Journal of the Japan Petroleum Institute, 51, (3), 119-133 (2008) 119

[Reveiw Paper]

Catalytic Hydrogenation of 2-Butyne-1,4-diol:

Activity, Selectivity and Kinetics Studies

Chandrashekhar V. Rode＊

Chemical Engineering & Process Development Div., National Chemical Laboratory, Pune 411008, INDIA

(Received August 7, 2007)

The reaction pathway for hydrogenation of 2-butyne-1,4-diol involves parallel and consecutive isomerization as
well as hydrogenation reactions forming other side products along with cis-2-butene-1,4-diol and butane-1,4-diol.　
Hence, achieving the highest selectivity to butene- and/or butanediol is critical from industrial point of view.　
Hydrogenation of butynediol is also of fundamental significance, due to its adsorption characteristics leading to
the formation of active species and their role in determining the product distribution.　Studies on designing various
catalyst systems including colloidal as well supported palladium nanoparticles for the hydrogenation of butynediol,
role of additives, catalyst pretreatment, kinetic studies carried out in our group has been presented in this review.　
Interestingly, almost complete selectivity to the intermediate olefinic diol was achieved with 1％ Pd/CaCO3_NH3
catalyst system.　This could be due to the competitive adsorption of ammonia on the palladium surface along
with the substrate 2-butyne-1,4-diol.　Studies on catalyst pretreatment and kinetics using palladium catalyst have
also been presented here.　Nanostructure palladium both colloidal as well as supported catalysts showed a very
high catalytic activity (10-40 times more) in the hydrogenation 2-butyne-1,4-diol to cis-2-butene-1,4-diol compared
with the corresponding conventional Pd catalysts.　For platinum based catalysts, formation of side products was
completely eliminated in the hydrogenation of butyne diol.　The increase in the basic strength of alkali metal
doped Pt catalysts measured by CO2-TPD, led to the increase in electron density of Pt hence, faster desorption and
higher selectivity to butenediol.　In the case of continuous hydrogenation, the selectivity pattern was completely
different from that found in the case of batch slurry reactor and by varying the contact time, the selectivity to both
butene- and butanediols could be varied over a wide range of conditions.

Keywords
Selective hydrogenation, 2-Butyne-1,4-diol, 2-Butene-1,4-diol, Catalyst pretreatment,
Nano palladium catalyst, Alkali metal doping

1.　Introduction cis isomer however, under hydrogenation conditions

isomerization is greatly suppressed due to fast desorp-
Catalytic hydrogenation of carbon_carbon multiple tion of the intermediate olefinic diol.　Moreover, the
bonds (alkynes and dienes) to partial/complete hydrogen- trans isomer is not known to have any significant indus­
ation products, i.e. monoenes and alkanes has been a trial applications.　On the other hand, the cis olefinic
topic of great importance from both fundamental as diol, B2D has wide ranging applications in the manu-
well industrial point of view1),2).　It is challenging to facture of agrochemicals and pharmaceutical, e.g. hydro-
achieve complete selectivity to olefinic compounds in formylation of B2D is an important step in the new vita-
such processes since the intermediate olefin of the first min A process4),5).　B2D is also a starting compound
hydrogenation step readily undergoes further hydrogen- for the manufacture of endosulfan, a very commonly
ation to give a saturated alkane product3).　One such used insecticide which is produced from butenediol by
industrial example is the catalytic hydrogenation of Diels-Alder reaction with hexachlorocyclopentadiene,
2-butyne-1,4-diol (B3D) for the manufacture of cis- followed by cyclization with thionyl chloride6) .　
2-butene-1,4-diol (B2D) and butane-1,4-diol (B1D).　 Butenediol is also used for the production of pyridoxine
The geometric cis isomer is predominantly obtained (Vitamin B6) and in mixtures with other compounds as
(＞99％) due to the syn addition of hydrogen over hetero- bactericide7),8) .　Annual production B2D is around
1) 5000 t worldwide.　The saturated product, butanediol
geneous catalysts under mild conditions .　The trans
isomer is regarded to be formed due to isomerization of of the hydrogenation of butynediol process is mainly
consumed for the production of polyurethanes, poly­
＊
E-mail: [email protected] butylene terephthalate (PBT), γ-butyrolactone and tetra-

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 120

Scheme 1　Reaction Pathway Leading to Various Products in the Hydrogenation of B3D

hydrofuran9),10) .　The global production of B1D is and/or organic amines also were used as catalyst sys­
about 0.4 million ton/year with an expected annual tems to improve selectivity (ratio of concentration of
growth rate of 4.5％.　Such a great demand for B1D is desired product formed to the concentration of substrate
due to the extensive use of spandex fibers (made from consumed) to the intermediate, B2D1),5)～8).　A mono­
tetrahydrofuran, THF) and PBT products11).　The reac­ metallic Pd/C catalyst was reported to give 60-70％ se­
tion pathway for hydrogenation of butynediol as shown lectivity to B2D while remaining is a mixture of saturated
in Scheme 1, which involves parallel and consecutive diol (B1D) along with other side products such as
reactions forming other side products such as γ-hydroxy γ-hydroxy butyraldehyde, n-butyraldehyde, butanol,
butyraldehyde, n-butyraldehyde, butanol, crotyl alcohol crotyl alcohol and acetal due to the double bond migra­
and acetal due to the possibility of double bond migra­ tion and hydrogenolysis of B2D in presence of a cata­
tion, condensation of γ-butyraldehyde and B1D and hy­ lyst4),5).　Hydrogenation of B3D has also been reported
drogenolysis of B2D in presence of a catalyst4),12)～14).　 in supercritical CO2 medium (entries 16-17, Table 1)
Musolino et al. have investigated in detail the effect of however, complete selectivity to B1D was obtained at
the addition of proton, solvent type and carbon support 100％ conversion of B3D in which the reactor wall (ss)
on the product distribution in the hydrogenation of B3D acted as a catalyst.　It is clear from the literature that
over 0.5％ Pd/C catalyst15).　From these studies, it is for butynediol hydrogenation, a monometallic catalyst
observed that achieving the highest selectivity to butene­ system gives saturated diol (B1D) as a major product
and/or butanediol is critical from industrial point of along with other side products while a combination of
view.　Hydrogenation of butynediol is also of funda­ two or more metals or in the presence of organic/
mental significance, due to its adsorption characteristics inorganic bases gives enhanced selectivity to B2D,
leading to the formation of active species and their role however, such catalyst systems lack in consistency in
in determining the product distribution.　The well activity, in subsequent catalyst reuse and moreover,
known Lindlar catalyst has been in commercial use for such processes require the complete removal of the
the semihydrogenation of B3D to B2D due to poisoning additives for obtaining highest purity of the product for
effect of Pb16),17), however, several other catalyst sys­ its end use in fine chemical or pharmaceutical sector.
tems have also been reported in the literature and a Studies on designing various catalyst systems for the
summary is presented in Table 1.　The noble metals hydrogenation of butynediol, role of additives, catalyst
such as palladium, ruthenium alone or in combination pretreatment, kinetic studies carried out in our group
with other metals such as zinc, lead, cadmium, copper has been presented in this review.　Interestingly, almost

