Separation and Purification of Furfuryl Alcohol Monomer and

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Separation and Purification of Furfuryl Alcohol Monomer and Oligomers using a Two-phase Extracting Process Xiaojun Chan, Patrick Yang, Carmenn Ooi, Jiajie Cen, Alexander Orlov, and TAEJIN KIM ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.6b01067 • Publication Date (Web): 28 Jun 2016 Downloaded from http://pubs.acs.org on June 28, 2016

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ACS Sustainable Chemistry & Engineering

Separation and Purification of Furfuryl Alcohol Monomer and Oligomers using a Two-phase Extracting Process Xiaojun Chan, † Patrick Yang, ‡ Carmenn Ooi, ‡ Jiajie Cen, † Alexander Orlov † and Taejin Kim* ,†, ‡

†Materials and Science Engineering Department, Stony Brook University, Room 314 Old Engineering, Stony Brook, NY 11794, U.S.A ‡Chemical and Molecular Engineering Program, Stony Brook University, Room 314 Old Engineering, Stony Brook, NY 11794, U.S.A E-mail: [email protected]

KEYWORDS: Furfuryl Alcohol oligomers; Liquid-liquid extraction; Salting out.

ACS Paragon Plus Environment

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ABSTRACT: Aqueous two-phase extraction processes were applied for the first time for the separation and purification of Furfuryl Alcohol monomer and oligomers. Deionized water was used as the liquid-liquid extraction solvent while magnesium sulfate acted as the salting out reagent. Furfuryl Alcohol preferentially partitioned to the water phase and could be further extracted from its aqueous solution due to the decreased solubility in salt rich phase. Various influence, such as partition coefficient and extractability was studied during the liquid-liquid extraction. The extraction by using deionized water resulted in a high oligomer content around ~94wt% in the separated furfuryl alcohol oligomer solution while the salting-out furfuryl alcohol showed a purity of ~92wt%.


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INTRODUCTION The scarcity of petroleum resources and the rise of greenhouse gases emission has caused an increased interest in finding alternatives, such as renewable biomass.1-4 One of the biomass conversion processes to make transportation fuel, such as bio-diesel and bio-jet fuels, is the oligomerization of C5-C9 chemicals derived from lignocellulosic materials. J.A. Dumesic et al., developed a cost-effective route for the formation of oligomers which produced from biomass derived γ-valerolactone.5,6 It was shown that the obtained C9~C18 oligomers have > 90% energy content of its monomer. Among the lignocellulose derived chemicals, Furfuryl Alcohol (FA) is also an attractive chemical that can be used to produce ordered carbons.7-9 Conversion of FA monomer into FA oligomers (OFAs) can be achieved through acid-catalyzed dehydration and condensation reactions.10 Recently our research group has been using metal oxides as catalysts for FA oligomerization reaction.11 Even though solid catalysts can be easily separated from the liquid products, further separation of FA monomer (reactant) and oligomers (products) is still required to acquire OFAs with a high purity. On the other hand, in order to prevent the formation of furfurl alcohol polymer (PFA), the conversion of FA monomer during oligomerization showed a relative low value.11 Thus, the separation and purification of unreacted FA monomer and oligomers are essential processes to increase the OFAs’ yield and to decrease the unreacted FA monomer wastes. It was reported that a liquid-liquid extraction process, which contains highly toxic, flammable and volatile solvents, such as diethyl ether and sodium hydroxide, can be used to wash out FA from its resin.12 Compared with other separation and purification method, such as distillation and chromatography, liquid-liquid extraction is a fast, low cost and low reagent consumption process.13 Table S1 shows the comparison of available liquid separation technologies with their advantages and disadvantages. In this paper, we introduced a


