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A: GENERAL
ELSEVIER
Abstract
The transesterification of triglycerides extracted from oilseeds to obtain biodiesel fuel yields up to
14% by weight of glycerol as by-product. The liquid-phase oxidation of glycerol with air on platinum
catalysts was investigated to prepare valuable oxidation products such as glyceric acid or dihydroxyacetone. The effect of the pH (pH range 2-11) and of different metal catalysts was studied. The
selectivity to glyceric acid can be as high as 70% at 100% conversion on Pd/C at pH 11. On Pt/C
catalyst, glyceric acid was still the main product (55% selectivity) ; but the deposition of bismuth on
platinum particles orientates the selectivity towards the oxidation of the secondary hydroxyl group to
yield dihydroxyacetone with a selectivity of 50% at 70% conversion.
Keywords: Dihydroxyacetone; Glyceric acid; Glycerol; Oxidation; Palladium, Platinum
1. Introduction
The transesterification with methanol of triglycerides extracted from oilseeds
(rapeseed, sunflower) yields so-called biodiesel, which may attain a production of
750 000 tonnes / year by 1995 [ 1 ]. Since this reaction yields up to 14 wt.- % glycerol
as by-product, a surplus of ca. 100 000 tonnes/year of this chemical would be added
to the present market of ca. 610 000 tonnes/year, and new outlets would have to
be found to absorb this surplus. Projects are under way to convert glycerol into
ester or ether derivatives to obtain various marketable products, e.g. biodegradable
surfactants [2]. Since glycerol 1 is already a highly functionalized molecule compared to hydrocarbons from petrochemistry, an advantageous outlet would be to
use it as feedstock for the production of valuable oxygenates.
*Corresponding
72445399.
tel. (+33)
166
OH
OH
OH
To date, the market for these chemicals is limited because of their high cost,
firstly because they are produced from glycerol (which presently has a high and
fluctuating cost), and secondly because their syntheses are expensive. In fact,
dihydroxyacetone and hydroxypyruvic acid are obtained by low-productivity fermentation processes, and glyceric acid by potentially polluting oxidation processes
with mineral acids [ 3]. Beside its use as a tanning agent in the cosmetics industry,
dihydroxyacetone at a lower market price could be more widely used as synthon
in organic synthesis [4]. Thus, dihydroxyacetone and hydroxypyruvic acid are
possible starting materials for OL-serine synthesis [ 5].
Platinum metals are more selective for the oxidation of primary alcohols than
for the oxidation of secondary alcohols [ 6,7] but their selectivity to the latter can
be greatly improved by associating them with p-electron metals, particularly heavy
metal atoms of Group IV (lead) and V (bismuth). In that way, for the oxidation
of gluconic acid, it was shown that the ratio SIS6, where $2 is the selectivity to
oxidation of the secondary alcohol next to the carboxylic group and $6 the selectivity
to oxidation of the terminal primary alcohol, increases from 0.086 on a Pt/C catalyst
to 12.4 on the same Pt/C catalyst after addition of lead atoms [8,9]. Kimura et al.
[10,11 ] have recently published a study on glycerol oxidation showing that the
addition of bismuth to platinum catalysts greatly improves selectivity towards the
secondary alcohol. In that way, a 20% yield in dihydroxyacetone (DHA) was
obtained in a batch reactor at 30% conversion on a l%Bi-5%Pt/C catalyst [ 10],
and a 30% DHA yield at 40% conversion was obtained in a fixed-bed catalytic
reactor with a 0.6%Bi-3%Pt catalyst supported on granular charcoal [ 11 ].
Taking into account our previous studies on oxidation of glyoxal [ 12,13] and
glucose [ 14,15 ], the oxidation of aqueous glycerol solutions with air was conducted
on platinum or palladium catalysts obtained by specific preparation methods.
2. Experimental
2.1. Glyceroloxidation procedure
Oxidation of aqueous solutions of glycerol was carried out at atmospheric pressure in a thermostated glass reactor of 500 ml equipped with a stirrer, a gas supply
..... I
167
t. .....
Fig, 1. Scheme of the reaction vessel and attachments. 1. stirrer; 2. thermometer; 3. condenser; 4. air inlet; 5.
flowmeter; 6. temperature regulator; 7. pH electrode; 8. pH meter; 9. pen recorder; 10. pump; 11. scale; 12. 02
electrode; 13. pO2 meter
168
product distribution. Analysis was carried out using high-performance liquid chromatography (HPLC) with UV and refractive index (RI) detectors after separation
on an ion exclusion column (Alltech OA-1000). The concentration of bismuth in
the solutions following reaction were measured by atomic absorption spectroscopy.
169
300 , , .
10
100
i
0
time (h)
Fig. 2. Effect of pH on the activity of 5%Pd/C catalyst for oxidation of glycerol. Consumption of glycerol (a)
and oxygen pressure in the solution (b) vs. time.
