DOI: 10.1002/slct.

201701815 Communications

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2 z Sustainable Chemistry
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Glucose Conversion to Furans in Alcohols Catalyzed by
6 Lewis Acidic Beta Zeolites and Brønsted Acidic Resins
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8 Eyas Mahmoud*[a]
9
10
Glucose was converted to 5-(hydroxymethyl)furfural (HMF) and
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the potential biodiesel additives 5-(ethoxymethyl)furfural (EMF)
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and 5-(isopropoxymethyl)furfural (IMF) by Lewis acidic zeolites
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and Brønsted acidic resins. The conversion occured by
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sequential isomerization and dehydration reactions in semi-
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aqueous mixtures containing ethanol or isopropanol. Sn-beta
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and Amberlyst 15 catalyzed the conversion of glucose to HMF
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and IMF in 53% yield in isopropanol containing 7.5 weight %
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water. The yield of undetected byproducts including humins
19
was 7%. The moderate yield is attributed to the increased
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selectivity of the isomerization reaction and the suppression of
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further reactions of HMF to byproducts such as levullinic acid,
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formic acid, and humins in the alcohols.
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24
25 Scheme 1. Simplified reaction scheme for the conversion of glucose to HMF
Only 3% of the 170 billion tons of lignocellulosic biomass
26 and 5-(alkoxymethyl)furfural in alcohols.
generated annually are used by mankind for fuels and
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chemicals production.[1] The utilization of this non-edible feed-
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stock as a resource could improve the sustainability of the
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chemical industry.[2] Cellulose, which comprises 40–50 wt% of 209 8C) for furans.[8] Alcohols such as ethanol and isopropanol
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lignocellulosic biomass, can be hydrolyzed to glucose at nearly are good solvents for the process because these chemicals are
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100% yield.[3] Glucose can be converted to 5-(hydroxymethyl) produced at a scale of millions of tons per year from feedstocks
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furfural (HMF), a platform chemical intermediate used in such as biomass.[9] Ethanol and isopropanol are relatively non-
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biorefineries, for fuels and chemicals production.[4] toxic and have boiling points of less than 100 8C.
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The conversion of glucose to HMF can be achieved by two To catalyze the glucose isomerization reaction, heteroge-
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reactions: glucose isomerization to fructose followed by neous, Lewis acids, such as Sn-beta, may be used in combina-
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fructose dehydration to HMF (Scheme 1).[5] Biomass-derived tion with Brønsted acidic resins, such as Amberlyst 15, to
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compounds such as ˜-valerolactone (GVL), tetrahydrofuran catalyze the fructose dehydration reaction to HMF.[10] Sn-beta
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(THF), and water have been used as solvents for this zeolite consists of a three-dimensional network of 12-ring pores
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conversion, resulting in 70% HMF selectivity at 90% glucose 6.68 Å wide with isolated Sn(IV) Lewis acid centers incorporated
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conversion.[6] The high selectivity is thought to be a result of in the zeolite beta framework.[11] Sn-beta can be synthesized
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the increase in the active furanose tautomers of fructose and through direct synthesis or post-synthesis techniques.[12] How-
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the suppression of the further transformation of HMF to ever, the use of neat alcohols as solvents results in low yield (<
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byproducts such as humins by simultaneous extraction into an 40%) for the conversion of glucose to furans.[13] For example,
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organic solvent.[7] In this work, a monophasic system using when using ethanol as a solvent, glucose can be converted to
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renewable solvents is reported, which avoids safety hazards an HMF derivative, 5-(ethoxymethyl)furfural (EMF), in 38%
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(THF forms highly explosive peroxides), maximizes selectivity, selectivity at 100% conversion using AlCl3.[14] Similarly, when
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and simplifies separation in an effort to make industrial-scale using the heterogeneous catalysts, Sn-beta and Amberlyst
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production economically viable (GVL has a boiling point of 131, glucose was converted to EMF in ethanol with a 31%
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selectivity at 100% conversion.[15] For these studies, nearly
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100% of the fructose produced by glucose isomerization is
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[a] Dr. E. Mahmoud converted to furans such as EMF. In alcohols such as ethanol,
52 University of South Carolina Sn-beta has a higher turnover frequency (TOF) for glucose
53 Department of Chemical Engineering
isomerization as compared to Sn-MCM-41 and Sn-MFI but only
54 Columbia, SC 29208 (USA)
E-mail: eyas6778@gmail.com a 45% fructose selectivity at 100% conversion.[16a] Sn-beta has
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Supporting information for this article is available on the WWW under been found to be a recyclable and regenerable catalyst for
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https://doi.org/10.1002/slct.201701815 glucose isomerization when using water and alcohols as
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solvents.[16] However, the low furans selectivity (< 50%) of commercial Brønsted acid resins, showed that these commer-
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glucose isomerization to fructose in a monophasic system cial catalysts adsorb of 4.74 and 1.65 mmol/g of ammonia.
