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A: GENERAL
ELSEVIER Applied Catalysis A: General 123 (1995) 123-144

Structure and reactivity of copper-zinc-cadmium


chromite catalysts
G.L. Castiglioni a, A. Vaccari a,., G. Fierro b M. Inversi b
M. Lo Jacono b, G. Minelli b, I. Pettiti b, p. Porta b, M. Gazzano c
Dipartimento di Chimica Industriale e dei Materiali, Universitdt di Bologna, Viale del Risorgimento 4,
40136 Bologna, Italy
u Centro del Consiglio Nazionale delle Ricerche su 'Struttura e Attivitgt Catalitica di Sistemi di Ossidi'
(SACSO), e/o Dipartimento di Chimica, Universitgt di Roma 'La Sapienza ', Piazzale AIdo Moro 5, 00185 Rome,
Ita(v
Centro del Consiglio Nazionale delle Ricerche su 'Struttura e Fisica delle Macromolecole' ( CSFM),
c/o Dipartimento di Chimica 'G. Ciamician ', Via Selmi 2, 40127 Bologna, Italy

Received 10 July 1994, revised 24 October 1994; accepted 24 October 1994

Abstract

Different mixed oxides containing Cu, Zn, Cd and Cr were obtained by heating hydroxycarbonate
precursors at various temperatures and in different atmospheres, and characterized by using X-ray
diffraction (XRD), infrared, diffuse reflectance spectroscopy, thermogravimetry, and BET and copper
surface area analysis. The reduction process and the phase evolution during reduction of the mixed
oxides was followed by temperature-programmed reduction and XRD. The mixed oxides were acti-
vated in an H J N 2 flow and then tested as catalysts in the vapour-phase hydrogenation of y-butyro-
lactone (GBL) and a solution of maleic anhydride (MA) in GBL (60:40 w / w ) . Depending on
composition, heating temperature and atmosphere, the samples contained different phases, such as
CuO, CdO, Cr203, CuCrO2, CuCrO4, ce-CdCrO4, cubic and tetragonal CuCr204, and cubic Cu-Zn
and Cu-Cd spinel-type phases. The partial substitution of Cu 2 + ions with Zn 2+ or Cd 2 + ions stabilizes
the cubic form of the spinel-type phases, which form via intermediate chromate phases. The final
product of reduction in all cases is metallic copper. Cubic CuCr204 is more reducible than the
corresponding tetragonal phase, which reduces to metallic copper through the intermediate formation
of CuCrO 2. The presence of zinc or cadmium promotes or inhibits, respectively, the copper reducibility
both in CuO and in the copper chromite spinel. In the hydrogenation of GBL, the Cu/Cr catalysts
obtained by calcination show similar behaviours, with a small increase in activity as a function of the
copper content. At the lower temperatures investigated the main products are tetrahydrofuran (THF)
and n-butanol, while at 548 K significant amounts of ethanol are observed, favoured by increasing
copper content. On the other hand, the Cu/Cr catalyst obtained by heating under a reduced oxygen
atmosphere, for which only tetragonal CuCrzO 4 is detected before reduction, shows a decrease in
catalytic activity. Partial substitution of the Cu 2+ ions gives rise to a decrease in GBL conversion,
with a considerable deactivation when Cd 2 + ions are present. Decreasing the H2/C 4 molar ratio gives

* Corresponding author. E-mail: cicatal@boifcc.cineca.it, Tel. ( + 39-51 ) 6443683, fax. ( + 39-51 ) 6443680.

0926-860X/95/$09.50 1995 Elsevier Science B.V. All rights reserved


S S D I O 9 2 6 - 8 6 0 X ( 94 ) 0 0 2 3 7 - 1
124 G.L. Castiglioni et al./Applied Catalysis A: General 123 (1995) 123-144

rise to a decrease in activity for all samples, without any significant change in the trend observed.
With the M A / G B L solution, the partial substitution of Cd 2+ ions for Cu 2+ ions also gives rise to
considerable deactivation. For the other catalysts, the main products at the lower temperatures are
GBL and succinic anhydride (SA), while at 548 K overhydrogenation and hydrogenolysis reactions
predominate. The presence of Zn 2+ ions gives rise to an increase in yield in GBL, due to an increase
in the hydrogenation activity toward SA, but the consecutive transformation of GBL at high temper-
ature to low cost by-products is not inhibited. On the other hand, the presence in the Cu/Cr catalyst
of only CuCr204 increases the yield in GBL, as a consequence of a strong inhibition of the overhy-
drogenation and/or hydrogenolysis reactions of GBL. With the M A / G B L solution, similar behaviours
are observed when the H2/C 4 molar ratio decreases. At the same time, however, the lack in the carbon
balance increases and a displacement towards high temperature of the maximum yield in GBL is
found.

Keywords: y-Butyrolactone; Chromite spinels; Copper reducibility; Hydrogenation; Maleic anhydride

1. Introduction

Copper-chromium mixed oxides in a partially reduced state are well known as


excellent catalysts for many reactions, such as hydrogenation of organic compounds
[ 1-5 ], alcohol decomposition or dehydrogenation of alcohols [ 6,7 ], ester hydro-
genolysis ] 8], etc. The resistance of chromite catalysts to heat and inhibitors seems
to be superior to that of metallic copper. Furthermore, some metal oxides (e.g.,
BaO) may be incorporated into the catalyst and act as promoters or stabilizing
agents.
Notwithstanding the many papers dealing with the characterization of these
systems [9-13], their composition and structure have not been completely
explained, taking into account also that these catalysts may be prepared, pretreated
and used in different ways, and that their nature can be varied by changing the
copper-to-chromium ratio.
The preparation and characterization of new Cu/Cr phases, distinguished by an
excess of chromium ions have also been reported [ 14-17]. For these catalysts
direct relationships have been reported between the activity, the concentration of
cuprous ions in an octahedral environment and the concentration of occluded
hydrogen [ 17-19].
In previous papers, we have shown that the synthesis of non-stoichiometric
spinel-type phases may be a key tool for the preparation of tailored catalysts with
specific activities in different hydrogenation reactions [ 20,21 ]. In particular, it was
found that the substitution of part of the copper ions with other divalent ions strongly
modifies the activity and yield of the catalysts [21-23]. The objective of the
research reported here was to investigate the reaction involved in the synthesis of
these spinel-type phases. The main goal was to document changes in the structure
and reactivity related to the presence of excess copper ions and to their partial
substitution with other divalent ions. In particular, we examined the vapour-phase
G.L. Castiglioni et al./Applied Catalysis A: General 123 (1995) 123-144 125

hydrogenation of maleic anhydride (MA) to y-butyrolactone (GBL) and tetrah-


ydrofuran (THF), which are widely required as solvents and industrial intermedi-
ates for the production of medicines and polymers [ 24-26 ]. Hydrogenation of MA
is an interesting way to produce GBL or THF, taking into account that (i) hazardous
feedstocks are not required; (ii) it is the most simple and direct way to produce
GBL and THF [24-26], and (iii) MA may be considered a feedstock, since it is
available in large amounts and at low cost as the result of the construction of large
fluid-bed plants (about 50 000 t/y) based on Alusuisse-Lummus and B P / U C B
technologies [ 25-28 ].

