Catalytic conversion of C12-C14 primary alcohols mixture into long-chain ketones

Article abstract of DOI:10.1016/j.catcom.2010.05.024

A charge of raw primary alcohols of high molecular weight from commercial plant was transformed into long-chain ketones fraction of potential commercial use. In this continuous flow method LaMnO₃/La-Al₂O ₃ catalyst was used. At 420 °C and a normal pressure mixture of 74.2 wt.% C₁₂ and 25.8 wt.% C₁₄ primary alcohols and toluene (weight ratio alcohols:toluene = 1:1) was converted into ketones with 73.4% yield in relation to the theoretical value. Ketones were analyzed by TLC, NMR and GC-MSD.

Full text of DOI:10.1016/j.catcom.2010.05.024

Catalysis Communications 11 (2010) 1143–1147
Contents lists available at ScienceDirect
Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
Catalytic conversion of C12–C14 primary alcohols mixture into long-chain ketones
b
c
Roman Klimkiewicz a, , Ireneusz Morawski , Janusz Trawczyński
⁎
a
Institute of Low Temperature and Structure Research, PAS, P.O.B. 1410, 50-950 Wrocław 2, Poland
Institute of Heavy Organic Synthesis “Blachownia”, Kędzierzyn-Koźle, Poland
Wrocław University of Technology, ul. Gdańska 7/9, 50-344 Wrocław, Poland
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
A charge of raw primary alcohols of high molecular weight from commercial plant was transformed into
long-chain ketones fraction of potential commercial use. In this continuous flow method LaMnO3/La–Al2O3
catalyst was used. At 420 °C and a normal pressure mixture of 74.2 wt.% C12 and 25.8 wt.% C14 primary
alcohols and toluene (weight ratio alcohols:toluene=1:1) was converted into ketones with 73.4% yield in
relation to the theoretical value. Ketones were analyzed by TLC, NMR and GC-MSD.
© 2010 Elsevier B.V. All rights reserved.
Received 19 March 2010
Received in revised form 21 May 2010
Accepted 28 May 2010
Available online 11 June 2010
Keywords:
Ketonization
Lanthanum manganite
Manganese
Alcohol fraction
Ketone fraction
1. Introduction
by selecting proper catalysts. It leads to the symmetric ketones with
2n−1 carbon atoms in relation to initial alcohol [19]. The use of
Mixtures of ketones have several applications. Ketones and
mixtures of ketones are useful organic solvents for painting,
agricultural, and other industries as intermediates for the preparation
of dyes, crop protection agents and drugs [1–3]. They are found to be a
satisfactory drilling fluid dispersant in aqueous drilling fluids [4],
reactive solvents to form coatings and foamed plastics [5,6], a stuff for
the ammoxidation to a mixture of nitriles [7].
Long-chain ketones can be used for the production of surfactants
in detergent compositions [8], particularly gemini surfactants [9–11].
They can be also used as special foam control agents in the paint,
paper and food industries and as foam inhibitors in soap-containing
detergents [12,13]. It is worth to mention that mixture of long-chain
ketones dispersed in fatty alcohols is also of commercial use [14].
Oxidation of hydrocarbons is a well-known method of ketones
production. Besides, they can be formed from carboxylic acids [15]
and also from alcohols. Liquid-phase oxidation of alcohols has some
disadvantages such as costly oxidants, inevitably resulting in the
formation of environmentally unfriendly by-products, basic-additives
and heavy-metal-solutions [16] or a solvent-dependent over- oxida-
tion [17]. Whereas, it is generally regarded that primary and
secondary alcohols are oxidized into corresponding aldehydes and
ketones [18], the accomplishment of primary alcohol transformations
in vapor-phase conditions over some oxide catalysts also enables
to receive ketones. The bimolecular reaction can occur successfully
alcohol mixture is an alternative method to obtain required non-
symmetric ketones [20]. Esters can be also used as raw materials for
such ketonization. One of the directions of use of such transformation
may be the synthesis of long-chain ketones [21]. For this purpose,
esters possessing high molecular weight, such as these ones
originating from the transesterification of fats [22] can be used [23].
Catalysts activity is usually tested with the use of model com-
pounds, reports dealing with catalytic performance for real feed are
less common. Despite of practical importance of primary alcohols
ketonization there are only few works addressed to conversion of real,
commercial feed [19]. Therefore, we assumed that such conversion
can be also applied when alcohols of higher molecular weight are use
as the raw material. The alcohols fraction—lauryl/myristyl alcohol (AL
C12–C14) [24,25] produced by the hydrogenation of methyl esters
from palm kernel oil (PKO) [26,27] or coconut oil (CNO) [28] are
considered as a potential feed for this transformation. Some bases for
detergents (sulfated and ethoxylated alcohols for shampoos) are
produced from fraction AL C12–C14 [24,29].
High activity and selectivity of the lanthanum manganite was
demonstrated in relation to unconventional conversion of 1-butanol
to heptanone-4 [30–32]. It is known that low specific surface area
(SSA) is one of the drawbacks of the perovskite-based catalysts.
Deposition of perovskites over refractory carrier possessing high SSA
is a convenient method for increasing their surface area accessible for
reactants and improvement of thermal stability. In this work, LaMnO3
mixed oxide with perovskite-like structure was supported on alumina
precoated with lanthanum oxide and used as a catalyst for primary
alcohols transformation.
⁎
Corresponding author. Fax: +48 71 3441029.
E-mail address: R.Klimkiewicz@int.pan.wroc.pl (R. Klimkiewicz).
1566-7367/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2010.05.024