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composed of alcohols by heterogeneous catalysts in a one-step For this conversion, the Lewis acid catalyzes the isomer-
3
process still has not been addressed. Such a system must ization of glucose to fructose. The Brønsted acid catalyzes the
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increase the selectivity of the glucose isomerization reaction dehydration of fructose to HMF (Scheme 1). In control experi-
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while suppressing secondary reactions of furans to humins in ments in ethanol run at 90 8C at a 0.159 M concentration of
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organic solvent by controlling the water content. glucose, glucose was converted to fructose by Sn-beta catalyst
7
Herein, for the first time a selective, one-step process (> with no furan products formed. However, it was discovered
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70%) for glucose conversion to furans in mixtures of ethanol or that after 4 h of reaction, 24% of glucose was converted to
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isopropanol and water is reported, which improves on previous undetected byproducts by HPLC. When catalyzed by Amber-
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results by decreasing the solvent’s boiling point, avoiding lyst 15 alone at the same conditions, glucose was only
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safety hazards through use of a non-toxic and non-explosive converted to the glycoside. Therefore, both Lewis and Brønsed
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solvent, and increasing the selectivity of the product through acid are required for furan production from glucose for these
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the addition of small amounts of water to the alchohol-based catalysts with the Brønsed acid dehydrating fructose to HMF.
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solvent. The process uses a cheaper and more abundant However, to maximize selectivity glucose must be isomerized
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feedstock while using renewable solvents and heterogeneous to fructose while minimizing byproduct formation (please see
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catalysts offering a new opportunity for a large-scale econom- supporting information for equations used to calculate yield,
17
ically viable process. conversion, and selectivity).
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To begin, the structural and textural properties of the The use of solvent mixtures containing alcohols and water
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synthesized zeolites were characterized by inductively coupled with Lewis acidic beta zeolite and Amberlyst catalysts
20
plasma optical emission spectroscopy (ICP-OES), powder X-ray increases the selectivity of the conversion of glucose to HMF as
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diffraction (XRD), nitrogen adsorption, scanning electron micro- compared to identical reactions run in neat alcohols. Running
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scopy (SEM), Fourier transform infrared spectroscopy (FTIR), the reactions in ethanol containing 2.5 weight (wt) % water
23
and temperature programmed desorption thermogravimetric improves the yield of the detected products to 65% at 68%
24
analysis (TPD-TGA). Sn-, Zr-, and Hf-beta zeolites with Si/M conversion as compared to 31% at 100% glucose conversion
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ratios of 230, 325, and 219 as determined by ICP-OES (M=Sn, Zr, for reactions in neat ethanol.[15] At this conversion in ethanol
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or Hf containing 1.08, 0.63, and 1.57 wt% of SnO2, ZrO2, or containing 2.5 wt% water, the selectivity to the furans HMF and
27
HfO2) were prepared as described in the supporting informa- EMF is 49% and the ratio of EMF/(EMF + HMF) is 80%. The
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tion.[17] The X-ray diffraction patterns of the calcined samples addition of increasing wt% of water decreases conversion and
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are consistent with the structure of zeolite beta, with no decreases the yield of products formed by etherification
30
evidence of impurities or detectable amounts of amorphous reactions (Figure 2). The decreasing conversion with increasing
31
material (Figure S1). Micropore volumes measured using nitro-
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gen adsorption isotherms show that Sn-, Zr-, and Hf-beta have
33
large microporous volumes (~ 0.20 cm3/g) characteristic of
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zeolite beta samples of good quality (Table S1).[18] SEM images
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of the synthesized beta zeolites show the typical truncated
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square by-pyramidal morphology of these materials with ~ 2-
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5 mm particle size (Figure 1).[19] FTIR using deuterated
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43
44
45
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47 Figure 1. SEM images of synthesized Sn-, Zr-, and Hf-beta zeolites (from left
Figure 2. Conversion of glucose to HMF and EMF in ethanol containing
48 to right). Scale bar 6 mm.
