Ind. Eng. Chem. Res.

1997, 36, 2885-2896 2885

Liquid Phase Hydrogenation of Maleic Anhydride and

Intermediates on Copper-Based and Noble Metal Catalysts
Uwe Herrmann and Gerhard Emig*
Lehrstuhl fu r Technische Chemie I der Universita t Erlangen-Nu rnberg, Egerlandstrasse 3,
D-91058 Erlangen, Germany

The liquid phase hydrogenation of maleic anhydride and intermediates was investigated using
copper-based and noble metal catalysts. The experiments were performed in a stirred tank
slurry reactor in discontinuous as well as continuous operation. Copper chromites and noble
metal catalysts were found to be suitable for the hydrogenation of maleic anhydride. However,
the hydrogenation of succinic anhydride proceeded with high selectivity to -butyrolactone and
1,4-butanediol on copper zinc catalysts, whereas other copper catalysts revealed no activity in
the formation of 1,4-butanediol. Selective sorption interactions of succinic anhydride with the
zinc surface were assumed to be responsible for this effect. Starting from -butyrolactone all
copper catalysts were active in the formation of 1,4-butanediol while noble metal catalysts showed
no or little activity. Kinetic models have been proposed for the hydrogenation of maleic anhydride
and intermediates on the basis of experimental data obtained in a continuously operated stirred
tank slurry reactor.

Introduction acetoxylation of 1,3-butadiene (Mitsubishi process)

1,4-Butanediol is of major interest as a starting
material for the production of important polymers.
Examples are polyurethanes and poly(butylene tere-
phthalate) based on 1,4-butanediol, which are mainly
used for engineering plastics as well as for the synthesis
of fibers, films, and adhesives. Furthermore, 1,4-
butanediol is a major feedstock for the production of
tetrahydrofuran, which is synthesized by homogeneous
dehydration. In 1992 in the U.S. above 50% of 1,4-
butanediol was converted to tetrahydrofuran (Weisser-
mel and Arpe, 1994). Tetrahydrofuran is applied as a
solvent for PVC and as a monomer for the formation of
polytetramethylene glycol, which is used as intermedi-
ate for Spandex fibers and polyurethanes (Weissermel
and Arpe, 1994; Harris and Tuck, 1990). Dehydroge-
nation of 1,4-butanediol on copper catalysts leads to the
formation of -butyrolactone, which is another major
solvent. The reaction of -butyrolactone with methyl-
amine or ammonia results in the formation of N-
methylpyrrolidone and 2-pyrrolidone. Both chemicals
are used as solvents, and additionally 2-pyrrolidone is
in demand as a raw material for pharmaceuticals
(Mitsubishi, 1988; Minoda and Miyajima, 1970).
Currently the majority of 1,4-butanediol is produced
by the Reppe process applied by BASF, Huls, DuPont,
and other several major companies (Brownstein, 1991).
Acetylene and formaldehyde are used as starting ma-
terials. In the U.S. in 1992 nearly 90% of the 1,4-
butanediol synthesized was produced according to the
Reppe process (Weissermel and Arpe, 1994). Several
disadvantages within the process led to the development
of alternative routes for the synthesis of 1,4-butanediol.
Disadvantages are, e.g., severe reaction conditions, the
use of acetylene (implying explosion hazard) and form-
aldehyde (with possible cancerogenic effects), and the
necessity to perform a multistep reaction pathway. The
most important alternatives to the Reppe process are
the hydrogenation of maleic anhydride or its esters, the
conversion of propylene oxide (Arco process), and the
* To whom correspondence should be addressed. E-mail:
emig@tc.uni-erlangen.de.
S0888-5885(96)00229-1 CCC: $14.00
(Tamura and Kumano, 1980; Tanabe, 1981).
Maleic anhydride has become an interesting feedstock
for the synthesis of -butyrolactone, 1,4-butanediol, and
tetrahydrofuran in the past. A major reason is the
improved and therefore more economic maleic anhy-
dride production with n-butane as starting material
(Contractor and Sleight, 1987). Competitive maleic
anhydride processes were established based on fluidized
bed processes used by, e.g., Lummus/Alusuisse (ALMA),
BP/UCB, and DuPont companies (Contractor, 1995). A
technical application of the maleic anhydride hydroge-
nation to 1,4-butanediol is currently performed in Japan
using a two-step process on NiRe and NiCo catalysts
(Weissermel and Arpe, 1994). The reaction pathway of
the hydrogenation of maleic anhydride to 1,4-butanediol
and tetrahydrofuran is illustrated in Figure 1. The
reaction proceeds via succinic anhydride which is con-
verted to -butyrolactone. The hydrogenation of -bu-
tyrolactone to 1,4-butanediol is followed by an acid-
catalyzed dehydration to tetrahydrofuran. As one can
see from Figure 1, the use of maleic anhydride results
in the production of the above mentioned high value
products within a single reaction path. Furthermore,
the composition of the product mixture can be influenced
substantially by a variation of the reaction conditions
(Brownstein and List, 1977).
Most publications regarding the hydrogenation of
maleic anhydride are patent literature. In general,
patent literature provides the coverage of a special
invention without giving comprehensive informations
on catalyst activities or kinetics. In most cases copper-
based catalysts are mentioned regarding the gas phase
hydrogenation of maleic anhydride to 1,4-butanediol and
tetrahydrofuran (Budge, 1990; De Thomas et al., 1992).
Liquid phase hydrogenation of maleic anhydride is
performed using copper-, cobalt-, or nickel-based cata-
lysts (Eggersdorfer et al., 1989; Budge et al., 1993) as
well as noble metal catalysts containing, e.g., Pd, Re,
or Ru (Freudenberger and Wunder, 1978; Attig and
Graham, 1989). Previous studies on the hydrogenation
of maleic anhydride were carried out mainly using
copper chromite catalysts. Experiments were performed
to investigate the influence of the catalyst composition
1997 American Chemical Society
2886 Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997