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Table 1　A Summery of Literature on Hydrogenation of Butynediol

Conversion Selectivity to
Sr. No. Catalyst used Reaction conditions Reference
[％] butenediol [％]
1 Pd/C, Pd_Pb 100 298-333 K 60-97 4
2 0.2-2％ Pd/C 30-100 303-353 K, 60-95 14
1.47-6.98 MPa
3 Supported 0.5％ Pd 80 303 K, 0.101 MPa 33 15
4 Supported 1％ Pd 100 323 K, 2.4 MPa, NH3 100 21
5 Pd/CaCO3 lead acetate 52 285-289 K Mixture 22
6 Nanosize Pd, Pt 100 293-393 K, 100 38
1.38-4.83 MPa
7 Colloidal Pd, Pt, 100 323 K, 2.4 MPa 99 39
Rh, Ru, Ni and
supported
8 Supported Pd, Pt, 100 323-353 K, 100 45
5％ Pd_2.5％ Pb/CaCO3 2.48-6.87 MPa, NH3
9 1％ Pt/CaCO3 100 293-463 K, Mixture 56
0.5-10 MPa
10 Pt doped with alkali 100 323-373 K, 100 58
2.4-6.8 MPa
11 1％ Pt/CaCO3 100 323-373 K, 1-7 MPa 63 60
12 5％ Ru/C — 318-353 K, Mixture 61
0.5-8.1 MPa
13 Raney Ni — 413-433 K, 15-30 MPa Mixture 62
Supported Ni 80 Mixture
Raney Ni_Cu — 45
14 1％ Pd/C 43 338 K, 0.304 MPa 100 63
100 low selectivity
15 5％ Pd/C, 1 wt％ wash ～100 Monolithic reactor, 100 64, 67
coat (0.35％ Pd) 293-333 K,
102-304 kPa
16 SS reactor wall 40-100 Supercritical CO2 ＜50 65
(7-16 MPa), H2
(2-6 MPa), 323 K
17 SS reactor wall 100 Supercritical CO2, 84 to B1D 66
323 K
18 Ni catalysts on — Liquid-phase Metal-support 68
13 different supports hydrogenation studies
19 Pd nanoparticle/γ-Al2O3 94 323 K, 0.6 MPa, H2 100 69
20 Pd/ACF 80-90 333 K, 0.6 MPa, H2 ＞97 70, 71
21 Pd_Zn/CaCO3 ＞95 303-353 K, Kinetic studies 72
0.8-3.5 kPa, H2

complete selectivity to the intermediate olefinic diol could be varied over a wide range of conditions.
was achieved with 1％ Pd/CaCO3_NH3 catalyst system.　
Also, it was for the first time that we showed platinum 2.　Experimental
based catalysts eliminated the formation of side prod­
ucts in the hydrogenation of butynediol.　The increase 2. 1.　Materials
in the basic strength of alkali metal doped catalysts 2-butyne-1,4-diol, butenediol and butanediol were
measured by CO2-TPD (temperature programmed de­ procured from Merck, India Ltd.　Palladium based cat­
sorption), would be responsible for the increase in elec­ alyst supported on carbon, alumina, silica and calcium
tron density of Pt hence, faster desorption and higher carbonates were prepared by the procedure given be­
selectivity to the intermediate butenediol could be low.　All the inert supports required for catalyst prepa­
achieved.　Stable Pd nano catalysts both in colloidal as ration were procured from M/s Loba Chemie, Bombay.　
well as supported forms were also prepared and found Freshly distilled solvents were used in all the experi­
to exhibit several folds higher activity and selectivity ments.　Hydrogen gas of ＞99.9％ purity was supplied
than the bulk Pd catalysts.　In the case of continuous by Indian Oxygen Ltd., Bombay.
hydrogenation in a fixed bed reactor, the selectivity pat­ 2. 2.　Catalyst Preparation
tern was completely different from that found in the Pd, Pt supported catalysts were prepared by dissolv­
case of batch slurry reactor and by varying the contact ing the required quantity of PdCl2 or PtCl4 in minimum
time, the selectivity to both butene- and butanediols amount of water, if necessary small quantity of dilute

