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JURY 15, 1946“
gas. KUHN, JR
'
' 2,403,930
ALKYLATION PROCESS
’ Filed Sept. 24, 1942
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STANDARD FREE ENERGY
1'19 9'42
0F REDUCTION OF M57211.
1
84L 7" PEI? GRAM £00m: -
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Law Of‘ FREE ACID
REDUCTION peooucr w.
.
IVE/6H7‘ PERCENT W540 -—
' 2500
3.;
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OFALKJ/AATE 590M 77/5
I
REACTION OF ISOBUTANE
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WITH ETHI/LEA/E //v THE
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PRfSENCé' 0F HYDRO/‘Z. 00 -
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23.2 40
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I'VE/6H7’ Pf'RCEA/T V/EZD 0F ALfO/LATE
BASED ‘ON'ETHVLENE CHARGED.
Carl .5‘. Kuhn, J1.
INVENTOR
BY PWQyM/MM/
@ZZZ/mbg
Patented July 16, 1946
2,403,930
UNITED STATES PATENT OFFICE
2,403,930
ALKY'LATION PROCESS
Carl S. Kuhn, Jr.,, Dallas, Tex., assignor to Socony-l
Vacuum Oil Company, Incorporated, New York,
N. Y.,, a corporation of New York
'
Application September 24, 1942, Serial No. 459,525
20 Claims. (Cl. 260-—G83.4)
1
2
This invention relates to the catalytic alkyla
pylene to the ethylene and the subsequent alkyla
tion of isoparaf?ns with olefins. More particu
tion of this ole?n mixture has been proposed with
the thought that the alkylation of the propylene
would simultaneously induce the alkylation. of
larly this invention relates to such a catalytic al
kylation process in which ethylene is the ole?nic
alkylating agent used.
Many catalytic processes for the alkylation of
isopara?inic hydrocarbons with ole?ns have been
developed in recent years. Such processes have
the ethylene‘. While some improvement in ethyl
ene alkylation is obtained, the increase in yield
of ethylene alkylate by this method is limited and
the process is complicated by the problem of
been particularly concerned with the alkylation
handling a mixture of two clef-ins.
of such isoparaf?ns as isopentane and isobutane 10
The primary object of my invention is to de
velop a catalytic process fer the alkylation of such
isoparaf?ns as isobutane, isopentane, and iso
hexane with ethylene to produce allrylates which
with such ole?nsv as propylene and butylene to
produce branched-chain hydrocarbons boiling in
the gasoline range and having a high octane
5
value. Typical of the catalytic agents which
are of value as high octane aviation and motor
have been used are the Friedel-Crafts catalysts, 15 fuel ingredients. More speci?cally an object of
especially aluminum chloride, boron trifluoride
and its complexes, sulphuric acid and hydro?uoric
acid and the like. The acid catalysts, sulphuric
acid and hydrofluoric acid, have received par
my invention is to develop such a catalytic alkyla
tion process in which hydro?uoric acid is the ef
fective catalytic agent used.
ticular attention as catalysts for the alkylation
Hydrofluoric acid offers many advantages as
the catalytic agent for such an alkylation process
reactions of the type mentioned above. Hydro
because of the ease with which it may be sep
fluoric acid has proven especially eliective as the
alkylation catalyst as disclosed in my copend
arated ‘from the reactants and products, and re
covered for reuse. Hydro?uoric acid is also ad
vantageous because of its noncorrosive action on
ing application Serial No. 326,097 filed February
25 steel equipment, and its low speci?c gravity en
21, 1940.
More recently various attempts have been made
abling ready agitation and emcienli contacting
to improve the effectiveness of the various al
of the immiscible acid with the hydrocarbon re
v‘kylation catalysts by the addition of certain salts
action mixture. As set forth in my aforemen
'of limited solubility or by the addition of cer
tioned copending application, the hydro?uoric
tain oxides of elements selected from group 5 of 30 acid is used either in the anhydrous form or as
the periodic system. Certain mercury salts alone
a concentrated aqueous acid of at least 90 percent
or in admixture with other metallic salts have
been claimed as giving improved results. Un
fortunately the information as to the salts which
should be used, the quantities of these salts, the
particular catalysts with which they are effective,
and the result to be obtained with their use is
too general and inde?nite to be of much assist
ance in predicting their utility in a speci?c al
kylation process.
Alkylation with ethylene as the ole?nic react
ant has proven particularly troublesome. While
concentration.
