20 material is` generally satisfactormbut for high
contents of fluorine-containing by-products, it
Although the exactr nature of composition of the
may' greatly ‘exceed 100 per cent. Because the
illumine-containing by-products has not been
mutual solubility of aromatic hydrocarbons and
completely investigated, they are Vbelieved to be
liquid hydroñuoric acid increases appreciably
mostly alkyl and/or aryl ñuorides, such as may
be derived from the valkylating agent and/or 25 with increase in temperature, elevated tempera
tures should usually be avoided; for example,
the original aromatic hydrocarbon. These by
the solubility of benzene in liquid hydroiluoric
products are not completely >removed by'wash
`acid increases from 2.0 weight per cent at 20° F.
ing the hydrocarbons with alkaline solutions.
to _5.0 Weight'per cent at 100° F. However, in
They tend to decompose at elevated tempera
tures, such as those employed in ‘fractional `dis 30 some instances the treatment may be advanta
tillation of the hydrocarbons, thereby forming ' geously carried out at an elevated temperature,
hydroñuoric acid, which is corrosive, especially
in the presence of moisture.
after which, for improved mechanical separation
of the hydrocarbon material and the acid, the
temperature may be lowered, say to a tempera
In the afore-mentioned copendingapplication
in the range of 10° to 50° F.
is disclosed treating of predominantly saturated .35 ture
Separation of the acid andthe hydrocarbon
hydrocarbon materials, specifically v-paraiìn hy
phases is'usually eiîected by gravitational set
drocarbons, with. liquid hydroñuoric acid to re
tling, aided if' desired by cooling. Centrifuga
moveV organic fluorine compounds. It >has now
tion may be used, but ordinarily it is not nec
been `found that treatment of aromatic' hydro
carbon materials with liquid hydroñuoric acidy
Freeing of the treated hydrocarbon material
elfects advantageous removal of organiefluorine
from dissolved hydroñuoric acid may be effected
compounds and of other compounds, ¿suchÍ as
by various means, >such asfdístilling, washing
alkylating agents, boron fluoride, and sulfur
with Water or alkalinesolutions, contacting with
45 metal salts or other compounds capable of com
bining with hydrogen fluoride, or thelike. ' How
matic hydrocarbon materials.
ever,> it is 'generally advantageous to remove the
Another object of this invention is to removev
dissolved hydroñuoric acid by fractional dis
lundesirable organic* fluorine-contaîning. com
tillation asl a low-boiling or azeotropic mixture
pounds irom aromatic hydrocarbon materials.
OtherV objects and advantages will be appar r50 with a low-boiling parafñn having three to flve
` An object of this invention is to purify aro
, carbon atoms per molecule, preferably a bu
entirom the followingr description, thela'c'com
tane. To this end, such a paraffin is added to
Y pariyingfdrawing, and/or >the.fappended claims._ Vthe
hydrocarbon material before, during, or after
fßccording to Athis invention, yremoval of'¿ or
contacting with liquidhydrofluorio acid, usu
ganie‘iludrine compounds and other compounds d the
tihatz’are relatively highly soluble in hydrofluoric 55 ally most advantageously after the acid phase
has been withdrawn from the hydrocarbon ma
terial. Because of its relative inertness, this
parafûn is preferably straight-chain rather than
carbon, which is returned to the treated hydro
. carbon material.
The propane-extracted acid
extract is preferably also fractionally distilled,
whereby the hydrofiuoric acid is recovered in an
This paraffin forms a mini
mum-boiling azeotropic mixture with hydrofiu
overhead fraction in condition suitable for re-use,
and any undecomposed organic fluo-rine com
oric acid. Under the proper conditions, the over
head fraction obtained on fractional distillation
pounds are withdrawn in an oily kettle fraction.
is such an azeotropic mixture;- however, in ac-`
` Understanding of some aspects of this invention
tual plant practice, when close control is not
may be facilitated by reference to the two figures
feasible, the composition of the overhead frac "l0 of 'the accompanying exemplifying drawing, which
tion may depart somewhat .from the exact Coin-> ..
are schematic flow diagrams illustrating specific
position of the azeotropic mixture at the pres
embodiments of the invention for the treatment
sure in use, although the process will have taken
of aromatic hydrocarbons produced by alkylation
advantage of the principleinvolved. ` ‘The low
in the presence. of a fluorine-containing catalyst.
boiling fraction carries with it, in the form of 15 For the alkylation of benzene or toluene with
a low-boiling mixture, any hydroiiuoric acid re
an olefin or a nonprimary alcohol having three
maining in solution in the hydrocarbon material,
thereby eifecting removal of the dissolved acid
, is suitablyhydrofluoric acid. For alkylation with
without the loss of acid'that would occur if the
ethylene, however, this catalyst is preferably, but
to five carbon atoms per molecule, this catalyst
removal were made by water-washing, alkali 20 n"ot necessarily, promoted by a minor proportion
washing, or the like, and without the increase
of boron fluoride, such as approximately l to 5
in temperature that would be necessary forre
mol per cent.A Some benefit appears to result from
moval of the acid by simple fractional distilla
the presence of a smallY proportion of moisture
tion. -Simple fractional distillation of the dis
in the hydrofiuoric acid-boron fluoride catalyst;
solved hydrofluoric acid,l without< prior addition 25 when an alcohol is the alkylating agent, water is
of a low-boiling parafûn, al'so'mayv be» practiced-_'
formed as a ley-product of the alkylation.