Table 1. Composition and Structure of Catalysts Used in Screening Experiments

type composition (wt %) composition (atom %) carrier/structure surface area (m2/g) supplier
G 66 26 Cu 33 Cu mixed oxide 30.8 Sud-Chemie AG
53 Zn 67 Zn without carrier
R 3-12 32 Cu 50 Cu mixed oxide on 118.7 BASF AG
32 Zn 50 Zn Al2O3
G 13 40 Cu 61 Cu spinel-type 46.7 Sud-Chemie AG
26 Cr 39 Cr
G22 33 Cu 46 Cu spinel-type 44.3 Sud-Chemie AG
27 Cr 38 Cr
11 Ba 16 Ba
G 99 36 Cu 50 Cu spinel-type 41.7 Sud-Chemie AG
32 Cr 44 Cr
2 Ba 3 Ba
2.5 Mn 3 Mn
R 3-11 30 Cu 100 Cu oxide on Mg2SiO4 211.6 BASF AG
T 4489 40 Cu 65 Cu mixed oxide 49.5 Sud-Chemie AG
15 Al 24 Al without carrier
7 Mn 11 Mn
PdRe/C 1 Pd 20 Pd mixed oxide on 1088.0 Degussa AG
4 Re 80 Re activated carbon
PdReCuZn/C 1 Pd 3 Pd mixed oxide on
4 Re 11 Re activated carbon
15 Cu 43 Cu
15 Zn 43 Zn
Pd/C 1.5 Pd 100 Pd oxide on activated carbon 806.8 Heraeus GmbH
Ru/C 1.5 Ru 100 Ru oxide on activated carbon 1220.9 Heraeus GmbH

Furthermore, experiments were carried out on a modi-

Figure 1. Reaction scheme of the hydrogenation of maleic
anhydride to 1,4-butanediol/tetrahydrofuran.
and structure on the catalytic activity of maleic anhy-
dride (Castiglioni et al., 1995; Messori and Vaccari,
1994). No emphasis was placed on the formation of 1,4-
butanediol.
The present paper includes an investigation of the
activity of different copper-based catalysts on each
reaction step, illustrated in Figure 1. Additional experi-
ments using noble metal catalysts provided a useful
comparison between both types of catalysts. Catalytic
activity toward the formation of 1,4-butanediol starting
from different substrates was stressed. On the basis
of the results obtained, the performance of different
types of catalysts was investigated in the continuous
way of operation, taking into account the industrial
relevance of a single-step hydrogenation to 1,4-bu-
tanediol. In order to obtain quantitative data, kinetic
measurements and a kinetic modeling were performed
for each reaction step using noble metal and copper zinc
catalysts.
Experimental Section
Catalysts and Reaction Procedure. The catalysts
used for hydrogenation of maleic anhydride, succinic
anhydride, and -butyrolactone are commercially avail-
able from companies BASF, Sud-Chemie, and Heraeus,
Germany. An exception is PdRe/C, which was synthe-
sized by Degussa, Germany, for laboratory use only. The
chemical composition and the designation of these
catalysts are illustrated in Table 1. As all catalysts
were supplied in the form of tablets, the material was
crushed and sieved to obtain the desired fraction of 80-
150 m. The experiments were performed using this
fraction unless otherwise mentioned. PdRe/C was sup-
plied as a wet powder of 25 m and used in this fraction.
fied PdRe/C catalyst impregnated with a copper zinc
acetate solution (PdReCuZn/C). The copper and zinc
contents in this catalyst were detected to be 15 wt %
each. Before use, the catalysts were dried and activated
in a fluidized bed in nitrogen and a mixture of nitrogen
and hydrogen, respectively. Drying was performed at
423 K for 1 h with pure nitrogen. The activation was
performed subsequently with 6 vol % hydrogen at 473
K for 1.5 h and finally at 473 K with 12 vol % hydrogen
for 15 h. After this procedure, which was applied to
noble metal based and copper-based catalysts, the
material was kept under nitrogen atmosphere to avoid
partial oxidation and to guarantee identical starting
conditions for all experimental runs. Hydrogen, nitro-
gen, and methane were supplied by Linde, Germany,
with >99.99% purity and used directly from the cylin-
der. The components maleic anhydride, succinic anhy-
dride, and -butyrolactone as well as n-tetradecane were
delivered by Fluka AG, Germany, with >99% purity.
Methane and n-tetradecane were used as internal
standards for the gaseous and liquid phase. 1,4-
Dioxane, which proved to be inert, was used as a solvent
in both discontinuous and continuous reactor operation
(>99% purity supplied by Merck, Germany).
The reaction conditions applied for discontinuous
experiments are illustrated in Table 2. Continuously
performed experiments were carried out at T ) 543 K
and p ) 7.5 MPa using a catalyst loading of 17.4 kg/
m3. The feed rates of liquid and gas were 4.2 mL/min
and 1000 normal mL/min, respectively. The feed con-
centration of maleic anhydride was 0.5 mol/L.
Kinetic measurements were performed by varying the
feed concentration and reactor pressure at constant feed
rates. Table 5 illustrates the range of operating condi-
tions. The liquid and gas feed rates were 6.5 mL/min
and 1000 normal mL/min. The particle size used was
80-150 m. The temperatures were kept constant at
T ) 418 K for maleic anhydride hydrogenation, T ) 543
K for succinic anhydride hydrogenation, and T ) 483
K for the hydrogenation of -butyrolactone. Activation
energies were determined by performing runs in tem-
perature ranges outlined in Table 5.