1144
R. Klimkiewicz et al. / Catalysis Communications 11 (2010) 1143–1147
Table 1
necessary to obtain 30 wt.% of LaMnO3 deposited on La–Al2O3. The
mixture was evaporated to produce viscous syrup which was carefully
decomposed at 350 °C. Produced solid material was grounded and
finally calcined for 2 h at 850 (900) °C. Material obtained in this way
was pressed, crushed, and screened—particles of 0.6–1.2 mm size
were used for catalytic tests.
The total acidity and the acid strength distribution were evaluated
by the temperature-programmed desorption of ammonia (TPD NH3)
according to the following procedure. Samples (2 g) were heated to
823 K under argon for 1 h then cooled to 453 K where adsorption of
pure ammonia was performed for 0.5 h followed by a purge with
argon at 453 K for 1 h in order to remove physically adsorbed NH3.
Finally, TPD NH3 measurements were started in argon with a heating
rate of 10 K/min.
Results of the ketonization of C12–C14 primary alcohol fraction on the LaMnO3/La–Al2O3
catalyst.
Reaction
temperature [%]
[°C]
Conversion Output of solid Yield of ketones from Selectivitya
product [g/h]
the solid product [%]
[%]
380
74
1.45
1.92
1.70
1.50
59.3
63.5
61.8
50.0
61.4
87.1
75.0
53.6
400
420
440
∼100
∼100
∼100
a
Selectivity=100 (experimental weight of produced ketones)/(theoretical weight
of ketones), see text below.
The ketonization of C12–C14 primary alcohols fraction was carried
out in a fixed bed flow reactor at atmospheric pressure. A quartz tube
reactor (10 mm of inner diameter) was loaded with 3 cm3 of the
catalyst and placed in a vertical pipe furnace Thermolyne F21100. The
outlet of the reactor was additionally heated to avoid the solid
products condensation.
Taking into account that 1-butanol ketonization was performed as
a model reaction for determination of LaMnO3/La–Al2O3 activity [31],
we decided to use the same reaction for controlling the catalyst's
activity before and after the reaction. This test was performed two
times: once before the experiments with the C12–C14 primary alcohol
fraction and then after these experiments test was repeated. The
2. Experimental
Alumina carrier was precoated with lanthanum compound to
inhibit the sintering and preventing of the reaction of perovskite
components with the support. Procedure of the carrier (La–Al2O3)
preparation is described elsewhere [31]. Supported LaMnO3 catalysts
were prepared by citrate process according following protocol. At first
the citric precursor of LaMnO3 was prepared by dissolution of La and
Mn nitrates in the suitable proportions to give a water solution. Then,
metal ions were complexed by the addition 1.2 mol of citric acid per
mol of metal to this solution. Powdered carrier was suspended in the
solution containing amount of citric precursor of the perovskite
Fig. 1. The 13C NMR spectra of the obtained ketone fraction.

