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2,408,167
Patented Sept. 24, 1946
] UNITED STATES PATENT ,jOFFlCE-ii;
. ’ Phillips Petroleum Company,
a corporation of
Delaware
No' Drawing. Application October 14, 1944, ,
Serial No, 558,734
13 Claims. (01. 2601-671)
,. This inyention relates? to alkylation processes.
vdrying the -treated ,materi'all“ Activation {may
In one of-its more important embodiments the
invention relates to ‘the alkylationof aromatic
compounds by reaction with ole?ns in the‘pres
with an. aqueous solutionof, the; fhydrelyzable salt , e
preferably be accomplishedby contacting the, gel
at temperatures approximating the boiling-point
ence of solid catalytic’materials. vIn a speci?c
embodiment this’ invention relates to an improved
process for the production of mono-alkyl deriva- '
of ’ the "solution. ,In thisfrna'rinerga;lpartQ'of, the
metal, presumablyin the form of a .hydrousioxide
or loose hydroxide compound formed by hydroly
.tives of aromatic hydrocarbons; by reaction with
sis} is selectively adsorbedby the. hydrous silica,
low-boiling- ole?n hydrocarbons haying two to
.
.
about .six carbon. atoms perv molecule.
and :is ‘not vremovedby v‘subsequent washings . A
‘preferred catalyst of this type, at ‘present, is a
_10
It, is well known to. alky-late aromatic com- -
‘silica-alumina catalyst, prepared by treating a
pounds such as the more common aromatic hy
lwet or partially dried hydrous silica gel with an
drocarbons, phenols, acids, and thelike by reac
aluminum salt solution, and. subsequently wash
tion with various alkylating reactants such as
ing andv drying thetreated material. , However,
clef-ins, alkyl halides, alcohols, and the like in .15, catalysts oi .a' very similar nature,’ but;r.differi_ng
among themselves as to one .ormore speci?eprop
the presence ofcatalysts such as the Well-known
Friedel-Crafts catalysts, sulfuric acid, phos
phoric acid, hydro?uoric acid, and in some in‘
stances also with solid granular materials such
.a-s- clays.
Some of these catalysts are extremely 20
corrosive and also often quite expensive, particu
larly when high catalyst losses result from, un-.
desired side reactions.v Various clay~type cat
alysts ~avoid these dif?culties, but are not’ nearly
erties, may be prepared by using, instead of an
aluminum salt, ahydrolyzable salt‘of. a metal
selected from group IIIBV or3from groupIVAof
the periodic system and may be referred to in
general as ,‘fsilica-alumina. type”-jcatalysts. @As
.listed inf‘Modern‘ inorganic .Qhemistry?’ by. J.
~W-.' Mellor (Long-mans, Green gig-Co; -(l,939);re_
vised and edited by G.._D.» Parkes) ‘on page 118
as active in promoting the alkylation reaction .25 group VIIIB consists of boron, aluminum, gallium,
so that as a result it is necessary to‘use relatively
indium and thallium, ‘and group VIVA: consists of
high reaction temperatures with,them.- All of
titanium, ‘zirconium,v hafnium and thorium.
these materials are capable ofv promoting ole?n ' lVlfore particularly, salts" of indium and thallium
polymerization and have -~require_d-. careful regu
' inaddition to aluminum in group‘I'IlIB, may be
lation of reaction conditions to maintain alkyla 3.0 used, and salts of titanium, zirconuim}, and
tionas the predominant;'reaction.. Even» with
,thorium in group IVA may be used-to treat silica
suitable'precautions it is not uncommon, to ob
tain poor yields, high catalyst ‘consumption and
non-selective alkylation.
'
.
>
-_gel and ,to'prepare cat-alystsgof this general type.
Boron :in, the- form of boric acid’, or a soluble
'borate such‘ as-sodium 'borate, may also be ,in- '
I have now found that aromatic compounds 35 corporated with ‘silica gel." Whether preparcduby
can be reacted with ole?n hydrocarbons to form
this method or by some modi?cation thereof, the
high yields of monoalkyl derivatives by using as
catalyst will containla major portion as silica, and
a catalyst solid adsorbent materials synthetically
a‘ minor portion of metal oxide. ‘The minor por
produced and comprising a high proportion "of
tion of metal oxide, such as alumina, will gener
silica and ‘a small proportion of, an. oxide of a
metal of group IIIB or of group IVA of the peri
odic system. In general these catalysts are pre
..ally not be in excess of 1-0 per centbyweight; and
.willmore often, andgenerally more "preferably,
vbevbetween about~;0.1 and 1.5 orIZper-centby
pared by ?rst forming an acidic gel or jelly .by
weight.
