Article

pubs.acs.org/IECR

An Acidic Two-Step Hydrothermal Process To Enhance Acetic Acid

Production from Carbohydrate Biomass
Yan Fang,† Xu Zeng,† Peng Yan,† Zhenzi Jing,‡ and Fangming Jin*,§
†
State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, and ‡School of
Materials Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, China
§
School of Environmental Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China

ABSTRACT: An acidic two-step hydrothermal process to improve acetic acid production was investigated. In the first-step
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reaction, levulinic acid is formed in the presence of an acid catalyst. In the second-step reaction, the levulinic acid is converted
into acetic acid via oxidation with newly supplied oxygen. The acetic acid yield from this two-step process was much higher than
that without the acid catalysts in the first step. The acetic acid yield reached 23% with a purity of 47% from glucose and 26% with
a purity of 52% from fructose. These yields were achieved at a reaction temperature of 523 K, a reaction time of 300 s, and pH
0.5 with HCl as an acid catalyst for the first step and at a reaction temperature of 523 K, a reaction time of 60 s, and an oxygen
supply of 100% for the second step.

1. INTRODUCTION were investigated for the separation and recovery of acetic

Biomass has received widespread attention as a source of clean
energy and as a raw material for different chemical feedstocks.
Carbohydrate biomass in particular has been of interest, as it
makes up the greatest proportion of biomass. Enzymatic
hydrolysis is a traditional method of biomass utilization.
However, the reaction rate and the efficiency of enzymatic
hydrolysis are limited, because microorganisms cannot easily
degrade biomass directly, particularly cellulose. Considering the
energy crisis and environmental problems, the development of
environmentally friendly and highly effective methods for the
conversion of carbohydrate biomass into useful chemicals is
strongly desired.1−3
Hydrothermal reactions are promising processes for biomass
conversion because high temperature water (HTW) is an
environmentally friendly reaction medium with outstanding
properties; specifically, it can act as an acid or base catalyst.4−10
Acetic acid is one of the stable products of hydrothermal
reactions and is also an important industrial raw material for the
production of other chemicals.11,12 There have been many
studies on the application of HTW as a reaction medium.13−15
Our group has conducted a series of studies on the conversion
of carbohydrate biomass into acetic acid under hydrothermal
conditions.16−19 In these studies, a two-step process, consisting
of a reaction in the absence of an oxygen supply (the first-step
reaction) and an oxidation reaction (the second-step reaction),
was proposed to enhance the acetic acid production from
carbohydrate biomass.20 Intermediate products such as 5-
hydroxymethyl-2-furaldehyde (HMF), 2-furaldehyde (2-FA),
and lactic acid are formed selectively in the first step, and the
oxidation of these intermediate products can produce a large
amount of acetic acid. The formation of HMF, 2-FA, and lactic
acid in the first step can be attributed to acid−base catalyst
behavior of HTW.15 For the scaleup of the production of acetic
acid, a continuous flow system for the two-step reaction was
developed.18 In addition, electrodialysis and reverse osmosis
acid.19
As shown in Figure 1, glucose and fructose easily dehydrate
to form HMF, which then rehydrates to form levulinic acid in
the presence of an acid catalyst. A strong acid can accelerate the
conversion of HMF into levulinic acid.21
Levulinic acid, as an intermediate of lignocellulosic feedstock
pretreatment, is a potential source for fuel production.2,22
However, based on the mechanism of the oxidation of high-
molecular-weight carboxylic acids,23 it is hypothesized that it is
easier to produce acetic acid from levulinic acid than from
furans. At the same time, acetic acid is in much greater demand
than levulinic acid and is usually produced from petrochemical
feedstock. In this paper, thus, an acidic two-step process is
proposed (Figure 1) for the conversion of carbohydrates into
acetic acid via levulinic acid to enhance the acetic acid
production from carbohydrate biomass. The first step reaction,
which is run in the absence of an oxygen supply, is a reaction in
the presence of an added acid catalyst that accelerates the
formation of levulinic acid. The second-step oxidation reaction,
which is run in the presence of oxygen, converts levulinic acid
formed in the first step into acetic acid. Compared with
previous research on acetic acid production by direct
oxidation16,17 and a two-step reaction without any catalyst18−20
whose intermediate products were mainly HMF and 2-FA, the
acidic two-step process is supposed to enhance the production
of acetic acid.
2. EXPERIMENTAL SECTION
2.1. Experimental Materials. Levulinic acid (≥97%) and
acetic acid (≥99.7%) obtained from Sigma-Aldrich-Fluka were
used to identify and quantitate the samples. Glucose (AR),
Received: November 1, 2011
Revised: February 29, 2012
Accepted: March 2, 2012
Published: March 2, 2012

