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Abstract. Carrageenan which is a renewable and abundant shows a potential as an energy feedstock. Carrageenan which
can be extracted from Eucheuma cottonii can decompose to hydroxymethylfurfural (HMF) and levulinic acid (LA). This
work is to study decomposition process of carrageenan to HMF and LA. Carrageenans were used and poured into
microwave tube filled with sulfuric acid solution. The reactions were performed at a temperature (160–190°C), a loading
concentration (0.025-0.15 g/mL) and batch times which is up to 120 min. The highest experimental HMF yield was 18.4
mol%, and LA was 29.7 mol%. The possible autocatalytic role of acetic acid (AA), formic acid (FA) and levulinic acid
which were produced during the reaction, was investigated by conducting reactions in the presence of these acids. As a
result, FA particularly shows a role as a catalyst.
INTRODUCTION
Eucheuma cottonii, one of red algae species is a good source of carrageenan. Thus, carrageenan is a renewable,
and abundant feedstock[1]. Carrageenan commonly can be extracted from Eucheuma cottonii and purified using
alkali method [2–5].
Carrageenan is carbon feedstock containing polysaccharides (4-76 wt%) which can be converted to biobased
chemical products such as HMF and Levulinic Acid [1,6–8]. HMF and Levulinic acid are the platform chemical
which has a wide range of industrial application i.e. resin, fungicide, polymers, and fuel [9]. Some process including
thermal, acid-catalyzed, and the microwave-assisted reaction has been performed to produce HMF and LA from
polysaccharides [6–8,9]. Besides LA, some organic acids such as acetic acid (AA) and formic acid are formed
during the reaction. This work is to study (1) the thermal decomposition of carrageenan to HMF and LA, and (2) the
autocatalytic effect during the reaction.
EXPERIMENTAL METHODS
Eucheuma cottoni used as Carrageenan source was bought from farmers in Situbondo, East Java, Indonesia.
Carrageenan was obtained from Sigma-Aldrich (Steinheim, Germany. LA (≥97%) and Acetic Acid (≥97%) were
obtained from Acros Organic (Geel, Belgium). Formic acid (≥95%) was purchased from Merck KGaA (Darmstadt,
Germany). HMF (≥99%) was obtained from Sigma Aldrich (Steinheim, Germany).
Carrageenan was prepared from Eucheuma cottonii and characterized following a previous study by
Manuhara[5]. Carrageenan was fed into one set microwave tube e filled with demineralized water. The mixtures
were mixed and heated to reaction temperature. Since the reaction time was completed, the product was filtered and
centrifuged to separate liquid product. The process variables were loading concentration, temperature and reaction
time. The liquid product was analyzed qualitatively and quantitatively using HPLC of Agilent Technology 1200
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series, equipped with an isocratic pump, a Bio-Rad Aminex HPX-87H organic acid column (300 mm x 7.8 mm) and
a Waters 410 differential refractive index detector. As the eluent, a constant flow rate of 0.55 ml/min of sulfuric acid
in water (5 mM) was used. The column temperature was set at 60 oC. Each sample was analyzed for 60 minutes. The
known compounds were used to calibrate HPLC to identify chromatogram peak area and draw the external
calibration curve. Thus, the unknown concentrations of components in the liquid phase was determined [7].
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The Product of Thermal Decomposition of Eucheuma cottoni carrageenan
The HPLC was used to identify the chemical products of thermal decomposition of carrageenan. Based on the
retention time, some compounds were successfully determined. As seen in Table 1and described in Fig 2, this work
recognized seven water-soluble compounds in the reaction mixtures. Clearly, in the course of the reaction, D-
galactose, D-glucose, and HMF are shown as intermediates in the reaction sequence. The concluding products are
LA, FA, and AA. Two compounds, LA and FA are the decomposition product of HMF. In the meantime, AA is
probably a product of hydrolysis of acetyl side groups in galactose and glucose. This reaction also found some
brown insoluble components called humins.
Thus, the product decomposition is in agreement with a proposed scheme in Fig. 3. Fachri [6-9] stated that
decomposition of poly/oligosaccharide is a hot spot reaction which produces monosaccharide at the beginning and
consecutively leads to HMF, AA, LA, and FA. In this work, carrageenan (polysaccharide) was converted to
galactose (GAL) and glucose (GLU) which go to HMF and AA. Further, HMF forms LA and AA. This finding is in
line with Khajavi [8] who reported the degradation of monosaccharides including galactose and glucose to HMF.
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FIGURE 3. Scheme of Eucheuma cottoni carrageenan thermal decomposition
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Fig. 4 also informs that as reaction getting longer, the yield of galactose, glucose and HMF decreases whereas
the yield of LA increases. This result fits with reaction scheme in Fig. 3 which implies that galactose and glucose
decompose to AA and HMF. Thus, HMF forms LA and FA.
The effect of loading concentration on yield is described in Fig. 5. Supposedly, as loading concentration
increases, the yield of LA increases. In this study, high loading concentration leads to high LA yield. For the
meantime, the highest HMF yield is gained at low loading concentration (160oC) whereas the yield gaining higher in
the temperature range of 170-190oC. It is likely that mass transfer plays a role in low temperature.
FIGURE 5. Effect of loading concentration on the yield of GLU, GAL, HMF, and LA
Autocatalytic effect
For the period of the reactions, organic acids such as AA, LA, and FA are produced which may catalyze most
reactions in the proposed reaction scheme (Fig. 3). To observe the catalytic effect initiated by these organic acids on
the reaction, a set of additional batch experiment was conducted using Eucheuma cottoni carrageenan as the starting
material and with one of the individual acids (AA, FA or FA). The experiments were performed at T=180⁰C,
Ccarr=0.04 g/mL, Cacid= 0.01 M. The results are given in Fig. 6.
When considering the galactose and HMF yield versus time profiles, it is evident that the presence of particularly
FA has a positive effect on the rate of reaction of galactose and HMF. All galactose and HMF react away
considerably faster when compared to the uncatalyzed reaction and the reaction in the presence of AA and LA.
These findings may be explained by considering the pKA values of both acids, 3.75 for FA , 4.6 for LA and 4.76
for AA, indicating that a stronger Brönsted acid leads to higher reaction rates due to a higher Brönsted acidity of the
solution. Thus, the formation of galactose and HMF is mainly due to autocatalytic effects of FA. These findings are
similar to studies reported by Ranoux et al.[10] and Fachri et al. [6], showed that the reaction of fructose to HMF is
strongly autocatalyzed by FA then Aa and LA.
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FIGURE 6. Effect of autocatalytic on the yield of GAL and HMF (T=180⁰C, Ccarr=0.04 g/mL, Cacid= 0.01 M)
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