582 INDUSTRIAL AND ENGINEERING CHEMISTRY
cooling bath was used to cool the ammonia to the adsorption
temperature. The gas then passed through the adsorbent which
was placed in an &inch U-tube dipping into the cooling bath.
Approximately 10 grams of adsorbent was used. A calcium
chloride-ice mixture was used in the agitated bath. Additional
cooling and temperature control was attained through the use of
dry ice.
During a run, ammonia gas was passed through the system
at a rate sufficient to ensure a positive pressure of about 10 mm.
of mercury above atmospheric pressure in the system. Adsorp-
tion a t the desired temperature was continued for 1 hour, which
was considered sufficient for equilibrium since the maximum
temperature rise of the adsorbent occurred in 10 minutes. De-
sorption was carried out by transferring the U-tube containing
the adsorbent to a water bath and heating to 100” C. for 1 hour.
The desorbed ammonia was absorbed in 2 N sulfuric acid. Back
titration with standard sodium hydroxide solution was used to
determine the amount of ammonia desorbed. An experimentally
determined dead space correction was applied to account for the
unadsorbed ammonia initially in the system.
The adsorptive capacities thus determined are actually dif-
Isomerization of ntanes
and Hexanes
NATURE AND CONTROL OF SIDE REACTIONS
B. L. EVERING, E. L. D’OUVILLE, A. P. LIEN, AKD R. C. WAILTGH‘
Research Department, Standard Oil Co. (Zndiana), Whiting, Znd.
NUMBER of publications have described the isomeriztt-
tion of butanes, pentanes, and hexanes (5, 19). Butanes
isomerize readily without side reactions under suitably controlled
conditions, while pentanes and hexanes disproportionate and
crack so readily that the isomerization reaction is secondary.
With pentanes the lower boiling products are mainly the result
of disproportionation between two molecules:
2CHa(CHz)&K --+ CJLo + CaH14
Although pentanes react primarily as shown above, small
amounts of higher boiling products are formed because of crack-
ing, and these lead to a hydrogen deficiency and gradual deactiva-
tion of the catalyst. The cracking (16)reaction is even more pro-
nounced in the case of hexanes and results in more rapid catalyst
deactivation.
A number of materials have been investigated as inhibitors
of the disproportionation and cracking reactions. Hydrogen
( 6 , 7 , 11, 15, 20, $6, 28), aromatics, naphthenes, and isobutane
(2-methyl propane) (6, 16, 18) have been reported to inhibit the
undesired side reactions in varying degrees. The present paper is
concerned with a more detailed account of the inhibiting effect
of hydrogen, aromatics, naphthenes, and isobutane and their
effect on catalyst life. All these materials inhibit the dispropor-
tionation of pentanes and increase catalyst life during isomeriza-
tion. Hexanes can be successfully isomerized only in the pres-
ence of hydrogen. Olefins nullify the effect of inhibitors and
accelerate the disproportionation and cracking reactions. Addi-
tional information on the role of hydrogen chloride as a catalyst
component is presented, supplementing that previously reported
1 Present address, Arapahoe Chemical Co , Boulder, Colo
Vol. 45, No.
ferences in adsorptive capacities a t the specified temperature
and 100” C., the temperature a t which desorption was carried
out. The small amount of ammonia remaining on the adsorbent
a t 100” C. is not considered significant for design of commercial
adsorbers.
RESULTS
The adsorption isobars are shown in Figure 1. Thc points
were obtained in a random order.
It is apparent that the two materials possess different adsorp-
tion characteristics. The fuller’s earth isobar increases sharply
as condensation temperature is approached. The isobar for
gas-adsorbent carbon indicates that the adsorptive capacity of
the carbon approaches a constant value as the condensation
temperature is approached.
LITERATURE CITED
(1) Deits, V. R . , “Bibliography of Solid Adsorbents,” U. S. Cane
Sugar Refiners, Washington, D. C. (1944).
(2) Emmett, P. H., Chem. Revs., 43,69-148 (1948).
RECEIVED
for review June 2 5 , 1952. Xovember 3, 1952.
ACCEPTED
(14). Finally a mechanism is proposed based on an intramolec-
ular rearrangement while the hydrocarbon is associated with the
ionized aluminum chloride-hgdrogen chloride complex.
In this work single experiments are often found to be mislead-
ing because of changes in the physical condition of the catalyst
during an experiment. Therefore the conclusions d r a m are
based for the most part on life studies which are considered more
reliable. These data are the outgrowth of the exploratory re-
search which led to the development of the Indiana pentane and
hexane isomerization processes.
CATALYST AND REAGENTS
The aluminum chloride was obtained from the Hooker Electro-
chemical Co. In early experiments the aluminum chloride was
resublimed under vacuum and stored in sealed glass ampoules.
An ampoule was opened just prior to an experiment, weighed,
and transferred as rapidly as possible to the reactor without other
precautions to avoid contact with moisture in the air. The
aluminum chloride as received gave substantially the same
results under these circumstances as the resublimed material
and therefore was used in all subsequent experiments. The
ratio of chlorine t o aluminum corresponded closely to that
found by Stevenson and Beeck (26) for their moist aluminum
chloride. The authors’ catalyst presumably had the approxi-
mate empirical formula of Al~Cls.~(OH)0.6 that they reported.
The hydrogen chloride was commercial anhydrous compressed
gas from the Harshaw Chemical Go. Hydrogen was obtained
from the National Cylinder Gas Co. and used as received.
The n-butane, isobutane, n-pentane, and 2,3-dimethylbutane
were Phillips Petroleum Co. technical grade hydrocarbons with
purity better than 95% by volume; they were used without fur-
ther purification. Pentanes and hexanes that were used in
large quantities were narrow cuts fractionated from virgin mid-
continent naphthas. The plant pentanes were 99+% C.;
 March 1953 INDUSTRIAL AND ENGINEERING CHEMISTRY 583