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similar liquid-liquid extraction process that use deionized water as a green solvent. In order to further recover the unreacted FA from aqueous solution, a salting-out effect can be applied. Previously, A. Eucken and G. Hertzberg discussed the salting-out results from the effective removal of the water solvent based on the hydration of electrolyte, while organic molecules doesn’t involve the hydration.14 Thus, a phase separation occurs when inorganic salts is added to a mixture of water/organic inter-miscible system because the solubility of organic molecules decrease in the aqueous solution.15 For example, C.E. Matkovich and G.D. Christian were able to separate acetone out of its aqueous solution with the formation of saturated calcium chloride solution.16 Previously, S. Glasstone et al., provided an empirical order for hydrophilic cations: Mg2+>Ca2+>Sr2+>Ba2+>Li+>Na+>K+>Rb+>Cs+ and anions: SO42- > C2H3O2- > Cl- > NO3- > ClO3> I- > CNS- indicating that both size and charge of ions affect salting out effect.16,17 Based on the results, we can hypothesize that MgSO4 is the strong salting out agent which improve the organic molecule separation from aqueous solutions. To the best of our knowledge, the effectiveness of solvent and salt for the FA extraction, however, were not investigated in detail. In the present study, we aim to provide the feasibility of using (1) deionized water (green solvent): FA monomer extraction from FA mixtures and (2) magnesium sulfate (salting-out agent): FA monomer separation from aqueous solutions during the FA monomer recovery process.

EXPERIMENTAL METHODS Materials. Deionized water (100% V/V) was obtained from Thermo Scientific. Magnesium Sulfate, (Anhydrous, ≥ 99.5%) was obtained from Sigma-Aldrich and used without further purification. FA oligomerization over tungsten oxide (FAmonomer/WO3 weight ratio = 10) was performed at


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100 oC for 6 hrs without additional solvent at ambient pressure.11 Prior to liquid-liquid separation, products (FA oligomers and monomer) were cooled down to room temperature and then separated with the tungsten oxides catalysts using a vacuum filtration.

Separation and purification of FA monomer and oligomers. During liquid-liquid extraction process, deionized water was added into the products with a volume ratio of 2:1 at room temperature. The fully mixed solution was centrifuged until the solution separates into two phases, an aqueous phase and an organic phase. After separated the top aqueous phase properly, it was stored in a labeled glass vial. The entire process was repeated for a total of eight times. Collected aqueous solutions were mixed with magnesium sulfate for water/FA monomer separation. Specifically, 1 g magnesium sulfate was first weighed into two 7 mL glass clear vials. Then 3 g of collected aqueous solution was added into the vial to be fully mixed with the salt. The salting out process was performed in ice bath in order to dissipate the heat which was generated by the reaction of magnesium sulfate with water. The top organic phase, mainly FA monomer, was stored for further detailed analysis.

Characterization. ௔ ௢ The concentration of FA in an aqueous phase (‫ܥ‬ி஺ ) and an organic phase (‫ܥ‬ி஺ ) was

determined by an Agilent 1200 High Performance Liquid Chromatography (HPLC) and a PerkinElmer Clarus 680 Gas Chromatograph (GC) correspondingly. HPLC method development and quantification studies were performed with an Agilent Eclipse XDB-C18 column (4.6 × 150 mm, 5 µm) and a mobile phase is comprising water (A) and acetonitrile (B). Separations were performed by gradient elution (80/20 A/B to 50/50 A/B in 8 min), followed by a 4 min column


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wash (10A/90B) and a re-equilibration period of 1 min. Flow rate, temperature, and injected sample volume were adjusted to 1.0 mL/ min, 25 °C, and 2.0 µL, respectively. Detection was performed at 254 nm. The GC was equipped with a flame ionization detector (FID) and a PerkinElmer Elite-5MS (30 m x 0.25 mm x 1.0 µm) capillary column. GC profile used was described as following: injector temp 250 oC; oven temp: 45 oC held for 4 min, 3 oC/min ramp to 250 oC, held for extra 20 min; detector temp 250 oC; 1 mL/min helium as carrier gas; 30:1 Split Ratio. The partition coefficient (D) of FA in oligomer/water system during separation was given by:

‫=ܦ‬

೚ ஼ಷಲ

(1)

ೌ ஼ಷಲ

௢ ௔ Where ‫ܥ‬ி஺ and ‫ܥ‬ி஺ are the concentration of FA in an organic and an aqueous phase,

respectively. In order to evaluate the efficiency of the extraction process, the extractability (E) was calculated as following:

‫=ܧ‬

ೌ ஼ಷಲ ×௏ೌ ೌ ×௏ ା஼ ೚ ×௏ ஼ಷಲ ೌ ೚ ಷಲ

× 100%

(2)

where Va and Vo are the volume of aqueous phase and organic phase, respectively. Combine (1) and (2) will provide equation (3):

‫=ܧ‬

ଵ ଵା஽×௏೚ /௏ೌ

× 100%

(3)

All the above data was collected after equilibrium was reached. Composition of the (1) initial oligomer solution, (2) organic phase (mainly FA oligomers) after 1st separation, and (3) top organic phase (mainly FA monomer) after salting-out (2nd separation) were identified on PerkinElmer Clarus 680 Gas Chromatograph equipped with a


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PerkinElmer SQ8T mass detector (MS). In order to calculate the concentration of each component, same GC profile and GC column was used in both GC/MS and GC/FID.

