Skip to main content
NCBI home page
ACS Omega logoLink to ACS Omega
. 2017 Sep 26;2(9):6123–6130. doi: 10.1021/acsomega.7b00771

Fabrication of a Novel and High-Performance Mesoporous Ethylene Tar-Based Solid Acid Catalyst for the Dehydration of Fructose into 5-Hydroxymethylfurfural

Shuang Zhang †,‡,✉, Zaihang Zheng †, Caiyi Zhao †, Long Zhang †,*
PMCID: PMC6644591  PMID: 31457859

Abstract

graphic file with name ao-2017-00771c_0009.jpg

In this article, a novel and high-performance mesoporous carbon-based solid acid catalyst was prepared using ethylene tar (ET) as a precursor, which is a byproduct of ethylene production. First, ET was carbonized at 550 °C by using magnesium acetate as the template. After that, the mesoporous ET-based solid acid catalyst was obtained by a one-step sulfonation process that removes the templates simultaneously. On the basis of these facts, the maximum yield of 5-hydroxymethylfurfural (5-HMF) in the presence of an ET catalyst during the dehydration of fructose can reach 87.8%. This effective catalytic activity is mainly attributed to the large specific surface area and high density of sulfonic acid groups existing in the ET catalyst. Moreover, no distinct activity drop was observed during five recycling runs that confirmed good recyclability and thermal stability of the ET catalyst. This research provides a novel and promising method for the utilization of ET as a low-cost, recyclable, and high-performance catalyst.

1. Introduction

With the huge consumption of fossil fuels, the research on biomass-based chemicals has become an attractive issue to solve the problem of energy scarcity.1,2 Among the numerous biomass-derived chemicals, 5-hydroxymethylfurfural (5-HMF) as an acid-catalyzed dehydration product of fructose is one of the versatile platform chemicals, which plays an important role in the synthesis of biofuels and other valuable chemical intermediates such as 2,5-furandicarboxylic acid, 2,5-furandicarbaldehyde, levulinic acid (LA), and so on.3,4 In recent years, great efforts have been taken for exploiting the effective way in promoting the formation of 5-HMF by the dehydration of cellulose, glucose, and fructose.3−7 A range of catalysts have been employed, including liquid acids,8−10 H-mordenites/zeolites,11−14 phosphates of transition metals,15−18 ion-exchange resins,19,20 and carbon-based solid acids.21−27 However, these catalysts usually have some disadvantages, such as separation difficulty, high price, low specific surface area, low activity, and poor thermal stability.

Recently, carbon-based solid acid from polynuclear aromatic hydrocarbons as the raw material has aroused researchers’ interest owing to its advantages in mechanical stability and chemical inertness.28 A lot of experiments have been conducted in investigating the preparation of a carbon-based solid acid catalyst with polynuclear aromatic hydrocarbons as the raw material. Hara et al. have reported a solid acid catalyst containing SO3H groups by the incomplete carbonization of naphthalene in concentrated sulfuric acid.29 The acid density of products can reach 4.9 mmol/g that is much higher than other traditional solid sulfonic acid catalysts. Daengprasert et al. have found that when sulfonated naphthalene-based catalyst is employed for the conversion of fructose into 5-HMF, the yield of 5-HMF can reach 29.8%.30 Tanemura et al. have reported the synthesis of strong acidic sulfonated naphthalene, pyrene, phenanthrene resins with p-xylylene glycol, or terephthalaldehyde as the cross-linking agent.31−33 In addition, they have also carried out the experiments in the synthesis of the strongly acidic sulfonated polynaphthalene, polypyrene, and polyanthracene via an oxidative coupling reaction using FeCl3 in nitrobenzene under nitrogen.34 These sulfonated condensed polynuclear aromatic (S-COPNA) resins are insoluble in boiling water and many hot organic solvents and can be recycled without an obvious loss of activity. Moreover, the activity of S-COPNA resins is much higher than that of conventional solid acids.

However, most of the reported catalysts from polynuclear aromatic hydrocarbons have low specific surface area and incomplete pore system, which reduces the probability of contact of reactants and the internal surface acidic sites of a catalyst.35−37 Furthermore, the expensive raw materials limit its wide-ranging applications. As a sort of byproduct in the production of ethylene, the output of ethylene tar (ET) is constantly increasing with the development of ethylene industry.38 As we know, ET has a high content of polynuclear aromatic hydrocarbon and a low content of branched hydrocarbon chains that can become an ideal candidate in preparing a mesoporous carbon-based solid acid catalyst. Until now, the recycled conversion of ET to useful materials is restricted that ET is mainly used for the production of carbon black, asphalt, and fuel oil. Other high-value-added applications originated from ET have yet not been developed.39 To solve this problem, we used ET as the raw material to prepare a mesoporous carbon-based solid acid catalyst in replacing expensive polynuclear aromatic hydrocarbons. Moreover, few papers have reported ET-based solid acid catalyst for the dehydration of fructose into 5-HMF.

In this work, a facile and effective method was carried out in preparing mesoporous ET-based solid acid. ET was used as the raw material, and magnesium acetate was used as the template. The mixture was carbonized at a certain temperature. In addition, a novel mesoporous ET-based solid-acid catalyst was prepared via a one-step sulfonation process by using concentrated sulfuric acid as the sulfonating agent. Compared with the traditional two-step method of removing templates followed by sulfonation, this method can further increase the specific surface area and simplify the preparation process. The catalytic activity and recyclability of the mesoporous ET-based solid acid catalyst have been studied in the reaction for the conversion of fructose to 5-HMF. Moreover, the effect of reaction conditions including reaction temperature, reaction time, catalyst dosage, and solvent and additive on the yield of 5-HMF and the conversion of fructose were systematically investigated. This method provides a new idea for the preparation of a novel and high-performance ET catalyst.