The acid removed by either type. of fractional
In the embodiment of Figurev 1, the alkylation
distillation is generally suitable for refuse in the
reactants enter the system by one or more inlets,
treatment of additional 'hydrocarbon material.
represented by inlet i l controlled by valve I2.
`Although the action of thehydro?luoric acid 30 For the sake of simplicity, the reactants may be
is not completely understood at- present,` it appears
taken` to be benzene and ethylene, without. re
to` be due chiefly to a preferential- solubility of
stricting the invention thereto. These reactants
organic fluorine compounds in the acid. Any
procedure that effects an intimate contacting be
tween the acid and the hydrocarbon phases, such
pass into alkylatorV 13„ in which they are intle
mately mixed with lthe catalyst, which enters the
system through inletil controlled by valvey i0.
As has been indicated, the catalyst may be differ
as those well-known. inthe art of extracting with
preferential solvents, is suitable. lUnduly pro-v
ent for different alkylating agents; in the present
longed contacting, in cases in which the acid may
specific instance, it comprises substantially anhy-r
react slowly with the aromatic hydrocarbon to
yield organic ñuorine com-pounds, should be
avoided. The contactingr preferably should b'e
effected in apparatus not subject to excessive
attack by hydrof‘luoric acid.
drous hydroñuoric acid and a minor proportion,
usually about 3 mol per cent, of boron fluoride.
Alkylator i3 may be any convenient reaction ves
sel having an agita'ting means and capable oi'
withstanding the alkylating conditions; The
reaction temperature may be broadly in thevrange
‘As oleiin and nonolefin alkylating agents may
react lwith hydrofl'uoric acid toV form organic 4:5 of about 50 to about 400° F. The optimum tem
Iìuorine'compounds, the hydrocarbon materials
perature rangev differs for different alkylating
to be treated by this process should be substan
agents, j being generally lower the higher, rthe
tially free from alkylating agents. 'v However,
number of carbon atoms in the alkylating agent;
relatively small- proportions o-f unsaturated hydro
in the present specific instance, it is usually pref
carbons or other'alkylating agents may be present, 50 erably in thefrange of 100 to 200° F. lfThe pres
for-the, fluorine compounds formed by reaction
sure may be as high as isdesired, but it need be
with the acid are preferentially dissolved by the
only sufñcient to maintain substantially all of
acid andare removed; in consequence, the treated
the reaction mixture in the liquid state. The
material is freed not only from organic fiuorine
average reaction time, or the time of .residence` of
compounds but also from unsaturated hydrocar~ 55 the
hydrocarbon phase in the -alkylaton generally
bons and/or other alkylatingf agents. Similarly,
may vary in the range of abouti» toÍlOO- minutes
many sulfur compounds are preferentially dis
or more, depending upon the. other reaction con
solved by the, acidV and are removed, so that the
ditions ; a time of 5 to l5Á minutes, more specifically
present process may be applied to the purifica
10 minutes, is usually preferred. Conditions out
tion of sulfur-containing hydrocarbon materials. 60 side of theser ranges are suitable in some cases;
'The hydroiluoric acid> extract is usually passed
the optimum conditions for any particular case
to a catalytic hydrocarbon conversion lstep 'to be
may be readily determined by trial by oneskilled
used as catalyst. >When not so used it'is treated
in the art. The mol ratio of benzene to` ethylene
to recover the acid, which'is then re-used. In
in the feed should be well in excess of 1;.1, prefer
such a case, `sinceA this acid extract contains 65 ably at least 10:1,` since the alkylation results
considerable dissolved varomatic hydrocarbon, it
generally improve with. increasey inthe benzene
is preferably ,preliminarily- extractedwith a low
to-,alkylating agent ratio. The proportion of
boiling paraiiînof three tofive carbon atoms per
catalyst preferably is in therange of about 0.2 to 4'
molecule, such as for example normal butanei
times the 'weight of hydrocarbon in the 'reaction
The extraction is preferably made at a low tem 70
After a suitable‘contact period, the resulting
which maysuch
be conveniently
as approximately
30° to
by 60°'
evaporative cooling, especially when thaparaiîin
is propane. The resulting paraffin extract is frac
tionally distilled torecover the aromatic hydro
alkylation mixture is passed throughA conduit._ l5
into` separator AI 6, ‘in Awhich it 'is separated Vinto a>
hydrocarbon phase and an acid or catalystphase.`
75 The hydrocarbon phase is passed'through Valved
. 2,408,173
suitable amounty of such'a parañ‘in maybe added
conduitY I1 'into ` treaterv or> extractor I8. yIls-.pre
viously discussed a light (or flow-boilinglparaf
through conduit 46 leading into conduit >3|.
