Novel solid acid catalyst for the production of 5-hydroxymethylfurfural with fructose dehydration

Abstract

BACKGROUND:

5-Hydroxymethylfurfural (5-HMF) is a high value-added platform compound which can be obtained by dehydration of hexose under acidic conditions.

OBJECTIVE:

In this paper, a novel impregnation strategy for the molecular sieves (ZSM-5) as carrier and phosphotungstic acid (TPA) as active ingredient is proposed, the influence of the fructose dehydration process were studied and eco-friendliness, low-cost 5-hydroxymethylfurfural (5-HMF) was successfully obtained.

METHOD:

The structure surface area, pore size, acidity and microstructure of solid acid catalysts were investigated by XRD, BET, NH₃-TPD and SEM. The influences of reaction temperature, reaction time, catalyst dosage on the yield of 5-hydroxymethylfurfural (5-HFM) were investigated.

RESULTS:

The results showed that TPA/ZSM-5 (mass ratio 20:10) has good dispersion and catalytic activity, fructose dosage 5 g, reaction temperature 140 °C, reaction time 2 h, catalyst dosage 0.5 g, and the yield of 5-hydroxymethylfurfural was 80.75% and after five times use the yield of 5-HMF remained above 75%.

CONCLUSION:

The novel solid acid TPA/ZSM-5 catalyst exhibited good catalytic activity and stability for the fructose dehydration to produce 5-HMF.

Keywords

Phosphotungstic acid catalyst fructose 5-Hydroxymethylfurfural

1. Introduction

Green chemistry is now considered an important goal to traditional energy shortage and environmental pollution [1]. As we know, the traditional energy needed by human beings include coal, oil and natural gas, which have made important contributions to the development of the whole human society. Unfortunately, with the rapid development of economy, these traditional energies will be continuously consumed and human will face an increasingly serious energy crisis. To solve this problem, searching for renewable, no pollution and clean new energy has attracted much attention from scholars [2,3]. Compared with traditional energy, biomass energy is a rich and renewable energy, which is considered as an important choice for countries in the world to solve traditional energy crisis and realize sustainable development strategy [4,5]. Therefore, it is of great significance for economic and scientific development to accelerate the development of effective utilization of biomass energy and convert it into chemical raw materials with high added value.

In recent years, the conversion of biomass to 5-hydroxymethylfurfural (5-HMF) has attracted significant attention. The important compounds with high added value can be obtained by hydrolysis, polymerization and hydrogenation of 5-HMF, such as 2,5-dimethylfuran, 5-hydroxymethylfurfuric acid, 5-formyl furfural, and 2,5-furanoic acid [6,7]. Therefore, 5-HMF has attracted enormous research interests. Meanwhile, it is also expected to become a breakthrough point in the use of renewable biomass resources for the synthesis of chemicals from traditional resources, its application prospect is very broad. Considering the synthesis of 5-HMF, fructose has been shown to react faster and with higher selectivity than other hexoses, and should thus be the focal point for 5-HMF research [8]. The existing literatures about dehydration of fructose to 5-HMF can be classified into three aspects: the reaction mechanism, the optimal synthesis conditions and the application market. However, according to the above three aspects, scholars have done a series of studies, such as catalyst types, reaction conditions and reaction solvents, etc. However, catalytic systems with promising industrial applications have not yet been developed [9].

As reported in the literature, organic acids [10], inorganic acids [11] or ionic liquids [12] as homogeneous catalysts showed good activities in the dehydration of fructose, glucose, sucrose and cellulose and other biomass materials to produce 5-HMF, but commonly used acid catalysts take several disadvantages, such as serious environmental pollution, difficult separation of reaction products, corrosion of equipment and so on, which are greatly limited in practical applications and difficult to be industrialized. Therefore, the development of heterogeneous catalysts with no pollution, easy separation of products and good stability has attracted much attention. At present, heterogeneous catalysts such as acid resin [13,14], H-type zeolite [15,16], phosphate [17–19], sulfonic acid functionalized carbon and alumina [20–23] have been studied for dehydration of fructose to produce 5-HMF.