© 2012 American Chemical Society 4759 dx.doi.org/10.1021/ie202506c | Ind. Eng. Chem. Res. 2012, 51, 4759−4763
Industrial & Engineering Chemistry Research
Figure 1. Proposed two-step process to enhance the acetic acid yield produced from carbohydrate biomass.
Figure 2. Effect of reaction conditions on the yield of acetic acid from the oxidation of levulinic acid.
fructose (BR) (obtained from Sinopharm Chemical Reagent
Corp. (SCRC), China), and levulinic acid (≥97%, Sigma) were
used as reagents. Hydrogen peroxide (30 wt %, AR, SCRC) was
used as a substitute for oxygen for experimental convenience.
Analytical reagent grade HCl, H2SO4, and H3PO4 obtained
from SCRC were used as acid catalysts. Deionized water was
used in all experiments, and nitrogen was used to purge the
reactor.
2.2. Experimental Procedure. All experiments were
conducted in a batch reactor (3/8 in. diameter, 1 mm wall
thickness, and 120 mm length) made of SUS 316 alloys with an
internal volume of 5.7 mL; the details of this reactor system
have been described in previous publications.15,24 A brief
introduction of the procedures follows. Reactants were put into
the reactor, which was then sealed and shaken to ensure
homogeneous mixing. After the loading procedure, the reactor
was immersed in a salt bath that was preheated to the desired
temperature. The reactor was shaken horizontally in the salt
bath until the desired reaction time was complete. After the
reaction, the reactor was immediately immersed in a cold water
bath to stop the reaction.
For the two-step process, the reactions were conducted as
follows. For the first-step reaction, the test material, deionized
water and HCl, H2SO4, or H3PO4 were added into the reactor.
For the second-step reaction, H2O2 was added to the cooled
reaction liquid for the oxidation reaction. The amount of
glucose and fructose was limited to 0.035 g, and the water fill,
defined as the ratio of the liquid amount to the total available
volume, in the first step was set at 35%. The oxygen supply was
defined as the ratio of the amount of oxygen (hydrogen
peroxide) supplied to the stoichiometric demand for complete
oxidation of the carbohydrate biomass assuming 1 mol of
hydrogen peroxide offers 1/2 mol of oxygen.
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2.3. Analytical Methods. After the reactions had finished
and the reactor had cooled down, the collected liquid sample
was filtered through a 0.45 μm filter, diluted with deionized
water, and then analyzed using GC−MS (Agilent 7890A/
5975C), HPLC (Agilent 1200), and total organic carbon
(TOC; Shimadzu TOC-VCPN) for qualitative and quantitative
analyses. The detailed analysis conditions for the GC−MS and
HPLC assays are available elsewhere.11,15 The data obtained are
the average of analyses on at least three samples, and the
relative standard deviation of the yields was within 5%.
3. RESULTS AND DISCUSSION
3.1. Acetic Acid Production via the Oxidation of
Levulinic Acid. Hydrothermal oxidation experiments with
levulinic acid under various conditions were first performed to
investigate whether levulinic acid can produce more acetic acid
than HMF can. As shown in Figure 2, the yield of acetic acid
reached approximately 30% for the oxidation of levulinic acid at
a reaction temperature of 523 K, a reaction time of 60 s, and an
oxygen supply of 100%. Besides, the yield of formic acid was 8%
at the optimum condition. As shown in Figure 2A, the acetic
acid yield did not remain constant after its optimum oxygen
supply probably because the acetic acid formed was oxidized
toward CO2 at an oxygen excess. In addition, as shown in
Figure 2B, after the optimum reaction time, the acetic acid yield
decreased. It was also probably because the formed acetic acid
was oxidized with an increase in reaction time. Since the reactor
was only partly filled, the effect of entrapped air was also
investigated. First, experiments without the addition of H2O2
(reaction time 60 s, reaction temperature 523, 548, and 573 K)
were conducted. The recovery rate of levulinic acid, which is
defined as the ratio of levulinic acid’s concentration after
reaction to the one before reaction, was above 98%. Second, we
dx.doi.org/10.1021/ie202506c | Ind. Eng. Chem. Res. 2012, 51, 4759−4763
Industrial & Engineering Chemistry Research Article

