Vapour phase Guerbet condensation of ethanol to 1-butanol on CsX zeolite
Nowadays, the conversion of ethanol into valuable chemical products is getting wider application.One of such promising processes is Guerbet condensation of alcohols, which permits the obtaining of 1-butanol from renewable raw materials that are alternatives to petroleum ones.Oxide systems combining...
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Catalysis and petrochemistry| _version_ | 1872009057936605184 |
|---|---|
| author | Patrylak, Lyubov K. Pertko, Olexandra P. Valihura, Karina V. Voloshyna, Yulia G. |
| author_facet | Patrylak, Lyubov K. Pertko, Olexandra P. Valihura, Karina V. Voloshyna, Yulia G. |
| author_institution_txt_mv | [
{
"author": "Lyubov K. Patrylak",
"institution": "V.P Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine. Kharkivske shosse, 50, Kyiv-02160, Ukraine"
},
{
"author": "Olexandra P. Pertko",
"institution": "V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the NAS of Ukraine, 1, Murmanska Str, Kyiv, Ukraine, 02094"
},
{
"author": "Karina V. Valihura",
"institution": "3L.V. Pisarzhevskii Institute of Physical Chemistryof National Academy of Sciences of Ukraine 31 Nauky Avenue, Kyiv, 03028, Ukraine"
},
{
"author": "Yulia G. Voloshyna",
"institution": "V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the NAS of Ukraine, 1, Murmanska Str, Kyiv, Ukraine, 02094"
}
] |
| author_sort | Patrylak, Lyubov K. |
| baseUrl_str | https://kataliz.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2024-12-24T10:38:54Z |
| description | Nowadays, the conversion of ethanol into valuable chemical products is getting wider application.One of such promising processes is Guerbet condensation of alcohols, which permits the obtaining of 1-butanol from renewable raw materials that are alternatives to petroleum ones.Oxide systems combining acid and basic sites in their composition are promising catalysts for such a transformation.In this study, the efficiency of the magnesium-aluminum oxide and zirconium-oxide catalysts was compared to the activity of the cesium form of X-type zeolite produced by hydrothermal ion exchange in the condensation of ethanol to 1-butanol. The integrity of the zeolite structure was confirmed by using the XRD and XRF analysis, as well as by the IR spectroscopy.The depth of exchange of native sodium for cesium was 82%. It was also found that cesium cations are localized only in ion-exchange positions of faujasite, in places SIII (supercages) and SI` (sodalite cages). CsX zeolite acid to basic sites ratio was found tobe close to optimal for this reaction. Cesium-containing zeolite at 300 °C showsethanol 35-55 % conversion and 20-25 % selectivity for 1-butanol, which is higher than the same characteristics for zirconium samples, but slightly inferior to magnesium-aluminum oxide catalysts. The obtained results indicate the promising use of zeolites of a similar nature in the process of condensation of ethanol to 1-butanol. |
| doi_str_mv | 10.15407/kataliz2023.34.050 |
| first_indexed | 2026-03-12T15:50:18Z |
| format | Article |
| fulltext |
50 Каталіз та нафтохімія, 2023, №34
Catalysis and Petrochemistry, 2023, 34
UDC544.473
https://doi.org/10.15407/kataliz2023.34.050
Vapour phase Guerbet condensation of ethanol to 1-butanol on CsX zeolite
Lyubov K. Patrylak 1, 2, Olexandra P. Pertko 1, Karina V. Valihura 3, 4, Yulia G. Voloshyna 1
1 V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of National Academy of Sciences of Ukraine
50 Kharkivske shose, Kyiv, 02160, Ukraine, e-mail: lkpg@ukr.net
2 National Technical University of Ukraine “Igor Sikorskyi Kyiv Polytechnic Institute”
37/4 Beresteiskyi Avenue, Kyiv, 03056, Ukraine
3 L.V. Pisarzhevskii Institute of Physical Chemistry of National Academy of Sciences of Ukraine
31 Nauky Avenue, Kyiv, 03028, Ukraine
4 Department of Chemical and Environmental Engineering, Higher Technical School of Engineering
University of Seville, Camino de los Descubrimientos w/n, 41092 Seville, Spain
Nowadays, the conversion of ethanol into valuable chemical products is getting wider application. One of
such promising processes is Guerbet condensation of alcohols, which permits the obtaining of 1-butanol from
renewable raw materials that are alternatives to petroleum ones. Oxide systems combining acid and basic sites in
their composition are promising catalysts for such a transformation. In this study, the efficiency of the magnesium-
aluminum oxide and zirconium-oxide catalysts was compared to the activity of the cesium form of X-type zeolite
produced by hydrothermal ion exchange in the condensation of ethanol to 1-butanol. The integrity of the zeolite
structure was confirmed by using the XRD and XRF analysis, as well as by the IR spectroscopy. The depth of
exchange of native sodium for cesium was 82 %. It was also found that cesium cations are localized only in ion-
exchange positions of faujasite, in places SIII (supercages) and SI` (sodalite cages). CsX zeolite acid to basic sites
ratio was found to be close to optimal for this reaction. Cesium-containing zeolite at 300 °C shows ethanol 35-55 %
conversion and 20-25 % selectivity for 1-butanol, which is higher than the same characteristics for zirconium
samples, but slightly inferior to magnesium-aluminum oxide catalysts. The obtained results indicate the promising
use of zeolites of a similar nature in the process of condensation of ethanol to 1-butanol.