one stock contained 12% isopentane (2-methylbutane), the other molecular reaction law, this afforded a ready means of correct-
42% isopentane. The olefin content was 0.06% by the Francis ing for the variable contact time and following the activity of
bromide-bromate method. The hexane-containing charge stock
was a light naphtha of 67' C. end point containing 0.009 the catalyst during a life study. Using octane number as a
weight % sulfur and had the composition shown in Table I. rapid measure of the degree of isomerization and substituting
octane number and time in the unimolecular reaction equation,
the rate constant k was obtained. T o avoid confusion this rate
TABLEI. COMPOSITION
OF MID-CONTINENT
LIGHT NAPHTHA constant is called the catalyst activity index, a. The value 01
is valid only for comparative purposes and is given by the fol-
Volume %
lowing expression:
Isopentane 1.5
n-Pentane 35.9
Cyclopentane 3.0 23 A
!2,2-Dimethylbutane 1.0 a = A log
2,3-Dimethylbutane 1.0
t B-C
2-Methylpentane 23.3
3-Methylpentane 13.4 where A = equilibrium octane number minus octane number of
n-Hexane 17.4 feed
Methylcyclopentane 3.0
Benzene 0.5 B = equilibrium octane number
C = octane number of product
Total 100.0 t = reaction time in hours
11. REACTIONOF PENTANES
TABLE OF INHIBITORS The equilibrium octane number was established experimentally
IN ABSENCE
u Hydrocarbon Mixed Pentanes& n-Pentane ( 7 ) . Thus the effect of inhibitors and other added materials
AlCls wt Yo of hydrocarbon 11.5 12.4 11.4 was determined by noting the change in catalyst activity during
HC1, 'wt. '% of hydrocarbon 3.3 3.3 3.3
Temperature, C. 100 100 66 a life study.
Contact time, min. 120 5 10
Butanes and lighter wt. % 55.0 42.5 14.5 REACTIONS OF PENTANES
Octane number (CF'RM) 81.1 80b6 66.8
Isopentane, vol. % based on C6 84 b 83 18.7
I n Table I1 are shown the results of bringing pentanes into
42 vol. % isopentane and 58 vol. % n-pentane.
Estimated from octane number. contact with aluminum chloride and hydrogen chloride. Al-
though the pentanes are isomerized at 100' C. to near an equilib-
rium mixture of isopentane and n-pentane, disproportionation
APPARATUS AND PROCEDURE t o products boiling below and above the pentanes was a major
reaction. Disproportionation is a rapid reaction, since 5 minutes
The apparatus has been described in detail (7). The reactors gave almost as large an amount of disproportionation products
had a capacity of 1490 ml. and were stirred mechanically at
1725 r.p.m. They were jacketed so that they could be quickly as 2 hours. Lowering the temperature t o 66' C. reduced dispro-
heated by steam or cooled by water; less than 5 minutes were portionation but also reduced isomerization proportionally, so
required t o reach reaction temperature or to quench by cooling. t h a t there was no substantial improvement in the ratio of isom-
Auxiliary equipment was provided for introducing measured erization t o disproportionation.
uantities of hydrocarbons, hydrogen chloride, and hydrogen.
8 rovision was made for the withdrawal of the liquid product
from the settled aluminum chloride catalyst.
A series of experiments was carried out as follows: 60

The reactor was charged with aluminum chloride, hydrocarbon, 80

hydrogen chloride, and the inhibitor. Agitation was started and
the reaction mixture was quickly raised t o temperature. After 40

a given time, agitation was stopped and the reaction mixture 60

8
was quickly cooled. The catalyst was allowed t o settle and the
bulk of the li uid Lydrocarbon product was withdrawn through 8 20
2
a bleed-out t&e extending two thirds of the way to the bottom W
of the reactor. The reactor was then recharged and the pro- d 40
W
I-
cedure repeated a number of times. =. I
I?:
As liquid roduct was withdrawn from the reactor into a W
z
-I

flask, the voktile products t h a t separated passed successively 4

through a soda-lime tube t o remove hydrogen chloride, a dry z
iceacetone condenser to condense light hydrocarbons, and ti w 80
n
wet-test meter t o measure the effluent hydrogen and any other 0
noncondensable gases. The products were first distilled in a e
low-temperature fractionating column packed with glass helices 60
and equivalent t o 20 theoretical plates to separate the butanes
and lighter from the liquid roducts. The composition of the
*
liquid products either was &ermined by careful fractionation
in a wire gauze packed column testing 60 to 80 theoretical plates
or was estimated by the determination of the motor-method
octane number (CFRM; ASTM D-357).
40
- = * - - .._ I. .
All the life studies on pentanes were made at 100' C. with 11.5 MOLES PENTANE / MOLE AICI,
weight yo aluminum chloride and 3.2 weight % hydrogen chlo-
ride based on charge. The contact time was held constant at 3 Figure 1. Isomerization of Pentanes
hours except in the first run, which was 2 hours; thus conversion A. Uninhibited
t o isopentane was a direct measure of catalyst activity. B. Inhibited with 0.5% of benzene
0 9% isopentane
The life studies on light naphtha were made at 165' C. (unless 0 $' 6 butanes and lighter
Q No benzene added
otherwise specified) with 10.7 weight yo aluminum chloride and
3.1 weight % hydrogen chloride based on charge. I n this case
it was not feasible t o use constant contact time throughout the A life study was made at 100' C. The results are shown in
life study because of the wide variation in catalyst activity; Figure l A , where isomerization and disproportionation are
therefore the isomerization of light naphtha t o near equilibrium plotted against the age of the catalyst. The hydrocarbon was
composition was obtained by varying the contact time. As the mixed pentanes containing 42 volume yo of isopentane. Ini-
isomerization reaction has been shown to follow closely a uni- tially the main reactions are disproportionation and isomeriza-
584 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 45, No. 3

