Dehydration of Carbohydrates to 5-Hydroxymethylfurfural over

Research Article pubs.acs.org/journal/ascecg

Cite This: ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

Dehydration of Carbohydrates to 5‑Hydroxymethylfurfural over Lignosulfonate-Based Acidic Resin Hao Tang,†,‡ Ning Li,*,†,§ Guangyi Li,† Wentao Wang,† Aiqin Wang,†,§ Yu Cong,† and Xiaodong Wang† †

State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, No. 457 Zhongshan Road, Dalian 116023, China ‡ University of Chinese Academy of Sciences, Beijing 100049, China § iChEM (Collaborative Innovation Centre of Chemistry for Energy Materials), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, No. 457 Zhongshan Road, Dalian 116023, China S Supporting Information *

ABSTRACT: Lignosulfonate-based renewable solid acids were first utilized as effective catalysts for fructose dehydration to produce 5-hydroxymethylfurfural (HMF). Among the investigated catalysts, the LF resin synthesized with formaldehyde and sodium lignosulfonate demonstrated the highest activity and good stability. Over it, ∼90% HMF carbon yield was reached at 393 K. On the basis of the characterization results of N2-physisorption, chemical titration, and microcalorimetric measurement of NH3 adsorption, the outstanding performance of LF resin should be interpreted by its higher acid strength and/or the synergistic effect of adjacent −SO3H, −COOH and phenolic −OH surface functional groups. We also explored the applicability of the LF resin for HMF production using other cheaper carbohydrates. Here, 73% HMF carbon yield was obtained from inulin hydrolysis/dehydration after the reaction was conducted over the LF resin at 393 K for 2.5 h. KEYWORDS: Carbohydrates, Dehydration, 5-Hydroxymethylfurfural, Lignosulfonate, Acidic resin

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INTRODUCTION Because of the great social concern about sustainable development and environmental issues (such as CO2 and SO2 emission), the conversion of renewable biomass to transportation fuels1,2 and high value-added chemicals3−5 has become a research hotspot. 5-Hydroxymethyfurfural (HMF) is an important platform compound widely used in biofuels synthesis (such 2, 5-dimethylfuran,6−9 jet fuel, or diesel range alkanes10,11) and useful chemicals (e.g., as 2,5-furandiyldimethanol,8,12,13 2,5-furandicarbaldehyde,14,15 2,5-furandicarboxylic acid,16,17 1,6-hexandiol,18 p-xylene,19,20 5-hydroxy-2,5-hexanedione,21,22 3-hydroxymethylcyclopentanone,23 etc.). Recently, the development of highly active, environmental friendly, easily separated, and reusable solid acid for carbohydrate dehydration to HMF has attracted great attention.24−27 Lignosulfonate is an important byproduct in the paper industry using the sulfite pulping process. In some literature,28 lignosulfonate has been suggested as a polyphenolic compound which contains −SO3H groups connected with aliphatic carbons. Because of its polyphenolic chemical structure, lignosulfonate can be polymerized with some oxygenates by condensation. The condensation products as obtained have −SO3H groups. As a potential application, they can be employed as solid acids for carbohydrate dehydration to HMF. So far, there is no reported work on this. In this paper, we prepared several renewable acidic resins with sodium lignosulfonate and biomass derived oxygenates. The © XXXX American Chemical Society

lignosulfonate-based resins have high activity for fructose dehydration to HMF. Among these catalysts, the LF resin synthesized with formaldehyde and sodium lignosulfonate demonstrated the highest activity. Over this material, higher HMF carbon yield than those on commercial catalysts (such as Amberlyst and Nafion resins) can be obtained at 393 K. To understand the outstanding performance of LF resin, the catalysts was characterized by mutiple techniques. The impacts of solvent, temperature, and recycle time on the performance of LF resin were explored. For future application, we also studied the applicability of LF resin for HMF production using cheaper carbohydrates.

