ISSN 1070-4272. Russian Journal of Applied Chemistry, 2006, Vol. 79, No. 1, pp. 89!92. + Pleiades Publishing, Inc., 2006.
Original Russian Text + E.V. Pyatnitsyna, M.M. El’chaninov, A.P. Savost’yanov, 2006, published in Zhurnal Prikladnoi Khimii, 2006, Vol. 79, No. 1,
Catalytic Hydrogenation of 2-Butyne-1,4-diol to 2-Butene-1,4-diol
at Atmospheric Pressure in the Liquid Phase
E. V. Pyatnitsyna, M. M. El’chaninov, and A. P. Savost’yanov
South-Russian State Technical University, Novocherkassk, Rostov oblast, Russia
Received October 10, 2005
Abstract-Selective hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol on suspended palladium and
Raney nickel catalysts at atmospheric pressure was studied. The optimal parameters of this reaction were
determined. Samples containing 90% 2-butene-1,4-diol were prepared.
2-Butene-1,4-diol (BED) is used to produce valu-
able materials such as Endosulfan (insecticide) ,
polyesters , alkyd resins , butadiene rubber ,
and plasticizers  for various branches of industry
and medicine. However, this monomer was not pro-
duced in Russia. Selective preparation of this mono-
mer by hydrogenation of 2-butyne-1,4-diol (BYD) is
of great practical interest.
Here we studied selective hydrogenation of BYD to
BED on suspended catalysts at atmospheric pressure.
Hydrogenation of BED to BYD was performed in
an aqueous suspensions on fine powders of palladium
catalysts containing 0.8 and 2.0% Pd and on Raney
99 9 9
OH OH OH OH
2-Butyne-1,4-diol was reduced in a 100-ml long-
necked reactor fixed on a shaker. To maintain the
required temperature of the reactor and buret, ther-
mostated water was passed through their jackets.
A weighed portion of BYD (1.32 g), water (20 ml),
and calculated amount of finely divided catalyst were
placed in the reactor. The reaction completion was
judged from the volume of hydrogen absorbed, which
was measured with a 300-ml gas buret. The palladium
catalysts (0.8 and 2.0 wt % Pd supported by OUB
carbon) was prepared by impregnation of the support
with hydrochloric acid solution of palladium(II) chlor-
ide, followed by reduction to metallic Pd with formal-
dehyde . The selective W-6 nickel catalyst was
prepared by leaching a nickel3aluminum Raney alloy
with a solution of sodium hydroxide (20 wt %) .
The hydrogenation products were analyzed on a
Tsvet chromatograph using a 2000 0 3-mm column.
The carrier gas was nitrogen; the column temperature
was 603200oC. The support was Chromaton Super
(0.1630.20 mm); the stationary phase was polyethyl-
ene glycol 15 000.
To determine the best hydrogenation conditions,
we studied the composition of the hydrogenation
products as influenced by the temperature in the range
from 30 to 70oC and the catalyst amount in the reac-
tion mixture in the range from 10 to 100% relative to
BYD. The results are summarized in Tables 1 and 2.
Chromatographic analysis of the products showed that
the target product is formed with 93394% selectivity
on both palladium catalysts, especially at 40350oC,
after absorption of hydrogen in the amount corre-
sponding to reduction of one p bond. When the
Pd/C-2 catalyst with higher metal content was used,
the weight fraction of BED did not noticeably change.
At 30 and 60370oC, the selectivity decreases. This is
due, in the first case, to a low reaction rate and, in
the second case, to an increase in the partial pressure
of water vapor and fast dehydration, isomerization,
and exhaustive hydrogenation.
Hydrogenation on a Raney Ni is slower. The BED
content in the reaction product is 73376%. Under
these conditions, g-hydroxybutyraldehyde (HBA),
isomerization product of BED, is formed in a large
amount. This compound is dehydrated and hydro-