Table 2. Operating Conditions for Discontinuous Catalyst Testing
substrate ci,0 (mol/L) pressure (MPa)
maleic anhydride 1.0 5.0
succinic anhydride 0.56 7.5
-butyrolactone 0.56 7.5
Figure 2. Reconstruction of the reactor head for continuous
operation: PI, pressure indicator.
Apparatus. Discontinuously Operated Reactor.
All experiments were carried out in a stainless steel (SS-
316) stirred tank reactor with 63.5 mm internal diam-
eter and 152 mm height (Parr Instruments, Model
4562). To provide a high gas-liquid interfacial area,
the turbine stirrer was replaced by a gas entrainment
impeller. The impeller speed was variable and could
be increased up to 1700 rpm. Liquid samples were
drawn by means of a sampling tube equipped with a
sinter metal filter to avoid the loss of suspended
catalyst. The liquid samples could be either injected
into the port of a gas chromatograph or fed into an
continuously operating evaporizer. Analysis of the
gaseous phase was performed by means of the sampling
loop of the gas chromatograph. Liquid samples were
analyzed by mixing the substrate with a defined amount
of n-tetradecane, which was inert under the applied
reaction conditions. Methane was used as internal
standard for the gaseous phase. Discontinuous experi-
ments were carried out by charging the reactor with the
desired amount of substrate, internal standard, and
solvent. Then catalyst was added under nitrogen
atmosphere. Finally, the reactor was pressurized and
heated up to the desired temperature. According to the
gas consumed, hydrogen was added discontinuously to
maintain a constant pressure.
Apparatus. Continuously Operated Reactor. In
order to carry out continuous experiments, some recon-
structions of the equipment had to be carried out. The
problem of maintaining a constant pressure and liquid
level inside of the reactor vessel during continuous runs
could be solved by adding an additional dip tube into
the reactor. As all outlets of the reactor head were
occupied, the tube was installed coaxially to the sam-
pling line as illustrated in Figure 2. The sampling line
was connected to a regulating valve which controls the
sampling frequency. The dip tube was fixed to an
overflow valve. This overflow valve simultaneously
controlled the pressure in the reactor and the level of
the liquid. To avoid loss of catalyst during continuous
operation, both the sample line and the dip tube were
provided with a sinter metal filter. A change in reactor
pressure could be easily achieved by the adjustment of
the overflow valve. The liquid level was varied by
replacing the dip tube. To carry out automatically
performed runs, all essential functions were controlled
Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 2887
temp (K) catalyst loading (kg/m3) particle size (m)
463 12 80-150 (PdRe/C: 25)
513 12 80-150 (PdRe/C: 25)
513 12 80-140 (PdRe/C: 25)
by a personal computer. The liquid phase was fed by a
Kontron 422 HPLC pump with a flow rate up to 20 mL/
min. The gas feed was provided by thermal mass flow
controllers (Brooks 5850 E) in the range 0-1000 normal
mL/min. Figure 3 shows the flow chart of the ap-
paratus.
Analytical Setup. Analysis of gaseous and liquid
reactants was performed by means of gas chromatog-
raphy (Hewlett-Packard 5890 Series II with flame
ionization detector and thermal conductivity detector).
The gas chromatograph was equipped with a medium
polar HP-5 column (cross-linked phenyl silicone) and a
polar HP-FFAP column (cross-linked polyethylene gly-
col). Both columns had 0.53 mm internal diameter and
were 30 m long. The analysis was optimized by using
temperature and pressure programs in the range from
353 to 503 K and 40 to 180 kPa. Quantitative analysis
of the compounds in the product mixture was performed
using a Hewlett-Packard 3396 Series II integrator.
Peak areas were converted into concentrations using the
internal standard method (Schomburg, 1987). Evalu-
ation of quantitative amounts of substrate and products
can be easily performed by means of the internal
standard in both discontinuous and continuous opera-
tion. The mass balance for any species i in the reactor
is
dci N
VR
dt
) V L,0ci,0 - V Lci + VR
j)1
ijrj (1)
Preliminary measurements of the residence time
distribution showed that the continuous stirred tank
reactor could be considered to be free from dead spaces
or bypass effects under the conditions used in the
present work. This results in uniform concentrations
in the reactor vessel and allows the use of the above
equation. The application of this equation for an
internal standard shows that in the case of chemical
inertness (rj ) 0) and in a stationary state of the reactor
(dci/dt ) 0) the concentration is constant assuming V L,0
) V L. Accordingly, the concentration of the standard
in the product mixture is known and can be used as a
reference for calculating the concentrations of the
reactants. On the basis of the concentrations of the
reactants the conversion Xi, yield Yk,i, and selectivity
Sk,i were calculated as follows:
||
ci,0 - ci ck i Yk,i
Xi ) Yk,i ) Sk,i )
ci,0 ci,0 k Xi
Results and Discussion
The main subjects which should be answered by the
present work are as follows: (i) Finding suitable cata-
lysts and reaction conditions for the hydrogenation of
maleic anhydride, succinic anhydride, and -butyrolac-
tone in the liquid phase. (ii) Determination of a suitable
subdivision of the multistep reaction into appropriate
steps using results achieved in discontinuously as well
as continuously performed experiments. (iii) Evaluation
of kinetics of the reaction steps outlined in Figure 1 in
2888 Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997

Figure 3. Flow chart of the apparatus: V, valve; manually actuated marked by a rectangle, automatically operated marked by a circle;
EV, evacuator; EP, evaporizer; S1, S2, sampling manually and automatically; M, stirring motor; PI, pressure indicator; PIC, pressure
indicator and controller; TI, temperature indicator; TIC, temperature indicator and controller; WI, weight indicator; FIC, flow indicator
and controller; LC, level controller.

Figure 4. Conversion of maleic anhydride vs reaction time on noble metal catalysts and copper chromites (left) and copper-based catalysts
(right) (T ) 463 K, p ) 5.0 MPa).
a continuously operated stirred tank slurry reactor
considering mass transfer resistances.
Hydrogenation in Discontinuous Operation. The
hydrogenation of maleic anhydride to succinic anhydride
is known to proceed rapidly (Kanetaka et al., 1970a).
Therefore mild reaction conditions were applied for this
step (see Table 2). Figure 4 illustrates the obtained
results using the catalysts mentioned above. The most
active catalysts for the hydrogenation of maleic anhy-
dride were found to be noble metals. No remarkable
differences in conversion can be discerned between
PdRe/C, Pd/C, and Ru/C catalysts. Copper chromites,
which provide an almost total conversion of the sub-
strate after 5 h reaction time, were less active. The
copper chromite G 22 unveils the lowest activity com-
pared to G 13 and G 99, which can be possibly reduced
to the smaller copper content. Copper-based catalysts
without spinel structure proved to be less active for the
hydrogenation of maleic anhydride. Among these cata-
lysts the copper zinc containing G 66 showed the
smallest activity, probably due to the absence of a
carrier material. A comparison between the copper
catalyst T 4489 and the copper chromite G 13, which
both contain 40 wt % of copper, unveils a higher activity
of the latter regarding the hydrogenation of maleic
anhydride. This effect illustrates the influence either
of the additional component chromium or of the pres-
ence of a spinel structure on the activity. The hydro-
genation of maleic anhydride results mainly in the
formation of succinic anhydride. The formation of
-butyrolactone is low under mild reaction conditions
using copper-based catalysts. The yield of -butyrolac-
tone for copper-based catalysts was below 5%. Regard-
ing noble metal catalysts, yields were 5% (PdRe/C),
13.5% (Ru/C), and 54% (Pd/C). The only byproduct
formed was tetrahydrofuran (YTHF,MA 1.2%) when