Keywords: ethanol condensation, 1-butanol, acid sites, basic sites, 1-butanol yield, process selectivity
Introduction
1-Butanol is widely used as a solvent, extractant, and raw material for the production of
methacrylates and butyl acrylate for coatings, enamels, and varnishes [1, 2]. A relatively new field of
application for 1-butanol is its addition to gasoline instead of ethanol [2-5]. The world production of
butanol-1 in 2017 was about 5.4 million tons, but according to forecast estimates, in the near future, the
demand for butanol will reach about 20 % of world fuel needs [6].
Traditionally, 1-butanol is obtained in the process of hydroformylation of petroleum-derived
propylene with subsequent hydrogenation of the obtained 1-butanol under high pressure conditions
(~ 30 MPa) using cobalt (Rh or Ru) catalysts in the first stage and nickel catalysts in the second stage [7].
Another commercial approach to obtaining butanol is the fermentation of carbohydrates by anaerobic
bacteria of the Clostridia class, the ABE (acetone-butanol-ethanol) process. The main problems with the
latter are the significant duration of the process, the high cost of the substrate, and the low concentration
of the obtained biobutanol [6, 8].
Guerbet condensation of alcohols, consisting of the doubling of the alcohol chain, is a promising
method of converting light alcohols into higher ones [9]. Currently, industrial production of higher
alcohols by Guerbet condensation is carried out on combined catalysts (liquid alkalis together with a solid
catalyst based on transition metals) [10-12]. Its implementation requires high-cost equipment design for
separation, purification, recovery, and processing of waste, as well as the use of catalysts with precious
Каталіз та нафтохімія, 2023, №34 51
Catalysis and Petrochemistry, 2023, 34
metals. As a result, the production of alcohols by Guerbet condensation is so far only profitable for the
particularly valuable higher alcohols C8+.
Therefore, there is considerable interest in the development of cheaper solid catalysts that would
allow the process to be implemented in flow mode, eliminating the problems of separating them from the
reaction mixture and the corrosion of the equipment. On the one hand, carrying out the reaction in the
vapor phase would allow the process to be implemented at atmospheric pressure, which, accordingly,
would have fewer technological limitations than in liquid-phase systems with high pressure [9].
Systems based on MgO-Al2O3and ZrO2 are considered promising for the development of effective
catalysts for the production of 1-butanol, for which there is a possibility of targeted regulation of structural-
dimensional and acid-base characteristics at the synthesis stage by changing the ratio of active components
in the composition of catalysts, the conditions of their formation, and also by introducing modifying
additives [13-15].
Works [13-15] show that for the effective conversion of ethanol into 1-butanol, the MgO-Al2O3
binary oxide catalyst must include Lewis acid-base pairs (Mg-O-Al) formed during the calcination of
hydrotalcites. The highest yield of 1-butanol (18 %) was achieved in the presence of a catalyst with a
Mg/Al ratio of 2. It was found that the modification of Mg-Al-oxide systems with cerium cations leads to
an increase in the concentration of acid and basic sites on the surface of the catalysts, which ensures an
increase in the specific rate of 1-butanol formation compared to the unmodified catalyst.
In paper [16] different metals (Cu, Ni and Co), at various metal loadings were deposited on the
alumina support. Consequently, the catalytic reactions were carried out in a continuous laboratory-scale
fixed bed reactor operated at 240 °C and 70 bar [16]. On the best catalysts, the selectivities towards
1-butanol close to 70 % were reached, while the ethanol conversions typically varied between 10 and
30 %. The latter strongly depends on the metal applied.
Rubidium-modified zeolites were also studied as catalysts for gas-phase condensation of lower
alcohols [17, 18]. The selectivity for butanol-1 was 40, 37, and 20 % on rubidium-modified zeolites
Rb-LiX, Rb-NaX, and Rb-KX, respectively. At the same time, samples without rubidium only catalyzed
dehydrogenation.
Selective zeolite catalysts for the alkylation of toluene with methanol in the side chain [19, 20] also
possess a combination of acidic and basic active sites. Moreover, according to the proposed reaction
mechanism, acid sites are responsible for alkylation of toluene in the benzene ring, while basic ones are
necessary for alkylation in the side chain. Faujasite-type zeolites modified with cesium act as effective
catalysts for this transformation [21].
Therefore, the purpose of this work was to evaluate the efficiency of a cesium-containing zeolite
of the faujasite-type in the gas-phase conversion of ethanol to 1-butanol, as well as to compare its activity
with magnesium-aluminumoxide and zirconiumoxide systems.
