Method for preparing 5-hydroxymethylfurfural under mild catalysis of aluminum ions

Abstract

The present application relates to a method for preparing 5-hydroxymethylfurfural under the mild catalysis of aluminum ions. The method comprises the following steps: S1, dissolving a carbohydrate and an aluminum ion salt in a solvent; S2, reacting same for 24-48 hours in a reaction atmosphere under the condition of 80-120°C; and S3, conducting filtering to obtain a 5-hydroxymethylfurfural sample, wherein the mass ratio of the carbohydrate to the aluminum ion salt is 1:1, and the mass-volume ratio of the carbohydrate to the solvent is (0.01-1 g):1 mL. In the solution of the present application, the reaction conditions are simple and mild, the yield of the obtained 5-hydroxymethylfurfural sample can reach 99.8%, and the 5-hydroxymethylfurfural sample has the same HPLC signals and the same infrared spectrum signals as a commercially available 5-hydroxymethylfurfural standard sample; moreover, no obvious byproduct peaks are observed in a nuclear magnetic resonance spectrum of the 5-hydroxymethylfurfural sample, indicating an extremely high product purity. Due to the high selectivity and high yield of the reaction, the separation and purification of 5-hydroxymethylfurfural are simplified, which facilitates subsequent reactions thereof.

Description

A method for mild catalytic preparation of 5-hydroxymethylfurfural by aluminum ion TECHNICAL FIELD

[0001] The present application relates to the field of chemical synthesis technology, for example, a method for mild catalytic preparation of 5-hydroxymethylfurfural by aluminum ion. BACKGROUND

[0002] Aluminum ion, as a kind of abundant, cheap and low-toxicity Lewis acid, has been widely used in the reaction of converting glucose into 5-hydroxymethylfurfural (HMF). Tangesermvi introduced Al 3+ Catalytic sites were introduced into the pore surface of sulfonated UiO-66, which improved the catalytic activity. In DMSO solution at 120℃ for 24 hours, the yield of 5-hydroxymethylfurfural was 63%[1]. Zuo et al. used AlCl3 as catalyst to catalytically convert glucose into HMF at 120℃, and obtained a yield of 55.8%[2]. In addition, using aluminum-based solid catalyst to catalyze the conversion of glucose into HMF in A-NADE medium (composed of water, BHC and ChCl), a HMF yield of 67.1% was obtained at 140℃[3]. Similarly, De and Yang used AlCl3 to convert glucose into 54% and 61% of HMF at 120℃ and 160℃ by microwave-assisted reaction[4,17]. Likewise, Shi et al. used aluminum sulfate to catalyze the conversion of cellulose into HMF in 2022, and obtained a HMF yield of 45.7% at 190℃[5]. By changing the solvent system, the yield of HMF was also successfully improved to 71.2%[6].

[0003] In addition to being used as a homogeneous catalyst, aluminum ion can also be used as a cocatalyst to play a role in a heterogeneous catalytic system by providing Lewis acidity and participating in the reaction, thereby improving the yield of HMF. For example, Li et al. prepared a catalyst as an acid site by loading a small amount of aluminum ion in carbon material. At a temperature of 150℃, the catalyst achieved a HMF yield of about 70%[7]. Tana and Pengfei disclosed a system using aluminum nitrate nonahydrate and fulvic acid as catalyst, which could photocatalyze glucose to generate a HMF yield of 60% in DMSO solution at 80℃ after 20 hours of light irradiation[8]. The main mechanism is that the coordination of fulvic acid and aluminum ion can enhance the light absorption capacity of the system, while reducing the energy barrier required for the reaction.

