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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)

(Tamura and Kumano, 1980; Tanabe, 1981).
1,4-Butanediol is of major interest as a starting Maleic anhydride has become an interesting feedstock
material for the production of important polymers. for the synthesis of -butyrolactone, 1,4-butanediol, and
Examples are polyurethanes and poly(butylene tere- tetrahydrofuran in the past. A major reason is the
phthalate) based on 1,4-butanediol, which are mainly improved and therefore more economic maleic anhy-
used for engineering plastics as well as for the synthesis dride production with n-butane as starting material
of fibers, films, and adhesives. Furthermore, 1,4- (Contractor and Sleight, 1987). Competitive maleic
butanediol is a major feedstock for the production of anhydride processes were established based on fluidized
tetrahydrofuran, which is synthesized by homogeneous bed processes used by, e.g., Lummus/Alusuisse (ALMA),
dehydration. In 1992 in the U.S. above 50% of 1,4- BP/UCB, and DuPont companies (Contractor, 1995). A
butanediol was converted to tetrahydrofuran (Weisser- technical application of the maleic anhydride hydroge-
mel and Arpe, 1994). Tetrahydrofuran is applied as a nation to 1,4-butanediol is currently performed in Japan
solvent for PVC and as a monomer for the formation of using a two-step process on NiRe and NiCo catalysts
polytetramethylene glycol, which is used as intermedi- (Weissermel and Arpe, 1994). The reaction pathway of
ate for Spandex fibers and polyurethanes (Weissermel the hydrogenation of maleic anhydride to 1,4-butanediol
and Arpe, 1994; Harris and Tuck, 1990). Dehydroge- and tetrahydrofuran is illustrated in Figure 1. The
nation of 1,4-butanediol on copper catalysts leads to the reaction proceeds via succinic anhydride which is con-
formation of -butyrolactone, which is another major verted to -butyrolactone. The hydrogenation of -bu-
solvent. The reaction of -butyrolactone with methyl- tyrolactone to 1,4-butanediol is followed by an acid-
amine or ammonia results in the formation of N- catalyzed dehydration to tetrahydrofuran. As one can
methylpyrrolidone and 2-pyrrolidone. Both chemicals see from Figure 1, the use of maleic anhydride results
are used as solvents, and additionally 2-pyrrolidone is in the production of the above mentioned high value
in demand as a raw material for pharmaceuticals products within a single reaction path. Furthermore,
(Mitsubishi, 1988; Minoda and Miyajima, 1970). the composition of the product mixture can be influenced
Currently the majority of 1,4-butanediol is produced substantially by a variation of the reaction conditions
by the Reppe process applied by BASF, Huls, DuPont, (Brownstein and List, 1977).
and other several major companies (Brownstein, 1991). Most publications regarding the hydrogenation of
Acetylene and formaldehyde are used as starting ma- maleic anhydride are patent literature. In general,
terials. In the U.S. in 1992 nearly 90% of the 1,4- patent literature provides the coverage of a special
butanediol synthesized was produced according to the invention without giving comprehensive informations
Reppe process (Weissermel and Arpe, 1994). Several on catalyst activities or kinetics. In most cases copper-
disadvantages within the process led to the development based catalysts are mentioned regarding the gas phase
of alternative routes for the synthesis of 1,4-butanediol. hydrogenation of maleic anhydride to 1,4-butanediol and
Disadvantages are, e.g., severe reaction conditions, the tetrahydrofuran (Budge, 1990; De Thomas et al., 1992).
use of acetylene (implying explosion hazard) and form- Liquid phase hydrogenation of maleic anhydride is
aldehyde (with possible cancerogenic effects), and the performed using copper-, cobalt-, or nickel-based cata-
necessity to perform a multistep reaction pathway. The lysts (Eggersdorfer et al., 1989; Budge et al., 1993) as
most important alternatives to the Reppe process are well as noble metal catalysts containing, e.g., Pd, Re,
the hydrogenation of maleic anhydride or its esters, the or Ru (Freudenberger and Wunder, 1978; Attig and
conversion of propylene oxide (Arco process), and the Graham, 1989). Previous studies on the hydrogenation
of maleic anhydride were carried out mainly using
* To whom correspondence should be addressed. E-mail: copper chromite catalysts. Experiments were performed to investigate the influence of the catalyst composition
S0888-5885(96)00229-1 CCC: $14.00 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-

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
Figure 1. Reaction scheme of the hydrogenation of maleic and hydrogen, respectively. Drying was performed at
anhydride to 1,4-butanediol/tetrahydrofuran. 423 K for 1 h with pure nitrogen. The activation was
performed subsequently with 6 vol % hydrogen at 473
and structure on the catalytic activity of maleic anhy- K for 1.5 h and finally at 473 K with 12 vol % hydrogen
dride (Castiglioni et al., 1995; Messori and Vaccari, for 15 h. After this procedure, which was applied to
1994). No emphasis was placed on the formation of 1,4- noble metal based and copper-based catalysts, the
butanediol. material was kept under nitrogen atmosphere to avoid
The present paper includes an investigation of the partial oxidation and to guarantee identical starting
activity of different copper-based catalysts on each conditions for all experimental runs. Hydrogen, nitro-
reaction step, illustrated in Figure 1. Additional experi- gen, and methane were supplied by Linde, Germany,
ments using noble metal catalysts provided a useful with >99.99% purity and used directly from the cylin-
comparison between both types of catalysts. Catalytic der. The components maleic anhydride, succinic anhy-
activity toward the formation of 1,4-butanediol starting dride, and -butyrolactone as well as n-tetradecane were
from different substrates was stressed. On the basis delivered by Fluka AG, Germany, with >99% purity.