Figure 3. Proposed mechanism of oxidation for levulinic acid.

have not found formic acid or acetic acid peaks in the HPLC
spectrogram, indicating that the effect of entrapped air on acetic
acid production could be omitted. The yield of acetic acid in
this paper was defined as the ratio of the amount of carbon in
acetic acid to the amount of carbon in the starting material.
Compared with acetic acid yield from furans in previous
research,15 levulinic acid yielded more acetic acid than furans
did. Based on the oxidation mechanism of high-molecular-
weight carboxylic acids in supercritical water,23 the oxidation
mechanism of levulinic acid is proposed, as shown in Figure 3.
One of the most likely attacks by a hydroxyl radical is at the α-
carbon, because the α-hydrogen of levulinic acid is the most
Figure 4. Effect of HCl, H2SO4, and H3PO4 on the yield of acetic acid.
active. The α-oxidation of 1 mol of levulinic acid finally gives First step: 523 K, 300 s, pH 1.5. Second step: 523 K, 60 s, oxygen
rise to 1 mol of acetic acid and 3 mol of formic acid, suggesting supply 100%).
that the highest yield of acetic acid based on the amount of
carbon should be 40%. In addition to attacking the α-carbon, a
hydroxyl radical might attack the β-carbon of levulinic acid to
form 2 mol of acetic acid and 1 mol of formic acid, which would
correspond to an acetic acid yield of 80%. Because the highest
acetic acid yield obtained in the experiments was approximately
30%, it is hypothesized that the α-oxidation of levulinic acid is
the primary reaction mechanism. These results also suggest that
if the β-oxidation could occur selectively, the yield of acetic acid
from levulinic acid would be greater.
3.2. Effect of Acid Catalyst and pH in the First Step on
Acetic Acid Production. Our previous study found that the
type of acid catalyst and the pH can greatly affect the levulinic
acid production from glucose. The highest yield of levulinic Figure 5. Effect of pH of the first step on the yield of acetic acid. First
acid from glucose was 55%, which was achieved when HCl was step: 523 K, 300 s, HCl. Second step: 523 K, 60 s, oxygen supply
used as an acid catalyst at pH 1.5 and 523 K for 300 s, and the 100%.
total highest yield of HMF and levulinic acid was approximately
50% when H3PO4 was used as an acid catalyst at pH 2.0 and 23% for glucose and 26% for fructose when the pH was 0.5. In
523 K for 300 s.25 To obtain a high acetic acid yield in the contrast, the yield of acetic acid was only approximately 10% for
acidic two-step reaction, the yield of levulinic acid must be high. both glucose and fructose when no acid catalyst was used.
Thus, experiments were conducted in which the acid catalyst These results show that the pH obviously affects the acetic acid
and the pH in the first-step reaction were changed while fixed yield. At a lower pH, the greater number of hydrogen ions
reaction conditions were maintained for the second step (523 accelerated the dehydration of glucose or fructose to form
K, 60 s, and oxygen supply of 100%). The reaction conditions HMF, and then the rehydration of HMF to form levulinic acid
in the second step were selected because our previous research allows the formation of more acetic acid. The decrease in the
showed that these conditions result in a higher yield of acetic acetic acid yield at a pH lower than 0.5 suggests that excessive
acid from the oxidation of most materials. As shown in Figure hydrogen ions promote the degradation of acetic acid and thus
4, HCl was more favorable for the conversion of both glucose result in a decrease in the acetic acid yield.
and fructose to acetic acid than H3PO4 and H2SO4 were. The 3.3. Effect of Reaction Conditions in the Second Step
yield of levulinic acid from glucose with HCl was also the Reaction on Acetic Acid Production. Keeping the first-step
highest;25 thus, the higher yield of acetic acid with HCl than reaction conditions fixed at 523 K for 300 s and pH 0.5 with
with H3PO4 or H2SO4 can be attributed to the acceleration of HCl as an acid catalyst, the effects of the second-step reaction
the formation of levulinic acid by HCl in the first-step reaction. conditions on the acetic acid production were determined by
As shown in Figure 5, in addition to pH 0.24, an increase in varying the temperature from 513 to 598 K, the reaction time
the pH (a decrease in the acidity) led to a significant decrease from 30 to 90 s, and the oxygen supply from 60 to 120%. These
in the yield of acetic acid. The highest yield of acetic acid was experiments allowed us to identify the optimum reaction
4761 dx.doi.org/10.1021/ie202506c | Ind. Eng. Chem. Res. 2012, 51, 4759−4763