0 0

0.5% BENZENE

209* BENZENE

1.0 % XYLENE
n

-I
z
40 IO a
UJ
z
w

0 50 I00 150 200

02
250 3
m
MOLES P E N T A N E / M O L E AlCl,
50 100 I50 200 250
MOLES PENTANE / MOLE AICI, Figure 3. Effect of Cyclohexane on Pentane Isomerization
Figure 2. Effect of Benzene Concentration and Xylene 5 % cyclohexane. €3 % isopentane, cb % butanes and lighter
on Pentane Isomerization 2.5% osclohexane. 0 o/p isopentane, c) % butanes and lighter

tion, both of which decline as the activity of the catalyst, decreases
on-ing to the formation of complex resulting from side reactions.
Because the isopentane content is known with somewhat less
certainty in the early stages of the life test, owing to the dispro-
portionation products, that portion of the curve is shown as a
dotted line. The isomerization activity of the cat,alyst declines
very rapidly and virtually no isomerization occurs after a cata-
lyst age of 55 moles of pentane per mole of aluminum chloride.
However, a t this point the catalyst is still active for dispropor-
tionation, as is shoxn by the product,ioii of 32y0 butanes and
lighter; apparently the disproportionation reaction requires a
less active catalyst than the isomerization reaction. During
this life test 1300 grams of butanes and lighter were formed by
disproportionation, Jv-ith only 44 grams entering into a complex
with the aluminurn chloride.
Products that formed out to 78 moles of pentanes per mole of
aluminum chloride were combined and fractionated on a 60-
theoretical-plate column. As shown in Table 111, large quantities
of hydrocarbons both lighter and heavier t'han pentanes are
formed, confirming the observation that the primary butane-
producing reaction is disproportionation. The fraction boiling
below pentane was mainly isobutane v i t h but a small amount of
n-butane and a trace of propane. The hexanes are a mixture
of the five isomers in approximately equilibrium proportions.
111. COVPOSITION
TABLE DISPROPORTIO\
OF PE:\TAAE ATIO\
PRODUCT
T o 1 o/c
Propane 1 0
n-Butane 5 0
Isobutane 28 0
Isopentane 15 5
n-Pentane 21 6
Hexanes 18 3
Heptanes and hearisi 10 6
Total ioo.0
EFFECT
OF ARoaraTIcs. A life test was made with 0.5 volume
% benzene added t o the mixed pentane feed containing 42
volume % isopentane. The effect in controlling the dispropor-
tionation of pentanes is shown in Figure 1B. The benzene
inhibited the disproportionation reaction to such an extent that
an average of only 4% butane was produced, whereas the isom-
erization reaction proceeded readily. There was a marked
increase in catalyst life; the catalyst was still producing a prod-
uct containing 66 volume r0
isopentane a t a catalyst age of
212 moles of pentane per mole of aluminuni chloride. The rise
in the isomerization curve to a maximum is attributed to the
better contact between catalyst and hydrocarbon; the better
contact results IT hen the solid aluminum chloride is converted
to the highly active liquid aluminum chloride-hydrocarbon com-
plex by the accumulation of unsaturated hvdrocarbons on the
catalyst. A subsequent decline in activity is the result of the
further accumulation of hydrocarbon, which tends to dilute the
catalyst without any further improvement in contact between
reactants.
TABLEIv. DISPOSITION
O F BENZENE
DURING ISOMERIZATION
OF PENTANES
55 2.0 1.30 0 07
169 2.0 1.94 0 15
29 0.5 0.27 0 02
159 0.5 0 41 0.06
At a catalyst age of 185 moles of pentanes per mole of alumi-
num chloride, the benzene was omitted. No immediate effect
on the disproportionation reaction appeared, probably because
sufficient benzene remained dissolved in the catalyst complex
to inhibit the reaction. However, in the subsequent run, also
u ithout added benzene, a large amount of disproportionation was
obtained. The inclusion of 0.5 volume % benzene in the follow-
ing run again inhibited the disproportionation.
d life study was made using 2.0 volume % benzene. Figure
2 compares these results with those obtained using 0.5 volume %
benzene. Increasing the benzene concentration from 0.5 to 2.0
volume yo results in an average decrease of 10% in isopentane
production; these results are in approximate agreement with
5lavity ( 1 6 ) . The increased benzene concentration reduces the
dispropoi tionation from 4.2 to 1.5m-eight %.
Other aromatics are not so effective as benzene. -4 mini-
mum of 1 volume % of xylene is necessary t o inhibit the dispro-
portionation of pentanes and the catalyst life is much shorter
than is obtained with benzene, as shown in Figure 2.
The aromatic inhibitor is partly extracted by the catalyst and
is partly converted during isomerization to toluene and higher
alkyl aromatics, as shown in Table IV for the case of benzene.
The evtraction of benzene is greatest in the early stages of the
life test. Toluene appears in the product in ainountc that in-
crease with the age of the catalyst.
EFFECT OF A-APHTHENES. Naphthenes are similar to ben-
zene in the inhibition of pentane disproportionation. Methyl-
cgclopentane and cyclohexane are effective as disproportiona-
tion inhibitors, as also is cyclopentane, which is discussed later.
I t is immaterial whether one starts with methylcyclopentane or
 March 1953 INDUSTRIAL AND ENGINEERING CHEMISTRY 585
erization is 35 to 40% lower with hydrogen than with benzene.
Disproportionation as measured by butane formation was 1.1
weight % for hydrogen as compared t o 2.1 weight % for benzene.
Although hydrogen is effective in maintaining catalyst life, it
suppresses the isomerization of pentanes. Hydrogen is consumed
in moderate amounts. I n experiments at 100' C., the hydrogen
consumption amounts t o about 0.0043 mole of hydrogen per
mole of isopentane produced.
G I 0
\o 0.590 BENZENE I

40 t
HYDROGEN 11 TABLE
VI.