of the results obtained, the performance of different Methane and n-tetradecane were used as internal
types of catalysts was investigated in the continuous standards for the gaseous and liquid phase. 1,4-
way of operation, taking into account the industrial Dioxane, which proved to be inert, was used as a solvent
relevance of a single-step hydrogenation to 1,4-bu- in both discontinuous and continuous reactor operation
tanediol. In order to obtain quantitative data, kinetic (>99% purity supplied by Merck, Germany).
measurements and a kinetic modeling were performed The reaction conditions applied for discontinuous
for each reaction step using noble metal and copper zinc experiments are illustrated in Table 2. Continuously
catalysts. performed experiments were carried out at T ) 543 K
and p ) 7.5 MPa using a catalyst loading of 17.4 kg/
Experimental Section m3. The feed rates of liquid and gas were 4.2 mL/min
Catalysts and Reaction Procedure. The catalysts and 1000 normal mL/min, respectively. The feed con-
used for hydrogenation of maleic anhydride, succinic centration of maleic anhydride was 0.5 mol/L.
anhydride, and -butyrolactone are commercially avail- Kinetic measurements were performed by varying the
able from companies BASF, Sud-Chemie, and Heraeus, feed concentration and reactor pressure at constant feed
Germany. An exception is PdRe/C, which was synthe- rates. Table 5 illustrates the range of operating condi-
sized by Degussa, Germany, for laboratory use only. The tions. The liquid and gas feed rates were 6.5 mL/min
chemical composition and the designation of these and 1000 normal mL/min. The particle size used was
catalysts are illustrated in Table 1. As all catalysts 80-150 m. The temperatures were kept constant at
were supplied in the form of tablets, the material was T ) 418 K for maleic anhydride hydrogenation, T ) 543
crushed and sieved to obtain the desired fraction of 80- K for succinic anhydride hydrogenation, and T ) 483
150 m. The experiments were performed using this K for the hydrogenation of -butyrolactone. Activation
fraction unless otherwise mentioned. PdRe/C was sup- energies were determined by performing runs in tem-
plied as a wet powder of 25 m and used in this fraction. perature ranges outlined in Table 5.
Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 2887
Table 2. Operating Conditions for Discontinuous Catalyst Testing
substrate ci,0 (mol/L) pressure (MPa) temp (K) catalyst loading (kg/m3) particle size (m)
maleic anhydride 1.0 5.0 463 12 80-150 (PdRe/C: 25)
succinic anhydride 0.56 7.5 513 12 80-150 (PdRe/C: 25)
-butyrolactone 0.56 7.5 513 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-
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
Figure 2. Reconstruction of the reactor head for continuous were 30 m long. The analysis was optimized by using
operation: PI, pressure indicator. temperature and pressure programs in the range from
353 to 503 K and 40 to 180 kPa. Quantitative analysis
Apparatus. Discontinuously Operated Reactor. of the compounds in the product mixture was performed
All experiments were carried out in a stainless steel (SS- using a Hewlett-Packard 3396 Series II integrator.
