Use of Kappaphycus alvarezii Biomass for the Production of

Aug 18, 2017 - Instituto de Química, Universidade Federal do Rio de Janeiro, Centro de Tecnologia, Cidade Universitária, Rio de Janeiro, Rio de Jane...
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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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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

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research. Our recent efforts in this area culminated in the development of a new bio-

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crude derived from carbohydrate derived isospropylidene ketals obtained from

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lignicelullosic biomass. Such bio-crude could be easily stored and its components

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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

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yielding a carbohydrate rich extract followed by its acid catalyzed ketalization with

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acetone. It was observed that the conditions used for acid hydrolysis of the K. alvarezii

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biomass impacted the final bio-crude composition of isopropylidene ketals. The best

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experimental condition for biomass hydrolysis, which resulted in a bio-crude with

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higher carbohydrate derived isopropylide ketals content after ketalization, was that

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using sulphuric acid solution at 0,180 M, 140°C, and 6.75 min of reaction time. Such

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bio-crude

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galactopyranose.

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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

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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

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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

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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

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to transform biomass into bio-feed produces more stable compounds than saturated

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hydrocarbons[16], e.g. aromatic and poly-aromatic.

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Recently, our group set up a project in order to develop a new strategy to introduce

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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

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ca. 30 % of monomeric carbohydrate diisopropylidene was obtained along with some

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isopropylidene derived ketals from di and trisacharides [20]. Later on it was

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demonstrated, through the use of 13C model compounds of these isopropylidene ketals,

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that such compounds are suitable for co-cracking with hydrocarbons leading mainly to

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the presence of labled13C in the fraction of monoaromatics[19].

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A reaction of the biomass carbohydrate polymers occurs through a sequence of

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complex events: (i) The diffusion of a solvent and protons through the polymeric

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matrix; (ii) the protonation of a glycosidic oxygen; (iii) the rupture of the glycosidic

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bond and the formation of an intermediate oxocarbenium ion; (iv) the reaction of the

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oxocarbenium ion with a nucleophilic (usually protic) solvent; (v) the diffusion of the

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reaction products in the liquid and (vi) the repetition of the cycle starting with the

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second step. As demonstrated for lignocellulosic biomass, such as sugar-cane biomass,

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the released carbohydrate from the solvolytic step can be in-situ reacted with the solvent

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acetone in order to produce its derived isopropylidene ketals. In continuation of this

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project, it is now necessary to establish the proof of concept for the bio-crudes ynthesis

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with non-lignocellulosic biomass. This is an important issue since the different

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biomasses possess different chemical composition and morphological structure, both

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imposing barriers to the depolimarization-ketalization process[20-22] and can

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potentially impact the final bio-crude composition. Thus, the study of the reaction of the

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non-lignocelullosic biomass from Kappaphycus alvarezii for producing this

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isopropylidene ketals based bio-crude is reported. The choice of K. alvarezii is related

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to its abundance and cultivation in the sea, which does not concur with the production

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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

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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

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composed by repeating units of α-D-galactopyranoside and 3,6-O-anhydro-α-D-

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galactose joined by alternated α-(1,3) and β-(1,4) glycosidic links [27, 28]. These bonds

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and carbohydrate monomers are different from those found in the sugarcane biomass

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making this source ideal for the present purpose.

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2 Results and Discussion

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Originally, the reaction developed for the synthesis of this new pentose/hexose

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mono and diisopropylidene ketals based bio-crude from sugar cane biomass consisted in

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react the bagasse in the presence of acetone as reactant/solvent and catalytic amounts of

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sulphuric acid at 90oC. The choice of acetone as the model carbonyl compound for the

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proof of concept comes from the fact that acetone itself can be obtained by green route

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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

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ketones (or aldehydes) would generate a pair of diastereoisomers for each ketal formed

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[19]. As a starting point, this procedure was employed on the washed and sundried

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K.alvarezii biomass. However, Liquid Chromatography-Mass Spectrometry (LC-MS)

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and Gas Chromatography-Mass Spectrometry (GC-MS) analysis of the oil obtained

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showed no isopropylidene ketals formation, being the oil formed mostly by

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condensation products from acetone. The thermogravimetric analysis of the recovered

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K.alvarezii biomass revealed that it was, in fact, inert to the reaction conditions

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employed, since it showed an identical dTG curve to the pristine biomass (see

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Supporting Information). On the other hand, temperatures higher than 90oC and

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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

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present case[18]. With this inertness and narrow window for optimization, the synthesis

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of the desired bio-crude was investigated through a two-step strategy: hydrolysis of the

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carbohydrate based polymers present in the K.alvarezii and ketalization of the resulting

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depolymerized carbohydrate-rich extract.

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Many reports are available in the literature concerning the hydrolysis of the

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carrageen present in the K.alvarezii biomass [27, 32,33]. In the present context, this

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approach comes with many concerns since the sulfated positions may prevent the

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synthesis of the desired ketals; i.e. the composition of the resulting carbohydrate based

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extract (its depolimerization and desulfatation grade) is of extreme importance for the

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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

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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

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As can be seen from the data present on Table 1, the acidic hydrolysis leads to high

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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

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temperature and longer reaction times (Entry 4 vs entry 3).

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With the main objective of synthesizing the desired ketal-based bio-crude, the

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extracts were submitted to the ketalization reaction with acetone under acid catalysis.

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The carbohydrate polymers present in the K.alvarezii biomass is based on the presence

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of

159

isopropylidene-α-D-galactopyranose (1) was monitored and quantified by LC-MS/MS

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in order to evaluate the success in the synthesis of the corresponding bio-crude. The

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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

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From the data presented in Table 2 it is clear that the method used to extract and

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hydrolyze the biopolymers influences the ketalization reaction for the synthesis of the

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bio-crude, in terms of the presence of 1. Higher amounts of 1 (44%, entry 2) were

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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

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temperature (Table 1, entry 4) furnished, after ketalization, a higher yield of bio-crude

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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

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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

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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

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extract II indicated that this bio-crude was free from nitrogen, being composed by

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53,57% of carbon and 7,83% hydrogen, a result consistent with the incorporation of

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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

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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-

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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

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extract II; (Ia) – chromatogram obtained from GC-FID analysis of compound 1; (Ib) –

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chromatogram obtained from GC-FID analysis of bio-crude produced from extract II;

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(IIa) – chromatogram obtained from GC-MS analysis of compound 1; (IIb) –

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chromatogram obtained from GC-MS analysis of bio-crude produced from extract II.

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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

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(a), 3.12 min (b) and 4.97 min (c).

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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

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(C12H20O6Na+) adducts of molecule C12H20O6.In mass spectrum (b) signals at m/z

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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

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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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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

273

real catalytic cracking conditions, to yield gasoline range hydrocarbons, the developed

274

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:

279

We acknowledge financial support and fellowships from FAPERJ, Petrobras, CAPES,

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and CNPq.

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5References

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