Butane moles
Mixed bentanes4, moles
AlCla grams
HC1, 'prams
OF PENTANES
CONVERSION
BUTANES
I N PRESENCE
OF

n-Butane
5.0
4.4
72
20.5
4.0
..3.. ...5
Iso-
butane
4.9
4.4
...
...
Temperature, C. 100 100 100
9 50 100 Is0 200 250 Reaction time, min. 120 180 180
rr
MOLES PENTANE / M O L E AlCl3 Butanes and lighter wt '3' of charge 42 4.5
Composition of liquid pkodouot, vol. 3
'%
Figure 4. Effect of Hydrogen on Pentane Isomerization Isopentane 51 51
P e n t a n e feed c o n t a i n i n g 1270isopentane
n-Pentane
Hexanes
16
29 ... ... ... 23
17
Heptanes and heavier 4 9
a 12% isopentane, 88% n-pentane.
cyclohexane, as they readily isomerize t o an equilibrium mixture
under these conditions. However, higher concentrations of
naphthenes are required. 100
A mixed pentane feed containing 5.0 volume yo added cyclo-
hexane was isomerized under the same conditions as in the pre-
vious life studies in which aromatics were used as inhibitors.
Comparison of the curves in Figure 3 shows that the conversion 80
1
to isopentane is slightly lower than with 0.5 volume % benzene,
but that the catalyst life is somewhat longer. Although an
exact quantitative relationship has not been established, Figure 3
shows that 5.0 volume yo cyclohexane is about as effective as H
5 60
0.5 volume yo benzene. A decrease in cyclohexane content to 0

2.5y0a t a catalyst age of 195 moles results in a doubling of the T

z
W
disproportionation reaction.
EFFECTOF HYDROQEN. Hydrogen is another effective inhib-
itor for the disproportionation of pentanes. Table V, showing
the effect of various hydrogen pressures on isomerization a t
F

4
40
r\\
100' C. indicates t h a t the minimum effective hydrogen pressure
lies between 130 and 200 pounds per square inch. At tempera- 20
tures as high as 150' C. a partial hydrogen pressure of 900
pounds per square inch is necessary. The critical pressure is
dependent not only on temperature, but also on catalyst activity
Thus the pressures quoted above for fresh catalyst will be lower
with less active catalyst. The effect of increasing the hydro- " IUU 13u
MOLES PENTANE /'MOLE AICI,
gen pressure above the critical value is to retard isomerization,
Figure 5. Effect of Olefins on Pentane
as well as to effect a slight additional decrease in the dispropor- Isornerization
tionation reaction.
0.38% a m y l e n e added to p e n t a n e feed c o n t a i n i n g 12%
isopentane
0.5% benzene. 0 70 i s o p e n t a n e 0 % b u t a n e s a n d
lighter
TABLEV. I N , T H E PRESENCE
OF PENTANES
CONVERS~ON OF 2 . 0 % benzene. Yo i s o p e n t a n e 70 butanes a n d
lighter
HYDROGEN
(Mixed pentanes containing 12% isopentane treated a t 100' C. for 120
minutes with 11.5% AlCla and 3.3% HC1 by weight)
EFFECT OF BUTANES. Table VI shows the effect of butanes on
Hydrogen pressure, Ib./sq. inch
At room temperature 100 150 200 250 the conversion of pentanes. A study was made using equal vol-
At reaction temperature 130 200 260 330 umes of n-butane and pentane in each of the first two runs, and
Butanes and lighter, wt. % of charge 69.5 2 3 2.2 1.8
Octane No. (CFRM) . . . 8 2 . 2 82.2 80 4 isobutane in like amount in the third run.' n-Butane was not
Isopentane, vol. % of pentanes 71 71 71 64
effective as a disproportionation inhibitor; the results were
approximately the same as in the runs in -which no inhibitor was
added. When isobutane was substituted for n-butane in the
Parallel life studies, as shown in Figure 4,were carried out on a third run of the study, the net production of butanes fell from an
mixed pentane feed (containing 12 volume % isopentane) a t average of 42 weight % based on pentanes in the first two runs
100" C. with 0.5 volume % benzene and with 260 pounds per t o 4.5 weight %. Although isobutane inhibits the formation of
square inch partial pressure of hydrogen. (A comparison be- light products, it leads to the formation of higher boiling products.
tween Figures l B , and 4 shows that despite the 30% difference These are attributed to alkylation of hydrocarbon from the
in isopentane content of the feeds, the isopentane contents of aluminum chloride-hydrocarbon sludge produced during the
the products from the benzene-inhibited runs differ by only 4 n-butane step.
to 6%.) Under the same conditions the rate of pentane isom- EFFECT OF OLEFINS. Pines and Wackher ($1)have reported a
586 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 45, No. 3
combined inhibition of added hydrogen and cyclic inhibitors.
A minimum effective hydrogen pressure is observed for the
hexanes as in the case of pentanes. At 100" C. a hydrogen
pressure of 1000 pounds per square inch is effective in inhibiting
side reactions; lowering the hydrogen pressure to 500 pounds per
square inch and increasing the reaction temperature to 156" C.
result in a gross amount of butane and lighter. Under these
same conditions the addition of 1.0% cyclopentane does not alter
the results, while the addition of 10% cyclopentane brings the
side reactions under control.