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 122

HCl was added to ensure the complete dissolution of gen.　This allowed the determination of hydrogen con­
the precursor.　Under stirring conditions, the slurry of sumption as a function of time, while maintaining the
support prepared in water was added to the above solu­ reaction at a constant desired pressure.　In a typical
tion at 353 K.　After 1 h, formaldehyde was added under hydrogenation experiment, known quantities of sub­
stirring.　Then the reaction mixture was cooled, filtered strate, solvent and catalyst was charged in a 600 ml au­
to obtain the catalyst, which was dried at room temper­ toclave.　The contents were first flushed with nitrogen
ature. and then with hydrogen.　After attaining desired tem­
The nanoparticle catalysts were prepared by using perature the system was pressurized with hydrogen to
two different reduction methods, (i) chemical reduction the required pressure.　The reaction was started by
(CRPd), (ii) radiolytic reduction using 60Co (RRPd).　 switching the stirrer on.　The progress of the reaction
In a chemical reduction method, a calculated amount of was monitored by the observed pressure drop in the res­
polymer (poly vinly pyrrolidone PVP, poly vinyl alco­ ervoir as a function of time.　The liquid analysis was
hol or poly methyl vinyl ether) was added to 15 ml of carried out using a Hewlett-Packard GC model 6890
2 mmol H2PdCl4 solution (prepared by addition of equipped with FID (hydrogen-flame ionization detctor)
35.5 mg of PdCl2 to a mixture of 98 ml of water and and a capillary column FFAP (0.32 mm i.d.×50 m,
2 ml of 0.2 M HCL (1 M＝1 mol・dm-3)).　To this solu­ length) with a temperature programming of 353-463 K
tion, 15 ml of ethanol was added.　The initial pH of at 303 K/min ramp.
the solution was found to be 3, which was adjusted to 7 2. 4.　Continuous Hydrogenation
by adding 10％ (w/w) sodium hydroxide.　This solu­ These experiments were carried out in bench scale,
tion was diluted to 50 ml by adding water and refluxed high-pressure fixed bed reactor supplied by M/s
in a 100 ml flask at 353 K for 3 h.　After 3 h, the color Geomechanique, France, consisting of a stainless-steel
changed to dark brown to form polymer protected Pd tube of 0.35 m length and 1.5×10-2 m inner diameter
nanoparticles.　In radiolysis method, the solution of that was heated by two tubular furnaces whose zones
H2PdCl4, ethyl alcohol and a polymer (PVP) was pre­ were independently controlled at the desired bed tem­
pared and diluted to 50 ml (as mentioned in chemical perature.　The reactor was provided with two thermo­
method) and 1 ml of isopropanol was added to this couples [Chromel-Alume thermocouples (type K)] to
solution.　This solution was then irradiated with measure the temperature at two different points.　The
gamma rays in 60Co source for 2 h at a dosing rate of reactor was equipped with mass flow controllers, pres­
0.36 Mrad/hour.　The dark brown solution of the nano sure indicator and controller (PIC) devices.　A storage
size catalyst particles was stored in airtight bottles for tank was connected to the metering pump through a
use in catalytic reactions.　Supported palladium nano volumetric burette in order to measure the liquid flow
particles were prepared from the palladium sol as pre­ rate.　The other end of the reactor was connected to a
pared above using poly (N-vinyl pyrrolidone, PVP) as a gas-liquid separator through a condenser.
stabilizer.　To this solution, under vigorous stirring The experiments were carried out over 10 and 20 g
and reflux conditions, ethanol and water (30 : 70) were of catalyst in the form of pellets having 4 mm diameter.　
added over a period of 3 h.　For depositing the sol on The section 5 cm above and 5 cm below the catalyst bed
to the support, activated carbon (2 g) was added to the was packed with inert packing (carborundum), thus pro­
above solution under stirring for 16 h after which the viding the catalyst bed depth of ～0.25 m.　The reactor
solid catalyst was separated by filtration.　Analysis of was flushed thoroughly with H2 at room temperature
colorless filtrate by atomic absorption spectroscopy before start of actual experiment.　After attaining the
showed negligible Pd concentration (＜5 ppm) ensuring desired temperature the reactor was pressurized with H2.　
the adsorption of total Pd on support resulting in Pd The liquid feed was ‘switched on’ after the reactor has
nanoparticles (0.25％ Pd loading) on carbon catalyst.　 reached the operating pressure and kept as it is for 1 h
In a similar manner, Pd nanoparticles were supported to obtain the constant liquid flow rate.　Liquid samples
on other supports such as alumina, silica and calcium were withdrawn at regular intervals of time and were
carbonate. analyzed by gas chromatography (HP 6890 series) OD­
2. 3.　Batch Hydrogenation 0.32 m, helium gas as carrier, FID detector, operating
The hydrogenation experiments were carried out in a temp. 80-190℃.　The liquid velocity was changed after
600 ml capacity autoclave (Parr Instruments Co., USA), confirming the steady state achievement.　The steady
which was equipped with arrangements for cooling state performance of the reactor was observed by analy­
coil, gas inlet/outlet and sampling of a liquid phase.　 sis of the reactant and products in the exit stream.
Automatic temperature control, variable agitation
speed, safety rupture disc, high temperature cut off and 3.　Palladium Catalysts
pressure recording by a transducer were also provided.　
A storage reservoir for hydrogen gas was used along Although, Ni- and Cu-based catalysts have been
with a constant pressure regulator for supply of hydro­ reported for butynediol hydrogenation, the reaction con-

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 123

Table 2　Screening of Pd Based Catalysts for Hydrogenation of formed was predominantly butane-1,4-diol with a se­
Butynediol lectivity to 2-butene-1,4-diol less than 10％.　In addi­
TOF×10-4 Product selectivity [％] tion to 2-butene-1,4-diol and butane-1,4-diol, other
Catalysts [h-1] products formed were γ-hydroxy butyraldehyde, n-
B1D B2D others
butyraldehyde, and butanol.　These products were sep­
1％ Pd/C 2.9 70.0 5.0 25.0
arated by column chromatography and identified by
1％ Pd/Al2O3 2.0 75.0 6.0 19.0
1％ Pd/MgCO3 0.7 0.0 100 0.0 GC-MS technique20).　For carbon and alumina sup­
1％ Pd/BaCO3 0.7 0.0 100 0.0 ports although, the activities were higher than those for
1％ Pd/NH4-ZSM-5 0.6 0.0 100 0.0 all other supports, selectivity to B2D was only 5-6％
10％ Ni_1％ Pd/CaCO3 0.7 0.0 100 0.0 and the other products formed were also in higher con­
1％ Pd/CaCO3 1.2 0.0 100 0.0
centrations (Table 2).　As seen from Scheme 1, the
1％ Pd/CaCO3a) 1.5 7.0 83.0 10.0
selectivity to the intermediate olefinic diol, B2D can be
a) Without ammonia. enhanced by eliminating or suppressing the isomeriza­
Reaction conditions: temperature 323 K; H2 pressure 2.4 MPa;
concentration of B3D 2.4 kmol・m -3; concentration of catalyst
tion step which is generally an acid catalyzed step21).　
0.86 kg・m-3; concentration of ammonia 0.117 kmol・m-3; agitation Thus, the selectivity to B2D increased dramatically
speed 13.3 Hz; liquid volume 1.5×10-4 m3 21). from 6 to 83％ when the support used was calcium car­
bonate, as compared to the carbon or alumina support.　
While studying the role of supports in B3D hydrogena­
ditions employed were quite severe such as 15-30 MPa tion, Fukuda has attributed decrease in polymerization
H2 pressure and temperature up to 443 K12).　Among due to calcium carbonate support however this conclusion
the noble metals, Pd has been successfully employed as was based only on lower hydrogen consumption and
an hydrogenation catalyst for reduction of various func­ analogy derived form hydrogenation of acetylene22),23).　
tional groups including C≡C, C=C, C=N, _ NO2, In our opinion, the increase in B2D selectivity is mainly
etc.3),13),18),19).　In the case of hydrogenation of butyne­ due to suppression of acid catalyzed isomerization step
diol (B3D), the high selectivity to butenediol (B2D) has which is quite consistent with basic nature of supports
been a scientific challenge for a long time, since, the like calcium carbonate, barium carbonate (entries 2-7,
subsequent hydrogenation of B2D gives saturated B1D Table 2) which is evident from the observed increase
as per the stoichiometric reactions (i) and (ii).　In our in pH from 2.3 to 3.8 for such supports.
study, several experiments were carried out in which 3. 2.　Role of Ammonia
product concentration versus time profiles were ob­ Additives such as quinoline, ammonia or other
served.　The results on the effect of supports, ammonia organic bases are reported for enhancing the selectivity
concentration, catalyst pretreatment and other reaction to alkenes in alkyne hydrogenations24),25).　We carried
parameters on the conversion of B3D and selectivity out a few preliminary experiments to investigate sys­
to B2D and kinetics are discussed in the following sec­ tematically the role of ammonia in enhancing the selec­
tions. tivity to B2D.　Experiments were carried out by adding
Various terms such as conversion of B3D, selectivity a known quantity of ammonia along with the substrate
of various products and turn over frequency (TOF, h-1) and the concentration-time profiles without and with
used in this paper are defined as follows: ammonia are presented in Fig. 1.　It was found that
B2D was the only product formed in presence of ammo­
initial conc. of B3D - final concc. of B3D
% Conversion = × 100 (1) nia whereas without ammonia, B1D and other side prod­
initial conc. of B3D
ucts such as γ-hydroxy butyraldehyde, n-butyraldehyde
conc. of product formed and butanol were also formed as are shown in Fig. 1(a)
% Selectivity = × 100 (2)
conc. of
o B3D consumed (all the side products are shown as ‘others’).　Figure 2
conc. of B3D consumed shows the effect of concentration of ammonia on cata­
TOF = (3) lyst activity and selectivity.　The selectivity of 2­
conc. of catalyst (active metal) × time
butene-1,4-diol increased from 83 to 100％, while the
3. 1.　Effect of Support TOF decreased from 1.77×104 to 1.33×104 h -1 with
In the case of an heterogeneous catalyst, activity of increase in concentration of ammonia from
the catalyst strongly depends on the nature of a carrier 0-0.215 kmol・m-3.　Beyond 0.117 kmol・m-3 concen­
on which it is deposited.　Hence, the activity of Pd on tration of ammonia, there was marginal decrease in
various supports was investigated for the hydrogenation TOF, while the selectivity remained constant.　Hence,
of B3D and the results are presented in Table 2.　The 0.117 kmol・m-3 was considered an optimum concentra­
catalyst activity is expressed as turn over frequency tion of ammonia in 2-butyne-1,4-diol hydrogenation.　
(TOF, h-1) based on complete conversion of B3D.　It The effect of ammonia can be twofold: (i) pH of 20％
was found that Pd supported on carbon and alumina aqueous solution of 2-butyne-1,4-diol is 2.3 which is
showed very high TOF (entries 1and 2) but the product highly acidic and increased to 3.8 by use of calcium

