Ze o I i te Cat a I ys t s

Hydrocracking and Hydroisomerization of n-Dodecane

Hans F. Schulzl and Jens H. Weitkamp
Carl Engler und Hans-Bunte-Institut f ur Lliineralol-und Kohleforschung und I nstitut f ur Gastechnik,
Feuerungstechnik und Wasserchemie der Universitat, Karlsruhe, West Germany
With a Pt/Ca/Y-zeolite, a C12-isomerization conversion maximum of 48% i s obtained, and up to a 100%
cracking conversion of the C12 pure primary cracking i s achieved. Pd/Mn-H/Y-zeolite and Pd/H/Y-zeolite
catalysts give poorer isomerization and show secondary cracking even at low cracking conversion level. Rel-
ative rates of individual primary and secondary cracking reactions ate given and related to the Clz-isomeri-
zate composition showing /3-scission proceeding from tertiary carbonium ions. 2-Methylisomers are primary
cracked products. Paraffin isomers with quaternary C-atoms could be produced by n-dodecane hydrocrack-
ing. The total observed branching of the cracked products i s correlated to contributions of primary and secon-
dary isomerization.
T he use of zeolites for heterogeneous catalysis, in particular
for mineral oil processing through reactions involving car-
bonium ions, in catalytic cracking, hydrocracking, and hydro-
isomerization is of increasing importance. Acidity and hydro-
genation activity of bifunctional zeolite catalysts may easily
be varied by ion exchange. Active components for hydro-
genation, normally noble metals such as platinum or pal-
ladium, are introduced to the pores of zeolites as ammonia
complexes and reduced to their elemental forms with hy-
drogen at ca. 500C. Thus, the metal is finely distributed,
probably mainly atomically in the pores of the zeolite
lattice (10, 16).
The composition of the reaction products from hydro-
cracking is principally dependent on reaction temperature
and the relationship of hydrogenation-dehydrogenation
activity to the acidity responsible for the cracking activity
of the bifunctional catalyst (1, 6, 8, 9, 11). The principal and
widely accepted reaction scheme of hydrocracking (6, 8, 12)
starts with the formation of olefins from paraffins at metallic
centers and the formation of carbonium ions from these
olefins at acidic centers. The ions may undergo rearrangement
and splitting according to certain rules of carbonium ion
behavior. Olefins resulting from carbonium ions are in turn
saturated to give a mostly paraffinic product. This general
reaction path of hydrocracking is by far simpler than that of
catalytic cracking, which involves additional polymerization,
alkylation, cyclization and aromatization, hydrogen transfer,
and coke formation that rapidly deteriorate catalyst activity.
Thus, hydrocracking is more accessible than catalytic crack-
ing to kinetic investigations.
Results of hydroisomerization on zeolite noble metal
catalysts have been publiqhed (3, 14, 16, bl ) , however, only
'To whom correspondence should be addressed.
by use of low molecular paraffins up to C7 as feed materials
which may easily be converted by isomerization associated
only with minor cracking. The products are analyzed without
great efforts. Hydrocracking of higher molecular paraffinic
hydrocarbons on highly active platinum on an amorphous
AlzO3- SiOz- catalyst has been reported by Coonradt and
Garwood (6) who pointed out the possibility of pure primary
cracking and the high degree of isomerization of the un-
cracked feed. However, no detailed analyses of cracked and
isomerized products were given. Literature on hydrocracking
of pure hydrocarbons with zeolite catalysts is limited (2,4,21).
Experimental
For the present investigation the following three catalysts
were used: 0.5% Pt/Ca/Y-zeolite (SK 200), 0.5% Pd/Mn-
H/Y-zeolite (SK 110), 0.5% Pd/H/Y-zeolite (SK loo), all
supplied from Union Carbide I nternational Corp., Linde
Division. The reaction conditions were molar ratio Hl/n-
dodecane =20, LHSV =1.0 h-l, and pressure =40 atm.
The reaction temperature was varied in the range from 250-
400C according to catalyst activity and required degree of
conversion. The high analytical sensitivity permitted quan-
titative results even at low conversion levels. Purity of n-
dodecane feed material was controlled by gas chromatography.
The flow type fixed bed reactor was designed for quantita-
tive experiments at small throughputs of 1-5 grams of hydro-
carbon feed per hour (Figure 1). The problem of continuously
feeding at a constant rate-e.g., only 1 gram n-dodecane per
hour to the reactor-was solved with a special saturator.
The n-dodecane in an amount of 50 grams was impregnated
on inactivated kieselguhr (100/100 g/g). This material was held
at an appropriate temperature in the saturator where the
stream of hydrogen passed the packing. The equilibrium
vapor pressure was attained even in about 1 mm of bed
46 Ind. Eng. Chem. Prod. Res. Develop., Vol. 1 1 , No. 1 , 1972
height. Thus, the hydrocarbon concentration in the feed gas
is independent of flow, and almost all of a saturator filling
can be used without changes in feed rate. For long duration
tests a second saturator in a parallel feed line is used.