2. Experimental Section

2.1. Materials

Fructose (>99%), 5-HMF (>99%), LA (>99%), and polyvinyl pyrrolidone K30 (PVP-K30, >98%) were obtained from Sigma Reagent Company. Isopropyl alcohol, magnesium acetate, concentrated sulfuric acid, and acetonitrile were purchased from Beijing Chemicals Co. Ltd. The crystal water of magnesium acetate was removed by heating it at 140 °C in an oven until it reaches a constant weight before use. ET was provided by PetroChina Jilin Petrochemical Company. The volatile molecules (<250 °C) of ET were removed by vacuum distillation before use.

2.2. Preparation of a Mesoporous ET-Based Solid Acid Catalyst

First, ET and magnesium acetate in a mass ratio of 2:8 were mixed by mechanical grinding. The mixture was heated to a certain temperature at a heating rate of 5 °C/min in a nitrogen atmosphere and maintained for 1 h. After cooling down to room temperature, the obtained carbonized product was taken out from the tube furnace. Then, a one-step method was employed to accomplish the dissolution of MgO and the sulfonation of a carbonized product by concentrated sulfuric acid at the same time. Along with concentrated sulfuric acid, the carbonized product was added into a three-necked flask and stirred at 150 °C for 15 h under the nitrogen atmosphere. After that, the system was cooled down to ambient temperature and washed with hot water until the filtrate became neutral. Finally, the product was dried in a vacuum oven at 80 °C for 12 h to obtain the mesoporous ET-based solid acid catalyst, which is denoted as the ET catalyst. The preparation process of the catalyst is shown in Scheme 1.

Scheme 1. Preparation Process of the ET Catalyst.

Scheme 1

Open in a new tab

2.3. Dehydration of Fructose

The reaction procedure was as follows: d-fructose, isopropyl alcohol, catalysts, and PVP-K30 were added into a stainless steel reactor with a Teflon liner equipped with a magnetic stirrer. Dehydration was initiated by heating the reaction system to a certain temperature. After the reaction was completed, the reactor was cooled to ambient temperature, and the catalyst was obtained by filtering under vacuum.4 At last, the catalyst was washed three times with ethanol and dried at 80 °C for 12 h for the next use. The filtrate was diluted with deionized water for the analysis of the conversion, yield, and selectivity.

The conversion of fructose was analyzed by an Agilent 1100 high-performance liquid chromatography (HPLC) system equipped with a refractive index detector using a COSMOSIL Sugar-D Packed column (250 mm × 4.6 mm and 5 μm) at 30 °C. The mobile phase was 75% acetonitrile and 25% water (v/v) to analyze the conversion of fructose at a flow rate of 1.0 mL/min.

The yield of 5-HMF was analyzed using an Agilent 1260 HPLC system equipped with a UV detector (284 nm) and an Extend-C18 column (250 mm × 4.6 mm and 5 μm) at 35 °C. The mobile phase was 5% methanol and 95% water (v/v) to analyze the yield of 5-HMF at a flow rate of 1.2 mL/min.

The conversion, yield, and selectivity are defined according to the following formula

2.3.
2.3.
2.3.

2.4. Characterization of the Catalyst

A Nicolet 6700 Fourier transform infrared (FT-IR) spectrometer was used to measure the presence of functional groups on the samples’ surface.

The standard back acid–base titration method was used to quantify the acid density of the catalysts. The catalyst was predried in a vacuum drying oven at 100 °C for 2 h prior to analysis, and then accurate 1.00 g of the catalyst was soaked in 50 mL of 0.1 M NaOH solution 24 h before back-titrating with 0.1 M HCl solution. The NaOH solution and HCl solution used in the experiment were calibrated. The acid density of the catalyst was measured three times, and then the results were averaged.

The X-ray diffraction (XRD) patterns of the samples were recorded with a Rigaku D/max-2500 diffractometer, applying Cu Kα radiation (λ = 0.1542 nm) under ambient temperature.

The nitrogen adsorption–desorption isotherms were obtained on a micromeritics TriStar II surface area. Before the tests, the samples were outgassed at 120 °C for 12 h under the nitrogen atmosphere. The specific surface areas and pore size distributions were calculated using the Brunauer–Emmett–Teller (BET) method and the Barrett–Joyner–Halenda (BJH) method, respectively.4

The mesoporous morphology of the catalyst was obtained on a JEM-2000EX transmission electron microscopy (TEM) technique with a working voltage of 200 kV.

The thermal stability of the catalyst was measured using a Q5000 thermogravimetric analysis (TGA) instrument under flowing nitrogen with a heating rate of 10 °C/min from 25 to 800 °C.

3. Results and Discussion

3.1. Effect of Carbonization Temperature on the BET Surface Area and Acid Density of the Catalyst

The detailed data for the specific surface area and acid density of the ET catalyst are presented in Table 1. Obviously, it can be observed that with the increase of carbonization temperature, the specific surface area of the ET catalyst gradually increases, be it for before sulfonation or for after sulfonation. In contrast to the specific surface area of the ET catalyst before sulfonation, the specific surface area of the ET catalyst after sulfonation decreases, be it for a one-step method or for a two-step method. This phenomenon is mainly caused by the collapse of a partial pore of the ET catalyst during the sulfonation reaction. Moreover, the specific surface area of the ET catalyst after sulfonation for the one-step method is higher than that of the two-step method in different temperatures. Therefore, it can be concluded that the simple one-step method can effectively prevent the collapse of the pores of the ET catalyst and obtain high specific surface area to some extent.

