Chemical Engineering Science 58 (2003) 627 – 632

www.elsevier.com/locate/ces

Kinetics of hydrogenation of maleic acid in a batch slurry reactor

using a bimetallic Ru–Re/C catalyst
R. V. Chaudharia;∗ , C. V. Rodea , R. M. Deshpandea , R. Jaganathana , T. M. Leibb , P. L. Millsc
a Homogeneous Catalysis Division, National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411 008, India
b DuPontEngineering Technology, Reaction Engng. Consultants, Wilmington, DE 19898-0001, USA
c DuPont Company, Chemical Sci. & Engng. Lab., Experimental Stn., Wilmington, DE 19880-0304, USA

Abstract

The hydrogenation of maleic acid was investigated using a bimetallic Ru–Re/C catalyst powder in a semi-batch stirred slurry reactor
with the main objective of developing a kinetic model that would provide reliable predictions of the observed reactant and product
distributions and selectivities. The combined e2ects of hydrogen pressure, catalyst loading and initial maleic acid (MAC) concentration
on the concentration vs. time pro4les were studied over the temperature range of 523–543 K. The direct hydrogenation of aqueous MAC
solutions with the Ru–Re/C catalyst powder showed that succinic acid (SAC), -butyrolactone (GBL) and tetrahydrofuran (THF) were
the major products while n-butanol (BuOH), methane and propane were the principal side products. The selectivities of GBL and THF
were found to be strongly dependent on the initial MAC concentration, H2 pressure, catalyst powder loading and reaction temperature.
Kinetic rate equations for the key steps in the reaction sequence were developed using the observed concentration vs. time pro4les as the
starting basis and the kinetic parameters were estimated using non-linear parameter estimation. The predictions of the semi batch slurry
reactor model were found to agree reasonably well with the experimental data. The kinetic data showed a strong substrate inhibition e2ect
for the consecutive reactions sequence with the extent of inhibition decreasing in the order of MAC ¿ SAC ¿ GBL. This observation
suggests that a high space-time yield to THF can be obtained in a slurry reactor with signi4cant liquid phase backmixing by the use of
elevated temperature and pressure and long slurry residence time. Implications for commercial implementation are also suggested.
? 2003 Elsevier Science Ltd. All rights reserved.

Keywords: Hydrogenation; Slurry reactor; Kinetics; Maleic acid; Ru–Re/C catalyst; Tetrahydrofuran

1. Introduction process). Obviously, such a process would require a highly

The hydrogenation of maleic acid (MAC) to tetrahydro-
furan (THF) is one of the several recent examples of a com-
mercial multiphase catalytic process using a slurry reactor
(Stadig, 1992). This route has economic and safe operational
advantages over the conventional acetylene-formaldehyde
based Reppe process and other processes based on ei-
ther hydrogenation of diethyl maleate or maleic anhydride
(Mabry, Pritchard, & Ziemecki, 1990; Schwartz, 1995).
Particularly, the direct hydrogenation of aqueous MAC to
THF eliminates the various reaction steps and unit opera-
tions that are required for the recovery of maleic anhydride,
esteri4cation and dehydration of 1,4-butanediol (Reppe
∗ Corresponding author. Tel.: +91-20-589-31-63;
fax: +91-20-589-32-60.
E-mail address: rvc@ems.ncl.res.in (R. V. Chaudhari).
eGcient catalyst system with high selectivity for THF in a
single step. This has been achieved in a recently commer-
cialized DuPont process (Rao, 1988; Stadig, 1992) for THF
in a bubble column slurry reactor. The salient features of
the new process are: (1) Specially designed bimetallic cat-
alysts (Pd–Re or Ru–Re) and (2) The design of a continu-
ous slurry bubble column reactor with continuous removal
of the volatile product (THF) under high temperature (200 –
250◦ C) and pressure (14 –20 MPa) conditions. However,
the hydrogenation of aqueous MAC proceeds with com-
plex multistep reactions. For this and other related reasons,
it poses a serious challenge in achieving a high space-time
yield to THF.
Several catalysts consisting of supported Pd, Ru, Re and
their combinations with nickel, molybdenum and cobalt
have been previously investigated (Fuchigami et al., 1994;
Schwartz, 1995) for the direct liquid phase hydrogena-
tion of MAC and succinic acid (SAC). A 5% Pd–Pb on