2. Experimental

All samples (Table 1 ) were obtained by coprecipitation at pH 8.0 from a solution


of the nitrates of the elements with a slight excess of NaHCO> The precipitates
were washed until the sodium concentration was lower than 0.1% w / w (as Na20),
then dried at 363 K and calcined for 24 h at 653,753 and 853 K. For Cat 1 and Cat
4, samples were also prepared by calcination of the precursor at 593 K and heating
at 753 K in vacuum ( P < 1.3 Pa), respectively. Cat 5 was obtained by heating the
same precipitate used for Cat 1 under reduced air pressure (ca. 66 Pa) at 653 K for
24 h.
X-ray diffraction (XRD) powder patterns for the unreduced materials were
recorded using a Philips PW 1050 / 81 diffractometer controlled by a PW 1710 unit
and Ni-filtered Cu Ko~ radiation. The phase evolution during the reduction process
was studied by XRD in an Anton-Paar HTKI0 camera attached to a Philips dif-
fractometer equipped with an inner heating block-sample holder, and with variable
temperature and feed controls. The samples calcined at 653 K were reduced step
by step in the temperature range 393-673 K for 10 min at each step of 20 K in a
flow of 45-50 ml min i of an H2/N2 mixture (6:94 v / v ) . The X-ray diffraction
patterns were recorded in the range of 2 0 = 28-44 , since this is the range in
which the strongest X-ray reflections of the initial and most likely reduced phases
present occur. An X-ray diffraction line originating from the platinum sample holder
was used as an internal standard reference line for comparison of the relative
intensities of the reflections of the phases present. The main results of the in situ
reduction XRD investigation are reported in Table 2 and the XRD patterns of the
most important samples are discussed in detail.
Diffuse reflectance (DR) spectra were recorded using a Cary 2300 spectrometer
equipped with an IBM PS2 computer for data acquisition and analysis, in the
40 000-4000 cm J range, covering the UV, visible and near-infrared regions.
Infrared (IR) spectra were recorded using the KBr disk technique and a Perkin-
Elmer 1700 Fourier-transform (FT-IR) spectrometer in the 4000-400 cm 1range.
A Carlo Erba Sorpty 1750 apparatus with nitrogen adsorption was used to meas-
ure the surface area of the samples.
126 G.L. Castiglioni et al. /Applied Catalysis A: General 123 (1995) 123 144

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G.L. Castiglioni et al./Applied Catalysis A: General 123 (1995) 123-144 127

Table 2
XRD data of the samples calcined at 653 K after in situ reduction; hydrogen uptake during TPR experiments and
copper surface area of the samples after reaction and further reduction

Sample" XRD (underH2) ~' H2 uptake (/xmol/gca,) c Copper surface area (mZ/gcu,,)

T (K)i. Phases~i. Observed Calculated

Cat 1 523 Cu , Cr203 3876 4315 28


Cat 2 473 Cu , Cr203 5392 6471 17
Cat 3 463 Cu , ZnCr204, Cr20~ 4091 5091 15
Cat 4 503 Cu , CdCr204, Cr203 4605 5362 5
Cat 5 583 Cu , Cr203 2000 4333 21

Composition as in Table I.
b XRD data after in situ reduction steps: starting temperature of the spinel reduction [ T (K) ~n], and phases detected
at the end of the reduction [ (phases~.) ].
Hydrogen uptake observed and calculated on the basis of the content of reducible species in the initial phases.

The carbonate content in the dried precipitates was determined, after chemical
attack with concentrated H z S O 4 and subsequent absorption of carbon dioxide in
0.1 M NaOH, by titration with 0.1 M HC1, using a digital microburette (Amel
model 233).
Thermogravimetric (TG) analysis was carried out using a Perkin-Elmer TGS-2
thermobalance, with a nitrogen flow of 50 ml min- ~ and a constant heating rate of
10 K min i For some samples the analysis was also carried out under a flow of
air.
The temperature-programmed reduction (TPR) tests of the samples calcined at
653 K were made in a home made apparatus using a n H z / N 2 flOW (6:94 V/V) of
50 ml min-~, with a heating rate of 1 K min - ~, starting from room temperature up
to 513 K. The weights of the samples were 38.7, 10.2, 11.0, 30.4 and 30.0 mg for
Cat 1, Cat 2, Cat 3, Cat 4 and Cat 5, respectively. A preliminary study showed that
the reduction profiles were not affected by diffusion phenomena up to a sample
mass of 100 mg. The amounts of both hydrogen uptake and water formed were
determined. The samples were always pretreated in an oxygen flow at about 650 K
in order to eliminate traces of impurities and adsorbed water. For Cat 5 the TPR
test was also carried out up to 873 K.
The catalytic tests were carried out using 2.0 +_0.2 g of catalyst calcined at 653
K (0.420-0.841 mm particle size) in a copper tubular microreactor (internal diam-
eter 2 ram, length 520 mm), operating at atmospheric pressure in the 453-573 K
range. The reactor was fed with a stream of M A / G B L solution (60:40 w / w ) in
hydrogen [ H2 / C4 = 170 and 69 ( mol / tool) ]. Preliminary catalytic tests with GBL
[Hz/GBL = 173 and 69 ( m o l / m o l ) ] were also carried out, taking into account
both that GBL is an intermediate in the hydrogenation of MA and that it is also the
solvent employed to feed MA, because most of the usual solvents react preferen-
tially with MA. The organic feedstock was introduced by an Infors Precidor model
5003 infusion pump. Before the catalytic tests, the samples were activated in situ
at atmospheric pressure in an H2/N2 flow (5:95 v / v ) , while progressively increas-
128 G.L. Castiglioni et al./Applied Catalysis A: General 123 (1995) 123-144

ing the temperature from room temperature (R.T.) to 598 K. The reaction products
were analyzed in-line without condensation using a Carlo Erba 4300 gas chromat-
ograph equipped with FID and two columns ( 3.2 m m 2.0 m) filled with Porapack
QS.
The surface area of the copper in the catalysts tested was determined in situ, after
reduction, by the nitrous oxide pulse technique at room temperature, as reported in
the literature [ 29,30].