316) stirred tank reactor with 63.5 mm internal diam- Peak areas were converted into concentrations using the
eter and 152 mm height (Parr Instruments, Model internal standard method (Schomburg, 1987). Evalu-
4562). To provide a high gas-liquid interfacial area, ation of quantitative amounts of substrate and products
the turbine stirrer was replaced by a gas entrainment can be easily performed by means of the internal
impeller. The impeller speed was variable and could standard in both discontinuous and continuous opera-
be increased up to 1700 rpm. Liquid samples were tion. The mass balance for any species i in the reactor
drawn by means of a sampling tube equipped with a is
sinter metal filter to avoid the loss of suspended
catalyst. The liquid samples could be either injected dci N
into the port of a gas chromatograph or fed into an
continuously operating evaporizer. Analysis of the
) V L,0ci,0 - V Lci + VR
ijrj (1)
gaseous phase was performed by means of the sampling
loop of the gas chromatograph. Liquid samples were Preliminary measurements of the residence time
analyzed by mixing the substrate with a defined amount distribution showed that the continuous stirred tank
of n-tetradecane, which was inert under the applied reactor could be considered to be free from dead spaces
reaction conditions. Methane was used as internal or bypass effects under the conditions used in the
standard for the gaseous phase. Discontinuous experi- present work. This results in uniform concentrations
ments were carried out by charging the reactor with the in the reactor vessel and allows the use of the above
desired amount of substrate, internal standard, and equation. The application of this equation for an
solvent. Then catalyst was added under nitrogen internal standard shows that in the case of chemical
atmosphere. Finally, the reactor was pressurized and inertness (rj ) 0) and in a stationary state of the reactor
heated up to the desired temperature. According to the (dci/dt ) 0) the concentration is constant assuming V L,0
gas consumed, hydrogen was added discontinuously to ) V L. Accordingly, the concentration of the standard
maintain a constant pressure. in the product mixture is known and can be used as a
Apparatus. Continuously Operated Reactor. In reference for calculating the concentrations of the
order to carry out continuous experiments, some recon- reactants. On the basis of the concentrations of the
structions of the equipment had to be carried out. The reactants the conversion Xi, yield Yk,i, and selectivity
problem of maintaining a constant pressure and liquid Sk,i were calculated as follows:
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
ci,0 - ci ck i Yk,i
Xi ) Yk,i ) Sk,i )
occupied, the tube was installed coaxially to the sam- ci,0 ci,0 k Xi
pling line as illustrated in Figure 2. The sampling line
was connected to a regulating valve which controls the Results and Discussion
sampling frequency. The dip tube was fixed to an
overflow valve. This overflow valve simultaneously The main subjects which should be answered by the
controlled the pressure in the reactor and the level of present work are as follows: (i) Finding suitable cata-
the liquid. To avoid loss of catalyst during continuous lysts and reaction conditions for the hydrogenation of
operation, both the sample line and the dip tube were maleic anhydride, succinic anhydride, and -butyrolac-
provided with a sinter metal filter. A change in reactor tone in the liquid phase. (ii) Determination of a suitable
pressure could be easily achieved by the adjustment of subdivision of the multistep reaction into appropriate
the overflow valve. The liquid level was varied by steps using results achieved in discontinuously as well
replacing the dip tube. To carry out automatically as continuously performed experiments. (iii) Evaluation
performed runs, all essential functions were controlled 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 hydrogenation of maleic anhydride. Among these cata-
considering mass transfer resistances. lysts the copper zinc containing G 66 showed the
Hydrogenation in Discontinuous Operation. The smallest activity, probably due to the absence of a
hydrogenation of maleic anhydride to succinic anhydride carrier material. A comparison between the copper
is known to proceed rapidly (Kanetaka et al., 1970a). catalyst T 4489 and the copper chromite G 13, which
Therefore mild reaction conditions were applied for this both contain 40 wt % of copper, unveils a higher activity
step (see Table 2). Figure 4 illustrates the obtained of the latter regarding the hydrogenation of maleic
results using the catalysts mentioned above. The most anhydride. This effect illustrates the influence either
active catalysts for the hydrogenation of maleic anhy- of the additional component chromium or of the pres-
dride were found to be noble metals. No remarkable ence of a spinel structure on the activity. The hydro-
differences in conversion can be discerned between genation of maleic anhydride results mainly in the
PdRe/C, Pd/C, and Ru/C catalysts. Copper chromites, formation of succinic anhydride. The formation of
which provide an almost total conversion of the sub- -butyrolactone is low under mild reaction conditions
strate after 5 h reaction time, were less active. The using copper-based catalysts. The yield of -butyrolac-
copper chromite G 22 unveils the lowest activity com- tone for copper-based catalysts was below 5%. Regard-
pared to G 13 and G 99, which can be possibly reduced ing noble metal catalysts, yields were 5% (PdRe/C),
to the smaller copper content. Copper-based catalysts 13.5% (Ru/C), and 54% (Pd/C). The only byproduct
without spinel structure proved to be less active for the formed was tetrahydrofuran (YTHF,MA 1.2%) when
Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 2889

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- catalysts. The rate of conversion on copper zinc cata-
drofuran on copper zinc catalysts proceeded simulta- lysts is comparable with noble metal catalysts, which
neously to -butyrolactone, which indicates a direct were active for both the hydrogenation of maleic anhy-
reaction pathway from -butyrolactone to tetrahydro- dride and succinic anhydride. The presence of zinc is
furan without 1,4-butanediol being formed as an inter- responsible for an increase of the activity in the hydro-
mediate. The direct hydrogenation of -butyrolactone genation of succinic anhydride resulting in a high rate
to tetrahydrofuran is no novelty and is described by of conversion. Castiglioni et al. (1993) found a positive
Turek et al. (1994) on the gas-phase hydrogenolysis of effect of zinc toward the conversion of succinic anhydride
dimethyl succinate. With none of the catalysts, 1,4- in the gas phase hydrogenation of maleic anhydride
butanediol was produced under the conditions applied using modified copper chromite catalysts. The copper
for the hydrogenation of maleic anhydride. chromites investigated in the present work showed a
As outlined above, the hydrogenation of succinic low activity in the hydrogenation of succinic anhydride
anhydride proceeded slowly at the reaction conditions compared to copper zinc catalysts. The copper catalysts
applied for the maleic anhydride conversion. For this R 3-11 and T 4489 as well as copper chromites showed
reason the investigation of the hydrogenation of succinic no activity in the formation of 1,4-butanediol. We found
anhydride was carried out at a higher temperature a conversion of succinic anhydride to -butyrolactone
using a higher pressure (see Table 2). Figure 5 shows of 100% and 70% on R 3-11 and T 4489, respectively,
the conversion of succinic anhydride versus operation after finishing the experiment. Figure 6 illustrates the
time. First of all, it can be seen that the order of activity product selectivities related to succinic anhydride after
observed on the hydrogenation of maleic anhydride has 5 h of reaction time. Besides the enhancement of the
changed regarding the conversion of succinic anhydride. conversion rate of succinic anhydride outlined above,
Copper zinc catalysts, which unveiled only a low activity zinc has a marked influence on the product selectivities.