0009-2509/03/$ - see front matter ? 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0009-2509(02)00588-2
628 R. V. Chaudhari et al. / Chemical Engineering Science 58 (2003) 627 – 632
silica catalyst for the hydrogenation of MAC has been
reported to give 86% selectivity for GBL along with var-
ious undesired side products, such as propionic acid and
butanol, but without the formation of THF (Fuchigami
et al., 1994). Several other patents describe the prepa-
ration of GBL using Pd catalysts along with alkali
metal salts (GriGths & Michel, 1987; Kusaka & Inajaki,
1996a, b). The formation of both THF and BDO via the liq-
uid phase hydrogenation of MAC has been reported using
Ru–Sn and Ru–Re catalysts (Hara & Endo, 1997; Budge,
Attig, & Pederson, 1996; Schwartz, 1995). Investigations
of both kinetics and reaction engineering aspects for the
hydrogenation of diethyl maleate (Chaudhari et al., 1999)
and the hydrogenation of maleic anhydride (Hermann &
Emig, 1997) were recently reported. However, there has
been no published literature on the hydrogenation of aque-
ous maleic acid (MAC) from the perspective of both
catalysis and reaction engineering. Considering the in-
dustrial importance of this complex multistep catalytic
reaction system, it was thought important to undertake a
systematic study on the product distribution, selectivity
and kinetic modeling. In this paper, a detailed investiga-
tion on product distribution, selectivity, impurity e2ects
and kinetic modeling for the liquid phase hydrogena-
tion of aqueous MAC solutions is presented using a 1%
Ru– 6% Re/C bimetallic catalyst. The catalyst evaluation and
kinetic experiments were performed using a semi-batch
stirred slurry reactor. Based upon the conclusions devel-
oped from the observed concentration vs time data, several
di2erent types of rate models were developed and discrim-
inated by non-linear kinetic parameter estimation using the
integral data. From this analysis, kinetic models were ob-
tained that provide a reasonable description of the intrinsic
kinetics for the various hydrogenation steps. Such infor-
mation provides the starting basis for further development
and optimization of various multiphase reactor perfor-
mance models for utilization in pilot or commercial scale
operations.
2. Experimental
2.1. Materials
Maleic Acid was prepared by hydrolyzing maleic anhy-
dride (MAN) in aqueous phase solutions. The pure MAC
was crystallized and checked for purity by measurement of
the melting point (MP) before being used in any near term
reaction experiments. In a typical case, the actual MP was
138◦ C, which was in close proximity to the literature value
of 140◦ C. The solvent used was distilled water. The cata-
lyst consisted of 1% Ru– 6% Re on Carbon powder (particle
size, dp = 3 × 10−5 m; particle density, p = 2 × 103 kg=m3 ,
surface area = 7:7 × 103 m2 =kg). The catalyst was activated
by contacting it with pure hydrogen gas at T = 523 K prior
to use.
Fig. 1. Schematic of the Reactor set up.
2.2. Reactor set-up
The reactions were performed using a 250 ml capacity
high pressure—high temperature reactor supplied by Parr
Instruments Co. USA. A schematic of the reactor set up is
given in Fig. 1. The autoclave was designed to operate at
a maximum temperature of 623 K and 20 MPa. All wetted
parts were constructed of Hastalloy-C since previous mate-
rials of construction tests showed that lower quality alloys
and steels were subject to corrosion under typical reaction
conditions. The reactor was equipped with a double bladed
variable speed stirrer with a magnetic drive. Automatic tem-
perature control was provided by using an external electri-
cally heated jacket and internal cooling coils. The latter was
connected to both air and water sources. Ports were also
provided with gas inlet/outlet tubings for gas supply and
gas venting. Other ports were equipped with valves and re-
lated hardware for sampling of the reactor gas and liquid at
various points during a reaction trajectory. For safety pur-
poses, a high pressure–high temperature cut-o2 facility was
also provided to the reactor, along with a rupture disc in the
event of overpressure.
The reactor was connected to a 250 cm3 hydrogen reser-
voir maintained at a pressure higher than that of the reactor,
using a forward pressure regulator. Hydrogen gas was sup-
plied to the reactor from this reservoir through a non-return
valve. The gas consumed during the course of the reaction
was as a result of demand was determined from the observed
pressure drop in the reservoir at di2erent time intervals. A
transducer connected to a pressure readout system was used
to monitor the instantaneous pressure in the both reactor and
H2 reservoir.
2.3. Procedure
In a typical hydrogenation experiment, known quanti-
ties of the substrate, catalyst and solvent were charged into
a clean and dry reactor. After installing the reactor head
and testing it for leaks, the autoclave contents were Nushed
2–3 times with N2 followed by H2 . The autoclave contents
were then heated to a desired temperature under slow stirring
