J.

of Supercritical Fluids 49 (2009) 227232

Contents lists available at ScienceDirect
The Journal of Supercritical Fluids
j our nal homepage: www. el sevi er . com/ l ocat e/ supf l u
Review
2-Butyne-1,4-diol hydrogenation in supercritical CO
2
: Effect of hydrogen
concentration
K. Kriaa, J.-P. Serin

, F. Contamine, P. Czac, J. Mercadier

Laboratoire Thermique Energtique et Procds, Ecole Nationale Suprieure en Gnie des Technologies Industrielles, Universit de Pau et des Pays de lAdour,
rue Jules Ferry BP 7511, 64075 Pau, France
a r t i c l e i n f o
Article history:
Received 29 August 2008
Received in revised form 13 January 2009
Accepted 14 January 2009
Keywords:
2-Butyne-1,4-diol
Hydrogenation
Supercritical CO
2
Modelling
Reaction kinetic
a b s t r a c t
Hydrogenation experiments of 2-butyne-1,4-diol, catalysed by carbon-supported palladium, have been
performed in a batch reactor using high pressurised carbon dioxide as reaction solvent. Carbon dioxide
pressure was kept to a constant value of 18MPa. The inuence of the hydrogen pressure, varying from
0.2 to 0.8MPa, on the conversion rate was investigated. Under these conditions, the reactive media is
monophasic. Finally, we tted our experimental results with a simple reaction kinetic model.
2009 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
2. Materials and methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
2.1. Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
2.1.1. Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
2.1.2. Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
2.2. Reaction experiments and methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
3.1. Hydrogenation without catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
3.2. Physical state of reactive mixture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
3.3. Hydrogenation in supercritical medium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
3.4. Effect of hydrogen concentration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
3.5. Kinetic model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
1. Introduction
The use of supercritical carbon dioxide (scCO
2
) is of interest in
the elds of industrial applications, foodindustry, pharmacy, devel-
opment of materials and environment [13]. ScCO
2
is particularly
attractive for synthesis reaction, because it is an environmen-
tally acceptable replacement to the harmful conventional organic
solvents due to its non-toxicity, its non-ammability, its moder-

Corresponding author. Fax: +33 5 59407801.

