Alkylation of isopropanol with ethanol in the presence of an Au-Ni/Al2O3 catalyst

Full text of DOI:10.1134/S0012500815050055

ISSN 0012ꢀ5008, Doklady Chemistry, 2015, Vol. 462, Part 1, pp. 130–132. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © A.V. Chistyakov, P.A. Zharova, M.V. Tsodikov, S.A. Nikolaev, A.E. Gekhman, I.I. Moiseev, 2015, published in Doklady Akademii Nauk, 2015, Vol. 462,
No. 3, pp. 310–312.
CHEMISTRY
Alkylation of Isopropanol with Ethanol
in the Presence of an Au–Ni/Al O Catalyst
2
3
a, b
a, b
a
c
A. V. Chistyakov , P. A. Zharova , M. V. Tsodikov , S. A. Nikolaev ,
d
a, b, d
Corresponding Member of the RAS A. E. Gekhman , and Academician I. I. Moiseev
Received January 29, 2015
DOI: 10.1134/S0012500815050055
One of the largestꢀscale products of biomass proꢀ
Bimetallic systems based on clusters of gold with
cessing is ethanol [1], which is mainly used as an ethꢀ nickel oxide have unusually high synergistic activity in
ylene source and an additive to gasoline fuel. Noteꢀ conversion of ethanol, a number of hydrocarbons, and
worthy, ethanol as a fuel additive has a number of seriꢀ their derivatives [7–10], which makes them attractive
ous drawbacks; therefore, the ethanol content of for producing
ethanol–gasoline mixtures does not exceed 10–15%
α
ꢀalcohols from ethanol.
Au, Ni, and Au–Ni catalysts were obtained using
[
2]. Catalytic processing of ethanol to produce more
HAuCl4 (Aldrich, specialꢀpurity grade), Ni(NO3)2
valuable products, linear
αꢀalcohols, including 1ꢀ
(
Aldrich, specialꢀpurity grade), and Al O3 (Aldrich,
2
butanol, can solve the challenge of efficient use of ethꢀ
anol as an additive to gasoline fuel. 1ꢀButanol requires
no changes in the design of the existing internal comꢀ
bustion engines. Moreover, the calorific value of 1ꢀ
butanol is 25% higher and it is less hygroscopic and
2
AOKꢀ63ꢀ11 (A1) grade, 160 m /g). An Au/Al O catꢀ
2
3
alyst was prepared by ion exchange from an aqueous
HAuCl4 solution according to a published procedure
[
11]. A NiO /Al O catalyst was obtained by incipient
x 2 3
less volatile, which makes it a promising energy wetness impregnation of a support with an aqueous
source, alternative to current gasoline fuels [3].
nickel nitrate solution as before [11]. The bimetallic
catalyst NiO /Au/Al O was produced by incipient
x
2
3
We found that ethanol is converted not only to
butanol, but also to 1ꢀhexanol and 1ꢀoctanol, which
are both valuable petrochemical products, and a feed
for synthesizing a wide range of compounds such as
wetness impregnation of freshly prepared Au/Al O
2
3
with an aqueous nickel nitrate solution. Before use, all
the catalysts were calcined in air for 3 h at 623 K.
linear
αꢀolefins, the corresponding acids, and others.
The catalytic tests were performed on an autoclaveꢀ
The known methods for obtaining butanol and higherꢀ type Parr 5000 Series multiple reactor system while
molecularꢀweight alcohols from ethanol use homogeꢀ continuously stirring for 5 h. The volume of the cataꢀ
neous catalysts and, in essence, are a development of lyst (spherical granules 1–2 mm in diameter) was
the Guerber reaction [4–6].
5 mL, and the substrate volume was 25 mL. The reacꢀ
tion products were analyzed on a real time basis by gas
chromatography and chromatography–mass specꢀ
trometry.
Isopropanol is also a product of biomass fermentaꢀ
tion and can be used for coprocessing with ethanol to
produce pentanolꢀ2, a structural predecessor of pipꢀ
erylene.
In the presence of the bimetallic system containꢀ
ing Au (0.1 wt %) and Ni (0.03 wt %) deposited on
the
γ
ꢀAl O3 surface (catalyst) at 275 С and a partial
°
2
substrate pressure of 100 atm, ethanol is converted to a
mixture of 1ꢀbutanol, 1ꢀhexanol, and 1ꢀoctanol at the
total selectivity reaching 85.2% and the ethanol conꢀ
version 63.5%. Note also the stability of the bimetallic
system, the activity and selectivity of which persist for
at least 50 h of work. A monometallic catalyst containꢀ
a
Topchiev Institute of Petrochemical Synthesis,
Russian Academy of Sciences, Leninskii pr. 29,
Moscow, 119991 Russia
b
Gubkin Russian State University of Oil and Gas,
Leninskii pr. 65, Moscow, 119991 Russia
c
Moscow State University, Moscow, 119992 Russia
Kurnakov Institute of General and Inorganic Chemistry,
ing Ni (0.03 wt %) on the
γ
ꢀAl O3 surface is inactive in
d
2
the studied process, and in the presence of a system
Russian Academy of Sciences, Leninskii pr. 31, Moscow,
1
19991 Russia
containing 0.1 wt % Au/Al O3 the selectivity in
2
eꢀmail: Chistyakov@ips.ac.ru
butanol is 16 mol % at an alcohol conversion of 34%.
130