different weight fractions of water. Reactions were run at 90 8C for 18 h at a
49 0.159 M concentration of glucose catalyzed by Sn-beta (Si/Sn = 230) and
50 Amberlyst 15.
51
acetonitrile displayed the 2305, 2301, 2302 cm 1 peaks for Sn-,
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Zr-, and Hf-beta. TPD-TGA using diethyl ether as a probe
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molecule resulted in 43, 55, and 80 mmol/g of diethyl ether wt% of water is due to the decreased rate of the fructose
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adsorbed per gram of catalyst for these samples corresponding dehydration reaction. In a 56 wt% solution of water in ethanol,
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to the formation of a 1:1 complex of diethyl ether and the the yield of detected products and byproducts by HPLC
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Lewis acid site.[17,20] NH3-TPD data on Amberlyst 15 and 70
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increases to 91% at 31% conversion. At this conversion, the In addition, Zr and Hf were investigated as Lewis acids for
1
selectivity to HMF is 73% with no EMF detected. the chemical conversion. Using the Lewis acidic molecular
2
Comparatively, in a solvent containing mostly isopropanol, sieves Zr- or Hf-beta in combination with Amberlyst 70 to
3
the selectivity for the conversion of glucose to furans is catalyze the conversion of glucose to HMF conversion in
4
enhanced as compared to the conversion for reactions run in a isopropanol containing 7.5 wt% water isopropanol results in
5
solvent containing ethanol and water. Additional experiments lower HMF selectivity and lower conversion (Table 1). Zr-beta
6
like those shown in Figure 2 were ran in isopropanol to
7
optimize yield. Glucose was converted to furans in 88%
8 Table 1. Glucose, mannose, fructose, and glycoside conversion vs. HMF
selectivity at 60% conversion in isopropanol containing
9 and IMF selectivity. Reactions were run at 110 8C in a 7.5 wt% solution of
7.5 wt% water at 110 8C using a combination of Sn-beta and water in isopropanol.
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Amberlyst 15 catalysts after only 6 h of reaction (Figure 3). The
11 Sample Conversion (%) HMF and IMF Selectivity (%)
12
Hf-beta (Si/Hf = 219) 24 55
13 Zr-beta (Si/Hf = 325) 10 44
14
15
16
and Amberlyst 70 catalyzed the conversion at 10% conversion
17
with a 44% furan selectivity after 8 h of reaction at 110 8C. Hf-
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beta and Amberlyst 70 catalyzed the conversion of glucose to
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HMF with 55% furans selectivity at 24% conversion at identical
20
conditions. These results demonstrate the significant effect
21
Lewis acid type has on reaction conversion, selectivity, and
22
furan yield. Increasing wavenumbers of vibration of probe
23
molecules from FTIR experiments correlate with greater Lewis
24
acidity and greater conversion.
