Chemical Engineering Journal 140 (2008) 555–561

C9-aldehyde hydrogenation over nickel/kieselguhr

catalysts in trickle bed reactor
Jong-Ki Jeon a , Jin-Heong Yim b , Young-Kwon Park c,∗
aDepartment of Chemical Engineering, Kongju National University, Gongju, Chungnam 314-701, Republic of Korea
bDivision of Advanced Materials Engineering, Kongju National University, Gongju, Chungnam 314-701, Republic of Korea
c Faculty of Environmental Engineering, University of Seoul, 90 Jeonnong-dong, Dongdaemun-Gu, Seoul 130-743, Republic of Korea

Received 15 June 2007; received in revised form 28 November 2007; accepted 3 December 2007

Abstract
The objective of the present study was to select the optimal catalyst and operating conditions for the manufacture of C9 -alcohol, using C9 -aldehyde
and hydrogen, in a trickle bed reactor. When CaO, Ce2 O3 or MgO was added as a promoter to the Ni/kieselguhr catalyst, the BET and Ni surface
areas were increased. In the reaction for the manufacture of C9 -alcohol, using C9 -aldehyde and hydrogen in a batch reactor, a Ni–MgO/kieselguhr
catalyst showed the highest activity. In addition, the catalyst using Na2 CO3 as a precipitant showed the highest activity. According to the result
of an experiment to find the optimal reaction conditions for C9 -alcohol synthesis, using C9 -aldehyde and hydrogen in a trickle bed reactor loaded
with Ni–MgO/kieselguhr catalyst, the highest yield of C9 -alcohol was 91.5 wt% at 130 ◦ C, 400 psi and WHSV = 3. The C9 -aldehyde hydrogenation
performance of the Ni–MgO/kieselguhr catalyst was similar to that of a Cu/ZnO/Al2 O3 catalyst, but superior to that of Cu–Ni–Cr–Na/Al2 O3 and
Ni–Mo/Al2 O3 catalysts. In a long-term catalysis test, the Ni–MgO/kieselguhr catalyst showed higher stability than the Cu/ZnO/Al2 O3 catalyst.
© 2007 Elsevier B.V. All rights reserved.

Keywords: C9 -aldehyde; Hydrogenation; C9 -Alcohol; Trickle bed reactor; Catalyst

1. Introduction Cu/ZnO/Al2 O3 , has been applied in the manufacture of butanol

and 2-ethyl hexanol [10,11], Cu–Ni–Co–Mg/Al2 O3 in the man-
The dimerization of n-butene produces mixed octene [1,2]. ufacture of 2-ethyl hexanol [12,13] and Cu–Ni–Na–Cr/SiO2 in
In addition, the hydroformylation of mixed octene and synthesis the manufacture of 2-ethyl hexanol [14]. The Ni-based cata-
gas produces C9 -aldehyde (isononyl aldehyde) [3,4]. Moreover, lyst, Ni–Mo/Al2 O3 , has been applied in the hydrogenation of
C9 -alcohol (isononyl alcohol) can be obtained from the hydro- nonyl aldehyde for the manufacture C9 -alcohol [15,16], but few
genation of C9 -aldehyde. C9 -alcohol is used as a plasticizer, cases using Ni/kieselguhr catalyst, which is widely used in other
detergent and solvent, etc. hydrogenation processes, have been applied to the hydrogena-
The commercial process of aldehyde hydrogenation uses a tion of C9 -aldehyde.
fixed bed reactor, with the reaction performed at temperatures The objectives of the present study were to establish a method
between 90 and 180 ◦ C and a pressure of 350 psi and between for preparing Ni/kieselguhr catalyst, and establish the operating
80–220 ◦ C and 1000–4000 psi in the gas and liquid phase reac- conditions for the manufacture of alcohol through the hydro-
tions, respectively. Various metals, including Cu, Ni, Mo, Co and genation of C9 -aldehyde produced from the hydroformylation
Rh, are used as catalysts in aldehyde hydrogenation, and they of mixed octene. For this purpose, a catalyst showing optimal
are sometimes synthesized into 2-, 3- or 4-component metals to performance through the investigation of the effects of the prepa-
be used as catalysts [5–9]. ration method of the nickel-based catalyst and the promoter on
Most commercial applications of aldehyde hydrogenation the hydrogenation of C9 -aldehyde was selected. In addition, the
catalysts are Cu- and Ni-based catalysts. The Cu-based catalyst, hydrogenation of aldehyde and the reaction performance of other
catalysts were compared using a trickle bed reactor. After estab-
lishing the optimal operating conditions of the selected catalyst,
∗ Corresponding author. Tel.: +82 2 2210 5623; fax: +82 2 2244 2245. the stability of the catalyst was confirmed through a long-term
E-mail address: catalica@uos.ac.kr (Y.-K. Park). test.