For quantitative recovery of the hydrocarbons from the
product stream, two traps at liquid air temperature were used,
the second filled with activated carbon for quantitative ad-
sorption of methane. Condensate and adsorbate were sepa-
rated in fractions of liquid and gaseous hydrocarbons whose
quantities were accurately determined at room temperature.
The gaseous hydrocarbons with compounds up to CS were
analyzed with a reoplex modified Ak1203gas chromatographic
column by applying a temperature program up to 190OC.
The liquid hydrocarbons were separated with 100-mm film
capillaries containing polypropylene glycol and squalane as
liquid phases. Temperature programmed capillary gas chroma-
tography of complex hydrocarbon mixtures Ca-Cle was re-
ported in earlier publications (18, 19).
Quantitat'ive values for individual hydrocarbons could be
derived from the chromatogram for almost all compounds
produced by cracking and in the (212-isomerizate fraction for
methylundecanes and ethyldecanes. Multiple branched Clz-
hydrocarbons were calculated cumulatively.
The electronically int'egrated values of peak areas from the
different chromatograms and the values of fraction quantities
were fed to a digital computer for total evaluation of each
experiment.
Results and Discussion
Cracking and I somerization Conversion. At a sufficient
high hydrogenat,ion activity of the catalyst and correspond-
ing high hydrogenation and dehydrogenation rat'es, a
ready exchange of chemisorbed CI 2-carbonium ions with
Clz-olefins from t,he gas phase takes place. Part of the
CI:-carbonium ions desorbs from the catalyst surface after
rearrangement (but before C-C cleavage) to give branched
olefins which, in turn, are hydrogenated to branched Clz-
paraffins. At low hydrogenation activity of the catalyst, in
general, only reactions in the sequence Clz-paraffin -+C12-
olefin - Clz-carbonium ion -+cracked products <Clz are
possible, and only low concentrations of branched feed hydro-
carbons can be detected in the reaction product.
Figure 2 shows the cracking and isomerization conversion
0 P t/ C O/ Y - ZEOLI TE
A Pd/Mn-H/Y-ZEOLI TE
N -DODECANE-
SATURATOR ''
C
EACTOR
G H
Figure 1 . Scheme of small scale reaction apparatus for
hydrocracking
(A) Active carbon plus molecular sieve tube for Hz-purification; (B) molten
salt bat h f or saturator t emperat ure control; (C) n-dodecane on kieselguhr;
(D) heat ed connection tube; (E) preheati ng zone; (F) 2 ml of catal yst, 0.2-
0.3 mm; ( G) liquid ai r cooling t r ap; (H) act i vat ed carbon t rop at liquid
ai r t emperat ure
as a function of temperature for different hydrocracking
catalysts. The additional curves for Co-Uo-&0s-SiO2,
sulfided CO-I LI O-A~~O~-S~OZ, and Co-hIo-Al2O~ were ob-
tained with n-hexadecane under similar conditions (23, 20).
The various catalysts are active in different regions of re-
action temperature-e.g., Pt/Ca/Y-zeolite below 300C
and CO-?\.IO-AIZOS at about 450OC. But the principal shape
of the curves is similar in most cases where there is a sufficient
hydrogenation activity related to cracking activity. The
conversion by isomerization increases with temperature and
then goes through a maximum when increasingly isomerized
Clz-molecules are cracked.
The different behavior of the sulfided Co-Mo-AlzO~-
SiO& catalyst with its relatively low hydrogenation activity
as related to its high acidity shows the transition in reactions
to normal catalytic cracking with a low maximum of feed
hydrocarbon isomerization conversion of only ca. 5%. On
Pt/Ca/Y-zeolite the maximum of isomerization conversion
of 48% is found at a cracking conversion of only 17% at
Figure 2. Hydrocracking and hydroisomerization conversion
Dependence on reacti on t emperat ure f or di f f erent bi functi onal catalysts
Ind. Eng. Chem. Prod. Res. Devel op., Vol. 1 1 , No. 1, 1972 47
Tabl e I. Mol ar Di stri buti on of Cracked Products wi t h Pt/Ca/-, Pd/Mn-H/-, and Pd/H/Y-Zeol i t e
Catal ysts at Di fferent Reacti on Temperatures
Moles of cracked products per 100 moles of C12cracked
Catalyst Pt/Ca/Y-zeolite . ~~_ _ PdlMn-H/Y-zeolite Pd/H/Y-zeolite
Temp, OC 265 275 285 300 350 250 275 300 325 350 400 275 300 325 350
CL2--
Conversion, yo
Cracking
Clz-isomerization
Methane
Ethane
Propane
13utaiies
Pentanes
Hexanes
Heptanes
Octanes
Konanes
Decanes
Undecanes
- c.4 +Cs 29.6 30.5 31.2 30.4
cs+c7 42.3 41.5 41.4 41.7
5 17
34 48
. . . . . .
. . . . .
6.7 6.7
29.7 30.4
42 3 41.9
43.5 43.5
42.3 41.2
29.5 30.7
6.3 6.0
. . . . . .
. . . . . .
' 12-*
56
35
. . .
, . .
7. 0
31.8
41.9
42.9
41.0
30.6
5.9
. . .