Figure 5. Conversion of succinic anhydride vs reaction time on noble metal catalysts and copper chromites (left) and copper-based
catalysts (right) (T ) 513 K, p ) 7.5 MPa).
Figure 6. Product selectivities on the hydrogenation of succinic anhydride (SA) after 5 h (T ) 513 K, p ) 7.5 MPa).
using copper zinc catalysts. The formation of tetrahy-
drofuran on copper zinc catalysts proceeded simulta-
neously to -butyrolactone, which indicates a direct
reaction pathway from -butyrolactone to tetrahydro-
furan without 1,4-butanediol being formed as an inter-
mediate. The direct hydrogenation of -butyrolactone
to tetrahydrofuran is no novelty and is described by
Turek et al. (1994) on the gas-phase hydrogenolysis of
dimethyl succinate. With none of the catalysts, 1,4-
butanediol was produced under the conditions applied
for the hydrogenation of maleic anhydride.
As outlined above, the hydrogenation of succinic
anhydride proceeded slowly at the reaction conditions
applied for the maleic anhydride conversion. For this
reason the investigation of the hydrogenation of succinic
anhydride was carried out at a higher temperature
using a higher pressure (see Table 2). Figure 5 shows
the conversion of succinic anhydride versus operation
time. First of all, it can be seen that the order of activity
observed on the hydrogenation of maleic anhydride has
changed regarding the conversion of succinic anhydride.
Copper zinc catalysts, which unveiled only a low activity
for the hydrogenation of maleic anhydride, were more
active than copper chromites or other zinc absent copper
Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 2889
catalysts. The rate of conversion on copper zinc cata-
lysts is comparable with noble metal catalysts, which
were active for both the hydrogenation of maleic anhy-
dride and succinic anhydride. The presence of zinc is
responsible for an increase of the activity in the hydro-
genation of succinic anhydride resulting in a high rate
of conversion. Castiglioni et al. (1993) found a positive
effect of zinc toward the conversion of succinic anhydride
in the gas phase hydrogenation of maleic anhydride
using modified copper chromite catalysts. The copper
chromites investigated in the present work showed a
low activity in the hydrogenation of succinic anhydride
compared to copper zinc catalysts. The copper catalysts
R 3-11 and T 4489 as well as copper chromites showed
no activity in the formation of 1,4-butanediol. We found
a conversion of succinic anhydride to -butyrolactone
of 100% and 70% on R 3-11 and T 4489, respectively,
after finishing the experiment. Figure 6 illustrates the
product selectivities related to succinic anhydride after
5 h of reaction time. Besides the enhancement of the
conversion rate of succinic anhydride outlined above,
zinc has a marked influence on the product selectivities.
The use of copper zinc catalysts (G 66, R 3-12) results
in the formation of a mixture of -butyrolactone and 1,4-
2890 Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997
Figure 7. Conversion of -butyrolactone vs reaction time on copper-based and noble metal catalysts (T ) 513 K, p ) 7.5 MPa) (left).
Selectivity to 1,4-butanediol vs conversion of -butyrolactone on different catalysts (T ) 513 K, p ) 7.5 MPz) (right).
Table 3. Product Selectivities on the Hydrogenation of -Butyrolactone after 5 h (%) (T ) 513 K, p ) 7.5 MPa)
G 66 R 3-12 G 13 G 22
1,4-butanediol 95.0 77.8 76.3 87.9
tetrahydrofuran 4.1 16.5 14.5 4.0
1-butanol 2.0 4.5 2.1 8.8
propionic acid 0 0 0 0
butanediol. Both copper zinc catalysts convert succinic
anhydride to valuable products with a selectivity of more
than 90%. The absence of zinc results in the formation
of -butyrolactone and small amounts of tetrahydrofu-
ran (R 3-11) and 1-butanol (T 4489). No 1,4-butanediol
is formed using these catalysts. The same refers to
copper chromites, which convert succinic anhydride to
-butyrolactone with poor selectivities below 80%.
Among noble metal containing catalysts, PdRe/C exclu-
sively showed an activity in the formation of 1,4-
butanediol. Pd/C and Ru/C are converting the substrate
to -butyrolactone and a small amount of propionic acid.
Other byproducts using PdRe/C are 1-butanol and
tetrahydrofuran. As illustrated in Figure 6 the presence
of zinc promotes the formation of 1,4-butanediol. Pos-
sibly zinc provides active sites for the hydrogenation of
-butyrolactone or enables the adsorption of -butyro-
lactone on the copper surface. Catalytic tests using
-butyrolactone as a starting material should give
further information on the role of zinc and copper on
the hydrogenation activities forming 1,4-butanediol.
Figure 7(left) shows the conversion of -butyrolactone
versus reaction time on the catalysts outlined in Table
1. Copper-containing catalysts unveil a comparable
activity independent of additional elements as, e.g.,
chromium, zinc, and aluminum. The horizontal line in
Figure 7(left) indicates the value for the equilibrium
conversion of -butyrolactone. It is exceeded due to the
formation of byproducts tetrahydrofuran and 1-butanol.
Table 3 illustrates the product selectivities referred to
-butyrolactone after 5 h of reaction time. A comparison
of Figures 5 and 7(left) indicates that the conversion of
-butyrolactone to 1,4-butanediol is possible on copper
catalysts in principle. Starting from succinic anhydride
the formation of 1,4-butanediol fails to proceed in the
absence of zinc even if high yields of -butyrolactone
were observed. It is likely that the presence of a small
amount of succinic anhydride prevents the adsorption
of -butyrolactone on copper-based, zinc-absent cata-
lysts. It is possible that the presence of zinc provides a
reduction of the coverage of the copper surface due to
selective adsorption of succinic anhydride. A similar
G 99 R 3-11 T 4489 PdRe/C Ru/C Pd/C
81.4 58.6 71.2 20.7 0 0
6.2 22.5 14.5 20.5 16.7 4.8
4.4 4.2 5.6 31.6 0 0
0 0 0 0 0 0
interaction of dimethyl succinate with zinc oxide on the
gas phase hydrogenolysis of dimethyl succinate is
reported by Turek et al. (1994) as well.
No higher catalytic activity is observed on the hydro-
genation of -butyrolactone on copper zinc catalysts
compared to copper catalysts in which zinc is absent.
This indicates that zinc or zinc oxide does not provide
additional sites for the chemical reaction of -butyro-
lactone to 1,4-butanediol but for the selective adsorption
of succinic anhydride. Noble metal catalysts which
showed a high rate of conversion for maleic and succinic
anhydride were little effective on the hydrogenation of
-butyrolactone. PdRe/C revealed an approximate 70%
conversion of the substrate which was unselective to 1,4-
butanediol as shown in Table 3. The use of Pd/C and
Ru/C resulted in little conversion of -butyrolactone.
Unknown byproducts formed on Pd/C resulted in a loss
of identified organic species of approximately 25% after
5 h of reaction. Figure 7(right) illustrates the selectivity
to 1,4-butanediol versus the conversion of -butyrolac-
tone. On PdRe/C the selectivity which is above 50% at
a 15% conversion of -butyrolactone decreases due to
the formation of tetrahydrofuran, 1-butanol and un-
known byproducts. The selectivities obtained with
copper-based catalysts are far better and remain at a
high level as illustrated for the copper zinc catalyst G
66. The selectivity to 1,4-butanediol obtained on R 3-12
decreases from approximately 100% due to the forma-
tion of tetrahydrofuran probably induced by the acid
carrier material Al2O3.
The results of discontinuously operated screening
experiments give reason for the assumption that a
hydrogenation of maleic anhydride to the target product
1,4-butanediol can be achieved using different types of
catalysts and/or reaction conditions. One possibility
may be the use of a noble metal catalyst for the
conversion of maleic anhydride to -butyrolactone in one
reactor unit. The formed -butyrolactone should be
easily converted in a second reactor using copper-based
catalysts. Another path may be the hydrogenation of
maleic anhydride to succinic anhydride followed by the

