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Use of Kappaphycus alvarezii biomass for the production of carbohydrate isopropylidene ketals based bio-crude. Matheus O. de Souza, Rafael Garrett, Marcelo Maciel Pereira, and Leandro S. M. Miranda Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.7b00765 • Publication Date (Web): 18 Aug 2017 Downloaded from http://pubs.acs.org on August 19, 2017
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Energy & Fuels
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Use of Kappaphycusalvareziibiomass for the production of carbohydrate
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isopropylideneketals based bio-crude.
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Matheus O. de Souza, Rafael Garrett, Marcelo M. Pereira,andLeandro S.M. Miranda*
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1
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Cidade Universitária, Rio de Janeiro, RJ 21949-909, Brazil
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*
[email protected] Instituto de Química, Centro de Tecnologia, Universidade Federal do Rio de Janeiro,
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Graphical Abstract
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Abstract:
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The production of bio-hydrocarbons is a challenging task, which stimulated research
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and the development of different approaches to introduce biomass into the standard
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refinery. However, they present drawbacks that demonstrate the need for continuous
16
research. Our recent efforts in this area culminated in the development of a new bio-
17
crude derived from carbohydrate derived isospropylidene ketals obtained from
18
lignicelullosic biomass. Such bio-crude could be easily stored and its components
19
converted into hydrocarbons under standard catalytic cracking conditions. In the present
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work we report the proof of concept in the synthesis of such bio-crude from non-
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lignocellulosic biomass. The biomass from K. alvarezii was used as a source for the
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production of a bio-crude enriched in carbohydrate derived isopropylidene ketals. For
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such, a two-step procedure was developed, i.e, acid hydrolysis of K. alvarezii biomass
24
yielding a carbohydrate rich extract followed by its acid catalyzed ketalization with
25
acetone. It was observed that the conditions used for acid hydrolysis of the K. alvarezii
26
biomass impacted the final bio-crude composition of isopropylidene ketals. The best
27
experimental condition for biomass hydrolysis, which resulted in a bio-crude with
28
higher carbohydrate derived isopropylide ketals content after ketalization, was that
29
using sulphuric acid solution at 0,180 M, 140°C, and 6.75 min of reaction time. Such
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bio-crude
31
galactopyranose.
32
galactopyranose was also identified in the bio-crude.
presented The
44%
(w/w)
compound
of
the
1,2;3,4-Di-O-isopropylidene-α-D-
6-O-methyl-1,2;3,4-Di-O-isopropylidene-α-D-
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1 Introduction
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Nowadays, energy is made available mainly from the cracking of fossil fuels,
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however, there is a growing consensus that its long term consequences are unacceptable.
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Therefore, many different attempts to search for alternative, renewable, energy sources
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have been put into practice, such as the development of solar cells, wind energy and the
39
use of biomass. However, despite all these efforts, renewable energy accounts for only
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12% of the world primary energy sources[1].We believe that one important reason for
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such disappointing number, that cannot be ignored, is that there is a whole established
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economy based on the fossil fuels deep rooted in our society, and that a change in such
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requires a deep change in our society itself. For example, the use of biomass as a
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renewable energy source, such as ethanol or biodiesel, requires investing in the
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construction of new refineries and its production is plagued, in the first case, by price of
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sugar in the stock market, and in the second, from the use of cultivable soil for the
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production of biodiesel instead of food.
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The production of biomass-based green energy is a big chemical challenge that
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needs to be addressed to bypass the economic barriers that prevent the development of a
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biomass economy that rivals to the oil economy. So, from the chemical point of view,
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the biggest challenge is that the standard oil refinery is based on a mature process that
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deals with poor reactive hydrocarbon feeds. In contrast, the densely functionalized
53
biomass compounds, such as carbohydrates and lignocellulose, are incompatible with
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these conditions used to crack hydrocarbons.
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Such situation imposes the development of different infrastructures in order to
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process biomass as an alternative to fossil fuels. On the other hand, such challenge to
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build a bridge between these two different chemical worlds, have been addressed by
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others. One of these is the fuel production through biomass transformation in aqueous 4 ACS Paragon Plus Environment
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phase. This approach is able to form a great variety of products, yet it requires a
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different production structure compared to that of standard refineries.[2-4].The second
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one consists in gasification coupled with Fischer-Tropsch process [5, 6]. This process,
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when applied to biomass, comprises several overlapping steps that require different
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temperatures, such as heating and drying, pyrolysis, oxidation and gasification
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[7].Besides, several reactions between volatile compounds and char or biomass have
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negative impact on the entire gasification process. Such events prevent this process
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from being complete and/or selective in only one-stage. Indeed, two-stage gasification
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improves the conversion of biomass into syngas, however, high temperature, up to
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1250oC is required [8].