Experimental
Catalyst synthesis
X-type zeolite (SiO2/Al2O3 = 2.3, TU 38.102168-85, static capacity for water vapor: 0.30 cm3/g,
for benzene vapor: 0.29 cm3/g, fraction 0.5-1 mm) was subjected to a two-time exchange for cesium
cations from a 1 N aqueous solution of nitrate (chemically pure, TU 6-09-437-83) for cesium form
synthesis. The ratio of solid to liquid phases in hydrothermal ion exchange was 1:5. Exchanges were
carried out sequentially at 140-150 °С for 2 h in a rotating stainless steel autoclave with intermediate
52 Каталіз та нафтохімія, 2023, №34
Catalysis and Petrochemistry, 2023, 34
washing with distilled water. The elevated temperature was used to destroy the hydrate shell of the
introduced cations and thereby increase the depth of the exchange. After completion of the procedure, the
sample was thoroughly washed with distilled water until the absence of NO3
- ions and dried in air.
Catalyst characterization
23Na, 27Al, 133Cs NMR spectra were recorded on an AVANCE 400 spectrometer (Bruker).
Recording was carried out in accumulation mode at frequencies ν 105.842, 104.261, and 52.482 MHz,
respectively. Chemical shifts δ were determined relative to the standards: solutions of NaCl, Al(H2O)6
3+
and CsNO3. The sample was placed in borate glass ampoule (5 mm diameter).
FTIR spectroscopy. IR spectra in the region of framework vibrations (400-1200 cm–1) were
recorded on an IR-Fourier spectrometer IR Affiniti-1s (Shimadzu, Japan) with a Specac Quest GS 10801-B
disturbed total internal reflection (ATR) attachment. The sample was applied to the surface of the diamond
prism of the ATR attachment, and the spectrum was recorded. The spectral resolution was 2 cm–1.
N2 adsorption. Low temperature nitrogen adsorption/desorption isotherms for samples were
measured on a Quantachrome Autosorb NOVA 1200e® automatic sorbometer (USA) after thermal
dehydration at 180 °C for 20 hours. Utilizing the NOVAW in 11.04 software, the parameters of the porous
structure were computed.
X-ray fluorescence (XRF) analysis. The elemental analysis of the samples were carried out by XRF
spectroscopy on the Oxford Instruments X-Supreme 8000 analyzer (Great Britain) using the mineral
analysis program.
XRD. The XRD patterns of the zeolite sample was recorded on a DRON-4-07 diffractometer in the
CuKα radiation of the anode line with a Ni filter in the reflected beam in the Bragg-Brentano shooting
geometry in the angular range of 3.5-80 degrees 2θ with a step of 0.05 degrees and exposure at a point of
1 sec.
Catalytic investigations
Catalytic studies were carried out in a flow unit under atmospheric pressure in a quartz reactor
(internal diameter 10 mm) with a fixed catalyst layer (0.5 g, 0.25-0.5 mm) at 300, 325 and 350 °C. Ethanol
(azeotrope 95.6 %, the rest H2O) was fed into the evaporator using a syringe infusion pump
(WHSV = 0.14 g∙gcat
–1∙h–1). Argon was used as a carrier gas at a flow rate of 10 ml/min. Reactants and
reaction products were analyzed on a NeoCHROM gas chromatograph equipped with a flame ionization
detector and a capillary column (HP-FFAP, 50 m×0.32 mm).
Catalytic activity of the catalysts was characterized by ethanol conversion (XEtOH):
⋅ 100, %,
where n0
EtOH is the initial amount of moles of ethanol in the feed, mol/h; nEtOH is unreacted ethanol at the
exit of reactor, mol/h.
Selectivity to products (Si) and butanol yield (YBuOH) have been calculated in accordance with:
⋅ 100, %,
⋅
100
, %,
where ni is amount of moles of identified product.
The productivity of the catalyst has been calculated using the formula:
⋅ ⋅ 0.8
100
, / .
Каталіз та нафтохімія, 2023, №34 53
Catalysis and Petrochemistry, 2023, 34
where YBuOH - yield of butanol, mol %; W - ethanol weight hourly space velocity mmolEtOH/(gcat·h), 0.8 -
is the maximum possible amount of butanol (g) that can be produced from 1 g of ethanol.
Results and Discussion
Catalyst characterization
Based on the X-ray fluorescence analysis data, the SiO2 to Al2O3 ratio in the zeolite framework
and the degree of cesium exchange were calculated to be 2.5 and 82 %, respectively. Therefore, during
the ion exchange procedure, the chemical composition of the aluminosilicate framework of the zeolite
undergoes only minor changes.
The porous characteristics of the original sodium form and the exchanged cesium form were
investigated by the low-temperature nitrogen adsorption/desorption. The calculated characteristics are
summarized in the Table. 1. As can be seen, as a result of the exchange of native sodium for cesium, the
BET surface (SBET) and the surface of micropores (Smiсro) are significantly reduced. Correspondingly, the
volumes of total pores (VΣ) and micropores (Vt
micro) also decrease. These effects can be related, firstly, to
the destruction of the sample and, secondly, to the almost twice larger size of the effective diameter of the
cesium cation (3.38 Å) compared to the sodium cation (1.9 Å). The second one is more realistic.