3. Results and discussion

3.1. Characterization of the precursors

All the dried precipitates (green in colour) show XRD patterns typical of quasi-
amorphous phases, with only the exception of Cat 4, in which a crystalline CdCO~
phase also is detected (Table 1 ). The precipitates were identified as hydroxycar-
bonates on the basis of IR analysis [31 ]. Independently from the chemical com-
position, all the samples display a large absorption band in the 600-400 cm I
range, attributable to a M - O vibration, the intensity of which is related to the
chromium content [ 32]. The presence of a chromium hydroxide-type phase may
thus be hypothesized, also taking into account the occurrence of an absorption band
of lower intensity at 830 c m - i. The splitting of the ~'3 frequency of carbonate with
the appearance of two bands in the 1500-1350 c m - l range (with a separation
between the peaks of about 100 c m - 1, typical of basic salts) and the presence of a
shoulder at about 1050 cm 1 are evidence of a basic salt with a low degree of
symmetry of the carbonate [ 31,33,34]. Moreover, the high intensity of the band at
1630 c m - 1 suggests that it is not only related to the bending vibration of water but
also to the presence of bicarbonate. In any case, the low degree of symmetry of
carbonate and the presence of bicarbonate are not in contradiction with each other,
and both species may be present at the same time. It can be seen from the data of
the analysis of the carbonates in the samples examined (Table 1 ), that the experi-
mental values are always lower than those calculated on the basis of the presence
of some possible hydroxy (carbonate)-type phases, such as malachite, aurichalcite,
hydrozincite or hydrotalcite-type phases. This fact may be explained taking into
account the tendency of the Cr 3+ ions to form polynuclear complexes containing
hydroxylic bridges, with the formation, in a basic environment, of a 'chromic
hydroxide' [35]. This hypothesis explains the very low amount of carbonate
detected for the sample with the highest chromium content (Cat 1 ).
The reflectance spectra of the precursors of Cat 1, Cat 2, Cat 3 and Cat 4 are
reported in Fig. la, b, c and d, respectively. Apart from the band (w) at lower
energy (ca. 5000 c m - l), due to surface water, the DR spectra show the occurrence
of several bands: bands (i) and (ii) at ca. 7000-8000 and 12 500 cm 1, respec-
tively, correspond to Cu 2 + ions in a distorted octahedral symmetry, while bands
G.L. Castiglioni et al./Applied Catalysis A: General 123 (1995) 123-144 129

(b)

g w ii iii iv

-g

5000 20000 1 t, O000


wavenumbers/cm-
Fig. 1. Diffuse reflectance spectra for the different precipitates dried at 363 K. (a) ,Cat 1 (Cu/Cr = 67:33); (b)
Cat 2 (Cu/Cr = 50:50); (c) Cat 3 ( C u / Z n / C r = 40:10:50); and (d) Cat 4 ( C u / C d / C r = 40:10:50, atomic
ratio percent).

(iii), (iv) and (v) at ca. 14 500, 18 000 and 24 000 c m - l, respectively, are due
to Cr 3+ ions in octahedral symmetry [36]. These observations are consistent with
the presence of hydroxy(carbonate)-type structures where the oxygen atoms are
nearly octahedrally coordinated to the metals.
The thermograms carried out in nitrogen on the precursors show in all cases a
total weight loss in the 31-35% range. The main loss occurs up to about 693 K and
may be attributed to the elimination of the coordinated water [ 37,38], even though
it is not possible to exclude a contribution related to partial decomposition of the
carbonates. The weight loss at higher temperatures may be attributed, on the basis
of the IR analysis, to the decomposition of the carbonates and small amounts of
chromates formed in the previous step. The temperature of this last transition is a
function of the composition of the system, and decreases with the lowering of the
chromium content and the partial substitution of the copper ions with other divalent
ions in the following order: Tcu > T c d > Tzn. It must be noted that this order does
not correspond to the decomposition temperature of the different carbonates and/
or hydroxycarbonates reported in the literature [ 37]. Indeed it seems more likely
to be related to the tendency to form spinel-type phases, whose order of formation
should be: Zn > Cd > Cu. The heating atmosphere influences the decomposition;
in particular, when TG analysis of Cat 2 was carried out in air (i.e. as during
calcination) a decrease in the temperature range of the loss of coordination water
was observed, with a corresponding increase in the amount of chromates formed.
Moreover, in this case it is possible to determine clearly the weight losses due to
carbonate and chromate decomposition, respectively, as a result of better recrys-
tallization of the system, which occurs in air at lower temperatures [37].
130 G.L. Castiglioni et al./Applied Catalysis A: General 123 (1995) 123-144

3.2. Characterization of the oxide catalysts

For each calcination temperature, the oxide phases identified in the XRD patterns,
by comparison with the JCPDS Powder Diffraction Files [39], are reported in
Table 1, together with the amounts of CuO calculated on the basis of XRD data
[40], the theoretical CuO content, the lattice parameters of the spinel phases and
the surface areas of the mixed oxides obtained at 653 K.
After calcination at 653 K for 24 h, the catalyst with the highest amount of
chromium (Cat 1 ) showed the presence of tetragonal CuCr204 spinel and Cr203.
Even though the chemical composition of the sample would also require the occur-
rence of CuO, no trace of tenorite is detected by XRD analysis. At a higher copper
content (Cat 2), poorly crystalline cubic CuCr204 spinel (mainly) and CuO are
observed. The partial substitution of Cu 2+ ions with Zn 2+ ions (Cat 3) again gives
rise to cubic spinel and CuO, while that of Cu 2+ ions with Cd 2+ ions (Cat 4) leads
to cubic spinel, CuO and a-CdCrO4. The presence of a chromate species, CuCrO4,
is also detected in Cat 1 calcined at 593 K, while no evidence of CuCrzO 4 spinel is
found after this treatment, notwithstanding the right Cu/Cr stoichiometric ratio.
Taking into account that amorphous dichromate-type phases are detected by IR
analysis [41 ] also in Cat 2 and 3 calcined at lower temperatures [23], a general
mechanism of formation of spinel phases through chromate intermediates (more
or less crystalline) and their successive autocatalytic decomposition may be sug-
gested [ 9,42]. It is worth noting that also for the chromium-rich sample Cat 1 (Cu/
C r = 3 3 : 6 7 ) , the formation of tetragonal CuCr204 spinel takes place via
intermediate CuCrO4, according to the following pathway:

Precipitate ---* CuCrO4 + Cr203

2CuCrO4 --~ CuCr204(tetragonal) + CuO + 3/202

CuO + Cr203 ~ CuCr204(tetragonal)