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 124

Reaction conditions: temperature 323 K, H2 pressure 2.4 MPa; concentration of B3D 2.26 kmol・m-3; concentra­
tion of catalyst 0.86 kg・m-3; agitation speed:13.3 Hz; liquid volume 1.5×10-4 m3, concentration of ammonia (for
b) 0.117 kmol・m-3 21).

Fig. 1　A Typical Concentration-time Profile without (a) and with (b) Ammonia for B3D Hydrogenation

Reaction conditions: temperature 323 K; H2 pressure 2.4 MPa;

concentration of B3D 2.26 kmol・m -3; concentration of catalyst
0.86 kg・m-3; agitation speed 13.3 Hz; liquid volume 1.5×10-4 m3 21).

Fig. 2　Effect of Concentration of Ammonia on TOF and Selectivity

Reaction conditions: temperature 323 K; H2 pressure 2.4 MPa;
concentration of B3D 2.26 kmol・m -3; concentration of catalyst
2.6 kg・m -3; concentration of ammonia 0.117 kmol・m -3; agitation
carbonate as the catalyst support.　However, this is speed 13.3 Hz; liquid volume 1.5×10-4 m3 21).
also acidic and causes the isomerization of 2-butene­
1,4-diol affecting its selectivity.　Addition of ammonia Fig. 3　Typical Concentration-time Profile for Hydrogenation of
further increased the pH of the reaction mixture up to B3D to B2D
9-9.5 eliminating the possibility of acid catalyzed iso­
merization step.　(ii) Another possible contribution of acetylene over Pd/Al2O3 catalyst, they have also reported
addition of ammonia to enhance the selectivity of 2­ very strong irreversible adsorption of acetylene as com­
butene-1,4-diol could be its competitive adsorption on pared to that of ethylene, which subsequently prevents
the catalyst surface along with the substrate 2-butyne­ the hydrogenation of ethylene26).　In addition, due to
1,4-diol.　It can be seen from Fig. 3 that until the con­ the presence of ammonia, the active catalyst sites are
version of 2-butyne-1,4-diol was nearly complete, fur­ also blocked by ammonia which prevent the adsorption
ther hydrogenation of 2-butene-1,4-diol to butane-1,4­ of 2-butene-1,4-diol.　The strong affinity of ammonia
diol was inhibited by the presence of 2-butyne-1,4-diol towards the metal surfaces has been illustrated by
due to its strong adsorption on the catalyst surface.　In Gland27).　It can be seen from Table 1, that 1％ Pd/
the work of Moses et al. on selective hydrogenation of CaCO3 with ammonia gives complete (100％) selectiv-