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EXPERIMENTAL SECTION

Catalyst Preparation. Amberlyst-15, Amberlyst-36, and Nafion212 were commercial acidic resins purchased from Sigma-Aldrich and Dupont, respectively. The lignosulfonate-based acidic resins were homemade using commercial available sodium lignosulfonate and some lignocellulosic oxygenates which contain carbonyl groups (e.g., formaldehyde, formic acid, acetaldehyde, furfural, and glucose) following a method reported in the literature.29 First, we prepared several polymers by the condensation of sodium lignosulfonate with lignocellulosic oxygenates. Typically, 1.2 mL (15 mmol) aqueous solution of lignocellulosic oxygenates was slowly added into a sodium lignosulfonate aqueous solution (3.0 g sodium lignosulfonate dissolved in 5.2 g water) under magnetic Received: February 14, 2018 Published: February 28, 2018 A

DOI: 10.1021/acssuschemeng.8b00757 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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ACS Sustainable Chemistry & Engineering

Figure 1. Fructose conversions, HMF carbon yields, and selectivity over the lignosulfonate-based acidic resins. Reaction conditions: 1 g fructose, 7 g dimethyl sulfoxide (DMSO), 0.1 g catalyst; 353 K, 1.5 h. The LF, LAce, LFur, LFA, LGlu stand for the lignosulfonate-based acidic resins synthesized using commercial sodium lignosulfonate and formaldehyde, acetaldehyde, furfural, formic acid, and glucose, respectively.

Figure 2. Fructose conversions, HMF carbon yields, and selectivity over acidic resins. Reaction conditions: 1 g fructose, 7 g DMSO, 0.1 g catalyst; 353 K, 1.5 h.

Table 1. Specific BET Surface Areas (SBET), the Amounts of Acid Sites on the Catalyst Surfaces, and the Initial NH3 Adsorption Heats on Different Catalysts amount of acid sites (mmol g−1)

catalyst

SBET (m2 g−1)a

chemical titrationb

NH3 chemisorptionc

initial NH3 adsorption heat (kJ mol−1)d

LF Nafion-212 Amberlyst-15 Amberlyst-36

2 2 41 13

2.37 1.08 4.68 4.01

0.83 0.10 4.09 1.46

160 168 156 155

a

Measured by N2-physisorption. bMeasured by chemical titration. Measured by NH3 chemisorption. dAccording to the microcalorimetric measurement of NH3 adsorption.

c

Figure 3. Adsorption heat versus NH3 coverage at 353 K on the LF, Nafion-212, Amberlyst-36, and Amberlyst-15 resins.

agitation. After the addition of 2.7 mL HCl solution (37 wt %) and vigorous stirring for 6 h at 363 K, the solid product was filtrated from the mixture, dried at 333 K overnight, and ion-exchanged with 2 mol L−1 H2SO4 solution (in proportion of 100 mL g−1) for 2 h. Finally, the resins were filtrated from the solution, repeatedly washed (until filter liquor become neutral), and desiccated overnight at 393 K. Activity Test. The dehydration (or hydrolysis/dehydration) of different carbohydrates was conducted in a glass batch reactor. Before the activity tests, the catalysts were dried for 5 h at 353 K. For each test, 1 g carbohydrate, 7 g solvent and 0.1 g catalyst were used. The mixture was magnetically agitated at a certain temperature for 1.5 h. After the activity test, the liquid products were quantitatively analyzed by an Agilent 1100 HPLC using a hodex SC1011 packed column (Ca2+, 300 mm × 8 mm)

and a refractive index detector using water as the mobile phase. The conversion of carbohydrate and HMF carbon yield (or selectivity) were calculated by following equations: Conversion of carbohydrate (%) = (1 − mol of the carbohydrate in product/mol of the carbohydrate in feedstock) × 100%; HMF carbon yield (%) = mol of carbon in the HMF generated during the reaction/mol of carbon in the carbohydrate feedstock × 100%; selectivity of HMF (%) = carbon yield of HMF/ conversion of carbohydrate × 100%. Because there is no C−C cleavage (or C−C coupling) reaction during the dehydration of carbohydrates to HMF, the carbon yields of HMF are equal to their molar yields. B