1385-8947/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2007.12.004
556 J.-K. Jeon et al. / Chemical Engineering Journal 140 (2008) 555–561

Fig. 1. Schematic diagram of the reaction system.

2. Experimental using a Micromeritics ASAP 2000 instrument. The nickel sur-

face area of the reduced catalyst was estimated from the amount
2.1. Catalyst synthesis of hydrogen chemisorbed onto the catalyst. This measurement
was carried out with a Micromeritics ASAP 2010. The average
Ni(NO3 )2 ·6H2 O (Junsei), Nickel acetate (Aldrich), size of the reduced nickel particles was estimated using an X-ray
Mg(NO3 )2 ·6H2 O (Yakuri), Ca(NO3 )2 ·4H2 O (Junsei), and diffractometer (Rigaku, D/MAX-III, 3 kW) employing Cu K␣
Ce(NO3 )3 ·6H2 O (Aldrich) were used as precursors, and radiation. The average nickel particle size was calculated from
kieselguhr (Fluka) was used as the support. Na2 CO3 (Yakuri), the width of the peak at 44.6◦ using Scherrer’s equation, which
NH4 OH (Yakuri) and urea (Aldrich) were used as precipitants. indicated Ni(1 1 1). To avoid contact with air, XRD spectra were
Hydrogen and nitrogen (Matheson, 99.999%) were further obtained using the reduced catalyst impregnated in oil.
purified using a molecular sieve trap.
Catalysts were prepared following the conventional pre- 2.3. C9 -aldehyde hydrogenation
cipitation method described by Suh et al. [17,18]. For the
nickel/kieselguhr catalyst, kieselguhr, Ni(NO3 )2 ·6H2 O, urea The hydrogenation reaction was carried out using a batch
and deionized water were introduced into a 4-neck flask to make reactor and a trickle bed reactor. The internal diameter and vol-
a 400 cm3 aqueous solution. After heating the solution to 90 ◦ C, ume of the batch reactor were 50 mm and 400 ml, respectively.
a precipitant solution was introduced via a metering pump. The The reactor had a manometer for measuring the hydrogen pres-
final pH of the solution was approximately 8. After filtering and sure, a programmable temperature controller for controlling the
washing, the catalysts were dried overnight in air at 120 ◦ C. After reaction temperature, an inner cooling coil, a thermocouple and a
pelletizing the catalyst powder, it was broken into uniform size heating jacket, etc. For storage of the hydrogen to be supplied to
between 2.0 and 2.8 mm. The prepared catalyst was used after the reactor and to measure its consumption, a 1 l hydrogen tank
reduction with hydrogen. and gas regulator were used, with the hydrogen and nitrogen
supplied to the reactor through a manifold with a manometer. In
2.2. Catalyst characterization a glove box in a nitrogen atmosphere, 200 g of C9 -aldehyde was
supplied to the reactor, along with 0.2 g of catalyst, which had
The BET surface area, pore volume and pore size distribu- been reduced. After installing a heating jacket onto the reactor,
tion were measured by nitrogen adsorption–desorption at 77 K air and moisture were purged using nitrogen. Under nitrogen
 J.-K. Jeon et al. / Chemical Engineering Journal 140 (2008) 555–561 557

Fig. 2. Trickle bed reactor for isononyl aldehyde hydrogenation.