+ e4+cs 31.2 18.6 15.3
+ C6 +c7 41 4 33.7 32.3
C6 +c6 21.4 22.1 22.2
- c3+C4 +cs . . . 16.6 20.8
99.5 100
0.47 . . .
0.1 0.5
0.1 0.6
9.0 48.5
38.9 101.2
46.3 66.4
44.2 43.3
40.3 8.1
25.9 . . .
3.4 . . .
. . . . . .
. . . . . . .
5
5
0.1
11.7
48.0
48.9
43.8
36.7
23.0
2.7
. . .
. . .
. . .
12 50
18 31
0.2 0.2
14.8 17.5
52.6 55.0
50.6 51.6
44.0 44.2
34.7 33.7
20.8 18.6
2.1 2.1
. . . . . .
. . . . . .
. . . . . .
100
. . .
0.1
0.3
19.6
57.3
53.2
44.2
32.9
16.9
1.6
. . .
. . .
100
. . .
0.4
1.1
42.9
89.9
62.0
45.6
16.2
1. 4
0.1
. . .
. . .
00
. . .
2.9
4.6
76.0
05.8
64.6
35.1
0.4
. . .
. . .
. . .
. . .
16
2.9
0.2
18.2
55.6
52.5
43.7
34.0
17.2
2.5
. . .
. . .
30
3.0
0.2
20.9
56.8
52.2
43.1
33.4
16.9
2. 3
. . .
. . .
. . .
49
3.0
0.2
22.1
57.8
53.9
44.3
32.3
15.3
2.1
. . .
. . .
63
2.2
0.1
0. 4
27.3
63.8
55.1
44.4
28.1
12.6.
2.5*
. . .
. . .
Total moles 200 200 201 208 269 215 220 223 226 260 289 224 226 228 234
a Inrluding 0.6 mole aromatics. * Including 0.8 mole aromatics.
275OC. Complete cracking of the Clz-feed is attained already
at 300C. The conversion of n-Clz by isomerization at low
temperatures (250-265C) on Pt/Ca/Y-zeolite is 7-10
times greater than that by cracking, showing a much greater
rate for carbonium ion rearrangement than for carbonium
ion cleavage. With Pd/Mn-H/Y-zeolite the lower hydro-
genation-dehydrogenation activity of the catalyst is limiting
for isomerization conversion, its maximum being only 30%.
At low temperatures conversion by isomerization is slightly
higher than that of cracking.
Distribution of Cracked Products. Table I gives the
molar distributions of the cracked products on the basis of
100 moles of n-dodecane cracked. On Pt/Ca/Y-zeolite
the sum of moles of cracked products is approximately
equal to 200 over almost the total region of cracking
conversion from 0- loo%, showing pure primary cracking.
There is a sufficient supply of C12-olefins by fast dehydro-
genation for immediate displacement of lower carbonium ions
from the acidic sites to prevent their secondary cracking.
The distribution of cracked products is symmetrical to C g
(half the C12feed molecule) with approximately equal values
for Cg, (26, and (27. Values for CS and are about 2/ 3 of the
former, and values for Cs and CB are relatively small. C1, Cz
and Cln, CI1 products are materially absent.
With Pd/Mn-H/Y-zeolite, even at a low conversion level
secondary cracking occurs and ranges from 15-26% with
increasing primary cracking conversion from 0 to ea. 100%.
The molar distribution of cracked products is correspondingly
asymmetrical with higher values for Cs, C4, and C3than for
C7, CS, and CQ, respectively. At higher temperatures than those
necessary for 100% of cracking conversion, the sum of moles
increases rapidly, and a sharp maximum at Cq is obtained.
Probability of Cracking Reactions. From the molar
distribution of cracked products, the relative probabilities
of distinct cracking reactions can be derived. This is
particularly true for the exclusive n-dodecane primary
cracking on the Pt/Ca/Y-zeolite catalyst. I n Table I1
this selectivity of dodecane cracking to CB +CS, C4 +CS,
C6 +C7, and C6 +C6 is reported.
The low values of cleavage to CB +CS could be related to
energetic effects since the C3fragment cannot form a tertiary
ion. But a remarkably low value of ea. 30Y0for the reaction
to C4 +CS cannot easily be explained because both fragments
can form energetically favored tertiary carbonium ions.
I sobutane is a common product of ionic hydrocarbon cracking.
A slight increase in the probability of this reaction with tem-
perature is observed. This selectivity will be discussed later
in coiinectioii with isomerization reactions which inseparably
accompany ioiiic cracking.
The probabilities of overall cracking reactions on Pd/Mn-
H/Y-zeolite and Pd/H/Y-zeolite can also be calculated from
48 Ind. Eng. Chem. Prod. Res. Develop., Vol. 11, No. 1 , 1972
the molar distributions of the cracked products and are
listed in Table I11 along with those for primary cracking on
Pt/Ca/Y-zeolite for a 50% cracking conversion level.