R. Klimkiewicz et al. / Catalysis Communications 11 (2010) 1143–1147
1145
Fig. 2. The 1H NMR spectra of the obtained ketone fraction.
second control test was preceded by 7 h regeneration of the catalyst in
air at 470 °C in the same reactor. The control trials were made at
3 cm3/h flow intensity of liquid 1-butanol (1 h−1 LHSV).
silica gel coated plates. Ketones were detected on the plates by
spraying a solution of 2,4-dinitrophenylhydrazine diluted in H2SO4.
This reagent gives a color reaction with aldehydes and ketones. Plates
were developed with a mixture of hexane–ethyl acetate.
The final ketone fractions were separated, solvent was removed
under vacuum, ketones were dried in a vacuum desiccator and
weighed. For analysis of the condensed products a high-resolution
time-of-flight (TOF) mass spectrometer (GCT Premier, Waters) with
an atmospheric-pressure solids analysis probe (ASAP) was used. NMR
spectra were acquired with NMR Bruker DRX 300 (1H and 13C, 300.13
and 75.48 MHz, respectively). X-ray diffraction (XRD) patterns of the
catalysts were obtained by a DRON-3 diffractometer operating at
40 kV and 30 mA, using CuKα radiation.
The C12–C14 primary alcohols fraction from IHOS “Blachownia”
industrial plant containing 74.2 wt.% C12 and 25.8 wt.% C14 alcohols
was dissolved in toluene (a weight ratio of 1:1; density of the mixture
—0.85 g/cm3). Such solution was fed to the top of the reactor and
dispersed in pre-heating zone using an infusion pump (Medipan 610-
2) with a volume flow of 3.7 cm3/h. Due to the additional heating of
the receptacle, the obtained solid product was partially deprived of
toluene. Product weight gain was monitored. Gaseous by-products
(see the transformation scheme below) were not analyzed. Toluene
remained in the so obtained samples was removed in a desiccator
under pressure of about 15–20 mmHg. Purification of received ketone
fractions was performed on a silica gel column [33]. The hexane–ethyl
acetate mixture with a volume ratio of 100:5 was used for column
elution. Fractions containing ketones were collected and further
purified by the column chromatography. The collected fractions from
the column were analyzed by thin-layer chromatography using a
3. Results and discussion
After removing toluene from the reaction products, ketones were
separated from the solid by column chromatography. It appeared that
ketones were the main component of the solid product. Other
Table 2
Results of control trials of 1-butanol conversion at 400 °C before and after experiments with the C12–C14 primary alcohol fraction and regeneration.
Test
Conversion
[%]
Selectivity [%]
Yield [%]
Butene
Butene
n-Butanal
Dipropyl ketone
Butyl butyrate
Others
n-Butanal
Dipropyl ketone
Butyl butyrate
Others
Before
After
53
56
8
9
8
10
73
70
9
8
2
3
4
5
4
6
39
39
5
4
1
2