Among the reported heterogeneous catalysts, such as Al, Al-Si, Zr phosphate [24], niobic acid [25], ion exchange resin [26,27] and zeolite molecular sieve (ZSM) [28], ZSM-5 has attracted much attention due to its good thermal stability, porous structure, adjustable acidity and reusability. Based on the available reported literature, the preparation of porous catalysts with ZSM-5 as carrier for the dehydration of fructose to produce 5-HMF has not been mature and needs to be studied. For example, tungsten trioxide supported zirconium dioxide [31,32], zirconium oxide supported phosphotungstic acid [33–35] was studied to catalytic fructose to prepare 5-HMF. In this paper, molecular sieves (ZSM-5) as carrier and phosphotungstic acid (TPA) as active ingredient to prepare phosphotungstic acid supported on molecular sieves catalysts were prepared by impregnation method, it was applied in 5-HMF production dehydration of fructose process. The effects of reaction temperature, reaction time and catalyst dosage on dehydration of fructose process were investigated, providing reference for monosaccharide dehydration to 5-HMF process.

2. Materials and methods

2.1. Chemicals

Fructose, 5-HMF, nitrogen, dimethyl sulfoxide (DMSO, phosphotungstic acid, molecular sieve, ammonia water and methanol).

2.2. Synthesis of phosphotungstic acid supported molecular sieves

TPA supported ZSM-5 catalyst is prepared by impregnation method, and the specific preparation process is as follows: the ZSM-5 was roasted for 4 h at 600 °C for activation, TPA was dissolved in water to prepare saturated solution, ZSM-5 was immersed for 24 h in the saturated solution of TPA (ZSM-5 and TPA were calculated according to the mass ratio), then dried for 3 h at 110 °C, calcined for 4 h at 250 °C, and cooled to room temperature to prepare TPA supported ZSM-5 catalyst. According to the quality difference between TPA and ZSM-5, five catalysts were prepared (A-TPA/ZSM-5 (5:10), B-TPA/ZSM-5 (10:10), C-TPA/ZSM-5(15:10), D-TPA/ZSM-5(20:10), E-TPA/ZSM-5(25:10)).

2.3. Materials characterizations

The crystal phase analysis of the catalyst samples were performed using a Rigakud Diffractometer/max-2500PC provided with room temperature, Cu Kα radiation (𝜆 = 1.5418 Å), a beam voltage of 40 kV, tube current 40 mA, wavelength 0.15406 nm and crack 1 nm.

The specific surface area and pore structure of the catalysts were measured from N₂ adsorption-desorption isotherms at 77 K on a Micromeritics AutosorbiQC surface area analyzer. The catalyst samples were degassed at 300 °C for 3 hours to remove the impurity gas and moisture adsorbed by the sample. According to the adsorption isotherm, the specific surface area, pore volume and average pore diameter were calculated by the Brunauer–Emmett–Teller (BET) method.

The total acidity of the catalyst was measured by NH₃-TPD (Micromeritics Auto Chem, Pulsar, USA). After the sample was heated and degassed in an ammonia atmosphere, the sample was lowered to room temperature to adsorb ammonia to saturation. The ammonia gas physically adsorbed on the surface is blown with helium gas, and desorbed at a temperature of 10 °C/min, the signal was detected by the TPD detector.

Microstructure of the catalysts were characterized by SEM with JSM-6360LV high and low vacuum scanning electron microscope.

2.4. Dehydration of fructose to HMF

The preparation of 5-HMF from fructose dehydration were studied, fructose (5 g), catalyst (0.3–1.5 g) and dimethyl sulfoxide (50 ml) as reaction solvent were mixed into three-necked flask of 100 ml. The reactor was placed in an oil bath, the reaction was conducted in the temperature range of 120–160 °C for 1–3 h at 180 rpm. After the reaction, the mixture was cooled to room temperature with ice water, and then separated by vacuum filtration. The upper clean solution was extracted and diluted 10 times with solvent (molar ratio of methanol to water 7:3) before liquid chromatography analysis.

The quantitative analysis of HMF was conducted by external standard method of liquid chromatography. The specific process as follows: five standard solutions of 5-HMF with different concentrations were prepared, the peak areas with different concentrations were measured by liquid chromatography, 5-HMF standard solution curve was drew based on different concentrations and peak areas, the regression equation was obtained from the curve. The 5-HMF was quantified by using a capillary column (8 mm × 300 mm × 6 μm) using solvent (molar ratio of methanol to water 7:3) as mobile phase and a column temperature of 30 °C, according to the size of the peak area, the yield of 5-HMF was calculated.

