Hydrodenitrogenation of isoquinoline

Yasuo Miki
*
, Yoshikazu Sugimoto
National Institute of Materials and Chemical Research, Tsukuba, Ibaraki 305, Japan
Received 25 August 1998; received in revised form 24 September 1998; accepted 28 September 1998
Abstract
To determine the formation and reactivity of addition compounds produced during hydrodenitrogenation (HDN), we
investigated the HDN of isoquinoline for a sulded NiMo/Al
2
O
3
catalyst operated under a hydrogen pressure of 12 MPa
(cold charge) in the temperature range 3003758C. The reaction products were classied into ve groups of compounds:
1. hydrogenated derivatives of isoquinoline (tetrahydroisoquinolines, decahydroisoquinolines, and their isomers);
2. nitrogen-containing ring-opened products (1-amino-2-(2-methylphenyl)ethane and 1-amino-1-(2-ethylphenyl)methane);
3. denitrogenated products (1-ethyl-2-methylbenzene, 1-ethyl-2-methylcyclohexane, and their isomers);
4. addition products (hydrocarbons with molecular weights of 238, 244, and 250 and nitrogen-containing compounds with
molecular weights of 249, 251, and 257); and
5. cracked products (toluene, ethylbenzene, dimethylbenzenes, and their hydrogenated derivatives).
Most of the nitrogen-containing addition compounds appear to be substituted on the nitrogen atom. The HDN of isoquinoline
was more than 10 times faster than the HDN of quinoline, whereas the hydrogenation of isoquinoline was difcult compared
to the hydrogenation of quinoline. The reaction network for the HDN of isoquinoline is also presented. # 1999 Elsevier
Science B.V. All rights reserved.
Keywords: Isoquinoline; Hydrodenitrogenation; Addition product; Reaction network; NiMo/Al
2
O
3
1. Introduction
Fossil fuel oils contain heteroatoms such as nitro-
gen, sulfur, and oxygen. The hydrotreating of nitro-
gen-containing (N-containing) and sulfur-containing
compounds has been studied in connection with their
storage stability and safety. In particular, a higher
degree of hydrodenitrogenation (HDN) recently has
become necessary because of the need to minimize the
deactivation of hydrotreating catalysts and to suppress
emission of nitrogen oxides. It is well known that
HDN is sometimes accompanied by side reactions that
form addition compounds that are more difcult to
decompose than the original reactant [17]. Moreover,
fuel oils include such N-containing compounds that
have lower reactivity as quinoline and carbazol. We
realized that to achieve higher levels of HDN it is
important to develop catalysts that have higher HDN
activities with reactive compounds and addition com-
pounds. In this study, we determined the formation of
addition compounds and their reactivities for second-
ary cracking on isoquinoline HDN.
Applied Catalysis A: General 180 (1999) 133140
*Corresponding author. Fax: +81-298-54-4487.
0926-860X/99/$ see front matter # 1999 Elsevier Science B.V. All rights reserved.
PII: S0926-860X(98)00346-9
2. Experimental
2.1. Materials
Extra-pure grade isoquinoline (Tokyo Kasei
Kogyo) was redistilled under reduced pressure
(1.3 kPa) and then dissolved in high purity hexadecane
(Tokyo Kasei Kogyo). The concentration of isoquino-
line in the mixture was 9.2 wt% (i.e., equivalent to
1.0 wt% N).
The catalyst used was Ketjenne-153, a hydrotreat-
ing catalyst containing 3% nickel and 15% molybde-
num supported on alumina. Although the catalyst was
supplied as a
1
8
in. extrudate, it was crushed and
screened to provide 1020 mesh granules that were
used in this work.
2.2. Procedure
Prior to use, the catalyst was presulded for 1 h
using a mixture of hydrogen sulde (10% by volume)
in hydrogen at 4508C and atmospheric pressure.
Details of the presulding has been given elsewhere
[8]. A stainless steel vibrating microautoclave (35 ml
inner volume) was used as the reactor. The reactor was
inserted in a large bronze block buried in a furnace in
order to maintain the reactor at a homogeneous and
steady temperature. The catalyst (0.5 g) and feed oil
(10 ml) were poured into the autoclave and allowed to
react under hydrogen (12 MPa, cold charge) in the
temperature range 3003758C for 1520 min. The
reaction temperature reached within 38C of the
expected temperature approximately 2 min after
initiating the reaction by using a preheated electric
furnace that was 35408C higher than the reaction
temperature.
