Académique Documents
Professionnel Documents
Culture Documents
C, and the H
+
concentrations were calculated based on the
complete dissociation of the acid [26]. The reactor was loaded with
70mL hydrochloric acidic solution and 0.5g guaiacol. After sealing
the reactor, nitrogen was used to purge the reactor, followed by
hydrogen if necessary. Then the reactor was heated to the desired
temperature 280
C for 3h.
L. Yang et al. / Journal of Molecular Catalysis A: Chemical 368369 (2013) 6165 63
catechol yield increase at lower pH values. Moreover, the presence
of hydrogen enhances the guaiacol conversion and catechol yields
dramatically. With the presence of hydrogen, the highest conver-
sion and yield are 83% and 76% at pH 1.8. On the other hand, it is
obvious from Fig. 1 that both the conversion and yield are much
higher in hydrogen than in nitrogen atmosphere. The selectivity
of catechol in these experiments is as high as 90% irrespective to
the gas phase composition. The results with metal chlorides (FeCl
3
,
CuCl
2
) as catalysts in hydrogen atmosphere were also shown in
Fig. 1. The metal chlorides induce an acidic environment which
favors the reaction. The pH of FeCl
3
and CuCl
2
solutions were 2.6
and3.8, respectively. The yieldwithFeCl
3
is higher thanwithCuCl
2
.
However, the yields in the reactions with the two metal chlorides
are substantially higher than the cases with only HCl at the similar
pH values, which indicates that the metal sites are involved in the
reaction.
3.2. Effect of pH on the reaction kinetics
The rate constants were calculated based on a rst-order kinet-
ics (Fig. 2) for the acid catalyzed reaction. If the reaction is truly
catalyzed by H
+
, the pseudo-rst-order reaction rate constant, k,
for the disappearance of guaiacol should be directly proportional to
the ion concentration in the solution. More specically the slope of
logk vs. pHshouldbe 1as wouldtypical for H
+
catalyzedreactions
[26].
In this work, the slope of the solid line drawn through the data
between pH 1.8 and 3.9 is about 1, which means the apparent
reaction order for H
+
is 1.0, same as that would be expected for a
reaction following specic acid catalysis. Nevertheless, as the pH
continues to increase from 3.9 to 5.8, the slope of the dash dot
line is about 0.25 instead of 1.0, indicating the reaction in this pH
range is not specically acid catalysis. Savage et al. proposed that
catalysis by water is a second possible pathway to generate the
1 2 3 4 5 6
-6.5
-6.0
-5.5
-5.0
-4.5
-4.0
-3.5
H2
N2
l
o
g
(
k
/
s
-
1
)
pH
Fig. 2. Effect of pH on the hydrolysis reaction rate constants at 280
C.
initial protonated intermediates in the hydrolysis of dibenzyl ether
[26]. It is known that the ion product increases by 34 orders of
magnitude from its value at ambient conditions to its maximum
value at around 250
C for 3h.
mechanismand an ionic pathway dominates the reaction. Step 1a
demonstrates an acid-catalyzed mechanismat a lowpH, while step
1b demonstrates water-catalyzed mechanismat a higher pH. Pro-
tonation of guaiacol in both step 1a and step 1b forms a charged
intermediate, which subsequently reacts with a water molecule to
eventually formcatechol, methanol and H
+
in step 2.
Step 1a is a process in which a smaller charge-to-volume ratio
intermediate is formed. Savage suggested that with the decrease
of solvent dielectric constant the formation of ions with smaller
charge-to-volume ratio is increasingly favored [28]. Water dielec-
tric constant decreases as the temperature increases. For example,
the dielectric constant is 21 at 300
C. Step 2 is
irreversible and rate-determining. H
+
released fromstep 2 goes to
two separate ways, of which one returns to step 1a to act as acid
catalyst and the other neutralizes with the OH
released in step 1b
to formwater acting as the catalyst for step 1b.