My invention is based upon my discovery that
the alkylation of isopara?ins with ethylene utiliz
butylene may be readily used as the ole?nic re
actant with any of the catalysts, and propylene
may be used as the ole?nic reactant where hy
dro?uoric acid is the catalytic agent used, satis
factory yields in the alkylation of isoparafiins with
ethylene have not been possible up to the present
time at least under the ordinary conditions of
temperature and pressure. The addition of pro
ing hydrofluoric acid as the catalytic agent may
be accelerated by the addition of certain metallic
salts of inorganic acids, which salts are charac
terized by being easily reducible. _I have found
that where hydro?uoric acid is the effective cata
lytic agent used for the alkylation, such factors as
solubility or insolubility of the salt in the acid,
and the periodic classification of the metallic
group are of no value in predicting the promo
tional effect of the metallic salt upon the al
kylation reaction. For example, the soluble mer
curic cyanide and the insoluble mercurous sul
phate are both effective promoters. On the other
hand the insoluble mercuric chloride and the
soluble potassium sulphate or sodium ?uoride are
of absolutely no value as promoters. Some of the
2,403,930
3
salts of mercury, for example, are excellent pro
moters, such as the cyanide and sulphate, while
the chlorides, not only fail to accelerate the re
action, but actually retard it.
I have found that the metallic salts of inor
ganic acids, whose standard free energies of re
duction to metal and non-aqueous acid are more
4
ethylene were added continuously over a period
of 140 minutes. During the addition of ethylene
a slight temperature rise occured and cold kero
sene was circulated through the cooling jacket to
maintain the temperature of the reaction mixture
at 20° C. After the addition of the ethylene was
completed the agitation was discontinued and
the mixture allowed to separate into two liquid
negative than about -8,000 calories per gram
phases. The upper phase consisted of the hydro
equivalent of free acid reduction product will
carbon reactants and the lower phase consisted
promote the alkylation of isoparaffms with ethyl
principally of the hydrofluoric acid. The hydro
ene. Typical of such salts are mercuric cyanide,
?uoric acid was withdrawn and the hydrocarbon
mercuric sulphate, and copper sulphate. Of these
phase was washed with water, dried, and frac
salts mercuric cyanide is particularly effective as
tionated to recover the material distilling above
a promoter.
My invention, therefore, broadly consists in the 15 25° C. The yield of alkylate ‘was 67.6 percent
based ‘on the Weight of ethylene charged and 97
treatment of an isopara?lnic hydrocarbon of the
percent by weight of this alkylate product dis
type of isobutane, isopentane, and isohexane with
tilled below 125° C. This product was composed
ethylene or with normally gaseous hydrocarbon
primarily of branched-chain hexanes and octanes
mixtures consisting predominantly of ethylene,
of high antiknock value.
preferably at normal or moderately elevated tem
peratures in the presence of a hydro?uoric acid
Example 2
catalyst and an easily reducible metal salt whose
A mixture of 312 parts by weight of concen
standard free energy of reduction to metal and
non-aqueous acid is more negative than about
trated hydrofluoric acid to which had been added
—8,000 calories and preferably more negative 25 55.8 parts by weight of mercuric sulphate and 581
than about —12,500 calories per gram equivalent
parts by weight of i-sobutane were placed in a re
actor as described in Example 1. To this agitated
of free acid reduction product. The metal salt
mixture was added 56 parts by weight of ethylene
forming group of such easily reducible salts is
over a period of 130 minutes. The temperature
characterized by the fact that the metal lies be
was maintained at 20° C. as in Example 1 and
low’ hydrogen in the electromotive force series.
after the reaction was completed the phases were
As mentioned above not all the salts of such
metals are effective, but only those having high
separated and recovered as described in Example
1. The yield of alkylate was 108.0 percent based
negative free energies of reduction. Examples of
on the weight of ethylene charged and 91 percent
salts which exert a promotional effect on the
'alkylation with ethylene are mercuric cyanide, 35 by weight of this alkylate distilled below 125° C.
mercuric sulphate, mercuric phosphate, mer-L
Example 3
‘curous sulphate, cupric sulphate and silver
cyanide.
The alkylation reactions are generally carried
out under suf?cient pressure to maintain the re
56 parts by weight of ethylene were added to
a mixture of 302 parts by weight of hydro?uoric
acid containing 50.2 parts by weight of mercuric
phosphate and 581 parts by Weight of liquid iso
actants in the liquid phase, in the manner usually
followed in alkylation reactions. In general, the
butane in a jacketed reactor in the manner de
conditions used for carrying out my process for
scribed in Example 1. The yield of alkylate was
alkylation with ethylene in the presence of hy 45 124.0 percent based on the weight of ethylene
' drofluoric acid, are the same as for the conven
charged ‘and of this alkylate 67 percent distilled
tional alkylation practice with this catalyst. The
0 improved results are e?ected by the addition of
a small quantity, preferably about 1 mol percent,
[of the metallic salts either as a solution or as
a ?nely divided suspension in the acid. If desired
the salt may also be introduced in the form of an
aqueous suspension or solution, provided that the
amount of water added is small, 'so that the con
centration of hydro?uoric acid does not fall below
about 90 percent as disclosed in my aforemen- '
tioned copending application. Addition of the
salt as a suspension in the hydrocarbons is also
possible.
' below 125° C.