2.3. Analysis
The reaction products were analyzed by using a
Hewlett-Packard 5880A gas chromatograph equipped
with a ame ionization detector and a Nphosphorous
detector. Separation was done over a fused-silica
capillary column (OV-1, 0.25 mm50 m). A Hew-
lett-Packard 5890 gas chromatograph interfaced to a
mass spectrometer (Hewlett-Packard 5970) was used
to identify each product by its mass spectrum.
The following chemical species were synthesized
by hydrogenation of isoquinoline over a Pt/Al
2
O
3
catalyst: 1,2,3,4-tetrahydroisoquinoline (14THIQ);
5,6,7,8-tetrahydroisoquinoline (58THIQ); cis-decahy-
droisoquinoline (cis-DHIQ); and trans-decahydroiso-
quinoline (trans-DHIQ).
3. Results
3.1. Analysis of the product types
The reaction products were classied into ve
groups of compounds:
1. hydrogenated derivatives of isoquinoline (14THIQ,
58THIQ, cis-DHIQ, and trans-DHIQ);
2. N-containing ring-opened products (1-amino-2-(2-
methylphenyl)ethane and 1-amino-(2-ethylphe-
nyl)methane);
3. denitrogenated products (1-ethyl-2-methylben-
zene, 1-ethyl-2-methylcyclohexane, and their iso-
mers);
4. addition products (hydrocarbons with molecular
weights (MWs) of 238, 244, and 250 and N-con-
taining compounds with MWs of 249, 251 and
257); and
5. cracked products (toluene, ethylbenzene,
dimethylbenzenes, and their hydrogenated deriva-
tives).
3.2. Hydrogenated derivatives of isoquinoline
One compound with an MWof 131, two compounds
with an MWof 133, and two compounds with an MW
of 139 were observed as hydrogenated derivatives of
isoquinoline that had not undergone ring-opening. The
compound with an MW of 131 was assigned as
dihydroisoquinoline, based on its mass spectrum. Its
yield decreased as the reaction temperature increased
from 3008C to 3508C, with its highest yield being
2 wt% at 3008C.
The two compounds with an MW of 133 were
14THIQ and 58THIQ. Fig. 1 shows their relative
yields, as the value of 58THIQ/(14THIQ58THIQ),
versus the reaction time. At 3008C the values were
nearly constant at 0.1, which suggests that the rate of
14THIQformation is about 10 times larger than that of
58THIQ formation. When the temperature increased
134 Y. Miki, Y. Sugimoto / Applied Catalysis A: General 180 (1999) 133140
above 3258C, this value increased with the increasing
reaction time. When the reaction temperature was
3508C and the reaction time was 30 min, the yield
of 58THIQ was higher than the yield of 14THIQ,
which indicates that the rate of 14THIQ ring-opening
exceeds that of 58THIQ formation. The major com-
pounds with an MWof 139 were cis-DHIQ and trans-
DHIQ. One minor compound with an MWof 139 was
also present. Two compounds with an MW of 135
were also observed. One compound with an MW of
135 has been reported to be hexahydroisoquinoline
[5]; however, in this study, these two compounds with
an MWof 135 were determined to be the ring-opened
products of 14THIQ, as described later.
Fig. 2 shows the yields of the THIQs and DHIQs as
a function of the reaction time. In the early stage of the
reaction the yield of the DHIQs was lower than the
yield of the THIQs. This suggests that hydrogenation
of THIQs to DHIQs is slower than hydrogenation of
isoquinoline to THIQs. On the other hand, when the
reaction time was 60 min or longer and the tempera-
ture was 3508C, the yield of the DHIQs was higher
than the yield of the THIQs. This suggests that ring-
opening of the DHIQs is lower than either ring-open-
ing or hydrogenation of the THIQs.
3.3. Ring-opening of isoquinoline
Two compounds with an MWof 135 were produced
in the HDN of isoquinoline. In the HDN of quinoline,
2-propylaniline was produced by ring-opening of
1,2,3,4-tetrahydroquinoline [9], suggesting that a
bond between saturated carbon atom and nitrogen
atom is cleaved selectively. In the HDN of isoquino-
line, two compounds, 1-amino-2-(2-methylpheny-
l)ethane and 1-amino-2-(2-ethylphenyl)methane, are
expected to produce from 14THIQ because there are
two different bonds between saturated carbon atom
and nitrogen atom. Fig. 3 shows the mass spectra of
these two compounds with an MW of 135 and two
reference compounds. The mass spectrum in Fig. 3(c)
Fig. 1. Relative yields of 14THIQ and 58THIQ as the value of
58THIQ/(14THIQ58THIQ).
Fig. 2. Yields of THIQs, DHIQs, and ring-opened compounds with an MW of 135 as a function of reaction time.