170
Table 1
Reaction data for glycerol oxidation
Catalyst
Preparation
mode"
Bi/Pt
mol
ratio
Initial
selectivity
to DHA
Maximum yield
(C~o)b
(%)
2
5%Pd/C
5%Pt/C
PtBi/C
PtBi/Cex
PtBi/Ccx
PtBi/C~
PtBi/C~
PtBi/Cco.
PtBi/C,,o~
(1)
( 1)
(2)
(2)
(3)
(3)
0.95
0.15
0.47
0.19
0.48
0.13
0.37
107
112
107
66
87
100
38
52
11
26
174
177
58
375
203
96
300
277
109
347
DHA
I(Y
250
77
40
80
70
80
70
80
GLYA
8( 100)" 70(90) c
12(65) d 55(90) d
30(40) ~
20(70)
30(60)
22(80)
28(60)
34(70)
37(75)
a Preparation mode, ( 1) loading of Pt by ion exchange with Pt(NH3) 3+, reduction by formaldehyde, loading of
bismuth by reduction of BiO +, (2) loading of Pt by impregnation with PtCI6 , reduction by formaldehyde,
loading of bismuth by reduction of BiO +, (3) coimpregnation of Pt and Bi, reduction by formaldehyde.
b Maximum yield at conversion given in parentheses.
CAtpH 11.
dAt pH 7.
c At pH2.
function of time and conversion, respectively. The maximum yield in GLYA (70%)
was obtained at ca. 90-100% conversion; the selectivities to the other reaction
products [DHA, tartronic (COOH-CHOH-COOH) and oxalic (COOH-COOH)
acids] were always smaller than 10% provided glycerol was present in the reaction
medium. Following 100% conversion (Fig. 3a), GLYA concentration decreased
at the expense of oxalic acid. Formic acid was probably formed transiently but
should be rapidly oxidized to carbon dioxide because Pd/C catalysts are active for
this reaction [ 16].
These results are in agreement with the present literature data on the oxidation
of aqueous solutions of alcohols on platinum metals and one may draw similar
conclusions: (i) the rate of oxidation of a primary alcohol function is higher than
that of a secondary alcohol [6,7]. (ii) the oxidation stops at the aldehyde stage
only in those instances where the primary alcohol function is located next to an
aromatic ring or a C = C double bond [ 7]. (iii) a basic pH increases the oxidation
rate because it favours the deprotonation of the hydroxyl group (first step of the
reaction) [6] or because it favours the desorption of the acid from the metal [ 17]
(last step of the reaction). At higher contact time, GLYA was oxidized to oxalic
rather than tartronic acid.
Palladium-bismuth catalysts were also used, but the deposition of bismuth on
the 5 wt.-% Pd/C catalyst decreased the rate of glycerol oxidation without improving the selectivity to GLYA or to DHA.
300
k
I~.
\
I
~2001
~
~
~
/
\+/
GLYA
"
DHA
Tartronicacid
Oxalicacid
_"
171
time (h)
80"
b
GLYA
* DHA
M Tartronieacid
o
60"
Ox~ '
_~ 40'~.
20"
-.
20
'~
40
60
80
100
172
a
40
< 30
1'a
-o 20
.~,
10"
0
0
20
40
glycerol
60
80
100
80
O0
(%)
conversion
50
40
< 3O
>.
rl
i2o
10'
0
-
2'0
40
glycerol
6'0
conversion
(%)
Fig. 4. Influence of the pH on the selectivity of glycerol oxidation on a commercial PtBi/C catalyst. DHA yield
( a ) and HPYA yield ( b ) vs. conversion.
The selectivity of the Pt/C catalyst was different from that of Pd/C. GLYA was
still the main product but its yield was lower (maximum yield 55% at 90% conversion) while a slightly higher yield in DHA was obtained (maximum yield 12%
compared to 8% on palladium).
173
the lower pH the oxidation of glycerol gives mainly dihydroxyacetone (50% selectivity at 60% conversion). The reaction at pH = 2 was carried out without any
addition of alkali; the initial pH of ca. 4 dropped rapidly to pH 2-1.5. At higher
contact time, the primary alcohol function was slowly oxidized to give HPYA
(23 % selectivity at 100% conversion). Subsequent experiments were conducted at
pH 2.