Example 4
56 parts by weight of ethylene were added over
a period of 120 minutes to a mixture of 310 parts
by weight of hydro?uoric acid to which had been
' added 25.4 parts by weight of silver cyanide, and
594 parts by weight of liquid isobutane in a jack
eted reactor in the manner described in Example
1. The yield of alkylate was 125.7 percent based
on the weight of ethylene charged and 86 percent
by weight of this alkylate distilled below 125° C.
Example 5
For the purpose of illustrating my invention 60
56 parts by weight of ethylene were added over a
the following speci?c examples are given. It is to
’ period of 110 minutes to a mixture of 298 parts by
be understood, however, that the invention is not
weight of hydrofluoric acid to which had been
to be limited by these examples, since variations
'_ therefrom may obviously be made by those skilled
added 94.5 parts by Weight of mercurous sulphate,
in the. art without departing from the scope of 65 and 581 parts by weight of liquid isobutane in a
jacketed reactor in the manner described in Ex
my invention.
Example 1
ample 1. The yield of alkylate was 178 percent
based on the weight of ethylene charged and '73
A mixture of 303 parts by weight of concen
percent by weight of this alkylate product dis
trated hydro?uoric acid (99 percent concentra
tilled below 125° C.
70
tion) to which had been added 30.3 parts by
Example 6
weight of copper sulphate, and 581 parts by
weight of liquid isobutane was placed in a reactor
provided with a suitable agitator and cooling
55 parts by weight of ethylene were added over
a period of l00'minutes to a mixture of 303 parts
jacket. The agitator was placed in operation and
to the agitated mixture 56 parts by Weight of 75 by weight of concentrated hydrofluoric acid to
23,403,930
' 6
‘which had been added 48.0 parts by weight of
mercuric cyanide, and 581 parts by weight of liq
these insoluble salts give the best results when
‘from 1.0 to 2.0 molipercent of the salt is used. In
order to obtain the desired sheet at least 0.5 mol
uid isobutane in a jacketed reactor in the man
ner described in Example 1. The yield of alkyl
ate was 180.5 percent based on the weight of
percent should be added.
.
In order to illustrate the effect of temperature
upon the reaction the following series of exam
ples ‘were performed. In these Examples 9 and
10 the quantites of reactants used, the conditions
ethylene charged and 78 percent by weight of this
alkylate product distilled below 125° C.
In order to show the effect of varying the con- >
centration of the salt upon the yield of alkylate
product the experiment. of Example 6 was re
and the procedure followed were the same as
used in Example 6, except that the temperature
peated using 1.90 mol percent of mercuric cyanide
and 0.25 mol percent of mercuric cyanide in Ex
amples '7 and 8, respectively, instead of the 1.25
mol percent used in the previous examples.
. at which the reaction was carried out was varied
as indicated in the following chart. However,
the reaction was carried out in a steel, high pres
sure autoclave so that su?icient pressure could be
maintained to keep the reactants in the liquid
The procedure followed was the same as that
phase. _In Example 11, the procedure of Exam
used in Example 6, except that the weight of mer
ple 7 was followed except that the reaction was
curic cyanide was varied as shown in the follow
ing chart wherein the quantities‘ of reactants,
I carried out at a lower temperature. ~
Mercuric
‘
Weight per
Exam- Isobutane, Ethylene, Hydro?uoric cyanide, Tam
gegfkyilelg
1e
parts by parts by acid per
mol per
0CD" boased 7n“ t
o.
' wt.
wt.
by wt.
cent of
EL F
,
'
'
9 ..... ...
10 .... .._
6 ..... -.
7 ..... -_
11 .... --
581
581
581
581
581
56
56
56
56
56
303
303
303
303
303
1. 25
1. 25
l. 25
1. Q0
1. 90
h ‘i
w '
8% y ene
added
125
58
20
20
-—3. 5
33- 8
128. 7
180. 5
105. 5
80. 0
From these experiments it can readily be seen
that the most favorable results are obtained by
the use of temperatures between about -l0° C.
and about 80° C. The lower yield at —3.5° C.
Weight per
Hydro- cent yield‘ of
in Example 11 as compared with the yield at 58°
?uoric Ethylene, £4332“ alkylate' 35 C. in Example _10 was due principally to the
acid, parts
by Dinghy’
based on
parts by
wt.
wt
we1ghtot
higher salt concentration in the former case.
wt.
'
ethylene add
The results at 20° C. indicate that a 'drop of
approximately 40 percent in yield is to be ex
products and'yields are tabulated for easy com
parison.
E
1
xglmp
e
0'
ltsobu'
aftus’a'?
p wt 7
'
ed
581
581
581
303
303
303
5c
55
56
75. 7
48. 0
9. 5
_
g
105.5 40
1.870. 5
G6. 0
pected due to this increase in concentration,
and the yields obtained at 58° C. and -3.5° C.