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at 353 K. As far as we know, this is the first report on the application of lignosulfonate-based acidic resins as solid acids for fructose dehydration. As we know, glucose and formic acid are two oxygenates from the hydrolysis (or hydrolysis/dehydration) of cellulose. These oxygenates have −CHO groups and can be used as aldehydes in some reactions. In this work, it was found that glucose and formic acid can also form polymers with sodium lignosulfonate. After being ion-exchanged with HCl solution, the condensation products can be converted into solid acids which are active for the dehydration of fructose. Among the lignosulfonate-based resins, LF demonstrated the highest activity and selectivity for the fructose dehydration to HMF. Over the LF resin, 78% fructose conversion and 49% HMF carbon yield were reached when the reaction was processed for 1.5 h at 353 K. For comparison, we also explored the activity of some commercial resins for the fructose dehydration. According to Figures 2 and S2, the LF has higher activity than Amberlyst-15, Amberlyst-36, and Nafion-212 resin for the dehydration of fructose to HMF. In view of the much lower cost, renewability, higher activity, and selectivity of the LF resin, we believe that it should be a prospective catalyst in industrial applications. To comprehend the outstanding performance of LF resin, we characterized the catalysts by multiple techniques. From N2-physisorption and chemical titration results (see Table 1), it was observed that the SBET and the amounts of acid sites on the catalyst surfaces decline in the sequence of Amberlyst-15 > Amberlyst-36 > LF, Nafion-212. This order is different with the one for their activity for the fructose dehydration (LF > Nafion212 > Amberlyst-15 > Amberlyst-36). Therefore, we cannot attribute the activity sequence of these acidic resins to their SBET or the amounts of acid sites on catalyst surfaces. From Table 1 and Figure 3, it was observed that the acid strengths of different resins (reflected by the initial NH3 adsorption heats) decline in the sequence of Nafion-212 (168 kJ mol−1) > LF (160 kJ mol−1) > Amberlyst-15 (156 kJ mol−1), Amberlyst-36 (155 kJ mol−1), which is in accord with the order of HMF carbon yields over these resins with the same amount of acid sites (see Figure 4). In the light of the above results, the higher acid strength of LF resin may be one cause for its higher activity than those of Amberlyst15 and Amberlyst-36 in the dehydration of fructose. It was also noticed from Table 1 that the amount of acid sites on the LF resin surface is evidently higher than Nafion-212 resin. This may be the