Catalysts prepared by method ( 1 ) (platinum loading by ion exchange and bismuth loading by redox reaction of BiO + ions on hydrogen-covered platinum particles) were characterized by high resolution TEM and by STEM-EDX analysis at
1.5 nm spatial resolution on thin sections of the catalyst grains cut with an ultramicrotome. As previously observed [ 12,13], the ion-exchange method leads to
platinum particles in the size range 1-2 nm, uniformly distributed throughout the
active charcoal grains. STEM-EDX analyses of individual particles in catalysts
prepared by ion exchange and moderately loaded with bismuth (Bi/Pt molar
ratio = 0.15) showed, as previously in the case of PdBi/C catalysts [ 14,15 ], that
bismuth was very uniformly deposited on the platinum particles. Analysis of bismuth on the catalysts and in the solutions after reaction showed that there was no
bismuth leakage from catalyst PtBi/C~x (Bi/Pt molar ratio = 0.15) nor from catalyst PtBi/C~x (Bi/Pt molar ratio = 0.47) during reaction.
The product distribution obtained with catalyst PtBi/C~x (Bi/Pt = 0.47) is given
as a function of time and conversion in Figs. 5a and 5b, respectively. The initial
selectivity in DHA was 80%, but it gradually decreased so that a maximum yield
of 30% DHA was attained at 60% conversion (Fig. 5b). From the data given in
Fig. 5a, DHA appears to be rather stable and does not transform into HPYA. Indeed,
DHA molecules, once formed, have little chance to be further oxidized because
carboxylic acids (GLYA and HPYA) formed concurrently can bond strongly to
the metal surface and prevent DHA adsorption. The ketoacid seems to be issued
directly from glycerol with an initial selectivity close to 20%, which then decreased,
whilst the HPYA yield grew steadily even at high conversion (in contrast with
DHA).
PtBi/Ci catalysts obtained by preparation method (2) (loading of platinum by
impregnation, formaldehyde reduction and loading of bismuth by surface redox
reaction of BiO ions on hydrogen-covered platinum particles) were characterized
by TEM. The particle sizes are slightly larger (size range 1--4 nm) than for the
catalysts prepared by method ( 1 ) and the particle distribution in the active charcoal
grains is less uniform. However, Table 1 shows that the selectivity data are almost
similar to those obtained with the previous catalysts, i.e. the initial selectivity to
DHA was 80% and the maximum DHA yield was ca. 30% at 60% conversion. The
B i/Pt molar ratios (0.19 and 0.48) did not change significantly following reaction
which confirmed that bismuth was not leached away during reaction.
Catalysts PtBi/Ccoi, prepared by method (3) (coimpregnation of platinum and
bismuth, formaldehyde reduction) gave higher yields in DHA (Fig. 6 and Table
1 ). The difference in yield between the three preparation methods was more pro-
174
GLYAD +GLYA
DHA
HPYA
=o 200
ffl
E 100
a
i
time (h)
50'
40'
GLYAD + GLYA
DHA
HPYA
30
"O
~,
20
10
0
20
40
60
80
00
Fig. 5. Product distribution obtained at pH 2 on a PtBi/Cex catalyst as a function of time (curve a) and glycerol
conversion (curve b); (GLYAD = glyceraldehyde).
nounced at lower bismuth concentrations. Thus, for a molar ratio Bi/Pt = 0.13, the
initial selectivity to DHA was 70%; the maximum DHA yield was 34% at 70%
conversion compared to ca. 21% on the two previous catalyst types. At higher
bismuth concentration (Bi/Pt molar ratio=0.37), a 37% yield in DHA was
obtained at 75% conversion. No bismuth leakage into the solution was detected. A
definitive interpretation of the improved selectivity of this catalyst must await a
detailed characterization of the structure of the bimetallic catalyst.
4. Conclusion
This preliminary study shows that, depending upon the reaction conditions and
upon the nature of the catalyst, it is possible to orientate the selectivity of glycerol
175
40
a
< 30
"r
Q 20
"o
--__0>,10
'-
Bi/Pt = 0.15
Bi/Pt = 0.47
b
30
20
_ D ~
10
19
l"
t=o48
1:
O ~ r
0.a7
.
20
40
60
80
glycerol conversion (%)
100
Fig. 6. DHA yield vs. conversion at different Bi ]oadings (Bi/Pt molar ratios) for various catalysts: (a) PtBi/
Cex, (b) PtBi/C~, (c) PtBi/Coo~.
oxidation towards the oxidation of the primary or secondary alcohol function. These
results are encouraging because although the reaction conditions and catalysts have
not yet been fully optimized, the following points are highlighted: (i) This is, to
our knowledge, the first report to indicate that a high selectivity to glyceric acid
(77% at 90% conversion) can be obtained by air oxidation of glycerol solutions
on palladium catalysts. This one-pot, clean catalytic oxidation could be used in
place of the present mineral acid oxidation to produce glyceric acid at a much lower
cost particularly if a cheaper glycerol, from triglyceride transesterification, was
available on the market. (ii) The previous results of Kimura et al, [ 10] on glycerol
oxidation using platinum-bismuth catalysts in a batch reactor were confirmed and
greatly improved since a 37% yield in dihydroxyacetone at 70% conversion was
obtained instead of 20% at 30% conversion.
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