for the hydrogenation of maleic anhydride, were more The use of copper zinc catalysts (G 66, R 3-12) results
active than copper chromites or other zinc absent copper 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 G 99 R 3-11 T 4489 PdRe/C Ru/C Pd/C
1,4-butanediol 95.0 77.8 76.3 87.9 81.4 58.6 71.2 20.7 0 0
tetrahydrofuran 4.1 16.5 14.5 4.0 6.2 22.5 14.5 20.5 16.7 4.8
1-butanol 2.0 4.5 2.1 8.8 4.4 4.2 5.6 31.6 0 0
propionic acid 0 0 0 0 0 0 0 0 0 0

butanediol. Both copper zinc catalysts convert succinic interaction of dimethyl succinate with zinc oxide on the
anhydride to valuable products with a selectivity of more gas phase hydrogenolysis of dimethyl succinate is
than 90%. The absence of zinc results in the formation reported by Turek et al. (1994) as well.
of -butyrolactone and small amounts of tetrahydrofu- No higher catalytic activity is observed on the hydro-
ran (R 3-11) and 1-butanol (T 4489). No 1,4-butanediol genation of -butyrolactone on copper zinc catalysts
is formed using these catalysts. The same refers to compared to copper catalysts in which zinc is absent.
copper chromites, which convert succinic anhydride to This indicates that zinc or zinc oxide does not provide
-butyrolactone with poor selectivities below 80%. additional sites for the chemical reaction of -butyro-
Among noble metal containing catalysts, PdRe/C exclu- lactone to 1,4-butanediol but for the selective adsorption
sively showed an activity in the formation of 1,4- of succinic anhydride. Noble metal catalysts which
butanediol. Pd/C and Ru/C are converting the substrate showed a high rate of conversion for maleic and succinic
to -butyrolactone and a small amount of propionic acid. anhydride were little effective on the hydrogenation of
Other byproducts using PdRe/C are 1-butanol and -butyrolactone. PdRe/C revealed an approximate 70%
tetrahydrofuran. As illustrated in Figure 6 the presence conversion of the substrate which was unselective to 1,4-
of zinc promotes the formation of 1,4-butanediol. Pos- butanediol as shown in Table 3. The use of Pd/C and
sibly zinc provides active sites for the hydrogenation of Ru/C resulted in little conversion of -butyrolactone.
-butyrolactone or enables the adsorption of -butyro- Unknown byproducts formed on Pd/C resulted in a loss
lactone on the copper surface. Catalytic tests using
of identified organic species of approximately 25% after
-butyrolactone as a starting material should give
5 h of reaction. Figure 7(right) illustrates the selectivity
further information on the role of zinc and copper on
to 1,4-butanediol versus the conversion of -butyrolac-
the hydrogenation activities forming 1,4-butanediol.
tone. On PdRe/C the selectivity which is above 50% at
Figure 7(left) shows the conversion of -butyrolactone
a 15% conversion of -butyrolactone decreases due to
versus reaction time on the catalysts outlined in Table
the formation of tetrahydrofuran, 1-butanol and un-
1. Copper-containing catalysts unveil a comparable
known byproducts. The selectivities obtained with
activity independent of additional elements as, e.g.,
chromium, zinc, and aluminum. The horizontal line in copper-based catalysts are far better and remain at a
Figure 7(left) indicates the value for the equilibrium high level as illustrated for the copper zinc catalyst G
conversion of -butyrolactone. It is exceeded due to the 66. The selectivity to 1,4-butanediol obtained on R 3-12
formation of byproducts tetrahydrofuran and 1-butanol. decreases from approximately 100% due to the forma-
Table 3 illustrates the product selectivities referred to tion of tetrahydrofuran probably induced by the acid
-butyrolactone after 5 h of reaction time. A comparison carrier material Al2O3.