The different values are obtained as follows: Reaction to
Cg +C3as moles of Cg, to Cs +Cq as moles of CS, to C? +
C5 as moles of C7, to Cg +cgas half the moles of C6, to C3+
C4 +Cg as the mean value of the differences of moles C3 -
C9and C5 - C7, and to C4 +Cq +C4 as l / 3 of the difference
between (C4 - Cs) and (C3 - Cg)/2 +(C5 - C7)/2. For
extensive secondary cracking at higher temperatures, the
negligence of t'he reaction c12to e6+C3 +c3is not tenable.
I n t'he case of secondary cracking, the reaction to C3 +
Cq+C s is obviously favored to C4 +C4 - t C4. h'ote the minor
secondary cracking of ( 26 as is seeii from almost the same
values for C6in all three distributions.
Thorough examination of all experimental data showed
that, as a good approximation, averaging the values of pri-
mary cracking observed with Pt/Ca/Y-zeolite (Table 11)
yields the probabilities of primary cracking reactions on
Pd/hln-H/Y-zeolite and Pd/H/Y-zeolite. On this basis the
probabilities of the single secondary cracking reactions can
be calculated and are given for the Pd/Mn-H/Y-zeolite at
5070 conversion in Table IV.
The contributious of the primary cracking products as
sources for secondary cracking follow the order C,S (11.8) >
CI (8.0) >cs (4.3) >C6 (<0.2) whereas the percentage
of primary products converted to lower molecular-weight
compounds by secondary cracking follows the sequence
C9 (67%) >CS (39%) >C7 (19%) >c6(<I %) with the
principally expected relative cracking probability in de-
pendence of molecular weight.
The remarkably sharp decrease in cracking reactivit,y from
C7 to Ce is the reason why n-paraffinic fractions up to C6
can be extensively isomerized with only minor cracking.
There is a surprising selectivity of these secondary cracking
reactions-e.g., 4.3 C9 convert to 0.9 (C3 +C6) and 3.4
(C4 +Cs), but 11.8 CS convert to 5.2 (C3 +Cj) and 6.6
(C4 +Cq), showing for cracking of CS an almost equal prob-
ability of splitting a C3 or C4fragment from a CS chain, but a
much lower probability for C3 t'haii C4 to be split from a Cg
chain.
Isomeri zati on of Cracked Products and Feed Hydro-
carbon. The extensive determination of individual iso-
mers in t,he reaction products is the basis for the discussion
of carbonium ion rearrangements involved in the hydro-
cracking reactions. I n principle one must question whether
isomerization takes place before or after the cracking steps
and how great tlie respective coutribution of these possi-
bilities is to total isomerization. I n spite of the important
mechanistic role of olefins, the reaction products may gener-
ally be regarded as paraffinic. Other types of hydrocarbons are
present only i u minute quantities (olefins <O.l %, naphthenes
<I %).
I n Table V the composition of the carbon number fractions
of the reaction products of n-dodecaue hydrocracking with the
three noble metal zeolite catalyst's at different characteristic
temperatures is listed.
Thermodynamic Considerations. The isomer composition
of paraffinic cracked products from hydrocracking with
bifunctional catalysts, especially at low temperatures, is
mainly governed by the kinetics of the reactions. I n particular
tlie ratios of iiidividual monomethyl paraffins to the corre-
sponding n-para%iis are greater than those for thermodynamic
equilibrium whereas the amounts of dimethyl compounds, es-
pecially those with quaternary C-atoms, are much smaller.
EOUILIBRIUM PI/Co/Y-ZEOLITE Pd/Mn-H/Y-ZEOLITE P d/H/Y - ZEOLl 'i
3- ME- PENI ANE 3-ME-PENTANE
P
1 2-ME-PENTANE 1 2- ME- f ' ENI AN~ 2-HE-PENTANE 2-ME-PENTANE
]
Mo
TEMPERAIURE. ' C
Figure 3. Thermodynamic equilibrium and experimental
composition of hexane fraction for different catalysts and
temperatures
Tabl e IV. Rel at i ve Probabi l i t y of Pri mary and Secondary
Cracki ng Reacti ons of n-Dodecane on Pd/Mn-H/Y-
Zeol i t e at 50% Cracki ng Conversi on
Temp, 3OOOC
Pri mary cracking Secondary cracking
I n Figure 3 the composition of the C6-fraction of the cracked
products from n-dodecane with Pt/Ca/Y - zeolite, Pd/Mn-
H/Y - zeolite, and Pd/H/Y-zeolite is plotted over the
reaction temperature along with the equilibrium com-
position. The accuracy of isomer equilibrium cornposition
calculated from thermodynamic values of literature (1 7 )
is debatable. According to our results considerable discrepan-
cies seem to exist, but the calculated values reflect the trends
in changes of isomer composition with temperature.
With increasing temperature the experimental composi-
tion alters toward that of equilibrium. The products at
low temperature are characterized by high values for 2-
methylpentane and low values for 2,2-dimethylbutane. At a
reaction temperature higher than that necessary for 100%
cracking conversion, there is a fast increase for 2,2-dimethyl-
butane, especially with Pt/Ca/Y- zeolite, indicating a fast
increase of secondary isomerization possibilities. This is of
importance under the practical aspects of producing high
octane number gasoline by hydrocracking and will be reported
in detail in a later publication. It is also of theoretical interest,
since i t has bren repeatedly stated in the literature that com-
pounds with quaternary C-atoms do not form by hgdro-
cracking ( 7, 8) .