In order to avoid the formation of intermediate CuCrO4, calcination at 653 K of


the C u / C r = 33:67 precipitate must be carried out at low oxygen pressure (ca. 66
Pa), as for Cat 5, for which only highly crystalline CuCr204 tetragonal spinel was
obtained (Table 1 ). Furthermore, the heating conditions as well as the partial
substitution of Cu e + ions with other divalent ions have a considerable effect on the
surface area of the samples obtained at 653 K.
When calcination is carried out up to 753 K, the sample with the highest chro-
mium content (Cat 1 ) shows the presence of more crystalline tetragonal CuCrzO4,
while some Cr203 is still visible. The Cr/Cu sample with higher copper content
(Cat 2) gives rise to an increase in the amount of the CuO side phase, with the
appearance of the tetragonal spinel phase, in addition to the cubic one already
observed at 653 K. The main effect of the partial substitution of copper with a
G.L Castiglioni et al. /Applied Catalysis A: General 123 (1995) 123-144 131

a (nm)
0,86

0,85

0 , 8 4

0,82
0 20 40 60 80 100
Cd/Cd+Cu
(atomic ratio %)

Fig. 2. Lattice parameter vs. cadmium atomic-% composition for copper-cadmium cubic spinel-type solid solu-
tions. (O) values for CuCr204 and CdCr204 [39]; ([2]) Cat 4 (Cu/Cd/Cr = 40:10:50, atomic ratio percent)
calcined at 753 K; (~) Cat4 heated at 753 K in vacuum.

second divalent metal (Cat 3 and Cat 4) is an increase in the stability of the cubic
structure of the spinel-type phase in comparison with the tetragonal one. Therefore,
cubic spinel-type phases may be obtained by controlled oxidation of the precipitates
with high copper content.
For the catalysts 2-4 calcined at 753 K, the amounts of CuO detected by quan-
titative XRD analysis approach a maximum of ca. 50% of the value calculated on
the basis of a phase composition CuO + stoichiometric spinel, showing the existence
of a consistent fraction of copper ions which escapes XRD detection, probably
present inside the spinel-type phase or as small CuO particles strongly interacting
with it [43].
It may be noted that the values of the unit cell parameter observed for the cubic
spinel (Table 1) present in Cat 4 calcined at 753 K (0.8432 nm) and in Cat 4
heated at 753 K in vacuum (0.8552 nm) are intermediate between the values given
for cubic CuCr204, 0.8344 nm, and cubic CdCr204, 0.8596 nm [39]. The unit cell
expansion observed in the spinel of Cat 4 in comparison to pure CuCr204 indicates
the presence of a Cu-Cd spinet-type solid solution, in agreement with the expec-
tations based on the isomorphous replacement in CuCr204 of a smaller ion (tetra-
hedral ionic radius for Cu 2+ equal to 0.57 A) with a larger one (tetrahedral ionic
radius for C d 2 + equal to 0.78 ,~) [ 44]. On the basis of the values for C u C r z O 4 and
CdCr204 as extreme members and hypothesizing that the Cu/Cd spinel type solid
solutions obey Vegard's law [45], the following results were obtained (Fig. 2):
- - For Cat 4 calcined at 753 K, a Cd/Cd + Cu atomic ratio of about 38%, in
agreement with the value of ca. 31%, calculated from the quantitative composition
determined by XRD analysis (Table 1 ).
- - For Cat 4 heated at 753 K in vacuum, a Cd/Cd + Cu atomic ratio of about
80%, in agreement with the value of ca. 85% calculated from the quantitative
composition determined by XRD analysis.
It should be noted that the formation of a spinel solid solution is also likely to
occur in Cat 3 since Cu z+ and Zn 2+ ions have more comparable sizes than Cu 2+
132 G.L. Castiglioni et al. /Applied Ccltalysis A: General 123 (1995) 123 144

and C d 2+ ions (tetrahedral ionic radii for Cu 2+ and Zn 2+ equal to 0.57 and 0.60
A, respectively) [44]. However, due to the similarity of the ionic radii for Cu 2+
and Zn 2+, which is reflected in the similar lattice parameters observed for cubic
CuCrzO 4 (0.8344 rim) and ZnCr204 (0.8328 rim) [39], the experimental value of
the lattice parameter for the cubic spinel in Cat 3 (0.833 nm) cannot lead to any
conclusion regarding the presence of a mixed Cu-Zn-Cr spinel.
It should also be noted that Cat 4 heated at 753 K in vacuum gives rise to CdO
and CuCrO2 (Cu + containing compound), in addition to the Cu-Cd cubic spinel
solid solution mentioned above.
For Cat 2, a further increase in calcination temperature (853 K) leads to an
increase in the amount of both segregated CuO and tetragonal spinel phase only
(Table 1 ), suggesting that the cubic structure represents an intermediate step in the
formation of the more stable tetragonal phase, according to the following scheme:
Precipitate ~ Chromate-type phase ~ Cubic spinel-type phase ~ Tetragonal
spinel-type phase

In any case, the nature of the elements present in the systems plays an important
part in this process, and it is possible to define the following order of stability for
the cubic spinel structure: C u / Z n / C r > C u / C d / C r > Cu/Cr.

3.3. Reduction of the catalysts

The temperature-programmed reduction (TPR) curves up to 513 K for the


various catalysts calcined at 653 K are shown in Fig. 3, while the amounts of
hydrogen uptake are reported in Table 2 (it is worth noting that the amounts of
water formed agree with the hydrogen uptake). A sample of pure Cr203, studied
as a reference compound, was not reduced at T < 873 K.
For Cat 5 (pure, tetragonal and highly crystalline CtlCrzO 4 spinel) a single peak
was detected (with a maximum at 408 K) related to the reduction of the copper
present in the spinel phase. However, the hydrogen uptake at the end of the TPR
test ( 513 K) corresponded to ( slightly less than) 50% of the copper content in the
copper chromite used (Table 2), showing that the Cu 2+ ions were only partially
reduced. The XRD analysis, made soon after the TPR tests, confirmed the total
absence of metallic copper and indicated the presence of CuCrO2 together with
unreduced CuCrzO4, while the XRD pattern after heating at 773 K in dynamic
vacuum of the sample previously reduced at 513 K, showed a better crystallization
of the CuCrO2 phase formed. It may be recalled that the formation of CuCrO2 has
already been reported in Cu-Cr oxide samples by Tonner et al. [46].
Another interesting feature, only evident in the TPR curve of Cat 5 (Fig. 3), is
that the base line for this catalyst is shifted to the hydrogen consumption side after
the reduction peak. This is an indication that reduction was still going on. The TPR
experiment on Cat 5 was repeated up to 873 K and the following results were found
(Fig. 4):
G.L. Castiglioni et al. /Applied Catalysis A: General 123 (1995) 123-144 133

a:',

_ ~ ~...._~CAT4
--CAT3

~.CAT 1
I I , I I I
273 323 373 /,23 /J3 523
T/K
Fig. 3. Temperature-programmed reduction (TPR) tests carried out up to 513 K for the samples obtained by
calcination at 653 K for 24 h. Cat 1: C u / C r = 33:67; Cat 2: C u / C r = 50:50; Cat 3: C u / Z n / C r = 40:10:50: Cat
4: C u / C d / C r = 40:10:50; Cat 5: C u / C r = 33:67 (atomic ratio percent), obtained by heating at 653 K for 24 h
under a reduced oxygen pressure.