In the above-outlined
_
‘procedure,
',_ 'the_'starting
reacting an ‘alkali metalsilicate with an excess
of an acid as by passing alkali: silicate solution 45-materia-ls are usually chosen from the‘water
into an excess ofaqueous mineral acid,‘ and al.
soluble silicates and. thecommercially available’
lowing the reaction mixtureto. set to a gel, wash
ing soluble material from the gel, treating or- ac
tivating the gel with an aqueous solution of a
.mineralacids. Sulfuric and hydrochloric acids
: are preferred. on economic I grounds, although.‘ any
acid may; be: used which will provide suitable. hy
suitable metal salt and subsequently washing and '-50 drogenjion concentration and form asilicahydro
2,408,167
4
3
gel of proper consistency. Thus, phosphoric,
ole?n polymerization reactions would adversely
acetic, nitric, and boric acids may be used in cer
tain instances. The gel formed should be acidic
and should be partially dried and washed free of
affect such an alkylation reaction rather than
promote the production of greater amounts of
monoalkyl derivatives of the aromatic com
pounds, since such a promoter would tend to in
crease the amount of ole?ns going to polymers.
In a preferred embodiment, my process oper
ates as follow: Hydrogen chloride in an amount
ranging from a trace up to a maximum of about
_ excess acid prior to activation, and the extent of
drying is carefully controlled since the eventual
catalyst activity is apparently somewhat depend
ent on the maintenance of the hydrous oxide
composition prior to the activation treatment.
The salt solution for activation may be prepared 10 1.0 per cent by weight is added tothe charge,
which comprises a major proportion of the com
from anyv water-soluble hydrolyzable salt of one
pound to be alkylated, for example, benzene, and
or more'of the metals indicated, with the sulfate
a minor proportion of ole?n. The ole?n used may
or chloride ‘being preferred. Other alternative
be a single ole?n or a mixture of ole?ns; the mole
salts include acetates and nitrates. The adsorp
ratio of benzene to ole?n in the charge may range
tion of the hydrous oxide by the silica gel proceeds
from 2:1 to 100: 1, but preferably should be in the
smoothly with hydrated silica gel, whereas vwith
range of about,5:1 to ‘10:1. Inert hydrocarbons
dried silica the adsorption and the activation may
be much less satisfactory; [Active catalysts are _ may or may not be present in the charge.
The charge is heated to the necessary reaction
preferably rinsed free of the salt solution and a
moderate concentration e?ect or "curing” may 20 temperature and is passed through a bed of gran
The ?nal washing then serves to remove unad-'
. ~ular silica-alumina catalyst under su?icient pres
. 'sure to maintain liquid phase. The optimum
sorbed salts and free acid, and the ?nal drying
which is performed at moderate temperatures
temperature depends on the nature of the partic
ular reactants, the activity of the catalyst, the
be obtained by partial drying of the rinsed gel. 7
produces hard, brittle "granules of gel containing
negligible quantities of compounds
25
other than
individual case.
silica and the metaloxide.
as 350° F. or as high as 700° F. _
generally be found to be between about 4 and “
However, if desired a catalyst
r
conditions so that the desired extent of conver
sion is obtained with a contact time of’ about 5
‘to 10 minutes. Since the activity of the catalyst
gradually decreases with continued use, it is nec
may be ground to a ?ne powder and incorporated
as a pa? of the ?owing reacting stream employ
ving any of the known so-called powdered cat- >
'
'
from 1 to 100 minutes, depending’ on ‘the various
conditions. Usually it will be desirable to adjust
or mass of granules of any suitable size which will ,
bons'.