Ind. Eng. Chem. Prod. Res. Devel op., Vol. 1 1 , No. 1 , 1972 49
Tabl e V. Composi ti on of Reacti on Products f r om n-Dodecane Hydrocracki ng
Cat al yst
Temp, " C
n-Butane
I sobutane
%-Pentane
I sopentane
%-Hexane
2-Methylpentane
3-Methy lpentane
2,3-Dimethylbutane
2,2-Dimethylbutane
n-Hep t ane
2-Methylhexane
3-Me thylhexane
3-Ethylpentane
2,3-Dimethylpentane
2,4-Dimethylpentane
2,2-Dimethylpentane
3,3-Dimethylpentane
2,2,3-Trimethylbutane
n-Octane
2-Methylheptane
3-Methylheptane
3-E thylhexane
4-Methylheptane
2,3-Dimethylhexane
2,CDimethylhexane
2,5-Dimethylhexane
3,4-Dimethylhexane
2,2-Dimethylhexane
3,3-Dimethylhexane
2-Ne thyl-3-ethylpentane
n-Sonane
2-Methyloctane
4-Methyloctane
3-Methyloctane
3-Ethylheptane
2,3-Dimethylheptane
2,4-Dimethylheptane
2,5-Dimethylheptane
3,5-Dimethylheptane
2,6 +4,4-Dimethylheptaneo
3,4-Dimethylheptane
2,2-Dimethylheptane
3,3-Dimethylheptane
n-Dodecane
2-Methyluhdecane
3-Methylundecane
4-Methy lundecane
5-Methy lundecane
6-Methylundecane
3-Ethyldecane
4-Ethyldecane
5-Ethyldecane
Multiple branched dodecanes
Mol % in carbon number fraction
Pt/Ca/Y-zeol i te
275 300 ' 350
32.6
67.4
a5.3
74.7
21.9
47.5
26.4
3.9
0 . 3
17.2
40.0
32.7
1. 8
4. 3
3. 2
0. 5
0. 3
0.0
14.2
28.9
28.1
3. 3
9. 8
2.6
5.2
5. 4
1 .o
0. 9
0. 5
0.1
8. 9
39.7.
22.0
3. 1
1. 9
3. 6
9. 5
2. 2
3. 8
4. 1
0. 7
0.5
42.9
5. 5
7. 1
6. 3
7. 0
3.7
1. 2
2.2
2. 3
21.8
34.8
65.2
25.7
74.3
24.1
43.5
26.3
3.7
2. 4
19.3
31.7
32.3
2. 2
5.0
3. 5
3. 4
2. 3
0. 3
15.1
21.3
24.6
3. 6
9. 1
3. 8
7. 9
5.5
1. 9
3. 8
2. 8
0.6
10.2
30. Se
17.3
3. 1
3. 4
5.5
10.1
2. 9
5. 9
5. 2
3. 1
2.5
11.5
6.7
8.1
6. 4
8. 3
4. 5
1. 5
2. 9
3.6
46.5
36.2
63.8
33.3
66.7
21.4
32.1
24.7
7. 4
14.4
15.7
26.1
30.4
2. 2
8. 2
5. 6
5. 6
4.4
1. 8
a
Pd/Mn-H/Y-zeolite
275 300 350
29.3
70.7
19.1
80.9
15.3
47.7
28.1
8. 3
0. 6
11.8
36.5
32.2
1.7
IO. 1
6. 3
0. 6
0. 5
0. 3
9. 5
24.4
29.2b
9. 8
5. 4
9. 0
9. 2
2. 1
0. 8
0. 4
0. 2
6.9
19.5
16.0
17.5
2. 3
4.9
5. 1
16.7f
6. 1
4.6
0. 2
0. 2
79.6
2.0
2. 8
2. 6
2. 8
1. 5
0.6
0. 8
0. 9
6. 4
33.3
66.7
20.9
79.1
19.2
44.6
27.5
7. 9
0. 8
15.6
34.3
31.9
2.0
8. 8
5.7
0. 8
0. 6
0.3
14.6
23.5
28.7b
9. 6
4. 7
8. 2
6. 4
2. 0
1. 2
0. 8
0. 3
10.2
19.2
15.6
17.6
3. 2
3.9
5. 4
13.2f
5. 0
4. 5
1. 1
1. 1
38.6
5. 0
6.6
6. 0
6. 4
4. 1
1. 6
2. 5
2.6
26.6
37 4
62 6
27 2
72 8
23 5
36 4
26 5
7 4
6 2
18 1
25 8
30 3
2 4
8 1
5 3
4 6
3 9
1 5
17 1
16 6
24 7b
8 0
4 1
8 1
10 l c
3 8
3 7
3 3
0 5
d
Pd/H/Y-zeol i te
275 300 350
25.5
74.5
11.7
88.3
9. 2
50.6
29.1
10.5
0. 6
7. 3
36.9
32.9
1. 6
11.7
8. 6
0.5
0. 3
0. 2
6. 4
24.1
28.3'~
9.2
6. 0
12.3
11.1
2.0
0. 3
0.2
0. 1
6.2
18.8
15.8
16.4
1. 5
3. 5
11.9
15.5'
6. 8
3. 6
0.0
0.0
96.53
0.25
0.39
0.28
0.40
0.21
0.06
0.09
0.09
1.70
30.9
69.1
18.0
82.0
14.5
46.7
27.8
10.4
0. 6
11.4
35.3
32.4
1. 6
10.5
7. 6
0. 5
0.4
0. 3
10.3
23.2
28.4b
10.1
5. 3
10.7
9. 0
2. 1
0. 5
0. 3
0.1
8. 5
18.0
15.9
16.3
1. 7
3. 5
10.9'
14.6f
6. 6
4.0
0.0
0.0
95.68
0.34
0.51
0.41
0.54
0.28
0.10
0.13
0.16
1.85
36.7
63.3
20.0
80.0
15.5
45.1
28.4
10.3
0. 7
12.2
34.3
32.8
1. 9
10.3
7. 1
0. 5
0. 5
0. 4
11.8
23.0
29.6b
9. 7
4.9
9. 8
7. 8
2. 2
0. 6
0. 3
0. 3
11.4
16.9
15.8
17.5
2. 4
3. 6
9.2
12,2/
5. 8
4. 4
0. 4
0. 4
94.08
0.46
0.73
0.62
0.80
0.43
0.15
0.25
0.27
2.21