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To further understand the relationship between Lewis and
26 Figure 3. Conversion of glucose to HMF and IMF in isopropanol containing Brønsted acid, further experiments were performed. It was
27 7.5 wt% water as a co-solvent as a function of time. Reactions were run at
110 8C using a 0.159 M concentration of glucose catalyzed by Sn-beta (Si/
demonstrated that increased Lewis acidity of the zeolite is
28
Sn = 230) and Amberlyst 15. required to increase the rate of the isomerization reaction of
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glucose to fructose. The Brønsted acid catalyst used affects the
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rate of isopropyl glycoside, byproduct, and furans production
31
(Table 2). An appropriate Lewis to Brønsted acid ratio is
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yield of detected molecules by HPLC following reaction is 93%
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with 80 mol% of the furan molecules being HMF and the other
34 Table 2. Glucose, mannose, fructose, and glycoside conversion vs. HMF
20% being IMF. The total yield of undetected products, which
35 and IMF selectivity at 110 8C with 0.02 g of Brønsted acid catalyst and Sn-
includes humins, is 7%. At 97% conversion, the selectivity to beta catalyst (150:1 molar ratio of glucose to Sn) in a 7.5 wt% solution of
36
the furans HMF and IMF decreases to 39%. This is due to the water in isopropanol.
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formation of more undetected byproducts such as humins. The Sample Conversion (%) HMF and IMF Selectivity (%)
38
addition of water to isopropanol suppresses the formation of
39 Amberlyst 15 60 88
products formed by the Meerwein-Ponndorf-Verley (MPV)
40 Amberlyst 70 31 64
reaction as previously shown.[21] Significant amounts of acetali-
41
zation products were not detected. The adsorption of reactants,
42
intermediates, and products affects HMF selectivity when using
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Brønsted acidic H-beta (Si/Al = 18) zeolite which more readily required to isomerize glucose and dehydrate fructose. Ether-
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converts HMF than fructose due to stronger adsorption.[22] The ification of glucose by the Brønsted acid leads to glycoside
45
use of a Lewis acid beta zeolite void of strong Brønsted acid formation and hydrolysis of HMF leads to side reactions. The
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sites in alcohols may decrease the conversion of HMF to macroporous polymeric catalyst, Amberlyst 70, is more active
47
humins by the zeolite. for dehydration than the styrene-divynlbenzene macroretricular
48
Further studies were conducted to make sure that the catalyst, Amberlyst 15, and yields 53% isopropyl glycoside as
49
reaction is operated in an optimal temperature window. compared to 32% isopropyl glycoside yield at the same
50
Increasing the temperature of reaction to 120 and 140 8C in reaction conditions. The furan molecule selectivity is also
51
isopropanol containing 7.5 wt% water increases conversion greater for Amberlyst 15 than Amberlyst 70 (Scheme 1).
52
from 52 to 63% after 2 h of reaction but decreases the total In conclusion, the results presented here are an improve-
53
yield of products and byproducts from 70 to 57%. The furans’ ment for the selective conversion (88% furan selectivity at 60%
54
selectivity also decreases at higher temperatures from 43 to conversion) of glucose to furans in alcoholic solvents. A good
55
32% when the reaction is catalyzed by Sn-beta and Amberlyst yield (53%) was observed using heterogeneous catalysts which
56
70. is an improvement over previous studies which use an ethanol-
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water solvent and AlCl3 catalyst, in microwave reactors using Romn-Leshkov, J. A. Dumesic, Green Chem. 2007, 9, 342; c) A. A.
1 Rosatella, S. P. Simeonov, R. F. M. Frade, C. A. M. Afonso, Green Chem.
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2 2011, 13, 754.
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3
alternative one-reactor, two-step reaction protocol for EMF [6] a) J. M. R. Gallo, D. M. Alonso, M. A. Mellmer, J. A. Dumesic, Green Chem.
