Science and Technology in Catalysis 1998

Copyright © 1999 by Kodansha Ltd.

76
Direct Hydrogenation of Aliphatic Carboxylic
Acids to Corresponding Aldehydes with
Cr203 Catalyst

Naoko YAMAGATA, Naoko FUJITA, Toshiharu YOKOYAMA and Takao MAKI

Research Center, Mitsubishi Chemical Corporation, 1000 Kamoshida-cho, Aoba-ku, Yokohama

227-8502, Japan

Abstract
A new process for the production of aliphatic aldehydes was developed and conunercialized.
Using highly pure Cr203 catalysts, we succeeded in hydrogenating aliphatic carboxylic acids
directly to corresponding aldehydes in excellent yields. Noteworthy was that acids with a C=C
double bond (e.g. 10-undecenoic acid [10-UDEA]) were selectively hydrogenated at the C=0 group
without hydrogenation or migration of their C=C bond to give 10-undecenal [10-UDEH].
Examination of the surface of Cr203 indicated its neutral property, which was believed to be the
reason for the high selectivity of this catalyst.

1. INTRODUCTION

Although the direct hydrogenation of carboxylic acids has been regarded as a desirable way to
produce aldehydes, it was not until recendy that a commercial process was developed. The first and
only example so far has been our process for the production of aromatic aldehydes using Cr doped
Z1O2 ^^ ^ catalyst. This catalyst, however, is not suitable when applied to the hydrogenation of
aliphatic carboxylic acids because of its low selectivity. As we started our research to find a catalyst
for the aliphatic aldehyde production, we chose 10-UDEA, an unsaturated aliphatic acid, as the
target of hydrogenation. A compound with two a -hydrogens is liable to undergo ketonization, and
its C=C double bond easily migrates or is hydrogenated, as was observed in the case when Cr/Zr02

Selective hydrogenation ^CHO 10-UDEH

10-UDEA I I V^^^^=c isomerization ^ , ^^^ 9-UDEH

^""^^^^^^^"^''^^ ^ a-UDEH
Undecanal
C = C hydrogenation
•
"'"°"'"^'°" • V, K.ton,

Scheme 1 Hydrogenation of 10-Undecenoic Acid

441
442 N. Yamagata et al.
or other oxides were used as catalysts (Scheme 1). In this report the catalytic performances and
characterization of Cr203 for the hydrogenation of 10-UDEA and other acids are discussed.

2. Experimental Section

^^2^3 ^ ^ prepared by the calcination of chromium hydroxide at 700 **C in an air stream.
Cr/Zr02 (Cr/Zr=5/100 atomic ratio) and Zr02 were prepared by the method previously described
[2]. Alumina was commercially obtained.
Hydrogenation of carboxylic acids was carried out under an atmospheric pressure by a
conventional flow system. The reaction products were analyzed by GLC.
The IR spectra of the absorbed species on oxides were recorded by using a Fourier transform
IR spectrometer (Nicolet, System 800). The samples for FT-IR analysis were prepared in the same
method as described previously [2].
TPD data were obtained using ammonia and carbon dioxide as probe gases. A sample was first
treated at 600^*0 in He flow, then pre-hydrogenated in a mixture of 5% hydrogen in Ar. Probe gas
was fed pulse-wise at 100X. After the probe gas was fully absorbed by the sample, temperature
was raised at a rate of lOT/min. until 600'^C. The desorbed gas was monitored with a TCD
detector.

3. Results and discussion

3.1. Hydrogenation of 10-undecenoic acid over various oxide catalysts

The hydrogenation of 10-UDEA was performed over various oxides ( Table 1 ). y -AI2O3
showed poor activity. When Zr02 was used as a catalyst, ketone was obtained as a major product.
The Cr/Zr02 catalyst suitable for aromatic aldehyde production showed better selectivity towards
UDEH formation, although migration of C=C double bond occurred. 9-UDEH and 8-UDEH were
observed as migration products. The ratio of 10-UDEH among these isomers is shown in the table
as "10-UDEH/Total-UDEH". On highly pure Cr203, 10-UDEA reacted to produce 10-UDEH in
very high selectivity. The formation of ketone or migration isomers was very low. Several
commercially available Cr203 were tested, but not all of them showed good selectivity. It was
found that impurities in Cr203, especially alkaline metals and alkaline earth metals, had a bad
influence on the catalytic performance. Even a small amount of impurities in Cr203 caused a

Table 1 Hydrogenation of lO-UDEA over Various Metal Oxide Catalysts

(Reaction conditions: H2 GHSV=1250 h'^' 10-UDEA/H2-2/98 TOI-%, 1 atm.)

Catalyst Temperature Conversion Selectivity (%) 10-UDEH

ofacid(%) Total-UDEH Ketone /Total-UDEH
Cr203
rc)
370 74 98 1 0.96
CrjOj' 370 32 43 55 0.87
Cr/Zr02 330 87 83 16 0.38
e
Z1O2 330 97 10 79
c
r.Al203 330 8 3 96
a) high purity Cr203, b) Cr203 including 1.4% of alkaline and alkaline earth metals as Impurities.
c) not analyzed.
 443

1 • • 77" 1
(b) ZK),
(c) O/ZrO,
3 (d) • 0,0,
O (•) C r , 0 , (alkali rfopad)
1
-e
o
O

O
O

100 200 300 40)

200 300 400

Temperature CC) Temperature ( C )

NH,-TPD Patterns CO, - T P D Patterns

Figure 1 Acid and Base Properties of Metal OxJde Surfaces

drastic decrease in activity and selectivity [1].