of Figures 5 and 7(left) indicates that the conversion of The results of discontinuously operated screening
-butyrolactone to 1,4-butanediol is possible on copper experiments give reason for the assumption that a
catalysts in principle. Starting from succinic anhydride hydrogenation of maleic anhydride to the target product
the formation of 1,4-butanediol fails to proceed in the 1,4-butanediol can be achieved using different types of
absence of zinc even if high yields of -butyrolactone catalysts and/or reaction conditions. One possibility
were observed. It is likely that the presence of a small may be the use of a noble metal catalyst for the
amount of succinic anhydride prevents the adsorption conversion of maleic anhydride to -butyrolactone in one
of -butyrolactone on copper-based, zinc-absent cata- reactor unit. The formed -butyrolactone should be
lysts. It is possible that the presence of zinc provides a easily converted in a second reactor using copper-based
reduction of the coverage of the copper surface due to catalysts. Another path may be the hydrogenation of
selective adsorption of succinic anhydride. A similar maleic anhydride to succinic anhydride followed by the
Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 2891
Table 4. Conversion and Product Yields on Continuous Hydrogenation of Maleic Anhydride (%) (T ) 543 K, p ) 7.5
G 66 R 3-12 G 99 R 3-11 T 4489 PdRe/C Ru/C Ru/C + R 3-12 PdReCuZn/C
maleic anhydride conversion 96.6 100 99.5 93.5 89.8 100 100 100 100
succinic anhydride 0 0 68.6 66.5 92.7 18.3 52.2 54.0 34.1
-butyrolactone 61.1 64.5 27.5 25.3 7.3 73.3 24.2 22.0 52.2
1,4-butanediol 16.9 26.0 0 0 0 0 0 0 0
tetrahydrofuran 6.0 4.9 0.2 0.6 0 0 0 2.7 0.8
1-butanol 0 0.8 0 0 0 0.7 0 0.9 0
propionic acid 0 0 0 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
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
Figure 8. Conversion of maleic anhydride and product yields on
continuous hydrogenation vs time-on-stream: MA, maleic anhy- propionic acid, no 1,4-butanediol was formed. The 1,4-
dride; SA, succinic anhydride; g-BL, -butyrolactone; 1,4-BD, 1,4- butanediol selectivity for the mechanical mixture of
butanediol; THF, tetrahydrofuran; n-BuOH, 1-butanol (T ) 543 Ru/C and R 3-12 was found to be zero as well. This
K, p ) 7.5 MPa). result is surprising regarding the fact that the sole use
of R 3-12 with the same loading as in the mixture
conversion of succinic anhydride to 1,4-butanediol over resulted in the formation of 1,4-butanediol without
copper zinc catalysts as illustrated in Figure 6. succinic anhydride being formed. PdReCuZn/C was not
Hydrogenation in Continuous Operation. Table active for the formation of 1,4-butanediol as well. The
4 illustrates the results of continuously performed activity toward the conversion of succinic anhydride
experiments. In addition to the experiments outlined decreased compared to the unmodified catalyst. The
above, a mechanical mixture of a noble metal catalyst impregnation with copper and zinc acetate may have
and a copper zinc catalyst (Ru/C + R 3-12) as well as a resulted in partial pore blockage. Both catalyst systems
modified PdRe/C catalyst (PdReCuZn/C) was used. (Ru/C + R 3-12 and PdReCuZn/C) indicate that the
Experiments on these catalysts were carried out to focus presence of copper and zinc is not sufficient for the
attention on the role of zinc on the hydrogenation of synthesis of 1,4-butanediol. The rapid formation of
maleic and succinic anhydride. Pd/C is not listed in succinic anhydride on the noble metal active sites
Table 4 due to marked deactivation found in the combined with an increase in the concentration of
continuous hydrogenation of maleic anhydride. The succinic anhydride in the liquid phase may be a reason-
catalyst G 99 was chosen as a representative for copper able explanation as discussed above (see Figure 4). The
chromites. coverage of the active copper sites with succinic anhy-
Table 4 illustrates that no succinic anhydride was dride at a high concentration inhibits the adsorption of
formed using copper zinc catalysts (G 66 and R 3-12). -butyrolactone and the formation of 1,4-butanediol. In
Similar to the results obtained in discontinuous hydro- support of this assumption the influence of succinic
genation of succinic anhydride, a mixture of -butyro- anhydride on the hydrogenation of maleic anhydride
lactone and 1,4-butanediol was formed. Byproducts was investigated separately. For this reason a continu-
were tetrahydrofuran and 1-butanol. The hydrogena- ous run was performed using a copper zinc catalyst (R
tion of maleic anhydride seems to proceed directly to 3-12) as outlined in Figure 8. After a time-on-stream
-butyrolactone and 1,4-butanediol. Figure 8 illustrates of approximately 100 min the maleic anhydride feed was
the conversion of maleic anhydride and the yields of the replaced by a mixture of succinic and maleic anhydrides.