[0004] ​In Zhang et al.’s study, aluminum ions were supported on an acidic phenol-formaldehyde resin, effectively promoting the conversion of glucose to HMF as a cocatalyst. After 2 hours of reaction at 170°C, the catalytic system successfully achieved a 47.4% HMF yield [9]. Jiménez-Morales et al.’s study demonstrated the significant catalytic effect of aluminum-doped MCM-41 silica catalysts in the dehydration of glucose to HMF. Its catalytic activity was derived from the synergistic effect of Brønsted acid sites in the catalyst and Lewis acid sites provided by aluminum ions, and after 2.5 hours of reaction at 195°C, the catalytic system achieved a 36% HMF yield

[0010] . Wang et al.’s study further demonstrated that aluminum ions supported on sulfonated carbon catalysts could efficiently catalyze the conversion of glucose at 140°C, with a yield of 75%

[0011] . Similarly, Hu et al.’s study showed that zeolites could also effectively catalyze glucose in the presence of aluminum ions, with a HMF yield of 50.3% at 150°C

[0012] .

[0005] In addition, Zhang and Teimouri’s studies showed that the combination of aluminum oxide fibers and aluminum ions also exhibited excellent catalytic effects in catalyzing the conversion of glucose to HMF. Under reaction conditions of 130°C and 190°C, these two studies achieved HMF yields of 57.4% and 60.1%, respectively [13, 14]. Similarly, SBA-15 was also proven to be an excellent carrier for aluminum ions [15, 18]. Tosuwan et al.’s study showed that by grafting aluminum ions onto SBA-15 carriers, a HMF yield of 25% could be achieved at 160°C

[0015] . Wang’s study showed that by adjusting the loading amount of aluminum ions on SBA-15 carriers, the Lewis acid sites in the catalyst could be precisely controlled, and a HMF yield of 55.7% was achieved at 170°C.

[0006] Despite the widespread use of aluminum ions in the process of converting glucose to HMF as a cocatalyst to increase Lewis acid active sites, there are still many problems in the existing technology.

[0007] Although the Lewis acidity of aluminum ions can promote the isomerization of glucose, in the reaction process involving them, the generation of by-products such as humus and humin often occurs due to excessively high temperatures. These by-products not only reduce the yield of 5-hydroxymethylfurfural, but also increase the difficulty of product separation and purification. Existing studies have shown that in the reaction of glucose conversion to HMF involving aluminum ions, it is almost impossible to achieve a yield of more than 70%. The extremely low yield and weak selectivity limit its practical application in industrial scale-up.

[0008] In existing aluminum ion-involved reactions, extremely high reaction temperatures (>120℃) are often required to drive the isomerization of glucose to fructose, but harsh reaction conditions often accompany the generation of by-products. This problem significantly increases the difficulty of subsequent product separation and purification. Under high temperature conditions, aluminum ions can react with other components in the reaction medium, leading to gradual deactivation of the catalyst. Catalyst deactivation not only affects the repeatability of the reaction, but also requires additional steps for regeneration or replacement, thereby increasing process costs.

[0009] Due to the low yield and low selectivity of existing processes, product separation from solvents becomes extremely difficult. While separating the target product, useless by-products must also be removed, which greatly increases the process cost. In addition, aluminum ion catalytic systems usually rely on specific solvents such as DMSO or ionic liquids, which are high in cost and difficult to recover on an industrial scale, further increasing the complexity and cost of the process.

[0010] Although aluminum ions themselves are less toxic, they can have adverse effects on the environment and organisms at high concentrations, especially in the case of long-term exposure. In addition, certain reaction conditions may require the use of strong acids or high-temperature operations, which not only increase the complexity of the process, but also pose potential safety risks. For example, the use of strong acids can cause corrosive damage, and high-temperature operations pose the risk of thermal runaway. Therefore, in industrial applications, these factors must be carefully evaluated to ensure the environmental friendliness and operational safety of the process. These problems further limit the widespread application of aluminum ion catalytic systems in large-scale production.

[0011] HMF is an important raw material for the synthesis of 2,5-furandicarboxylic acid (FDCA), and is currently the most studied synthesis route. FDCA has a wide range of uses, including the production of succinic acid, as a macrocyclic ligand and corrosion inhibitor, and is considered one of the 12 most valuable chemical products from biomass. However, due to the aforementioned problems of low yield and selectivity and difficult product separation in the synthesis of HMF, it is extremely challenging to produce high-purity HMF on a large scale at low cost, which in turn affects the efficient production of FDCA.