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The last approach consists in the one-step thermo-conversion of biomass into bio-
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oil, i.e. pyrolysis [9-11]. Despite its simple hardware and flexibility, the obtained bio-oil
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presents several disadvantages, e.g., highly acidic, unstable and composed of poly-
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aromatics. Therefore, previously to bio-oil introduction into the refinery, it is mandatory
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a pre-treatment that consumes high hydrogen amounts and occurs at high pressure
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(HDO process) [12-14]. An alternative is to perform pyrolysis in the presence of a
75
catalyst (CPO process), thus improving the bio-oil quality. It is important to point out
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that at the moment co-process bio-oil (CPO) in FCC only shows economic feasibility up
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to 5 wt% of bio-oil in gasoil[15]. On thermodynamic bases, applying high temperature
78
to transform biomass into bio-feed produces more stable compounds than saturated
79
hydrocarbons[16], e.g. aromatic and poly-aromatic.
80
Recently, our group set up a project in order to develop a new strategy to introduce
81
biomass into the “standard oil refinery” different from those mentioned above [17, 18].
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Such strategy was based in synthesizing a complete different, more “refinery friendly”
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and easy to make bio-crude. Such bio-crude was mainly composed by carbohydrate 5 ACS Paragon Plus Environment
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isopropylidene ketals. In a proof of concept, in a previous report, [17, 19] sugarcane
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biomass was reacted with acetone in a mildly acidic media and a bio-crude composed of
86
ca. 30 % of monomeric carbohydrate diisopropylidene was obtained along with some
87
isopropylidene derived ketals from di and trisacharides [20]. Later on it was
88
demonstrated, through the use of 13C model compounds of these isopropylidene ketals,
89
that such compounds are suitable for co-cracking with hydrocarbons leading mainly to
90
the presence of labled13C in the fraction of monoaromatics[19].
91
A reaction of the biomass carbohydrate polymers occurs through a sequence of
92
complex events: (i) The diffusion of a solvent and protons through the polymeric
93
matrix; (ii) the protonation of a glycosidic oxygen; (iii) the rupture of the glycosidic
94
bond and the formation of an intermediate oxocarbenium ion; (iv) the reaction of the
95
oxocarbenium ion with a nucleophilic (usually protic) solvent; (v) the diffusion of the
96
reaction products in the liquid and (vi) the repetition of the cycle starting with the
97
second step. As demonstrated for lignocellulosic biomass, such as sugar-cane biomass,
98
the released carbohydrate from the solvolytic step can be in-situ reacted with the solvent
99
acetone in order to produce its derived isopropylidene ketals. In continuation of this
100
project, it is now necessary to establish the proof of concept for the bio-crudes ynthesis
101
with non-lignocellulosic biomass. This is an important issue since the different
102
biomasses possess different chemical composition and morphological structure, both
103
imposing barriers to the depolimarization-ketalization process[20-22] and can
104
potentially impact the final bio-crude composition. Thus, the study of the reaction of the
105
non-lignocelullosic biomass from Kappaphycus alvarezii for producing this
106
isopropylidene ketals based bio-crude is reported. The choice of K. alvarezii is related
107
to its abundance and cultivation in the sea, which does not concur with the production
108
of food, once it pocesses high photosynthetic yield and its cultivation on the open sea 6 ACS Paragon Plus Environment
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does not requires fertilizers [23-25]. K. alvarezii is seaweed is native from Southeast
110
Asia and it is considered the major source of carrageenan, an important feedstock for
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production of plenty of goods [23, 24,26]. Carrageenan is a sulfated linear biopolymer
112
composed by repeating units of α-D-galactopyranoside and 3,6-O-anhydro-α-D-
113
galactose joined by alternated α-(1,3) and β-(1,4) glycosidic links [27, 28]. These bonds
114
and carbohydrate monomers are different from those found in the sugarcane biomass
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making this source ideal for the present purpose.