products formed over a copper zinc on alumina catalyst The concentration of maleic anhydride remained at 0.5
(R 3-12) versus time-on-stream. A noticeable formation mol/L, the succinic anhydride concentration was 0.3 mol/
of succinic anhydride occurs only at the beginning of L. Figure 9 illustrates the conversion of maleic anhy-
the reaction. In a steady state, no desorption of succinic dride and the yields of the products before and after the
anhydride into the solution could be observed. Similar addition of succinic anhydride versus time-on-stream.
results were obtained using a copper zinc catalyst The yields of the products are related to the feed
without a carrier (G 66). In continuous operation 1,4- concentration of maleic anhydride, before as well as
butanediol is formed exclusively in the case of copper after the addition of succinic anhydride. The vertical
zinc catalysts, thus supporting the influence of zinc line marks the time the feed was replaced. As supposed
discussed above. Figure 8 indicates that the effect of above, the yield of 1,4-butanediol decreased immedi-
zinc is not based on an adsorption mechanism only ately, indicating the coverage of the active copper
because no saturation could be observed after 9 h of surface with succinic anhydride. The decrease in the
time-on-stream. In the stationary state of the reactor yield of -butyrolactone illustrates that succinic anhy-
the mass balance was found to be approximately 100%, 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; Figure 10. Evaluation of pore diffusional resistances for different
THF, tetrahydrofuran; n-BuOH, 1-butanol (T ) 543 K, p ) 7.5 reaction steps using eq 6: MA, maleic anhydride; SA, succinic
MPa). anhydride; g-BL, -butyrolactone.

Table 5. Range of Operating Conditions for Kinetic

Measurements above 150 m only in the case of the hydrogenation of
maleic anhydride. No clear tendency could be observed
ci,0 pressure loading for the catalyst fraction in the range of 80-150 m used
substrate (mol/L) (MPa) temp (K) (kg/m3) catalyst for kinetic measurements. However, no decrease in the
maleic anhydride max 0.57 2.5-7.5 393-463 0.5 Ru/C reaction rate could be discerned on the hydrogenation
succinic anhydride max 0.57 6.0-9.0 503-543 10 Ru/C of succinic anhydride and -butyrolactone when varying
-butyrolactone max 2.5 3.0-9.0 433-493 10 CuZnOx/ the particle diameter from 56 to 350 m. This indicated
that intraparticle diffusion limitations were absent
active than succinic anhydride formed on the hydroge- during kinetic measurements of these reaction steps.
nation of maleic anhydride. The evaluation of a theoretical criterion (see Appendix)
Kinetic Analysis. Mass-Transfer Limitations. quantifying intraparticle diffusional resistances is il-
On the basis of the results obtained above, kinetic lustrated in Figure 10 for typical runs on different
measurements were carried out in the continuous way reaction steps. It can be discerned that the threshold
of operation. Starting from maleic anhydride and value of 0.2 is exceeded in the case of the hydrogenation
succinic anhydride a Ru/C catalyst was used. The of maleic anhydride, indicating that the kinetic mea-
hydrogenation of -butyrolactone was investigated quan- surements for this reaction step could be affected by
titatively over a copper zinc catalyst (R 3-12). Table 5 pore diffusional resistances. The hydrogenation of
illustrates the reaction conditions applied in kinetic succinic anhydride and -butyrolactone can be consid-
experiments. The analysis of mass transfer effects was ered to be free from this kind of limitation, which
performed both experimentally and theoretically based supports the experimental observations.
on suitable criteria (see Appendix). Due to the existence Kinetic Analysis. Kinetic Measurements and
of a three-phase reaction, gas-liquid, liquid-solid, and Modeling. The discrimination of different rate equa-
intraparticle diffusional resistances may influence the tions was performed by means of parameter estimation
rate and selectivity of the chemical reaction (Ram- using a gradient method with the log-likelihood function
achandran and Chaudhari, 1983; Rode and Chaudhari, (LLF) as objective function (Steiner et al., 1989). The
1994). The influence of the gas-liquid mass transfer value of LLF and the weighted sum of residual squares
was investigated experimentally by varying the agita- were chosen as a criterion for the quality of the
tion speed at constant reaction conditions. The varia- approximation as well as parity plots.