[0012] Biocatalytic processes can produce FDCA under mild conditions and achieve certain yields

[0019] . However, these processes are only suitable for low concentrations of HMF and the production efficiency is significantly reduced

[0010] . In addition, the byproducts generated during the preparation of HMF can significantly inhibit the catalytic activity of subsequent HMF oxidation

[0021] . Currently, the processes for preparing FDCA from glucose or fructose based on one-pot method generally have the problem of low yield and selectivity, the root cause of which is that too many byproducts are generated during the conversion of glucose or fructose to HMF, thereby hindering the conversion efficiency of HMF in the subsequent oxidation reaction. For example, Chen et al. prepared 2,5-furan dicarboxylic acid (FDCA) from fructose, and the total yield could reach 88.4%

[0022] . However, the addition of high temperature and base led to the generation of byproducts, thereby limiting higher yield and the feasibility of industrial production[22, 23].

[0013] Naim et al. studied the common byproducts (such as glucose (GLU), fructose (FRU), lactic acid (LA), formic acid (FA), and sodium nitrate (NaNO3)) in the production of HMF, and found that in the presence of glucose (GLU), the yield of 2,5-furan dicarboxylic acid (FDCA) decreased significantly from 100% to 24%, and fructose (FRU) was converted to unidentified byproducts, thereby inhibiting the reaction

[0024] . Their experiments also verified that the byproducts in the HMF reaction solution could significantly affect the subsequent oxidation process of HMF, leading to a decrease in product yield and the generation of non-target products. Similarly, Liu et al. found that compared with commercial HMF samples, the laboratory-prepared HMF led to a significant decrease in the yield and selectivity of FDCA during the oxidation process, and the content of unreacted HMF was higher. Specifically, the selectivity of FDCA decreased from 88.3% to 37.4%, and the yield decreased from 88.3% to 25.7%, which was mainly due to the influence of impurities in the sample

[0025] . In addition, Zuo et al. used the crude HMF solution after dehydration of fructose for oxidation without removing impurities, and the product obtained contained a certain amount of 5-formyl-2-furan carboxylic acid (FFCA), with a content of about 4000 ppm

[0026] . Tamboli et al. tried to prepare FDCA directly from glucose or fructose by one-pot method, and the final yield of FDCA was 56% and 78%, respectively

[0027] . This lower yield was mainly due to the residual glucose or fructose in the solution, which hindered the active sites of the catalyst, thereby inhibiting the oxidation reaction of HMF to FDCA. SUMMARY

[0014] The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

[0015] The application provides a mild reaction condition HMF preparation process, and improves the yield and purity of HMF.

[0016] The application provides the following technical solutions:

[0017] A method for preparing 5-hydroxymethylfurfural by mild catalysis of aluminum ions, comprising the following steps:

[0018] S1. Dissolving a carbohydrate and an aluminum ion salt in a solvent;

[0019] S2. Reacting under a reaction atmosphere at 80-120 DEG C for 24-48 hours;

[0020] S3. Filtering to obtain a 5-hydroxymethylfurfural sample;

[0021] The mass ratio of the carbohydrate and the aluminum ion salt is 1:1, and the mass-volume ratio of the carbohydrate and the solvent is 0.01g-1g:1mL.

[0022] In an embodiment, in step S2, the reaction temperature is 90 DEG C.

[0023] In an embodiment, in step S2, the reaction time is 36 hours.

[0024] In an embodiment, the mass-volume ratio of the carbohydrate and the solvent is 0.01g-0.2g:1mL.

[0025] In an embodiment, the mass-volume ratio of the carbohydrate and the solvent is 0.15g:1mL.

[0026] In an embodiment, the carbohydrate comprises glucose, fructose or sucrose.

[0027] In an embodiment, the aluminum ion salt comprises aluminum nitrate, aluminum sulfate or aluminum chloride.

[0028] In an embodiment, the reaction atmosphere is an air atmosphere or an inert gas atmosphere.