4
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5 Scott, J. A. Dumesic, ACS Sustainable Chem. Eng. 2013, 1, 554.
zeolite followed by Amberlyst15, which achieved a 53% furans
6 [7] Y. J. Pagan-Torres, T. F. Wang, J. M. R. Gallo, B. H. Shanks, J. A. Dumesic,
selectivity at 87% glucose conversion in ethanol.[13] Following ACS Catal. 2012, 2, 930.
7
the reaction, zeolite membrane separation may be used to [8] A. I. Torres, P. Daoutidis, M. Tsapatsis, Energy Environ. Sci. 2010, 3, 1560.
8
separate water from alcohols by pervaporation and HMF can [9] a) P. S. Nigam, A. Singh, Prog. Energy Combust. Sci. 2011, 37, 52; b) T.
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10 [10] a) M. Moliner, Y. Romn-Leshkov, M. E. Davis, Proc. Natl. Acad. Sci. U. S. A.
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11
HMF followed by HMF separation.[24] ACS Catal. 2011, 1, 408; c) J. Wang, J. Ren, X. Liu, J. Xi, Q. Xia, Y Zhu, G.
12
Lu, Y Wang, Green Chem. 2012, 14, 2506.
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The procedures used for catalyst synthesis and characterization 2002, 124, 3194; b) C. Hammond, S. Conrad, I. Hermans, Angew. Chem.
16
in addition to those for reaction experiments are provided in Int. Edit. 2012, 51, 11736.
17 [13] H. Li, S. Saravanamurugan, S. Yang, A. Riisager, Green Chem. 2016, 18,
the supporting information. Supplementary catalyst character-
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19
[15] C. M. Lew, N. Rajabbeigi, M. Tsapatsis, Ind. Eng. Chem. Res. 2012, 51,
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21 Acknowledgement [16] a) C. M. Osmundsen, M. S. Holm, S. Dahl, E. Taarning, Proc. Roy. Soc. A.
22 2012, 468, 2000; b) M. Moliner, Y. Romn-Leshkov, M. E. Davis, Proc. Natl.
This work was supported U.S. Department of Energy, Office of Acad. Sci. USA 2010, 107, 6164.
23
Science, Office of Basic Energy Sciences, under Award DE- [17] E. Mahmoud, J. Yu, R. J. Gorte, R. F. Lobo, ACS Catal. 2015, 5, 6946.
24
SC0001004. Dr. Eyas Mahmoud acknowledges support by the [18] J. D. Lewis, S. Van de Vyver, A. J. Crisci, W. R. Gunther, V. K. Michaelis, R. G.
25 Griffin, Y. Romn-Leshkov, ChemSusChem 2014, 8, 2255.
National Science Foundation Graduate Research Fellowship under
26 [19] J. M. Newsam, M. M. J. Treacy, W. T. Koetsier, C. B. De Gruyter, Proc. R.
Grant 1247394. Dr. Eyas Mahmoud thanks SACHEM Co. for Soc. London, Ser. A 1988, 420, 375.
27
providing tetraethylammonium hydroxide. [20] S. Roy, K. Bakhmutsky, E. Mahmoud, R. F. Lobo, R. J. Gorte, ACS Catal.
28
2013, 3, 573.
29 [21] A. Corma, M. E. Domine, S. Valencia, J. Catal. 2003, 215, 294.
30 Conflict of Interest [22] J. S. Kruger, V. Choudhary, V. Nikolakis, D. G. Vlachos, ACS Catal. 2013, 3,
31 1279.
The authors declare no conflict of interest. [23] Y. Yang, C. Hu, M. M. Abu-Omar, Bioresour. Technol. 2014, 116, 190.
32
[24] a) Z. Wang, Q. Ge, J. Shao, Y. Yan, J. Am. Chem. Soc. 2009, 131, 6910; b) A.
33 Huang, W. Yang, J. Liu, Sep. Purif. Technol. 2007, 56, 158; c) L. Lai, Y.
34 Keywords: ethanol · glucose · HMF · isomerization · zeolites Zhang, ChemSusChem 2011, 4, 1745.
35
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