 R. V. Chaudhari et al. / Chemical Engineering Science 58 (2003) 627 – 632
MAC FAC
SAC
PA GBL HBA
BDO BuOH
PrOH MeOH
THF Butane
Propane
Methane
FAC Fumaricacid; PA Propionic acid, HBA Hydroxybutyraldehyde
Fig. 2. Reaction pathway for hydrogenation of maleic anhydride.
(ca:50 rpm). After the desired temperature was attained, the
autoclave was quickly pressurized to the requisite pressure
with H2 and the reaction was started by adjusting the ag-
itation speed to 900 rpm. The cumulative H2 consumption
was determined from the decrease in the hydrogen pressure
in the reservoir vessel as a function of time. The liquid sam-
ples were withdrawn at speci4c time intervals and analyzed
(see below) to determine the reactant and product concen-
trations. At the end of the reaction, the autoclave was cooled
to room temperature and a gas sample was withdrawn for
analysis of the 4nal gas phase products. This gas phase anal-
ysis was essential to ensure that the cracking of the products
to hydrocarbons was negligible. Following this procedure,
the contents in the reactor were discharged and the liquid
samples analyzed for reactant and products.
2.4. Analysis
The analysis of the reactants and products was performed
using both high-pressure liquid chromatography (HPLC
model HP 1050) and gas-liquid chromatography (GLC, HP
5840). Both MAC and SAC were analyzed by HPLC us-
ing a lichrospher RP-18 column, with an overall length of
250 mm. HPLC grade water was used as the mobile phase
at a Now rate of 1 ml=min. The HPLC detector wavelength
was set at = 206 cm−1 for SAC and 254 cm−1 for MAC.
Other reaction products such as GBL, THF and n-BuOH
were analyzed on GLC on a 1=4 × 6 column packed with
80/100 mesh of 5%PEG 1500 on Chromosorb W-AW using
a N2 carrier gas Now rate of 20 ml/min. The column was
temperature programmed from 60◦ C to 140◦ C at the rate
of 45◦ C=min.
3. Results and discussions
Hydrogenation of maleic acid proceeds through a series
of consecutive and parallel reactions as represented by the
reaction scheme shown in Fig. 2. Initial experiments were
629
carried out to study the product distribution and selectivity
behavior using the Ru–Re/C catalyst. The experiments were
performed using the semi-batch slurry reactor to observe
concentration-time pro4les for a given set of initial condi-
tions. The e2ect of catalyst loading, H2 pressure, MAC con-
centration and temperature was investigated, the results of
which are discussed in the following sections.
3.1. Preliminary experiments
In order to obtain reliable kinetic parameter estima-
tion, it is important to ensure that all the key products are
identi4ed. Also, the material balance based upon reactants
consumed and products formed should be satis4ed within
reasonable error limits for an assumed stoichiometry. Fi-
nally, to achieve consistent catalyst performance for the
kinetic study, the preactivation procedure had to be stan-
dardized. This was particularly important for Ru–Re/C
catalyst system since initial performance tests indicated that
in-situ activation of the catalyst by treatment with H2 in a
batch slurry mode at 573 K and 13 MPa did not lead to re-
producible concentration vs time data. This procedure also
had a disadvantage since the preactivation was required be-
fore each kinetic run, which also led to inconsistent results.
In another modi4ed procedure, the aqueous slurry of the
catalyst was pretreated with H2 at 523 K and 13 MPa for
1 h. The resulting activated catalyst was 4ltered, dried and
stored in dry conditions. This procedure was found to give
a catalyst, which produced consistent concentration vs time
data. It was also noted that the catalyst did not deteriorate
on storage since the activity of the catalyst was retained
even after a few weeks. The catalyst treated in this fashion
was used further for all studies.
Catalytic hydrogenation of MAC is a complex multistep
reaction so that determining the reaction scheme for a spe-
ci4c catalyst system is necessary. Among the numerous re-
actions possible, the isomerisation of MAC to fumaric acid
[FAC] is a non-catalytic reaction. Under reaction conditions
isomerisation of MAC to FAC was observed, but no iso-
merisation was observed when FAC hydrogenation was in-
vestigated. Since, the rates of hydrogenation of both MAC
and FAC to SAC were similar, the isomerisation of MAC
to FAC was not considered in the kinetic analysis.
3.2. Product distributions and selectivity
A typical concentration pro4le observed in hydrogenation
of aqueous MAC is shown in Fig. 3. The principal products
formed were: succinic acid (SAC), -butyrolactone (GBL),
tetrahydrofuran (THF) and n-butanol (BuOH). These reac-
tion species accounted for more than 92% of the material
balance. Fumaric acid, butanediol and other products were
not observed with Ru–Re/C catalyst during hydrogenation.
Under certain extreme conditions (e.g., initial concentration
of MAC = 3:45 kmol=m3 , catalyst loading = 2 × 102 kg=m3
630 R. V. Chaudhari et al. / Chemical Engineering Science 58 (2003) 627 – 632