RESULTS AND DISCUSSION Extraction of FA monomer from its Oligomer solution. The schematic representation of FA monomer extraction from monomer-oligomer mixture using deionized water and salt is shown in Figure S1. In the first step, with the addition of deionized water, two clear liquid phase were formed; (1) an aqueous phase (top) and (2) an organic phase (bottom). In the second step, FA monomer can be separated from an aqueous solution by salting-out. As shown in Figure 1, with increasing the number of an extraction process, the amounts of organic phase gradually decreased which explained that FA monomer was continuously removed from mixed products. After the total eight time separations, we observed a tremendously decreased volume of organic phase compared to original FA monomeroligomer mixture. Based on the FA monomer and oligomer molecular structure information, observed trends can be predictable. Because FA oligomers do not contain hydroxyl group (-OH) except for terminal-OH dimer, FA oligomer solubility in water should be very low. This result provides that the use of deionized water is very efficient due to the difference of FA monomer and oligomers solubility in water. The detailed study of the partition of FA in oligomer/aqueous solution is shown in Figure 2 and Table S2. According to the partition equilibrium law, the partition coefficient should remain the same at constant temperature in immiscible liquids. However, in the oligomer and aqueous solution, the partition coefficient (D) for FA gradually decreases with increasing the number of extraction up to 4th steps. For instance, D values were 0.38 and 0.24 at 1st and 4th


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extraction, respectively. Note that during the entire process, the absolute concentration of FA monomer decreases with increasing extraction steps in both organic and aqueous solutions. The decrease of D values in the 1st~3rd steps can be explained by volume exclusion effect.18-20 In the 1st~3rd FA extraction steps, because of the higher FA monomer concentration compare to other steps, volume exclusion effect is not significant which results in higher concentration of FA monomer in organic phase and higher partition coefficient (D). From the 4th step, higher oligomer volume with increasing extraction process enhances volume exclusion effect which results in lower D values. Note that although we can’t rule out the oligomer solubility effect on D value deviation from the partition equilibrium law, we hypothesized that oligomer solubility is very small and can’t affect D values. R. Babu et al., observed similar ‘volume exclusion effect’ in PEG/salt system where the partition coefficient of Bromelain and polyphenol oxidase decreased with an increase of PEG molecular weight and concentration.21 Figure 2 also shows the extractability (E) values which calculated by equation 3 for each extraction step. The extractability increased from 86.5% (1st step) to 92.6% (6th step) and then level off. This results can be predicted because extractability (E) is proportional to the reciprocal of the partition coefficient (D) and volume ratio. As shown in Table S2, volume ratio (ܸ௢ /ܸ௔ ) after FA extraction does not change significantly and remains at a values of approximately 0.40. It is possible that during the last several washes, since FA oligomers dominated the composition of the organic phase and absolute FA monomer concentrations were not changed much, ‘volume exclusion effect’ can be restricted and limited the further develop of the extractability (and partition coefficient (D)). The products’ distributions in oligomer phase after eight time extraction steps were compared with those of initial solution. (Figure 3) Three groups were classified for comparison:


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Furfuryl alcohol monomer (C5); short chain-length oligomers (C9~C15); and long chain-length oligomers (>C15). Figures 3(a) shows that initial oligomer solution contains ~70wt% FA, ~17wt% short chain-length oligomers and ~12wt% long chain-length oligomers. After FA monomer extraction from organic phase, the FA monomer concentration decreased to ~6wt% while FA oligomers dominated the rest (~56wt% for short chain-length oligomers and ~38wt% for long chain-length oligomers). Note that the ratio of short to long chain-length oligomers (C9~C15 wt%/>C 15 wt% ≈ 1.4) was not changed much before and after FA monomer extraction. Thus, Fig. 3(a) results confirm that deionized water extracted FA monomer very efficiently, while oligomers distributions were constant in the organic phase. A detailed FA dimer and trimer composition distributions in the short chain-length oligomers are presented in Figure 3(b). It is observed that D3 (ether bridge dimer) and D5 (terminal-OH dimer) are dominant species before and after FA monomer extraction. It was also noticed that relative wt% of D5 decreased while other dimer and trimer products’ relative wt% increased or unchanged, suggesting that D5 dimer was dissolved in the deionized water by the interaction between terminal-OH and water molecules, followed by extraction from organic phase. Consequently, the decreasing of dimer D5 in oligomer solution results in the wt% changing of other dimers. The evidence of D5 transport from organic phase to aqueous solution will be discussed in the following section.

Extraction of FA monomer from its Water solution. After extraction of FA monomer from organic phase with deionized water, the next step in the process was separation of FA monomer from water solution. Figure 4 shows that FA monomer was gradually separated from aqueous solution with the formation of saturated magnesium sulfate solution. It was observed that the equilibrium between the saturated solution


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and FA phase was achieved within 60 min. The composition of the FA phase, as shown in Figure 5, indicates that it contains ~92.2wt% of FA monomer. Meanwhile, we observed the presence of small amounts of dimer and trimer with a total amount of ~7.8wt%. Based on the similar ratio of short to long chain-length oligomers in before and after FA monomer extraction steps (see Figure 3), we expected the existence of long-chain length oligomers in the aqueous solution. However, under the GC method conditions investigated, we couldn’t observe the trace amount of >C15 chemicals. In the previous section, we hypothesized that D5 can be dissolved in deionized solvent during the FA monomer extraction from organic phase. Figure 5 (b) provides that very high D5 dimer portion (~60 wt%) in the dimer and trimer distributions after salting-out process. Along with dimer D5, other dimers and trimer were also found in the FA phase, even though some of them has very low content. This result provides that small amounts of dimers and trimer can be also dissolved in deionized water while FA monomer is the dominant extracted species. Previously, Tabata et al., reported that the salting-out organic solvent contains water and salts, which results in a different acceptability compared to the corresponding pure organic solvent.22 Chung et al., also investigated the phase separation by the addition of sodium chloride (NaCl) to a mixture of 2-propanol and water and found a small amount of NaCl in the 2-propanol phase by using atomic absorption spectrophotometry (AAS).23Although we can’t exclude the presence of water and salts due to the difficulty of perfect separation of FA monomer and oligomer from aqueous phase, based on the HPLC and GC analysis, we can conclude that dominant separated products in the salting-out process are FA monomer and can avoid the presence of trace amounts of water and salts. Instead of the salting-out method, distillation method can be applied because of the different boiling points (FA: 170 oC and Water: 100 oC). However, because FA monomer thermally decomposes at 100 oC and converts into oligomers, recovery of higher purity FA


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monomer can’t be obtained through the distillation process. The extraction and separation processes reported here using deionized water as a green solvent offer significant advantages in not only target oligomer collection but also unreacted FA monomer’s efficient recovery.

CONCLUSION Deionized water as a green solvent could be used efficiently for the FA monomer extraction from acid catalyzed FA products, with a high extractability. Furthermore, unreacted FA monomer and trace amounts of oligomers can be also separated from aqueous solution using the salting-out method with magnesium sulfate. (Figure S1) After two-step extraction and separation processes, ~84wt% FA monomer was recovered: (1) ~91wt% FA monomer extraction from FA monomer/oligomers and (2) ~92wt% FA monomer separation from the aqueous solutions. Even though small amount of oligomers were found in the salting-out FA, the reported methodology lead to improve the biomass derived platform chemical’s, such as furfuryl alcohol (FA), purification and recovery from mixed products.

ASSOCIATED CONTENT Supporting Information. One table (S1) lists the available liquid separation technologies with their advantages and disadvantages. One table (S2) lists the partition coefficient, Volume ratio Vo/Va, and extractability during liquid-liquid extraction of FA. One schematic figure (S1) explain the separation and purification process. This material is available free of charge via the Internet at http://pubs.acs.org.