'
- The contact time in the catalyst bed may vary
terial can be used in simple equipment as a bed
alyst techniques which are used in the petroleum
industry for cracking and reforming hydrocar
Ordinarily, however, the‘ pre
ferred temperature will be in the range of 400 to
600° F., ‘although it may in some cases be as low
The ?nal, drying should not be conducted at
too high a temperature, and generally a tempera
ture no higher than the initial reaction tempera
ture in'the subsequent alkylation reaction will be
found to be quite satisfactory. The catalytic ma
about 20 mesh.
quantity of hydrogen chloride present, the con
tact time, etc., and should be determined for’weach
a
'
' I have found that the activity of this speci?c
‘catalytic material is markedly enhanced by in-
essary gradually to increase the temperature, the
contact time and/or the vhydrogen chloride con
tent of the feed in order to maintain the desired
per-pass conversion. The presence of hydrogen
chloride materially increases the life of the‘cata
lyst.
After passing through the catalyst bed the
corporating inv the reaction mixture 2. small 4-45 hydrocarbon stream goes to a system of frac
tionators wherein it is separated into various frac
tions including unreacted ole?n (if any), un
small as 0.01 ‘per cent ‘of the reactants will be
reacted benzene, alkylate fraction or ‘fractions,
vsufficient to give adequate results, and in any
and residue. The unreacted benzene and ole?n
'event it will generally‘ not be necessary to employ
‘may be used to make up fresh hydrocarbon
more than about '1 per cent of the reactants by
amount of hydrogen chloride. Often amounts as
weight of hydrogen chloride. Preferably the re
action mixture is maintained substantially free
from moisture. 'If desired the hydrogen chloride
can beintroduced in combined form as an alkyl
charge.‘v
’
h
7
Obviously, many modifications may be intro
duced in this process. ' For example, a portion of
the effluent from the ‘catalyst bed may be recir
chloride, but even with this modi?cation the?
amount of alkyl chloride which is added need not
‘exceed that amount which is equivalent to the
culated with the fresh feed, thus decreasing the
small amount of hydrogen chloride just men
portions of sili'ca-aluminaof progressively in
creasing activity; portionwise addition of ole?n
tioned. Hydrogen halides other than hydrogen
chloride are relatively inferior when attempts are
made to substitute them for hydrogen chloride in
the present process. Hydrogen ?uoride attacks
and adverselya?ects the solid catalytic material
‘while hydrogen bromide and hydrogen iodide
tend to undergo undesirable decomposition re-"'
actions. The catalystswhich I use in my inven
tion‘ have been previously proposed for use as
ole?n polymerization catalysts and it has also
ole?n concentration in the feed to the catalyst
bed; the catalyst bed may consist of a series of
at points along the bed may be practiced; etc. >
The hydrogen chloride may be conveniently added
to the charge in the form of an alkyl chloride
instead of the free hydrogen ‘chloride itself, as
previously mentioned. This is especially applica
ble when the alkyl chloride is the same as would
be produced'by the reaction of hydrogen chlo
ride with the ole?n being used in the alkylation.
The following data illustrate advantages to be
‘gained from the practice of my invention.
been ‘found that hydrogen ‘halides and alkyl
In a series of runs, mixtures of benzene, propyl
"halides act as promoters for the polymerization 70
ene, isobutylene, isobutane, and a small amount
of ole?n hydrocarbons by these catalysts. This
of octenes, with and without approximately 0.1
fact, however, is believed to emphasize an un
per cent by weight of HCl, were passed contin
expected characteristic of the present invention
uously at temperatures ranging from 400' to 700°
since it is believed that a promoter which is known
F. and at pressures of 1000 to 1700 p. s. i. through
‘to increase the activity of such solid catalysts for
2,408,167.
'
6
> It willbe appreciatedthat theteachingsofxthis‘
a "bed .of 14-40. gmesh dehydrated. silicaealumina
catalyst. The e?l'uent mixture from‘ the catalyst
disclosure may be .followedand applied by one
skilledin the artxin connection with the practicev
of‘ numerous speci?c applications ‘and modi?ca
examined. The. data pertaining to these experi-'
ments :arepresented 1n the; following table:
5. t1ons :of my invention. Therefore the invention.
bed
each case was collected and. subsequently
. With H'Ol (0.1%)
Withoutv H01
'Run' 1 ‘Rnn'2 'Run 3 Run 4 Run 5 Run‘o" Run”?
