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Патент USA US2405874

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Äu., §39 l
‘ Filed Nov. 2, 1942
ë - invenîors'. Edwin F. Bullard
John Anderson
. I
Sumner H. McAllìs'fzr
bg *heir* AHorneg//ß i . ',. fg,
Patented Aug. 13, 1946
r vorricle >
" 2,405,874f ' i
ALKYLATION oF Artor/nrrl'e`
Edwin F. Bullard, Oakland, John Anderson;
Berkeley, and Sumner H. McAllister, Lafayette,`
Calif., assignors to Shell~ Development Com
pany, San Francisco, Calif., a corporation of
Application November 2, 1942, Serial No. 464,286 l
11 Claims.
(Cl. 26d-671)- î
hydrocarbon to be alkylated before they are used
-This invention relates to the reaction of aro
matic hydrocarbons with alkylating agents and
particularly to the production of motor fuels
and motor fuel components by alkyl-ation of such
in the process.
hydrocarbons. It deals with an improved method Ul
for carrying out such alkylations whereby prod
ucts having superior characteristics may be ob
Alkylating agents Whichpmay be used in the
process include oleñns, particularly suitable frac
tions of petroleum crackingvproducts containing
ethylene, prop_ylena» isobutylene, normal butyl
enes, the amylenesor mixtures of one o1' >more
such olefms.„'¿,1nstead of the oleñns, polymers
thereof'ma’yg-be- used, „Not only may ethers, al
An important object of the invention is to pro
vide a more efñcient and economical method of 10 cohols and esters corresponding to the foregoing
oleñns beemployed, but also ctherethers, alco
alkylating aromatic hydrocarbons in the vapor
hols and esters, such as dimethyl, methyl-ethyl,
phase. Another object is to improve vapor phase
methyl-isopropyl, di-normal propyl, ethyl-iso
propyl and like ethers, methyl and higher pri
methods of reacting benzene and the like in the
presence of solid acid alkylation catalysts. A
further object is to increase the yield of desirable
mary alcohols, may be used. Either inorganic or
organic esters such as halides, ksulfates, phos
phates, borates, formates, acetates and the like
may be employed as alkylating agents. The al
alkylation products by reacting aromatic hydro
carbons with oleiins. Still another object is to
produce aromatic alkylation products having
kylating agent-.may be used in a pure or sub
superior properties, particularly as regards their
motor fuel characteristics. Other objects and 20 stantiallypure former as', mixtures of one or
kmore ,alkylating agents with or without other
advantages of the process of the invention will
materials which do?not interfere with the desired
be apparent from the following description.
Various methods of alkylating benzene and
As >catalyâtsfor the process, acids are used.
higher aromatic hydrocarbons have been pro
posed from time to time, but they have not been 25 Most preferably the chosen acid catalyst is em
ployed with a suitable carrier so that it may con
successful because of their inefficient conversion
veniently be used in solid form as packing for
of the starting materials »and/or their poor qual
ity of products.
It has now been found that
these disadvantages of prior alkylation methods
may be overcome by the use of an improved re
action system employing, preferably, more ad
tower or tube type reactors. Acids of phosphorus
are particularly suitable for this purpose, par
30 ticularlymixtures of ortho or meta phosphoric
acid or pyrophosphoric` acid with kieselg‘uhr or
other suitable clays or earths such as areV de
vantageous reaction conditions.
scribed in U..S. Patent 1,993,513. However, other
catalysts such as sulfuric acid, hydrogen fluoride
The new process may be applied to the alkyla
tion of a wide variety of aromatic hydrocarbons,
although when used for the production of motor
fuels or motor fuel components volatility consid
erations make it more advantageous to use lower
or the like adsorbed on porous supports. or as a
coating or ñlm on non-porous packing material
or the like may also be used in the process. It
boiling aromatic hydrocarbons, particularly ben
is also feasible to 'employ liquid acid alkylation
zene and toluene. Where such considerations
are of lesser importance, higher boiling com
catalysts inthe process.
pounds may be employed. ThusJ ethyl benzene,
vapor phase with a substantial excess of aromatic
the xylenes, propyl or isopropyl benzene, mes
itylene,-the butyl benzenes, the cymenes, and
The alkylation is preferably carried out -in the
hydrocarbons‘based on the alkylating agent used.