3. Results and discussion

3.1. Characterization of phosphotungstic acid supported molecular sieves

3.1.1. Composition and structure

The crystal structure of solid acid catalyst was examined to determine the successful synthesis of phosphotungstic acid supported molecular sieves based on the wide-angle XRD results. The XRD patterns of ZSM (line A) as reported in Fig. 1 exhibits three characteristic peaks at 7.8°, 8.7° and 23.04°, while TPA/ZSM-5 (line B-F) catalysts show other three characteristic peaks at 25.4°, 34.5° and 53.3°. It was also found that this peak was wider than the bare TPA support, and shifted to higher diffraction angle with the increase of TPA loading, indicating that the active component of TPA was incorporated into the porous ZSM structure and showed higher dispersion.

Fig. 1.

XRD profiles of different catalysts.

3.1.2. Porosity

The specific surface area, pore volume and pore diameter data of the carrier and catalyst are shown in Table 1. In the preparation process of TPA/ZSM-5 catalyst, with the increase of TPA loading, the specific surface area, pore volume and pore diameter of TPA-ZSM-5 catalyst decrease, which is consistent with the general rule of supported solid acid catalysts. When the specific surface area of the catalyst is larger, The better the dispersion performance of TPA on the surface of ZSM-5, the higher the degree of dispersion, the more acid centers were formed, which is beneficial to the activity of the catalyst. However, when the TPA loading is too large, the ZSM channel may be severely blocked, thus reducing the catalytic activity of the catalyst, which was certainly related to the inelastic and non-rigid porous structure during the adsorption cycle [36–38].

Table 1
Textural property of TPA/ZSM-5

Entry Sample Specific surface area (m² g⁻¹) Pore volume (cm³ g⁻¹) Pore diameter (nm)

1 ZSM-5 328.2 0.269 3.58

2 A 263.2 0.228 3.47

3 B 234.9 0.192 3.36

4 C 195 0.187 3.19

5 D 157.0 0.149 3.06

6 E 100.6 0.132 2.97

Entry	Sample	Specific surface area (m² g⁻¹)	Pore volume (cm³ g⁻¹)	Pore diameter (nm)
1	ZSM-5	328.2	0.269	3.58
2	A	263.2	0.228	3.47
3	B	234.9	0.192	3.36
4	C	195	0.187	3.19
5	D	157.0	0.149	3.06
6	E	100.6	0.132	2.97

3.1.3. Acidity

The acidity of the solid acid catalysts was measured by NH₃-TPD, including the number of acid sites and acid strength. Figure 2 shows the NH₃-TPD profiles of ZSM-5 carrier and TPA/ZSM-5 catalysts with different TPA loading. As reported in the literature [39], the activity of solid acid catalyst mainly depends on the acidity, the surface of TPA/ZSM-5 solid acid catalyst has both L (weak) acid and B (strong) acid centers, when the acidity of the catalyst was strong, the fructose dehydration transitions; when the acidity was weak, the activity of the catalyst was low. According to NH₃ desorption temperature, the acid sites of ZSM-5 carrier can be classified as weak- (100–300 °C) and strong- (400–650 °C) strength. With the increase of TPA loading, both L (weak) acid and B (strong) acid centers of TPA/ZSM-5 solid acid catalyst becomes weaker and weaker, but the activity of the TPA/ZSM-5 catalyst was getting better and better. Therefore, the suitable TPA loading was beneficial to dehydration of fructose to 5-HMF.

Fig. 2.

NH₃-TPD profiles of different catalysts.

3.1.4. Microstructure

The SEM images of different catalysts are given in Fig. 3 TPA/ZSM-5(20:10) catalysts have smooth surface, small particle size and porous structure, which is helpful to improve the activity of fructose dehydration to 5-HMF.

Fig. 3.

SEM images of different catalysts. (a) TPA/ZSM-5 (5:10); (b) TPA/ZSM-5 (10:10); (c) TPA/ZSM-5 (10:10); (d) TPA/ZSM-5 (20:10); (e) TPA/ZSM-5 (25:10).

3.2. Optimization of reaction conditions

3.2.1. Influence of TPA loading

In order to screen the optimal catalyst system, several catalysts such as A(TPA/ZSM-5(5:10)), B(TPA/ZSM-5(10:10)), C(TPA/ZSM-5(15:10)), D(TPA/ZSM-5(20:10)) and E(TPA/ZSM-5(25:10)) were employed for the catalytic dehydration of fructose to HMF under the same reaction conditions, and their catalytic results are shown in Fig. 4 Compared to the activity of several catalysts, the D catalyst has better catalytic performance than other catalysts in dehydration of fructose to 5-HMF, the yield of 5-HMF reached 80.75%.