Pressure, psig _________________________________ ..' _____________________ _'_ _______ __
'Eemp., °'F.f(avg.)_
__ _ _ _
_.__
1', 000
. 1, 100
1, 100‘
504.
l, 000
502
1, 500'
410
518
8Z6
4. 7 '
482.
541.
0..
4.3
11. 6
11:1
____
.................. __
30.0
14.0
-0. 0.
5. 2
30.0 ‘
5. 4
2. 7
3.0
2. 8
3. 6
3.3
3.2
2. 7
9. 2
25. 0'
30. 4
37. 8‘
26. U‘
'63. 5:
Flow rate, vol./vo1. catalyst/hm
1
Fresh feed.___
Recirculation
Contact time, mi
1, 500
_ _ ._
__________ __
7
Composltionof’fresh feed‘, wt. per cent:
‘
O. 0"
7. 0
1, 700
.
70
'
30.10
12. 8
5. 5'
7; 7
30.0
10. 9
0. 0
7.8
’
Propylene_ ____________________________ __; ............................. -Isobutylene _ l _ . _ _ _ _ _ . . . _ . _ _
. _ _ _ _ ..
,
.
2. 6
4. 5 I
ISobIlt?ne ____ -_
' 26. 0
25. 1 '
BGDZBDEL___--
66.4
67. 3
67. 7
64. 3;
48. 5
1. 3
1. 3
_ 1. 3
0.0
0. 0
100. 0
100. 0
Octenes- - .
Total ____________________________ __
100. 0
Benzene/ole?n rnol ratio infresh feed_ -_ -__
100. 0 . .100. 0
6. 4
Alkylate 1 yield, wt. per cent in e?iuent ______ __
..._
Alkylate 1' yield, Wt. per cent of. reacted ole?n ___________________________________ -_
Alkylate l composition, wt. per cent:
-
Lighter than cumene (194-2930 F.)_
Cumene cut (293—318°'F;)__.___.__Tert..butyl benzene cut (318-356° F
14. 4 I
248
_
3. 2
32. 2
37. 4
‘
Residue (>356° F.) __________________ _.
Total
6. 6
7. 0
14.0 '
13.6
233
248
7. 5
4, (1 .
5. 8
1. 9
4. 9
15.0
5. 2
42. 6
27. 7
48. 0.
21.0
31. 8
297. 5
27. 2
29. 1
24. 8v
16.0
100. O.
100. 0
100. 0
100. 0
92
92
91
69v
88?
94
'64
92
68
9275
78
62
.95
30
51 _
v51
24
O. 0
1002.0
4. 1
14.3
41-9
14.8
14.9
163
185'
l0. 3
3'; 1
40. 4'
25. 6r .
33. 5 -
100. 0
'27. 8
63. 9
100;.0 '
110
40.3 ,
28. 7 -
4. 9
’
0. .7 ‘
2. 3
7. 1
182
3;"4
-
41. 6'
30.5
23.‘?
24.8
100. 0
100. 0
Conversions, wt. per cent:
1
' Propylene converted _____ _.
Isobutylene converted.“
Reacted CaHu to cumene_ .__
Reacted i-ClHs to 't-butylbenzen
__-._
_-.
_
_.
66
~
Inspection oflightalkylate(combined cumene-t-butylbenzene fractions):
'
17
.
Unsaturates content, wt. per cent ____ ..' _______ .___ __________________________ ..
2. 6
- Autiknock blending values 3-0 (+4 ml. TEL, Rich) IM‘EP _________________ .1 -._ _____
4. 9
2 477
5. 5
18
_l_____- _';-__.~__
86
_
97'
65‘
28
‘39
'
12v
'96‘
90
51
,
11
250
3-363. ______,_ ______ __
1' Free of benzene and lighter materials.