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 125

ity to 2-butene-1,4-diol with reasonably good TOF and conditions were: temperature, 323-353 K; H2 pressure,
hence this catalyst system has been used for further 2.4-6.87 MPa; catalyst concn., 0.43-1.75 kg・m -3;
kinetic studies. B 3 D c o n c n . , 1.13-4.46 k m o l・m - 3 ; N H 3 c o n c n . ,
3. 3.　Catalyst Pretreatment 0.215 kmol・m-3.
The supported metal catalysts can be activated by 3. 4. 1.　Initial Rate Data
suitable pretreatment procedure particularly, by hydro­ The analysis of initial rate is useful in understanding
gen in the case of hydrogenation catalysts14),28).　In the the dependency of the reaction rate on individual reac­
literature, catalyst pretreatment studies have been mainly tion parameters and also in assessing the importance of
focused on the effect of gases such as H2, O2, N2O and mass transfer effects21).　In all the experiments, H2
CO treatment of palladium catalysts for acetylene consumption versus time was observed along with liq­
hydrogenation28)～30).　The influence of pretreatment of uid phase reactant/product concentration profiles.　The
Pd/C catalyst on activity and selectivity in hydrogena­ hydrogen consumption versus time data observed under
tion of other alkyne substrates have also been report­ different conditions were fitted by a second order poly­
ed14),31).　In the present work, the effect of catalyst pre­ nomial from which the initial rates were calculated20),21).
treatment with both H2 and B3D on the activity and 　The dependencies of the initial rates on various reac­
selectivity has been investigated.　For H2 pretreatment, tion conditions such as temperature, H2 pressure, cata­
the catalyst and the solvent (water) were stirred under lyst and B3D concentrations were observed.　A linear
H2 atmosphere for 60 min.　Then B3D was charged dependence of initial rate with respect to catalyst load­
under hydrogen atmosphere, H2 pressure was adjusted ing was distinctly observed indicating the absence of
to 2.4 MPa and the run was continued.　For substrate external gas-liquid mass transfer resistance.　Initial
pretreatment, fresh catalyst and known quantity of 20％ rates were also found to be independent of agitation
aqueous solution of 2-butyne-1,4-diol was stirred under speed again confirming the absence of external gas-
N2 atmosphere at 323 K for 60 min.　Then H2 was liquid mass transfer resistance under the conditions of
introduced and the reaction continued at conditions the present work34).　Rate of reaction was found to
described earlier.　The pretreatment results along with increase initially with increase in H2 pressure up to
those without pretreatment were compared and the 5.49 MPa21) .　At lower (＜5.49 MPa) pressure, B3D
following results emerge: (a) substantial increase in and H2 would be chemisorbed on the catalyst surface
activity of catalyst with H2 pretreatment (by 36％); (b) with some free active sites available.　As the H2 pres­
marginal decrease in the catalyst activity (approx.　 sure increases the rate would increase until all surface
10％) B3D pretreatment; (c) slight decrease in selectivity sites are occupied by H2.　Further increase in H2 pres­
of B2D (from 100 to 97％) due to B1D formation in the sure, would only marginally affect the hydrogenation
case of H2 pretreated catalyst.　It is well known that rate.　A negative order rate dependence was observed
the nature of active species in supported Pd catalyst with respect to the initial B3D concentration which indi­
changes due to catalyst pretreatment and the extent of cated that the adsorption of 2-butyne-1,4-diol is impor­
metal dispersion significantly influences the activity tant and needs to be considered in the proposed rate
and selectivity pattern14),28),32),33).　It is believed that α­ equation.
and β-Pd_hydride complexes are formed during hydrogen­ 3. 4. 2.　Kinetic Model
ation and that β sites promote alkane formation33) .　 In a three phase slurry reactor, gas-liquid, liquid-solid
The increase in TOF on H2 pretreatment with a drop in and intraparticle diffusional resistances are likely to be
B2D selectivity observed in this work suggested the for­ present, hence the contribution of various mass transfer
mation of highly active β-Pd _H sites during H2 pre­ steps in the present system were quantitatively assessed
treatment. by the well known criteria35).　In this approach, signifi­
3. 4.　Kinetic Studies cance of gas-liquid, liquid-solid and intraparticle mass
The preliminary experiments on selective hydrogen­ transfer effects represented by factors α1, α2 and Φexp
ation of 2-butyne-1,4-diol to 2-butene-1,4-diol, using respectively were calculated34),35).　These factors are
1％ Pd/CaCO3 with ammonia showed that the material defined as the ratios of the observed rate of reaction to
balance according to the stoichiometric reaction (i) was the maximum rates of gas-liquid, liquid-solid and intra-
＞97％ in all experiments.　The moles of B3D consumed particle mass transfer rate, respectively.　This analysis
and the product (B2D) formed was as per the stoichiom­ showed that the values of α1, α2 and Φexp at different
etric consumption of hydrogen and hence, for the temperature were well below 0.1, 0.1 and 0.2, respec­
kinetic runs, the absorption of H2 in the reservoir with tively, confirming that the rate data obtained were in
time was observed under different operating conditions.　 kinetic regime.　Also, as discussed in 3. 4. 1. above,
No side products were detected in the range of condi­ the initial rate of reaction showed a linear dependence
tions studied and no hydrogenation was found to occur with respect to catalyst loading and also was in­
in the absence of catalyst, which indicated the absence dependent of agitation speed, indicating the absence of
of any homogeneous reactions.　The range of operating external mass transfer resistances.　In the present

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work, the initial rate of hydrogenation was found to for nano catalysts, for B3D hydrogenation, was about
vary linearly with H2 pressure up to 5.87 MPa, beyond 10-40 times higher than that of the conventional cata­
which it was almost zero order for all the temperatures lysts as shown in Fig. 5 as concentration-time profiles
and also the ammonia concentration has an appreciable for hydrogenation of B3D under the same conditions.　
effect on the rate of reaction, hence a rate equation con­ In the case of Pd nanoparticle catalyst, time required for
sidered was of the form: the completion of reaction is about 40 times less than
wk2 A* Bl that required for the conventional Pd catalyst which has
RA = (4) directly led to the highest TOF (0.15×105 h-1) among
(1 + K A A*+ K B Bl + K C D)2
all the catalysts20),39).　This activity was also much higher
Where, w: concentration of catalyst (kg・m-3), k2: reac­ than that reported for hydrogenation of dehydrolinalool
tion rate constant (m3)2/(kmol)kg・sec, A＊: dissolved (a substrate with acetylenic triple bond similar to
concentration of hydrogen (kmol・m-3), Bl: concentra­ butynediol) to linalool using Pd colloids stabilized in
tion of B3D (kmol・m -3), D: the concn. of ammonia micelle cores of block copolymers40).　Interestingly,
(m3・kmol-1); KA, KB, KC: equilibrium constants for H2, the selectivity to B2D achieved for nanoclusters catalyst
B3D and ammonia, respectively (m・ 3
kmol-1).　The values was as high as 91％.　The higher selectivity may also
of kinetic parameters obtained were21): k2, 1.103; KA,
12.26; KB, 3.37; and KC, 16.28.　This model was also
examined further for its suitability under integral condi­
tions and the model predictions were compared with the
experimental concentration-time data which showed an
excellent agreement (Fig. 4).　The activation energy
evaluated from the Arrhenius plot was 39.42 kJ・mol-1 21).
3. 5.　Palladium Nano Catalysts
Metal nanoparticles have been reported for their im­
portance in surface chemistry, catalysis and electronic
microdevices36).　Due to their unique characteristics
such as very high aspect ratio, short range ordering,
enhanced interactions with the environment and self-
structuring for optimum performance in chemisorption
and catalysis, metal nanoparticles have been recently
applied as novel catalysts for various reactions such as
hydrogenation, hydroformylation, hydration etc. for
achieving higher activity and selectivity than the corre­
sponding bulk catalysts37).　Hence, we attempted to
synthesize Pd nanoparticles both in colloidal form and Reaction conditions: pressure 2.4 MPa; concentration of ammonia
also on supports and evaluated them for the hydrogen­ 0.117 kmol・m-3; initial concentration of B3D 2.26 kmol・m-3; con­
centration of catalyst 0.86 kg・m-3; agitation speed 13.3 Hz; total vol­
ation of B3D.　Aqueous colloids of several metals such ume 1.5×10-4 m3 21).
as Pt, Rh, Ru, Pd and Ni were prepared by chemical re­
duction as described earlier38).　The activity observed Fig. 4　Concentration-time Profiles for Different Temperatures

Reaction conditions: temperature 323 K; H2 pressure 2.4 MPa; concentration of Pd 3×10-5 mol39).