It has already been Suggested that in alkylating
homologues, naphthalene and its corresponding
benzene 1an excess be used to suppress formation
substitution products, and the like -may be used. 45 of higher alkylation products. Such excess ben
The source of the aromatic starting material is
zene is not suñìcient for most efficient reaction
-not important. The coal tar industry provides la
and it has been found desirable to use at least
convenient source of benzene, toluene, etc., but
and more preferably ñve to ten or more,
petroleum fractions containing these compounds,
mols `of the aromatic -hydrocarbons being al
particularly the highly aromatic fractions obtain 50 kylated
per mol Yof oleñn or equivalent alkylating
able by catalytic reforming or hydroforming, are
the process of the invention. In this
also useful. Such fractions may advantageously
way not onlylare undesirable side reactions such
be subjected to extraction with suitable solvents,
as the formation >of poly-alkylated products sub
for example, as described in U. S. Patent 2,114,524,
stantially eliminated, but. also high conversions
to increase the concentration of the aromatic
of the alkylating agent to valuable products are
The reaction is most advantageously carried
out under superatmospheric pressure; preferably
known but it has been found desirable to submit
at least one-tenth, and preferably at least one
fourth, of such aromatic hydrocarbon to treat
ment with sulfuric acid under the previously de
pressures of 200 toA 400 pounds per square inch
are used. The temperature and time of contact
which will be most desirable will depend upon the
scribedïconditions before returning it to the al
kylation unit. The treatment may be effected
along with or separately from the treatment of
the initial feed.
particular catalyst used and the alkylating agent
chosen. For the alkylation of benzene with ole
The attached drawing shows, diagrammatical
iins such as propylene in the presence of phos 10
ly, an assemblage of apparatus particularly
phoric acid, a temperature of about 200° C. to
adapted for producing cumene by reaction of
400° C., preferably about 250° C, to 300° C., and
-with propylene according to the inven
a hydrocarbon feed rate of about 0.1 to 0.8 gallon
tion. In the drawing only the more important
per hour per pound of catalyst are most advan
pieces of equipment are indicated for the most
tageous. This combination of reaction conditions
since the location of auxiliary equipment
gives results which are markedly superior with
pumps, valves, storage tanks, pressure-,
respect to yields, conversions and efficiency of op
temperature- and flow-regulating and measuring
eration to those obtained by other methods. ~
devices, heat exchangers, and the like will be evi
It has previously been considered that alkyla
to those skilled in the art. In the arrange
tion of aromatic hydrocarbons accomplished a
ment of the drawing, benzene from a source not
suiñcient purification -of the reactants and prod
shown,y is fed by line I to a mixer 2 in which it
ucts so that no other treatment was" necessary.
is contacted with sulfuric acid introduced via
However, to obtain» the -best results according to
line 3. The resulting mixture passes by line 4 to
the- present invention, it is desirable to treat the
settler 5 from which acid is taken olf by line 6
feed stocks used, especially the aromatic hydro
and returned to mixer 2 by lines l and 3. A
carbon, for removal of undesirable components,
of the acid maybe continuously or inter
particularly sulfur-containingoompounds such as
mittently withdrawn from the system by line 8.
thiophen'e, since otherwise these compounds un
The partially treated benzene is conducted by line
dergosimultaneous reaction and appear in the
product, materially reducing its quali-ty especially
for motor fuel use. Such treatment not only im
proves the quality of the product and-simplifies
its further processing, but also improves the ef
fective life ofthe catalyst in the process.
ï »For the ¿treatment of benzene, for example, it
is-‘preferredto use sulfuric acid of about 90% to
100% concentration' at a temperature of about 10°
Cl‘to. 60° C.,»-preferably about 98% concentration
at about20°~C.’ A ratio of acid to benzene above
1 tolO by volume is’desirable 'and ratios- of about
0.16:1 to 025:1 are preferred. The acid and ben
zene may be intimately contacted by agitation in
a mixer or other vessel, countercurrent now in a
9, together with fresh acid introduced by line I0,
30 to mixer II where a’ further intimate mixing is
effected. The resulting emulsion is taken by line
I2 to settler I3 in which the acid and hydrocar
bon phases are again separated.> The separated
acid is taken off byline I4 and a part returned
35 to the second reaction stage by line I5 while the
remainder is conducted to line 3 by line I6 to
furnish the partially spent acid for the first re
action stage. The thus-treated hydrocarbon is
fed by line I'I to mixer I8 which is supplied, con
40 tinuously or intermittently,` with a caustic from
line I9. The caustic-benzene mixture is fed via
.line 20 to settler 2l from which caustic is with
drawn by line 22. The withdrawn caustic is re
turned to mixer I8 for further use by lines 23 and
45 I'I, a part being withdrawn as necessary by line
tower which may or may not contain >packing to
promote-'intimate mix-ing, or. in any other suit
able manner. A contact time of acid with. ben
zenegof at least 3Yminutes, and more preferably/i
to -6 minutes or longer, is desirable. 'Contact in
a plurality ofreactionstages is advantageous in
reducingfthe amount of acid required for treat 50
been caustic-treated in theY same manner as the
acid-treated benzene introduced via lines 26 and
bon is Washed with a base such asl aqueous caus
duced via lines 26 and 29 and thus be caustic
ment of a givenv volume of aromatic hydrocarbon.