Table 1. Specific Surface Area Analysis, Acid Density Analysis, and the Yield of 5-HMF Obtained in Different Carbonization Temperaturesa,b,c,d,e.

  BET surface area (m2/g)
  
  
    after sulfonation
 acid density (mmol/g)
 the yield of 5-HMF (%)
carbonization temperature (°C) before sulfonation one-step two-step one-step two-step one-step two-step
400 66.41 5.06 2.00 4.21 4.17 42.1 42.0
450 159.01 27.62 9.12 4.21 4.20 43.5 42.5
500 644.70 333.89 52.48 4.35 4.20 69.9 50.3
550 939.34 552.40 280.19 4.99 4.28 87.8 66.8
600 1040.25 816.71 732.36 3.83 3.52 53.1 49.6
Open in a new tab
a

Mixing mass ratio of ET/Mg(CH3COO)2 is 2/8.

b

Before sulfonation: removal of templates with 2 M dilute sulfuric acid.

c

One-step method: removal of templates and sulfonation were performed simultaneously, sulfonation temperature 150 °C, sulfonation time 15 h, and incomplete carbonized products/concentrated sulfuric acid (g/mL) = 1/10.

d

Two-step method: first, the removal of templates with 2 M dilute sulfuric acid and then sulfonated at 150 °C for 15 h, and incomplete carbonized products/concentrated sulfuric acid (g/mL) = 1/10.

e

Yield of 5-HMF: reaction temperature 130 °C, reaction time 140 min, fructose 0.5 g, catalyst 0.25 g, isopropyl alcohol 7 mL, and PVP-K30 0.2 g.

As shown in Table 1, with the increase of carbonization temperature, the acid density of the ET catalyst obtained by the one-step method or the two-step method first increases and then decreases. The increase of the specific surface area leads to the increase in the binding sites of the SO3H groups and an incomplete carbonized product. As a result, the acid density of the ET catalyst gradually increases. However, when the carbonization temperature further increases, more carbons are formed, resulting in a rigid structure and rendering sulfonation difficult.21 Therefore, the acid density of the ET catalyst decreases.

The yields of 5-HMF obtained by the one-step method and the two-step method are also presented in Table 1. The yield of 5-HMF obtained by the one-step method is higher than that of the two-step method in different carbonization temperatures. Obviously, this is because the specific surface area and acid density of the one-step method are higher than those of the two-step method. When the carbonization temperature is 550 °C, the catalyst obtained by the one-step method not only has the highest acid density (4.99 mmol/g) and a relatively high specific surface area (552.4 m2/g) but also can obtain the highest yield of 5-HMF (87.8%). On the basis of these data, the ET catalyst is chosen in the following experiments.

3.2. Mesoporous Structure of the Catalyst

The mesoporous structure of the ET catalyst was verified by N2 adsorption isotherm and pore size distribution. As shown in Figure 1a, it can be seen that the characteristic type IV isotherm and a typical H2 hysteresis loop appear in the relative pressure (P/P0) range of 0.4–0.7, and the specific surface area calculated by the BET method is about 552.4 m2/g. The BJH pore size distribution indicated that the average pore size is about 37 nm, as shown in Figure 1b. On the basis of the analysis, this mesoporous structure is beneficial for the utilization of the inner surface active sites of the ET catalyst.

Figure 1.

Figure 1

Open in a new tab

N2 adsorption isotherm (a) and BJH pore size distribution plot (b) of the ET catalyst.

3.3. FT-IR Spectra

The FT-IR spectra of ET are presented in Figure 2a. The strong peak at 3440 cm–1 is assigned to the characteristic stretching vibration of the phenolic O–H groups. The peak at 2924 cm–1 is ascribed to the stretching vibration of C–H groups for saturated hydrocarbon. The absorption peak at 1631 cm–1 is assigned to the stretching vibration of C=C groups in the aromatic nucleus. The weak peak at 746 cm–1 is originated from the out-of-plane bending vibration of C–H groups in the aromatic ring. In addition, the FT-IR spectra of the carbonized product and the ET catalyst are presented in Figure 2b,c. The adsorption of the carbonized product at 503 cm–1 is due to the incorporation of magnesium oxide. The increase in the intensity of C=C groups of the ET catalyst illustrates that sulfonation promotes the further polycondensation of carbonized products.31,40 The adsorption bands of the ET catalyst at 1230, 1040, and 619 cm–1 are ascribed to the S=O vibration, indicating the presence of SO3H groups on the ET catalyst.

Figure 2.

Figure 2

Open in a new tab

FT-IR spectra of ET (a), carbonized product (b), and ET catalyst (c).