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AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]

ACKNOWLEDGMENTS We would like to thank the Advanced Energy Center (AERTC) at the Stony Brook University for providing facility. We acknowledge funding support from the National Science Foundation (NSF-CBET-1546647).

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(6) Braden, D. J.; Henao, C. A.; Heltzel, J.; Maravelias, C. T.; Dumesic, J. A. Production of Liquid Hydrocarbon Fuels by Catalytic Conversion of Biomass-derived Levulinic Acid. Green Chem. 2011, 13, 1755-1765. (7) Men, X. H.; Zhang, Z. Z.; Song, H. J.; Wang, K.; Jiang, W. Functionalization of carbon nanotubes to improve the tribological properties of poly (furfuryl alcohol) composite coatings. Compos. Sci. Technol. 2008, 68, 1042-1049. (8) Yi, B.; Rajagopalan, R.; Foley, H. C.; Kim, U. J.; Liu, X.; Eklund, P. C. Catalytic polymerization and facile grafting of poly (furfuryl alcohol) to single-wall carbon nanotube: preparation of nanocomposite carbon. J. Am. Chem. Soc. 2006, 128, 11307-11313. (9) Müller, H.; Rehak, P.; Jäger, C.; Hartmann, J.; Meyer, N.; Spange, S. A concept for the fabrication of penetrating carbon/silica hybrid materials. Adv. Mater. 2000, 12, 1671-1675. (10) Bertarione, S.; Bonino, F.; Cesano, F.; Jain, S.; Zanetti, M.; Scarano, D.; Zecchina, A. Micro-FTIR and Micro-Raman Studies of a Carbon Film Prepared from Furfuryl Alcohol Polymerization. J. Phys. Chem, B. 2009, 113, 10571-10574. (11) Chan, X.; Nan, W.; Mahajan, D.; Kim, T. Comprehensive investigation of the biomass derived furfuryl alcohol oligomer formation over tungsten oxide catalysts. Catal. Commun. 2015, 72, 11-15. (12) Barr J. B.; Wallon S. B. The chemistry of furfuryl alcohol resins. J. Appl. Polym. Sci. 1971, 15, 1079-1090. (13) Ebrahimzadeh, H.; Yamini, Y.; Kamarei, F.;Shariati, S. Homogeneous liquid–liquid extraction of trace amounts of mononitrotoluenes from waste water samples. Anal. Chim. Acta. 2007, 594, 93-100.


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(22) Masaaki, T.; Kumamoto, M.; Nishimoto, J. Chemical properties of water-miscible solvents separated by salting-out and their application to solvent extraction. Analytical sciences. 1994, 10, 383-388. (23) Chung, Nguyen Huu. Studies on the homogeneous liquid-liquid extraction of metal ions using the mixtures of 2-propanol with water. Ph.D. Dissertation, Saga University, Japan, 2004.


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List of Table Table S1. Comparison of liquid separation technologies Table S2. Partition coefficient, Volume ratio Vo/Va, and extractability during liquid-liquid extraction of FA

List of Figures Figure 1. Volume of organic phase during liquid-liquid extraction Figure 2. Partition coefficient of FA (square symbol) and Extractability (round symbol) during liquid-liquid extraction Figure 3. Compare of (a) compositions in FA oligomer mixtures and (b) Dimer & Trimer Distribution in short chain-length oligomers. Left and Right bar charts in (a) and (b) showed before and after liquid-liquid extraction, respectively. Figure 4. Salting-out phenomena in FA/water solution by adding magnesium sulfate Figure 5. (a) Composition of FA monomer and oligomers and (b) Dimer & Trimer Distribution after salting-out process Figure S1. Schematic representation of (a) partitioning behavior of furfuryl alcohol in oligomer/water solution and (b) salting out of furfuryl alcohol from water solution. ( ) Furfuryl alcohol; (

) oligomers; ( ) water; ( ) salt.


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Figure 1. Volume of organic phase during liquid-liquid extraction


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Figure 2. Partition coefficient of FA (square symbol) and Extractability (round symbol) during liquid-liquid extraction


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Figure 3. Compare of (a) compositions in FA oligomer mixtures and (b) Dimer & Trimer Distribution in short chain-length oligomers. Left and Right bar charts in (a) and (b) showed before and after liquid-liquid extraction, respectively.


