Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 1, pp. 104−107.
Pleiades Publishing, Ltd., 2014.
Original Russian Text E.V. Pyatnitsyna, I.M. El’chaninov, M.M. El’chaninov, 2014, published in Zhurnal Prikladnoi Khimii, 2014, Vol. 87, No. 1, pp. 110−113.
Chemical Method for Removal of Impurities Impairing
the Quality of Commercial 1,4-Butanediol Produced
by the Reppe Method
E. V. Pyatnitsyna, I. M. El
chaninov, and M. M. El
Platov South-Russian State Polytechnic University (NPI), ul. Prosveshcheniya 32, Novocherkassk,
Received December 12, 2013
Abstract—Quantitative dependence of the amount of impurities in commercial 1,4-butanediol that affect the car-
bonyl number, γ-hydroxybutyraldehyde and its acetate with 1,4-butanediol, on the service life of the catalyst was
determined. Hydrazine hydrate, 2,4-dinitrophenylhydrazine, and hydroxylamine hydrochloride were studied as
reagents binding these impurities and raising the content of the main substance in the target product. A procedure
is suggested for obtaining puriﬁ ed 1,4-butanediol. The optimal reagent is a mixture of a 30% aqueous solution of
hydrazine hydrate with hydrochloric acid.
1,4-Butanediol (B1D) is one of the main compo-
nents in manufacture of polybutylenetherephthalate
and polyurethanes . However, its wide use for this
purpose is hindered by the presence of impurities, such
as γ-hydroxybutyraldehyde (HBA) and its labile de-
rivative, cyclic acetal. Because of the reaction in which
polyurethanes are synthesized is highly sensitive to these
substances, the problem of puriﬁ cation of commercial
1,4-butanediol is of interest for both foreign and domes-
tic researchers. For example, the American company Du
Pont has patented a method for puriﬁ cation of B1D by its
crystallization from a mixture that contains, in addition to
the main substance, tetrahydrofuran (THF), water, and im-
purities . This method yields good results in laboratory
practice, but its being complicated and labor consuming
will hardly enable its industrial implementation.
Our study is devoted to analysis of chemical methods
for B1D puriﬁ cation and development of a rather simple
technique for this purpose.
To obtain statistical data on the quantitative depen-
dence of HBA and its acetal with B1D on the service
life of the catalyst, we subjected selected samples of
commercial B1D to a chromatographic analysis during
the whole service run cycle of the catalyst.
The study was carried out with a Tsvet-100M-152
instrument with a ﬂ ame-ionization detector, metallic
column (2 m long and 3 mm in diameter) packed with
N-super chromaton or N-AW-DMCS of the 0.16–0.20-
mm fraction with 15% poly(ethylene glycol) (PEG)
having a molecular mass of 15 000–20 000.
The chromatographic analysis data for samples of
commercial B1D are presented in Table 1. An analysis of
the statistical data demonstrated that the content of HBA
varies within the range 0.05–0.26%. The content of the
acetal also increases by the end of the run to nearly 0.24%;
however, no clearly pronounced dependence of these
impurities on the catalyst run could be obtained. Nev-
ertheless, just these results would be expected for com-
mercial B1D because any amount of the aldehyde above
the optimal value is either evaporated or is immediately
converted to the acetal and its concentration depends on
the operation efﬁ ciency of rectiﬁ cation columns, rather
than on the catalyst run. Previous studies have shown that
the acetal is removed together with the B1D head fraction