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R. Klimkiewicz et al. / Catalysis Communications 11 (2010) 1143–1147
1.57 g/h of toluene) should yield 2.97 g/h of product containing
1.43 g/h of ketone fraction and 1.57 g/h of toluene. Since, at 400 °C the
solid product was produced at 1.92 g/h, the difference 1.08 g/h can be
related to evaporated toluene and unidentified by-products of the
reaction. Solid product separated in this way still contained toluene.
Drying in a desiccator resulted in a 36.5% weight loss. Thus, 1.22 g/h of
ketone fraction was obtained at 400 °C. This represents an efficiency
of 85.3% as compared to the theoretical value. Similarly, 1.70 g/h solid
product was obtained at 420 °C. The greater difference (1.3 g/h)
indicates a higher degree of toluene evaporation and a larger share of
side destruction reactions and/or secondary condensations. Drying of
such samples in a desiccator resulted in 38.1% weight loss. Thus, at
420 °C the ketone fraction was obtained with the efficiency 1.05 g/h,
i.e. 73.4% yield in relation to the theoretical value.
Obtained fraction of ketones was characterized by means of GC–
MS and NMR. The 13C NMR spectra (Fig. 1) revealed the 210 ppm
signal of C-carbonyl group. Other signals should be assigned in
descending order, starting from the CO group: 31.95 ppm—second
carbon in chain, 29.65 ppm—third methylene carbon, etc. The last
signal—22.73 ppm is assigned to methyl carbons. The 1H NMR spectra
(Fig. 2) show a triplet at 0.88 ppm (CH3 group) and a large multiplet
1.25 ppm (CH2 groups). These alpha and beta groups are shifted
2.38 ppm and 1.55 ppm, respectively. Additional signal at beta CH2
(probably due to H2O, shift 1.56) increases the integration by 2.
Results of GC–MS measurements have confirmed that material
labeled as “ketone fraction” contains the expected ketones of high
molar mass.
It was found that the catalyst's activity was stable during the run,
exhibiting low tendency to formation of carbon deposits of resin and
tar type accumulating on it. After the test catalyst remained in the
reactor and was regenerated by heating at 470 °C for 4 h under air
flow. Model test with the use of 1-butanol (Table 2) showed that both
the fresh and the regenerated catalysts exhibit the same activity and
selectivity for 1-butanol conversion. Also the XRD patterns of the
LaMnO3/La–Al2O3 material before and after catalytic test do not show
noticeable differences (Fig. 3). LaMnO3 is very well dispersed on the
surface of La-stabilized alumina and only weak signals of lanthanum
manganite are visible on the XRD pattern of both fresh and used
material.
Properties of the LaMnO3/La–Al2O3 catalyst are presented and
discussed elsewhere [31]. Here it is worth to remind that this material
possesses relatively high specific surface area (46.0 m2/g), concen-
tration of basic and acidic sites 0.22 and 0.55 mmol/m2, respectively.
Results of cyclohexanol decomposition on this material show that
dehydrogenation of cyclohexanol to cyclohexanone proceeds in
higher extent than dehydration to cyclohexene (CHON/CHEN selec-
tivity ratio 3.1) which suggests that basic sites are more reactive than
acidic ones. This has significant implications for dehydrogenation.
Nevertheless, the acid centers also play an important role in relation
to the secondary conversion of aldehydes to ketones [30]. From TPD
NH3 analyses, we found that the total acidity of LaMnO3/La–Al2O3 was
as high as 0.284 mmol NH3/g. For comparison the total acidity of La-
doped alumina carrier was measured and the value of 0.362 mmol
NH3/g was found. Higher acidity of carrier alone than catalyst
supported on this material results from participation of acidic sites
of alumina. These sites are then covered by less acidic mixed oxide
deposited on the carrier's surface. It is worth to note that
concentration of acidic sites determined for LaMnO3/La–Al2O3 by
TPD NH3 method is lower than concentration determined previously
by titration method. This difference is related with peculiar character
of each procedure. Nevertheless, acidic sites are more abundant than
basic ones.
Fig. 3. XRD patterns of LaMnO3 perovskite supported on stabilized alumina before and
after test and regeneration.
compounds were present in minor trace amounts, as it was confirmed
by thin-layer chromatography. The best results of tests performed at
400 and 420 °C are shown in Table 1. It was found that at lower or
higher reaction temperatures, conversion or selectivity is lower than
these ones obtained at 400–420 °C. The semi-product, resulting from
the reaction at 380 °C contained over 25% of unreacted alcohols. After
the test at 420 °C, at the full conversion, the ketones efficiency
dropped to 53.6%. The brownish product contained 46.4% of
hydrocarbons and other unidentified compounds resulting from the
cracking and the other side transformations [19,21,23].
The transformation follows the general reaction scheme [19,21]:
Thus, this transformation causes the loss of one carbon atom in
relation to two molecules of alcohols, regardless of the length of the
chain. Therefore, the atom economy of this method increases with
increasing alcohol's carbon chain length. This difference in the carbon
balance has been taken into account in the calculations below.
Since, during ketonization of equimolar mixture of primary
alcohols RCH2OH and R'CH2OH, three ketones are produced in the
quantitative relations resulting from the probability:
RCOR : RCOR' : R'COR'=1/4 : 1/2 : 1/4 [21].
In this event, the average molecular weight of the mixture of
ketones C11COC11, C11COC13 and C11COC13 is equal to 366 Da.
As the molar ratio of alcohols C12:C14 in the raw material
was =3:1, one can assume that the probability of quantitative
relations of received ketones will be close to:
RCOR : RCOR' : R'COR'=5/8 : 1/4 : 1/8.
The expected average molecular weight of the mixture of so
obtained ketones is 352 Da.
If we assume full conversion and selectivity only to ketones, the
3.14 g/h of raw material (including 1.57 g/h of alcohol fraction and
Table 3
Acid strength distribution determined by TPD NH3.
Sample
Concentration of acid centers with equal strength, %
473–
523–
573–
623–
673–
723–
773–
The share of acid strength distribution is shown in Table 3. It can be
clearly observed that deposition of 30 wt.% of LaMnO3 develops
mainly weak and medium acid sites (desorption temperature
Td =473–673 K) at the charge of strong acid sites (Td N773 K).
523 K
573
623
673
723
773
823
La–Al2O3
LaMnO3/La–Al2O3
4.0
5.2
9.1
14.9
18.5
20.9
20.4
20.9
20.1
17.2
15.3
13.5
12.6
7.3

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1147
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