After thev acid treatment the aromatic hydrocar
24. The treated benzene is taken off by line 25
and mixed with propylene or propylene-contain
ing hydrocarbon which may advantageously have
2l. Alternatively, the propylene may be intro
treated along with the benzene. In either case
the mixture of propylene and treated benzene is
55 conducted by line 29 to reactors«30 which are
Merely treating the feed stocks before alkyla
shown as a bank of tubes through which the re
tion is not suíîicient to obtain the best results in
action mixture flows in parallel. The reactors
the present process. It has been found neces
contain Ygranules of phosphoric acid or other suit
sary to return to the sulfuric acid treating stage
acid catalyst not shown and are heated by
at least _a part of the excess unreacted aromatic 60
steam or other means also not shown. They are
hydrocarbon recovered from the product. - Since
preferably constructed to withstand pressures of
this aromatic hydrocarbon has been previously
the order of 1000 pounds per square inch. As
subjected to the sulfuric acid treatment as well
previously indicated, however, other forms of re
as to the alkylating conditions, it would be
thought that it would'be ideal material for re 65 actors may be used and the reaction mixture may
flow through> two or more reactors in series in
cycling directly to the alkylation and that fur
tie soda before being used in the alkylation step
of the invention.
ther treatment could not possibly be of advan
tage. It was surprising therefore' to discover that
by’ feeding a part of this stream to the sulfuric
acid treating unit instead of to the alkylation re
action, materially improved results, especially
with respect to product quality, were obtained.
The exact nature of allthe changes in the recycle
stead of through all reactors in parallel as shown.
Line 40 is provided -for introducingl steam or other
activating or controlling agent as may be required
to maintain the activity of the catalyst. l It may
also be used to introduce fresh-catalyst or cata
lyst-regenerating agents.v
f "
The reacted -hydrocarbon mixture, comprising
cumene and ,unreacted' ¿benzene and ‘_propylene
benzene or other aromatic hydrocarbon which
any inert materials introduced-„with the feed
are >responsible for ¿the improvedY results‘ïisV not 75
or otherwise, is withdrawn from the reactors by
line 3| and conducted to depropanizer column 32
Example IVk
in which the lower boiling components are sep
The ¿effect of sulfuric acid treatment of the
`benzene feed on the quality of the reaction prod
ucts was shown by the following comparative runs
made with coal tar >benzene which was reacted
with propylene in the presence of solid phosphoric
acid catalyst using a reaction temperature of 200°
arated and taken off overhead by line r3.3.l _The
remaining cumene and benzene are taken'oiï as
bottoms by line 34 and fed to debenzeni'zer col
umn 35 from which the unreacted _benzene is re
moved by line 36 and returned to the reaction by
line 31 after withdrawal of a part of line 38 for
C. to 250° C. and a pressure of 250 pounds per
square inch. The benzene in one case was used
treatment with sulfuric acid in mixersl 2 and Il
along with the fresh benzene feed. The cumene 10 directly and in the other case was treated with 25
poundsv of 98% sulfuric acid per barrel at about
produced is recovered by line 39.
The following examples further illustrate the
20° C.. The molar ratio of benzene to oleñn in
advantages ofthe process, although no limitation
each .case was 5:1 and the feed rate was 1800 to
2000 grams,n of ,hydrocarbon per liter of catalyst
on the invention is to be inferred therefrom as the
same principles may be applied to the reaction of 15 per hour.
the same or other aromatic hydrocarbons with
other alkylating agents.