Table 4. Conversion and Product Yields on Continuous Hydrogenation of Maleic Anhydride (%) (T ) 543 K, p ) 7.5
MPa)
G 66 R 3-12 G 99 R 3-11
maleic anhydride conversion 96.6 100 99.5 93.5
succinic anhydride 0 0 68.6 66.5
-butyrolactone 61.1 64.5 27.5 25.3
1,4-butanediol 16.9 26.0 0 0
tetrahydrofuran 6.0 4.9 0.2 0.6
1-butanol 0 0.8 0 0
propionic acid 0 0 0 0
Figure 8. Conversion of maleic anhydride and product yields on
continuous hydrogenation vs time-on-stream: MA, maleic anhy-
dride; SA, succinic anhydride; g-BL, -butyrolactone; 1,4-BD, 1,4-
butanediol; THF, tetrahydrofuran; n-BuOH, 1-butanol (T ) 543
K, p ) 7.5 MPa).
conversion of succinic anhydride to 1,4-butanediol over
copper zinc catalysts as illustrated in Figure 6.
Hydrogenation in Continuous Operation. Table
4 illustrates the results of continuously performed
experiments. In addition to the experiments outlined
above, a mechanical mixture of a noble metal catalyst
and a copper zinc catalyst (Ru/C + R 3-12) as well as a
modified PdRe/C catalyst (PdReCuZn/C) was used.
Experiments on these catalysts were carried out to focus
attention on the role of zinc on the hydrogenation of
maleic and succinic anhydride. Pd/C is not listed in
Table 4 due to marked deactivation found in the
continuous hydrogenation of maleic anhydride. The
catalyst G 99 was chosen as a representative for copper
chromites.
Table 4 illustrates that no succinic anhydride was
formed using copper zinc catalysts (G 66 and R 3-12).
Similar to the results obtained in discontinuous hydro-
genation of succinic anhydride, a mixture of -butyro-
lactone and 1,4-butanediol was formed. Byproducts
were tetrahydrofuran and 1-butanol. The hydrogena-
tion of maleic anhydride seems to proceed directly to
-butyrolactone and 1,4-butanediol. Figure 8 illustrates
the conversion of maleic anhydride and the yields of the
products formed over a copper zinc on alumina catalyst
(R 3-12) versus time-on-stream. A noticeable formation
of succinic anhydride occurs only at the beginning of
the reaction. In a steady state, no desorption of succinic
anhydride into the solution could be observed. Similar
results were obtained using a copper zinc catalyst
without a carrier (G 66). In continuous operation 1,4-
butanediol is formed exclusively in the case of copper
zinc catalysts, thus supporting the influence of zinc
discussed above. Figure 8 indicates that the effect of
zinc is not based on an adsorption mechanism only
because no saturation could be observed after 9 h of
time-on-stream. In the stationary state of the reactor
the mass balance was found to be approximately 100%,
Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 2891
T 4489 PdRe/C Ru/C Ru/C + R 3-12 PdReCuZn/C
89.8 100 100 100 100
92.7 18.3 52.2 54.0 34.1
7.3 73.3 24.2 22.0 52.2
0 0 0 0 0
0 0 0 2.7 0.8
0 0.7 0 0.9 0
0 0 15.6 0 3.0
indicating that succinic anhydride is not adsorbed
irreversibly on the zinc surface. It seems that the
presence of zinc also affects the kinetics of the hydro-
genation which is currently investigated in further
studies.
The use of copper catalysts in which zinc is absent
resulted in the formation of succinic anhydride and
-butyrolactone. Consistent with the results found in
the discontinuous hydrogenation of succinic anhydride,
no formation of 1,4-butanediol was observed.
Similar results were obtained using the noble metal
catalysts PdRe/C and Ru/C. The hydrogenation of
maleic anhydride led to the formation of a mixture
mainly containing succinic anhydride and -butyrolac-
tone. Byproducts were tetrahydrofuran, 1-butanol, and
propionic acid, no 1,4-butanediol was formed. The 1,4-
butanediol selectivity for the mechanical mixture of
Ru/C and R 3-12 was found to be zero as well. This
result is surprising regarding the fact that the sole use
of R 3-12 with the same loading as in the mixture
resulted in the formation of 1,4-butanediol without
succinic anhydride being formed. PdReCuZn/C was not
active for the formation of 1,4-butanediol as well. The
activity toward the conversion of succinic anhydride
decreased compared to the unmodified catalyst. The
impregnation with copper and zinc acetate may have
resulted in partial pore blockage. Both catalyst systems
(Ru/C + R 3-12 and PdReCuZn/C) indicate that the
presence of copper and zinc is not sufficient for the
synthesis of 1,4-butanediol. The rapid formation of
succinic anhydride on the noble metal active sites
combined with an increase in the concentration of
succinic anhydride in the liquid phase may be a reason-
able explanation as discussed above (see Figure 4). The
coverage of the active copper sites with succinic anhy-
dride at a high concentration inhibits the adsorption of
-butyrolactone and the formation of 1,4-butanediol. In
support of this assumption the influence of succinic
anhydride on the hydrogenation of maleic anhydride
was investigated separately. For this reason a continu-
ous run was performed using a copper zinc catalyst (R
3-12) as outlined in Figure 8. After a time-on-stream
of approximately 100 min the maleic anhydride feed was
replaced by a mixture of succinic and maleic anhydrides.
The concentration of maleic anhydride remained at 0.5
mol/L, the succinic anhydride concentration was 0.3 mol/
L. Figure 9 illustrates the conversion of maleic anhy-
dride and the yields of the products before and after the
addition of succinic anhydride versus time-on-stream.
The yields of the products are related to the feed
concentration of maleic anhydride, before as well as
after the addition of succinic anhydride. The vertical
line marks the time the feed was replaced. As supposed
above, the yield of 1,4-butanediol decreased immedi-
ately, indicating the coverage of the active copper
surface with succinic anhydride. The decrease in the
yield of -butyrolactone illustrates that succinic anhy-
dride, which is adsorbed from the bulk phase, is less
2892 Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997
Figure 9. Influence of succinic anhydride on the continuous
hydrogenation of maleic anhydride: MA, maleic anhydride; SA,
succinic anhydride; g-BL, -butyrolactone; 1,4-BD, 1,4-butanediol;
THF, tetrahydrofuran; n-BuOH, 1-butanol (T ) 543 K, p ) 7.5
MPa).
Table 5. Range of Operating Conditions for Kinetic
Measurements
catalyst
ci,0 pressure loading
substrate (mol/L) (MPa) temp (K) (kg/m3) catalyst
maleic anhydride max 0.57 2.5-7.5 393-463 0.5 Ru/C
succinic anhydride max 0.57 6.0-9.0 503-543 10 Ru/C
-butyrolactone max 2.5 3.0-9.0 433-493 10 CuZnOx/
Al2O3
active than succinic anhydride formed on the hydroge-
nation of maleic anhydride.
Kinetic Analysis. Mass-Transfer Limitations.
On the basis of the results obtained above, kinetic
measurements were carried out in the continuous way
of operation. Starting from maleic anhydride and
succinic anhydride a Ru/C catalyst was used. The
hydrogenation of -butyrolactone was investigated quan-
titatively over a copper zinc catalyst (R 3-12). Table 5
illustrates the reaction conditions applied in kinetic
experiments. The analysis of mass transfer effects was
performed both experimentally and theoretically based
on suitable criteria (see Appendix). Due to the existence
of a three-phase reaction, gas-liquid, liquid-solid, and
intraparticle diffusional resistances may influence the
rate and selectivity of the chemical reaction (Ram-
achandran and Chaudhari, 1983; Rode and Chaudhari,
1994). The influence of the gas-liquid mass transfer
was investigated experimentally by varying the agita-
tion speed at constant reaction conditions. The varia-
tion of the agitation speed did not result in a significant
change in the reaction rate above 800 rpm. The
evaluation of the criterion regarding the gas-liquid
mass transfer, calculating the parameter R1, resulted
in values below 0.01 for all reaction steps investigated.
This fact indicates the absence of gas-liquid mass
transfer resistances, confirming the experimental re-
sults.
The analysis of restrictions due to the liquid-solid
mass transfer was performed theoretically by calculat-
ing the parameter R2, which represents the ratio of the
observed rate of reaction to the maximum rate of the
liquid-solid mass transfer. The analysis showed that
even at high reaction rates the value of R2 was below
0.07, indicating the absence of liquid-solid mass trans-
fer limitations as well.
For the investigation of pore diffusional resistances
the particle size was varied while other reaction pa-
rameters were kept constant. The decrease of the
reaction rate was significant for particle diameters
Figure 10. Evaluation of pore diffusional resistances for different
reaction steps using eq 6: MA, maleic anhydride; SA, succinic
anhydride; g-BL, -butyrolactone.
above 150 m only in the case of the hydrogenation of
maleic anhydride. No clear tendency could be observed
for the catalyst fraction in the range of 80-150 m used
for kinetic measurements. However, no decrease in the
reaction rate could be discerned on the hydrogenation
of succinic anhydride and -butyrolactone when varying
the particle diameter from 56 to 350 m. This indicated
that intraparticle diffusion limitations were absent
during kinetic measurements of these reaction steps.
The evaluation of a theoretical criterion (see Appendix)
quantifying intraparticle diffusional resistances is il-
lustrated in Figure 10 for typical runs on different
reaction steps. It can be discerned that the threshold
value of 0.2 is exceeded in the case of the hydrogenation
of maleic anhydride, indicating that the kinetic mea-
surements for this reaction step could be affected by
pore diffusional resistances. The hydrogenation of
succinic anhydride and -butyrolactone can be consid-
ered to be free from this kind of limitation, which
supports the experimental observations.
Kinetic Analysis. Kinetic Measurements and
Modeling. The discrimination of different rate equa-
tions was performed by means of parameter estimation
using a gradient method with the log-likelihood function
(LLF) as objective function (Steiner et al., 1989). The
value of LLF and the weighted sum of residual squares
were chosen as a criterion for the quality of the
approximation as well as parity plots.
Figure 11 represents the effective reaction rate of the
hydrogenation of maleic anhydride to succinic anhydride
versus concentration of the substrate. The rate shows
an approximately linear increase with the concentration
of maleic anhydride, while the influence of the pressure,
i.e., the hydrogenation concentration in the solution, is
less significant. The analysis of the fit of different
models including a power law model as well as mecha-
nistically deduced equations showed that the smallest
lack of fit was obtained using the following model:
r ) kcMAmcH2n (2)
A further simplification of this model can be achieved
regarding the results for any pressure separately cH2n
) constant, leading to the equation
r ) kcMAm (3)