116
2 Results and Discussion
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Originally, the reaction developed for the synthesis of this new pentose/hexose
118
mono and diisopropylidene ketals based bio-crude from sugar cane biomass consisted in
119
react the bagasse in the presence of acetone as reactant/solvent and catalytic amounts of
120
sulphuric acid at 90oC. The choice of acetone as the model carbonyl compound for the
121
proof of concept comes from the fact that acetone itself can be obtained by green route
122
from acetic acid or ethanol [29-31]. Additionally, it originates, from the analytical point
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of view, a simple and easy to handle ketal mixture, once the use of non symmetric
124
ketones (or aldehydes) would generate a pair of diastereoisomers for each ketal formed
125
[19]. As a starting point, this procedure was employed on the washed and sundried
126
K.alvarezii biomass. However, Liquid Chromatography-Mass Spectrometry (LC-MS)
127
and Gas Chromatography-Mass Spectrometry (GC-MS) analysis of the oil obtained
128
showed no isopropylidene ketals formation, being the oil formed mostly by
129
condensation products from acetone. The thermogravimetric analysis of the recovered
130
K.alvarezii biomass revealed that it was, in fact, inert to the reaction conditions
131
employed, since it showed an identical dTG curve to the pristine biomass (see
132
Supporting Information). On the other hand, temperatures higher than 90oC and
133
increasing amounts of acid leads to the decomposition of the desired ketals, a finding 7 ACS Paragon Plus Environment
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that narrows the window available for optimization of the reaction conditions in the
135
present case[18]. With this inertness and narrow window for optimization, the synthesis
136
of the desired bio-crude was investigated through a two-step strategy: hydrolysis of the
137
carbohydrate based polymers present in the K.alvarezii and ketalization of the resulting
138
depolymerized carbohydrate-rich extract.
139
Many reports are available in the literature concerning the hydrolysis of the
140
carrageen present in the K.alvarezii biomass [27, 32,33]. In the present context, this
141
approach comes with many concerns since the sulfated positions may prevent the
142
synthesis of the desired ketals; i.e. the composition of the resulting carbohydrate based
143
extract (its depolimerization and desulfatation grade) is of extreme importance for the
144
success of the intended approach.
145 146
The depolimerization was studied under acidic condition and microwave irradiation. The results are depicted in Table 1.
147 148 149
150
Table 1
Table 1: Acid hydrolysis of the K. alvarezii biomass Entry
Extract
T (°C)
t (min)
Residual K. alvarezii mass (%)
Yield of the carbohydrate based extract (%) 90.8 + 0.1
1
I
130
16.75
9.2 + 0.1
2
II
140
6.75
9.6 + 0.8
90.8 + 0.8
3
III
130
6.75
10.7 + 0.6
89.8 + 0.6
4
IV
140
16.75
10.8 + 0.5
89.5 + 0.5
a: Reaction conditions: Sulphuric acid 0,180 M
151
As can be seen from the data present on Table 1, the acidic hydrolysis leads to high
152
amount of extract, where only about 10% of the original biomass is recovered. These 8 ACS Paragon Plus Environment
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data show that, quantitatively, there is no difference in the extracts obtained in higher
154
temperature and longer reaction times (Entry 4 vs entry 3).
155
With the main objective of synthesizing the desired ketal-based bio-crude, the
156
extracts were submitted to the ketalization reaction with acetone under acid catalysis.
157
The carbohydrate polymers present in the K.alvarezii biomass is based on the presence
158
of
159
isopropylidene-α-D-galactopyranose (1) was monitored and quantified by LC-MS/MS
160
in order to evaluate the success in the synthesis of the corresponding bio-crude. The
161
results are depicted in Table 2. For experimental details see supporting information:
162 163
D-Galactose,
so
its
correspondent
diisopropylidene
ketal
1,2;3,4-Di-O-
Table 2: Production of the 1,2;3,4-Di-O-isopropylidene-α-D-galactopyranose (1) from the extracts of K. alvarezii biomass Entry
Extractused
1 2 3 4
I II III IV
Bio-crude yield (%) 9.1 + 1.2 18.6 + 1.4 4.9 + 0.5 21.8 + 1.4
1 (% w/w) 3.4 + 3.6 44.3 + 1.7 1.1 + 0.8 23.5 + 9.3
164
165
From the data presented in Table 2 it is clear that the method used to extract and
166
hydrolyze the biopolymers influences the ketalization reaction for the synthesis of the
167
bio-crude, in terms of the presence of 1. Higher amounts of 1 (44%, entry 2) were
168
obtained from extract II. This extract was synthesized under shorter reaction times and
169
higher temperatures (Table 1, entry 2). Extract III, where shorter reaction times and
170
lower temperatures were employed (Table 1, entry 3), yields very poor amounts of the
171
desired ketal, probably due to insufficient depolymerization/desulphoration of the
