ISSN 1070-4272, Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 6, pp. 773−779. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © N.G. Grigor’eva, A.M. Suleimanova, M.R. Agliullin, B.I. Kutepov, 2014, published in Zhurnal Prikladnoi Khimii, 2014, Vol. 87, No. 6,
INORGANIC SYNTHESIS AND INDUSTRIAL
Synthesis of Carboxylic Acid Esters in the Presence
of Micro- and Mesoporous Aluminosilicates
N. G. Grigor’eva, A. M. Suleimanova, M. R. Agliullin, and B. I. Kutepov
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, pr. Oktyabrya 141, Ufa, 450075 Russia
Received February 18, 2014
Abstract—The catalytic properties of zeolites НY, НBeta, and НZSM-12 and of mesoporous amorphous
aluminosilicate in liquid-phase esteriﬁ cation of aliphatic (monobasic С
, dibasic С
) and aromatic
(benzoic, trimellitic, phthalic) carboxylic acids with butanol were studied. Zeolite HBeta appeared to be the most
active catalyst. Procedures were developed for preparing esters in the presence of zeolitic catalyst НBeta, ensuring
100% selectivity of ester formation at 90–98% conversion of the acid.
Carboxylic acid esters are one of the most demanded
classes of organic compounds. The ﬁ elds of their applica-
tion are very diverse: solvents, fruit essences, aromatiz-
ers, preservatives, components of lubricating oils and
hydraulic ﬂ uids, biodiesel, etc. [1–4]. In the total volume
of production of polymer plasticizers, the share of esters
is about 85%, and the total volume of their production
exceeded 5 million tons annually .
The majority of industrial procedures for ester syn-
thesis consist in direct esteriﬁ cation of carboxylic acids
with alcohols at elevated temperature (100–200°С) in the
presence of various catalysts. Traditional acid catalysts
for esteriﬁ cation are sulfuric, hydrochloric, phosphoric,
benzenesulfonic, and p-toluenesulfonic acids. To remove
them from the crude ester after the synthesis, it is neces-
sary to perform neutralization with a base agent and a
series of washings with water, which gives rise to a large
amount of liquid wastes and to the product loss. The
drawbacks of using mineral acids are possible tarring of
organic compounds and formation of by-products as a
result of alcohol dehydration. Furthermore, with sulfuric
acid as catalyst, unsaturated compounds arising from side
reactions undergo sulfonation, and sulfonic acid esters
Progress in the development of modern esteriﬁ cation
technologies is associated with the replacement of mineral
and organic acids by heterogeneous catalysts.
The use of synthetic microporous aluminosilicates
(zeolites) and mesoporous metallosilicates as catalysts
of ester synthesis has been reported recently [6–12].
The majority of studies dealing with esteriﬁ cation in the
presence of zeolitic catalysts concern synthesis of acetic
or phthalic acid esters. Preparation of esters of other
mono- and dicarboxylic acids in the presence of zeolites
has been studied insufﬁ ciently.
This study was aimed at developing efﬁ cient proce-
dures for preparing butyl esters of various aliphatic and
aromatic carboxylic acids, based on using microporous
crystalline aluminosilicates (zeolites НY, НBeta, НZSM-
12) and mesoporous amorphous aluminosilicates.
Zeolites of structural types FAU (Y), BEA (Beta), and
MTW (ZSM-12) in the H form, and also mesoporous
aluminosilicate (MAS) were studied as catalysts.
The starting zeolite NaY (molar ratio SiO
М = 4.9) was prepared by the procedure described in
. The NaY decationization (replacement of Na
ions by Н
) was performed from an NН
in three steps with intermediate calcination at 540°С
for 4 h. The Na
exchange in zeolite НY was 95%.
–Beta (M = 18) and NH
(M = 34), synthesized at the Angarsk Plant of Catalysts