Figure 11. Rate of maleic anhydride hydrogenation vs substrate
concentration: points; experimental; line, model prediction (model
M1) (T ) 418 K).
Table 6 shows the parameter values n, m, k, and k
as well as the 95% confidential intervals regarding both
a separate and a total consideration of the reactor
pressure. The order for maleic anhydride proved to be
m 0.8-1.0. The rate dependency on the hydrogen
concentration results in a value for the exponent n of
approximately 0.33. Similarly results were obtained by
Kanetaka et al. (1970b), who found a first-order reaction
mechanism for the hydrogenation of maleic anhydride
on a NiRe catalyst using a power law model. The model
prediction (model M1) is marked by the line in Figure
11, the experimental values are represented by single
points. The activation energy for the hydrogenation of
maleic anhydride was calculated to be 39.5 kJ/mol by
varying the reaction temperature in the range from 418
to 463 K.
The results of the hydrogenation of succinic anhydride
to -butyrolactone are illustrated in Figure 12. An
influence of the hydrogen concentration could not be
discerned while the reactor pressure was increased from
6.0 to 7.5 and 9.0 MPa, resulting in a zero-order reaction
for hydrogen. The dependency of the reaction rate on
the succinic anhydride concentration is pronounced only
for low values, indicating a saturation of substrate for
high succinic anhydride concentrations. Table 7 reveals
a power law model (B1) and a simple mechanistically
deduced model (B2) applied for the hydrogenation of
succinic anhydride. On the basis of the absence of an
influence of hydrogen, other mechanistical models were
deduced without taking the corresponding hydrogen
concentration in the potential term into consideration.
Rate equations including the adsorption of succinic
anhydride or the desorption of -butyrolactone as the
rate-determining step did not comprise significant
parameters. The evaluation of different kinds of models
showed that no significant values could be calculated
for the adsorption constants of water, hydrogen, and
-butyrolactone. Model B2 comprises both facts, the
surface reaction as the rate-determining step and the
adsorption of succinic anhydride. The variation of the
reaction temperature and evaluation of the results
based on model B2 led to the calculation of the activa-
tion energy for the hydrogenation of succinic anhydride
of 117.96 kJ/mol. The model prediction according to
model B2 is marked by the line in Figure 12; the
experimental values are represented by single points.
The hydrogenation of -butyrolactone to 1,4-butane-
diol has to be regarded as reversible in the range of
Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 2893
Figure 12. Rate of succinic anhydride hydrogenation vs substrate
concentration: points, experimental; line, model prediction (model
B2) (T ) 543 K).
reaction conditions used in the present work. The
calculation of an equilibrium constant for the reaction
of -butyrolactone and hydrogen to form 1,4-butanediol
was performed via integration of the vant Hoff equation
using an increment method (Reid and Sherwood, 1988).
The equilibrium constant was calculated to be Ke )
17.78 L2/mol2 at T ) 483.15 K, which is in good
agreement with the experimental data obtained in the
discontinuous stirred tank reactor. The evaluation of
different models including adsorption or desorption as
a rate-determining step did not result in convergent
solutions. The same applies for rate equations, which
include an adsorption of 1,4-butanediol in the adsorption
term. The remaining models L1-L3 differ in the kind
of adsorption of hydrogen on the active sites. Model L1
includes a four-step mechanism, which comprises (a) the
adsorption of -butyrolactone and (b) the adsorption of
hydrogen on the same kind of active site according to
the Langmuir adsorption theory. Step c is the formation
of an adsorbed intermediate (I-s) in the reaction of
-butyrolactone and hydrogen and is considered to be
rate determining. Finally step d represents the forma-
tion of 1,4-butanediol by the reaction of the adsorbed
intermediate and hydrogen. The reaction scheme for
model L1 is proposed to be as follows:
K1
(a) -BL + s \
y z -BL-s
K2
(b) H2 + s \
y z H2-s
K3
(c) -BL-s + H2-s y\z I-s + s
K4
(d) I-s + H2-s y\z 1,4-BD + 2s
Model L2 takes into account the presence of two
different kinds of active sites. Except for this, the
reaction scheme corresponds completely to model L1.
The fit of the experimental data for the models L1 and
L2 showed no significant differences, which indicates
that no clear statement can be given regarding the kind
of active sites. Model L3 includes an Eley Rideal
mechanism which embodies the reaction of adsorbed
-butyrolactone with hydrogen from the bulk phase. The
formation of an intermediate by adsorbed -butyrolac-
tone and bulk phase hydrogen was supposed to be the
rate-determining step. The evaluation of model L3
2894 Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997