172
biopolymer. On the other hand, the extract obtained at longer reaction times and higher
173
temperature (Table 1, entry 4) furnished, after ketalization, a higher yield of bio-crude
174
with lower amounts of 1, indicating that some decomposition of the carbohydrate would
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have been occurred. The sequence for the synthesis of bio-crude represented in scheme
176
1. Depolimerization of Carragenaan and Agarose through acid hydrolysis
O OH
Carbohydrate rich Hydrolisate
Ketalization
O O
+ Other isopropylidene Ketals
O O
1,2;3,4-Di-O-isopropylidene - -D-galactopyranose (1)
177 178
Scheme 1: Sequence of events from K.alvarezii biomass to the bio-crude
179
With the use of non-lignocelullosic biomass, the incorporation of nitrogenated
180
compounds may me of concern since K.alvarezii is reported to contain up to 6% of
181
proteins [34, 35]. Fortunately, the elemental analysis of the bio-crude produced from
182
extract II indicated that this bio-crude was free from nitrogen, being composed by
183
53,57% of carbon and 7,83% hydrogen, a result consistent with the incorporation of
184
acetone in the carbohydrate rich extract structure due to the increase % of C (the
185
theoretical elemental analysis expected for 1 is 55,7 % C, 7,7% H and 36,9% O). The
186
bio-crude synthesized from extract II was also analyzed by gas-chromatography in order
187
to evaluate the presence of low molecular weight compounds such as furanes. The GC-
188
FID and GC/MS analysis of the bio-crude indicated only the presence of galactose and
189
hexose derived ketals. All peaks present in Figure 1 IIb present a mass spectra
190
fragmentation pattern of hexose derived isopropylidene Ketals [18] (for details on their
191
Identification see SI). In both analysis, 1 can be seen as the major component of the bio-
192
crude.
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Figure 1 – Chromatograms obtained from compound 1 and bio-crude produced from
194
extract II; (Ia) – chromatogram obtained from GC-FID analysis of compound 1; (Ib) –
195
chromatogram obtained from GC-FID analysis of bio-crude produced from extract II;
196
(IIa) – chromatogram obtained from GC-MS analysis of compound 1; (IIb) –
197
chromatogram obtained from GC-MS analysis of bio-crude produced from extract II.
198
The bio-crude obtained from extract II was then evaluated through liquid
199
chromatography-high-resolution mass spectrometry, as depicted in Figure 2, in an
200
attempt to identify other components present.
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201 202
Figure 2: LC-HRMS chromatogram ofthebio-crude extract II from K. alvarezii.
203 204
Despite of the presence of several peaks in the chromatogram, only those eluted
205
at 2.35 min, 3.12 min and 4.97 min resulted in a mass spectra that could be associated to
206
isopropylidene ketals of carbohydrates present in K. alvarezii (Figure 3).
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Figure 3. High resolution mass spectra obtained by LC-MS of peaks eluted at 2.35 min
209
(a), 3.12 min (b) and 4.97 min (c).
210
The assignment of a molecular formulae to a specific ion was done taking into
211
account the possibilities of molecular adducts of proton [M + H]+, sodium [M + Na]+ or
212
ammonium [M + NH4]+. Hence, in the mass spectrum (a) signals at m/z 278.15927 and
213
m/z 283.11464 were attributed to the ammonium (C12H24O6N+) and sodium
214
(C12H20O6Na+) adducts of molecule C12H20O6.In mass spectrum (b) signals at m/z
215
261.13315 and m/z 278.15923 were attributed to proton (C12H21O6+) and ammonium
216
(C12H24O6N+) adducts of molecule C12H20O6, the same molecular formulae as observed
217
for mass spectrum (a). Furthermore, both molecules from peaks (a) and (b) have
218
fragmented in the ionization source generating the m/z 203, that can be related to an
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hexose sodium adduct. Injection of a standard solution of (1) allowed us to infer that
220
peak (b) corresponded to compound 1,2;3,4-Di-O-isopropylidene-α-D-galactopyranose
221
and peak (a) corresponds to an isomer of the referred isopropylidene ketal formed as
222
during the ketalization reaction. In the mass spectrum (c) the chemical formulae
223
C13H23O6+and C13H26O6N+ were assigned to signals at m/z 275.14863 and m/z
224
292.17520. However, comparing to compound 1,2;3,4-Di-O-isopropylidene-α-D-
225
galactopyranose, the compound from peak (c) showed one carbon and two hydrogen
226
additional atoms, which could be explained by a methyl group attached to it. Previous
227
works [27, 28] have already reported the presence of 6-O-methyl-α-D-galactopyranose
228
on carrageenan from K. alvarezii, suggesting that the chemical formulae C13H23O6+and
229
C13H26O6N+would probably be a proton and ammonium adduct of 6-O-methyl-1,2;3,4-
230
Di-O-isopropylidene-α-D-galactopyranose (2), respectively.