Industrial & Engineering Chemistry Research
conditions for the second step of the acetic acid production
pathway.
As shown in Figure 6A, the acetic acid yield first increased
with increasing temperature, peaking at 523 K, and then
Figure 6. Effect of reaction conditions of the second step on the yield
of acetic acid.
decreased with further increases in the reaction temperature.
Figure 6B shows the effect of the oxygen supply between 60
and 120% on the second step. The oxygen supply significantly
affected the yield of acetic acid. The acetic acid yield increased
as the oxygen supply increased and reached a maximum of 23%
for glucose and 26% for fructose with an oxygen supply of
100%. At higher oxygen supplies, the yield of acetic acid
decreased. As illustrated in Figure 6C, the yields of acetic acid
from glucose and fructose followed the same trend, with an
initial increase followed by a decrease with increasing reaction
time from 30 to 90 s; 60 s was the optimum reaction time for
the second step for both glucose and fructose.
Table 1. Composition of the Sample after Reactiona
first-step reaction
yield (%)
material levulinic acid acetic acid formic acid
glucose 41 0.9 8 1.3
fructose 48 1 9
a
First step: 523 K, 300 s, pH 0.5, HCl. Second step: 523 K, 60 s, oxygen supply 100%. bThe ratio of carbon of the sample after the reaction to the
initial carbon of the reagent.
Article
On the basis of the results presented above, the optimum
reaction conditions for producing acetic acid were a reaction
temperature of 523 K, a reaction time of 300 s, and pH 0.5 with
HCl as an acid catalyst for the first step and a reaction
temperature of 523 K, a reaction time of 60 s, and an oxygen
supply of 100% for the second step. Under the optimum
reaction conditions, the yield of acetic acid was as high as 23%
for glucose and 26% for fructose, yields that are much higher
than that by the conventional wet oxidation of glucose and the
two-step process without any acid catalyst. The purity of the
acetic acid also increased to 47% for glucose and 52% for
fructose compared with only 30% for the conventional direct
oxidation. The purity of acetic acid was defined as the
percentage of organic carbon content in acetic acid in a liquid
sample relative to the TOC of the liquid sample after the
reaction. In addition to acetic acid, the main product was formic
acid, and its yield stayed constant at approximately 11%; thus,
the purity of total acetic acid and formic acid was approximately
72% for glucose and 79% for fructose. After the first-step
reaction, the levulinic acid yield was 48% for fructose and 41%
for glucose, while only a yield of lower than 1% of acetic acid
was observed in the presence of acid catalyst. Since the highest
yield of acetic acid obtained from levulinic acid in this paper
was 30%, the acetic acid yield contributed by levulinic acid was
about 14% for fructose and 12% for glucose. As a result, 54% of
the acetic acid yield from fructose and 52% of the acetic acid
from glucose were contributed by the intermediate product of
levulinic acid in this study. The pH of solution after the first-
step and the second-step reaction was also examined. As shown
in Table 1, the pH increased to 1.3 for glucose and 1.4 for
fructose after the first-step reaction probably due to the
formation of levulinic acid resulting in the decrease of acidity.
Then, the pH further decreased to 1.1 for glucose and fructose
after the second-step reaction. That was most likely because
more acid was formed after the second step.
4. CONCLUSIONS
The acidic two-step process proposed in this paper can greatly
enhance the conversion of monosaccharides such as glucose
and fructose into acetic acid compared to that by conventional
wet oxidation and the two-step process without any acid
catalyst. The yield of acetic acid reached 23% from glucose and
26% from fructose, which occurred at a reaction temperature of
523 K, a reaction time of 300 s, and pH 0.5 with HCl as an acid
catalyst for the first step and a reaction temperature of 523 K, a
reaction time of 60 s, and an oxygen supply of 100% for the
second step. HCl was more favorable for acetic acid production
than H2SO4 and H3PO4. In addition to the high yield of acetic
acid, the purity of acetic acid was also high, reaching 47 and
52% for glucose and fructose, respectively. The other main
product is formic acid, and its yield stayed approximately 11%.
second-step reaction
yield (%)
pH TOC recoveryb (%) acetic acid formic acid pH TOC recoveryb (%)
83 26 11 1.1 49
1.4 83 23 11 1.1 50
4762 dx.doi.org/10.1021/ie202506c | Ind. Eng. Chem. Res. 2012, 51, 4759−4763
Industrial & Engineering Chemistry Research Article