(i) The first part of reduction results in a sharp peak plus a shoulder after the
peak, the end occurring at 603 K; the integrated areas of the peak and of the shoulder

~c

I I I
~"~-CAT5
I I
273 373 473 573 673 773 873
T/K
Fig. 4. Temperature-programmed reduction (TPR) test carried out up to 873 K for Cat 5 ( C u / C r = 33:67, atomic
ratio percent), obtained by heating at 653 K for 24 h under a reduced oxygen pressure.
134 G.L. Castiglioni et al. /Applied Catalysis A: General 123 (1995) 123-144

C LIe $$

A 523 K

211

202 ~6 ~12
220 [ 200
,,I
/,/. ] (0 3'2 2'8
2 E)/degrees
Fig. 5. XRD patterns for Cat 5 (Cu/Cr = 33:67, atomic ratio percent, obtained by heating at 653 K for 24 h under
a reduced oxygen pressure) subjected to in situ reduction (H2/N2 = 6/94 v/v) at different temperatures. At the
bottom the X-ray lines ( relative intensities and hkl indexes) of the reference tetragonal CuCr204 spinel are reported
[39]. Asterisk, double asterisk and Cu indicate the X-ray lines of Pt internal reference, Cr203 and Cu , respec-
tively.

correspond to the reduction of about 50% of the copper present (Table 2). The
XRD pattern taken after reduction at 603 K showed the presence of CuCrO2. If we
recall that, originally, Cat 5 is a highly crystalline (large particles) tetragonal
CuCr204 spinel and that after reduction at 513 K, CuCr204 was still found in the
XRD pattern, it may be reasonably assumed that the sharp peak is due to the
reduction of the spinel surface layers, and the successive shoulder to the reduction
of the bulk spinel, both processes giving rise to CuCrO>
(ii) The second part of the reduction gives a large region in the range 603-823
K (the integrated area corresponds to 50% of molar copper reduction), and is
reasonably related to the successive reduction of the Cu + ions present in CuCrO2
to metallic copper. The XRD pattern at the end of reduction (873 K) confirms the
presence of only Cu + Cr203.
The XRD carried out during the in situ reduction confirmed that Cat 5 is difficult
to reduce. The following features regarding the reduction of the bulk structure of
the solid emerge from the data reported in Fig. 5 (only the most relevant temper-
atures are shown): (i) at 523 K the pattern is the same as that taken at room
temperature and tetragonal CuCr204 is the only phase present; (ii) the initial point
of disappearance of the spinel phase occurs much later than for the other samples
G.L. Castiglioni et al. /Applied Catalysis A: General 123 (1995) 123-144 135

(583 K) ; (iii) only at 613 K can the appearance of Cu be detected (note the shift
towards higher 2 0 values of the X-ray line at ca. 43); and (iv) the sample is
completely reduced only at 673 K with the formation of cubic Cr203 [39], and
metallic copper with a low degree of crystallinity (in the other catalysts the Cu X-
ray line at 2 0 = 43 is much stronger and narrower than here).
Another interesting feature is shown by the TPR curve of Cat 1 (Fig. 3). We
may recall that in this sample, despite the stoichiometry corresponding to CuCr204
(as Cat 5), only tetragonal CuCr204 and Cr203 (both phases with a low degree of
crystallinity) were found by XRD analysis. The detection of Cr203 by XRD, but
not of a corresponding amount of CuO, may be the result, as also suggested by
Laine et al. [47], of some amount of non-crystalline copper, e.g. well dispersed or
occupying defect sites in the spinel phase. In situ reduction XRD analysis carried
out on Cat 1 showed that: (i) the first evidence of Cu formation is detected at 523
K; and (ii) the tetragonal CuCr204 spinel is completely reduced at 573 K with the
formation of hexagonal T-Cr203 and Cu (with a low degree of crystallinity).
Therefore, the first TPR peak is due to the reduction to metallic copper of the non-
crystalline copper (finely dispersed CuO or Cu 2+ ions located at some point defects
in the spinel), and the second peak to the reduction of CuCrzO 4 [ 47-49]. However,
in contrast to that found for Cat 5, the reduction of the spinel phase occurs com-
pletely to Cu (without the intermediate formation of CuCrO2), with good agree-
ment between the values of observed and calculated hydrogen uptake (Table 2).
We can thus infer that in Cat 1 considerable interaction exists between the CuO
and CuCr204 particles, and that reduction of the spinel is strongly catalyzed by the
metallic copper formed by reduction of CuO. However, CuCr204 also promotes,
even though to a lesser extent, the CuO reducibility, taking into account that
complete reduction of CuO alone was observed to occur under the same experi-
mental conditions at least 40 K later [50].
Confirmation of the synergetic promoter catalytic effect of metallic copper and
CuCr204 on the CuCr204 and CuO reducibility, respectively, is also obtained from
the TPR experiment on Cat 2 (where the CuO content is higher than in Cat 1 ). In
situ reduction XRD analysis confirmed that the initial disappearance of the cubic
CuCr204 spinel phase and formation of metallic copper occur at a lower temperature
(473 K) for Cat 2 than for Cat 1. The end of the reduction occurs at 493 K, with
the formation of cubic Cr203 and metallic copper with a high degree of crystallinity.
For Cat 3, where in comparison with Cat 2 there is a partial substitution of copper
ions with zinc ions and where the phases present are CuO and cubic chromite
(Table 1), the TPR experiment shows the occurrence of a first peak with two
successive shoulders. By analogy to Cat 2, the first peak and the first shoulder are
related to the reduction to Cu of the copper in CuO and CuCrzO4, respectively.
The second shoulder may be attributed to the reduction of Cu 2+ in a mixed copper-
zinc spinel-type phase, which although not directly detectable by XRD, can rea-
sonably be considered to be present in this sample, in analogy with that observed
for Cat 4. Based on the observed reduction temperature, it seems, moreover, that
136 G.L. Castiglioni et al. /Applied Catalysis A: General 123 (1995) 123 144