3.3. Effect of hydrogen pressure
The inuence of hydrogen pressure on the reaction is show in
Fig. 3. It depicts the effect of H
2
pressure on the conversion and
yield at pH 1.8, 2.0 and 5.8. It is obvious that hydrogen effec-
tively enhances the reaction. The highest conversionreaches 99%at
pH=1.8 with a yield of catechol as high as 90%. This result is much
higher compared to other guaiacol conversion reactions [912]
reported earlier in which the highest yield of catechol is no more
than 50%. Here we almost get nearly complete yield.
Thus, it is beyond doubt that hydrogen indeed takes part in the
reaction based on the fact that not only higher hydrogen pressure
benets the reaction (Fig. 2) but also hydrogen exceeds nitrogen on
motivating the reactionwithfaster reactionrate (Fig. 3). Inaddition
to Scheme 1, we propose here a reaction pathway (Scheme 2) to
illustrate howhydrogentakes part inthe reactionbased ona newer
route(shownas inScheme3) intheconversionsequences proposed
by Walling and Bollyky [29]. Scheme 3 presents that hydrogen is
polarized by alkyl cations. In our reaction, the polarity of reaction
H
O
OH
OH
OH
+ CH
4
+ H
+
+ H
2
Scheme 2. Polarization of H
2
by the reaction intermediate.
R
+
+ H
2
RH + H
+
Scheme 3. Polarization of H
2
by R
+
.
Fig. 4. Gas mass spectrometry of gas products.
intermediate which is shown in Scheme 1 in the solution is much
stronger than alkyl cations, so it makes sense that hydrogen takes
part in the reaction with polarization by the intermediate. In the
other word, the intermediate not only reacts with water to form
catechol and methanol shown in Scheme 1 but also reacts with
hydrogen to form catechol and methane shown in Scheme 2. In
addition, we identied gas products with a gas mass spectrometer
(HIDEN HPR20) and nd CH
4
is indeed produced (Fig. 4).
3.4. The relative selectivity of phenol and catechol
Fig. 5 depicts the effect of atmosphere and pH on the relative
selectivity of phenol and catechol. As the pH increases from 1.8
to neutral 5.8, the phenol/catechol mole ratio steadily increases
in the product. The formation of phenol can be attributed to a
radical reaction mechanism that is guaiacol splitting into phenol
and methanol. Methanol has been identied by GCMS. On the
other hand, compared to hydrogen, nitrogen benets phenol for-
mation dramatically. In the other words, nitrogen favors radical
reaction while hydrogen favors ionic reaction, which can further
verify Scheme 2 that hydrogen participates in ionic reaction.
1 2 3 4 5 6
0.00
0.05
0.10
0.15
0.20
0.25
0.30
p
h
e
n
o
l
/
c
a
t
e
c
h
o
l
m
o
l
e
r
a
t
i
o
in N
2
in H
2
pH
Fig. 5. Effect of atmosphere and pHon the relative selectivity of phenol to catechol.
L. Yang et al. / Journal of Molecular Catalysis A: Chemical 368369 (2013) 6165 65
3.5. Effect of NaOH on the reaction
Hydrolysis of guaiacol in NaOH solution at pH=10.4 (measured
at ambient condition) was tested, and the other reaction condi-
tions were the same as acidic reactions (280
C, 3h, N
2
). The results
showed that basic solution did catalyze the reaction of the pro-
duction of catechol but produces a large amount of undesirable
char visually, in contrast to almost no char formation with acid
catalysis. This phenomenon is in accordance with the hydrolysis of
polysaccharides forming simple sugars such as glucose, fructose,
and xylose, to which acid hydrolysis is more commonly practiced
because base hydrolysis leads tomore side reactions andthus lower
yields [23].
4. Conclusions and perspective
This work shows an efcient and novel chemical sequence to
produce green catechol from guaiacol, an intermediate of bio-
waste, lignin. The route ligninguaiacolcatechol is feasible. High
conversion of guaiacol and yield of catechol were obtained at 99%
and 89%, respectively with 1MPa hydrogen at pH=1.8 for 3h at
280