The total purity of acetic acid and formic acid was acetic acid production from carbohydrate biomass. Environ. Sci.
approximately 72% for glucose and 79% for fructose. Technol. 2005, 39, 1893.

■
(16) Jin, F. M.; Kishita, A.; Moriya, T.; Enomoto, H.; Sato, N.
AUTHOR INFORMATION Production of acetate for use as a roadway deicer by wet oxidation of
organic waste. Abstracts of Papers, 220th National Meeting of the
Corresponding Author American Chemical Society, Washington DC, Aug 20−24, 2000;
*E-mail: fmjin@sjtu.edu.cn. American Chemical Society: Washington, DC, 2000; U355.
Notes (17) Jin, F. M.; Kishita, A.; Moriya, T.; Enomoto, H.; Sato, N. A new
The authors declare no competing financial interest. process for producing Ca/Mg acetate deicer with Ca/Mg waste and

■
ACKNOWLEDGMENTS
The authors gratefully acknowledge the financial support of the
National Natural Science Foundation of China (No.
21077078), the National High Technology Research and
Development Program of China (No. 2009AA063903), and
the Projects of International Cooperation by Shanghai
Committee of Science and Technology, China (No.
09160708100).
acetic acid produced by wet oxidation of organic waste. Chem. Lett.
2002, 31, 88.
(18) Jin, F.; Zhou, Z.; Kishita, A.; Enomoto, H.; Kishida, H.; Moriya,
T. A new hydrothermal process for producing acetic acid from biomass
waste. Chem. Eng. Res. Des. 2007, 85, 201.
(19) Jin, F. M.; Zhang, G. Y.; Jin, Y. J.; Watanabe, Y.; Kishita, A.;
Enomoto, H. A new process for producing calcium acetate from
vegetable wastes for use as an environmentally friendly deicer.
Bioresour. Technol. 2010, 101, 7299.
(20) Jin, F. M.; Zheng, J.; Enomoto, H.; Moriya, T.; Sato, N.;

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Higashijima, H. Hydrothermal process for increasing acetic acid yield
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