gas, the temperature was raised. After the reaction tempera- Fig. 3. Effect of promoters on XRD spectra of the nickel/kieselguhr catalyst
ture had been reached, hydrogen was infused to 3 atm, and then after reduction.
removed, and the process repeated three times. Again, the reactor
was filled with hydrogen to the reaction pressure, and the stirrer 3. Results and discussion
rotated. The reaction product was collected at regular intervals,
and analyzed using gas chromatography. 3.1. Effect of promoter on catalyst characteristics
Fig. 1 shows the reaction system for the hydrogenation of
C9 -aldehyde. A trickle bed reactor (Fig. 2) was used as the reac- In the previous study, we found that the BET surface area
tor, which was made using an 80 cm length of SUS tube with increased due to the increase in microporosity by adding a small
a 0.5-in. outer diameter. The C9 -aldehyde was injected using amount of magnesium to a kieselguhr-supported nickel cata-
a high-pressure metering pump, with the flow rate of hydrogen lyst [19]. With the addition of magnesium, the catalysts became
controlled using a mass flow controller (MFC). The temperature more difficult to reduce, but presented higher metallic area. The
of the reactor was controlled using a tubular furnace, with a pro- 4 wt% magnesium-promoted catalyst showed highest activity
grammable temperature controller, and the reaction pressure was in triglyceride oil hydrogenation, which appeared to be due to
controlled using a back pressure regulator. Ten grams of catalyst the increase of metallic area as well as maintaining mesoporos-
was loaded into the reactor, with the upper and lower parts of the ity to avoid the effect of diffusion limitation. For the 8 wt%
reactor loaded with alumina beads, and the spaces between them magnesium-promoted catalyst mostly has micropores, which
filled with catalyst. The catalyst was reduced with hydrogen at can cause a diffusion limitation. In this regards, the promoter
normal pressure. When the reaction temperature and pressure quantity was fixed at 4 wt% in this study.
were reached, the flow rate of hydrogen was kept constant using Table 1 shows changes in the physical properties of the cata-
an MFC, and C9 -aldehyde fed to the reactor at a constant rate lyst when either CaO, MgO or Ce2 O3 was added as a promoter,
using a metering pump. To monitor changes in the activity of the at 4 wt%, to the Ni/kieselguhr catalyst. The BET surface area
catalyst according to the reaction time, samples were collected of the Ni/kieselguhr catalyst was 107 m2 /g, but if CaO, MgO or
at regular intervals, and analyzed using GC (Agilent 6890). The Ce2 O3 was added as a promoter, the BET surface area increased
conversion, selectivity and yield of C9 -aldehyde were calculated to 122, 153 or 149 m2 /g, respectively. In addition, the pore size
from the GC results.
Table 2
Table 1 Effect of precipitant on physical properties of catalysts (catalyst:
Effect of promoter on physical properties of Ni/kieselguhr catalysts Ni–MgO/kieselguhr)
Catalysta BET surface Average pore Ni particle size Precipitant BET surface Average pore Ni particle
area (m3 /g) diameter (Å) (Å) area (m3 /g) diameter (Å) size (Å)
Ni/kieselguhr 107 56 47 Na2 CO3 + urea 153 41 29
Ni–CaO//kieselguhr 122 52 34 NH4 OH + urea 36 141 20
Ni–MgO/kieselguhr 153 41 29 Na2 CO3 180 48 28
Ni–Ce2 O3 /kieselguhr 149 40 29 NaHCO3 161 50 34
a (NH4 )2 CO3 153 52 34
Ni 40 wt%, promoter 4 wt%.
558 J.-K. Jeon et al. / Chemical Engineering Journal 140 (2008) 555–561

Table 3
Effect of reduction condition on Ni particle size over Ni–MgO/kieselguhr
Calcination Reduction Flow rate of hydrogen Ni particle
temperature (◦ C) (ml/min) size (Å)

