ISSN 0965ꢀ5441, Petroleum Chemistry, 2016, Vol. 56, No. 2, pp. 125–130. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © V.O. Samoilov, D.N. Ramazanov, A.I. Nekhaev, A.L. Maksimov, 2016, published in Neftekhimiya, 2016, Vol. 56, No. 2, pp. 144–149.
Heterogeneous Catalytic Conversion of Glycerol
with nꢀButyl Alcohol
V. O. Samoilov*, D. N. Ramazanov, A. I. Nekhaev, and A. L. Maksimov
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
*eꢀmail: samoilov@ips.ac. ru
Received February 12, 2015
Abstract—The etherification of glycerol with
exchange resins and zeolite catalysts in an autoclave reactor has been studied. It has been shown that styrene–
divinylbenzene ionꢀexchange resins are effective catalysts for the production of glycerol ꢀbutyl ethers: the
glycerol conversion is about 98% with an ꢀbutyl ether selectivity of about 88 mol % (140°C, 5 h, 5 wt %
Amberlyst 36 catalyst, and 10 wt % glycerol in ꢀbutanol). Zeolites Y and
in the H+ form exhibit comparable
specific activity (glycerol conversion of no more than 25% under similar conditions) in combination with
high selectivity for glycerol diꢀ ꢀbutyl ethers (up to 28%).
nꢀbutyl alcohol at 140°C in the presence of sulfonated cationꢀ
n
n
n
β
n
Keywords: glycerol, ethers, sulfonated cationꢀexchange resins, green chemistry
DOI: 10.1134/S0965544116010060
Bioglycerol conversion to high value added prodꢀ tages are amphiphilicity, the possibility of producing
ucts is an important issue in the production of biofuels both protic and aprotic alkyl glycerol solvents, the posꢀ
and “green” counterparts of petrochemicals (petroꢀ
chemicals substituents). One of the possible ways for
glycerol derivatization is the production of ethers. An
sibility of “tuning” the physicochemical properties of
the solvent via replacing the substituents, and finally
biodegradability, which is of crucial importance for
detergents. Some glycerol ethers are extensively used
as components of cosmetics [8]. A common feature of
the above areas of application is a high value added of
the product (incommensurable with that of motor fuel
components) whether it be a surfactant or an octane
booster.
intriguing prospect is open by the use of
hol, which can be derived from carbohydrateꢀcontainꢀ
ing vegetable raw materials. Ethers of glycerol and
nꢀbutyl alcoꢀ
nꢀ
butyl alcohol can be prepared using components only
of vegetable origin; owing to this feature, these ethers
are environmentally safe compounds that do not form
harmful substances during decomposition and are
entirely carbonꢀneutral during combustion.
It has been previously reported on advances in the
preparation of glycerol ethers with ethanol [9], tert
ꢀ
Glycerol ethers exhibit a number of interesting
physicochemical properties. First, glycerol ethers are
of interest as solvents (monoꢀ and diethers as protic
solvents and triethers as aprotic solvents) for paint
materials and fine organic synthesis processes because
the ethers are characterized by high solubility and bioꢀ
degradability and fairly high viscosity, dielectric perꢀ
meability, and surface tension [1]. In addition, glycꢀ
erol ethers can be promising fuel components: a signifꢀ
icant number of studies are focused on the effect of
additives of glycerol ethers (particularly cyclic) on the
quality of motor fuels [2–5]. Depending on the strucꢀ
ture of the substituent, glycerol ethers can be octaneꢀ
boosting gasoline components [2] or diesel fuel comꢀ
ponents. Glycerol dimethyl ethers have a cetane numꢀ
ber of about 58 [6]; it is only logical to assume that
butanol [10], benzyl alcohol [11], 1ꢀpentanol, 1ꢀhexꢀ
anol, 1ꢀoctanol, and 1ꢀdodecanol [12, 13]. Gaudin
et al. [13] have briefly reported a number of experiꢀ
ments with nꢀbutanol in the presence of sulfonated
cationꢀexchange resins exhibiting high activity and
selectivity for glycerol etherification. Nandiwale et al.
[14] described the reaction catalyzed by zeolites ,
β
ZSMꢀ5, and Kꢀ10. Sulfonated cationꢀexchange resꢀ
ins, which are sulfonated styrene–divinylbenzene
polymer matrices, exhibit acid strength, acidity, and
surface properties that are appropriate for the producꢀ
tion of ethers from alcohols. On the other hand, glycꢀ
erol ethers—both acyclic (e.g., tertꢀbutyl) or cyclic
(solketal)—can be produced with high selectivities by
catalysis over zeolites Y and [10, 15]. Therefore, zeoꢀ
β
lite catalysts, along with ionꢀexchange resins, have
been selected as the objects of this study.
glycerol nꢀbutyl ethers will have a considerably higher
cetane number. In addition, glycerol ethers exhibit a
certain surface activity [1] and may be of interest as
The main aims of this study are the screening of
promising hydrotropes [7]. In this case, the key advanꢀ various heterogeneous catalysts in the reaction
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