PSI PSI

PS I PS I

-- NO HYDROGEN -
Figure 6. Isomerization of Light Naphtha -

0.05
-' I
II , I I
-
1
promotional effect of olefins during isomerization studies with 0 40 80 I20
MOLES FEED / MOLE A I C 1 3
carefully purified materials. When pentane was isomerized
with 0.38% added amylene in the presence of 0.5 and 2.0% ben- Figure 7 . Effect of Hydrogen Pressure on Light
zene, respectively, the results shown in Figure 5 were obtained. Naphtha Isomerization
Catalyst activity increased slightly, but butanes and lighter
increased rapidly from the usual 4 to IO%, then declined as the
catalyst lost activity for both isomerization and disproportiona- TABLEVII. EFFECT
OF OLEFINSAKD HIGHER
PARAFFINS
ON
tion. Increasing the inhibitor to 2.0% benzene produced the PENTANEDISPROPORTIONATION
same effect t o a lesser degree and led to more rapid deactivation n- n.
of the catalyst despite a decrease in disproportionation. Under Hexane, Octane,
Amylene, 0.5% 3% 3%
these circumstances the olefin acts as a disproportionation pro-
Mixed pentanesa, ml. 1000 500 1000 1000
moter; addition of more benzene to control the increased dispro- Inhibitor Benzene Isobutane Benzene Benzene
portionation formed larger amounts of alkylated benzene with Inhibitor, vol. % based on Cs 0.5 100 0.5 0.5
AICh, grams 72 72 72 72
resulting decrease in catalyst life. HC1, grams 20.5 20.5 20.5 20.5
Further effects of olefins on disproportionation inhibitors are Temperature, C. 100 100 100 100
Contact time, min. 180 60 180 60
shown in Table VII. Increasing the olefin content to equal
Catalyst Age,
that of the benzene inhibitor (0.5%) leads to even greater dis- Moles Cs/MoIe AlCl Butanes, Wt. %
proportionation than shown in Figure 5. When pentanes are 16
29
inhibited with an equal volume of isobutane, the addition of 42
only 0.5 % amylene immediately destroys the effectiveness of 45
68
14
4
the inhibitor. This is presumably associated with the instability
12% isopentane.
of the hydrocarbons of higher niolecular weight resulting from Butanes derived from pentane disproportionation.
alkylation. This assumption appears to be verified by the results
obtained on adding n-hexane and n-octane t o benzene-inhibited
pentanes, as shown in Table VII. The addition of 3% n-hexane
TABLEVIII. EFFECTOF HYDROGEK AND NAPHTHENES
ON
had no effect, whereas 3% n-octane caused immediate dispropor- ISOMERIZATION O F z,%DIMETHYLBUTASE
tionation.
Experiment 1 2 3 4
Cyclopentane vol. % None None 1.0 10.0
REACTIONS OF HEXANES AlCh, wt. % Lased on hydro-
carbon 10.7 11.0 10.5 11.6
The hexanes behave in many respects in a manner similar to HCI, wt. %
' based on hydro-
carbon 3.2 3.1 3.1 3.5
the pentanes, but because of the increased chain length side reac- Temperature, C. 100 156 157 160
Contact time mm. 20 10 10 10
tions are more pronounced. For instance, butanes derived from Hydrogen, Ib:/sq. inch 1000 600 500 500
hexanes result more from a cracking reaction than dispropor-
Butanes and lighter, wt. % of
tionation, thus creating a greater hydrogen deficiency and more charge 0.5 32.6 30.0 2.2
rapid deactivation of the catalyst. Ipatieff (IO),Grummitt (8), Composition of liquid urod-
Bishop (9), and their coworkers have shown that the hexanes uct, vol. 7 0
Pentanes 0.2 41.5 ... 5.1
decompose mainly to pentanes and butanes in the presence of 2,2-Dimethylbutane 4.4 8.9 ... 21.6
aluminum halides and hydrogen halides at elevated tempera- 2,3-DimethyIbutane 46.9 4.5 ... 6.3
2-Methylpentane 31.6 14.4 ... 37.8
tures. 3-Methylpentane 16.6 7.3 . . I 11.9
n-Hexane and heavier 0.3 22.0 ... 11.3
EFFECTOF INHIBITORS. The results summarized in Table Cyclopentane ... ... ... 6.0
VI11 show that these side reactions can be controlled by the
March 1953 INDUSTRIAL AND ENGINEERING CHEMISTRY 587

no promotional effect t o hydrogen chloride, Beeck (g6) believes

that hydrogen chloride retards the isomerization reaction, while
others (18, 14) assign a promotional effect to hydrogen chloride.
The present data show that hydrogen chloride definitely has a
promotional effect and plays a vital role in the catalysis, as shown
in Figure 10. When light naphtha is isomerized with aluminum
chloride in the absence of hydrogen chloride, there is a rapid
decline in catalyst activity even though hydrogen is present.
The initial activity of the catalyst is attributed to occluded
hydrogen chloride contained in the catalyst. After a catalyst
life of only 50 moles of light naphtha per mole of aluminum
chloride, the catalyst was essentially inactive. When 2.7 weight
% hydrogen chloride based on light naphtha was introduced,
the activity immediately increased and compared favorably
with the life study curve obtained with hydrogen and hydrogen
chloride.
--
OCTANE NUMBER -MOTOR