cY

~~~ 533 K

A i'' ......

2e/degrees
Fig. 6. XRD patterns for Cat 4 (Cu/Cd/Cr - 40:10:50, atomic ratio percent, calcined at 653 K for 24 h ) subjected
to in situ reduction (HJN2 = 6/94 v/v) at different temperatures. At the bottom the X-ray lines (relative
intensities and hkl indexes) of the reference cubic spinel ( dashed lines) and of a-CdCrO~ (full lines) are reported.
Asterisk, double asterisk, T and Cu indicate the X-ray lines of Pt internal reference~ Cr203, CuO (tenorite) and
Cu , respectively.

zinc plays a promoter role toward copper reducibility. In situ reduction XRD
analysis confirmed that the initial disappearance of the spinel phase and the for-
mation of metallic copper occur for Cat 3 at a slightly lower temperature (463 K),
than for Cat 2 (473 K, Table 2).
Interpretation of the TPR curves of Cat 4 is not easy, but the most probable
hypothesis is that the higher reduction temperatures (in comparison with those
observed for Cat 2 and 3) indicate the presence of cadmium chromate and of a
copper-cadmium mixed spinel-type phase as inhibitors toward the copper reduci-
bility of both CuO and copper chromite. The peak with a maximum at 423 K may
be assigned to the simultaneous reduction of CuO and Cr 6 + (of the chromate) to
Cr 3+. The second peak with a maximum at 431 K is attributable to the complete
reduction to metallic copper of Cu 2+ in the chromite phase. This hypothesis is
confirmed by the XRD in situ reduction analysis. For Cat 4, where the oxide
products present are CuO, Cu/CdCr204 and o~-CdCrO4,the first evidence of metal-
lic copper is observed at 503 K (Fig. 6).

3.4. Catalytic activi O,


The activity of the catalysts obtained by reduction of the samples calcined at 653
K was investigated in the MA and GBL hydrogenation reactions; in the former case
G.L Castiglioni et al. /Applied Catalysis A: General 123 (1995) 123-144 137

the feedstock was a M A / G B L solution (60:40 w / w ) . In these tests the H 2 / C 4


molar ratio in the feedstock must be optimized to avoid saturation and/or deacti-
vation phenomena. In this regard, a value of about 100 (mol/mol) is generally
claimed in the patent literature as the minimum ratio for the hydrogenation of MA
or its esters [51-54]; therefore the catalytic behaviours were studied using two
ratios above and below this value, obtained by maintaining the hydrogen flow
constant and increasing the organic feedstock. It must be noted that, with the M A /
GBL solution as the feedstock, a yield in GBL of 43% corresponds to the amount
introduced as solvent. For all the samples investigated the tests carried out at T < 473
K showed mainly surface adsorption and/or condensation phenomena, while at
T> 573 K hydrogenolysis and cracking predominated.
In the tests carried out using GBL as feedstock and the higher H2/GBL molar
ratio, the Cu/Cr catalysts (Cat 1 and Cat 2) showed similar behaviours, with a
small increase in activity as a function of the copper content (Table 3A). At the
lower temperatures investigated, the main products are tetrahydrofuran (THF) and
n-butanol (owing to the overhydrogenation reaction), while at 548 K the formation
of significant amounts of ethanol was observed, evidence of considerable hydro-
genolysis activity. The formation of ethanol was favoured at the higher copper
content. The complement of the yield data of Table 3, as well as those of Table 4,
has to be attributed both to light products (mainly hydrocarbons) and to irreversible
surface adsorption with tar formation.
The partial substitution of copper ions with zinc (Cat 3) or, especially, with
cadmium ions (Cat 4) gives rise to a decrease in GBL conversion. In particular,
while zinc is responsible only for small differences, with cadmium a considerable
deactivation of the catalyst is observed. The decrease in catalytic activity observed
for the zinc containing sample is in contrast with the data relative to the hydrogen-
ation of crude oxoaldehydes previously reported [22], evidencing a direct rela-
tionship between optimum catalyst composition and organic feedstock. In any case,
it is possible to establish, as a function of the divalent ions present, the following
order of activity toward GBL: Cu > Cu/Zn >> Cu/Cd.
To evidence the role of the free copper in GBL hydrogenation, the activity of
Cat 5 was also studied. This catalyst has the same atomic composition as Cat 1, but
was obtained by heating under reduced air pressure. For Cat 5 only tetragonal
CuCr204 was detected by XRD analysis, while for Cat 1 Cr203 was also found,
thus suggesting, on the basis of the stoichiometry, the presence of a fraction of CuO
which escapes XRD detection (Table 1). It can be seen from Table 3, part A that
for Cat 5 the GBL conversion is much lower than for Cat 1 and Cat 2, on account
of the lack of free copper in this sample; however, it is noteworthy that this sample
is not fully inactive in the reaction examined. Therefore, the free copper obtained
from CuO is not the only phase responsible for hydrogenation of the GBL, but
rather the copper fraction obtained by reduction of tetragonal C u C r 2 0 4 also takes
part in the catalytic reaction, although with lower activity. Comparing the yields in
the different products for Cat 1 and Cat 5, decreases in THF, n-butanol and ethanol
138 G.L. Castiglioni et al. / A p p l i e d Catah,sis A: General 123 (1995) 123 144

Table 3
Catalytic activity in the hydrogenation of y-butyrolactone ( P = 0.1 MPa: catalyst compositions as in Table 1 )

Sample React. temp. ( K ) G B L cony. (%) Yield (on carbon atom basis) ( % )

CH40 C2H~O Acetone C~HsO THF C~H~oO BuAc

A H J G B L = 173 (mol/mol)
Cat 1 485 51 0 < I < I < 1 28 6 0
518 81 0 3 0 0 35 21 0
548 100 2 26 1 0 24 24 2
Cat 2 485 59 0 1 < 1 1 36 6 0
518 92 0 7 1 0 40 18 0
548 100 1 49 < 1 0 28 10 3
Cat 3 485 42 0 0 0 0 25 9 0
518 69 1 4 < 1 0 24 29 0
548 i00 4 31 < 1 0 17 26 4
Cat 4 485 0 0 0 0 0 0 0 0
518 11 0 0 0 0 0 0 1
548 18 < 1 0 0 0 1 0 6
Cat 5 485 15 0 0 0 0 12 9 3
518 37 1 1 0 < 1 13 17 0
548 79 15 8 < I 1 16 17 8

B H2/GBL = 69 (mol/mol)
Cat 1 485 19 0 < 1 0 < l 8 2 0
518 32 < 1 4 1 l 19 27 1
548 66 0 1 < 1 1 14 10 1
Cat 2 485 23 0 < 1 0 1 11 3 0
518 48 0 1 1 1 20 13 < 1
548 77 < I 9 1 1 24 26 < 1
Cat 3 485 14 0 < 1 0 < 1 < 1 3 0
518 37 0 1 < I < 1 13 15 < I
548 73 1 10 1 1 19 26 2
Cat 4 485 < 1 0 0 0 0 0 0 0