3.4. X-Ray Diffraction

The ET, carbonized product, and ET catalyst are analyzed by XRD. The XRD pattern of ET is presented in Figure 3a. The XRD pattern displayed a C(002) diffraction peak at 2θ = 22.76°, which is attributed to the amorphous carbon composed of aromatic carbon sheets oriented in a considerably random fashion.41 The definitive C(101) graphite peak at 2θ = 42.84° indicated the presence of more graphite-like structures.41 The XRD pattern of the carbonized product is presented in Figure 3b, displaying diffraction peaks at 36.80°, 42.83°, 62.01°, 74.52°, and 78.38°, which are consistent with the XRD spectrum of magnesium oxide.42 Magnesium oxide is the decomposition product of magnesium acetate after releasing CO and CO2 gas under high temperature. No other peaks are found because the diffraction peaks of the catalyst matrix are obscured by strong diffraction peaks of magnesium oxide. The XRD pattern of the ET catalyst is presented in Figure 3c. There is not a large difference in the XRD patterns between ET and the ET catalyst, suggesting that carbonization and the sulfonation process did not affect the microstructure of ET so much.34 Moreover, there are no diffraction peaks of magnesium oxide in Figure 3c, which indicated that the templates have been completely removed.

Figure 3.

Figure 3

Open in a new tab

XRD patterns of ET (a), carbonized product (b), and ET catalyst (c).

3.5. Morphology of the Catalyst

The TEM image of the mesoporous ET catalyst is shown in Figure 4. It can be seen that these mesopores are distributed randomly and that the morphology of the catalyst is also irregular. In addition, the formation of these disordered mesopores is due to the dissolution of the nanosized MgO.43,44 Furthermore, the average pore diameter of the catalyst on the TEM image is roughly consistent with the BJH pore size distribution plot.

Figure 4.

Figure 4

Open in a new tab

TEM image of the ET catalyst.

3.6. Thermal Stability of the Catalyst

The TGA curves of the ET catalyst are shown in Figure 5. The TGA curves illustrated that a slight weight loss appears at 70–110 °C, which is attributable to the loss of free moisture adsorbed on the surface of the ET catalyst. The TGA curve tends to be flat at 110–320 °C, which indicated that there is almost no weight loss in this temperature range. After 320 °C, the apparent weight loss of the catalyst is observed because of decomposition. Therefore, the catalyst has good thermal stability below 320 °C.

Figure 5.

Figure 5

Open in a new tab

TGA curve of the ET catalyst.

3.7. Catalytic Dehydration of Fructose by the ET Catalyst

3.7.1. Influence of Reaction Conditions

The dehydration reaction of fructose to produce 5-HMF with the ET catalyst in isopropyl alcohol was evaluated at different temperatures. The results in Figure 6a show that high temperature is beneficial to the conversion of fructose. When the reaction temperature increases from 110 to 130 °C, the selectivity of 5-HMF increases from 64.8 to 71.4% and the yield of 5-HMF increases from 52 to 64.2%. The low selectivity and yield below 130 °C are ascribed to the existence of partial dehydrated intermediates. When the temperature is higher than 130 °C, the yield and selectivity decrease. This is because 5-HMF is decomposed into LA, 5-HMF self-polymerization, or cross-polymerization at high temperature.45 Therefore, the temperature of 130 °C is selected as the optimum temperature for the fructose dehydration into 5-HMF over the ET catalyst.

Figure 6.

Figure 6

Open in a new tab

Effect of reaction conditions on the conversion of fructose into 5-HMF with the ET catalyst. (a) Effect of the reaction temperature (fructose 0.5 g, reaction time 120 min, catalyst 0.2 g, isopropyl alcohol 8 mL, and PVP-K30 0.1 g). (b) Effect of the reaction time (fructose 0.5 g, reaction temperature 130 °C, catalyst 0.2 g, isopropyl alcohol 8 mL, and PVP-K30 0.1 g). (c) Effect of the dosage of a catalyst (fructose 0.5 g, reaction temperature 130 °C, reaction time 140 min, isopropyl alcohol 8 mL, and PVP-K30 0.1 g). (d) Effect of the dosage of isopropyl alcohol (fructose 0.5 g, reaction temperature 130 °C, reaction time 140 min, catalyst 0.25 g, and PVP-K30 0.1 g). (e) Effect of the dosage of PVP-K30 (fructose 0.5 g, reaction temperature 130 °C, reaction time 140 min, catalyst 0.25 g, and isopropyl alcohol 7 mL).

From the results presented in Figure 6b, a series of dehydration reactions of fructose were carried out at different time ranges from 110 to 150 min. With the increase of reaction time from 110 to 140 min, the yield of 5-HMF increases from 63.8 to 66.2% and the conversion of fructose increases from 86.5 to 95.4%. Nevertheless, prolonging the reaction time from 140 to 150 min results in a slight decrease in the yield of 5-HMF and a continuous increase in the conversion of fructose. This phenomenon may be due to the formation of polysaccharides in humans.46 Consequently, 140 min is selected as the ideal time for the dehydration of fructose into 5-HMF with the ET catalyst.

As shown in Figure 6c, the dosage of the catalyst has a significant effect on the dehydration reaction of fructose. The yield, selectivity, and conversion rapidly increase within the dosage of the catalyst in the range of 0.1–0.25 g; the results can be ascribed to an increase in the amount of available sulfonic acid sites. Further increase in the dosage of the catalyst results in a slight decrease in yield and selectivity. The main reason is that an excessive catalyst can lead to a consequent formation of various intermediate, parallel, and consecutive products.16 Thus, the optimum catalyst dosage is 0.25 g and the yield of 5-HMF can reach 81.8%.