Characterization. N2 Physisorption. Specific BET surface areas (SBET) of the acidic resins were surveyed by N2 physisorption conducted by an ASAP 2010 apparatus. Before the measurements, the samples were degassed at 393 K for 3 h. Chemical Titration. Amounts of acid sites on acidic resins surfaces were determined by chemical titration method.29,30 For each measurement, 0.02 g catalyst was used. The sample was dispersed into 20 mL NaOH solution (0.01 mol L−1) by sonication and then centrifuged. The filtrate was titrated using 0.01 mol L−1 HCl (precalibrated by a standard NaOH solution) using methyl orange as indicator. The molar amount of acid sites per gram catalyst was calculated according to the consumption of HCl solution. NH3 Chemisorption. Amounts of acid sites on the investigated catalysts were characterized by NH3 chemisorption on a Micromeritics AutoChem II 2920 Automated Catalyst Characterization System. First, 0.1 g catalyst was heated at 373 K in He flow for 1 h. After baseline was stabilized, NH3 (1 mL) were pulsed onto the catalyst until the saturation was reached. The amounts of acid sites were deduced according to NH3 consumption in the tests. Microcalorimetric Measurement of NH3 Adsorption. Microcalorimetric measurements of ammonia adsorption for the investigated acidic resins were carried out at 353 K by a BT2.15 heat-flux calorimeter (France, Seteram). The specific mass of sample with similar amount of acid sites was evacuated in a quartz cell at 353 K overnight under high vacuum to remove the physically adsorbed substance. The differential heat as a function of acid site coverage on the catalyst was determined by repeatedly inputting small amount of ammonia onto the samples until the equilibrium pressure attained 0.667−0.800 kPa. Then the system was evacuated overnight to get rid of the physically bonded ammonia and a second adsorption was conducted. Fourier Transform Infrared Spectroscopy (FT-IR). The FT-IR spectrum of LF resin was collected by a Bruker Equinox 55 spectrometer using a extended KBr beam splitter and a deuterated triglycine sulfate (DTGS) detector. The spectrometer was manipulated at a resolution of 4 cm−1 in the absorbance mode. Before the test, the LF resin was blended with KBr at a ratio of 1/100 by weight and pressed to self-supporting tablets. Solid 13C NMR Spectroscopy. Solid 13C NMR spectroscopy of the LF resin was acquired by a Bruker Avance-III 500 MHz spectrometer.

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RESULTS AND DISCUSSION

Dehydration of Fructose. First of all, we studied the fructose dehydration over lignosulfonate-based acidic resins prepared with sodium lignosulfonate and lignocellulosic aldehydes (e.g., formaldehyde, acetaldehyde, furfural). From Figures 1 and S1 in the Supporting Information, we noticed that all of these lignosulfonate-based acidic resins are very effective for fructose dehydration. Over them, evident conversions of fructose to HMF (>25%) were reached when the reaction was processed for 1.5 h

Figure 4. Fructose conversions, HMF carbon yields, and selectivity over different acidic resins. Reaction conditions: 1 g fructose, 7 g DMSO; 353 K, 1.5 h. To unify the amount of acid sites as 0.28 mmol, the masses of catalysts were deduced according to the amounts of acid sites on these resin surfaces quantified by chemical titration (see Table 1). C


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effect of fluorine enhances the acid strength of the −SO3H group on the Nafion resin surface and makes it greater than those over LF and Amberlyst resins. LF resin is a lignosulfonate-based polymer which has −SO3H groups connecting with the aliphatic carbons. The −SO3H groups in Amberlyst resins are located on an aromatic ring. In contrast, the −SO3H groups on LF resin are bonded on aliphatic carbons. Because the benzene ring’s electronic donor effect is more evident than that of alkyl group, the acid strength of −SO3H group on the Amberlyst resins is lower than that over the LF resin. Another possible explanation for the outstanding activity of LF resin is the synergism effect of the adjacent −SO3H, −COOH, and phenolic −OH functional groups.26,31 According to the FTIR spectrum illustrated in Figure 5, the LF resin has multiple

reason why the HMF yield over LF resin is greater than that over Nafion-212 resin when same weight catalysts were used. The acid strength order of the investigated resins may be rationalized by their chemical structures. In particular, Nafion resin is perfluorinated sulfonic acid resin, while Amberlyst resin is sulfonic-acid-functionalized polystyrene. The electron-withdrawing

Table 2. Correspondence between the Peaks at Different Chemical Shifts to the Carbon Atoms on Various Functional Groups

Figure 5. FT-IR spectrum of the LF resin obtained by the protonation of the condensation product of sodium lignosulfonate and formaldehyde.

chemical shift (ppm)

assignment38−40

180 159 117

carboxyl group phenol group benzene ring

Figure 6. Solid 13C NMR spectroscopy of the LF resin which was obtained by the protonation of the condensation product of sodium lignosulfonate and formaldehyde. D