Table 1. Charaterictics of porous structure of zeolite samples according to low temperature nitrogen
adsorption/desorption
Sample
SBET,
m2/g
Smiсro,
m2/g
Vt
micro,
cm3/g
VΣ,
cm3/g
Vmicro/VΣ
R,
nm
NaX 689 669 0.279 0.323 0.86 0.9
CsX 345 329 0.140 0.180 0.79 1.0
The degree of exchange for cesium cations and the integrity of the crystal structure of the CsX
catalyst were confirmed by NMR.
0 -100 -200
-116 ppm
27Al, ppm133Cs, ppm
a
-160 ppm
200 100 0 -100
65 ppm
c
60 30 0 -30 -60
2,2 ppm
23Na, ppm
b
Fig. 1. 133Cs (a), 23Na (b), and 27Al (c) NMR spectra for CsX sample
The 133Cs spectrum of the CsX sample is a superposition of two signals with chemical shifts of
-116 ppm and -160 ppm (Fig. 1 a), which indicates the presence of cesium in the sample in ion exchange
positions. The first intense signal corresponds to cesium cations in the SIII positions of the supercages of
the faujasite structure, and the second to cations in the SI' positions in the sodalite cages [22]. The 23Na
spectrum (Fig. 1 b) is dominated by the signal (δ = 2.5 ppm) corresponding to residual sodium cations in
54 Каталіз та нафтохімія, 2023, №34
Catalysis and Petrochemistry, 2023, 34
hexagonal prisms (SI sites) [23]. Significant in intensity signals, which would indicate the presence of
sodium cations in sodalite cages and/or in supercages, are not observed in the 23Na NMR spectrum of the
CsX sample. All this confirms the high degree of exchange of the original sodium cations for cesium
cations.
The only signal of tetrahedrally coordinated aluminum present in the 27Al spectrum (Fig. 1 c)
(δ = 65 ppm [24, 25]) proves the integrity of the crystal structure of the sample.
0 5 10 15 20 25 30 35 40 45 50 55 60
0
20
40
60
80
100
I,
%
2, degree
111
220 222
533
642
511
555
840
664
733
711
666620
660/822
882
Fig. 2. XRD pattern of CsX sample. Main characteristic lines in accordance with [26, 27]
The main lines of the XRD pattern (Fig. 2) correspond to the faujasite zeolite phase, however due
to the change in the sample cationic composition and the addition of cesium cations, there is a
redistribution of the strength of several reflexes in comparison to the native sodium form [26]. There were
no cesium-containing compounds in the crystalline form in the sample.
400 500 600 700 800 900 1000 1100 1200
0
20
40
60
80
100
%
T
, cm-1
445
557
667
740
954
1060
as (Si-O-T)s (Si-O-T)as (O-T-O)
1
2
Fig. 3. IR spectrum of CsX (1) sample in comparison with spectra of origin NaX (2) zeolite in the region
of lattice vibrations
The analysis of IR spectra (Fig. 3) showed the preservation of the type X zeolite characteristic
absorption bands [28] and the invariance of the zeolite structure after ion exchange. In particular, in the
spectrum of the CsX sample compared to the spectrum of the original NaX zeolite, there is no high-
frequency shift of the absorption band related to asymmetric valence vibrations of T-O bonds of tetrahedra
(954 cm–1), and therefore, structural dealumination of the CsX sample does not occur. Also, the absorption
Каталіз та нафтохімія, 2023, №34 55
Catalysis and Petrochemistry, 2023, 34
band in the region of 900 cm–1, which is often associated with various types of structural defects, is not
observed in the CsX spectrum.
Catalytic properties
Before the reaction, the catalyst was activated by dehydration in an argon flow up to 500 °С with
exposure for 1 h. After cooling to 300-350 °C, the reaction mixture was fed. Ethanol conversion and
selectivity for the main products were calculated based on their quantities recorded in the time period from
0.5 to 6 h from the start of the experiment.
The dependences of ethanol conversion and product selectivity on time on stream (TOS) for 6 h
are shown in Fig. 4. As is known, in addition to the target reaction of the formation of 1-butanol (BuOH),
a number of other side transformations occur [13-15]. The target product 1-butanol reacts both with itself
(self-condensation) and with the original ethanol (cross-condensation) with the formation of higher
alcohols: 2-ethyl-1-butanol, 1-hexanol (HeOH), 2-ethyl-1-hexanol, and 1-octanol. Dehydration of
1-butanol and the formation of a mixture of butenes (But) also occur. In addition, ethylene (Et), light C2-4
transformation byproducts, acetaldehyde, diethyl ether, acetone, ethyl acetate, heavier C6+ condensation
products (higher aldehydes, ketones, and aromatics) were recorded among the byproducts.
The initial conversion of ethanol (TOS = 0.5 h) at 300, 325, and 350 °C in the presence of the CsX
catalyst has close values of 31-35 %. At 350 °C, XEtOH significantly increases at TOS = 1 h to 58 %, while at
300 and 325 °C, the ethanol conversion values during the experiment do not exceed the initial ones. For all
investigated temperatures, a decrease in XEtOH over time is observed, presumably due to catalyst deactivation.