Figure 8. Effect of Hydrogen Pressure on Butane

Formation from Light Naphtha

Light naphtha having the composition shown in Table I

contains both benzene and naphthenes. However, cyclic inhib-
itors alone are not sufficient for suppressing side reactions of
hexanes and for increasing catalyst life, as shown in Figure 6.
ISOMERIZATION
In the absence of hydrogen the catalyst activity declines rapidly
and the catalyst is essentially inactive a t a catalyst age of 70
moles of light naphtha per mole of aluminum chloride. Carry-
ing out the isomerization of light naphtha under 500 pounds per
h 1
square inch of hydrogen pressure and a t 165' C. produces a
remarkable increase in catalyst life, as shown in Figure 6. The
activity declines rapidly a t first, then levels out and is essentially
constant a t a catalyst life of 240 moles of light naphtha per mole
\ DISPROPORTIONATION
AND
CRACK ING
I
of aluminum chloride. The significance of the difference in the 12 I I I I J O
catalyst activity index, a,a t a catalyst life of 100 moles of light 0 200 400 600 800
naphtha per mole of aluminum chloride for operation in the HYDROGEN PRESSURE - P.S.I.
presence and absence of hydrogen, may be expressed in terms of Figure 9. Effect of Hydrogen Pressure on Isomeriza-
octane number improvement. In the absence of hydrogen 1- tion and Decomposition of Light Naphtha
hour contact time produces only a 1.5 CFRM increase as com-
pared to a 14.0 CFRM increase in the presence of hydrogen,
MECHANISM OF REACTION
This remarkable capacity of hydrogen for inhibiting side reac-
tions during isomerization and for supplying the hydrogen defi- A great deal has been written on the mechanism of the isom-
ciency t o maintain catalyst life is the basis for the neohexane and erization reaction (3, 18, 17, 2S, bV). Although there is some
naphtha isomerization processes operated during the war for difference of opinion, a majority favors a carbonium ion mecha-
aviation gasoline production ( 6 , M ) . nism. The present investigation leads one to believe that there
Figure 7 shows the effect of hydrogen pressure on the isomeri- has been some oversimplification.
zatiqn of light naphtha a t 100' c. Catalyst life increases as the Any mechanism must adequately take into account the follow-
hydrogen pressure is increased. Figure 8 shows the effect of ing facts:
hydrogen pressure on butane formation for these same experi-
ments. The production of butanes and lighter becomes pro- Reaction takes place in the catalyst phase.
gressively less as the hydrogen pressure is increased. The sup- Hydrogen chloride is a necessary component of the catalyst.
pression of butane formation by hydrogen explains a t least in Hydrogen, aromatics, naphthenes, and isobutane inhibit dis-
proportionation.
part the longer catalyst life obtained a t the higher hydrogen Disproportionation is inhibited without appreciably affecting
pressures. Furthermore, hydrogen has a minor effect on sup- isomerization.
pressing isomerization. Analysis of the products produced a t Olefins destroy the effect of inhibitors and increase dispro-
various hydrogen pressures showed a small but definite decrease portionation and cracking.
Minimum hydrogen pressure necessary to inhibit dispropor-
in 2,2-dimethylbutane with increase in hydrogen pressure, as tionation and cracking increases with chain length.
shown in Figure 9. The same effect of hydrogen pressure was Suppressing effect of inhibitors on isomerization increases
observed for the isomerization of cyclohexane to metliylcyclo- with decrease in chain length.
pentane (14). When a cross plot of Figure 8 is prepared a t an Formation of aluminum chloride-hydrocarbon sludge increases
with increase in chain length.
80 CFRM level and placed on Figure 9 for comparison, the Hydrogen is consumed.
effect of hydrogen pressure on the disproportionation and crack-
ing reactions as measured by butane formation varies exponen- Brown, Pearsall, and Eddy ( 4 ) have shown that no interaction
tially while the effect of hydrogen pressure on suppressing isom- occurs between pure aluminum chloride and pure hydrogen
erization is a linear function. chloride, but that in the presence of a basic aubstance-i.e.,
HYDROGEN CHLORIDE AS AN ACTIVATOR.There are considera- a proton acceptor-a complex is formed in which the aluminum
ble differences in opinion concerning the effect of hydrogen chloride and hydrogen chloride are associated stoichiometrically.
chloride when added to aluminum chloride. Pines ( $ 1 ) ascribes On this basis i t is postulated that the proton acceptors, which
888 INDUSTRIAL AND ENGINEERING CHEMISTRY
are present as impurities in the commercial reagents employed
in this work, serve to force the following reaction to the right.
Proton acceptor (moisture, oxygen, olefins, etc.) + HCl +
AICh
r
[proton y c e p t o r 1
1+
AIC1,-
I t is further postulated that it is the resulting product, in the
form of an ionized complex, which acts as the effective catalyst.
I active fragment three potential carbonium ions are forme 1,
I
I I
This ionized complex does not differ particularly from a c d i -
bonium ion, especially as more recently carbonium ions have
been generally assumed to be associated x i t h the catalyst en-
vironment (24). I n the carbonium ion mechanism the cai-
bonium ion is depicted as attracting a hydride ion from a hydro-