Untreated Sulfuric
Example I
To show the advantages of a high ratio of ben 20
zene to alkylating agent, a series of test runs were
made with a solid phosphoric acid catalyst, using
Sulfur in the benzene (wt. per cent)_____ '
Oleiîns in the benzene (wt. per cent) _ __;
0. 47
0. 76
0. 09
Sulfur in the cumene (wt. per cent) _ _ _ __
0. 51
a reaction temperature of 200° C. to 250° C. and a
pressure of 250 pounds per square inch. The hy
drocarbon feed rate was 2000 grams per hour per
liter of catalyst for each of the different benzene
The'propylene conversions and cumene yields for
different periods of catalyst use were as follows:
propylene mixtures used. The following results
Mol ratio benzene to oleiin
Cumene in
the product
converted p
Per cent
Per cent
5-6 ___________ __
The effect of pressure on the reaction was de
termined in a series of tests using a solid phos
phoric acid catalyst and a feed containing 5 mols
87. 5
The products were tested as 5% and 10% blends
in 100 O. N. aviation gasoline with a ñnal tetra
40 ethyl lead content of 4.0 cc. per gallon.
VEaxrmple AII
of benzene per mol of propylene.
treated benzene
(Wt. %)
' a
(Wt- %)
1-2 _______ __
Using sulfuric acid
caétttsìf“ ‘Prowler Ci‘àuëâlâe Prowler@ @ditte
Using untreated
Gallons of cu~
mene produced
per pound of
were obtained:
Rating in 3-C engine test
Product from untreated
Feed rate
ärssugî lágrâìmsof
y T0931-
Sq àà)
P TOPY1 @ne
h.1`- Der
non 111
the feed
ggg. Pagar Cinthe
10% blend____. Iso-octane+l.l
° C'.
Per cent
2,0 0
8.2 20o-250
4, 000
blend ____ ._
Is -octane
Product from sulfuric `
acid-treated benzene
°° ° a
Is -
fle d
cc. of Iso-octane-l-Lö cc. of lead
lead tetraethyl.
Copper dich gum (mg./100 ml.)
Per cent
Per cem)
5‘7 blend ________________________ __
Example HI
103]o blend _______________________ ,_
Effect of temperature was determined in com
parative tests using a feed rate of 2000 grams of 60 Considering the small amount of cumene in these
blends, the effect of the sulfuric acid treatment of
hydrocarbon per hour per liter of catalyst space,
the benzene is seen to be remarkable.
a benzene to propylene mol ratio of 5 to 1, and a
pressure of 250 pounds per square ` inch.
propylene concentration in the feed was 8%--8.2% .
Cumene in ‘
the product
Per cent
Example V
Benzene was alkylated with isobutylene using
the same apparatus as that employed in the pre
ceding example. A catalyst temperature of 250°
yPer cent
l75°-200° C __________________________ __
60 70
200°-250° C __________________________ ._
The catalyst life under these conditions was of the
order of 80 gallons of cumene per pound of cata
C. Was used. The isobutylene conversion was
'70% when using a 4.9 to 1 ratio of benzene to
oleñn, and '76%, using a 6.2 to 1 ratio.
With beta butylene in place of isobutylene, the
conversion was 69% when using a .4.9 to 1 ben
zene to oleñn ratio. In all cases the product con
tained about 85% butyl benzene and was practi
lyst. At higher temperatures the life decreases. 75 cally free from oleñn polymers.
We claim as our invention:
arating unreacted benzene from the reaction
products and contacting the separated Vbenzene
- 1. A process of producing cumene which com
prises treating benzene with sulfuric acid of at
least 90% concentration at about 10° C, to 60° C.
>with concentrated sulfuric acid for a time suf
ñci'ent'to substantially reduce the thiophene con
for a time sufficient to reduce the thiophene con
tent thereof, and returning the sulfuric acid
tent thereof, admixing the treated benzene with
treated benzene to reaction with further isopro
propylene in the ratio of 3 to 10 mols of benzene
pylating agent.