Most of the dehydration reactions of fructose are chosen using dimethyl sulfoxide (DMSO) as the solvent;47−50 however, the high boiling point of DMSO (189 °C) is not conducive to the separation of 5-HMF. Therefore, we choose isopropyl alcohol with the low boiling point (82 °C) as the solvent.10 The effect of the dosage of isopropyl alcohol on the dehydration reaction of fructose is given in Figure 6d. It can be seen that the solvent has little effect on the conversion of fructose. However, when using 6 mL of isopropyl alcohol, the selectivity and the yield of 5-HMF are lower, and the color of the reaction mixture is dark brown. It indicates the formation of condensation products such as coke.51 The yield of 5-HMF remains nearly unchanged when the dosage of isopropyl alcohol is in the range of 7–10 mL. Hence, 7 mL of isopropyl alcohol is chosen as the appropriate dosage of the solvent in subsequent experiments.

The effect of the dosage of additive PVP-K30 on the reaction was also investigated. PVP-K30 is a kind of green hydrophilic polymer, which contains the monomer structure of N-methyl pyrrolidinone (NMP) and the chain structure of polyethylene. It has been confirmed that NMP can absorb water produced in the reaction and inhibit a series of side reactions during the dehydration of fructose, such as polymerization, condensation, and hydration of 5-HMF and degradation of 5-HMF producing LA, formic acid, and so on.52 The effect of the dosage of additive PVP-K30 on the reaction is shown in Figure 6e. With the increase of the dosage of PVP-K30, the conversion of fructose between 94 and 97.9% is not significantly changed. However, the yield and selectivity of 5-HMF first increase and then decrease. When the dosage of PVP-K30 is 0.2 g, the yield and selectivity reach a maximum value of 87.8 and 89.7%, respectively. It can be seen that the addition of PVP-K30 can inhibit the occurrence of the side reaction, but excess addition will lead to a viscous system, which are not conducive to the formation of 5-HMF. Thus, the proper dosage of PVP-K30 is 0.2 g.

As shown in Table S1, when no catalyst was used, 9.2% conversion of fructose and 2.1% yield of 5-HMF were obtained. In addition, it is found that 5-HMF (87.8%), LA (5.5%), and other unknown byproducts can be obtained by using the ET catalyst (550 °C) of the highest acid density. In addition, the catalytic performances of the ET catalyst were compared with that of Amberlyst-15 and SBA-15-SO3H. We can see that Amberlyst-15 has a high acid density and a low specific surface area. SBA-15-SO3H has a high specific surface area and a low acid density. The maximum yield of 5-HMF was obtained by using the ET catalyst, which is higher than that of Amberlyst-15 and SBA-15-SO3H. Hence, it can be concluded that the catalyst with high surface area and high acid density is beneficial to the formation of 5-HMF. Moreover, the apparent activation energy of the reaction can be decreased by using the ET catalyst (Table S2).

3.7.2. Recyclability of the Catalyst

The recyclability of the catalyst is of vital importance for industrial production. Thus, the recyclability of the ET catalyst was examined five times in repeated reactions under the optimum reaction conditions. After each recycling experiment, the recovered catalyst was washed three times with ethanol and dried at 80 °C for 12 h before the next test.2 As shown in Figure 7, it can be seen that the yield, conversion, and selectivity decrease only 10.0, 7 and 5% after five cycles, respectively. Thus, the results demonstrated that the ET catalyst can be reused in the dehydration of fructose.

Figure 7.

Figure 7

Open in a new tab

Recyclability of the ET catalyst.

4. Conclusions

ET, as a byproduct in the ethylene industry, is readily available at low cost; yet, it has barely been developed toward any economically and technically rewarding applications. In this work, ET has been successfully used to prepare a novel and high-performance mesoporous ET-based solid acid catalyst by a one-step sulfonation process that removes the templates simultaneously. It demonstrates that the ET catalyst has excellent catalytic performance in the conversion of fructose into 5-HMF because of its large specific surface area and high density of sulfonic acid groups. Under the optimum reaction conditions, the maximum yield of 5-HMF can reach 87.8%, and no distinct activity drop was observed during five recycling runs that confirmed good recyclability and thermal stability of the ET catalyst. The apparent activation energy of the reaction can be decreased by using the ET catalyst. Moreover, on the basis of these facts, the synthetic route of this novel catalyst provides a promising method for the utilization of ET.

Acknowledgments

This work was supported by the financial support of the Jilin Provincial Scientific and Technologic Development Project (no. 20140309016GX) and the Science and Technology Project of the Education Department of Jilin Province (no. JJKH20170552KJ).

Supporting Information Available

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsomega.7b00771.

  • Surface properties and catalytic performances of different catalysts; effect of different temperatures on the conversion of fructose without catalyst; effect of different temperatures on the conversion of fructose with ET catalyst; and apparent rate constants of the conversion of fructose at different temperatures (PDF)

The authors declare no competing financial interest.

Supplementary Material

ao7b00771_si_001.pdf (213.9KB, pdf)