Fig. 4.

Influence of different loading catalysts for dehydration of fructose to 5-HMF.

3.2.2. Influence of reaction temperature

To further optimize the yield of 5-HMF from fructose dehydration, the influences of the process critical variables including the reaction time, reaction temperature and catalyst dosage on the conversion of fructose were investigated as a function of time. Figure 5 illustrates the yield of 5-HMF also gradually increased from 60.5% to 80.75% with variation in temperature from 120 °C to 140 °C and marginally decreased to 49.06% at 160 °C. This observation indicates that the fructose dehydration reaction was greatly affected by temperature, when the reaction temperature was low, the rate of fructose dehydration to 5-HMF was relatively slow, and it took a long time to complete the reaction; when the reaction temperature was high, although it is beneficial to accelerate the reaction rate and shorten the formation time of 5-HMF, it will more easily lead to coking and carbonization, and catalyst activity decreased or even deactivated. As reported in the literature, the optimized reaction temperature (140 °C) is found very mild for dehydration of fructose, reflecting the high efficiency of the present TPA/ZSM-5(20:10) solid acid catalyst.

Fig. 5.

Dehydration of fructose to 5-HMF versus reaction temperature over the D(TPA/ZSM-5(20:10)) catalyst.

3.2.3. Influence of reaction time

The consequence of reaction time on the dehydration of fructose to 5-HMF was studied and the observations were depicted in Fig. 6. The yield of 5-HMF increased first and then decreased, during the initial 1 h, the yield of 5-HMF rapidly goes up to 65.27%, when the reaction time of 2 h, the yield of 5-HMF reached the maximum with the value of 80.75%, however, the reaction time was further increased to 3 h, the yield of 5-HMF was found slowly decreasing. This indicates that the free collision between the 5-HMF molecule and itself or other molecules leads to polymerization reaction, resulting in its yield less than the polymerization rate. At the same time, further decomposition reaction may occur when the yield of 5-HMF increases to a certain extent. Hence, it is difficult to improve the production of 5-HMF by extending the reaction time.

Fig. 6.

Dehydration of fructose to 5-HMF versus reaction time over the D(TPA/ZSM-5(20:10)) catalyst.

3.2.4. Influence of catalyst dosage

As TPA/ZSM-5(20:10) catalyst shows good catalytic activity for the dehydration of fructose to 5-HMF. The effect of catalyst dosage for the dehydration of fructose to 5-HMF was studied and results were shown in Fig. 7. The catalyst dosage is one of the factors affecting the yield of 5-HMF. When the catalyst dosage was increased from 0.3 g to 0.5 g, the yield of 5-HMF was significantly increased due to the available of more number of L (weak) acid and B (strong) acid active sites. The further increased of catalyst dosage dose not lead to a higher 5-HMF formation. The reason is that with the increase of catalyst dosage, the color of the recovered catalyst changed from white to black, and with the further increase of catalyst dosage, the black became more and more obvious. At the same time, the catalyst also had obvious deformation, which indicated that the catalyst itself will occurs agglomeration, which leads to the relative reduction of the acid point of the catalyst and the contact area with the reaction raw material becomes smaller, so that the reaction raw materials are not completely, resulting in a decrease in the yield of 5-HMF.

Fig. 7.

Dehydration of fructose to HMF versus catalyst dosage over the D(TPA/ZSM-5(20:10)) catalyst.

3.2.5. Appropriate process conditions

In order to determine the appropriate reaction conditions for the dehydration of fructose to 5-HMF, the yield of 5-HMF was taken as the experimental index, and the influences of reaction temperature, reaction time and catalyst dosage on the yield of 5-HMF from fructose dehydration were further investigated, and L₉(3^₄) orthogonal table was used for orthogonal experiment. The factor levels are shown in Table 2.

According to the results of range analysis in Table 3, it can be seen that the reaction temperature has the greatest influence on the yield of 5-HMF, followed by the catalyst dosage, and finally the reaction time. The optimal reaction conditions are the reaction temperature 140 °C, the reaction time 2 h, and the catalyst dosage 0.5 g, the reaction solvent 50 mL, under such conditions, the yield of 5-HMF is 80.75%.