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ACS Sustainable Chemistry & Engineering functional groups. On the basis of literature,29 the shoulder band at 3020 cm−1 may be assigned to stretching vibration of −CH2− formed during the phenol-aldehyde condensation of sodium lignosulfonate and formaldehyde. The peaks at 1228 and 1034 cm−1 should be attributed to the sym-stretching of OSO and SO3−H stretching in −SO3H groups,30,32,33 respectively. The bands at 1115 and 1320 cm−1 represent the in-plane bending vibration of aromatic C−H34 and syringyl ring breathing with C−O stretching,35 respectively. The peaks at 1403 and 1605 cm−1 represent the characteristic vibrations of aromatic ring.29,34,36 The wavenumber at 1714 cm−1 indicated the presence of −COOH group on the LF resin surface.33,37 The wide peak at 3139 cm−1 should be attributed to the phenolic −OH groups linked with the neighboring oxygen atoms or −SO3H groups by hydrogen-bonds.29 Similar structural information on LF resin was observed from the solid 13C NMR spectrum (see Figure 6 and Table 2). To verify the synergism effects between −SO3H and −COOH groups (or between −COOH and adjacent −OH groups) in the dehydration of fructose, we did some additional experiments. First, we compared the activity of acetic acid, Amberlyst-15 or a mixture of acetic acid and Amberlyst-15 (denoted as acetic acid + Amberlyst-15). According to Figure S3, the HMF carbon yield and selectivity over the acetic acid + Amberlyst-15 are evidently higher than those over acetic acid (or Amberlyst-15 resin). Based on this result, we can see that there is a synergistic effect between −SO3H and −COOH groups in the dehydration of fructose. Second, we also compared the fructose dehydration activity of glycolic acid, acetic acid, o-hydroxy-benzoic acid and benzoic acid. According to expectations, higher carbon yield of HMF was achieved when glycolic acid and o-hydroxy-benzoic acid (see Figure S4 in the Supporting Information). Therefore, we think that there is a synergism effect between −COOH and adjacent −OH groups in fructose dehydration. The solvent effect was explored. Better results were achieved over the LF resin when the reaction was conducted in DMSO (see Figure 7). Based on the literature,41−43 this phenomenon can be comprehended from dual aspects: (1) The utilization of DMSO as the solvent can decrease the water in the reaction system. As the result, both rehydration and the humin formation were inhibited. (2) DMSO is favorable for furanoid form of fructose which can be readily dehydrated to HMF. On the contrary, low fructose conversion and HMF carbon yield were achieved using water as solvent, which can be comprehended by

following three reasons: (1) The dehydration and hydration are reversible reactions. Therefore, water is detrimental for HMF production by fructose dehydration from the point of view of reaction equilibrium. (2) Water has lone pair electrons. For this reason, it can play the role of Lewis base to compete with substrate for acid sites (or the active sites in frutcose dehydration). (3) HMF can be readily hydrolyzed to produce levulinic and formic acids at the same time, which may also decline the HMF carbon yield or selectivity. The impact of reaction temperature on the catalytic performance the LF resin was also studied. From Figure 8, it was

Figure 8. Fructose conversion, HMF carbon yield, and selectivity over the LF resin as a function of reaction temperature. Reaction conditions: 1 g fructose, 7 g DMSO, 0.1 g LF resin; 1.5 h.

noticed that the fructose conversion and HMF carbon yield over the LF resin increased with the increment of reaction temperature and reached the maximum at 393 K, then stabilized with the further increase of reaction temperature. For real applications, we studied the influence of fructose/ catalyst mass ratio on the performance of LF resin. It was found that the LF resin is very effective for the dehydration of fructose. Over it, high fructose conversion (90%) and carbon yield of HMF (65%) were achieved at the initial subtract/catalyst mass ratio of 100 (see Figure 9). We also checked the reusability of the LF resin. From Figures 10 and S5, we can see that the LF resin is stable. No significant deactivation was noticed during the four repeatedly usages under the investigated conditions. From Table S1 in the Supporting Information, evident decreases in the SBET and the amount of

Figure 7. Fructose conversion, HMF carbon yield, and selectivity over the LF resin as a function of solvent. Reaction conditions: 1 g fructose, 7 g solvent, 0.1 g LF resin; 353 K, 1.5 h. E


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Figure 9. Fructose conversions, HMF carbon yield, and selectivity over the LF resin. Reaction conditions: 1 g fructose, 7 g DMSO; 393 K, 1.5 h.