References

  1. Zhao H.; Holladay J. E.; Brown H.; Zhang Z. C. Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural. Science 2007, 316, 1597–1600. 10.1126/science.1141199. [DOI] [PubMed] [Google Scholar]
  2. Shen Z.; Yu X.; Chen J. Production of 5-Hydroxymethylfurfural from fructose catalyzed by sulfonated bamboo-derived carbon prepared by simultaneous carbonization and sulfonation. BioResources 2016, 11, 3094–3109. 10.15376/biores.11.2.3094-3109. [DOI] [Google Scholar]
  3. Dutta S.; De S.; Saha B. Advances in biomass transformation to 5-hydroxymethylfurfural and mechanistic aspects. Biomass Bioenergy 2013, 55, 355–369. 10.1016/j.biombioe.2013.02.008. [DOI] [Google Scholar]
  4. Xu H.; Miao Z.; Zhao H.; Yang J.; Zhao J.; Song H.; Liang N.; Chou L. Dehydration of fructose into 5-hydroxymethylfurfural by high stable ordered mesoporous zirconium phosphate. Fuel 2015, 145, 234–240. 10.1016/j.fuel.2014.12.072. [DOI] [Google Scholar]
  5. Chermahini A. N.; Shahangi F.; Dabbagh H. A.; Saraji M. Production of 5-hydroxymethylfurfural from fructose using a spherically fibrous KCC-1 silica catalyst. RSC Adv. 2016, 6, 33804–33810. 10.1039/c6ra03382b. [DOI] [Google Scholar]
  6. Dutta S.; Wu K. C.-W. Enzymatic breakdown of biomass: enzyme active sites, immobilization, and biofuel production. Green Chem. 2014, 16, 4615–4626. 10.1039/c4gc01405g. [DOI] [Google Scholar]
  7. Lee Y.-C.; Chen C.-T.; Chiu Y.-T.; Wu K. C.-W. An Effective Cellulose-to-Glucose-to-Fructose Conversion Sequence by Using Enzyme Immobilized Fe3O4-Loaded Mesoporous Silica Nanoparticles as Recyclable Biocatalysts. ChemCatChem 2013, 5, 2153–2157. 10.1002/cctc.201300219. [DOI] [Google Scholar]
  8. Defaye J.; Gadelle A.; Pedersen C. The behaviour of d-fructose and inulin towards anhydrous hydrogen fluoride. Carbohydr. Res. 1985, 136, 53–65. 10.1016/0008-6215(85)85185-5. [DOI] [Google Scholar]
  9. Asghari F. S.; Yoshida H. Acid-catalyzed production of 5-hydroxymethyl furfural from d-fructose in subcritical water. Ind. Eng. Chem. Ind. Eng. Chem. Res. 2006, 45, 2163–2173. 10.1021/ie051088y. [DOI] [Google Scholar]
  10. Lai L.; Zhang Y. The Production of 5-Hydroxymethylfurfural from Fructose in Isopropyl Alcohol: A Green and Efficient System. ChemSusChem 2011, 4, 1745–1748. 10.1002/cssc.201100489. [DOI] [PubMed] [Google Scholar]
  11. Guo X.; Cao Q.; Jiang Y.; Guan J.; Wang X.; Mu X. Selective dehydration of fructose to 5-hydroxymethylfurfural catalyzed by mesoporous SBA-15-SO3H in ionic liquid BmimCl. Carbohydr. Res. 2012, 351, 35–41. 10.1016/j.carres.2012.01.003. [DOI] [PubMed] [Google Scholar]
  12. Kruger J. S.; Nikolakis V.; Vlachos D. G. Aqueous-phase fructose dehydration using Brønsted acid zeolites: catalytic activity of dissolved aluminosilicate species. Appl. Catal., A 2014, 469, 116–123. 10.1016/j.apcata.2013.09.030. [DOI] [Google Scholar]
  13. Rac V.; Rakić V.; Stošić D.; Otman O.; Auroux A. Hierarchical ZSM-5, beta and USY zeolites: acidity assessment by gas and aqueous phase calorimetry and catalytic activity in fructose dehydration reaction. Microporous Mesoporous Mater. 2014, 194, 126–134. 10.1016/j.micromeso.2014.04.003. [DOI] [Google Scholar]
  14. Swift T. D.; Nguyen H.; Erdman Z.; Kruger J. S.; Nikolakis V.; Vlachos D. G. Tandem Lewis acid/Brønsted acid-catalyzed conversion of carbohydrates to 5-hydroxymethylfurfural using zeolite beta. J. Catal. 2016, 333, 149–161. 10.1016/j.jcat.2015.10.009. [DOI] [Google Scholar]
  15. Asghari F. S.; Yoshida H. Dehydration of fructose to 5-hydroxymethylfurfural in sub-critical water over heterogeneous zirconium phosphate catalysts. Carbohydr. Res. 2006, 341, 2379–2387. 10.1016/j.carres.2006.06.025. [DOI] [PubMed] [Google Scholar]
  16. Carniti P.; Gervasini A.; Biella S.; Auroux A. Niobic acid and niobium phosphate as highly acidic viable catalysts in aqueous medium: fructose dehydration reaction. Catal. Today 2006, 118, 373–378. 10.1016/j.cattod.2006.07.024. [DOI] [Google Scholar]
  17. Khemthong P.; Daorattanachai P.; Laosiripojana N.; Faungnawakij K. Copper phosphate nanostructures catalyze dehydration of fructose to 5-hydroxymethylfufural. Catal. Commun. 2012, 29, 96–100. 10.1016/j.catcom.2012.09.025. [DOI] [Google Scholar]
  18. Antonetti C.; Melloni M.; Licursi D.; Fulignati S.; Ribechini E.; Rivas S.; Parajó J. C.; Cavani F.; Galletti A. M. R. Microwave-assisted dehydration of fructose and inulin to HMF catalyzed by niobium and zirconium phosphate catalysts. Appl. Catal., B 2017, 206, 364–377. 10.1016/j.apcatb.2017.01.056. [DOI] [Google Scholar]