1 Tested in a blend containing 5% of light alkylate composited from several runs.
1 Tested in a blend containing 10% of light alkylate composited from several-runs.
The data in this table show that'the presence
of H01 substantially reduces the temperature at
is not to be unduly limited- by thelspeci?c details
fractions, respectively, is considerably higher,
by weight'of the reactants of hydrogen chloride
discussed in this ‘disclosure and various speci?c
which conversion is ‘effected. Thus, in runs 1, 2, 40 modi?cations can be practiced without departing
from the spirit of the disclosure'or fromthe scope
and 3, wherein HCl was present, more than 90
of'the claims.
per cent of the total ole?n was converted at ap
I claim:
proximately 500° F.; whereas in runs 4, 5, 6, and
1. An improved process for the reaction of hens
'7 temperatures approaching ‘700° F. were neces
zene-with propylene 'to formiisopropyl benzene,
sary to produce high ‘total-ole?n conversion in
which comprises passing a; hydrocarbon mixture
the absence of HCl. Furthermore, the percent
comprising propylene'and a molar vexcess of hen
age of converted propylene and isobutylene re
zene together with not more than about 1 per cent
acting to form‘cumene and tertiary butyl benzene
and the ole?n content of these fractions is lower,
in‘ the absence of HCl. The relatively higher
through a bed of a solid granular catalyst'at a
reaction temperature not greater than about 600°
F. and at a ‘reaction pressure to promote union
of said propylene and: benzene“ to form isopropyl
yield of tertiaryibutylbenzene fractions in runs 1,
2 and 3 ‘shows'that the alkylation reaction‘is fa
benzene; said granular catalyst comprising silica.
vored by the presence of HCl even when the ole
and not more than about 2 per cent by weight'of
?ns are especially easily polymerized, such as
isobutylene. Thus, the presence of HCl greatly 55 alumina and prepared by passing an. aqueous a1
favors the simple addition reaction between ben
zene and ole?n and. is accordingly an important
kali silicate into an excess of» an aqueous mineral
acid and allowing the mixture to set‘to a'silicic
acid gel, washing said gel with water and only
advantageous factor in the synthesis of speci?c
partially drying same to form a hydrous acidic
compounds from speci?c reactants.
The antiknock data show that the 3-0 (+4.0 60 silica gel, contacting said silica gel with an aque
ous solution of a hydrolyzalbl'e alumi-nmnsaltat
ml. TEL, Rich) blending value of the composite
light alkylate produced in the presence of H01
is over 30 per cent higher than that produced'in
, a temperatureIv approximating 'thexboiling point of
the absence of such a promoter. The data show
further‘ that the yield of light alkylate based on
ole?n converted was 4.0 to 100 per cent higher
when HCl was present. These" are very impor
tant factors in'the'manufacture of aviation gaso
activated gel with water to removefreeacid and
salts, and ?nally drying" said activated and
washed gel ‘to form. hard granules.
2. An improvediprocess for the production of
line components.
7
said solution to activate said gel, washing said
an alkyl benzene from av low-boiling ole?n and
benzene, which comprises passinga hydrocarbon
My process offers the additional advantages, 70 mixture comp-rising a low-boiling: ole?n and a
molar excess of [benzene together with not more
due to the lower reaction temperature, that less
than about 1 per cent by weight of the reactants
expensive equipment is required in commercial
of. hydrogen chloride througha bed of a solid
operation and that the catalyst life is increased
granular catalyst at a reaction temperature not
by the reduced rate of deposition of carbonaceous
75 greater than. about'700-°' F. and asuperatmospher
material.
.
'
.
2,408,167
8
7
id pressure to promote union of said ole?n and
benzene to form a corresponding alkyl benzene,
said granular catalyst comprising silica, and not
more than about 2 per cent by weight of alumina
and prepared by passing an aqueous alkali sili
cate into an excess of an aqueous mineral acid
and allowing the mixture to set to a silicic acid
gel, washing said gel with water and only par
tially drying same to form a hydrous acidic silica
gel, contacting said silica gel with an aqueous 10
solution of a hydrolyzable aluminum salt at a
temperature approximating the boiling point of
said solution to activate said gel, washing said
activated gel with water to remove free acid and
solid granular catalyst under conditions of tem
perature and pressure such as to promote union
of said low-boiling ole?n and benzene to form a
corresponding alkyl benzene, said granular cat
alyst comprising silica and a minor amount of
alumina and prepared by reacting an alkali sili
cate with an excess of a mineral acid to form a
silicic acid gel, washing said gel with water and
only partially drying same to form a hydrous
acidic silica gel, contacting the resulting silica
gel with an aqueous solution of a hydrolyzable
aluminum salt to activate same by adsorption of
hydrous aluminum oxide thereon, and subse
quently washing and drying the resultant acti
salts, and ?nally drying said activated and 15 vated material to form said granular catalyst.
washed gel to form ‘hard granules.