The highest selectivity for 1-butanol of 31 % is achieved at 300 °C, but it decreases over time.
Also, the yield of the target product is very small due to low ethanol conversion. At 350 °C, the selectivity
for 1-butanol is stable over time at a level of 20 %, and the yield is 10 % (TOS = 2 h). In general, it was
established that in the presence of CsX zeolite, there is a predominant formation of C6+ products of deep
condensation–further transformations of 1-butanol with ethanol and other compounds with the formation
of higher oxygenates (aldehydes/ketones) and possibly aromatics.
The results of catalytic tests on the synthesized sample are summarized in Table 2 in comparison
with magnesium-aluminum and zirconiumoxide catalysts [13-15].
Table 2. Catalytic properties of zeolite CsX and comparison samples (Mg-Al [13], Zr [14, 15])
Sample TOS, h XEtOH, mol % SBuOH, mol % YBuOH, mol %
CsX1 2 50 20 10
CsX1 4 43 23 10
CsX2 2 15 26 4
CsX2 4 13 22 3
Mg-Al-22 2 27 65 18
Mg-Al-Ce-22 2 20 70 14
Mg-Al-Ce-12 2 12 68 8
ZrO2
1 2 10 20 2
ZrO2-Ce-101 2 13 32 4.2
1 – 350 °C; 2 – 300 °C
As can be seen, cesium-containing zeolite X occupies an intermediate position between
magnesium-aluminumoxide samples and zirconium samples in terms of its efficiency, demonstrating at
350 °C 1-butanol yields at the level of 10 % with selectivity for 1-butanol about 20 % at medium level of
ethanol conversion (43-50 %).
56 Каталіз та нафтохімія, 2023, №34
Catalysis and Petrochemistry, 2023, 34
Fig.4. Catalytic performance of CsX sample in ethanol conversion in a flow mode during 6 h time on
stream
Since the presence of both acidic and basic sites in the catalysts is necessary for the targeted
transformation, it was interesting to compare the samples according to this indicator. Table 3 shows the
acid to basic sites ratio determined by using desorption of ammonia and carbon dioxide for the comparison
samples, as well as the zeolite sample. For the latter, this ratio is given based on the yield of the products
of alkylation of toluene with methanol in the side chain (basic sites) and into the benzene ring (acid sites)
[21], which was stable in the temperature range from 400 to 500 °С.
Каталіз та нафтохімія, 2023, №34 57
Catalysis and Petrochemistry, 2023, 34
Table 3. Acid-to-basic sites ratio (Са/Сb) in the samples
Sample Са/Сb Sample Са/Сb
CsX 3.2 * Mg-Al-2 2.9
ZrO2 1.9 Mg-Al-Ce-2 3.0
ZrO2-Ce-10 1 Mg-Al-Ce-1 2.6
* calculated using data for alkylation of methanol in side chain and in the benzene ring
The highest yields of 1-butanol are characterized by samples in which acid sites three times
predominate over basic ones (Mg-Al-2 and Mg-Al-Ce-2). Significantly smaller ratios for zirconium
samples significantly worsen their activity. On the other hand, the synthesized zeolite sample has a slightly
higher than optimal proportion of acid sites, which is obviously related to its intermediate activity. The
productivities of the catalysts were 0.3-0.4, 0.24, and 0.04-0.06 mmol/gcat/h for Mg-Al-oxides, CsX, and
ZrO2-based catalysts, respectively.
Thus, taking into account the good performance of cesium-modified zeolite X, the latter can be
used as a basis for further research. The additional introduction of cesium by impregnation, as well as the
addition of cerium, which performed well on magnesium-aluminum and zirconium oxide samples, also
look promising.
Conclusions
According to the results of X-ray diffraction and X-ray fluorescence analysis, NMR, and
IR spectral studies, the CsX zeolite synthesized by ion exchange with a high degree of sodium to cesium
exchange retained its crystalline structure. In particular, in the 133Cs NMR spectrum of zeolite, there are
two signals of chemical shifts, -116 and -160 ppm, reflecting cesium cations in supercages and sodalite
cages (sites SIII and SI', respectively). The chemical shift at 2.5 ppm reflects residual sodium cations in
hexagonal prisms. Signal of tetrahedrally coordinated aluminum confirms the high crystallinity of the
sample. The latter is confirmed by diffraction data and IR spectra of vibrations in the region of the zeolite
framework. CsX zeolite demonstrates results comparable to magnesium-aluminumoxide systems in the
conversion of ethanol to 1-butanol in flowing vapor phase conditions, which indicates the perspective of
further research on similar nature zeolite samples.
The obtained results confirm that the number of acid sites in the catalyst should be three times
greater than the number of basic sites for an effective course of ethanol conversion into the target direction
of the formation of 1-butanol and the minimization of side reactions.