ñnysuch as.abutane,`ma'y be added tothe. aro
matic hydrocarbon material ~prior to its extraction
with liquid hydrofluoric acid. If such an oper
isv preferably 'passed through rconduit 4 I controlled
l. yFrom extractor ïI ßithe hydrofluoric acid extract`
by'valveAZ'rv and -.through recycle conduit I4 ïto
alkylator I3;».to be used inthe alkylation step;
ation is practiced, a suitable amount of such a
parañîn maybe addedthrough conduit 45 lead
ing into conduit I1. The alkylation catalyst phase
if desired, however, any part of the extract mayr
be withdrawn from the system through outletz43
phase VandV acid-soluble .organic compoundsV of
relatively high molecular weight, including some
ilumine-containing compounds, that is withdrawn
liquid extract, containing aromatic hydrocarbons
controlled by valve 44. The preferentiallydis-may be> discharged in part or entirely from the
compounds kcarried by this extract. to
systemthrough valved conduit 8, or it‘may Abe
alkylator .I 3 advantageously enter, at least in part;
recycled, at leastin’part, as by pump I9, through
into. the alkylation, .thereby increasing the over
valved conduit 2D and acid-recycle conduit I4,
allryieldof alkylate. >If it is desired toextract
back to a1ky1ator.I3;.hoWever, at least a part of
dissolved aromatic hydrocarbons from'the ., hy
it Vis _preferably passed` through valved conduitr 2|
droiiuoric acid phasewith a light (low-boiling)
into fractionator 22. ~ InV this fractionator, the 15
paraflin of three to five carbon atoms per mole
catalyst phase' is fractionally distilled into the
cule, as previously discussed, any part lor all of
f following. fractions; a fraction, comprising chiefly
the catalyst phase passed from the bottom of `ex- ’
boron fluoride, hydrofluoric acid, and some low
tractor I8 may be passed through valved conduit
boiling organic fluorine compounds, that is passed
4 to extractor 5, wherein it is'contacted with a
through valved conduit 23 intorecycle'conduit~ I4, 20 liquid,
low-boiling paraiîin, such as normal bu
by which it is recycled to alkylator I3; a fraction,
tane, introduced through conduit 6. The eX
comprising chiefly hydrofluoric acid, that is passed
tracted hydrofluoric acid, now relatively free of
through Aconduit 2'4 `'controlled by valveA 25 into
aromatic hydrocarbons, is passed through con
extractor I8; and a- fraction, comprising unre
acted benzene which was dissolved-inthe catalyst 25 duit 'I for rsuitable treatment, as discussed. . The
andV some dissolved hydrogen ñuoride, is dis
charged through conduit 3 and, if desired,'may. be
subjected tov distillation in suitable equipment,
through outlet 28 controlled .by valve 21. "The
as illustrated by fractionatorr32.
unreacted benzene maybe recovered, as by frac 30 such.
In the embodiment .of .Figure 2, the alkylation
tional ,.distillation, and may be returned tothe
reactants and thealkylation catalyst,which again
system, by meansnot shown.
forthe sake of 'simplicity may be taken'to be
In extractor I8, the hydrocarbon phase ¿enter
and ethylene and hydrofluoric acidpro
ingV fromconduit I1 is contacted in a counter
current manner withthe hydroñuoric acid` en
tering from conduit 24, whereby unreacted'alkyl
ating agent, dissolved boron-fluoride, and organic
ñuorine-cont'aining Icy-products of the alkylation
step are removed from the -hydrocarbon phase,
moted byboron fluoride, respectively, enter the
system by one or more inlets, such as inlet 5I
controlled by valve >52 and inlet 49 controlled by
, valve 53, respectively, into treating means .53. In
this means, the hydrocarbons pass generally up
presumably' by preferential solution in the acid. 40 wardly through a lower, alkylator section 54 and
then upwardly through an upper, extractor sec
Hydrofluori'c acid‘sufflcient to compensate for any
tion `55. In >the alkylator section they are in
losses occurring anywhere in the system mayA be
timately contacted in a generally countercurrent
added through inlet 28 controlledby valve129; if
manner with the catalyst, which enters at least
desired, his make-up acid may be advantageously
added t0' extractor I8 at a point downstream, in 45 in part at thetop of the alkylator section from
acid-recycle conduit 55, whereupon alkylation oc
the hydrocarbon stream, to the pointof entry of
curs. On-passing upwardly into and throughthe
the hydroñuoric acid» from fractionator 22. Any
extractor section, the resulting hydrocarbon mix
losses of boron iiuoride are made up by additionr`
is countercurrently contactedr with lsubstan
of this promoter through inlet 9.