a At 350C, no octanes, nonanes, and dodecanes in product. 3-RIethylheptane aqd 3-ethylhexane not resolved. Peak overlapping with
At 35OoC, no nonanes and dodecanes in product. e 2-Methyloctane and 4-methyloctane not resolved. 1 2, s- a naphthenic compound.
Dimethylheptane and 3,5-dimethylheptane not resolved. Q 2,6-Dimethylheptane and 4,4-dimethylheptane not resolved.
50 Ind. Eng. Chem. Prod. Res. Devel op., Vol. 11, No. 1, 1972
I ' " ' ' I " ' ' ' ' I ' T I
P I /Co/Y - ZEOLI TE PdIMn-HIY-ZEOLIIE Pd/H/Y-Zf OLllE
I
1M 180 300
P 2u
L
260 280 30
I f MPEPAI URE, 'C
280 100 310 340
Figure 4. Influence of temperature on isomerization of f eed
and cracked products
Influence of Reaction Temperature. Figure 4 shows the sum
of moles of branched paraffins in carbon number fractions
of the products in dependence of reaction temperature for the
three zeolite catalysts. Note the following interrelationships:
For all catalysts at higher reaction temperatures, the con-
tent of branched hydrocarbons in the CIZ feed fraction in-
creases but decreases in the cracked products. A comparison
of the three catalysts shows that branching in the cracked
products gives the highest values and branching in the C12-
fraction the lowest. But the differences between the three
catalysts are much greater in the degree of isomerization of
the '212-fraction than of the cracked products.
The difference in the degree of Clz-isomerization with the
three catalysts can be related to the differences in hydrogena-
tion activity, permitting a high isomerization when the re-
action Clz paraffin + CIZ olefin is fast, compared with that
of carbonium ion cleavage. The chemisorbed Clz secondary
carbonium ions resulting from n-olefin addition to the proton
of an acidic center are mainly rearranged to tertiary ions.
For fast exchange of n-Clz olefins from the gas phase with
branched C12carbonium ions, the mean degree of branching
of the chemisorbed C12carbonium ions is lowered, resulting
in a decrease of branching in the cracked products. I n addition
the degree of branching in the cracked products is lowered by
easy availability of Cl2 olefins and fast exchange between Clz
olefins with lower carbonium ions from cracking, resulting
in a shorter residence time of the cracked products at the
acidic centers and a corresponding reduction of their secon-
dary rearrangement and cleavage probabilities.
With increasing reaction temperature the C12-isomerization
conversion increases because of the increase in C12 olefin
and carbonium ion exchange rate. But the degree of isomer-
ization in the cracked products is lowered because of the in-
crease in relative stability of secondary carbonium ions re-
lated to that of the tertiary ones. A different hydrocracking
reaction is observed with bifunctional catalysts of only
minor acidity as Co-hIo-A120s. I n contrast to our results,
hydrocracking of n-hexadecane at a low cracking conversion
level yields almost totally n-paraffinic cracked products,
indicating a hydrogenolytic cleavage of carbon-carbon bonds.
Feed isomerization is nevertheless observed at higher con-
version levels and is supposed to proceed at the weakly
acidic centers of the A1203(IS, 20).