carbon to form a new carbonium ion, which then undergoes
rearrangement. The rearranged (isomerized) carbonium ion
in turn attracts a hydride ion from another hydrocarbon mole-
cule, thus propagating the chain. The carbonium ion niecha-
nism theory is believed to be inadequate, as it does not account
for the fact that inhibitors have a pronounced effect on the dis-
proportionation reaction but only a relatively small effect 011
isomerization. The present results are believed to be nioie ade-
quately explained by picturing the isomerization reaction as tak-
ing place through association of the hydrocarbon with the
ionized complex, m-hereby activation occurs followed by rear-
rangement. This concept does not differ substantially from that
advanced by Heldman ( 9 , 13) and later by Powell and Reid ( $ 3 )
and Beeck et al. (1,50). Catalytic action may be pictured as a
simultaneous proton-anion attack on the hydrocarbon mole-
cule in a manner similar to the push-pull mechanism conceived
by Swain (27) to explain displacement reactions of organic
halides. Thus as shown below, the electrophilic proton portion
of the catalyst attracts the hydrogen on the second carbon atom
in the hydrocarbon chain through distoition of the elections in
the C-H bond. At the same time the nucleophilic AIC1,-
portion of the catalyst attracts the hydrogen on the opposite
side of the third carbon atom The qimultaneous attack effects
Vol. 45, No. 3
an over-all electron displacement, which results in an intramolec-
ular rearrangement while the hydrocarbon is associated with
the catalyst. This activated complex-intramolecular rearrange-
ment mechanism has the desirable feature of depicting the
role of the catalyst and can account for variations in isomeriza-
tion due to acid strength.
H
H H
CH, : C C : CH,---
H H
Figure 9 suggests that the isomerization and disproportiona-
tion reactions are proceeding by different mechanisms. It is
postulated that the disproportionation reaction arises when the
activated hydrocarbon moves under certain circumstances far-
ther than some critical distance from the catalyst environment,
thus giving rise to a free active fragment which is a carbonium
ion or ie similar to a free carbonium ion. This carbonium ion
can do several things: It can undergo hydride ion transfer with
another hydrocarbon molecule, thus propagating the chain, or
lose a proton t o become an olefin which may add to the aluminum
chloride to form aluminum chloride-hydrocarbon sludge or reform
a carbonium ion. W-hen sufficient carbonium ions are formed-
for example, when the temperature is raised or olefins are added-
the chances of reaction of a carbonium ion with an olefin increase.
In the case of pentanes, reaction of a carbonium ion with a C,
olefin leads to a Clo carbonium ion. Such a large carboniuni
ion is extremely unstable and may break into two propylene
molecules and a Cq carbonium ion. In other words, from one
which leads to an accelerated zero-order chain reaction. Thia
implies the necessity for keeping the free carbonium ion concen-
tration below a critical value to avoid gross disproportionation
of the hydrocarbon. This is what aromatics, naphthenes, and
hydrogen do as inhibitors; they react with carbonium ions, thu-
controlling the carbonium ion concentration. From this it ma\-
be seen horr the disproportionation reaction can be inhibited
without appreciable effect on the isomerization reaction.
Besides disproportionation, wherein a hydrogen balance i -
maintained, there is the additional side reaction of crackin:,
n-hich leads to hvdrocarbons of lorver molecular weight and a
hydrogen deficiency. This cracking reaction becomes mor e
pronounced with increase in the length of the hydrocarbon chain.
This leads largely to the formation of aluminum chloride-hydro-
carbon sludge, which deactivates the catalyst. Besides inhibiting
the disproportionation reaction by adding to free carbonium
ions, hydrogen is also capable of reacting with the hydrocarbon
attached t o the aluminum chloride to split off saturated hydro-
carbons of low molecular weight, thus regenerating the cata
I p t . This later reaction leads to the hydrogen consumption
observed during isomerization in the presence of hydrogen.
ACKYOWLEDGMENT
The authors are indebted to the numerous members of the
Standai'd Oil Go. (Indiana) Research Laboratories who contrih-
uted their advice and services, and especially to E. TTT. Thiele,
l3.H. Shoemaker, and J. A. Bolt.
LITERATURE CITED
( I ) Beeck, O., Otvos, Y. W., Stevenson, D. P., and Wagner, C. D.,
J . Chem. Phus., 16, 255 (1948).
(2) Bishop, J. W., Burk, R. E., and Lankelma, H. P., J. Am. Chem.
Sot., 67, 914 (1945).
(3) Bloch, H. S., Pines, H., and Schmerling, L., Ihid., 68, 153
(1946).
March 1953 INDUSTRIAL AND ENGINEERING CHEMISTRY
(4) Brown, H. C., Pearsall, H., and Eddy, I . P., Ibid., 72, 5347
(1950).
(5) Egloff, G., Hulla, G., and Komarewsky, V. I., “Isomerization
of Pure Hydrocarbons,” New York, Reinhold Publishing
Corp., 1942.
(6) Evering, B. L., Fragen, N., and Weems, G. S., Chem. Eng. News,
22, 1898 (1944).
(7) Evering, B. L., and d’ouville, E. L., J . Am. Chem. SOC.,
71, 440
(19491.
(8) Grummitt, O., Sensel, E. E., Smith, W. R., Burk, R. E., and
Lankelma, H. P., Ibid., 67, 910 (1945).
(9) Heldman, J. D., Ibid., 66, 1786 (1944).