y ‘
`From extractor . IB' lthe ‘treated hydrocarbon
material is forced, as by pump 30, through con
duit 3I into Vfractionator 32, in which it is frac
tionally distilled into the following fractions: a '
relatively small light fraction that may be with
tially pure anhydrous hydrofluoric acid that enters
the upper‘part of the extractor rsection from con
duit 5'I, whereupon organic ñuorine-containing
by-products, boron fluoride, and unconsumed
alkylatin‘g agents are removed from the hydro
carbon mixture. From the upper part of treat
drawn through outlet 33 controlled by valve 34 55 ing means 53, which extends .upwardly somewhat
-but that usually Vis passed, at least in part,'to
beyond extractor section 55 to preclude substantial
alkylator I3, as .through conduit 35 controlled
entrainment of the acid phase, the extracted hy
by valve 36, since it comprises chieñyhydrofluoric
drocarbon mixture is forced as by pump 58,
acid that was carried in solutionrin the treated
through conduit 59 into fractionator 60.
hydrocarbon material coming from the extractor 60 kThe hydrofluoric acid entering treating means
53 Afrom conduit 51 passes downwardly through
AI8;- a relatively` large medium `fraction vthat is
extractor section 55 and then joins the catalytic
material entering from conduit 56. AWhen the
comprises boron fluoride, as in the pres
valve 38, since it corx'ip'risesk chieñy unrea'cted 65 catalyst
instance, the proportion of ,boron
benzene; and -an alkylate kfraction» comprising
ñuoride» entering through .inlet 49 is preferably
chiefly, in this specific embodiment, ethylbenzene,
sò adjusted that the average composition, of the
practically acid-free and that is recycledV to
alkylator I3, as through conduit 3'I controlled by
that is withdrawn.throughoutlet 3S controlled by
catalystin alkylator section 54 is that desired,
valve 40 to .storage or. to additional processing
such as for example l to 5 mol per cent of boron
steps, notl shown, such'asA concentration steps, 70 fluoride and 95 to 99 mol per cent hydroñuoric
dehydrogenation steps to convert ethylbenzene to
styrene, or the like»4 If it is desired to conduct
this distillation in the presence of a light îä(or
acid. . When the catalyst is substantially pure
hydroiluoric acid and does not comprise boro-n
as when the alkylating agent is relative
low-boiling) paraffin, as previously discussed, and
lyA highly reactive or is an olefin .or nonprimary
such has not been. added through conduit> ’45, 'a - 75
alcohol-z or three to i-lve carbon atoms per mole-V
cule,y all fresh catalyst, namely hydroiiuoric acid,
ator,».not;shown, in. whichit: is separatedinto two
fractions. TheI light fraction, which comprises
the unreacted benzene, the catalytic. material
may enter.- the system through inlet; 'I8` controlled
by‘valve. 19, in which case inlet «lilY may be» omit
ted or unused. Inl alkylator section~ 54. thecata
drocarbon phase. may be passed into a. fraction
lyst. is intimately mixed with the alkylation mix
ture in any desired manner, but the general> di
rectionof the acid continues to be. downward,
From the bottom of the alkylator` section, the
acid orv catalyst phase isforced,- as by pump 6l, 10.
through conduit 52, valve. 63‘,_andxconduit 56back
tothe top of the. alkylator section; however, in
stead- of being thus. recycled to the alkylation
step, any desired part, or all, of it may be, sent
through valve 64. into fractionator 65 forl purìñ.
dissolved inv theV hydrocarbon> phase. and some of
theY organic~ fluorine compounds, is> returned> to`
the. alkylation. stepçr, the, alkylate fraction is> exf
tracted with, liquid hydrofluoric acid. to. remove;
the residua-l` organic ?luorine compounds, and is
then freed from dissolved hydroiluorie acidv in
yaccordance with the description already given.r
The hydroñuoric acid extract is preferably sent
to the alkylation step, but if desired part or all
of' it may be passed into a fractionator, in which
it is freedV by fractional distillation from higher
cation or reviv-íñcation, and ordinarily in com
boiling. organic compounds and from which, it
mercial operationa part; is: so sent either contin
may be returned to the extraction step or senttQ
uously or intermittently,
the, alkylation. step. The hydroiìuoric acid phase
In fractionator 65,` the acid phase is fraction
separated from theA alkylation mixture may be.
ally distilled into-` the following fractions: a. frac 20. recycled directly to the alkylation. sten,v or. part or
tion, comprising chiefly hydroiluoric, acid, boron
all of it may be similarly fractionally distilled in
fluoride, and some organic ?luorine compounds,
the same or a differentfractionator, from which
that. is passed through conduit 6.5. controlled by
it. may be returned to the alkylation step; or seht
valve 6.7. and through conduit 56f into alkylator
to the extraction step, asis desired.