Fig. 5　Concentration-time Profiles for Hydrogenation of Butynediol Using (a) Conventional Pd Catalyst
and (b) Colloidal Pd Catalyst

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Table 3　Comparison of Chemical and Radiolytic Reduction

Methods on the Performance of Pd Nanoparticles39)

B3D hydrogenation
Particle
Method of
PVP/Pd size TOF× Selectivity [％]
preparation
[nm] 10-5 [h-1] B1D B2D
Chemical 1 7.1 3.0 1.0 99
method 10 6.1 3.2 1.8 98.2
(CRPd) 20 6.0 4.3 1.6 98.4
30 5.5 4.6 1.6 98.4
40 5 5.7 8.8 91.2
Fig. 6　TEM Photograph for Pd Nanoparticles Prepared by (a)
Radiolytic 1 5.2 3.6 1.0 99.0 Chemical Method (AV＝80 kV; magnification＝40,000×)
method 10 5.0 3.2 1.7 98.3 and (b) Radiolytic Method (PVP/Pd: 40) (AV＝80 kV; mag­
(RRPd) 20 4.0 3.0 1.6 98.4 nification＝80,000×)39)
30 3.0 2.8 1.5 98.5
40 1 2.4 1.4 98.6
nanoparticles formed by chemical and radiolytic reduc­
tion methods.　TEM (transmission electron micro­
be due to the fact that readsorption of the first hydrogen­ scope) photographs of Pd nanoparticles (Fig. 6)
ation product is unlikely due to the weakly bound showed a distinct morphological change depending on
ligand (stabilizer) surrounding the nanoparticles.　 the method of preparation of nanoparticles.　Pd parti­
Influence of the surrounding ligands (stabilizer) on the cles prepared by ethanol reduction, showed particles
selectivity is evidenced from the observation of change with a square outline from which three dimensional
in 2-butene-1,4-diol selectivity with the change in the shapes determined were found to be cubic.　Similar
stabilizer in the present work39). morphology was observed for Pt and Au nanoparticles
In our work, the effect of the method of reduction on prepared by H2 gas and hydroxylamine hydrochloride
the morphology of metal nanoparticles and to investi­ as the reducing agents respectively41),42).　In contrast to
gate the effect of nanoparticle shapes on their catalytic this, the radiolytic reduction of PdCl2 gave colloidal Pd
activity.　For this purpose, the transition metal nano­ particles of spherical and oval shapes, 1-5 nm diameter.　
particles were prepared by reducing the corresponding The final structure and size of the clusters depend on
metal precursors by chemical and radiolytic methods39).　 the mechanism of growth process.　Effect of concen­
Several nanoclusters Pd catalyst samples were prepared tration of solvent and screening of various stabilizers
by varying the concentration of stabilizing polymer was also investigated in our work39).
(PVP) in each method.　The activity results along with Due to the inherent advantages of heterogeneous cat­
the particle sizes of various nanoclusters catalysts are alysts, recently Nadgeri et al. have reported supported
presented in Table 3.　It was found that the catalyst Pd nanoparticles in a narrow range of 3-5 nm for B3D
activity of RRPd (radiolytic reduction) catalyst was hydrogenation43) .　SEM (scanning electron micro­
higher than that of CRPd (chemical reduction) catalyst scope) of the sample after the deposition of Pd sol on
when PVP/ Pd ratio was 1, which was in accordance the carbon support clearly showed the palladium parti­
with the fact that the particle size of RRPd was less cles dispersed on the support which was also confirmed
(5.2 nm) than that of CRPd sample (7.1 nm).　As PVP/ by a simultaneous EDX (electron dispersive X-ray fluo­
Pd ratio was increased from 10 to 40, the activity trend rescence spectrometer) of the same sample with small
was reversed with respect to particle sizes and CRPd particles as a focus was taken and a plot of energy of
samples showed higher catalyst activities than that of X-rays emitted versus intensity is shown in Fig. 7.　
RRPd samples.　The catalyst activity of CRPd was The peaks corresponding to small particles were char­
maximum for PVP/PD ratio of 40, inspite of the fact acteristic of Pd metal obtained between 2-3 keV, ensur­
that particle size of RRPd sample was one 1/5th of that ing adsorption of Pd onto the carbon44).　The inter­
of CRPd sample.　The selectivity to B2D obtained was action between the negative charge of oxygen containing
more than 98％ for the Pd catalysts having PVP/Pd groups on an activated carbon surface and the cationic
ratio in the range of 1-30.　A further increase in PVP/Pd PVP causes the polymer to occupy the adsorption sites
ratio to 40 caused a marginal decrease in B2D selectivity on the carbon.　Supported nanoparticle Pd catalyst
from 98 to 91％ due to the formation of B1D.　In the showed the highest activity (an order of magnitude
case of catalysts prepared by the radiolytic method, the higher than the bulk Pd catalyst) for hydrogenation of
particle size reduced to 1 nm with increase in concen­ B3D to B2D.　Turn over frequency (TOF, h -1) for
tration of PVP.　Surprisingly, the activity was found to nanoparticle catalyst is higher due to the enhancement
reduce with decrease in particle size (Table 3).　This in rate of hydrogenation as evident from the hydrogen
trend can be attributed to difference of shape of the Pd absorption versus time plot for B3D shown in Fig. 8.　

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This dramatic enhancement of activity of supported Pd from those for the bulk palladium catalyst.　Since it
nanocluster catalyst is mainly due to the narrow particle was ensured quantitatively that external mass transfer
size distribution giving an average size of 4 nm, and effects were absent, the lower activation energy for the
very high dispersion of Pd0 nuclei.　The pulse titration nanoparticle Pd/C catalyst is purely due to its specific
(hydrogen) studies (Table 4) showed that the metal dis­ adsorption characteristic that is different from the bulk
persion found for the nano catalyst was＞65％ higher Pd catalyst.　Further study such as in-situ infrared and/
than that for the bulk Pd/C catalyst.　The low Pd load­ or adsorption isotherms need to be carried out to reveal
ing (0.25％) as well as the decreased average crystallite the nature of adsorption.
size (H/Pd ratio＝1) from 12.7 nm (bulk Pd) to 7.6 nm Another interesting feature of our catalyst was a change
for the nano catalyst contribute to a very high metal dis­ in selectivity pattern, the commercially used 1％ Pd/C
persion leading to the enhancement in the catalyst ac­ catalyst gave saturated diol, B1D as a major product45),46),
tivity.　The apparent activation energy of hydrogen­ while the supported Pd nanocluster catalyst gave almost
ation of butynediol to butenediol over Pd nanoparticle complete selectivity to the intermediate olefinic diol,
catalyst evaluated in our work was 13.6 kJ・mol-1 which B2D.　It is believed that α- and β-Pd_hydride species are
is about one third than that observed in the case of bulk formed during hydrogenation and that β sites promote
Pd catalyst (39.42 kJ・mol-1)21).　Such a dramatic de­ alkane selectivity due to mainly higher amount of
crease in apparent activation energy for nanoparticle Pd hydrogen dissolved within the particles47),48).　However,
catalyst suggests either (i) being a gas-liquid-solid reac­ it has been shown that for very small particles,
tion, the reaction could be operating under conditions β-Pd _ hydride phase is rarely formed49),50) , hence
such that the mass transfer resistances are significant or a dramatic size reduction in the case of nanocluster Pd/
(ii) the different adsorption characteristic of butynediol C catalyst could lead to the enhanced selectivity to the
olefinic diol.　The increased effect of steric hindrance
(geometric effect) due to the stabilizer in the case of the
protected Pd nanoparticles also contributes to the higher
selectivity to the olefinic diol39).