Temperature Influence for Individual Isomers. If we assume
that carbonium ion cleavage generally starts from tertiary
ions (according to the rule of 0-scission) , 2-methylparaffins
should be kinetically favored cracked products. However,
- Hz
0.8 1 i
in m 19 Irn
Figure 5. Influence of reaction temperature on ratio 2-
Me-al kane/3-Me-al kane in hexane and heptane fraction
with different catalysts
I EMP ERAI URi . 'C
Figure 6. Influence of reaction temperature on n-dodecane
isomerization with Pt/Ca/Y-zeolite
this selectivity is widely reduced by the fast methylshift
isomerization reaction and can only be observed in the com-
position of the cracked products where it is favored by low
temperature arid conditions of low secondary isomerization,
in particular, with a high hydrogenation activity of the
catalyst when there is a rapid displacement of the cracked
product ions from the acidic centers by C ~Z olefins. These
interrelationships are confirmed by Figure 5 which shows the
ratio of 2-methyl to 3-methylisomers for Cg and C, for the
three catalysts in dependence of reaction temperature.
The experiment,al ratios for the cracked products start with
high values at low temperature, the corresponding ratios at
low temperature being greater for Pt/Ca/- than for Pd/SIii-
H/- and for Pd/H/Y-zeolit'e. With increasing temperature
a decrease of ratios 2-Me-alkane/3-hIe-alkaneJ especially in
the range of temperature necessary for lOOyocracking coii-
version, is observed. Further increase in temperature does
not change the ratios substantially. Their values are in agree-
ment with those reported for equilibrium by CiaIIett'a arid
Hunter (b). This is proof of the primary character of 2-
methylparaffins as products of n-paraffin cracking and a fast
methylshift reaction as compared with desorption rate of the
carbonium ions. The same behavior occurs for the ratio 2-
methyl- to 3-methylparaffins at C,.
Composition of C12Fraction. With increasing temperature
occurs an increase in monobranched paraffins. With a greater
gradient an increase in multiple-branched paraffins in the C ~Z
product fraction is observed (Figure 6). EthyIparaffins C12
are kinetically derived from methylparaffins C12 by a fast
Ind. Eng. Chem. Prod. Res. Devel op., Vol . 1 1 , No. 1, 1972 51
---A-
t
N-OOOECANE - CL + i g
c5 c 7
'1-2 H I I
wy' -
N-OOOECENE
'1, H@
CARBONIUM SEC:C,2 I ONS -
A- *
c e
-
I I - H @ +2 H
METHYLUNOECANES
Figure 7. Mechanism of primary n-dodecane hydrocracking
alkylshift reaction ( I S , 20) and, therefore, kinetically belong
to the same group of isomers.
At higher isomerization conversion levels, the increasing
gradient for the formation of multiple-branched paraffins
can be partially related to multiple adsorption and desorption,
but at a low conversion level the observed degree of isomeriza-
tion, even to dimethyl CI, compounds, should be produced
during one chemisorption step. The extensive hydroisomer-
ization associated with hydrocracking of paraffins results in
Considerably low pour points of the products, a quality es-
pecjally demanded for jet fuels.
The composition of the monomethyl C12fraction (Table VI )
varies only gradually with temperature. The small value for
6-methylundecane is due to only half the statistical prob-
ability for formation of this isomer as compared with the
~ ~ ~ ~~~~
Tabl e VI. Composi t i on of Cl z-Monomet hyl i somers
(Mol %) on Pt /Ca/Y-Zeol i t e at Di f f erent
React i on Temperat ures
Temp, OC
Isomer 2 5 0 265 275 205 300
2-Methylundecane 13 6 16 8 18 7 19 9 19 7
3-Methylundecane 24 3 24 3 24 1 24 0 23 8
4-Methylundecane 23 0 21 9 21 2 20 4 19 0
5-Methylundecane 26 3 24 7 23 5 22 9 24 4
6-Methylundecane 12 8 12 3 12 5 12 8 13 1
others. The low values for 2-methylundecane correspond for
the first to a general thermodynamic tendency for methyl-
branching in the 2-position as compared to branching at
internal positions of a paraffinic chain. But considerably low
values for 2-methylundecane at low temperatures do occur,
indicating a remarkably low rate of its formatioii from the
n-aliphatic chain. This kinetically controlled trend for 2-
methylparaffins as isomerization products follows the opposite
direction than that of 2-methylparaffins as cracked products
when changing the temperature.
Relationship Between CI2 Isomerizate Composition and Prob-
ability of Individual Cracking Reactions. As pointed out earlier,
carbonium ion cleavage at low temperatures substantially
proceeds after rearrangement and starts from the tertiary
ions, thus making possible an interrelationship between C1.
isomerizate composition and probability of individual crack-
ing reactions as indicated in the reaction scheme of Figure 7.