E-mail address: [email protected] (J.-P. Serin).
ate critical parameter and a potentially easy separation [46]. In
addition, scCO
2
affords some potential advantages: a complete mis-
cibility with hydrogen, high diffusivity, and good mass and thermal
transport properties. Thus, it has been attracting much attention in
the selective hydrogenations [710]. A number of heterogeneously
catalysed hydrogenations have been successfully carried out in
scCO
2
, often with higher reaction rates and different product dis-
tributions, in comparison with hydrogenations in organic solvents
[1121].
We focused in the present study on the hydrogenation of 2-
butyne-1,4-diol which is an important product in ne chemicals as
well as its hydrogenated derivatives. This reaction is generally car-
0896-8446/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.supu.2009.01.004
228 K. Kriaa et al. / J. of Supercritical Fluids 49 (2009) 227232
Fig. 1. Photograph of the pilot.
ried out in a triphasic, gas +liquid+solid catalyst system. Hydrogen
is the main component of the gas phase whereas the liquid phase
is composed of the solvent (aqueous solution or organic solution),
reactants and products. This three-phase reaction has been studied
over a variety of different catalysts. The use of catalytic supports
like Ni or NiCu requires severe conditions [22]. Today, the use of
catalysts containing noble metals as palladium or platinum makes
it possible to work with more exible operating conditions [22].
Several experimental studies used palladium as catalyst for the
hydrogenation of 2-butyne-1,4-diol [2229]. The impact of the cat-
alyst support nature or the solvent effect on both conversion and
selectivity were investigated. They all are ina triphasic mediumand
create side-products such as n-butanol or crotyl-alcohol.
The present objective is to carry out hydrogenation reaction in
a homogeneous (supercritical) mediumwith the aimof decreasing
the organic solvent consumption (environmental standards) using
palladium as catalyst.
In the framework of our study, hydrogenation of 2-butyne-1,4-
diol in scCO
2
has been carried out at a xed temperature of 323.15K
with Pd/C catalyst. The concentration proles and the inuence of
hydrogenation pressure have been discussed. Finally, we obtained
numerical parameters of a simple kinetic model which ts our
experimental results.
2. Materials and methods
2.1. Materials
2.1.1. Chemicals
Hydrogenandcarbondioxide were suppliedby Air Liquide, with
a stated purity of 99.998mol%.
2-Butyne-1,4-diol (purity: 99%), cis-2-butene-1,4-diol (purity:
95%), butane-1,4-diol (purity: 99%), ethanol (purity: 99.5%) were
supplied by MERCK,
Glycerol (purity: 98%) was supplied by Prolabo.
2.1.2. Catalyst
5wt.% Pd/C catalyst, particle size between 50 and 100m.
2.2. Reaction experiments and methods
The hydrogenation experiment of 2-butyne-1,4-diol is per-
formed with an apparatus consisting of a one-litre stainless steel
reactor in which it possible to implement reaction until 30MPa
and 473K (Fig. 1). This autoclave has three potential feeders and
one outlet line equipped with a gasliquid separator (cyclonic in
order to limit the drive of the liquid phase). The reaction temper-
ature is maintained constant by a circulation of oil in an external
jacket connected to a thermostat (Fig. 2). A variable speed stirrer
agitates themixture. Safetyarrangements likerupturedisc andhigh
temperature cut-off are also provided.
The hydrogenation of 2-butyne-1,4-diol is carried out at
323.15K, in the presence of 0.07g of catalyst. In this study the pilot
is used in batch mode. First, the reactor is loaded with the catalyst
and the reactive mixture. Then, liquid carbon dioxide is pumped
into the reactor up to 18MPa while the desired reaction tempera-
ture is set. The propeller stirrer turns at 600rpm and a mass ow
controller measures the quantity of hydrogen introduced into the
autoclave. It is important tostir themixturewhilehydrogenis intro-
duced because hydrogen is greatly soluble in carbon dioxide. If the
mixture is not agitated during this step, a time evolution of the
total pressure only due to the slow mixing of carbon dioxide and
hydrogen is observed.
The initial composition of the reactive mixture is given
in Table 1. Glycerol, the internal standard, and ethanol are also
present. Indeed, ethanol is usedtodissolve2-butyne-1,4-diol which
is initially on a solid form. In addition, ethanol has previously been
indicated as a good co-solvent to improve the solubility of organic
compound in carbon dioxide. The start of the reaction is noted
when the hydrogen is loaded into the reactor. Samples are taken at
regular intervals through a sampling valve xed to a dip tube in the
middle of the reactor. The sample is collected in a vial, and bubbled
through a measured amount of ethanol. The analysis of the samples
Fig. 2. Schematic diagram of the reactor system.
K. Kriaa et al. / J. of Supercritical Fluids 49 (2009) 227232 229
Table 1
Composition of the reactive mixture.