7. An improved process for the production of
3. An improved process for the Production of -
a monoalkyl derivative of an alkylatable aromatic
hydrocarbon, which comprises passing a hydro
a monoalkyl derivative of an alkylatable aro
matic hydrocarbon, which comprises passing a
hydrocarbon mixture comprising an ole?n hy
carbon mixture comprising an ole?n hydrocarbon 20 drocarbon of not more than 6 carbon atoms per
molecule and a molar ‘excess of an alkylatable
of not more than 6 carbon atoms per molecule
aromatic hydrocarbon together with not more
and a molar excess of an alkylatable aromatic
than about 1 per cent by weight of the reactants
hydrocarbon together with not more than about
of hydrogen chloride through a bed of a solid
1 per cent by weight of the reactants of hydrogen
chloride through a bed of a solid granular cata 25 granular catalyst under conditions of tempera
ture and pressure such as to promote union of
lyst under conditions of temperature and pres
said ole?n and said aromatic hydrocarbon to
sure such as to promote union of said ole?n and
form a corresponding monoalkyl derivative
said aromatic hydrocarbon to form a correspond
ing monoalkyl derivative thereof, said granular
thereof, said granular catalyst comprising silica
catalyst comprising silica and not more than 30 and a minor amount of an oxide of a metal se
lected from groups IHB and IVA of the periodic
about 2 per cent by weight of alumina and pre
system and prepared by reacting an‘ alkali sili- ‘
pared by passing an aqueous alkali silicate into
an excess of an aqueous mineral acid and allow- ’
cate with an excess of a mineral acid to form a
'silicic acid gel, Washing said gel with water and
ing said gel with water and only partially drying 35 only partially drying same to form a hydrous
acidic silica gel, contacting the resulting silica
same to form a hydrous acidic silica gel, contact
ing the mixture to set to a silicic acid gel, wash
ing said silica gel with an aqueous solution of a
hydrolyzable aluminum salt at a temperature ap
gel with an aqueous solution of a hydrolyzable
salt of a metal selected from groups H13 and IVA
of the periodic system to activate same by adsorp
p'roximating the boiling point of said solution to
activate said gel, washing said activated gel with 40 tion of a hydrous oxide of said metal thereon, and
subsequently washing and drying the resultant
water to remove free acid and salts, and ?nally
activated material to form said granular catalyst.
drying said activated and washed gel to form
8. An improved process for the production of
hard granules. ~
'
>
a monoalkyl derivative of an alkylatable aromatic
'4. ‘The process of claim 3 in- which said min
hydrocarbon, which comprises passing a hydro
eral acid is sulfuric acid and in which said alum
carbon mixture comprising an ole?n hydrocarbon
inum salt is aluminum sulfate.
of not more than 6 carbon atoms per molecule
5. An improved process for the production of
a monoalkyl benzene from a low-boiling ole?n
and benzene, which comprises passing a hydro
carbon mixture comprising a low-boiling ole?n
and a molar excess of benzene together with not
more‘ than about 1:per cent by Weight of the re
actants of hydrogen chloride through a bed of a
solid granular catalyst under conditions of temg
and a 'molar excess of an alkylatable aromatic
hydrocarbon together with not more than about
1 per cent by weight of the reactants of hydrogen
chloride through a bed of a solid granular cata
lyst under conditions of temperature and pres
sure such as to promote union of said ole?n and
said aromatic hydrocarbon to form a correspond
perature and pressure such as to promote union 55 ing monoalkyl derivative thereof, said granular
catalyst comprising silica and a minor amount of
of said low-boiling ole?n and benzene to form a
corresponding alkyl benzene, said granular cata
an oxide of a metal selected from group IIIB of
lyst comprising silica and a minor amount of
alumina and prepared by reacting an alkali sili
the periodic system and prepared by reacting an
silicic acid gel, washing said gel with water and
only partially drying same to form a hydrous
acidic silica gel, contacting the resulting silica
and only partially drying same to form a hydrous
acidic silica gel, contacting the resulting silica
alkali silicate with an excess of a mineral acid to
cate with an excess of a mineral acid to form a 60 form a silicic acid gel, washing said gel with Water
gel with an aqueous solution of aluminum sulfate
to activate same by adsorption of hydrous alumi
num oxide thereon, and subsequently washing
and drying the resultant activated materialto
form said granular catalyst.