Table 6. Rate Equations and Parameters with 95% Confidence Intervals on the Hydrogenation of Maleic Anhydride; k,
k, Rate Constants; m, n, Reaction Orders for Maleic Anhydride and Hydrogen (T ) 418 K)
model rate equation pressure (MPa) k, k (Lm+n-1/(molm+n-1 s)) m n
M1 r ) kcMAmcH2n 2.5-7.5 2.77 10-4 ( 4.67 10-5 0.79 ( 0.12 0.33 ( 0.10
M2 r ) kcMAm 2.5 2.15 10-4 ( 8.67 10-5 0.99 ( 0.17
M3 r ) kcMAm 5.0 2.50 10-4 ( 1.80 10-4 0.97 ( 0.62
M4 r ) kcMAm 7.5 2.00 10-4 ( 5.33 10-5 0.69 ( 0.20

Table 7. Rate Equations and Parameters with 95% Confidence Intervals on the Hydrogenation of Succinic Anhydride;
k1, k2, Rate Constants; KSA, Sorption Constant for Succinic Anhydride; m, n, Reaction Orders for Succinic Anhydride
and Hydrogen (T ) 543 K)
model rate equation k1 (Lm+n-1/(molm+n-1 s)) m n
B1 r) k1cSAmcH2n 2.61 10-4 ( 4.50 10-5 0.48 ( 0.11 0.56 10-5 ( 0.07
k2 (1/s) KSA (L/mol)
B2 r ) k2cSA/(1 + KSAcSA) 1.61 10-3 ( 4.22 10-4 7.70 ( 3.18

Table 8. Rate Equations on the Equilibrium Reaction on the Hydrogenation of -Butyrolactone

L1 L2 L3

(
k3K1K2 cBLcH2 -
cBD
KecH2 ) (
k3K1K2 cBLcH2 -
cBD
KecH2 ) (
k2K1 cBLcH2 -
cBD
KecH2 )
( ) ( ) ( )
r) r) r)
cBD 2 cBD cBD
1 + K1cBL + K2cH2 + (1 + K1cBL) 1 + K2cH2 + 1 + K1cBL +
cH2K2K4 cH2K2K4 K3cH2

Table 9. Parameters with 95% Confidence Intervals on the Hydrogenation of -Butyrolactone for Model L1a
model k3 (mol/(L s)) K1 (L/mol) K2 (L/mol) Ke (L2/mol2) K4 (mol/L)
L1 3.20 10-3 ( 2.10 10-3 0.82 ( 0.58 1.12 ( 1.29 207.5 ( 3325.6 143.0 ( 10442.2
a k , rate constant for the rate-determining step; K , K , sorption constants for -butyrolactone and hydrogen; K , equilibrium constant
3 1 2 e
for the overall reaction of -butyrolactone and hydrogen to 1,4-butanediol; K4, equilibrium constant for the reaction of hydrogen and
intermediate forming 1,4-butanediol (T ) 483 K).

be confirmed for a high concentration, e.g., starting from

pure -butyrolactone.