Reaction conditions: B3D 0.34 mol; catalyst 0.25％ Pd/CaCO3; H2

pressure 2.4 MPa; agitation 1000 rpm44).
Fig. 7　EDX of Pd Nanoparticles Supported on Carbon (a) Pd
Nanoparticles and (b) Carbon44) Fig. 8　Hydrogen Consumption vs. Time Plot

Table 4　Catalyst Characterization by Pulse Titration44)

Dispersion Metal surface area H2 adsorbed Crystallite size

Catalyst
[％] [m2・g-1] [μmol・g-1] [nm]
Pd/C bulk 8.8 0.10 1.03 12.7
Pd/C nano 14.7 0.16 1.73 7.6

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Scheme 2　Hydrogenation of B3D in Absence of Ammonia45)

4.　Platinum Catalysts

Although, Pd has been known as a very good catalyst

for the alkyne hydrogenations, it has also a strong activ­
ity towards double-bond isomerization due to which
several side products are normally formed in the hydro­
genation of B3D51).　In order to compare systematically
the performance of Pd and Pt catalysts we screened Pd
and Pt catalysts on various supports and it was found
that for Pt/CaCO3 catalyst, the products formed were
butenediol and butanediol.　No other side products
were observed.　B3D being an acetylenic compound, is
adsorbed strongly on the catalyst surface through two σ
metal carbon bonds can lead to the formation of several
types of species, which can be of dissociative or asso­
ciative nature and can exist at the same time on the cat­ Reaction conditions: temperature 323 K; concentration of B3D
alyst surface52),53).　Since, such species have very short 2.26 kmol・m-3; concentration of catalyst 0.86 kg・m-3; concentration
lifetime, it is very difficult to characterize them.　The of ammonia 17.5 mmol; agitation speed 13.3 Hz; liquid volume 1.5×
10-4 m3 45).
probable reaction pathway for the formation of B1D and
B2D in absence of ammonia and under the conditions of Fig. 9　Effect of Pressure on B1D Formation
the present work is shown in Scheme 2.　According to
this scheme, the dissociative and associative adsorption
of B3D, would give rise to the formation of carbyne and selectivity to B2D was achieved when Pt/CaCO3_NH3
carbene type intermediates.　Formation of B1D is pos­ catalyst system was used, possibly due to ammonia
sible either directly from carbyne type intermediate or occupying the available vacant sites on the catalyst sur­
via B2D hydrogenation through carbene species.　 face, which are responsible for the formation of carbyne
Carbyne and carbene type of intermediates have very species45).
short lifetime, however, the existence of ethylidyne 4. 1.　Alkali Metal Doped Pt Catalysts
intermediate on Pt (111) surfaces has been established In our continuing efforts for developing a more
by Somorjai et al. in acetylene hydrogenation54) .　 selective catalyst for this fundamentally as well as in­
Formation of carbyne type species is more favored dustrially important system, we focused our attention on
by accessible multiple sites and at high H2 partial studying the influence of the surface properties of bulk
pressures.　As shown in Fig. 9, selectivity to B1D platinum catalysts modified by introducing a solid (e.g.
increased with increase in H2 pressure indicating more an alkali metal carbonate) with basic properties for tai­
formation of carbyne species, which was also in accord­ loring the selectivity pattern in the hydrogenation of
ance with the earlier reports53),54).　Nearly complete 2-butyne-1,4-diol55)～58).　Though addition of ammonia

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increased the selectivity, it is always desirable to develop on the surface by alkali metal atoms (Li to Cs), to en­
catalysts consisting of promoters in solid state itself hance the selectivity to intermediate diol, B 2D.　
to obtain high purity products.　Therefore, the major Figure 10(b), shows the increase in B2D selectivity
objective of this work was to study the influence of the with increase in basic strength of (expressed in terms of
surface properties of bulk platinum catalysts modified chemisorbed CO2) doped catalysts while going from Li
by introducing a solid (e.g. an alkali metal carbonate) to Cs.　Among these catalysts, Li doped Pt showed the
with basic properties for tailoring the selectivity pattern lowest selectivity (90％, still higher than the undoped
in the hydrogenation of 2-butyne-1,4-diol.　The specific catalyst), while Cs doped Pt catalyst showed complete
surface areas of the platinum catalysts doped with vari­ selectivity to B2D.　A systematic change in the basic
ous alkali metals along with their activity (TOF, h-1) strength of the catalysts would cause an electron trans­
are presented in Table 5.　It was observed that the fer to Pt.　The increased electron density of Pt retards
surface area of the catalyst decreased with the alkali its capacity to share electrons with the adsorbate mole­
metal doping which was consistent with the increase in cules of reactant, intermediates and hydrogen.　As was
the sizes of doped alkali metals from Li to Cs.　The observed, the alkali metal doping enhanced the selectiv­
selectivity pattern presented in Fig. 10(a) show that 1％ ity to B2D, due to fast desorption of B2D before it got
Pt/CaCO3 catalyst gave 83％ selectivity to 2-butene­ readsorbed and get hydrogenated further to B1D.　
1,4-diol and 17％ selectivity to butane-1,4-diol in the Addition of ammonia (an electron donor) to the reaction
absence of any dopant.　As the platinum catalyst was mixture in hydrogenation of B3D over platinum catalyst
doped with alkali metals starting from Li to Cs, selec­ also exhibited enhanced selectivity to B2D45).　Similar
tivity to B2D increased from 83 to 100％ and that of observation has been reported for K-doped palladium
B1D decreased from 17 to 0％.　The Cs doped Pt cata­ catalyst in the case of acetylene hydrogenation59) .　
lyst showed complete selectivity to B2D without forma­ While studying B3D conversion versus B2D selectivity
tion of B1D.　We attempted to study the electronic pattern, almost complete selectivity to B2D was ob­
effect by changing the atoms surrounding a metal atom served up to 23％ conversion of B3D.　The selectivity
to B2D decreased from 99 to 83％ (the remaining prod­
Table 5　Activity of Alkali Metal Doped Platinum Catalysts58) uct was B1D) with increase in conversion from 30 to
99.6％58).　Thus, the formation of B1D was suppressed
Crystallite until almost all B3D was consumed confirming again
Catalyst Doped alkali TOF×10-4 Surface area
size of Pt
code carbonate [h-1] [m2・g-1] the strong adsorption of B3D on the catalyst surface
[nm]
similar to the behaviour of palladium based catalysts21).
1aa) — 1.98 28.22 12.4
4. 2.　Continuous Hydrogenation of B3D to B2D and
1b Li2CO3 1.62 32.42 10.8
1c Na2CO3 1.60 34.32 10.5 B1D
1d K2CO3 1.55 35.42 9.8 For 1％ Pt/CaCO3 catalyst, the products of B3D
1e Rb2CO3 1.35 38.36 8.0 hydrogenation formed were B2D and B1D and Table 6
1f Cs2CO3 1.16 41.5 7.2 shows the variation of conversion and selectivity as a
a) Pt/CaCO3. function of contact time defined as a ratio of catalyst

Reaction conditions: temperature 323 K; H2 pressure 2.4 MPa; concentration of B3D 2.26 kmol・m-3; concen­
tration of catalyst 0.86 kg・m-3; agitation speed 13.3 Hz; liquid volume 1.5×10-4 m3.　Doping in catalysts: 1a,
no doping; 1b, Li2CO3; 1c, Na2CO3; 1d, K2CO3; 1e, Rb2CO3; 1f, Cs2CO3 58).