  19. Qi X.; Watanabe M.; Aida T. M.; Smith R. L. Catalytic dehydration of fructose into 5-hydroxymethylfurfural by ion-exchange resin in mixed-aqueous system by microwave heating. Green Chem. 2008, 10, 799–805. 10.1039/b801641k. [DOI] [Google Scholar]
  20. Morales G.; Melero J. A.; Paniagua M.; Iglesias J.; Hernández B.; Sanz M. Sulfonic acid heterogeneous catalysts for dehydration of C6-monosaccharides to 5-hydroxymethylfurfural in dimethyl sulfoxide. Chin. J. Catal. 2014, 35, 644–655. 10.1016/s1872-2067(14)60020-6. [DOI] [Google Scholar]
  21. Wang J.; Xu W.; Ren J.; Liu X.; Lu G.; Wang Y. Efficient catalytic conversion of fructose into hydroxymethylfurfural by a novel carbon-based solid acid. Green Chem. 2011, 13, 2678–2681. 10.1039/c1gc15306d. [DOI] [Google Scholar]
  22. Qi X.; Guo H.; Li L.; Smith R. L. Acid-catalyzed dehydration of fructose into 5-hydroxymethylfurfural by cellulose-derived amorphous carbon. ChemSusChem 2012, 5, 2215–2220. 10.1002/cssc.201200363. [DOI] [PubMed] [Google Scholar]
  23. Ordomsky V. V.; Schouten J. C.; van der Schaaf J.; Nijhuis T. A. Foam supported sulfonated polystyrene as a new acidic material for catalytic reactions. Chem. Eng. J. 2012, 207–208, 218–225. 10.1016/j.cej.2012.06.068. [DOI] [Google Scholar]
  24. Wang L.; Zhang J.; Zhu L.; Meng X.; Xiao F.-S. Efficient conversion of fructose to 5-hydroxymethylfurfural over sulfated porous carbon catalyst. J. Energy Chem. 2013, 22, 241–244. 10.1016/s2095-4956(13)60029-7. [DOI] [Google Scholar]
  25. Mondal D.; Chaudhary J. P.; Sharma M.; Prasad K. Simultaneous dehydration of biomass-derived sugars to 5-hydroxymethyl furfural (HMF) and reduction of graphene oxide in ethyl lactate: one pot dual chemistry. RSC Adv. 2014, 4, 29834–29839. 10.1039/c4ra05049e. [DOI] [Google Scholar]
  26. Karimi B.; Mirzaei H. M.; Behzadnia H.; Vali H. Novel Ordered Mesoporous Carbon Based Sulfonic Acid as an Efficient Catalyst in the Selective Dehydration of Fructose into 5-HMF: the Role of Solvent and Surface Chemistry. ACS Appl. Mater. Interfaces 2015, 7, 19050–19059. 10.1021/acsami.5b03985. [DOI] [PubMed] [Google Scholar]
  27. Yu I. K. M.; Tsang D. C. W. Conversion of biomass to hydroxymethylfurfural: A review of catalytic systems and underlying mechanisms. Bioresour. Technol. 2017, 238, 716–732. 10.1016/j.biortech.2017.04.026. [DOI] [PubMed] [Google Scholar]
  28. Okamura M.; Takagaki A.; Toda M.; Kondo J. N.; Domen K.; Tatsumi T.; Hara M.; Hayashi S. Acid-catalyzed reactions on flexible polycyclic aromatic carbon in amorphous carbon. Chem. Mater. 2006, 18, 3039–3045. 10.1021/cm0605623. [DOI] [Google Scholar]
  29. Hara M.; Yoshida T.; Takagaki A.; Takata T.; Kondo J. N.; Hayashi S.; Domen K. A carbon material as a strong protonic acid. Angew. Chem., Int. Ed. 2004, 43, 2955–2958. 10.1002/anie.200453947. [DOI] [PubMed] [Google Scholar]
  30. Daengprasert W.; Boonnoun P.; Laosiripojana N.; Goto M.; Shotipruk A. Application of sulfonated carbon-based catalyst for solvothermal conversion of cassava waste to hydroxymethylfurfural and furfural. Ind. Eng. Chem. Res. 2011, 50, 7903–7910. 10.1021/ie102487w. [DOI] [Google Scholar]
  31. Tanemura K.; Suzuki T.; Nishida Y.; Horaguchi T. Synthesis of the sulfonated condensed polynuclear aromatic (S-COPNA) resins as strong protonic acids. Tetrahedron 2011, 67, 1314–1319. 10.1016/j.tet.2010.11.077. [DOI] [Google Scholar]
  32. Tanemura K.; Suzuki T.; Nishida Y.; Horaguchi T. Synthesis of the strongly acidic sulfonated condensed polynuclear aromatic (S-COPNA) resins using aromatic aldehydes as cross-linking agents. Polym. Bull. 2012, 68, 705–719. 10.1007/s00289-011-0574-0. [DOI] [Google Scholar]
  33. Tanemura K.; Suzuki T. Sulfonated polypyrene (S-PPR) as efficient catalyst for esterification of carboxylic acids with equimolar amounts of alcohols without removing water. Tetrahedron Lett. 2013, 54, 1972–1975. 10.1016/j.tetlet.2013.01.126. [DOI] [Google Scholar]
  34. Tanemura K.; Suzuki T.; Horaguchi T. Synthesis of sulfonated polynaphthalene, polyanthracene, and polypyrene as strong solid acids via oxidative coupling polymerization. J. Appl. Polym. Sci. 2013, 127, 4524–4536. 10.1002/app.38045. [DOI] [Google Scholar]