Conclusions

(i) Catalyst testing in a discontinuous stirred tank

Figure 13. Rate of -butyrolactone hydrogenation vs substrate
concentration: points, experimental; line, model prediction (model
L1) (T ) 483 K).
resulted in a worse fit of the experimental data com-
pared to the models discussed above. Table 8 illustrates
the rate equations on the equilibrium reaction on the
hydrogenation to -butyrolactone for the models L1-
L3. The parameter values with the corresponding
(95% confidence intervals for model L1 are shown in
Table 9. Figure 13 illustrates the experimental and
calculated values based on model L1 for the hydrogena-
tion of -butyrolactone. The fit is satisfactory for higher
concentrations of -butyrolactone, while calculations for
small concentrations result in remarkable deviations.
The activation energy calculated for this step is 39.1 kJ/
mol. The zero-order dependence of -butyrolactone
found in literature (Kanetaka et al., 1970b) could only
reactor showed that the hydrogenation of maleic anhy-
dride, succinic anhydride, and -butyrolactone is pos-
sible in principle using copper catalysts. If succinic
anhydride was used as a substrate, only copper zinc
catalysts revealed activity in the formation of 1,4-
butanediol. No differences between different copper
catalysts could be observed starting with -butyrolac-
tone. We propose that zinc is not participating in the
hydrogenation reaction but provides vacant active cop-
per sites due to selective adsorption of succinic anhy-
dride. This effect results in a formation of 1,4-
butanediol on the hydrogenation of succinic anhydride
on copper zinc catalysts. However, by use of copper
catalysts in which zinc is absent, no formation of 1,4-
butanediol was observed, which could be due to the
coverage of the active copper sites even with a small
amount of unreacted succinic anhydride. Noble metal
catalysts were active for the hydrogenation of maleic
and succinic anhydrides. No or little activity was
observed on the hydrogenation of -butyrolactone to 1,4-
butanediol depending on the active component.
(ii) With continuously operated experiments, the
target product 1,4-butanediol was formed using copper
zinc catalysts only. It is noticeable that the continuous
hydrogenation of maleic anhydride on copper zinc
catalysts proceeded without succinic anhydride present
in the bulk phase of the liquid. The selective adsorption
on zinc combined with a positive effect on the reaction
kinetics makes copper zinc catalysts suitable for the

one-step hydrogenation to -butyrolactone/1,4-butane-
diol starting from maleic anhydride. A subdivision into
different reaction units becomes unnecessary.
(iii) Kinetic measurements were performed in a
continuously stirred tank reactor. A power law model
was suitable for the quantitative modeling of the
hydrogenation of maleic anhydride. The kinetic model
established for the succinic anhydride hydrogenation is
based on a hyperbolic rate equation. Hydrogenation of
-butyrolactone can be described using a Langmuir-
Hinshelwood type kinetic based on the reversible char-
acter of the reaction.
Nomenclature
ci ) concentration of reactant i (mol/L)
ci,0 ) concentration of reactant i for t ) 0/feed concentration
(mol/L)
cMA ) concentration of maleic anhydride (mol/L)
cSA ) concentration of succinic anhydride (mol/L)
c-BL, cBL ) concentration of -butyrolactone (mol/L)
c1,4-BD, cBD ) concentration of 1,4-butanediol (mol/L)
cH2 ) concentration of hydrogen (mol/L)
cH2* ) concentration of hydrogen at the gas-liquid inter-
face (mol/L)
dP ) diameter of a catalyst particle (m)
D ) molecular diffusion coefficient (m2/s)
Deff ) effective molecular diffusion coefficient (m2/s)
k, k, k1, k2, k3 ) rate constants [depending on the model;
see Tables 6-9]
K1, K2, K3, K4 ) sorption constants [depending on the
model; see Tables 8 and 9]
KSA ) sorption constant for succinic anhydride (L/mol)
Ke ) equilibrium constant for the hydrogenation of -bu-
tyrolactone (L2/mol2)
kLaB ) volumetric gas-liquid mass transfer coefficient (1/
s)
kSaP ) volumetric liquid-solid mass transfer coefficient (1/
s)
LLF ) log-likelihood function
m ) reaction order for maleic and succinic anhydride
n ) reaction order for hydrogen
p ) pressure (MPa)
reff ) effective rate of reaction (mol/(L s))
rj ) rate of reaction j (mol/(L s))
Sk,i ) selectivity of product k referred to substrate i
t ) time (s, min)
T ) temperature (K)
VR ) reaction volume (m3)
V L,0 ) volumetric rate of liquid feed (m3/s)
V L ) volumetric rate of product liquid (m3/s)
Xi ) conversion of substrate i
Yk,i ) yield of product k referred to substrate i
Greek Letters
R1 ) gas-liquid mass transfer parameter defined by eq 4
R2 ) liquid-solid mass transfer parameter defined by eq
5 Castiglioni, G. L.; Gazzano, M.; Stefani, G.; Vaccari, A. Selective
 ) porosity of the catalyst particle
ij ) stoichiometric coefficient of species i in reaction j
exp ) parameter for the estimation of internal diffusion
resistance defined by eq 6
FP ) density of the catalyst particle (kg/m3)
) tortuosity factor of the catalyst particle
Acknowledgment
These results were obtained within the framework of
SFB 222. We thank the Deutsche Forschungsgemein-
schaft for their financial support of this work. We also
Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 2895
wish to express our thanks to the above mentioned
companies for supplying the catalysts used.
Appendix
For determination of the contributions of the mass
transfer steps present in a three-phase catalytic system,
the following criteria were used (Ramachandran and
Chaudhari, 1983):
1. The limitation due to the gas-liquid mass transfer
is negligible if
reff
R1 ) < 0.1 (4)
kLaBcH2*
2. The limitation due to the liquid-solid mass
transfer is negligible if
reff
R2 ) < 0.1 (5)
kSaPci
3. Internal diffusion resistances can be neglected if
x
dP FPreff
exp ) < 0.2 (6)
6 wDeffci
The mass transfer coefficients kLaB and kSaP were
calculated using the correlations of Calderbank and
Moo-Young (1961) and Levins and Glastonbury (1972).
The effective diffusion coefficient Deff was calculated as
Deff ) (/)D. The ratio / was assumed to be 0.1. The
molecular diffusion coefficients for organic substrates
and for hydrogen were calculated as proposed by Wilke
and Chang (1955) and Akgerman and Gainer (1972).
The solubility of hydrogen in 1,4-dioxane was calculated
by using the regular solution theory (Hildebrand et al.,
1970).
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Received for review April 22, 1996
Revised manuscript received July 23, 1996
Accepted July 25, 1996X
IE960229G
X Abstract published in Advance ACS Abstracts, June 15,
1997.