518 1 0 0 0 <1 0 0 0
548 3 0 0 0 < 1 I 0 0
Cat 5 485 9 0 0 0 0 4 < 1 1
518 18 <1 <1 0 <1 5 7 2
548 43 2 2 < 1 < 1 10 18 < I

G B L = 'y-butyrolactone; C H 4 O = methanol: C2H60 = ethanol; C 3 H g O = n-propanol" T H F = tetrahydrofuran:


C 4 H I o O = n-butanol; B u A c = butyric acid.

yields were generally observed for the last catalyst, confirming its reduced hydro-
genating capacity, although at the higher temperatures these differences became
smaller.
As the H J G B L molar ratio in the feedstock decreased, a significant decrease in
the GBL conversion was observed for all samples, mainly attributable to surface
saturation, as evidenced also by the greater lack in the carbon balance (Table 3,
part B). The trends as a function of the catalyst composition are similar to those
discussed above; however, it is worth noting that at the lower Hz/GBL molar ratio,
G.L. Castiglioni et al. /Applied Catalysis A." General 123 (1995) 123-144 139

Table 4
Catalytic activity in the hydrogenation of the M A / G B L (60:40 w / w ) solution ( P = 0.1 MPa; catalyst c o m p o -
sitions as in Table 1 )

Sample React. M A conv. Yield (on carbon atom basis) ( % )


temp. ( K ) (%)
GBL SA CH40 C2H60 Acetone C~H~O THF C4HmO BuAc

A HJC4 = 170 (mol/mol)


Cat 1 485 100 47 23 0 0 0 0 I 1 1
518 100 55 6 0 1 < I 1 18 9 0
548 100 5 2 1 11 11 < 1 23 37 0
Cat 2 485 100 56 26 0 0 0 0 0 I 1
518 100 39 6 0 1 1 1 24 12 0
548 100 2 0 1 19 l < 1 27 27 1
Cat 3 485 100 69 26 0 0 0 < 1 < 1 2 3
518 100 47 0 0 2 < 1 < 1 22 18 0
548 100 4 0 3 24 I 1 24 36 5
Cat4 485 37 39 17 0 0 0 0 0 0 1
518 68 39 23 0 0 0 0 0 0 1
548 82 39 30 0 0 0 0 0 0 1
(2at 5 485 100 60 13 0 0 0 0 0 0 0
518 100 88 15 0 0 0 0 5 0 0
548 100 37 0 4 2 < 1 1 10 15 0

B H/C4 69 (tool~tool)
Cat 1 485 100 44 11 0 0 0 0 < 1 0 0
518 100 68 12 0 0 0 <1 2 <1 1
548 100 46 0 0 1 1 1 16 15 2
Cat 2 485 100 51 10 0 0 0 0 0 < 1 < I
518 100 76 I1 0 0 0 1 1 <1 <1
548 100 51 14 < 1 < 1 1 1 15 16 1
Cat 3 485 100 58 12 0 0 0 < I < I < I < 1
518 100 80 10 0 < 1 0 3 3 < 1 1
548 100 40 9 < I 4 1 3 17 18 2
Cat 4 485 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
518 28 39 10 0 0 0 0 0 0 0
548 50 41 9 0 0 0 0 0 0 < 1
Cat 5 485 100 39 7 0 0 < 1 0 0 < 1 0
518 I O0 65 7 0 0 < 1 0 < 1 1 < 1
548 100 89 15 0 0 < 1 < 1 2 1 3

M A = maleic anhydride: SA = succinic anhydride; G B L = y-butyrolactone; CH~O = methanol; C~H60 =


ethanol; C~HsO = n-propanol: T H F = tetrahydrofuran; C~H.~O = n-butanol; B u A c = butyric acid.

the main low cost by-product observed at 548 K is n-butanol (resulting from the
overhydrogenation reaction) instead of ethanol (which results from the hydrogen-
olysis reaction), confirming a general decrease in activity under these conditions
[551.
In the tests carried out using the M A / G B L solution and the higher H 2 / C 4 molar
ratio (Table 4, part A), the catalytic behaviours of the Cu/Cr systems (Cat 1 and
Cat 2) are similar, as also observed for GBL, and depend on the copper content. It
must be noted that GBL is only up to 518 K the main product, whereas succinic
anhydride (SA) is present for both the catalysts at almost all temperatures. There-
140 G.L. Castiglioni et al. /Applied Comlysis A: General 123 (1995) 123-144

fore, for these systems the limiting step for the GBL production is the hydrogenation
of SA to GBL, which, in turn, may rapidly form other products. The increase in
temperature gives rise to a higher conversion of SA and also an increase in the
hydrogenation or overhydrogenation of the GBL to THF and n-butanol, respec-
tively, as well as the hydrogenolysis reaction to ethanol and acetone.
The presence of the second divalent element strongly modifies the catalytic
behaviour, in particular, the partial substitution of copper ions with zinc ions (Cat
3) is responsible for an increase in the hydrogenation activity towards SA which
gives rise to an increase in the yield in GBL. Cat 3 does not show remarkable
differences at 548 K in comparison with Cu/Cr catalysts, although this system
produces higher amounts of Cr-C2 alcohols and butyric acid. Therefore, zinc
increases the rate of the limited step, but does not inhibit the overhydrogenation
and/or hydrogenolysis of GBL.
Partial substitution of cadmium ions for copper ions ( Cat 4), as previously shown
with GBL, gives rise to an almost complete disappearance of the catalytic activity,
giving rise to SA only. This system is the only catalyst tested in which residual
amounts of MA are detected at all the temperatures investigated together with a
consumption of GBL. The increase in the yield in SA observed for this catalyst
only by increasing the temperature, can be mainly attributed to the desorption of
organic compounds adsorbed during the previous tests at 485 K. Finally, this
catalyst presents the greatest lack in the carbon balance, due to highly irreversible
surface adsorption phenomena.
In comparison to Cat 1, the catalyst containing only CuCr204 (Cat 5) shows an
increase in the yield in GBL, mainly attributable to the decrease in the reactions
involving GBL with formation of THF, n-butanol and hydrogenolysis products. On
the other hands, it is difficult to rationalize the differences in SA yields, which
depend considerably on reaction temperature. Therefore, on the basis of these data,
it may be hypothesized that the free copper obtained by reduction of CuO is
responsible for the overhydrogenation and/or hydrogenolysis reactions of GBL,
while the selective hydrogenation of the MA to GBL seems to involve mainly the
copper fraction obtained by reduction of chromite-type phases.
With decreasing H2/C 4 molar ratio the maximum yield in GBL increases for all
catalysts (Table 4, part B), the maximum however, takes place at temperatures
higher than those detected for the higher H2/C4 molar ratio. The yield in SA does
not seem to be strongly influenced by the temperature and the high values observed
for Cat 2 and Cat 5 at 548 K may again be attributed to desorption phenomena.
Also under these conditions the partial substitution of copper ions with a second
divalent ion strongly modifies the catalytic behaviour, although no significant
differences in the trends were detected in comparison to the behaviour discussed
above for the higher H 2 / C 4 molar ratio. In particular, zinc ions achieve greater