Acknowledgments
The authors express their gratitude to the senior researcher, candidate of chemical sciences O.I. Oranska
and leading engineer Yu.I. Gornikov (O.O. Chuiko Institute of Surface Chemistry, NAS of Ukraine) for conducting
an X-ray diffraction analysis of the samples, and the senior researcher, candidate of chemical sciences
V.V. Trachevskyi (Technical center of National Academy of Sciences of Ukraine) for NMR measurements.
References
1. Ndaba B., Chiyanzu I., Marx S. n-Butanol derived from biochemical and chemical routes: A review.
Biotechnol. Reports, 2015, 8, 1–9.
2. Rajesh Kumar B., Saravanan S. Use of higher alcohol biofuels in diesel engines: A review. Renew. Sustain.
Energy Rev., 2016, 60, 84–115.
3. Roberto W., Trindade S., Gonçalves R., Santos D. Review on the characteristics of butanol, its production and
use as fuel in internal combustion engines. Renew. Sustain. Energy Rev., 2016, 69, 642–651.
58 Каталіз та нафтохімія, 2023, №34
Catalysis and Petrochemistry, 2023, 34
4. Niemisto J., Saavalainen P., Pongracz E., Keiski R.L. Biobutanol as a potential sustainable biofuel - assessment
of lignocellulosic and waste-based feedstocks. J. Sustain. Dev. Energy, Water Environ. Syst., 2013, 1, 58–77.
5. Valihura K.V., Soloviev S.O. Catalysts for vapor phase condensation of С1-С4 alcohols with carbon chain
elongation. Catalysis and Petrochemistry, 2020, 29, 32–51.
6. Nanda S., Golemi-Kotra D., McDermott J.C., Dalai A.K., Gökalp I., Kozinski J.A. Fermentative production of
butanol: Perspectives on synthetic biology. New Biotechnol., 2017, 37, 210–221.
7. Uyttebroek M., Van Hecke W., Vanbroekhoven K. Sustainability metrics of 1-butanol. Catal. Today, 2015,
239, 7–10.
8. Zheng J., Tashiro Y., Wang Q., Sonomoto K. Recent advances to improve fermentative butanol production:
Genetic engineering and fermentation technology. J. Biosci. Bioeng., 2015, 119, 1–9.
9. Gabriëls D., Hernández W. Y., Sels B., Van Der Voort P., Verberckmoes A. Review of catalytic systems and
thermodynamics for the Guerbet condensation reaction and challenges for biomass valorization. Catal. Sci.
Technol., 2015, 5, 3876–3902.
10. Patent US 8779216 B2. Wick A. and Mahnke E.U. Method for producing guerbet alcohols. 2014.
11. Patent US 20130068457 A1. Thach S., Shong R., Dwarakanath V., Winslow G. Method of manufacture of
guerbet alcohols for making surfactants used in petroleum industry operations. 2013.
12. Patent WO 2013120757 AI. Thach S., Shong R., Dwarakanath V., Winslow G. Alcools de guerbet en tant que
substituts de la Vaseline. 2013.
13. Larina O.V., Valihura K.V., Kyriienko P.I., Vlasenko N.V., Balakin D.Yu., Khalakhan I., Čendak T.,
Soloviev S.O., Orlyk S.M. Successive vapour phase Guerbet condensation of ethanol and 1-butanol over
Mg-Al oxide catalysts in a flow reactor. Appl. Catal. A, Gen., 2019, 588, 117265.
14. Vlasenko N.V., Kyriienko P.I., Yanushevska O.I., Valihura K.V., Soloviev S.O., Strizhak P.E. The effect of
ceria content on the acid–base and catalytic characteristics of ZrO2-CeO2 oxide compositions in the process of
ethanol to n-butanol condensation. Catal. Letter, 2020, 150, 234–-242.
15. Vlasenko N.V., Kyriienko P.I., Valihura K.V., Yanushevska O.I., Soloviev S.O., Strizhak P.E. Effect of
modifying additives on the catalytic properties of zirconia in the process of ethanol conversion to 1-butanol.
Theor. Exp. Chem., 2019, 55, 43–49.
16. Riittonen T., Eränen K., Mäki-Arvela P., Mikkola J.-P. Continuous liquid-phase valorization of bio-ethanol
towards bio-butanol over metal modified alumina. Renew. Energ., 2015, 74, 369–378.
17. Yang C., Meng Z.Y. Bimolecular condensation of ethanol to 1-Butanol catalyzed by alkali cation zeolites.
J. Catal., 1993, 142, 37–44.
18. Gotoh K., Nakamura S., Mori T., Morikawa Y. Supported alkali salt catalysts active for the guerbet reaction
between methanol and ethanol. Stud. Surf. Sci. Catal., 2007, 130, 2669–2674.
19. Pertko O.P., Voloshyna Yu.G., Kontsevoi A.L., Trachevsky V.V. Ethylbenzene formation and its conversion
towards coke in the side‑chain methylation of toluene on a basic X zeolite. J. Porous Mat., 2021, 28, 1713–1723.
20. Song L., Lia Zh., Zhang R., Zha o L., Li W. Alkylation of toluene with methanol: The effect of K exchange
degree on the direction to ring or side-chain alkylation. Catal. Commun., 2012, 19, 90–95.