, would seem to be of about the same order after
adjustment for the difference in concentration is
Mercuric cyanide was chosen as the promoter
made. vAt temperatures much above 60° C., and
in these studies because it is soluble in the hydro
particularly above about 125° C., the yield falls
?uoric acid catalyst. The effect of varying the 45 off very rapidly. The drop in yield below 0.0" C.
concentration of a soluble promoter may be de
is apparently much less rapid, but this drop, plus
termined more accurately, since the concentra
the increased d'iiiiculty in carrying out the ex
tion of the promoter remains unaffected} by the
eihciency of the agitation. An insoluble pro
' othermic reaction at low temperature levels,
“would. render temperatures, much. vbelow about
moter, on the other hand, will tend to settle to 50 -~l0° C. undesirable. The temperature for the
the bottom of the reaction vessel and its promo
ethylene alkylation with promoted hydro?uoric
tional effect will depend not only upon the
acid is therefore preferably maintained within
amount in the reactor relative to the amount of
the range of from about ——l0-° C. to about 80° C.
catalyst, but also upon the e?iciency of agitation.
with the. best results being obtained at temper
These two factors combined determine the e?’ec- .
atures below 30° C.
tive amount of promoter actually present in the
In. order to illustrate the fact that the pro
reaction interface in the case of insoluble pro
moters.
moters used in my process have a very long life
and are not used up appreciably in the course
The above group of examples with mercuric
of the ethylene» alkylation, the following experi
cyanide showed that the highest yields were ob 60 ment.
was performed.
tained when about 1.25 mol percent of mercuric
cyanide was added to the hydro?uoric acid cata
Example 12
lyst. At 0.25 mol percent the yield was‘ much
The experiment of Example 6 was repeated ex
less, and this represents about the minimum
amount that may be used to obtain a worthwhile 65 cept‘ that the run was continued for 10 hours,
promotional effect. At 1.90 mol percent the yield
fell off to about 60 percent of that obtained at
1.25 mol percent. The preferred range of salt
addition for mercuric cyanide and the other hy
dro?uoric acid soluble salts is from 0.2 to 2.0 mol
percent, with the best results being obtained by
the use of from 1.0 to 1.5 mol precent of the salt.
In the case of hydrofluoric acid insoluble salts,
during which time 279 parts by weight of ethylene
were added along with an additional 3'75 parts
by weight of isobutane. No noticeable drop in
catalyst activity took place, showing that the
mercuric cyanide promoter has an appreciable
catalyst life. The yield of alkylate in this case
was 153.0 percent based on the weight of ethyl
an upper limit to the amount of salt addition will
ene charged, and 74 percent by weight of this
alkylate product distilled below 125°C.
have ‘little meaning. With eiiicient agitation
Inv order to illustrate my invention further
. 2,408,930
the following series of experiments was performed
‘utilizing equimolar ratios of various metallic cy
"copper sulphate, mercuric sulphate and. silver
.anides in suspension or in solution in the acid
cyanide favor the ‘production of a higher per
centage of lower boiling alkylate products than
catalyst. The procedure outlined in Example 1
the more active salt promoters such as mercuric
was followed in all the experiments except that 5 cyanide and mercurous sulphate. Mercuric phos
the amount of the individual cyanide salts used
phate apparently is an exception to this general
was varied as indicated. in the following chart:
rule since the production of total alkylate product
Weight per
_
_
v
=
‘Example No‘ "
'
l
'
centkyfielél of
Salt used in Catalyst,
Metal 59'“
'
Isobutane,
Ethylene,
a
parts by wt. parts by wt. parts by wt. parts by wt.
'
'
'
m 6
g?ggtoé
ethylene add-
ed
Zinc term-cyanide“ _'______ ..
_ 65. 0
33.7
2110
303v
303
303
22. 3
62.5
303
_ 303
49. 3
303
1
Lead cyanide- _'_____ _.
Barium cyanide._-..
_
580
580
580
56
as
56
.6802
580
0
i 1.9
5.2 i
56
56
- "580
'
56
'
_
e. s
‘10.4
>
12.5
.
36.0
303
580
56
15. 3
Silver cyanide _____________ ..
25.4
310
594
56
125.7
Mercuric cyanide ________ ____
48. 0
303
581
56
180. 5
‘ . An‘interesti'ng feature of my invention-‘His
2 " when this salt is used is about the same as that
obtained by the use of silver cyanide but with
such‘ factors as temperature, catalyst concentra
this salt the percentage of lower boiling alkylate
tion, and selection of salt promoter may be used
material is considerably below that obtained
1to control= the proportion of ethylene which 'is
even with the more active salt promoters.
1 converted to alkylate products boiling below 1125"
For comparison purposes the following experi
' C., principally hexanes, heptanes and; octane‘s. :
The following chart is a tabulation of the re
ment was performed to show the relative amount
sults obtained in Examples‘ 1 'to 11, wherein sub
stantially the‘same quantities of isobutane, ethyl
or ethylene converted to ethylene-isobutane al
kylate using unpromoted hydro?uoric acid as the
,ene and hydro?uoric acid catalysts were used.