tion of the agitation speed did not result in a significant Figure 11 represents the effective reaction rate of the
change in the reaction rate above 800 rpm. The hydrogenation of maleic anhydride to succinic anhydride
evaluation of the criterion regarding the gas-liquid versus concentration of the substrate. The rate shows
mass transfer, calculating the parameter R1, resulted an approximately linear increase with the concentration
in values below 0.01 for all reaction steps investigated. of maleic anhydride, while the influence of the pressure,
This fact indicates the absence of gas-liquid mass i.e., the hydrogenation concentration in the solution, is
transfer resistances, confirming the experimental re- less significant. The analysis of the fit of different
sults. models including a power law model as well as mecha-
The analysis of restrictions due to the liquid-solid nistically deduced equations showed that the smallest
mass transfer was performed theoretically by calculat- lack of fit was obtained using the following model:
ing the parameter R2, which represents the ratio of the
observed rate of reaction to the maximum rate of the r ) kcMAmcH2n (2)
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- A further simplification of this model can be achieved
fer limitations as well. regarding the results for any pressure separately cH2n
For the investigation of pore diffusional resistances ) constant, leading to the equation
the particle size was varied while other reaction pa-
rameters were kept constant. The decrease of the
reaction rate was significant for particle diameters r ) kcMAm (3)
Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 2893

Figure 12. Rate of succinic anhydride hydrogenation vs substrate

Figure 11. Rate of maleic anhydride hydrogenation vs substrate
concentration: points, experimental; line, model prediction (model
concentration: points; experimental; line, model prediction (model
B2) (T ) 543 K).
M1) (T ) 418 K).
reaction conditions used in the present work. The
Table 6 shows the parameter values n, m, k, and k calculation of an equilibrium constant for the reaction
as well as the 95% confidential intervals regarding both of -butyrolactone and hydrogen to form 1,4-butanediol
a separate and a total consideration of the reactor was performed via integration of the vant Hoff equation
pressure. The order for maleic anhydride proved to be using an increment method (Reid and Sherwood, 1988).
m 0.8-1.0. The rate dependency on the hydrogen The equilibrium constant was calculated to be Ke )
concentration results in a value for the exponent n of 17.78 L2/mol2 at T ) 483.15 K, which is in good
approximately 0.33. Similarly results were obtained by agreement with the experimental data obtained in the
Kanetaka et al. (1970b), who found a first-order reaction discontinuous stirred tank reactor. The evaluation of
mechanism for the hydrogenation of maleic anhydride different models including adsorption or desorption as
on a NiRe catalyst using a power law model. The model a rate-determining step did not result in convergent
prediction (model M1) is marked by the line in Figure solutions. The same applies for rate equations, which
11, the experimental values are represented by single include an adsorption of 1,4-butanediol in the adsorption
points. The activation energy for the hydrogenation of term. The remaining models L1-L3 differ in the kind
maleic anhydride was calculated to be 39.5 kJ/mol by of adsorption of hydrogen on the active sites. Model L1
varying the reaction temperature in the range from 418 includes a four-step mechanism, which comprises (a) the
to 463 K. adsorption of -butyrolactone and (b) the adsorption of
The results of the hydrogenation of succinic anhydride hydrogen on the same kind of active site according to
to -butyrolactone are illustrated in Figure 12. An the Langmuir adsorption theory. Step c is the formation
influence of the hydrogen concentration could not be of an adsorbed intermediate (I-s) in the reaction of
discerned while the reactor pressure was increased from -butyrolactone and hydrogen and is considered to be
6.0 to 7.5 and 9.0 MPa, resulting in a zero-order reaction rate determining. Finally step d represents the forma-
for hydrogen. The dependency of the reaction rate on tion of 1,4-butanediol by the reaction of the adsorbed
the succinic anhydride concentration is pronounced only intermediate and hydrogen. The reaction scheme for
for low values, indicating a saturation of substrate for model L1 is proposed to be as follows:
high succinic anhydride concentrations. Table 7 reveals
a power law model (B1) and a simple mechanistically K1
deduced model (B2) applied for the hydrogenation of (a) -BL + s \
y z -BL-s
succinic anhydride. On the basis of the absence of an
influence of hydrogen, other mechanistical models were (b) H2 + s \
y z H2-s
deduced without taking the corresponding hydrogen
concentration in the potential term into consideration. K3
Rate equations including the adsorption of succinic (c) -BL-s + H2-s y\z I-s + s
anhydride or the desorption of -butyrolactone as the
rate-determining step did not comprise significant K4
parameters. The evaluation of different kinds of models (d) I-s + H2-s y\z 1,4-BD + 2s
showed that no significant values could be calculated
for the adsorption constants of water, hydrogen, and Model L2 takes into account the presence of two
-butyrolactone. Model B2 comprises both facts, the different kinds of active sites. Except for this, the
surface reaction as the rate-determining step and the reaction scheme corresponds completely to model L1.
adsorption of succinic anhydride. The variation of the The fit of the experimental data for the models L1 and
reaction temperature and evaluation of the results L2 showed no significant differences, which indicates
based on model B2 led to the calculation of the activa- that no clear statement can be given regarding the kind
tion energy for the hydrogenation of succinic anhydride of active sites. Model L3 includes an Eley Rideal
of 117.96 kJ/mol. The model prediction according to mechanism which embodies the reaction of adsorbed
model B2 is marked by the line in Figure 12; the -butyrolactone with hydrogen from the bulk phase. The
experimental values are represented by single points. formation of an intermediate by adsorbed -butyrolac-
The hydrogenation of -butyrolactone to 1,4-butane- tone and bulk phase hydrogen was supposed to be the
diol has to be regarded as reversible in the range of 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 -
KecH2 ) (
k3K1K2 cBLcH2 -
KecH2 ) (
k2K1 cBLcH2 -
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.