[0029] In an embodiment, the solvent comprises dimethylformamide or dimethyl sulfoxide.

[0030] In an embodiment, the reaction system further comprises a solid heterogeneous catalyst, and the solid heterogeneous catalyst comprises zirconium oxide, cerium dioxide, aluminum oxide, activated carbon, silicon dioxide, titanium dioxide, diiron trioxide or tungsten oxide.

[0031] The technical solution claimed in the application achieves the following beneficial effects:

[0032] 1) The 5-hydroxymethylfurfural is selectively synthesized from sugars (such as glucose, fructose, sucrose, etc.) under low temperature conditions with the catalysis of various aluminum ion salts. The reaction can be carried out in air or inert atmosphere, and the reaction conditions are simple and mild, avoiding the use of high temperature and high pressure and highly toxic chemical raw materials.

[0033] 2) The yield of the obtained 5-hydroxymethylfurfural sample can reach 99.8%, and the HPLC signal is the same as that of the commercially available standard sample of 5-hydroxymethylfurfural. The infrared spectrum signal is the same as that of the commercially available standard sample of 5-hydroxymethylfurfural, and no obvious by-product peak is observed in the nuclear magnetic resonance spectrum of the 5-hydroxymethylfurfural sample, indicating that the purity of the obtained product is extremely high. The high selectivity and high yield of the reaction also greatly simplify the separation and purification of 5-hydroxymethylfurfural, which is beneficial to the subsequent reaction.

[0034] 3) The aluminum ion salt catalyst used is cheap and easy to obtain, and can be recycled and reused multiple times. At the same time, this method can be compatible with other heterogeneous catalytic systems. The high selectivity and high yield of the product make the separation of 5-hydroxymethylfurfural very simple. It is a green, environmentally friendly, economical and efficient synthesis method with wide application prospect, and is suitable for industrial scale production.

[0035] Other aspects can be apparent after reading and understanding the accompanying drawings and detailed description. BRIEF DESCRIPTION OF DRAWINGS

[0036] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiment description. Obviously, the drawings in the following description are only embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creating laborious work on the basis of the provided drawings.

[0037] Figure 1 is an elution time diagram of 5-hydroxymethylfurfural commercially available standard sample (HMF STD) and sample to be tested in high performance liquid chromatography (HPLC).

[0038] Figure 2 is a standard curve diagram of the concentration of 5-hydroxymethylfurfural commercially available standard sample and HPLC signal.

[0039] Figure 3 is a nuclear magnetic resonance spectrum (NMR) comparison diagram of 5-hydroxymethylfurfural standard sample and sample to be tested.

[0040] Figure 4 is a Fourier transform infrared spectrum (FTIR) comparison diagram of 5-hydroxymethylfurfural standard sample and sample to be tested in DMSO solvent.

[0041] Figure 5 is a Fourier transform infrared spectrum (FTIR) comparison diagram of 5-hydroxymethylfurfural standard sample and purified sample to be tested.

[0042] Figure 6 is a graph of 5-hydroxymethylfurfural yield versus the amount of aluminum nitrate nonahydrate added.

[0043] Figure 7 is a graph of 5-hydroxymethylfurfural yield versus reaction time.

[0044] Figure 8 is a graph of 5-hydroxymethylfurfural yield versus reaction temperature. DETAILED DESCRIPTION

[0045] In order to make the purposes, technical solutions and beneficial effects of the embodiments in the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative effort belong to the scope of protection of the present application.

[0046] EMBODIMENT

[0047] The present embodiment provides a method for preparing 5-hydroxymethylfurfural by mild catalysis of aluminum ions, comprising the following steps:

[0048] S1. Dissolving a carbohydrate and an aluminum ion salt in a solvent;

[0049] S2. Reacting under a reaction atmosphere at 80-120°C for 24-48 hours;

[0050] S3. Filtering to obtain a 5-hydroxymethylfurfural sample;

[0051] The mass ratio of the carbohydrate to the aluminum ion salt is 1:1, and the mass-volume ratio of the carbohydrate to the solvent is 0.01g-1g:1mL.