‘The chart shows the total yield'and the weight
catalyst.
Example 20
_ of total alkylate product distilling below 125°
C. for different alkylating conditions of temper
fature, salt promoter concentration and for vari
"ous typical salt promoters.
1
h
' 1
"xamp e
‘x
No.
'
of isobutane were placed in a jacketed reactor
cgncentriion mo
“It promoter
per cent
in H. F
Mercuric cyanide_....
10
6-
do...
. do--
I ‘11
_.
do
8-
__d0...
6...
, 7_
...._
T
.,
'
emp., _
° 0.
33.8
84.9
58
20
128.7
180.5
_ 91.6
_ 78.3
‘1.90
—3.5
800
“ 55.0
0.25 ‘
20
66.0
95.0
20
; '20
- 180.5
H 105.5
1.78.3
‘455.6
1.
__
Copper sulphate.
1.25
20. -
.
Mercuric sulphate
l. 25
20»
.
distilling
below
125° C.
125
- 2.
_.
yield of
alkylate
1.25
1.25
1.90;
,Silver cyanide____
Wt. per cent
Wt. t ' of alkylate
per'cen
product
1.25
1. 25
._.._do.__
..... ._
__ _..__do_______.._-.
~_ 4.
-1A_.miXture of 303»v parts by weight of concen
trated ‘hydro?uoric acid and 581 parts by weight
_l.25
, 67.6
~ -- 108.0
'20
125.7
‘j
96.7
.
-9l.0
86.1
p 6.
_
Mercuric cyanide.____
1.25
20
. v 180. 5
- 5.
_-.
Mercnrous sulphate-..
1. 25-
20v
~>l78.0
72.9
_
Mercuric phosphete__.
1.25
20 i
' 124.0
‘67.3‘
3.--.
'
'
.
'
78.3,
> From-a studyof the abovechart it appears that
vprovioled:withan agitator. To the well agitated
increasing the temperature up‘t'o 60° C. increases
the percentage of material distilling below 125° C,
_- mixture 56 parts by weight of ethylene were add
I Where the reaction is carried out at a tempera
‘- "Lure of 125° C; the percentage of lower boiling ma
edj continuously over a period of 120 minutes
while maintaining the temperature below 30° C.
has described in the preceding experiments. The
terial decreases along with the sharp drop in the F’". mixture ‘was drawn‘_ o? and the hydrocarbon
._.-_phase separated was analyzed to ascertain the
yield of total alkylate noted above... Likewise a
.percentage of the ethylene charged converted to
' decrease in the concentration of the salt promoter
alkylate. The yield was 23.2 weight percent.
produces an increase in the'percentage of mate
rial distilling below~l25° C; Nearly a 30 percent a 5., 7 While varying the reaction conditions and the
~-isobutane-ethylene ratio will vary the weight
increase in the weight percent of low ‘boiling al
kylate product is obtained by reducing the salt
promoter concentration in the catalyst from 1.90
, to 0.25 mol percent. Since the greatest yield of
c total alkylate occurs at an intermediate salt pro
moter concentration, operation at about l-mol .
» percent represents a compromise in thepropor
. tion of lower boiling alkylate product produced
»_ and at the same time results in the highest pro
duction ,of total alkylate.
~
.In general the ‘less active promoters such as
percent . yield of alkylate based on ethylene
charged slightly, this figure of 23.2 percent repre
sents a typical ?gure and conversions of the gen
..eral order of about '25 percent are obtained for
the unepromoted alkylation with ethylene. ‘
Theforegoing experiments illustrate the utility
7: “of my invention. Under normal liquid phase al
‘_ kylating conditions hydro?uoric acid alone will
?gproduce yields of alkylate from the isopara?in
ethylene reaction of not more than about 30 per
2,403,930
10
cent based on the weight of ethylene charged.
in every case on the basis of one gram equivalent
By the addition of a small quantity, of the gen
of free acid reduction product, e. g.,
eral order of about 1 mol percent, of metallic salts
AgCN
(S01id)+1/zH2
(gas)->
of inorganic acids whose standard free energy of
Ag (solid) +l-ICN (gas)
reduction to metal and non-aqueous acid (AFzss) 5
AFz9a=-—l2,100 calories
is more negative than about —8,000 calories per
1/2HgCliz (solid) +1/2Hz (gas) ~>
gram equivalent of free acid reduction product.