Table 2
Factor level table

Factor Reaction temperature (°C) Reaction time (h) Catalyst dosage (g)

level a b c

1 130 1 0.5

2 140 2 0.8

3 150 3 1.2

Factor	Reaction temperature (°C)	Reaction time (h)	Catalyst dosage (g)
level	a	b	c
1	130	1	0.5
2	140	2	0.8
3	150	3	1.2

Table 3

Results of range analysis

Mean value	Reaction temperature (°C)	Reaction time (h)	Catalyst dosage (g)
I_j∕k _j	155.31	164.17	194.34
II_j∕k _j	200.88	188.72	166.63
III_j∕k _j	158.71	162.01	153.93
Dj	22.785	13.355	20.205

Fig. 8.

Dehydration of fructose to 5-HMF versus frequency over the D (TPA/ZSM-5(20:10)) catalyst.

3.3. Stability and reusability of the catalyst

The stability and reusability of the catalyst is an important factor to evaluate the heterogeneous system for catalyzed dehydration of fructose to 5-HMF. Under the optimal reaction conditions: fructose 5 g, reaction temperature 140 °C, reaction time 2 h and catalyst 0.5 g, D (TPA/ZSM-5 (20:10)) was used as catalyst to investigate the reusability of the catalyst, the results are shown in Fig. 8. It can be seen from Fig. 8 that after 5 cycles of catalyst D (TPA/ZSM-5(20:10)), the yield of 5-HMF dropped slightly, but the yield of 5-HMF remained above 75% (80.75% in the first cycle versus 75.12% in the fifth cycle). Compared with the first reaction cycle, a small loss of catalytic activity may be due to blocking of acid sites by some adsorbed intermediates or humus.

4. Conclusions

In this work, phosphotungstic acid supported molecular sieve (TPA/ZSM-5) catalyst was prepared by impregnation method to efficiently dehydrate fructose to 5-HMF. The yield of 5-HMF product is greatly influenced by the number of acid sites of the molecular sieve, the catalyst dosage and reaction conditions. TPA/ZSM-5(20:10) catalyst exhibits high catalytic activity and stability, giving a HMF yield of 80.75% at fructose dosage 5 g, reaction temperature of 140 °C, reaction time of 2 h, catalyst dosage of 0.5 g, after five times use, the yield of 5-HMF remains above 75%.

Footnotes

Acknowledgements

This work is supported by the Science Education Research Project of Liaoning Province (20191362103), Natural Science Foundation of Liaoning Province (2019-ZD-0347), and Basic Research Project of Education Department of Liaoning Province (LJKZ1401).

Conflict of interest

None to report.

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Novel solid acid catalyst for the production of 5-hydroxymethylfurfural with fructose dehydration

Abstract

BACKGROUND:

OBJECTIVE:

METHOD:

RESULTS:

CONCLUSION:

Keywords

1. Introduction

2. Materials and methods

2.1. Chemicals

2.2. Synthesis of phosphotungstic acid supported molecular sieves

2.3. Materials characterizations

2.4. Dehydration of fructose to HMF

3. Results and discussion

3.1. Characterization of phosphotungstic acid supported molecular sieves

3.1.1. Composition and structure

Table 1 Textural property of TPA/ZSM-5 Entry Sample Specific surface area (m2 g−1) Pore volume (cm3 g−1) Pore diameter (nm) 1 ZSM-5 328.2 0.269 3.58 2 A 263.2 0.228 3.47 3 B 234.9 0.192 3.36 4 C 195 0.187 3.19 5 D 157.0 0.149 3.06 6 E 100.6 0.132 2.97

3.2.1. Influence of TPA loading

Table 2 Factor level table Factor Reaction temperature (°C) Reaction time (h) Catalyst dosage (g) level a b c 1 130 1 0.5 2 140 2 0.8 3 150 3 1.2

4. Conclusions

Footnotes

Acknowledgements

Conflict of interest

References

Table 1
Textural property of TPA/ZSM-5

Entry Sample Specific surface area (m² g⁻¹) Pore volume (cm³ g⁻¹) Pore diameter (nm)

1 ZSM-5 328.2 0.269 3.58

2 A 263.2 0.228 3.47

3 B 234.9 0.192 3.36

4 C 195 0.187 3.19

5 D 157.0 0.149 3.06

6 E 100.6 0.132 2.97

Table 2
Factor level table

Factor Reaction temperature (°C) Reaction time (h) Catalyst dosage (g)

level a b c

1 130 1 0.5

2 140 2 0.8

3 150 3 1.2