[0052] In a preferred scheme, in step S2, the reaction temperature is 90°C, and the reaction time is 36 hours.

[0053] In a preferred scheme, the mass-volume ratio of the carbohydrate to the solvent is 0.01g-0.2g:1mL, and more preferably 0.15g:1mL.

[0054] In a preferred scheme, the carbohydrate comprises glucose, fructose or sucrose, the aluminum ion salt comprises aluminum nitrate, aluminum sulfate or aluminum chloride, the reaction atmosphere comprises an air atmosphere or an inert gas atmosphere, and the solvent comprises dimethylformamide or dimethyl sulfoxide.

[0055] In a preferred scheme, the reaction system further comprises a solid heterogeneous catalyst, and the solid heterogeneous catalyst comprises zirconium oxide, cerium dioxide, aluminum oxide, activated carbon, silicon dioxide, titanium dioxide, diiron trioxide or tungsten oxide.

[0056] The above embodiments and the technical effects brought by the embodiments will be further described in detail in combination with specific application examples.

[0057] Application Example 1

[0058] The 36 mg (0.2 mmol) of glucose and 30 mg (0.08 mmol) of aluminum nitrate nonahydrate were dissolved in 2 mL of dimethylformamide solvent, and the reaction was heated and stirred at 90°C under an argon atmosphere for 24 hours. After the reaction was completed, the reaction solution was collected by filtration. The content of the generated 5-hydroxymethylfurfural sample was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, and compared with a commercially available 5-hydroxymethylfurfural standard sample, and finally a yield of about 93% was obtained.

[0059] The obtained dimethylformamide filtrate was washed with saturated brine for multiple times, dried with anhydrous sodium sulfate, and then rotary evaporated under reduced pressure, and then purified by column chromatography. Finally, about 21.8 mg of 5-hydroxymethylfurfural product was obtained. No obvious by-product peaks were observed in the nuclear magnetic resonance spectrogram, which was consistent with the result of high performance liquid chromatography, indicating that the product had extremely high purity.

[0060] Application Example 2

[0061] The 36 mg (0.2 mmol) of glucose and 30 mg (0.08 mmol) of aluminum nitrate nonahydrate were dissolved in 2 mL of dimethyl sulfoxide solvent, and the reaction was heated and stirred at 90°C under an argon, nitrogen and air atmosphere for 24 hours, respectively. After the reaction was completed, the reaction solution was collected by filtration. The content of the generated 5-hydroxymethylfurfural sample was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, and compared with a commercially available 5-hydroxymethylfurfural standard sample, and finally a yield of about 99%, 97% and 98.3% was obtained, respectively.

[0062] The obtained dimethyl sulfoxide filtrate was washed with saturated brine for multiple times, dried with anhydrous sodium sulfate, and then rotary evaporated under reduced pressure, and then purified by column chromatography. Finally, about 24 mg, 23.1 mg and 23.3 mg of 5-hydroxymethylfurfural product was obtained, respectively. No obvious by-product peaks were observed in the nuclear magnetic resonance spectrogram, which was consistent with the result of high performance liquid chromatography, indicating that the product had extremely high purity.

[0063] Application Example 3

[0064] 300 mg (15% mass fraction) of glucose and 300 mg (15% mass fraction) of aluminum chloride hexahydrate were dissolved in 2 mL of dimethyl sulfoxide solvent, and heated and stirred at 90°C under argon, nitrogen and air atmospheres respectively for 36 hours. After the reaction was completed, the reaction solution was filtered and collected. The content of 5-hydroxymethylfurfural generated was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with comparison with a commercially available 5-hydroxymethylfurfural standard sample. Finally, yields of about 56%, 54.9% and 54.2% were obtained respectively.

[0065] The obtained dimethyl sulfoxide filtrate was washed with saturated brine for multiple times, dried with anhydrous sodium sulfate, rotary evaporated under reduced pressure, and purified by column chromatography. Finally, about 105.4 mg, 102.2 mg and 108.5 mg of 5-hydroxymethylfurfural product was obtained respectively. No obvious by-product peaks were observed in the nuclear magnetic resonance spectrogram, which was consistent with the result of high performance liquid chromatography, indicating that the product had extremely high purity.