-
gel with an aqueous solution of a hydrolyzable
salt'of a metal selected from group IIIB of the
periodic system'to activate/same by adsorption
of a vhydrous oxide of said metal thereon, and
subsequently washing and drying the resultant
activated material to form said granular catalyst.
6. An improved process for the production of
9. An improved process for the production of
a monoalkyl benzene from a low-boiling ole?n 70 a monoalkyl derivative of an alklatable aromatic
and benzene, which comprises passing a hydro
hydrocarbon, which comprises passing a hydro
carbon mixture comprising a low-boiling ole?n
carbon mixture comprising an ole?n hydrocar
and a molar excess ‘of benzene together with not
more than about 1 per cent by weight of the re
bon of not more than 6 carbon atoms per mole
cule and a molar excess of an alkylatable ‘aro
actants of hydrogen chloride through a bed of a
matic hydrocarbon together with not more than
2,408,167
10
about 1 per cent by weight of the reactants of
hydrogen chloride through a bed of a solid granu
lar catalyst under conditions of temperature and
pressure such as to promote union of said ole?n
cess of an aqueous mineral acid and allowing the
mixture to set to a silicic acid gel, washing said
.~ gel with water and only partially drying same
and said aromatic hydrocarbon to form a cor
said’silica gel with an aqueous solution of a hy
drolyzable aluminum salt at a temperature ap
responding moncalkyl derivative thereof, said
granular catalyst comprising silica and a minor
amount of an oxide of a metal selected from group
IVA of the periodic system and prepared by re
acting an alkali silicate withan excess of a min
eral acid to form a silicic acid gel, washing said
gel with water and only partially drying same to
form a hydrous acidic silica gel, contacting the
to form a hydrous acidic silica gel, contacting
proximating the boiling point of said solution to
activate said gel, washing said activated gel with
Water to remove free acid and salts, and ?nally
10 drying said activated and washed gel to form
hard granules.
'
V
'
13. An improved process for the alkylation of
‘an alkylatable organic compound by reaction
with an ole?n hydrocarbon, which comprises
resulting silica gel with an aqueous solution of
a hydrolyzable salt of a metal selected from 15 passing a reaction mixture comprising an ole?n
hydrocarbon and a molar excess of an alkylatable
group IVA of the periodic system to activate same
organic compound together with not more than
by adsorption of a hydrous oxide of said metal
about 1 per cent by weight of the reacants of hy
drogen chloride into contact with a solid cata
granular'catalyst.
'
20 lytic material under conditions of temperature
and pressure such as to promote union of said
10. The process of claim 7 in which isopropyl
ole?n and said alkylatable aromatic compound
benzene is produced from propylene and benzene.
to form a corresponding monoalkyl derivative
11. The process of claim 7 in which a butyl
thereon, and subsequently washing and drying
the resultant. activated material to form said
benzene is produced froma butylene and ben- ‘
thereof, said solid catalytic material comprising
25 silica and a minor amount of an oxide of a metal
selected from groups IIIB and IVA of the pe
12. An improved process for the reaction of
zene.
benzene with isobutylene to form tertiary butyl
benzene, which comprises passing a, hydrocarbon
riodic system and prepared by reacting an alkali
silicate with an excess of a mineral acid to form
a silicic acid gel, washing said gel with water
mixture comprising isobutylene and a molar ex
cess of benzene together with not more than 30 and only partially drying same to form a hydroul
about 1 percent by weight of the reacants of hy
acidic silica gel, contacting the resulting silica
drogen chloride through a bed of a solid granular
gel with a aqueous solution of a hydrolyzable salt
of a metal selected from groups IIIB and IVA of
catalyst at a reaction temperature not greater
than about 600° F. and at a reaction pressure to
the periodic system to activate same by adsorp
promote union of said isobutylene and benzene 35 tion of a hydrous oxide of said metal thereon, and
subsequently washing and drying the resultant
to form tertiary butyl benzene, said granular cat
activated material to form said granular cata
alyst comprising silica and not more than about
lyst.v
2 per cent by weight of alumina and prepared
by passing an aqueous alkali silicate into an ex
HAROLD J. HEPP.
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