(10) Ipatieff, V. N., and Grosse, A. V., IND. ENG.CHEM.,28, 461
(1936).
(11) Ipatieff, V. N., and Schmerling, L., Ibid., 40, 2354 (1948).
(12) Komarewsky, V. I., and Ulick, S. C., J. Am. Chem. SOC.,69, 492
(1947).
(13) Leighton, P. A., and Heldman, J. D., Ibid., 65, 2276 (1943).
(14) Lien, A. P., d’Ouville, E. L., Evering, B. L., and Grubb, H. M.,
IND. ENG.CHEM.,44, 351 (1952).
(15) McAllister, S. H., Ross, W. E., Randlett, €I. E., and Carlson,
G. J., T r a n s . Am. I n s t . Chem. Engrs., 4 2 , 3 3 (1946).
(16) Mavitv. J. M.. Pines. H.. Wackher. R. C.. and Brooks. J. A,.
IN=:ENG.CHEM.,40, 2374 (1948).
(17) Oblad, A, G., and Gorin, M. H., Ibid., 38, 822 (1946).
(18) Perry, S. F., Trans. Am. I n s t . Chem. Engrs., 42, 639 (1946).
Correlating Diffusion Coefficients
in Liquids
DONALD F. OTHMER AND MAHESH S. THAKAR
Polytechnic Institute of Brooklyn, Brooklyn 2, N . Y .
D TFFUSION coefficients in liquids are increasinglv important
in many theoretical and engineering calculations involving
mass transfer, such as absorption, extraction, distillation, and
chemical reactions. Comparatively few such data have been
published, however, and methods for their correlation and for
prediction of data on other substances are needed.
A simple method of correlation is presented which allows easy
and accurate extrapolation and interpolation of available data,
and the prediction of such data when not available. The method
follows the principle used t o correlate many other properties of
matter in previous papers of this series-namely, plotting logarith-
mically the property of one material against the same property
or the vapor pressure of a reference material. I n this manner,
vapor pressures (a), gas solubilities and partial pressures (1‘7),
adsorption pressures ( 1 5 ) , vapor compositions, equilibrium con-
stants, activity coefficients, relative volatilities, electromotive
forces (9, 1 1 ) , viscosities (IO),reaction rate constants ( I d ) , sur-
face tensions ( l a ) , densities ( 1 3 ) , and azeotropic compositions
( 1 6 ) have already been correlated. The theoretical background
for such a plot may vary, b u t the method usually follows the sim-
ple steps for making a vapor pressure plot (8):
1. On a sheet of logarithmic paper indicate vapor pressures of
water-on the X axis and of the
a standard substance-e.g.,
substance in question on the Y axis; then calibrate the X axis
with values of temperatures corresponding t o the vapor pres-
sures of the standard substance.
2 . Erect temperature ordinates.
3. Plot points and connect with a straight line, the slope of
which is the ratio of the molal latent heat of the substance to that
of the reference substance. This ratio is much more nearly
constant a t all temperatures-and the line more nearly straight-
than the latent heat itself from a plot of log P us. 1 /T.
DEVELOPMENT OF LOGARITHMIC PLOT FOR DIFFUSION
COEFFICIENTS
The variation of diffusion coefficients with temperature has
been assumed by Wilke ( 1 9 ) t o be related to the Stokes-Einstein
589
Pines, H., in “Advances in Catalysis,” Vol. I, p. 251, edited by
Frankenburg, Komarewsky, and Rideal, New York, Academic
Press, 1948.
Pines, H., Kvetinskas, B., Kassel, L. S., and Ipatieff, V. N.,
J . Am. Chem. SOC.,67, 631 (1945).
Pines, H., and Wackher, R. C., Ibid., 68, 595 (1946).
Ibid., p. 699.
Powell, T. M., and Reid, E. B., Ibid., 67, 1020 (1945).
Schmerling, Louis, paper presented before Division of Petroleum
Chemistry, 119th Meeting, AM. CHEM. SOC., Cleveland,
Ohio.
Schuit, G. C. A., Hogg, H., and Verheus, J., Rec. trau. chim., 59,
793 (1940).
Stevenson, D. P., and Beeck, O., J . Am. Chem. Soc., 70, 2890
(1948).
Swain, C. G . , Ibid., 70, 1119 (1948).
Swearingen, J, E., Geckler, R. D., and Nysewander, C. W.,
T r a n s . Am. I n s t . Chem. Engrs., 42, 573 (1946).
Wackher, R. C., and Pines, H., J . Am. Chem. SOC.,6 8 , 1642
(1946).
Wagner, C. D., Beeck, O., Otvos, Y . W., and Stevenson, D. P.,
J . Phys. Chem., 1 7 , 4 1 9 (1949).
RECEIVED for review June 14, 1952. ACCEPTED October 20, 1952.
Presented before the Division of Petroleum Chemistry at the 111th Meeting
of the AMERICAN CHEMICAL SOCIETY, Atlantic City, N. J.
law-i.e., directly proportional to the absolute temperature and
inversely proportional t o the viscosity of the liquid.
Eyring (6) and others (3,4,18) have suggested that diffusion
is a rate process which varies as a n exponential function of
temperature. Thus:
D = KeEd/RT
(1)
Taking logarithms and differentiating,
The Clausius-Clapeyron equation for the vapor pressure of
liquids is:
dT
d l o g P = -L (3)
RT2
At the same temperature, if Equation 2 is divided b y Equation 3,
there results:
(4)
If E J L is assumed constant, this can be integrated t o give:
Log D = Ed log P +C (5)
Equation 5 indicates that, if diffusion coefficients are plotted
on logarithmic paper against vapor pressures of a reference liquid
at the same temperatures, a straight line results with slope of
EaIL.
Diffusion coefficients of different substances are plotted
this way in Figure 1. The X or vapor pressure axis is calibrated
t o give a temperature scale by known values from a standard
table. The energy of activation of diffusion can be calculated
from the slope of the line and the latent heat of vaporization of
the reference substance a t t h a t temperature.