1/2I-Ig (liquid) +I~IC1 (gas)
yields of from about 65 to about 180 percent of
AF298=—-900
calories
alkylate product based on ethylene charged are
obtained under otherwise similar alkylating con lo
The theoretical reason underlying the relation
ditions. In general the higher the free energy
ship between the free energy of reduction of the
metal salts and the effectiveness of these salts as,
of reduction of the metallic salt, the higher will
promoters for the conversion of ethylene to alkyl
be the yield of alkylate product. As shown on the
ate in the presence of hydro?uoric acid is not
chart. in the drawing, mercuric cyanide and mer
curous sulphate whose free energies of reduction
clear. Very little is known about the mechanism
of the reaction between paraf?ns and ole?ns in
are approximately —l6,500 and —13,'700 respec
tively, gave yields of over 175 percent, based on
the presence of acidic catalysts, and therefore it
ethylene charged, whereas cupric sulphate whose
is impossible to de?nitely explain the activating
free energy of reduction is about —9,000 gave a
yield slightly in excess of 67 percent. In con
trast thereto mercuric chloride and silver ?uoride
whose free energies of reduction are less than
-8,000 calories per gram equivalent of free acid
effect of the easily reducible metal salts on these
acid catalysts. I have found, however, that no
property of the salts will better relate their com
reduction product not only did not improve the
yield of 23.2 percent obtained with the unpro
rnoted hydro?uoric acid, but actually gave
lower yields.
that only certain salts of the metals, particularly
the sulphates, cyanides and phosphates are sulfi
ing agents. From a smooth curve drawn through
these values it can be seen that where the free
process as a batch operation in which ethylene is
introduced into a vigorously agitated mixture of
position to their catalytic activity than their free
energies of reduction.
From a study it appears
ciently easily reducible to make them useful as
promoters of acidic alkylation catalysts. In any
The effect of the various salts tested as pro
event, I have found that all the metallic salts
moters for the conversion of ethylene to alkylate
whose free energy of reduction is more negative
in the presence of hydro?uoric acid is best illus 30 than -8,000 calories, with the single exception
trated by a study of the drawing, wherein the free
of silver sulphate, are effective.
energy of reduction of the metal salts is plotted
In the foregoing description of my invention
against the weight percent yield of alkylate based
I have referred to the term standard free energy
on the weight of ethylene charged. The free en
of reduction (AFZBB). By this term I mean the
ergies of reduction of certain of the typical metal 35 free energy of reduction, measured at 25° C. and
lic salts studied were plotted against the weight
determined on the basis of one gram equivalent ‘
percent yield of alkylate from the ethylene ob
of free acid reduction product.
tained when these salts were used as the promot
In the speci?c examples I have illustrated the
energy of reduction of the metallic salt is less than
about --7,500 calories no promotional effect is
obtained since the curve lies to the left of the
23.2 percent of alkylate product yield line which
represents the conversion obtained with the un
promoted hydro?uoric acid. At —-7,500 the yield
isoparaf?n and catalyst. Obviously my process
is well adapted to continuous operation as is con
ventional in alkylation practice with butylene,
and operation in this manner is preferable for
large scale, commercial practice.
.
The ethylene used in my process need not
necessarily be pure. The gas may contain inert
~gaseous materials such as normal paraf?ns, and
metallic salts will assert a de?nite promotional
effect upon the alkylation reaction. This increase 50 small amounts of other ole?ns.
In the foregoing description of my invention
in the amount of conversion obtained apparently
and in the appended claims, the term “isoparaf
continues uniformly with increasing free energy
?ns” includes aliphatic, saturated hydrocarbons
of reduction of the metallic salt until the per
having a tertiary carbon atom and having from
centage conversion reaches about 180 percent
yield of the alkylate product, after which the 55 four to six carbon atoms.
The above description of my invention is mere‘
curve levels on at slightly above 180 percent yield.
1y illustrative of the preferred mode of operation
Of the many salts which I have tested only one
exception to the foregoing rule has been observed.
thereof, and my invention should not be limited
except as indicated in the appended claims.
This salt is silver sulphate which is an easily re
ducible salt comparable with mercurous sulphate 80
I claim:
and for which nearly a 180 percent yield would
1. A process for‘ the alkylation of isopara?ins
be expected. However, in the case of silver sul
with ethylene which comprises contacting the
phate no promotional effect toward the isobu
isoparafiin with the ethylene in the presence of
tans-ethylene reaction was observed. I believe
hydro?uoric acid of at least 90 percent concen
that the peculiar behavior of silver sulphate is 05 tration and a metallic salt of an inorganic acid
caused by its formation of a stable double salt
whose standard free energy of reduction to metal
with the hydro?uoric acid which double salt has
and non-aqueous acid is more negative than
much different properties than the silver sulphate
about —8.000 calories per gram equivalentgcf.
alone. This property of silver sulphate to form
free acid reduction product, which saltsdo not
very stable double salts with certain concentrated 70 form stable double salts with the acid catalyst.
acids has been reported by J. Kendall and A. W.
and are characterized by being the salt of a metal
Davidson in the Journal of American Chemical
below hydrogen in the clectromotive force series.
Society, volume 43, on pages 979\ ‘I 990‘ (1921).