section 54:. a fraction, comprising chiefly hydro 25. The hydrofluoric acid used in the extraction
fluoric: acid, that is` passed through valve 15 and
should be concentrated, and in some instances
conduit 51 into. the upper part of extractor sec
may be> substantially anhydrous. Generally any
tion 55;. and a fraction, comprising benzene that
small',` fortuitous. amount of waterwill not be del
was. dissolved in the acid phase and acid-soluble
eterious, and at times it may be desirable to en
organic compounds of relatively high molecular 30. sure the presence Ofça few-per centof Water. In
weight, including some. iìuorine-containing com
nearly all cases, however,- concentrated hydro
pounds, t'hat is` passed through. conduit 58 con
?luoric acid will refer to acid having; a strength
trolled by valve 6€!A to` separator 15. In, separator
greater than 90.. per cent, and most generally
10;. this fraction is. heated to distill oli the- ben
greater than 95 per cent. The same will be truc
zene- and to decomposev the iîluorineV compounds « for the hydroiiuoric acid used. for alkylation,
to liberate. hydrofluoric acid; the; benzene and
By fractionator, as. used in this; specification, is
thehydroñuoric acid are passed to alkylator sec
meant any system of` fractional-distillation de
tion 54, as through conduit 'H controlled by valve
vices. that will eiîect the results indicated; it may
'(2. The residual high-boiling material is With
consist of one. or more than one fractionating
drawn from separator lí). through outlet 13 con
trolled by Valve. '14.r
40 column, as is found to be. necessary or desirable
for»V any particular case in accordance with. the.
Hydroiiuoric acid sufficient in amount to com
pensate for any losses occurring anywhere, in the
system is preferably added` through inlet 'I8 c_on
trolled by valve 7:9; if desired, this make-up acid
may be advantageously added to extractor sec
tion 5,5 ata point downstream, in the hydrocar
bon stream, to the point of entry ofthe. hydroflu
oric acid from fractionator- 65.
In fractionator til, the extracted hydrocarbon
mixture coming thereto through conduit 59 is `
fractionally distilled into the following fractions:
a relatively small light fraction, comprising
chieíly hydroiluoric. acid, that may be withdrawn
through outlet 8l!Y controlled by valve 8l but. that 55
usually is recycled to some. suitable point in the
system, asv by being passed through conduit 82A
controlled by valve 83 into conduit. 55 and thence
well-known art of fractional` distillation, Many
other well-known devices not specifically shown
or described in this specification,
kno-wn to contributey to or improve
mentorl the. results indicated herein,
corporated or used without> passing
scope of this, invention or the. spirit
which are
the attain
may be in
beyond> the
of' this dis-Y
Some aspects of the invention atei further, illllS
trated; bythe following examples, which should
not,_ however, be construed as necessarily limit
ing the invention.
Example I
Benzene. was alkylated with propylene in a
s_ma-ll continuous pilot plant. comprising a 7450
cc. reactor having a` 1725 R. P. M. turbomixer.
to alkylator section 54; a relatively large medium
The catalyst was anhydrous hydroñuoric acid;
fraction, comprising chiefly practically acid-free
benzene, that is recycled through valve 84 and 6.0 the volume ratio of hydrocarbons to catalyst in
the reactor wasmaintained at 1.3:1. The mol
conduit 85 to alkylator section 54; and an alkyl
ratio of. benzene to. propylene in the feed was
ate` fraction, chieily ethylbenzene, that is with
83:1. The temperature was 118"- F.; the time
drawn through outlet 85 controlled by valve 81
to. storage or to additional processing steps,l not 6,5 of residenceof the hydrocarbon phase in the re
actor was 20.3 minutes. The yield of total al
kyla-tewas 249 perY cent by» weight of the propyl
In the embodiments of; Figures 1 and 2, all of
ene. The» total alkylate contained 93.5 per cent
the- hydrocarbon mixture resulting from the al
by volume of- isopropylbenzene, 5.5 per cent. of
kylation step is shown to be extracted with hy
diisopropylbenzene, and 1.0 per` cent of> heavier
drofluoric acid. Extraction of all of this hydro 7.0 product. The isopropylbenzene fraction con
carbon mixture, however, is noty always neces,
tained 0.0059. per cent byV weight of organic iiu
sary; in fact, certain advantages follow if only
crine. and 0.0117- per cent byv weight vof organic
the actual alkylate is so extracted. Thus, after
the al'kylation step and after separation of the
When. such _an isopropylbenzene fraction is
hydrocarbon phase from the acid phaseLthe. hy
75 countercurrently extracted with, approXimatehfY a
„2,408,178 '
third of its lovvn volume of anhydrous hydrofluoric
acid, the organic ilu'orinegïand sulfur are sub
stantially -completely `removed, therebyA improv,
ing the isopropylbenzene for >use `as van'ingre‘dient
in high-octane aviation fuel. "Because of 'the rel- ,
lliquid ’hydroiluoric acid phase, separating the tre
"sulting hydroiiuoric acid Vextract ."from theïhydroi
carbon material, and freeing the extracted iiy
drocarbon material from a small proportion-of
Adissolved hydroiluoric acid.