– 400 100 23
– 450 100 29
– 500 100 30
– 450 50 24
300 ◦ C, 4 h 450 100 29

Ni–MgO/kieselguhr catalysts prepared using Na2 CO3 + urea,

NH4 OH + urea, Na2 CO3 , NaHCO3 or (NH4 )2 CO3 as the precip-
itant. In the case of the catalyst prepared using NH4 OH + urea
as a precipitant, the size of the nickel particles was the small-
est, but most were 100–1000 Å large macropores, with relatively
fewer mesopores and, as a consequence, the BET surface area
was very small. In addition, the average pore size was around
Fig. 4. Effect of precipitant on pore size distribution of catalysts. 140 Å, much larger than that of other catalysts. The catalysts pre-
pared using Na2 CO3 + urea, Na2 CO3 , NaHCO3 or (NH4 )2 CO3
of the Ni/kieselguhr catalyst was reduced from 56 Å to 52, 41 as the precipitant showed similar pore size distribution pat-
and 40 Å. Fig. 3 shows XRD spectra of the nickel/kieselguhr terns, with a large portion of 40 Å large mesopores; also,
catalysts with the promoter. The peak of nickel decreases with the size of the nickel particles was similar. The BET surface
the addition of CaO, MgO or Ce2 O3 . The size of the Ni particle area was the largest in the catalyst prepared using Na2 CO3 as
of the Ni/kieselguhr catalyst calculated from the width of the the precipitant (Table 2). The effects of the reduction condi-
peak at 44.6◦ using Scherrer’s equation was 47 Å, but if CaO, tions of the Ni–MgO/kieselguhr catalyst were also investigated.
MgO or Ce2 O3 was added as a promoter, size of the Ni particle Table 3 shows the effects of the reduction temperature and
decreased to 34, 29 and 28 Å, respectively. hydrogen flow rate. Fig. 6 shows the effect of reduction con-
dition on XRD spectra of the Ni–MgO/kieselguhr catalyst.
3.2. Effect of catalyst preparation method on catalyst When the reduction temperature was raised from 400 to 500 ◦ C,
characteristics the size of Ni particles increased from 23 to 30 Å. The high
hydrogen flow rate also enlarged the size of the Ni particles.
When preparing a catalyst using the precipitation method, Conversely, when comparing the catalyst reduced through 4 h
various kinds of alkali compounds are used as precipitants.
The present study used common precipitants, such as Na2 CO3 ,
Na2 CO3 + urea, NH4 OH + urea, NaHCO3 and (NH4 )2 CO3 , to
examine their effects on the characteristics of the catalyst.
Table 2 and Fig. 4 show changes in the characteristics of
the catalyst according to the precipitant used in preparing the
Ni–MgO/kieselguhr catalyst. Fig. 5 shows XRD spectra of the

Fig. 5. Effect of precipitant on XRD spectra of the Ni–MgO/kieselguhr catalyst Fig. 6. Effect of reduction condition on XRD spectra of the Ni–MgO/kieselguhr
after reduction. catalyst.
 J.-K. Jeon et al. / Chemical Engineering Journal 140 (2008) 555–561 559

Table 4
Effect of reaction condition on activity and selectivity (catalyst: Ni–MgO/kieselguhr)
Temperature (◦ C) Pressure (psi) Feed flow rate (cm3 /min) Conversion (%) Selectivity (%) Yield (%)

130 400 0.2 97.5 91.0 88.7

130 400 0.6 98.9 92.5 91.5
130 600 0.2 98.1 88.8 87.1
130 800 0.2 91.0 88.9 80.9
130 800 0.6 67.9 79.0 53.6
175 400 0.2 99.8 59.0 58.9
175 400 0.6 99.1 71.3 70.7
175 800 0.2 99.9 62.6 62.5
175 800 0.6 98.0 69.5 68.1