ALKYLATION OF ISOPROPANOL WITH ETHANOL
131
70
50
30
10
1
2
Conversion, %
Selectivity
in butanol,
mol %
Selectivity
in hexanol,
mol %
Selectivity
octanol,
mol %
Ethanol conversion and selectivity of the formation of the main products versus reactant partial pressure when ethanol is in the
) supercritical and ( ) subcritical states.
(1
2
The obtained result significantly exceeds in converꢀ 50 vol % isopropanol was characterized by conversions
sion and selectivity the analogues described in of the initial substrate of 28.9 and 38.85%, respectively.
the literature. For example, a method for producing The differences in conversion of the initial substrates
1
ꢀbutanol in the presence of 0.8 wt % Au/Al O3 and can be explained by competitive sorption of reactants.
2
2
0 wt % Ni/Al O was proposed [12], which demonꢀ The data in the table show that the reaction products
2
3
are dominated by the target product, pentanolꢀ2 (a
structural precursor of piperylene), and also 2ꢀpenꢀ
tanone. These compounds are the products of the
direct interaction of ethanol and isopropanol, and this
confirms that there is a crossꢀcoupling reaction, which
links the carbon backbones of the initial alcohols.
Probably, the excess surface isopropanol concentraꢀ
tion and, as a consequence, the coreactant deficiency
lead to the formation of a considerable amount of aceꢀ
tone.
strated selectivities in 1ꢀbutanol of 35 and 62% at conꢀ
versions of the initial alcohol of 6 and 5%, respectively.
Importantly, under the optimal ethanol conversion
conditions, ethanol is in the supercritical state (critical
point of ethanol is at 241
can be the cause of so high process efficiency. Below
40 , the ethanol conversion abruptly decreases and
the selectivity drops to virtually zero. Reducing ethaꢀ
nol saturated vapor pressure to 60 atm at 275 (i.e.,
°С and 63 atm [13]), which
2
°С
°С
below the critical pressure value) leads to a decrease
in the ethanol conversion to 33.5% at selectivities in
Thus, in the presence of a bimetallic catalyst conꢀ
taining active components at much lower concentraꢀ
tions in comparison with the known analogues, there
is synergism of the catalytic activities of the deposited
goldꢀ and nickelꢀcontaining components, which conꢀ
sists in the nonadditive increase in the ethanol converꢀ
1ꢀbutanol and 1ꢀhexanol of 26 and 3.8 mol %; 1ꢀoctanol
was not detected in the reaction products (figure). It
can be assumed that supercritical conditions are the
most favorable for the interaction of substrates with
active sites on the catalyst surface.
sion and the selectivity of the formation of linear
ꢀ
α
To expand the feedstock base, alkylation of isoproꢀ
panol, a byꢀproduct of fermentation synthesis of alcohols. For the first time, in the presence of a bimeꢀ
butanol and ethanol [3], was performed. Reactions of tallic Au–Ni/Al O heterogeneous catalyst, alkylation
2 3
alkylation of secondary alcohols with primary alcohols of isopropanol with ethanol was performed. In the
were described [14] for the case of homogeneous metal products of coꢀconversion of isopropanol and ethanol,
complex catalysis in alkaline media, similar to the the concentration of pentanolꢀ2, a structural predeꢀ
Guerber reaction [4].
cessor of piperylene, is 38.33 wt %.
In this work, in the presence of heterogeneous sysꢀ
The obtained results demonstrated the possibility
tems, the reaction of a mixture of 50 vol % ethanol and of the direct highꢀefficient production of fuel compoꢀ
DOKLADY CHEMISTRY Vol. 462
Part 1
2015

132
CHISTYAKOV et al.
Composition of the products of coꢀconversion of a mixture of and the Council for Grants of the President of the
5
0 vol % ethanol and 50 vol % isopropanol
Russian Federation for Support of Leading Scientific
Schools (grant no. MKꢀ5328.2014.3).
Concentration
Compound
mol %
wt %
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Translated by V. Glyanchenko
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2015

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