Components Concentrations (mol m
3
)
2-Butyne-1,4-diol 2.32
Ethanol 13.2
Glycerol 0.763
Hydrogen 27.5113
CO
2
17200
is conducted by gas chromatography method. The gas chromato-
graphis equippedwitha 30m0.32mminternal diameter TR-wax
column, and a ame ionization detector. The carrier gas is helium.
The oven temperature program is: 373.15K for 1min, a ramp to
523.15K at a rate of 15Kmin
1
, and 523.15K for 3min. The injector
and detector temperatures are set to 593.15 and 623.15K, respec-
tively. Glycerol is used as internal standard for quantitative GC
analysis.
3. Results and discussion
Hydrogenations of 2-butyne-1,4-diol were performed at differ-
ent hydrogen concentrations. The effect on kinetics was studied.
3.1. Hydrogenation without catalyst
One study made by Zhao et al. [30] proves that hydrogenation
of 2-butyne-1,4-diol in scCO
2
medium can be promoted by a stain-
less steel reactor (SUS 316) wall without any catalyst. That is why
we primarily chose to carry out the reaction reproducing the oper-
ating conditions of Zhao. In order to initiate the reaction, several
tests have been carried out, like increasing the hydrogen pressure
or the reaction temperature from 323.15 to 353.15K. Nevertheless,
no conversion was observed. Unfortunately, the reaction cannot
start without catalyst. Consequently, our hydrogenation experi-
ments have been done in presence of carbon-supported palladium
catalyst.
3.2. Physical state of reactive mixture
Since the autoclave is not equipped with a sapphire window,
it is not possible to detect visually the physical state of the reac-
tive mixture. To answer this problem, samples have concurrently
been taken from different levels of the reactor (from the top, the
middle and the bottom of the reactor). The analyses of the samples
allowed us to determine the physical state of the reactive mixture:
homogeneous or heterogeneous (vapour and liquid phases). In all
experiments introduced here, the mixture is supercritical.
3.3. Hydrogenation in supercritical medium
This work focuses on the investigation of hydrogen concentra-
tion inuence on the distribution of products obtained from the
2-butyne-1,4-diol hydrogenationunder supercritical conditions. All
reactions were performed using 5wt.%Pd/C catalyst, at a xed tem-
perature of 323.15K.
First of all, no side products have been detected during hydro-
genation of 2-butyne-1,4-diol in supercritical medium. In all
experiments, the distribution proles of the components are sim-
ilar to those presented in Fig. 3. The 2-butyne-1,4-diol content
rapidly decreases. The concentration prole of the 2-butene-1,4-
diol admits an extremum. Then, the amount of the intermediate
product rst increases, passes through a maximum value, and
decreases down to zero. The butane-1,4-diol is produced as soon as
the reaction begins and its content increases with time. After 2h, 2-
butyne-1,4-diol and 2-butene-1,4-diol have quantitatively reacted
Fig. 3. Prole and result of numeric simulation of the hydrogenation of butynediol
in supercritical CO
2
, expressed as mole percentage of () butynediol and reaction
products (() butenediol and(+) butanediol) vs. time(min), at 323.15K, 2.75E2mol
of H
2
and 18MPa of CO
2
pressure. RRMSD=34.0%.
Fig. 4. Reaction scheme for the hydrogenation of 2-butyne-1,4-diol in supercritical
medium.
and the conversion rate into butane-1,4-diol is 100%. The reaction
scheme is given in Fig. 4.
3.4. Effect of hydrogen concentration
The effect of hydrogen concentration on the conversion pro-
les of 2-butyne-1,4-diol, 2-butene-1,4-diol and butane-1,4-diol
was studied over a range from 0.2 to 0.8MPa and at 323.15K. The
results are shown in Fig. 5. In all experiments, 2-butyne-1,4-diol
is completely converted into butane-1,4-diol in 2h. As we could
imagine, the higher the hydrogen concentration is, the faster the
2-butyne-1,4-diol reacts. Then, in20min, only 40%of the 2-butyne-
1,4-diol has reacted at the lowest hydrogen pressure, against more
than 80% at the highest one. The overall rate of hydrogenation
increases when the hydrogen concentration increases. Indeed, the
higher the amount of hydrogen, the faster the butane-1,4-diol
formationis. Nevertheless, this effect seems weaker at highconcen-
trations of hydrogen. Experimental butane-1,4-diol concentration
proles are very close when working with a hydrogen concentra-
tion greater than 0.056kmol/m
3
. The effect of hydrogen pressure
on2-butene-1,4-diol concentrationprole is similar to the effect on
butane-1,4-diol. The coordinate of the extremum is a characteris-
tic point of the prole. Experimentally, when the hydrogen content
increases, this point appears sooner, but its value is smaller. So, the
maximum for the intermediate product content is observed with
the minimum hydrogen concentration.
3.5. Kinetic model
The hydrogenation of butynediol consists of two consecutive
reactions (Fig. 4).
The mass balances for 2-butyne-1,4-diol and the reaction prod-
ucts give the following system of differential equations:

da(t)
dt
= k
1
[H
2
]
m
1
a(t)
n
1
(1)
db(t)
dt
= k
1
[H
2
]
m
1
a(t)
n
1
k
2
[H
2
]
m
2
b(t)
n
2
(2)
dc(t)
dt
= k
2
[H
2
]
m
2
b(t)
n
2
(3)
230 K. Kriaa et al. / J. of Supercritical Fluids 49 (2009) 227232
Fig. 5. Concentration prole for 2-butyne-1,4-diol (A), 2-butene-1,4-diol (B) and
butane-1,4-diol (C), as a function of reaction time for different hydrogen concentra-
tions (() 2.75 E2kmol/m
3
, (*) 3.75 E2kmol/m
3
, () 5.65 E2kmol/m
3
, (+) 7.00
E2kmol/m
3
, () 11.30 E2kmol/m
3
).
where a(t), b(t) and c(t) represent the concentrations of 2-butyne-
1,4-diol, 2-butene-1,4-diol and butane-1,4-diol, respectively.
The parameters of kinetic reaction are obtained by minimising
the following objective function:
f
obj
=
3

i=1
np

j=1

y
exp
i,j
y
calc
i,j
y
exp
i,j

(4)
where i represents the component, np is the number of experimen-
tal result. y
exp
and y
calc
are the experimental value and the value
estimated by the model, respectively.
Table 2 presents the parameters estimated by tting the simu-
lated curves to the experiment data. The predictions of the model
equations are in good agreement with the experimental results for
the effect of hydrogen pressure on the conversion of 2-butyne-1,4-
diol, the selectivity of 2-butene-1,4-diol and butane-1,4-diol, and
Table 2
Kinetic parameters for the hydrogenation of 2-butyne-1,4-diol in supercritical
medium.
Parameter Value
n
1
1
n
2
1
m
1
0.34
m
2
0.67
k
1
0.26mol
0.34
l
0.34
min
1
k
2
0.81mol
0.67
l
0.67
min
1
the overall rate of hydrogenation. In Figs. 3, 59, the experimental
data are presented as points; the continuous lines are the results of
the numerically resolution of the mass balances (Eqs. (1)(3)). The
root mean square deviation ranges from 17.9 to 34% according to
the experiment. This deviation is dened as:
RRMSD(%) =

i=1
1
np
np

j=1

y
exp
i,j
y
calc
i,j
y
exp
i,j

2
(5)
The relative simplicity of the kinetic model explains the values of
the deviation. Nevertheless, no trend of the deviation with hydro-
gen pressure has been noticed.
Fig. 6. Result of numeric simulationfor hydrogenationof 2-butyne-1,4-diol insuper-
critical carbon dioxide with 3.75 E2kmol/m
3
of hydrogen, at 323.15K and 18MPa
of CO
2
pressure (() butynediol, () butenediol, (+) butanediol). RRMSD=17.9%.
Fig. 7. Result of numeric simulationfor hydrogenationof 2-butyne-1,4-diol insuper-
critical carbon dioxide with 5.65 E2kmol/m
3
of hydrogen, at 323.15K and 18MPa
of CO
2
pressure (() butynediol, () butenediol, (+) butanediol). RRMSD=26.2%.
K. Kriaa et al. / J. of Supercritical Fluids 49 (2009) 227232 231
Fig. 8. Result of numeric simulationfor hydrogenationof 2-butyne-1,4-diol insuper-
critical carbon dioxide with 7.00 E2kmol/m
3
of hydrogen, at 323.15K and 18MPa
of CO
2
pressure (() butynediol, () butenediol, (+) butanediol). RRMSD=26.5%.
Fig. 9. Result of numeric simulationfor hydrogenationof 2-butyne-1,4-diol insuper-
critical carbon dioxide with 11.30 E2kmol/m
3
of hydrogen, at 323.15K and 18MPa
of CO
2
pressure (() butynediol, () butenediol, (+) butanediol). RRMSD=25.0%.
4. Conclusions
The hydrogenation of 2-butyne-1,4-diol has been carried out
in an homogenous medium catalysed by carbon-supported pal-
ladium. The solvent of the reaction was high pressurised carbon
dioxide. The experimental results obtained in this work show that
no side products are detected and the conversion to butane-14-
diol is complete in a maximum of 2h. Compared to the other
works made on the hydrogenation of 2-butyne-1,4-diol, these
results show the interest to work with supercritical carbon diox-
ide. Moreover, the inuence of the hydrogen concentration on
the reaction was investigated. The higher the hydrogen concen-
tration, the shorter the reaction time for the overall conversion
to the nal product is. In addition, the time of total conversion
is shorter when the hydrogen concentration increases. However,
the maximum of the intermediate product, 2-butene-1,4-diol,
is observed for the minimum hydrogen concentration. Even if
it is difcult to compare our results with those obtained in
biphasic mixture, because the conditions (pressure and tem-
perature levels, catalysts,. . .) are different, it seems that the
reaction velocity is higher in supercritical media. Finally, a sim-
ple kinetic model was proposed. The model parameters were
estimated by tting the simulated curves to the experimental
data.
Acknowledgements
We wish to thank the Conseil Rgional dAquitaine for his nan-
cial support to this work.
LaTEP is a member of the PILA network: High research and tech-
nological resources in multi-disciplinary actions (http://web.univ-
pau.fr/scf-PILA).
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