calcinations at 300 ◦ C, with that reduced without calcinations, Fig. 8 shows the results of a hydrogenation experiment
almost no difference was observed in the size of the Ni parti- according to the precipitant used. The catalyst prepared using
cles. Na2 CO3 showed the highest reaction activity. As shown in
Table 2, the catalyst using NH4 OH as the precipitant showed the
3.3. C9 -aldehyde hydrogenation in a batch reactor lowest reaction activity due to its significantly smaller surface
area.
Fig. 7 shows the result of C9 -aldehyde hydrogenation in the
batch reactor at 120 ◦ C and 100 bar using the Ni/kieselguhr cat- 3.4. C9 -aldehyde hydrogenation in a trickle bed reactor
alyst, to which 4 wt% CaO, MgO or Ce2 O3 was added as a
promoter. During the initial 60 min of the reaction, the catalysts In order to find the optimal reaction conditions, C9 -aldehyde
with CaO, MgO or Ce2 O3 showed higher reaction activities than hydrogenation reactions were performed in the trickle bed reac-
that without the promoter, with the catalyst containing MgO tor with the Ni–MgO/kieselguhr catalyst (Figs. 1 and 2). While
showing the highest activity. changing the reaction temperature and pressure and the flow rate
This result can be explained by changes in the catalyst char- of the reactant C9 -aldehyde, changes in the yield of C9 -alcohol,
acteristics. The addition of the promoters MgO, CaO or Ce2 O3 which is an indicator of the catalyst activity, were measured. As
increase the BET surface area, reduce the pore size down to shown in Table 4, the reaction temperature was changed from
around 40 Å and decrease the size of the Ni particles. If the 130 to 175 ◦ C, the reaction pressure from 400 to 600 psi and
pores of catalyst are too small, it will affect the diffusion resis- 800 psi, and the space velocity of the reactant C9 -aldehyde from
tance. As the pore size is reduced by the addition of a promoter, 1 to 3 h−1 . Here, the flow rate of hydrogen was changed from
the BET surface area increases, but most pores are mesopores, 30 to 90 cm3 /min, along with the change in the flow rate of
with an average size of 40 Å, which prevents the increase in the C9 -aldehyde. First, with respect to the change in the reaction
diffusion resistance. In addition, the decrease in the size of the activity caused by the reaction temperature, the alcohol yield
Ni particles increases the surface area of Ni, which explains the was increased by 10–20% at 130 ◦ C compared to 175 ◦ C when
increase in the reaction activity. If the size of the nickel particles the reaction pressure and flow rate of C9 -aldehyde were kept
decreases, a large number of Ni atoms will exist on the surface; constant. Compared to 130 ◦ C, the octene content of the prod-
that is, as there are many active sites where reaction takes place, uct at a reaction temperature of 175 ◦ C was 24–29% higher. This
the reaction rate will be accelerated.

Fig. 7. Effect of promoter on C9 -alcohol yield over Ni/kieselguhr catalyst in a Fig. 8. Effect of precipitant on C9 -alcohol yield over Ni/kieselguhr catalyst in
batch reactor (120 ◦ C, 100 bar). a batch reactor (120 ◦ C, 100 bar).
560 J.-K. Jeon et al. / Chemical Engineering Journal 140 (2008) 555–561

Fig. 9. Comparison of C9 -aldehyde hydrogenation over various catalysts [Cat A:

CuO/ZnO/Al2 O3 (60:30:10); Cat B: Cu–Ni–Cr–Na/Al2 O3 (Cu 0.3%, Ni 4.5%, Fig. 10. Long-term performance in a trickle bed reactor (reaction temperature:
Cr 0.07%, Na 0.03%); Cat C: Ni–Mo/Al2 O3 (NiO 4.0%, MoO3 20.0%); Cat D: 130 ◦ C; reaction pressure: 400 psi).
Ni–MgO/kieselguhr (Ni 60%)].