Y. Miki, Y. Sugimoto / Applied Catalysis A: General 180 (1999) 133140 135
suggests that this compound is 1-amino-2-(2-phenyl-
ethyl)methane compared with the mass spectrum in
Fig. 3(a). It is rather difcult to assign the molecular
structure shown in Fig. 3(d), we consider this com-
pound is 1-amino-2-(2-methylphenyl)ethane. The
yields of these amines increased with increasing reac-
tion time at 3008C (Fig. 2), but decreased with
increasing reaction time at 3508C. This suggests that
HDNof these amines is slower than formation of these
amines at 3008C, but faster at 3508C.
No compounds with an MW of 141 were found in
this reaction, even though three compounds with this
MW were found for reactions done on quinoline under
conditions similar to those used in this study [9]. There
are two possible reasons for this: ring-opening of
DHIQs may be very slow, and HDN values of the
cyclohexylamines formed by hydrogenation of ami-
nophenyl compounds may be signicantly higher than
of those formed by the hydrogenation of aminophenyl
compounds.
3.4. HDN products
The HDN products of isoquinoline consist of three
major compounds (1-ethyl-2-methylbenzene (EMB)
and cis- and trans-1-ethyl-2-methylcyclohexane
Fig. 3. Mass spectra of ring-opened compounds with an MW of 135 and two reference compounds.
Fig. 4. Yields of EMB and EMCHs as a function of reaction time.
136 Y. Miki, Y. Sugimoto / Applied Catalysis A: General 180 (1999) 133140
(EMCHs)) and six minor compounds (one compound
with an MWof 126 and ve compounds with an MW
of 124). The ve compounds with an MW of 124
disappeared after rehydrogenation on a Pt/Al
2
O
3
catalyst at 3008C. This indicates that these compounds
are not C
9
-bicycloalkanes but C
9
-cycloolenes. There
was no formation observed for a compound with an
MWof 118, which would correspond to methylstyrene.
The yield of EMB decreased after reaction times
longer than 60 min at temperatures of 3508C or higher
(Fig. 4(a)); in contrast, the yield of the EMCHs
increased as the yield of EMB decreased (Fig. 4(b)).
These results suggest that EMB is produced by the
HDN of isoquinoline and that EMCHs are formed by
the secondary hydrogenation of EMB. The ring-open-
ing of 14THIQ without benzenoid ring hydrogenation
was previously observed [10]. The compounds with an
MW of 124 are considered to be formed by ring-
opening of the 14THIQ followed by HDN.
3.5. Addition reaction of HDN intermediates
Hydrodenitrogenation has been frequently observed
to proceed with the formation of N-substituted deri-
vatives. Such derivatives are relatively stable and do
not readily undergo further reactions [15]. In the
HDN of quinoline, N-addition products have been
observed as well as N-containing addition products
[7,9]. In the reaction of isoquinoline, N-absent addi-
tion compounds and N-containing addition com-
pounds were also produced.
Of the N-absent addition compounds, three had an
MW of 238, 12 had an MW of 244, and two had an
MW of 250. The total yield of these compounds
increased with increasing temperature and reaction
time (Fig. 5), but the values were very low compared
to those previously reported for quinoline [9]. The
maximum yields were 13% and 0.26% for quinoline
and isoquinoline, respectively.
Of the N-containing addition products, there were
eight major compounds with an MW of 251, four
minor compounds with an MW of 247, two minor
compounds with an MW of 249, and six minor
compounds with an MW of 257. Fig. 6 shows the
yield of the N-containing addition compounds as a
function of the reaction time and temperature. This
gure shows that the secondary decomposition of the
N-containing addition compounds was difcult at
3008C, but proceeded more easily at 3258C or higher
temperatures.
3.6. Secondary cracking of HDN products
Formation of hydrocarbons with eight or fewer
carbon atoms was observed for reaction temperatures
up to 3258C. The main compounds formed were
cyclohexane, toluene, ethylbenzene, and o-xylene.
The maximum value of their total yield was 5%.
Fig. 5. Total yields of N-absent addition compounds as a function
of reaction time.
Fig. 6. Total yields of N-containing addition compounds as a
function of reaction time.
Y. Miki, Y. Sugimoto / Applied Catalysis A: General 180 (1999) 133140 137
4. Discussion
4.1. Structure of addition compounds
The total yield of the addition compounds
decreased with the decomposition of the N-containing
addition compounds (Fig. 7). These results differ from
those obtained from the quinoline reaction [9], where
the yield of the N-absent addition compounds
increases with the decomposition of the N-containing
addition compounds. These results indicate that most
of the N-containing addition compounds from quino-
line are substituted on the carbon atom, whereas those
from isoquinoline are substituted on the N atom.