per mol of oleñn and contacting the mixture un
’7. A process of producing an alkyl benzene
der a pressure of between 250 and 600 pounds
with a solid phosphoric acid catalyst at a tem 10 which comprises reacting a substantial molar ex
cess of benzene with an alkylating agent under
perature of 200° C. to 300° C. using a space Veloc
a pressure of at least 250 pounds per square inch
ity of 0.1 to 0.6 gallon of hydrocarbon per pound
in the presence of Ia solid acid alkylating catalyst,
of catalyst per hour, fractionating the resulting
separating unreacted benzene from the reaction
products to separate unreacted benzene, and re
products and contacting the separated benzene
turning at least 4a part of `the thus-recovered
with concentrated sulfuric acid for a time suf
benzene to said sulfuric acid treatment for fur
ñcient to substantially reduce the thiophene con
ther reactîon in the process.
thereof, and returning the sulfuric acid
2. A process of producing cumene which com
treated benzene to reaction with further alkylat
prises passing a mixture of benzene and propylene
ing agent.
in a molar ratio of at least 4 to 1 over a solid 20
8. A process of producing an alkyl benzene
which comprises contacting benzene with concen
trated sulfuric acid for a time suflicient to sub
phosphoric acid catalyst at a temperature of 200°
C. to 300° C. and a pressure of at least 250 pounds
per square inch, separating at least a part of the
stantially reduce the thiophene content thereof,
unreacted benzene from the products, contacting
and reacting a molar excess of the resulting ben
at least a part of said separated benzene with 25 zene 'With an alkylating agent in the presence of
sulfuric acid of at least 90% concentration, and
a solid acid alkylation catalyst under a pressure
returning the acid-treated benzene for further re
0f '250 to 600 pounds.
action in the presence of said phosphoric acid
9. A process of alkylating an aromatic hydro
carbon which comprises treating said hydrocar
3. A process of producing cumene which' com
with at least one-tenth of its Volume of con
prises treating benzene with sulfuric acid of at 80 bon
centrated sulfuric acid for a time sufficient to
least 90% concentration for a time suflicient to
materially reduce the thiophene content thereof,
reduce the thiophene content thereof, reacting
¿and reacting a molar excess of the resulting aro
the acid-treated benzene with propylene in the
matic hydrocarbon with an alkylating agent un
presence of a solid phosphoric acid catalyst under 35
der a pressure of at least 250 pounds per square
a pressure of at least 250 pounds using aV molar
inch in the presence of a solid acid alkylation cat
ratio of benzene to propylene of at least 4 to 1 and
alyst under alkylation conditions.
a temperature between 200° C. and 300° C., and
recovering the resulting cumene.
10. A process of alkylating an aromatic hydro
carbon which comprises treating said hydrocar
4.0 boniwith sulfuric acid of at least 90% concentra
prises contacting benzene with between one-tenth
tion at 10° C. to 60° C. for a time of at least 5
and one-fourth of its volume of sulfuric acid of
minutes sufiicient to materially reduce the thio
95% to 100% concentration for a period of 5 to 10
L1. A process of producing cumene which com
phene content thereof, reacting a molar excess of
the resulting aromatic hydrocarbon with an al
kylating agent in the presence of a solid acid al
minutes at about 10o C. to 30° C. sufficient to ma
terially reduce the thiophene content thereof,
neutralizing the acid-treated benzene, and con
kylation catalyst under alkylation conditions, sep
arating unalkylated aromatic hydrocarbon from
tacting a mixture of said benzene Vand an iso
propyl-ating agent containing at least three times
the stoichiometric amount of benzene to isopro
pylating agent with a solid acid alkylation cat
the reaction products, and returning at least a
part thereof to said sulfuric acid treatment.
alyst under alkylation conditions.
5. A process of producing cumene which com
11. A process of alkylating an aromatic hydro
carbon which comprises reacting a molar excess
of said hydrocarbon with an alkylating agent un
der a pressure of at least 250 pounds per square
inch in the presence of a solid acid alkylation
prises contacting benzene with concentrated sul
furie acid for a time suñîcient to substantially
reduce the thiophene content thereof, and react 55 catalyst under alkylation conditions, separating
ing a molar excess of the resulting benzene with
unalkylated aromatic hydrocarbon from the re
an isopropylating agent in the presence of a solid
action products and contacting at least a part
acid alkylation catalyst under a pressure of 250
thereof _ with sulfuric acid for a time sufficient
to’600 pounds.
to materially reduce the thiophene content there
6. A processof producing cumene which com 60 ofgand returning the thus-treated hydrocarbon
prises reacting a substantial molar excess of ben
to the alkylation reaction.
zene with an isopropylating agent under a pres
sure of at least 250 pounds per square inch in the
presence of a. solid acid alkylating catalyst, sep
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