[0066] Application Example 4

[0067] 300 mg (15% mass fraction) of glucose and 300 mg (15% mass fraction) of aluminum sulfate octadecahydrate were dissolved in 2 mL of dimethyl sulfoxide solvent, and heated and stirred at 90°C under argon, nitrogen and air atmospheres respectively for 36 hours. After the reaction was completed, the reaction solution was filtered and collected. The content of 5-hydroxymethylfurfural generated was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with comparison with a commercially available 5-hydroxymethylfurfural standard sample. Finally, yields of about 44.5%, 41.7% and 42.8% were obtained respectively.

[0068] The obtained dimethyl sulfoxide filtrate was washed with saturated brine for multiple times, dried with anhydrous sodium sulfate, rotary evaporated under reduced pressure, and purified by column chromatography. Finally, about 84.7 mg, 88.5 mg and 87.4 mg of 5-hydroxymethylfurfural product was obtained respectively. No obvious by-product peaks were observed in the nuclear magnetic resonance spectrogram, which was consistent with the result of high performance liquid chromatography, indicating that the product had extremely high purity.

[0069] Application Example 5

[0070] 300 mg (15% mass fraction) of glucose and 300 mg (15% mass fraction) of aluminum nitrate nonahydrate were dissolved in 2 mL of dimethyl sulfoxide solvent, and heated and stirred at 90°C under argon, nitrogen and air atmospheres respectively for 36 hours. After the reaction was completed, the reaction solution was filtered and collected. The content of 5-hydroxymethylfurfural generated was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with comparison with a commercially available 5-hydroxymethylfurfural standard sample, and finally about 99.8%, 99.7% and 99.5% yields were obtained respectively.

[0071] The obtained dimethyl sulfoxide filtrate was washed with saturated brine for multiple times, dried with anhydrous sodium sulfate, then rotary evaporated under reduced pressure, and purified by column chromatography. Finally, about 205 mg, 202.3 mg and 203.6 mg of 5-hydroxymethylfurfural product was obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the result of high performance liquid chromatography, indicating that the product purity was extremely high.

[0072] Application Example 6

[0073] 300 mg (15% mass fraction) of glucose and 300 mg (15% mass fraction) of aluminum nitrate nonahydrate were dissolved in 2 mL of dimethyl sulfoxide solvent, and heated and stirred at 90°C under argon, nitrogen and air atmospheres respectively for 36 hours. After the reaction was completed, the reaction solution was filtered and collected. The content of 5-hydroxymethylfurfural generated was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with comparison with a commercially available 5-hydroxymethylfurfural standard sample, and finally about 99.8%, 99.7% and 99.5% yields were obtained respectively.

[0074] The obtained dimethyl sulfoxide filtrate was washed with saturated brine for multiple times, dried with anhydrous sodium sulfate, then rotary evaporated under reduced pressure, and purified by column chromatography. Finally, about 205 mg, 202.3 mg and 203.6 mg of 5-hydroxymethylfurfural product was obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the result of high performance liquid chromatography, indicating that the product purity was extremely high.

[0075] Application Example 7

[0076] 300 mg (15% mass fraction) of glucose and 300 mg (15% mass fraction) of aluminum nitrate nonahydrate were dissolved in 2 mL of dimethyl sulfoxide solvent, and heated and stirred at 90°C under argon, nitrogen and air atmospheres respectively for 36 hours. After the reaction was completed, the reaction solution was filtered and collected. The content of 5-hydroxymethylfurfural generated was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with comparison with a commercially available 5-hydroxymethylfurfural standard sample, and finally about 99.8%, 99.7% and 99.5% yields were obtained respectively.