2. A process for the alkylation of isoparai‘?ns
In the foregoing description 0; my invention
with ethylene which comprises contacting the
I have referred to the free energJ of reduction 16 isopara?in with the ethylene in the presence of
of alkylate product begins to rise sharply and at
values greater than about —8,000 calories the
2,403,930
11
12
hydro?uoric acid of at least 90 percent concen
acid catalyst and are characterized by being the
tration and mercuric cyanide.
with ethylene which comprises contacting the
salt of a metal below hydrogen in the electro
motive force series.
10. A process for the alkylation of isoparaf?ns
isopara?in with the ethylene in the presence of
hydro?uoric acid of at least 90 percent concen
with ethylene which comprises contacting the
isopara?ln with ethylene in the presence of hy
tration and mercurous sulphate.
4. A process for the alkylation of isoparaf?ns
dro?uoric acid of at least 90 percent concentra
3. A process for the alkylation of isoparat?ns
tion and from 0.2'to 2.0 mol percent, based on
the amount of hydro?uoric acid, of a hydro
isopara?ln with the ethylene in the presence of 10 ?uoric acid soluble metallic salt of an inorganic
acid, whose standard free energy of reduction to
hydrofluoric acid of at least 90 percent concen
metal and non-aqueous acid is more negative
tration and silver cyanide.
than about —8,000 calories per gram equivalent
5. A process for the alkylation of isobutane
of free acid reduction product, which salts do
with ethylene which comprises contacting the
isobutane with the ethylene in the presence of 16 not form stable double salts with the acid cat
alyst, and are characterized by being the salt of
hydro?uoric acid of at least 90 percent concen
a metal below hydrogen in the electromotive force
tration and a metallic salt of an inorganic acid
‘ series.
whose standard free energy of reduction to metal
11. A process for the alkylation of isoparaf?ns
and non-aqueous acid is more negative than
about —8,000 calories per gram equivalent of free 20 with ethylene which comprises contacting the
isoparal?n with ethylene in the presence of hy
acid reduction product, which salts do not form
dro?uoric acid of at least 90 percent concentra
stable double salts with the acid catalyst, and
tion and from 1.0‘ to 1.5 mol percent, based on
are characterized by being a salt of a metal
the amount of hydrofluoric acid, of a hydro?uoric
below hydrogen in the electromotive force series.
acid soluble metallic salt of an inorganic acid.
6. A process for the alkylation of isoparaffins '
whose standard free energy‘ of reduction to metal
with ethylene which comprises contacting the iso
and non-aqueous acid is more negative than
para?in with the ethylene in the presence of hy
about —8,000 calories per gram equivalent of free
dro?uoric acid of at least 90 percent concentration
acid reduction product, which'salts do not form
and a metallic salt of an inorganic acid whose
standard free energy of reduction to metal and 30 stable double salts with the acid catalyst, and are
characterized by being the salt of a metal below
non-aqueous acid is more negative than about
hydrogen in the electromotive force series.
-8,000 calories per gram equivalent of free acid
12. A process for the alkylation of isobutane
reduction product, which salts do not form sta
with ethylene which comprises contacting the
ble double salts with the acid catalyst and are
characterized by being the salt of a metal below 35 isobutane with the ethylene in the presence of
hydro?uoric acid of at least 90 percent concen
hydrogen in the electromotive force series, main
tration and from 1.0 to 1.5 mol percent of mer
taining the temperature of the reaction mixture
curic cyanide based on the amount of hydro
between —l0° and about 80° C., and maintain
?uoric acid.
ing a pressure sullicient to keep the isopara?‘in
13. A process for the alkylation of isopara?ins
in the liquid phase.
with ethylene which comprises contacting the
7. A process for the alkylation of isobutane
isopara?in with the ethylene in the presence of
with ethylene which comprises contacting the iso_
hydro?uoric acid of at least 90 percent concen
butane with the ethylene in the presence of hy
tration and from 1.0 to 2.0 mol percent based on
dro?uoric acid of at least 90 percent concen
tration and a metallic salt of an inorganic acid 45 the amount of hydro?uoric acid, of a hydrofluoric
acid insoluble metallic salt of an inorganic acid
whose standard free energy of reduction to metal
whose standard free energy of reduction to metal
and non-aqueous acid is more negative than
and non-aqueous acid is more negative than
about -—-8,000 calories per gram equivalent of free
about ——8,000 calories per gram equivalent of free
acid reduction product, which salts do not form
stable double salts with the acid catalyst and are 50 acid reduction product, which salts do not form
stable double salts with the acid catalyst, and
characterized by being the salt of a metal below
are characterized by being the salt of a metal
hydrogen in the electromotive force series, main
below hydrogen in the electromotive force series.
taining the temperature of the reaction mixture
14. A process for the alkylation of isopara?‘ins
between ——10° and about 80° C., and maintain
ing a pressure su?lcient to keep the isobutane in 55 with ethylene which comprises contacting the
isoparaf?n with the ethylene in the presence of
the liquid phase.