was probably because, in the case using the Ni–MgO/kieselguhr yield with Ni–MgO/kieselguhr was similar to that with
catalyst, a high reaction temperature decomposes the reactant Cu/ZnO/Al2 O3 , but higher than that with Cu–Ni–Cr–Na/Al2 O3
C9 -aldehyde into the octene and, as a result, the selectivity of and Ni–Mo/Al2 O3 .
C9 -alcohol decreases, despite the high conversion; the yield of Using the result of the experiment for establishing the opti-
C9 -alcohol was also lower at a higher temperature. mal reaction conditions, the stability of the catalyst was tested
Next, with respect to the effect of reaction pressure, when in a long-term operation. The trickle bed reactor was filled with
the pressure was raised from 400 to 800 psi, the yield of C9 - 10 g Ni–MgO/kieselguhr, and the reaction performed under the
alcohol generally decreased at each temperature. At the low optimal operation conditions (130 ◦ C, 400 psi, WHSV = 3 h−1 )
temperature of 130 ◦ C, no significant change in the activity was for 120 h, and the change in the catalyst activity monitored.
observed until 600 psi, but as the pressure was raised to 800 psi, Fig. 10 shows the result of the long-term test. With respect
the conversion and selectivity of C9 -aldehyde decreased and, as a to the conversion, no significant change was observed over the
result, the catalyst activity was considerably reduced. This trend 120 h of the experiment. However, the quantity of high-boiling-
was more noticeable when the flow rate of C9 -aldehyde was point by-products generated from C9 -aldehyde hydrogenation
high. The quantity of high-boiling-point by-products (HBPBP) slightly increased, which decreased the alcohol selectivity and,
also increased at the higher pressure of 800 psi. Conversely, at as a consequence, the selectivity for C9 -alcohol was decreased
the higher temperature of 175 ◦ C, no remarkable decrease was by 2.1% over the 120 h ration time. Consequently, the yield of
observed in relation to the reaction pressure. The effect of the C9 -alcohol at the beginning of the reaction was 91.5%, but this
C9 -aldehyde flow rate on the catalyst activity was less than that was decreased to 89.4% after 120 h. On the other hand, compared
of the reaction temperature and pressure. However, at a low with the result of a long-term experiment using Cu/ZnO/Al2 O3 ,
temperature and high pressure (130 ◦ C, 800 psi), as well as at a the activity of the Ni–MgO/kieselguhr catalyst lasted longer.
high temperature and low pressure (175 ◦ C, 400 psi), the yield
of C9 -alcohol changed rapidly, by around 10–23%, in relation 4. Conclusions
to the C9 -aldehyde flow rate. In the case of Ni–MgO/kieselguhr,
the change in activity according to reaction temperature was the When a promoter, either CaO, Ce2 O3 or MgO, was added to
most remarkable. To some degree, with a pressure increase at a the Ni/kieselguhr catalyst, the BET surface area increased, as
low temperature the activity was reduced, but was only slightly did that of the Ni. In the reaction for the manufacture of C9 -
affected by the flow rate of reactant C9 -aldehyde. alcohol, using C9 -aldehyde and hydrogen in a batch reactor, the
Conversely, as mentioned in Section 1, the catalysts Ni–MgO/kieselguhr catalyst showed the highest activity. More-
reported for the hydrogenation of aldehyde include over, the Ni–MgO/kieselguhr catalysts, using Na2 CO3 as the
Cu–Ni–Cr–Na/Al2 O3 , Ni–Mo/Al2 O3 and Cu/ZnO/Al2 O3 precipitant showed the highest activity.
[10–16]. Fig. 9 shows the result of C9 -aldehyde hydrogenation According to the result of an experiment for optimizing the
in a trickle bed reactor using these catalysts. In the conversion reaction conditions for the manufacture of C9 -alcohol, using
of C9 -aldehyde, Cu/ZnO/Al2 O3 and Ni–MgO/kieselguhr C9 -aldehyde and hydrogen in a trickle bed reactor loaded with
showed similar activities. In addition, the yield of high- Ni–MgO/kieselguhr catalyst, the C9 -alcohol yield was 91.5 wt%
boiling-point by-products was 3.8% with Cu/ZnO/Al2 O3 at 130 ◦ C and 400 psi, with WHSV = 3 h−1 . The C9 -aldehyde
and 4.0% with Ni–MgO/kieselguhr, which were both lower hydrogenation performance of the Ni–MgO/kieselguhr catalyst
than the 14.7 and 10.2% recorded for Cu–Ni–Cr–Na/Al2 O3 was similar to that of Cu/ZnO/Al2 O3 , but superior to that of
and Ni–Mo/Al2 O3 , respectively. Accordingly, the C9 -alcohol Cu–Ni–Cr–Na/Al2 O3 and Ni–Mo/Al2 O3 . When the stability of
 J.-K. Jeon et al. / Chemical Engineering Journal 140 (2008) 555–561 561

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