  35. Kang S.; Ye J.; Chang J. Recent advances in carbon-based sulfonated catalyst: preparation and application. Int. Rev. Chem. Eng. 2013, 5, 133–144. [Google Scholar]
  36. Takagaki A.; Toda M.; Okamura M.; Kondo J. N.; Hayashi S.; Domen K.; Hara M. Esterification of higher fatty acids by a novel strong solid acid. Catal. Today 2006, 116, 157–161. 10.1016/j.cattod.2006.01.037. [DOI] [Google Scholar]
  37. Boonoun P.; Laosiripojana N.; Muangnapoh C.; Jongsomjit B.; Panpranot J.; Mekasuwandumrong O.; Shotipruk A. Application of sulfonated carbon-based catalyst for reactive extraction of 1,3-propanediol from model fermentation mixture. Ind. Eng. Chem. Res. 2010, 49, 12352–12357. 10.1021/ie1019003. [DOI] [Google Scholar]
  38. Ge C.; Yang H.; Wang J.; Qiao W.; Long D.; Ling L. Highly effective utilization of ethylene tar for mesophase development via a molecular fractionation process. RSC Adv. 2016, 6, 796–804. 10.1039/c5ra20651k. [DOI] [Google Scholar]
  39. Wu M.-b.; Shi Y.-y.; Li S.-b.; Guo N.; Wang Y.-w.; Zheng J.-t.; Qiu J.-s. Synthesis and characterization of condensed poly-nuclear aromatic resin using heavy distillate from ethylene tar. New Res. Carbon Mater. 2012, 27, 469–475. 10.1016/s1872-5805(12)60027-4. [DOI] [Google Scholar]
  40. Li S.; Sun Q.; Wang Y.; Wu M.; Zhang Z. Curing mechanism of condensed polynuclear aromatic resin and thermal stability of cured resin. China Pet. Process. Petrochem. Technol. 2015, 17, 9–16. [Google Scholar]
  41. Yu J. T.; Dehkhoda A. M.; Ellis N. Development of biochar-based catalyst for transesterification of canola oil. Energy Fuels 2011, 25, 337–344. 10.1021/ef100977d. [DOI] [Google Scholar]
  42. Huang L.; Li D.-Q.; Lin Y.-J.; Wei M.; Evans D. G.; Duan X. Controllable preparation of Nano-MgO and investigation of its bactericidal properties. J. Inorg. Biochem. 2005, 99, 986–993. 10.1016/j.jinorgbio.2004.12.022. [DOI] [PubMed] [Google Scholar]
  43. Morishita T.; Soneda Y.; Tsumura T.; Inagaki M. Preparation of porous carbons from thermoplastic precursors and their performance for electric double layer capacitors. Carbon 2006, 44, 2360–2367. 10.1016/j.carbon.2006.04.030. [DOI] [Google Scholar]
  44. Morishita T.; Tsumura T.; Toyoda M.; Przepiórski J.; Morawski A. W.; Konno H.; Inagaki M. A review of the control of pore structure in MgO-templated nanoporous carbons. Carbon 2010, 48, 2690–2707. 10.1016/j.carbon.2010.03.064. [DOI] [Google Scholar]
  45. Carniti P.; Gervasini A.; Marzo M. Absence of expected side-reactions in the dehydration reaction of fructose to HMF in water over niobic acid catalyst. Catal. Commun. 2011, 12, 1122–1126. 10.1016/j.catcom.2011.03.025. [DOI] [Google Scholar]
  46. Chheda J. N.; Román-Leshkov Y.; Dumesic J. A. Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and poly-saccharides. Green Chem. 2007, 9, 342–350. 10.1039/b611568c. [DOI] [Google Scholar]
  47. Musau R. M.; Munavu R. M. The Preparation of 5-Hydroxymethyl-2-Furaldehyde (HMF) from d-Fructose in the Presence of DMSO. Biomass 1987, 13, 67–74. 10.1016/0144-4565(87)90072-2. [DOI] [Google Scholar]
  48. Rajabbeigi N.; Ranjan R.; Tsapatsis M. Selective adsorption of HMF on porous carbons from fructose/DMSO mixtures. Microporous Mesoporous Mater. 2012, 158, 253–256. 10.1016/j.micromeso.2012.03.047. [DOI] [Google Scholar]
  49. Saha B.; Abu-Omar M. M. Advances in 5-Hydroxymethylfurfural Production from Biomass in Biphasic Solvents. Green Chem. 2014, 16, 24–38. 10.1039/c3gc41324a. [DOI] [Google Scholar]
  50. Osatiashtiani A.; Lee A. F.; Brown D. R.; Melero J. A.; Morales G.; Wilson K. Bifunctional SO4/ZrO2 catalysts for 5-hydroxymethylfufural (5-HMF) production from glucose. Catal. Sci. Technol. 2014, 4, 333–342. 10.1039/c3cy00409k. [DOI] [Google Scholar]
  51. Shimizu K.-i.; Uozumi R.; Satsuma A. Enhanced production of hydroxymethylfurfural from fructose with solid acid catalysts by simple water removal methods. Catal. Commun. 2009, 10, 1849–1853. 10.1016/j.catcom.2009.06.012. [DOI] [Google Scholar]
  52. Abid S.; Gharbi R. E.; Gandini A. Polyamide-imides bearing furan moieties. 1. Solution polycondensation of aromatic dianhydrydes with 2-furoic acid dihydrazides. Polymer 2004, 45, 6469–6478. 10.1016/j.polymer.2004.06.065. [DOI] [Google Scholar]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

ao7b00771_si_001.pdf (213.9KB, pdf)

Articles from ACS Omega are provided here courtesy of American Chemical Society

RESOURCES