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Figure 4. Salting-out phenomena in FA/water solution by adding magnesium sulfate


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Figure 5. (a) Composition of FA monomer and oligomers and (b) Dimer & Trimer Distribution after salting-out process


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For Table of Contents Use Only.

Separation and Purification of Furfuryl Alcohol Monomer and Oligomers using a Two-phase Extracting Process Xiaojun Chan,† Patrick Yang,‡ Carmenn Ooi,‡ Jiajie Cen,† Alexander Orlov† and Taejin Kim* ,†, ‡ †

Materials and Science Engineering Department, Stony Brook University, Stony Brook, NY 11794, U.S.A ‡ Chemical and Molecular Engineering Program, Stony Brook University, Stony Brook, New York 11794, U.S.A

Synopsis: Separation and purification of furfuryl alcohol (FA) from FA monomer/oligomers mixtures are achieved by using water (green solvent) and magnesium sulfate. The graphic dimensions: 3.3 inches wide by 1.875 inches deep


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ACS Paragon Plus Environment Figure 1. Volume of organic phase during liquid-liquid extraction


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Figure 2. Partition coefficient of FA (square symbol) and Extractability (round symbol) during liquid-liquid extraction


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Figure 3. Compare of (a) compositions in FA oligomer mixtures and (b) Dimer & Trimer Distribution in short chain-length oligomers. Left and Right bar charts in (a) and (b) showed ACS Paragon Plus Environment

before and after liquid-liquid extraction, respectively.


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Figure 4. Salting-out phenomena in FA/water solution by adding magnesium sulfate


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Figure 5. (a) Composition of FA monomer and oligomers and (b) Dimer & Trimer Distribution after salting-out process



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Separation Technology Liquid-liquid Extraction1,2

Advantages Low energy consumption Operable at ambient condition Fast

Distillation

Membrane 5 Separation

Relative low purity level Relative high solvent consumption High solvent consumption Time consuming

Chromatography3,4 High purity level

2

Disadvantages

High purity level

High energy consumption Not suitable for heat sensitive products

Low chemical waste Operable at ambient condition

High capital cost

Table S1. Comparison of liquid separation technologies


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Volume Volume FA monomer (mL, Before Extraction) (mL, After Extraction) Extraction Steps Organic Aqueous Oligomer D.I. water (Vo) (Va) 1st 5.0 10 4.2 10.3 2nd 3.9 7.8 3.2 8.0 3rd 3.1 6.2 2.6 6.5 4th 2.3 4.6 1.9 4.8 5th 1.6 3.2 1.3 3.3 6th 1.2 2.4 1.0 2.5 7th 0.9 1.8 0.8 1.9 8th 0.8 1.6 0.7 1.7

Vo/Va

0.41 0.39 0.39 0.40 0.39 0.40 0.39 0.39

Partitial Extractability Coefficient (%) (D) 0.38 0.35 0.29 0.24 0.22 0.21 0.19 0.20

86.5 87.8 89.8 91.2 91.9 92.4 92.8 92.6

Table S2. Partition coefficient, Volume ratio Vo/Va, and extractability during liquid-liquid extraction of FA ACS Paragon Plus Environment


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Figure S1. Schematic representation of (a) partitioning behavior of furfuryl alcohol in oligomer/water solution and (b) salting out of furfuryl alcohol from water solution. ( ) Furfuryl alcohol; ( ) oligomers; ( ) water; ( ) salt.


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For Table of Contents Use Only.

Separation and Purification of Furfuryl Alcohol Monomer and Oligomers using a Two-phase Extracting Process Xiaojun Chan,† Patrick Yang,‡ Carmenn Ooi,‡ Jiajie Cen,† Alexander Orlov† and Taejin Kim* ,†, ‡ †

Materials and Science Engineering Department, Stony Brook University, Stony Brook, NY 11794, U.S.A ‡ Chemical and Molecular Engineering Program, Stony Brook University, Stony Brook, New York 11794, U.S.A

Synopsis: Separation and purification of furfuryl alcohol (FA) from FA monomer/oligomers mixtures are achieved by using water (green solvent) and magnesium sulfate. The graphic dimensions: 3.3 inches wide by 1.875 inches deep


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Separation and Purification of Furfuryl Alcohol Monomer and

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