1.0 1.0 80
3
Concentration of Reactants / Products kmol/m

Predicted
70
GBL - 543K
MAC THF - 543K
0.8 SAC 0.8
GBL 60 GBL - 523K
THF THF - 523K
BuOH

Selectivity %
50
0.6 0.6

40

0.4 0.4 30

20
0.2 0.2
10

0.0 0.0
0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Time, min Time, min

Fig. 3. Concentration Time Pro4le for hydrogenation of MAC us- Fig. 5. Plot of selectivity as a function of time; E2ect of temperature. Re-
ing Ru–Re/C catalyst. Reaction conditions: temperature = 523 K; total action conditions: temperature=523 K; total pressure=13:91 MPa; MAC
pressure = 13:91 MPa; MAC concentration = 0:862 kmol=m3 ; catalyst concentration = 0:862 kmol=m3 ; liquid phase volume = 100 × 10−6 m3 .
loading = 50 kg=m3 ; liquid phase volume = 100 × 10−6 m3 .

80 3.3. Kinetic modeling

3
, 100 kg/m
, 50 kg/m
3
The main objective of the present work was to study
GBL the intrinsic kinetics of hydrogenation of MAC to prod-
60 .......... THF
ucts using Ru–Re/C catalyst. For this purpose, the kinetic
data were obtained over the following range of conditions:
Selectivity, %

(i) catalyst loading = 20–100 kg=m3 ; (ii) total pressure =

40
7:60–15:30 MPa and (iii) initial MAC concentration=0:43–
1:29 kmol=m3 at a temperature of 503–543 K. In each exper-
iment, the liquid samples were withdrawn and analyzed from
20 time to time and the concentration vs. time pro4les were
obtained. In all experiments, the material balance obtained
was ¿ 92%. Considering the product distribution observed
0 with Ru–Re/C catalyst, the following reaction scheme was
0 200 400 600
considered:
Time, min
A + C1 → C2 ; (1)
Fig. 4. Plot of selectivity as a function of time; E2ect of catalyst loading.
Reaction conditions: temperature = 523 K; total pressure = 13:91 MPa;
MAC concentration = 0:862 kmol=m3 ; liquid phase volume =
2A + C2 → C3 ; (2)
100 × 10−6 m3 .
2A + C3 → C4 ; (3)
and T = 523 K) GC analysis of a reactor head gas sample
A + C4 → C5 ; (4)
taken at the end of reaction showed traces of light hydro-
carbon products such as methane and propane from crack- where, A = H2 ; C1 = MAC; C2 = SAC; C3 = GBL; C4 =
ing type reactions. Until the conversion of MAC was nearly THF; C5 = n-butanol. The general trends observed (see
completed, the hydrogenation of SAC to subsequent prod- Fig. 3) indicate a strong substrate inhibition e2ect in the
ucts was negligible. Similarly, the conversion of GBL to order: MAC ¿ SAC ¿ GBL.
THF occurred only after SAC was consumed. These obser- In the interpretation of the rate data, integral concen-
vations indicate that MAC and SAC are strongly adsorbed tration-time data were used since the initial rate approach is
on the catalyst surface when compared to GBL and inhibit not very useful for analysis of complex multistep reactions.
further hydrogenation of GBL to THF. This trend suggests The initial rate data were only used to assess the signi4-
a requirement of severe conditions to achieve higher THF cance of external and intraparticle mass transfer e2ects us-
selectivity. The results on selectivity of THF and GBL as a ing the quantitative criteria suggested by Ramachandran and
function of catalyst loading and temperature are shown in Chaudhari (1983) for three phase catalytic reactions. This
Figs. 4 and 5. This suggests that THF selectivity increases analysis revealed that in the range of conditions studied in
with an increase in catalyst loading and temperature. this work, all the mass transfer resistances were negligible.
 R. V. Chaudhari et al. / Chemical Engineering Science 58 (2003) 627 – 632 631