Fig. 10　Effect of Alkali Metal Doping (a) and Basicity (b) on Selectivity Pattern

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Table 6　Activity and Selectivity Pattern for Continuous Hydrogen­ with the experimental results60).
ation of B3D over 1％ Pt/CaCO3 Catalyst60)

W/F Conversion Selectivity [％] 5.　Conclusions

Sr. No.
[h] [％] B1D B2D
Based on our work on hydrogenation of B3D using
1 0.33 14 34 66
various catalyst systems, the following conclusions can
2 0.50 30 42 58
3 0.66 40 49 51 be drawn.
4 1.11 55 59 41 (1) Pd on carbon and alumina supports gave high TOF
5 2 78 73 27 and butane-1,4-diol as the major product, while cis-
2-butene-1,4-diol was selectively obtained with Pd/
CaCO3_ NH3 catalyst system.　Ammonia played an
important role in improving the selectivity towards
butenediol.　Hydrogen pretreatment of the catalyst was
found to enhance the catalyst activity possibly due to
the formation of highly active β-Pd_H sites.　The cata­
lyst was found to retain its activity up to ten recycles
giving a total TON of 1.86×104, which is an order of
magnitude higher than the literature value.　A rate
equation has been proposed based on the initial rate
data and intrinsic kinetic parameters were evaluated.　
The activation energy was found to be 39.42 kJ・mol-1.　
A theoretical model was also developed to predict the
concentration versus time profiles and the predicted and
observed results were found to agree well under wide
range of conditions.
(2) Pd nanocluster catalysts stabilized by a polymer
were prepared by two methods in which metal precur­
Reaction conditions: liquid flow rate 20 ml・h -1; catalyst weight sor reduction was accomplished by a chemical reagent
20 mg; H2 flow rate 20 l・h-1 60).
and with γ irradiation from a 60Co source.　These cata­
Fig. 11　Effect of Hydrogen Pressure on the Selectivity of B2D and lysts showed a very high catalytic activity (10-40 times
B1D more) in hydrogenation B3D to B2D compared with the
corresponding conventional Pd catalysts.　However,
loading to the liquid flow rate (W/F, h).　Obviously, the chemically reduced nanoclusters of Pd catalyst was
the conversion of B3D increased with increase in con­ more active than that prepared by radiolysis method.　
tact time.　The selectivity pattern was completely dif­ The other important parameters found to affect catalytic
ferent from that found in the case of batch slurry opera­ activity and selectivity were type and concentration of
tion in which B1D selectivity was very much higher stabilizing polymer and solvent to water ratio in chemi­
(83％) than the B2D selectivity (17％)45).　As can be cally reduced method.　The supported palladium
seen from Table 6, varying the contact time at different nanoparticles also showed a very high catalytic activity
conversion levels could vary the selectivity to both B2D with ease of separation and recyclability.　These
as well as B1D over a wide range.　This is an attractive nanoparticles were characterized by SEM-EDX and
option for a commercial operation where the desired their size distribution was found to be in the range of
products mix of B1D and B2D can be achieved depend­ 3-5 nm.
ing on the fluctuation in the market demand.　It was (3) Hydrogenation of B3D using Pt/CaCO3 gave a mix­
interesting to note that with increase in H2 pressure, the ture of B1D and B2D without formation any other side
selectivity pattern of B2D and B1D was exactly opposite products (unlike the Pd catalyst).　A very high selec­
to each other (see Fig. 11).　In the lower range of H2 tivity to the intermediate olefinic diol (B2D) in hydrogen­
pressure (10-40×105 Pa), the difference between the ation of B3D could be achieved by platinum catalysts
selectivities of B2D and B1D was larger and eventually doped with alkali metals as compared to the mono­
50 : 50 formation of B2D and B1D could be obtained at metallic platinum catalysts.　Selectivity enhancement
70×105 Pa H2 pressure.　In this work, data was col­ of B2D was mainly due to the suppression of second
lected for various inlet conditions such as liquid flow stage hydrogenation of B2D to B1D due to enhanced
rate, H2 flow rate, catalyst loading, temperature under electron density of platinum as indicated by increase in
steady state conditions and a reactor model was devel­ the basic strength of platinum catalysts doped with
oped for continuous B3D hydrogenation.　The predic­ alkali metals.
tions of the model equations was in good agreement (4) Continuous hydrogenation of B3D was also studied

J. Jpn. Petrol. Inst., Vol. 51, No. 3, 2008

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要　　　旨

2-ブチン-1,4-ジオールの水素化触媒反応：活性，選択性，速度論研究

Chandrashekhar V. Rode

Chemical Engineering & Process Development Div., National Chemical Laboratory, Pune 411008, INDIA

2-ブチン-1,4-ジオール水素化反応では，cis-2-ブテン-1,4-ジ 選択性が増大すること，ナノ構造を有するパラジウムコロイド
オールとブタンジオールが得られるが，並行反応や逐次的異性 および担持パラジウム触媒では cis-2-ブテン-1,4-ジオールへの
化反応により種々の化合物が副生する。工業的にはブテンジ 水素化活性が通常の含浸触媒と比べて 10 ～ 40 倍も向上するこ
オールとブタンジオールの選択性を制御することが重要とな とが分かった。また，白金触媒はパラジウム触媒よりも 2- ブ
る。この選択性制御においては，基質である 2-ブチン-1,4-ジオー チン-1,4-ジオール水素化反応は低いが副反応が抑制されること
ルの活性点への吸着特性が重要となる。本総説では，担持パラ が分かった。特に，塩基強度の大きなアルカリを添加した白金
ジウムナノ粒子触媒，パラジウムコロイドそして担持白金触媒 触媒においては，中間種の脱離が促進され cis-2-ブテン-1,4-ジ
による 2-ブチン-1,4-ジオールの水素化反応における添加物効 オールの選択性が向上すること，連続水素化反応システムを用
果，触媒前処理効果，速度論的解析結果について示す。1％ いて白金触媒により水素化反応を行うと，接触時間を変えるこ
Pd/CaCO3 触媒では反応系内にアンモニアを添加させることで， とにより cis-2-ブテン-1,4-ジオールとブタンジオールの生成比
ブタンジオールの生成が抑えられ cis-2-ブテン-1,4-ジオールの を広い範囲で制御できることが分かった。

J. Jpn. Petrol. Inst., Vol. 51, No. 3, 2008