1070-4272/03/7609-1399$25.00C2003 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 76, No. 9, 2003, pp. 1399!1404. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 9,
2003, pp. 1439!1444.
Original Russian Text Copyright + 2003 by Rogov, Sabylin, Khvorov.
OF SYSTEMS AND PROCESSES
Liquid!Vapor Equilibrium in the Isobutanol!
n-Butanol!Butyl Butenyl Ether Ternary System, Azeotropy
in Butyl Alcohols!Butyl Butenyl Ether!Water Systems,
and Separation of Their Components by Distillation
M. N. Rogov, I. I. Sabylin, and A. P. Khvorov
All-Union Research Institute of Pertochemistry, Joint-Stock Company, St. Petersburg, Russia
Salavatnefteorgsintez Joint-Stock Company, Salavat, Bashkortostan, Russia
Received June 2002; in final form, March, 2003
Abstract-Liquid3vapor equilibria and azeotropy in isobutanol3n-butanol3butyl butenyl ether ternary system
and in isobutanol-butyl butenyl ether and n-butanol3butyl butenyl ether binary systems were studied experi-
mentally and calculated, as well as azeotropy in butyl alcohols3butyl butenyl ether3water systems under
atmospheric and reduced pressure. Recovery of commercial butyl alcohols by distillation of alcohol3ether
fractions was studied.
To decrease losses of commercial products in oxo-
synthesis of butyl alcohols, recovery of butyl alcohols
by distillation of the alcohol3ether fraction should be
optimized by mathematical simulation. The simulation
requires knowledge of parameters of the liquid3vapor
equilibrium and azeotropy in isobutanol3n-butanol3
butyl butenyl ether ternary system and in binary sys-
tems of these compounds.
Oxosynthesis of butyl alcohols yields alcohol3ether
fractions as a by-product in amount of 10315% of
the produced butyl alcohols. The content of butyl
alcohols in these fractions is 50370%.
This fraction is used today as a fuel component.
Feasibility study shows that recovery of more that
50% of saleable butyl alcohols gives a profit with fast
pay-back of investments.
The alcohol3ether fraction contains also saturated
ethers (dibutyl ether, diisobutyl ether, butyl iso-
butyl ether) and the corresponding C
ethers are formed in the step of C
acetal degradation when butyric aldehydes are hydro-
genated to form butyl alcohols. The acetals are present
in the raw material to be hydrogenated as by-products
of propylene hydroformylation .
The liquid3vapor equilibria in butyl alcohol3
ether systems have been extensively
studied [23 6]. These processes are simulated well by
UNIFAC group procedure . At the same time, no
data on the equilibria in butyl alcohol3unsaturated C
ether systems are reported. Hence, equilibria in these
systems cannot be simulated.
To study the liquid3vapor equilibria in the latter
systems, we prepared unsaturated C
butenyl ether (BBE).
The synthesis of BBE involves two steps. The first
is preparation of C
acetal, dibutyl butyral, from
n-butyric aldehyde and n-butanol purified by distil-
acetal was distilled under reduced pressure and
thermolyzed on calcium phosphate catalyst at 2003
220oC under atmospheric pressure to form n-butanol
The unsaturated C
ether was isolated by distilla-
tion. The boiling point at 760 and 100 mm Hg
is 145.4oC and 83.7oC, respectively; density d
0.773 kg m
; refractive index n
No physicochemical properties of this ether are re-
ported in available handbooks. All the other chemicals
used in this work were thoroughly purified; their
physicochemical parameters were consistent with the
published data .
The liquid3vapor equilibrium was studied on a
circulation unit connected with a manostat. The
design of the unit provided minimal consumption
of chemicals. The vapor condensed in a receiver was