I n Table VI1 a comparison is given between the composi-
Tabl e VII. Rel at i onshi p Bet ween Composi t i on of Monomet hyl undecanes (Mol yo) and
Probabi l i t y of Pr i mar y Cracki ng Reacti ons on Pt /Ca/Y-Zeol i t e
265' Ct % - 275' C, %
Met hyl - Met hyl -
205' C, %
Methyl -
undecaner Reaction undeca.ner Reaction undecaner Reaction
2-Methylundecane
- c4 +cs
6-Methylundecane
- c4 +cs
3-Methylundecane
- cs+c7
5-Methylundecane
-+Cs +CTi -+ Ca +CS
4-Methylundecane
* C6 +c6
29.1 29.6 31.2 30.5 32.7 31.2
49.0 48.8 47.6 47.8 46.9 47.6
21.9 21.7 21.2 21.7 20.4 21.4
Tabl e VIII. Tot al , Pri mary, and Secondary Isomeri zat i on Branchi ng Steps f or n-Dodecane
Hydrocracki ng wi t h Di f f erent Cat al yst s and Temperat ures
Values related to 100 moles of Clz cracked
Reaction Pt/Co/Y-zeol i te Pd/Mn-H/Y-zeolite Pd/H/Y-zeolite
temp, Pri mary Secondary
Total Pri mary Secondary Total Pri mary Secondary Tot al
OC
250
265
275
285
300
163 115
163 127
163 138
163 149
167 153
48
36
25
14
14
190 127 63
183 132 51
174 143 31
196 149
182 143
47
39
52 Ind. Eng. Chem. Prod. Res. Devel op., Vol. 1 1 , No. 1, 1972
tion of the rnonon.iethylisomers Cl, and the probability of
individual cracking reactions at different reaction tempera-
tures in the temperature range of pure primary cracking
mit,h Pt/Ca/Y - zeolite.
These values show remarkable consistency and are re-
garded as proof of the reaction scheme in Figure 7. I n par-
ticular t'his reaction scheme explains the low values for the
cracking react'ion of Clz to C4 +CS as a consequence of the
low values of the tertiary 2-methylundecyl and &methyl-
undecyl cations from which the primary products Cc +CS
we derived. In addition t'he reaction scheme holds for t'he
slight increase in probability of this particular primary
cracking reaction with temperature, owing to the small rate
of formation of the 2-methylundecyl cation at low tempera-
tures. The selectivity of primary cracking reactions does not
substantially alter with increasing Clz-isomerization to di-
met'hylparaffins because a similar suppression of 2-methyl
branching for t'his group of isomers is expected.
Pri mary and Secondary I somerization of Cracked
Products. On the basis that n-paraffin hydrocracking at
I OK temperatures includes isomerizat,ion of secondary
to tertiary carbonium ions and these are cleaved, it is
possible to distinguish between primary isomerization
taking place at the stage C12 before cracking and secondary
isomerization at the stage of the smaller cracked products
after cracking (Table VIII).
Total isomerization of the cracked products is calculated as
the number of tertiary C-atoms in the cracked products per
100 moles of cracked dodecane. A quat'ernary C-atom is
taken as two tertiary C-at,oms because it is probably formed
by alkylshift from a dialkylisomer with two tertiary C-atoms,
and thus two branching steps are involved for its formation.
Primary isomerization is derived from the composition of the
C12 isomerizate as the number of tertiary atoms per 100
moles of branched C1? paraffins in the product. Secondary isom-
erization is calculated as the difference of total and primary
isomerizat,ion.
The values of Table VI I I show that at low temperature
at least */ 3 of the total isomerization originates from branching
steps before cracking. Total isomerization increases with
decreasing hydrogenation activity, especially because of a
greater contribution of secondary isomerization owing to a
greater residence time of the smaller carbonium ions from
cracking at the acidic sites. The decrease of the values for
secondary cracking with increasing temperature may occur
partially because with increasing t'emperature, more secondary
carbonium ions might be cleaved. Thus, by the applied method
of calculating, a greater proportion of total isomerization is
regarded as primary iustead of secondary.
Conclusions
The reactions of chemisorbed carbonium ions have been the
subject of intensive scientific discussions in connection with
catalyt8ic cracking on acidic catalysts. But the complexity of
the sit'uation, owing to iiumerous consecutive reactions at the
necessary high temperature level, only allowed the decision
of general trends but no determination of individual reaction
paths. With strongly acidic molecular sieves combined with a
highly active dehydrogenation-hydrogenation catalyst in the
presence of hydrogen, a much lower reaction temperature can
be applied. If the formation of carbonium ions is feasible via
olefins, the selectivity of the primary reactions of the car-
bonium ions becomes observable. Thus, from the present re-
sults i t appears that secondary carbonium ions, derived from
n-paraffins and n-olefins, respectively, are rearranged to
tertiary cations. These are split under formation of 2-methyl-
branched chains as primary products which might be re-
arranged, in turn, with the relative rates of individual
reactions strongly governed by competitive chemisorption.
Acknowledgment
The authors express their sincere gratitude to H. Pichler,
Director of the Carl Engler und Hans-Bunte-I nstitut fiir
Rlineralol-und Kohleforschung and the I nstitut fiir Gastech-
nik, Feuerungstechnik und Wasserchemie der Universitat
Karlsruhe.
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RECEIVED for review J une 21, 1971
ACCEPTED September 20, 1971
Presented at the Division of Petroleum, 161st hleeting, ACS,
Lo? Angeles, Calif., April 1971.
Ind. Eng. Chem. Prod. Res. Develop., Vol. 1 1 , No. 1 , 1972 53