2. A process for the removal of >organic'í'luo’rin‘e
atively high proportion of sulfur, theresulting
hydrofluoric acid extract is preferablyprelimi
compoundsv from aromatic hydrocarbon . materials
containing the same, which vcomprises contacting
such a hydrocarbon material with liquidhyîdro
acid, correlating the relative .amounts of
fractional >distillation, before itis ,passed tothe 110 fluoric
said‘hydrocarbon and hydrofluoric acid and :the
alkylation step.
_' .. '
temperature of contacting so as to insure `the
Example II
presence cfa »liquid hydrocarbon phase 'and'o‘f
a liquid'hydroíiuoric acid phase, V'separating the
Benzene is alkylated with ethylene in the „pres“
narily freed from most’ of its contentiofv >sulfur
compounds, Which are relatively higheboiling, by ~
resulting hydrofluo-ric acid extract .from the-hy;
,drocarbon material, and distilling ïfromfthe‘vfex
tracted hydrocarbon material »any residual,y jdis
l‘ence fof an approximately equal volume of hydroh ï
iluoric acid promoted with approximately> 3,-mol
'per cent of boron fluoride, at a temperature of
>approximately 150° F. and a` contact. time of
solved hydroiiuoric acid.y
v3. A process of treating aromatic hydrocarbon
«approximately 10 minutes. Y The resulting mix
containing vorganic fluorine compounds,
:ture of hydrocarbons and catalyst is allowed to 20 material
which comprises adding to said materia-1 -an »rap
settle into a hydrocarbon phase and a `catalyst
'preciable fraction of its own volume of a parañ'in
having three to five carbon atoms per molecule, »
phase. The hydrocarbon phase isvcountercur
rently extracted With-substantially pure anhy- ,
drous hydrofluoric acid, whereby it is freed from
contacting the resulting mixture with liquid hyl
drofluoric acid, Ycorrelating the relative ‘amounts
of said hydrocarbon Aand ,hydr'ofluoric acid -and
ja small proportion of dissolved >boron fluoride
and »organic iiuorine, compounds, among which
`is ethyl fluoride-_ >The extracted hydrocarbon
phase is freedifrom dissolved’y hydrofluoric acid,
,as by`addition of „normal butane andîdistillation
the temperature oi- contacting so as to vinsure the
presence `of a liquid hydrocarbon phase and-uffa
liquid hydroflucric acid phase, separating the
resulting hydrofluoric acid extractirom the hy:
drocarbon material, and' freeing the extracted hy
of the butane _and the hydrofluoricv acid as a low
boiling mixture; it is thenv _f-ractionally distilled
to isolate Vthe fluorine-iree ethylbenzene. The
jacid extract is fortified by the addition of enough
drocarbon material Yfrom 'the added> paraffin and
’ from dissolved hydrofluoric acid by fractional
boron fluoride to make the total content of this
compound approximately 3 mol rper cent, and
f carbon material containing organic' fluor-ine :com--`
.the fortified acid is passed to the alkylation step
to be used as the catalyst for ethylâtion of addi»
4. A process loftreating an aromatic hyd-ro#
pounds, which comprises contacting' said hydro
carbon material with vliquid hydroliuoric lacid,
correlating the relative amounts of'sa-idr hydrol
An especially useful specific application of the
carbon and hydrolluoric acid and the tempera
invention is in the manufacture of ethylbenzene, 40 ture of contacting so as to insure the Vpresence
which is useful as an ingredient in aviation fuel v
of a liquid hydrocarbon‘phase and of a liquid
Yand which is readily dehydrogenated to Vstyrene
for use in the manufacture of synthetic rubber.
The alkylation of benzene with ethylene requires
more or less drastic or adverse conditions, such
as a reaction temperature appreciably aboveV room
temperature. Undersuch drastic Yor-adverse con,- .
.ditions, the alkylation tends to give .a vproduct
hydroiluoric acid phase, separating the resulting
Vhydrofluoric` acid extract Vfrom the hydrocarbon
material, adding to Athe lextractedA :hydrocarbon
material an appreciable amount Yof a vliqueiled
Aparaffin having three -to yfive carbon atoms> 'per
y molecule, andy fractionally distilling the resultt
containing a relativelyhigh `proportion of ¿un-re
acted alkylating agent, heavy unsaturatedhy.
drocarbons, andß‘organic ilumine-containing com
pounds -such as alkyl fluorides and complex ad
dition' products of the alkylating agent with the
catalyst'. rExtraction of the product, `either be- ‘
ing'mixture to remove the addedparafñznfand
the hydrofluoricacid remaining dissolved-in the
5. The process of claim 4, in
Vparaflin is normal butane.
k6. The process of claim v1, in which ther-mix
ture of hydrocarbon material and hydrofluoric
fore or after the separation from the unreacted 55 acid is contacted at a temperature in the range
benzene', with hydroi‘luoricv acid
with this invention effects an excellent removal
of these materials, thereby improving'the quality
ofthe alkylation product.