(i) Catalyst testing in a discontinuous stirred tank

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-
Figure 13. Rate of -butyrolactone hydrogenation vs substrate butanediol on the hydrogenation of succinic anhydride
concentration: points, experimental; line, model prediction (model
L1) (T ) 483 K).
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
resulted in a worse fit of the experimental data com- coverage of the active copper sites even with a small
pared to the models discussed above. Table 8 illustrates amount of unreacted succinic anhydride. Noble metal
the rate equations on the equilibrium reaction on the catalysts were active for the hydrogenation of maleic
hydrogenation to -butyrolactone for the models L1- and succinic anhydrides. No or little activity was
L3. The parameter values with the corresponding observed on the hydrogenation of -butyrolactone to 1,4-
(95% confidence intervals for model L1 are shown in butanediol depending on the active component.
Table 9. Figure 13 illustrates the experimental and (ii) With continuously operated experiments, the
calculated values based on model L1 for the hydrogena- target product 1,4-butanediol was formed using copper
tion of -butyrolactone. The fit is satisfactory for higher zinc catalysts only. It is noticeable that the continuous
concentrations of -butyrolactone, while calculations for hydrogenation of maleic anhydride on copper zinc
small concentrations result in remarkable deviations. catalysts proceeded without succinic anhydride present
The activation energy calculated for this step is 39.1 kJ/ in the bulk phase of the liquid. The selective adsorption
mol. The zero-order dependence of -butyrolactone on zinc combined with a positive effect on the reaction
found in literature (Kanetaka et al., 1970b) could only kinetics makes copper zinc catalysts suitable for the
Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 2895
one-step hydrogenation to -butyrolactone/1,4-butane- wish to express our thanks to the above mentioned
diol starting from maleic anhydride. A subdivision into companies for supplying the catalysts used.
different reaction units becomes unnecessary.
(iii) Kinetic measurements were performed in a Appendix
continuously stirred tank reactor. A power law model
was suitable for the quantitative modeling of the For determination of the contributions of the mass
hydrogenation of maleic anhydride. The kinetic model transfer steps present in a three-phase catalytic system,
established for the succinic anhydride hydrogenation is the following criteria were used (Ramachandran and
based on a hyperbolic rate equation. Hydrogenation of Chaudhari, 1983):
-butyrolactone can be described using a Langmuir- 1. The limitation due to the gas-liquid mass transfer
Hinshelwood type kinetic based on the reversible char- is negligible if
acter of the reaction.
R1 ) < 0.1 (4)
Nomenclature kLaBcH2*
ci ) concentration of reactant i (mol/L) 2. The limitation due to the liquid-solid mass
ci,0 ) concentration of reactant i for t ) 0/feed concentration transfer is negligible if
cMA ) concentration of maleic anhydride (mol/L) reff
cSA ) concentration of succinic anhydride (mol/L) R2 ) < 0.1 (5)
c-BL, cBL ) concentration of -butyrolactone (mol/L) kSaPci
c1,4-BD, cBD ) concentration of 1,4-butanediol (mol/L)
cH2 ) concentration of hydrogen (mol/L) 3. Internal diffusion resistances can be neglected if
cH2* ) concentration of hydrogen at the gas-liquid inter-

face (mol/L) dP FPreff
dP ) diameter of a catalyst particle (m) exp ) < 0.2 (6)
6 wDeffci
D ) molecular diffusion coefficient (m2/s)
Deff ) effective molecular diffusion coefficient (m2/s) The mass transfer coefficients kLaB and kSaP were
k, k, k1, k2, k3 ) rate constants [depending on the model; calculated using the correlations of Calderbank and
see Tables 6-9] Moo-Young (1961) and Levins and Glastonbury (1972).
K1, K2, K3, K4 ) sorption constants [depending on the The effective diffusion coefficient Deff was calculated as
model; see Tables 8 and 9] Deff ) (/)D. The ratio / was assumed to be 0.1. The
KSA ) sorption constant for succinic anhydride (L/mol) molecular diffusion coefficients for organic substrates
Ke ) equilibrium constant for the hydrogenation of -bu- and for hydrogen were calculated as proposed by Wilke
tyrolactone (L2/mol2) and Chang (1955) and Akgerman and Gainer (1972).
kLaB ) volumetric gas-liquid mass transfer coefficient (1/ The solubility of hydrogen in 1,4-dioxane was calculated
by using the regular solution theory (Hildebrand et al.,
kSaP ) volumetric liquid-solid mass transfer coefficient (1/
LLF ) log-likelihood function
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 ) porosity of the catalyst particle
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