21. Voloshyna Yu.G., Pertko O.P., Patrylak L.K. Effect of the method of modification of zeolite X on selectivity
of catalytic methylation of toluene. Theor. Exp. Chem., 2019, 54(6), 395–400.
22. Norby P., Poshni F.I., Gualtieri A.F., Hanson J.C., Grey C.P. Cation migration in zeolites: an in situ powder
diffraction and MAS NMR study of the structure of zeolite Cs(Na)-Y during dehydration. J. Phys. Chem. B,
1998, 102(5), 839–856.
23. Sanchez-Sanchez M., Vidal-Moya J.A., Blasco T. Nuclear magnetic resonance investigation on the adsorption
of pyrrole over alkali-exchanged zeolites X. Stud. Surf. Sci. Catal., 2004, 154, 1769–1776.
24. Jiang J., Lu G., Miao Ch., Wu X., Wu W., Sun Q. Catalytic performance of X molecular sieve modified by
alkali metal ions for the side-chain alkylation of toluene with methanol. Microporous Mesoporous Mater.,
2013, 167, 213–220.
Каталіз та нафтохімія, 2023, №34 59
Catalysis and Petrochemistry, 2023, 34
25. Hunger M., Schenk U., Weitkamp J. Mechanistic studies of the side-chain alkylation of toluene with methanol
on basic zeolites Y by multi-nuclear NMR spectroscopy. J. Mol. Catal. A: Chem., 1998, 134, 97–109.
26. http://www.iza-structure.org/databases/
27. Klika Z., Weiss Z., Mellini M., Drabek M. Water leaching of cesium from selected cesiummineral analogues.
Appl. Geochem., 2006, 21, 405–418.
28. Król M., Kolezynski A., Mozgawa W. Vibrational spectra of zeolite Y as a function of ion exchange.
Molecules, 2021, 26(2), 342.
Надійшла до редакції 09.05.2023
Парофазна конденсація етанолу до 1-бутанолу за Гербе на цеоліті CsX
Любов K. Патриляк 1, 2, Олександра П. Пертко 1, Каріна В. Валігура 3, 4, Юлія Г. Волошина 1
1 Інститут біоорганічної хімії та нафтохімії ім. В.П. Кухаря Національної академії наук України
Харківське шосе, 50, Київ, 02160, Україна, lkpg@ukr.net
2 Національний технічний університет України «Київський політехнічний інститут імені Ігоря Сікорського»
Берестейський просп., 37/4, Київ, 03056, Україна
3 Інститут фізичної хімії імені Л.В. Писаржевського Національної академії наук України
просп. Науки, 31, Київ, 03028, Україна
4 Відділ хімічної та екологічної інженерії, Вища технічна школа інженерії
Університет Севільї, 41092, Севілья, Іспанія
Перетворення етанолу у цінні хімічні продукти набуває все ширшого застосування. Одним із таких
перспективних процесів є конденсація спиртів за Гербе, що дозволяє отримувати 1-бутанол із
альтернативної нафтовій відновлювальної сировини. Багатообіцяючими каталізаторами такого
перетворення є оксидні системи, що поєднують у своєму складі кислотні та основні центри. У даній роботі
оцінено активність у конденсації етанолу до 1-бутанолу цезієвої форми цеоліту типу Х, одержаної
гідротермальним іонним обміном, а також проведено порівняння її ефективності з магній-алюміній-
оксидними та цирконій-оксидними каталізаторами. Цілісність цеолітної структури підтверджено методами
рентгенофазового та рентгенофлуорисцентного аналізу, а також ІЧ-спектроскопії. Ступінь обміну натрію
на цезій склав 82 %. Знайдено також, що катіони цезію локалізовані лише у іонообмінних позиціях
фожазиту – в місцях SIII (великі порожнини) та SI` (содалітові комірки). Встановлено, що цеоліт CsX має
близькі до оптимального для даного перетворення співвідношення між кількістю кислотних та основних
центрів. Цезійвмісний цеоліт за 350 °С демонструє 35-55 % конверсію етанолу та 20-25 % селективність за
1-бутанолом, що є вищим за показники для цирконієвих зразків, але дещо поступається магній-алюмінієвим
каталізаторам. Одержані результати свідчать про перспективність використання цеолітів близької природи
у процесі конденсації етанолу до 1-бутанолу.