Because the invention may be practiced other
Wise than as specifically illustrated and described,
and because many modifications and variations
within -the spirit and scope of the invention Will
be obvious` to those skilled inthe art, the inven
>~tien should not be unduly restricted by the fore
going speciñcation.
I claim:
of 10 to 50"k F. prior to the »separationY of the .hy
droiluoric acid extract.
7. The process 'of claim 1, `in which said aro- y
matic hydrocarbon material is at least a part of
a, hydrocarbon mixture produced in the lpresence
of a catalyst comprising at least one fluorina
containing compound.
8. The process of claim 1, in which said aro
matic hydrocarbon material is at least îpar't ‘of
the hydrocarbon mixture resulting from alkyl'a
tion of at least one aromatic hydrocarbon 'in
1. A process for the «removal of organic fluorine
compounds from aromatic hydrocarbon materials
containing the same, which comprises contacting 70
such a hydrocarbon material with liquid hydro
fluoric acid, correlating the relative amounts Vof
said hydrocarbon and hydrofluoric acid andthe
temperature of contacting so as to insurev r:the . ,
Vpresence of 'a liquid hydrocarbon phase and-'of a
thepresence of Ya catalyst comprising at least
one fluorine-co'ntaining compound. ‘
" N
9."The process of claim 1, »in which said varo'
matic hydrocarbon material is vat least 'a Daft
of the hydrocarbon mixture resulting >from 'alkyl
ation of at least one aromatic hydrocarbon'in
the presence of hydrofluoric acid las» alkylation
`2,408, 173
10. The process of claim 1, in which said aro
matic hydrocarbon material is at least a part of
kylating an alkylatable aromatic hydrocarbon in
the presence of a liquid'alkylation catalyst com
the hydrocarbon mixture resulting from alkyla
prising hydroiluoric acid, passing a. resulting
mixture of hydrocarbons and catalyst to separat
ing means, separating a hydrocarbon liquid phase
tion of benzene in the presence of a catalyst com
prising a major proportion of hydrofluoric acid
and a minor proportion of boron fluoride.
11. The process of claim l, in which said con
from said liquid catalyst, contacting said hydro
carbon liquid phase with substantially pure con
tacting is countercurrent.
centrated liquid hydroiluoric acid to eiîect a
“purification of said hydrocarbon phase, passing
12. The process of claim l, in which said aro
matic hydrocarbon material is at least a part of
liquid hydroiluoric acid eiiluent from said con
the hydrocarbon mixture resulting from alkyla
tacting to said alkylation, and removing dis
tion of at least one aromatic hydrocarbon in
the presence of a catalyst comprising a major
proportion of hydrofluoric acid and a minor pro
portion of boron fluoride, and in which said hy
droñuoric acid extract is used as at least a part
of the catalyst for the production of additional
hydrocarbon material.
' `
solved hydroiluoric acid from a hydrocarbon
phase eil‘luent from said contacting.
19. The process of claim 18, in which said
catalyst is hydroiiuoric acid promoted with ap
proximately 1 to 5 mol per cent of boron fluoride.
20. An improved process for the alkylation of
an aromatic hydrocarbon, which comprises pass
ing a liquid mixture of an alkylatable aromatic
13. In a process of alkylating an aromatic hy
drocarbon with an alkylating agent selected from 20 hydrocarbon and an alkylating agent 'to the
the group consisting of oleiìns having two to
lower part of a treating means comprising a
five carbon atoms and of polar nonprimary alkyl
lower alkylating Zone and an upper extracting
compounds having three to ñve carbon atoms
zone, passing to the upper part of said alkylating
in atleast one nonprimary alkyl group in the
zone a liquid catalyst comprising recycled cat
presence of a fiuorine-containing catalyst, the
alytic material and hydroñuoric acid from said
improvement which comprises extracting at least
zone as hereinafter recited, intimate
a part of the resulting alkylation hydrocarbon
product with substantially pure liquid hydro
i'luoric acid for a time that is suiiicient for eiîect
ing substantial removal of organic ñuorìne-con
taining by-products of the alkylation.