Figure 12. Inulin conversions, HMF carbon yields, and selectivity over the LF resin at different reaction times. Reaction conditions: 1 g inulin, 7 g DMSO, 0.1 g LF resin; 393 K.

hydrolysis/dehydration of sucrose or inulin. This result can be interpreted because sucrose is a disaccharide of glucose and fructose. Inulin is composed of chain-terminating glucosyl moieties and a repetitive fructosyl moiety linked by β(2,1) bonds.45 With the extending of reaction time to 2.5 h, 73% HMF carbon yield was obtained on the LF resin using inulin as substrate (see Figure 12). In application, this is advantageous because inulin is the main component of Jerusalem artichoke tuber which can grow on barren land.45

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CONCLUSIONS Renewable LF resin was reported as an effective, selective and stable solid acid catalyst for the fructose dehydration to HMF. The outstanding catalytic performance of LF resin can be interpreted by higher acid strength and the synergistic effect between different surface acidic groups. Under the optimized reaction conditions, ∼90% HMF carbon yield was obtained from the fructose dehydration over LF resin. The LF resin is also applicable for the HMF production using cheaper carbohydrates. For example, 73% HMF carbon yield was obtained from the hydrolysis/dehydration of inulin.

Figure 10. Fructose conversion, HMF carbon yield, and selectivity over the LF resin as the functions of recycle time. Reaction conditions: 1 g fructose, 7 g DMSO, 0.1 g LF resin; 393 K, 1.5 h.

acid sites over the LF resin were observed after it was used in the dehydration of fructose, which can be rationalized by the coke which was formed on the LF resin surface. Dehydration of Other Carbohydrates. The applicability of the LF resin for the dehydration of cheaper carbohydrates was investigated. To facilitate the comparison, the tests were conducted at 393 K for 1.5 h (i.e., the optimized conditions for fructose dehydration). Based on Figure 11, the chemical structure of the substrate has evident impact on the HMF carbon yield (or selectivity) from carbohydrate dehydration. As other acidic resin,41,44 the HMF carbon yield over the LF resin was very low when we used glucose as the substrate. However, high HMF carbon yield was obtained from the

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.8b00757. Detailed information for the separation of DMSO and HMF (PDF)

Figure 11. Substrate conversions, HMF carbon yields, and selectivity over the LF resin. Reaction conditions: 1 g carbohydrate, 7 g DMSO, 0.1 g LF resin; 393 K, 1.5 h. F


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AUTHOR INFORMATION

Corresponding Author

*Tel.: +86-411-84379738. Fax: +86-411-84685940. E-mail: [email protected] (N.L.). ORCID

Ning Li: 0000-0002-8235-8801 Aiqin Wang: 0000-0003-4552-0360 Yu Cong: 0000-0001-5544-1303 Xiaodong Wang: 0000-0002-8705-1278 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS

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REFERENCES

This work was funded by the National Natural Science Foundation of China (no. 21690080; 21690082, 21776273, 21721004, 21672210 and 21506213), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020100), the National Key Projects for Fundamental Research and Development of China (2016YFA0202801), Dalian Science Foundation for Distinguished Young Scholars (no. 2015R005), Department of Science and Technology of Liaoning Province (under contract of 2015020086-101), and 100-talent project of Dalian Institute of Chemical Physics (DICP).

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Dehydration of Carbohydrates to 5-Hydroxymethylfurfural over

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