The mass balance equations for the various reactant/product 1.0 1.0

3
Concentration of reactants / products,kmol/m
species in a semi-batch slurry reactor are given below: Predicted
MAC

dC1 0.8 SAC 0.8

= −r1 ; (5) GBL

dt THF
BuOH
0.6 0.6
dC2 r2
= r1 − ; (6)
dt 2 0.4 0.4

dC3 (r2 − r3 )
= ; (7)
dt 2 0.2 0.2

dC4 r3
= − r4 ; (8)
dt 2
0.0 0.0
0 100 200 300 400 500 600
Time, min
dC5
= r4 ; (9) Fig. 6. Concentration time pro4le for hydrogenation of MAC using
dt
Ru–Re/C catalyst. Reaction conditions: temperature = 503 K; total
pressure = 13:91 MPa; MAC concentration = 0:862 kmol=m3 ;
with initial conditions : t = 0; C1 = C0 ; C2 to C5 = 0: catalyst loading = 50 kg=m3 ; liquid phase volume = 100 × 10−6 m3 .
(10)

The above system of equations were solved consider- 1.0 1.0

Concentration of Reactants / Products, kmol/m3

ing several forms of rate equations based on Langmuir– Predicted
Hinshelwood (L–H) type models by a fourth order Runge 0.8
MAC
SAC 0.8
Kutta method combined with an optimization program to GBL
THF
simulate the experimental concentration-time data obtained BuOH

(8 experiments at each temperature) at di2erent reaction

0.6 0.6

conditions in a temperature range of 503–543 K. A detailed

procedure for model discrimination and the di2erent sta- 0.4 0.4

tistical criteria used were similar to those described earlier

(Rajashekharam, Nikalje, Jaganathan, Mills, & Chaudhari, 0.2 0.2

1997). The following rate equation based on a dual site L-H

model was found to satisfactorily represent all the data.
∗
wkj A Ci
rj = : (11)
(1 + KA A∗ + K1 C1 + K2 C2 + K3 C3 )2
The adsorption equilibrium constant is denoted by
K (m3 =kmol), and Cj denotes the concentration of the jth
species at the catalyst surface. The equilibrium solubility
of hydrogen in water can be calculated by Henry’s law as
follows:
∗
A = HePH2
In Eq. (12) A∗ denotes the equilibrium solubility in
kmol=m3 ; PH2 denotes the partial pressure of hydrogen
in atmosphere and He denotes the Henry’s law constant
of solubility in kmol=m3 =atm. The values of Henry’s
constant of solubility at various temperatures were deter-
mined experimentally as: 8:8 × 10−3 ; 1:56 × 10−2 and
3:50 × 10−2 kmol=m3 atm, at 503, 523 and 543 K, respec-
tively. A comparison between the model predictions and
the experimental data for a few cases is shown in Figs. 3, 6
and 7, which shows an excellent agreement (average error
¡ 6:0%). The estimated rate and adsorption equilibrium
parameters are given in Table 1. From the temperature
dependence of the rate constants, the activation energies
for the four reactions were found to be 165, 108, 106 and
53:8 kJ=mol respectively.
0.0 0.0
0 100 200 300 400
Time, min
Fig. 7. Concentration time pro4le for hydrogenation of MAC us-
ing Ru–Re/C catalyst. Reaction conditions: temperature = 543 K; total
pressure = 13:91 MPa; MAC concentration = 0:862 kmol=m3 ; Catalyst
loading = 50 kg=m3 ; Liquid phase volume = 100 × 10−6 m3 .
4. Conclusions
(12)
Kinetic modeling for the hydrogenation of aqueous maleic
acid solution has been studied in a slurry reactor using a
bimetallic Ru–Re/C catalyst. The reaction rates were found
to be strongly inhibited by MAC and SAC as indicated by
an L–H type of rate form with a negative reaction order.
Consequently, the selectivity of THF increases only after of
MAC and SAC approach nearly complete conversion. The
selectivity of THF also increased signi4cantly at higher cat-
alyst loading, H2 pressure and temperature. This behavior
suggests that the conversion of GBL to THF is a slower
step, compared to other hydrogenation reactions. Rate equa-
tions have been proposed and intrinsic kinetic parameters
estimated based upon experimental concentration-time data
at di2erent catalyst loading, H2 pressure and MAC con-
centrations in a temperature range of 503 to 543 K. The
predictions of a semi batch slurry reactor model agreed
632 R. V. Chaudhari et al. / Chemical Engineering Science 58 (2003) 627 – 632

Table 1
Rate Parameters for Hydrogenation of MAC

Temperature k1 × 105 k2 × 106 k3 × 106 k 4 × 107 KA K1 K2 K3

(K)

503 1.251 4.102 2.098 2.841 0.2011 0.989 0.508 0.0511

523 9.584 8.881 2.912 5.345 0.3042 1.513 0.901 0.1312
543 25.281 28.013 9.452 7.334 0.4997 2.519 1.981 0.3140

Units of kj : (m3 =kmol)(m3 =kg s); units of KA and K1 to K3 : (m3 =kmol).

with experimental data reasonably well for a wide range of References

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