amounts of GBL (especially at 518 K), whereas cadmium ions almost completely
deactivate the catalyst, with a further decrease in MA conversion.
G.L. Castiglioni et al. /Applied Catalysis A: General 123 (1995) 123-144 141

It is worth noting that also at lower H2/C 4 molar ratio, Cat 5, in which no free
copper (i.e. obtained by reduction of CuO) is present, exhibits the best yield in
GBL, although at 548 K instead of 518 K, in agreement with the decrease in activity
previously discussed. Therefore, once again the absence of free copper seems to
have a positive effect in the vapour phase hydrogenation of MA to GBL.
Finally, XRD analysis carried out after reaction and following passivation by
nitrous oxide, shows for all the samples the presence of a poorly crystalline spinel-
type phase together with well crystallized metallic copper, in agreement with only
surface oxidation of the particles by nitrous oxide [ 29,30]. However, no significant
differences were observed in comparison to the XRD patterns obtained by reduction
at the same temperature. Furthermore, no direct relationship was found between
the copper surface area (Table 2) and the catalytic activity in the hydrogenation of
both GBL and M A / G B L solution (Tables 3 and 4); for example, Cat 1 showed
the highest copper surface area, while Cat 2 was the most active in GBL hydrogen-
ation. The very low value detected for Cat 4, the catalyst which also showed the
lowest hydrogenation capacity towards both the feedstocks investigated, should be
noted.

4. Conclusions

Tetragonal CuCr204 spinel can be obtained directly by heating the stoichiometric


precipitate ( C u / C r = 33:67, atomic ratio percent) at low oxygen pressure; while
in calcination the spinel forms via intermediate CuCrO4. Furthermore, with increas-
ing copper content (Cu/Cr = 50:50, atomic ratio percent), the chromate decom-
position gives rise at first to a cubic spinel-type phase, which then transforms to
the tetragonal form as temperature is further increased, with a corresponding
increase in the amount of CuO detected by XRD analysis.
The partial substitution of copper ions with zinc or cadmium ions stabilizes the
cubic spinel-type phase, which contains both copper and other divalent cations, as
evidenced by XRD data of C u / C d / C r ternary samples heated at 753 K in different
conditions. Cubic Cu/Cr spinel is more reducible than the tetragonal form, which,
furthermore, reduced to metallic copper through the intermediate formation of
CuCrOz. Zinc exerts a promoting effect on the copper reducibility, that takes place
at lower temperatures, while cadmium acts as an inhibitor, displacing the reduction
towards high temperatures.
The presence of free metallic copper (obtained by reduction of CuO) and its
amount in the catalyst strongly determine the hydrogenation activity towards GBL,
although the copper fraction obtained by reduction of tetragonal CuCr204 also
shows a lower activity. However, no direct relationship was observed between
catalytic activity and copper surface area.
The partial substitution of copper ions with zinc ions gives rise to a small decrease
in activity, while that with cadmium ions almost completely deactivates the catalyst.
142 G.L. Casti,glioni et al. /Applied Catalysis A: General 123 (1995) 123-144

It is worth noting that the Cd-containing catalyst (Cat 4) shows a very low copper
surface area, which cannot be justified simply on the basis of differences in crys-
tallite size in comparison to the other samples. Therefore, it may be hypothesized
that during the activation and/or reaction, a partial reduction of cadmium ions also
takes place, with formation of copper-rich alloys at the surface of the particles. The
presence of a small amount of metallic cadmium does not modify the XRD powder
pattern of the copper particles, but may have a considerable influence on their
physicochemical or catalytic properties [56-58]. However, it is worth noting that
no direct evidence of the presence of these surface copper-rich alloys was observed
during this study, on account also of the techniques employed. Therefore, this
hypothesis has to be confirmed by further investigations using surface analysis
techniques.
On the other hand, in the catalytic tests with MA/GBL solution, the presence of
free copper has a negative effect, favouring the hydrogenation of GBL to THF or,
mainly, overhydrogenation and hydrogenolysis reactions at the higher tempera-
tures. In fact, comparing the different Cu/Cr catalysts (Cat 1, Cat 2 and Cat 5),
the best yields in GBL, independently from the H2/C4 molar ratio, were obtained
with Cat 5, in which only the copper fraction obtained by reduction of tetragonal
CuCr204 is present. For this catalyst a very low tendency to overhydrogenation or
hydrogenolysis reactions is observed at both the H2/C 4 molar ratios investigated
(Table 4).
Furthermore, the important role of the spinel and/or spinel-type phases is con-
firmed by the catalytic behaviour of the samples in which part of the copper ions
was substituted by zinc or cadmium ions (Cat 3 and Cat 4). Also in this case, the
presence of cadmium ions (Cat 4) gives rise to a considerable deactivation, similar
to that previously discussed for the test with GBL, while the presence of zinc ions
gives rise to a small increase in the yield in GBL, by favouring the hydrogenation
of SA. However, it must be pointed out that this catalyst also exhibits at the higher
temperatures high overhydrogenation and hydrogenolysis activities, probably on
account of the presence of free copper.
Therefore, a knowledge of the mechanism of formation of the chromite catalysts
appears to be very important in order to understand the structural relationships
between composition, precipitation and heating conditions. In this way it will be
possible to define a general preparation method, by changing the heating atmosphere
and/or a partial substitution of the copper ions with appropriate divalent ions, to
synthesize catalysts with specific activity and selectivity, as a function also of the
organic feedstock investigated.

Acknowledgements

Financial support for this study from the Italian National Research Council
(CNR, Rome) is gratefully acknowledged.
G.L. Castiglioni et al. /Applied Catalysis A: General 123 (1995) 123-144 143

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