'
hydro?uoric acid of at least 90 percent concen
8. A process for the alkylation of isobutane
tration and more than 0.5 mol percent based on
with ethylene which comprises contacting the
the amount of hydro?uoric acid, of a hydro
isobutane with the ethylene in the presence of
hydro?uoric acid of at least 90 percent concen 60 ?uoric acid insoluble metallic salt of an inorganic
acid, whose standard free energy of reduction to
tration and mercuric cyanide, maintaining the
metal and non-aqueous acid is more negative
temperature between —10° and about 80° C. and
than about —8,000 calories per gram equivalent
maintaining a pressure sufficient to keep the iso
of free acid reduction product, which salts do
butane in the liquid phase.
9. A process for the alkylation if isopara?ins 65 not form stable double salts with the acid cat
alyst, and are characterized by being the salt
with ethylene which comprises contacting the
of a metal below hydrogen in the electromotive
isopara?in with the ethylene in the presence of
force series.
hydrofluoric acid of at least 90 percent concen
15. A process for the alkylation of isobutane
tration and from 0.1 to 10 mol percent of the
amount of hydro?uoric acid of a metallic salt of 70 with ethylene which comprises contacting the
isobutane with the ethylene in the presence of
an inorganic acid whose standard free energy of
hydro?uoric acid of at least 90 percent concen
reduction to metal and non-aqueous acid is more
tration and a metallic salt of an inorganic acid
negative than about ——8,000 calories per gram
whose standard free energy of reduction to metal
equivalent of free acid reduction product, which
salts do not form stable double salts with the 75 and non-aqueous acid is more negative than
with ethylene which comprises contacting the
2,408,930
13
14
about —-8,000 calories per gram equivalent of
free acid reduction product, which salts do not
form stable double salts with the acid catalyst
tration and a metallic salt of an inorganic acid
whose standard free energy of reduction to metal
and non-aqueous acid is more negative than
about ——8,000 calories per gram equivalent of
‘free acid reduction product, which salts do not
form stable double salts with the acid catalyst,
and are characterized by being the salt of a metal
and are characterized by being the salt of a metal
below hydrogen in the electromotive force series,
maintaining the temperature of the reaction mix
ture between 0 and about 30° C., and maintain
ing a pressure su?’lcient to keep the isobutane in
the liquid phase.
below hydrogen in the electromotive force series,
maintaining the temperature of reaction mixture
16. A process for the alkylation of isobutane 111 within the range of between -—10° and about
125° C., and controlling the ratio of alkylate prod
isobutane with the ethylene in the presence of
uct boiling below 125° C. to alkylate product boil
hydro?uoric acid of at least 90 percent concen
ing above 125° C. by controlling the tempera
tration and mercuric cyanide, maintaining the
ture at which the reaction is carried out within
temperature at about 20° C. and maintaining a , the temperature range.
pressure su?icient to keep the isobutane in the
19. A process for the alkylation of isoparaf?ns
with ethylene which comprises contacting the
liquid phase.
17. A process for the alkylation of isopara?ins
with ethylene which comprises contacting the
isopara?in with the ethylene in the presence of ‘
hydro?uoric acid of at least 90 percent concen
tration and a metallic salt of an inorganic acid,
soluble in hydro?uoric acid, whose standard free
energy of reduction to metal and non-aqueous
acid is more negative than about —8,000 calories
per gram equivalent of free acid reduction prod
uct, which salts do not form stable double salts
with the acid catalyst, and are characterized by
being the salt of a metal below hydrogen in the
electromotive force series, and controllling the
ratio of alkylate product boiling below 125° C. to
alkylate product boiling above 125° C. by con
trolling the concentration of the salt in the hy
dro?uoric acid.
'
18. A process for the alkylation of isopora?ins f
with ethylene which comprises contacting the
isopara?in with the ethylene in the presenceof
hydrofluoric acid of at least 90 percent concen
with ethylene which comprises contacting the
isopara?in with the ethylene in the presence of
hydro?uoric acid of at least 90 percent concen
tration and a salt, of a metal below hydrogen in
the electromotive force series with an inorganic
acid, whose standard free energy of reduction
to metal and non-aqueous acid is more negative
than about —8,000 calories per gram equivalent
of free acid reduction product, other than silver
sulphate.
_
20. A process for the alkylation of isobutane
with ethylene which comprises contacting the
isobutane with the ethylene in the presence of
hydro?uoric acid of at least 90 percent concen
tration and a salt, of a metal below hydrogen in
the electromotive force series with an inorganic
acid; whose standard free energy of reduction to
metal and non-aqueous acid is more negative
than about -—8,000 calories per gram equivalent
of free acid reduction product, other than silver
sulphate.
CARL S. KUHN, JR.
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