231
In ordertoconfirm the suggested structure of (2), thestandard 1,2;3,4-Di-O-
232
isopropylidene-α-D-galactopyranose (1) was methylated at the remaining hydroxyl at
233
the 6-position using sodium hydride and iodomethane in THF, yielding 46% of
234
compound (2). The comparison of the reaction product with the bio-crude by LC-
235
MS/MS confirmed the peak (c) as the6-O-methyl-1,2;3,4-Di-O-isopropylidene-α-D-
236
galactopyranose (2) since retention time, mass spectrum and chemical formulae match
237
with the synthetic standard (figure 4).
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238 239
Figure 4.Chromatograms obtained from (a) bio-crude extract II from K. alvarezii(b)
240
standard solution of 1,2;3,4-Di-O-isopropylidene-α-D-galactopyranose and (c) standard
241
solution of 6-O-methyl-1,2;3,4-Di-O-isopropylidene-α-D-galactopyranose.
242
The bio-crude was also analyzed by thermogravimetry and its curve compared to those
243
of 1 and 2, as depicted in figure 5.
244
100
2
A
B
0
(2) (1) BC
(2) (1) BC
245
-2
DTG (%/min)
80
Mass Loss (%)
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40
-4 -6
246
-8 -10 -12
20
247
-14 -16
0 50
248
100
150
200
250
300
350 O
Temperature ( C)
400
450
500
50
100
150
200
250
300
350
400
450
500
O
Temperature ( C)
249
Figure 5–Thermogravimetric (A) and Differential thermogravimetric (B) curves
250
obtained from compounds 1, 2 and bio-crude from Extract II.
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251
The thermogravimetric (TG) and differential thermogravimetric (DTG) curves
252
depicted on Figure 5 show similar profiles for compounds 1, 2 and the bio-crude.
253
Compounds 1 and 2 present almost 100% of weight losses at similar temperature
254
ranges: compound 1 weight loss starts at 120°C and finishes at 175°C while compound
255
2 weight loss starts at 130°C and finishes at 195 °C. Bio-crude from Extract II presents
256
a weight loss equivalent to 80% of its weight within a temperature range which begins
257
at 130°C and finishes at 200°C. This results together with those from the
258
chromatographic and elemental analysis demonstrate that the ketalization reaction of
259
extract II yields a carbohydrate derived Isopropylidene-ketal rich bio-crude with 1 as its
260
major component. The minor components other then 2, are expected to be derived from
261
the ketalization of di and trissaccharides, as already observed for the bio-crude derived
262
from sugar-cane biomass. However, due to the differences in the composition of the
263
carbohydrate polymers, their structure could not be accessed by the existing analytical
264
method.
265
In conclusion, the proof of concept for the synthesis of a new isopropylidene ketal rich
266
bio-crude from non-lignocelullosic biomass is reported. Such bio-crude from K.
267
alvarezii biomass was synthetized in a two-step procedure and contains up to 44% of
268
1,2;3,4-Di-O-isopropylidene-α-D-galactopyranose 1, depending on the reaction
269
conditions used in the hydrolytic step. In addition to compound (1), an isomeric hexose
270
derived diisopropylidene ketal and 6-O-methyl-1,2;3,4-Di-O-isopropylidene-α-D-
271
galactopyranose (2) were also identified in the bio-crude. Once, as previously reported
272
[17, 19], a bio-crude composed of carbohydrate isopropylidene ketals are able, under
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real catalytic cracking conditions, to yield gasoline range hydrocarbons, the developed
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conditions herein reported to obtain a rich carbohydrate isopropylidene ketals bio-crude
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from Kappaphycus alvarezii allows the introduction of this biomass into the standard 16 ACS Paragon Plus Environment
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refinery. Our studies concerning its cracking under FCC conditions will be reported in
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due course.
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4 Acknowledgments:
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We acknowledge financial support and fellowships from FAPERJ, Petrobras, CAPES,
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and CNPq.
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