14E- In a process of alkylating benzene with
ethylene in the presence. of a catalyst compris
ing a major proportion of hydrofluoric acid and
a minor proportion of boron iiuoride, the im
provement which comprises extracting at least
a part of the resulting alkylation hydrocarbon
product with concentrated relatively pure liquid
ly and countercurrently contacting said liquid
mixture in said alkylating zone with said liquid
catalyst under alkylating conditions to,effect
alkylation of said aromatic hydrocarbon, with
drawing from the bottom of said treating means
liquid catalyst effluent from said alkylating zone
and passing a portion of said catalyst as said
recycled catalytic material to said treating means
at an intermediate part between said extracting
'zone and said alkylating zone, passing substan
tially pure concentrated liquid hydrorluoric acid
to an upper part of said extracting zone, pass
ing a liquid hydrocarbon mixture resulting from
hydrofluoric acid for a time that is sufficient for
effecting substantial removal of organic ?luorine 40 said alkylation upwardly from said alkylating
Ycontaining by-products of the alkylation.
Zone into the lower part of said extracting Zone,
15. In a process of alkylating an aromatic hy
countercurrently and intimately contacting said
drocarbon with an alkylating agent in the pres
pure hydro?luoric acid and said hydrocarbon
ence of a iluorine-containing catalyst, the im
provement which comprises extracting the al
kylation product with liquid hydroiluoric acid.
16. A process of purifying an aromatic hydro
carbon material containing organic fluorine >and
sulfur compounds which comprises removing said `
organic iluorine and sulfur compounds by liquid
phase extraction with substantially purehydro
fluoric acid.
17. In a process for the alkylation of an aro-Y
matic hydrocarbon in the presence of a catalyst
containing a major proportion of hydroñuoric
acid and a minor proportion of boron fluoride,
mixture in said extracting zone, passing result
ing liquid hydrofluoric acid from the lower part
of said extracting zone to the upper part of said
'alkylatingqzona passing the resulting extracted
'hydrocarbon mixture from the top of said ex
tracting zone and from the top of said treating
means, and- recovering therefrom alkylated aro
matic hydrocarbons so produced.
2l. A process for the removal of organic iiuo
rine compounds from an laromatic hydrocarbon
material vcontaining the same as an impurity,
which comprises contacting such an aromatic hy
drocarbon material with liquid hydrofluoric acid,
wherein the alkylate contains organic fluorine
correlating the relative amounts of said hydro
compounds, the improvement which comprises
carbon material and said hydroñuoric acid and
contacting in liquid phase a hydrocarbon frac
the temperature of contacting so as to insure the
tion containing an alkylate from thealkylation 60 presence
of a liquid hydrocarbon phase and a
step with concentrated liquid hydroñuoric acid
liquid hydrofluoric acid phase, separating the
under conditions such that there is a negligible
amount of reaction of hydrocarbons catalyzed
by said hydrofluoric acid and such that there is a
reduction in the content of organic iluorine com
resulting hydrofluoric acid extract from the aro
pounds in said hydrocarbon fraction, separating
matic hydrocarbon material, contacting said ex
tract with a liquid paraiïin hydrocarbon having
three to five carbon atoms permolecule under
conditions of temperature and relative propor
a hydrocarbon phase and a hydrofluoric acid
tions such as to insure the presence of separate
phase, passing at least a portion of said hydro
liquid hydrocarbon and hydrofluoric acid phases,
ñuoric acid phase as catalyst to an alkylation
separating the resulting hydrocarbon extract, and
step for producing said alkylate, and removing
subjecting both said extracted aromatic hydro~
dissolved hydroñuoric acid from said hydrocarbon
carbon material and said hydrocarbon extract to
fractional distillation to recover relatively fluo
18. An improved process for the alkylation of
rine-free aromatic` hydrocarbon materials.
an aromatic hydrocarbon, which comprises al
A22. >The process of claim 2l in which each said
contacting step is conducted ata temperature
conditions of temperature and relative propor
.between about 20 and 100° F.
23. A process for the removal of organlc sulfur
compounds from an aromatic hydrocarbon ma
terial containing the same as yan impurity, which
comprises contacting such an aromatic hydro
'liquid‘hydrocarbon and hydroiiuoric acid phases,
carbon materialwith liquid hydro?luoric acid,
correlating the relative amounts of said hydro
carbon material and saidhydrofluoric acid andy
the temperature of contacting so as to insure the
presence of a liquid vhydrocarbon phase and a
liquid hydrofluoric acid phase, separating the
tions such as to insure the presence of separate
separating the resultingv hydrocarbon extract, Y
.and subjecting both said extracted aromatic hy
drocarbon material andsaid hydrocarbon extract
tok fractional distillation to recover relatively sul»
fur-free aromatic hydrocarbon materials.
24. The process of claim 2 in which said conu
tacting is conductedat a temperature between
about 20 and 100° F.
25. The process of claim 23 in which said ex
. traction is conducted at a temperature between
resulting hydroñuoric acid extract from the aro
about 2o and 100° F.
matic hydrocarbon material, contacting said ex
tract with a liquid parafñn hydrocarbon having -15
three to ñve carbon atoms per molecule under
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