ISSN 0965ꢀ5441, Petroleum Chemistry, 2016, Vol. 56, No. 3, pp. 230–236. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © M.A. Nikitina, V.L. Sushkevich, I.I. Ivanova, 2016, published in Neftekhimiya, 2016, Vol. 56, No. 3, pp. 248–254.
Dehydration of 2,3ꢀButanediol over Zeolite Catalysts
M. A. Nikitina, V. L. Sushkevich, and I. I. Ivanova
Faculty of Chemistry, Moscow State University, Moscow, Russia
eꢀmail: IIIvanova@phys.chem.msu.ru
Received November 16, 2015
Abstract—2,3ꢀButanediol as a product of biomass processing is a cheap alternative raw material for synthesis
of methyl ethyl ketone (MEK) and butadieneꢀ1,3. The catalytic activity of Alꢀ and Zrꢀcontaining BEA zeoꢀ
lites and an aluminaꢀbased catalyst in 2,3ꢀbutanediol dehydration has been investigated. It has been shown
that the presence of Brönsted (HꢀBEA) or Lewis (Al O ) sites leads to the selective formation of MEK and
2
3
the combination of two types of sites (ZrꢀBEA) facilitates the formation of heavy products of condensation.
Keywords: 2,3ꢀbutanediol, butadiene, methyl ethyl ketone, zeolites, ZrꢀBEA, Lewis sites, Brönsted sites
DOI: 10.1134/S0965544116030099
2,3ꢀButanediol is a biomass processing product strength of active sites, it is possible to affect the proꢀ
that is produced from sugars by fermentation [1–5]. cess selectivity at relatively low temperatures (250–
Butanediol can be used as a solvent, and its esters find 300°C).
applications in pharmaceutical and cosmetic indusꢀ
The aim of this study was to examine the influence
of type and strength of acid sites on the selectivity of
tries [6]. However, 2,3ꢀbutanediol products methyl
ethyl ketone and butadieneꢀ1,3 are of most interest.
Methyl ethyl ketone (MEK) is widely used as an
organic solvent and a reactant for synthesis of its perꢀ
oxide [7–9]. Butadiene is required in synthesis of varꢀ
ious synthetic rubbers [10–13]. There is a lack of butaꢀ
diene on the world market today; thus, alternative proꢀ
cesses for its production are of great importance.
2
,3ꢀbutanediol dehydration process. As a catalyst with
Brönsted acid sites, zeolite BEA with ratio of Si/Al =
5 was chosen. To obtain a BEA (75)ꢀbased system
7
with Lewis acidity, a ZrꢀBEA catalyst was synthesized.
BEA type zeolites are widely used as catalysts of variꢀ
ous processes [20–22], and the possibility to modify
them with metals, such as tin and zirconium, expand
their application area.
Industrial processes for MEK production differ
from those of butadiene, but the feedstock for the
manufacture of both compounds is С4 fraction of the
oil refining products. Ketone is most often produced
EXPERIMENTAL
A commercial zeolite available from Zeolyst (trade
name CP 811Eꢀ150) with Si/Al = 75 ratio in Hꢀform
from nꢀbutylene through formation of 2ꢀbutanol [7].
Butadiene is mainly obtained from the pyrolysis С4
fraction using selective solvents. Besides, a process for
butadiene production via butane and butylene dehyꢀ
drogenation (Houdryꢀprocess) is also widely used
(
HꢀBEA) was used as original BEA(75) zeolite.
Zirconium was introduced into catalyst by postsynꢀ
thetic modification. Zeolite BEA(75) was dealumiꢀ
nated by triple treatment with concentrated HNO3
[
10]. The former butadiene production process
followed by treatment with a ZrOCl2 8H O solution
⋅
requires high pyrolysis capacity, and the latter requires
2
high energy expenditure because of high reaction temꢀ in DMSO. The isomorphous substitution of Zr for Al
peratures. Thus, butanediol as a biomass processing in tetrahedral positions of the zeolite framework was
product is a cheap alternative feedstock for MEK and proved by XPS, NMR, and UV spectroscopy techꢀ
butadieneꢀ1,3 synthesis.
niques.
Catalyst with low concentration of sites was dealuꢀ
minated BEA zeolite (deAl BEA), which contained
both Brönsted and Lewis sites. A reference catalyst
Various acid systems (metal oxides, heteropoly
acids, zeolites, etc.) can serve as a dehydration cataꢀ
lysts [14–19]. Under certain reaction conditions, high
yields of a particular product can be achieved. To reach
a high yield of diene, reaction is most frequently carꢀ
was
All samples were calcined in a dried air flow at
50 for 6 h.
Elemental composition was determined by Xꢀray
γ
ꢀAl O3 (UOP) as a material with Lewis acidity.
2
5
°C
ried out at elevated temperatures (350–450°C). Under
milder conditions, the main product of 2,3ꢀbutanediol
dehydration is MEK [15, 17]; however, by varying of fluorescence (XRF) analysis. The measurements were
catalyst composition, its surface characteristics, and made on a Spektroskan MaksGF2E scanning waveꢀ
230