Ключові слова: конденсація етанолу, 1-бутанол, кислотні центри, оснόвні центри, вихід 1-бутанолу,
селективність процесу
|
| id | oai:katalizorgua:article-92 |
| institution | Catalysis and petrochemistry |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-03-12T15:50:18Z |
| publishDate | 2023 |
| publisher | V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | katalizorgua/ed/eaf635d97951ca23ad97391c617c88ed.pdf |
| spelling | oai:katalizorgua:article-922024-12-24T10:38:54Z Vapour phase Guerbet condensation of ethanol to 1-butanol on CsX zeolite Vapour phase Guerbet condensation of ethanol to 1-butanol on CsX zeolite Patrylak, Lyubov K. Pertko, Olexandra P. Valihura, Karina V. Voloshyna, Yulia G. ethanol condensation, 1-butanol, acid sites, basic sites, 1-butanol yield, process selectivity ethanol condensation, 1-butanol, acid sites, basic sites, 1-butanol yield, process selectivity Nowadays, the conversion of ethanol into valuable chemical products is getting wider application.One of such promising processes is Guerbet condensation of alcohols, which permits the obtaining of 1-butanol from renewable raw materials that are alternatives to petroleum ones.Oxide systems combining acid and basic sites in their composition are promising catalysts for such a transformation.In this study, the efficiency of the magnesium-aluminum oxide and zirconium-oxide catalysts was compared to the activity of the cesium form of X-type zeolite produced by hydrothermal ion exchange in the condensation of ethanol to 1-butanol. The integrity of the zeolite structure was confirmed by using the XRD and XRF analysis, as well as by the IR spectroscopy.The depth of exchange of native sodium for cesium was 82%. It was also found that cesium cations are localized only in ion-exchange positions of faujasite, in places SIII (supercages) and SI` (sodalite cages). CsX zeolite acid to basic sites ratio was found tobe close to optimal for this reaction. Cesium-containing zeolite at 300 °C showsethanol 35-55 % conversion and 20-25 % selectivity for 1-butanol, which is higher than the same characteristics for zirconium samples, but slightly inferior to magnesium-aluminum oxide catalysts. The obtained results indicate the promising use of zeolites of a similar nature in the process of condensation of ethanol to 1-butanol. Перетворення етанолу у цінні хімічні продукти набуває все ширшого застосування. Одним із таких перспективних процесів є конденсація спиртів за Гербе, що дозволяє отримувати 1-бутанол із альтернативної нафтовій відновлювальної сировини. Багатообіцяючими каталізаторами такого перетворення є оксидні системи, що поєднують у своєму складі кислотні та основні центри. У даній роботі оцінено активність у конденсації етанолу до 1-бутанолу цезієвої форми  цеоліту типу Х, одержаної гідротермальним іонним обміном, а також проведено порівняння її ефективності з магній-алюміній-оксидними та цирконій-оксидними каталізаторами. Цілісність цеолітної структури підтверджено методами рентгенофазового та рентгенофлуорисцентного аналізу, а також  ІЧ-спектроскопії. Ступінь обміну натрію на цезій склав 82 %. Знайдено також, що катіони цезію локалізовані лише у іонообмінних позиціях фожазиту – в місцях SIII (великі порожнини) та SI` (содалітові комірки). Встановлено, що цеоліт CsX має близькі до оптимального для даного перетворення співвідношення між кількістю кислотних та основних центрів. Цезійвмісний цеоліт за 350 °С демонструє 35-55 % конверсію етанолу та 20-25 % селективність за 1-бутанолом, що є вищим за показники для цирконієвих зразків, але дещо поступається магній-алюмінієвим каталізаторам. Одержані результати свідчать про перспективність використання цеолітів близької природи у процесі конденсації етанолу до 1-бутанолу. V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2023-09-07 Article Article application/pdf https://kataliz.org.ua/index.php/journal/article/view/92 10.15407/kataliz2023.34.050 Catalysis and petrochemistry; No. 34 (2023): Catalysis and petrochemistry; 50-59 Каталіз та нафтохімія; № 34 (2023): Каталіз та нафтохімія; 50-59 2707-5796 2412-4176 10.15407/kataliz2023.34 en https://kataliz.org.ua/index.php/journal/article/view/92/88 Copyright (c) 2023 Catalysis and petrochemistry |
| spellingShingle | ethanol condensation 1-butanol acid sites basic sites 1-butanol yield process selectivity Patrylak, Lyubov K. Pertko, Olexandra P. Valihura, Karina V. Voloshyna, Yulia G. Vapour phase Guerbet condensation of ethanol to 1-butanol on CsX zeolite |
| title | Vapour phase Guerbet condensation of ethanol to 1-butanol on CsX zeolite |
| title_alt | Vapour phase Guerbet condensation of ethanol to 1-butanol on CsX zeolite |
| title_full | Vapour phase Guerbet condensation of ethanol to 1-butanol on CsX zeolite |
| title_fullStr | Vapour phase Guerbet condensation of ethanol to 1-butanol on CsX zeolite |
| title_full_unstemmed | Vapour phase Guerbet condensation of ethanol to 1-butanol on CsX zeolite |
| title_short | Vapour phase Guerbet condensation of ethanol to 1-butanol on CsX zeolite |
| title_sort | vapour phase guerbet condensation of ethanol to 1-butanol on csx zeolite |
| topic | ethanol condensation 1-butanol acid sites basic sites 1-butanol yield process selectivity |
| topic_facet | ethanol condensation 1-butanol acid sites basic sites 1-butanol yield process selectivity ethanol condensation 1-butanol acid sites basic sites 1-butanol yield process selectivity |
| url | https://kataliz.org.ua/index.php/journal/article/view/92 |
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