Fig. 8(a) and (b) shows a typical mass spectra of
compounds with MWs of 247 and 251, respectively. It
is difcult to distinguish the position of substitution
based only on the spectra.
4.2. Percent hydrodenitrogenation
As mentioned in Section 3.1, isoquinoline pro-
duced ve types of compounds: hydrogenated isoqui-
noline, ring-opened compounds, addition compounds
(with and without N), HDN compounds, and second-
ary cracked compounds. From these compound types,
we calculate the percentage of HDN by summing the
following yields:
Fig. 7. Total yields of N-containing and N-absent addition
compounds as a function of reaction time.
Fig. 8. Mass spectra of N-containing addition compounds with MWs of 247 and 251.
138 Y. Miki, Y. Sugimoto / Applied Catalysis A: General 180 (1999) 133140
1. the yield of the N-absent addition compounds,
2. half the yield of the N-containing addition com-
pounds,
3. the yield of the HDN compounds, and
4. the yield of the secondary cracked compounds
(calculated as compounds with nine carbon atoms).
A plot of the percent of HDN as a function of the
reaction time and temperature (Fig. 9) shows that the
HDN of isoquinoline proceeds more readily than that
of quinoline [9], differing from the hydrogenation
results described in Section 3.2.
4.3. Reaction network
A revised reaction network for the HDN of iso-
quinoline, including the addition reactions, is pre-
sented in Fig. 10, where the structures shown in
parentheses indicate intermediates that were not
observed in the products. Ring-opening of 14THIQ
is considered to be the rate-controlling step. Ring-
opening of the DHIQs is difcult compared to the
ring-opening of 14THIQ, but amines produced from
the DHIQs are easily cracked and are not observed in
the products. Ethylmethylcyclohexanes are consid-
ered to be formed in two routes, via DHIQs and
Fig. 9. Percent of HDN as a function of reaction time.
Fig. 10. Revised reaction network for the HDN of isoquinoline.
Y. Miki, Y. Sugimoto / Applied Catalysis A: General 180 (1999) 133140 139
rehydrogenation of ethylmethylbenzene. Addition
reactions proceed preferentially to form derivatives
on the Natom, which return to the original compounds
by decomposition. As a minor reaction, addition
compounds substituted on the carbon atom are pro-
duced, which are converted by hydrodenitrogenation
into N-absent addition compounds.
5. Conclusion
In the hydrodenitrogenation of isoquinoline, large
amounts of N-containing addition compounds and
small amounts of N-absent addition compounds were
formed. Most of the N-containing addition com-
pounds seem to be substituted on the N atom.
The hydrogenation of isoquinoline to 1,2,3,4-tetra-
hydroisoquinoline is difcult compared to the hydro-
genation of quinoline; 1,2,3,4tetrahydroquinoline is
thought to be in thermodynamical equilibrium with
quinoline at 3008C. On the other hand, the HDN of
isoquinoline was more than 10 times faster than the
HDN of quinoline.
These results have allowed us to dene a revised
reaction network that includes addition reactions.
References
[1] G. Hadjiloizou, J.B. Butt, J.S. Dranoff, J. Catal. 135 (1992)
27.
[2] J. Sonnemans, W.J. Neyens, P. Mars, J. Catal. 34 (1974)
230.
[3] J.A. Anabtawi, R.S. Mann, K.C. Khulbe, J. Catal. 63 (1980)
456.
[4] R.K. Gupta, R.S. Mann, A.K. Gupta, J. Appl. Chem.
Biotechnol. 28 (1978) 641.
[5] Z. Kafka, M. Kuras, J. Novac, L. Vodicka, Fresenius' Z. Anal.
Chem. 321 (1985) 475.
[6] R.A. Flinn, O.A. Larson, H. Beuther, Hydrocarbon Process.
42(9) (1963) 129.
[7] C.N. Satterfield, S.H. Yang, Ind. Eng. Chem. Process Des.
Dev. 23 (1984) 11.
[8] Y. Miki, Y. Sugimoto, Fuel Proc. Technol. 43 (1995)
137.
[9] Y. Miki, Y. Sugimoto, Nippon Kagaku Kaishi (1997),
p. 677.
[10] L. Vivier, V. Dominguez, G. Perot, S. Kasztelan, J. Mol.
Catal. 67 (1991) 267.
140 Y. Miki, Y. Sugimoto / Applied Catalysis A: General 180 (1999) 133140