The decrease in selectivity was mainly due to Table 2
ketone formation. The FT-IR Spectroscopy of Adsorbed
10-UDEA on Oxides after Hydrogenation
3.2. NH3 and CO2 TPD on oxides
The acid-base properties of the catalyst Stretching Flrequency(ciif *)
surfaces were characterized by NH3 and CO2- Ketone Carboxylate
TPD (Figure 1). Compared to other oxides, pure peak Vas Vcs
Cr203 had less amount of acidic sites and almost
CrjOj . 1530 1420
no basic sites. When alkali was doped on Cr203,
Cr203alkall +++ 1560 1440
the acidic sites vanished and basic sites appeared. + 1540 1455
Cr/Zr02
ZrOj ++ 1540 1455
3.3. FT-IR spectra of adsorbed species on y .AI2O3 - 1570 1460
oxides
The FT-IR spectra of the adsorbed species
after the hydrogenation of 10-UDEA showed the
existence of bidentate carboxylate species
adsorbed on the metal oxide surfaces (Table 2,
Figure 2). In our previous paper[2], we assumed
the carboxylate species to be the intermediate in
the hydrogenation of aromatic carboxylic acids on
zirconia. Also on Cr203, carboxylate was
regarded as an intermediate.
Cr203 gave the lowest carboxylate stretching
frequency among the oxides. The IR peak for
ketone was observed on the surface of some
catalysts which showed high ketone selectivity.

3.4. Hydrogenation of various carboxylic acids

Cr203 catalyst exhibited high selectivity in ' 1800 1700 1600 1500 1400 1300 1200
the hydrogenation of other aliphatic carboxylic WAVENUMBER

acids as well (Table 3). Saturated carboxylic Figure 2 FT-IR Spectra of the Absorbed Species

acids showed better selectivities than 10-UDEA. on Metal Oxide Surfaces

Rsactant «nd Oxidat »n ai fonowr.
9-Octadecenoic acid was hydrogenated to 9- (a) UDEA-Cr/ZrO,(b>U0EA-Cr,0, (o) LauHo Add - Cr,0»
(d) UDEA - Cr,0,(anuili doped) (.) UDEA - ZrO, (0 UDEA - r -AI.O,
octadecenal in an excellent yield.
444 N. Yamagata et al.

Table 3 Hydrogenation of Various Cari>oxylic Acids over Cr^Oj Catalyst ^^

Cart)oxylic acids Temp. Conversion Selectivity to

CC) (%) aldehydes (%)
Decanoic acid 350 91 97
Dodecanoic acid 350 97 96
Octadecanoic acid 350 98 93
9-Octadecenoic acid 350 96 97
Cyclohexanecariioyylic acid 370 92 98
a)H2-GHSV=1250hr-l, acid/H2-2/98%.

3.5. Discussion
Results from TPD indicate that the surface of highly pure Cr203 has very small amount of
acidic sites and no basic sites. Basic sites on the surface seem to mediate ketonization, which is
suggested by the TPD data of aklaline-doped Cr203. The carboxylate on the alkaline-doped Cr203
seems to be adsorbed near the alkaline metal, since the positions of its carboxylate stretch modes are
similar to those found by infrared spectrum for sodium 10-undecenoate. The alkaline or alkaline
earth metals are thought to deactivate the acidic sites and cause new basic sites to appear, which
become active sites for ketone formation.
The interpretation of the FT-IR data has to wait for further examination, but since the
carboxylate ion paired to sodium cation shows higher wavenumber, and the carboxylate on y -
AI2O3, generally regarded to be an acidic oxide, also gave the highest frequency among the oxides
tested, it seems that the lowest shift of Cr203 is due to the smallness of charge or weakness of its
Lewis acidic sites. Other factors like ionicity of carboxylate-metal bonds may be also relevant.
The mechanism for the migration of C=C double bond is not yet clear. The interaction of C=C
double bond with the surface of the oxide seems to be suppressed on Cr203 by some reason,
probably because of the character of its Lewis acidic sites.
The unique surface property of pure Cr203 can easily be destroyed by impurities, and this is
why the commercially available Cr203 generally shows poor selectivity. The uniformity of the acid
sites on the surface of highly pure Cr203 seems to be an important factor. Moreover our recent
research shows that the uniformity of the crystal structure of Cr203 is also important for the
catalytic performances. This will be discussed elsewhere.

4. Conclusion

Highly pure Cr203 was found to give an excellent selectivity in hydrogenating unsaturated
aliphatic carboxylic acids without ketonization or C=C double bond migration. The neutrality of the
surface of Cr203 plays a critical role in its high selectivity.
This new process, compared to the conventional methods, gives not only a higher yield and
selectivity, but is environmentally friendly because it produces no waste. The process was further
refined and has been successfully commercialized since last year for the production of aldehydes
such as 10-UDEH and dodecanal.

References
[1] T. Yokoyama, N. Fujita andT. Maki, Stud. Surf. Sci. Catal., 92, (1994), 33L
[2] T. Yokoyama, T. Setoyama, N. Fujita, T. Maki and K. Fujii, Appl. Catal., 88 (1992), 149.