[0077] The obtained dimethyl sulfoxide filtrate was washed with saturated brine for several times, dried with anhydrous sodium sulfate, then rotary evaporated under reduced pressure, and purified by column chromatography. Finally, about 219 mg, 213 mg and 218.7 mg of 5-hydroxymethylfurfural product was obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the result of high performance liquid chromatography, indicating that the product purity was extremely high.

[0078] Application Example 8

[0079] 3 g (15% mass fraction) of glucose and 3 g (15% mass fraction) of aluminum nitrate nonahydrate were dissolved in 20 mL of dimethyl sulfoxide solvent, and heated and stirred at 90°C under argon, nitrogen and air atmosphere respectively for 36 hours. After the reaction was completed, the reaction solution was filtered and collected. By high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectrum (NMR) analysis, combined with comparison with the commercially available 5-hydroxymethylfurfural standard sample, the content of the generated 5-hydroxymethylfurfural was determined, and finally about 95%, 93% and 94.3% yield was obtained respectively.

[0080] The obtained dimethyl sulfoxide filtrate was washed with saturated brine for several times, dried with anhydrous sodium sulfate, then rotary evaporated under reduced pressure, and purified by column chromatography. Finally, about 219 mg, 213 mg and 218.7 mg of 5-hydroxymethylfurfural product was obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the result of high performance liquid chromatography, indicating that the product purity was extremely high.

[0081] Application Example 9

[0082] 30 g (15% mass fraction) of glucose and 30 g (15% mass fraction) of aluminum nitrate nonahydrate were dissolved in 200 mL of dimethyl sulfoxide solvent, and heated and stirred at 90°C under argon, nitrogen and air atmosphere respectively for 48 hours. After the reaction was completed, the reaction solution was filtered and collected. By high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectrum (NMR) analysis, combined with comparison with the commercially available 5-hydroxymethylfurfural standard sample, the content of the generated 5-hydroxymethylfurfural was determined, and finally about 98%, 96.8% and 95% yield was obtained respectively.

[0083] The obtained dimethyl sulfoxide filtrate was washed with saturated brine for several times, dried with anhydrous sodium sulfate, then rotary evaporated under reduced pressure, and purified by column chromatography. Finally, about 219 mg, 213 mg and 218.7 mg of 5-hydroxymethylfurfural product was obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the result of high performance liquid chromatography, indicating that the product purity was extremely high.

[0084] Application Example 10

[0085] 30 g (15% by mass) of fructose and 30 g (15% by mass) of aluminum nitrate nonahydrate were dissolved in 200 mL of dimethyl sulfoxide solvent, and the reaction was stirred and heated at 90°C for 48 hours under an argon, nitrogen, and air atmosphere, respectively. After the reaction was completed, the reaction solution was filtered and collected. The content of 5-hydroxymethylfurfural generated was determined by high-performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, in comparison with a commercially available 5-hydroxymethylfurfural standard sample, and finally, yields of about 97%, 96.6%, and 94.8% were obtained, respectively.

[0086] The obtained dimethyl sulfoxide filtrate was washed with saturated brine several times, dried with anhydrous sodium sulfate, and then rotary evaporated under reduced pressure, and then purified by column chromatography. Finally, 5-hydroxymethylfurfural products of about 20.7 g, 20.4 g, and 20.3 g were obtained, respectively. No obvious by-product peaks were observed in the nuclear magnetic resonance spectrogram, which was consistent with the results of high-performance liquid chromatography, indicating that the product purity was extremely high.

[0087] Application Example 11

[0088] 30 g (15% by mass) of sucrose and 30 g (15% by mass) of aluminum nitrate nonahydrate were dissolved in 200 mL of dimethyl sulfoxide solvent, and the reaction was stirred and heated at 90°C for 48 hours under an argon, nitrogen, and air atmosphere, respectively. After the reaction was completed, the reaction solution was filtered and collected. The content of 5-hydroxymethylfurfural generated was determined by high-performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, in comparison with a commercially available 5-hydroxymethylfurfural standard sample, and finally, yields of about 91.4%, 94.7%, and 94.2% were obtained, respectively.

[0089] The obtained dimethyl sulfoxide filtrate was washed with saturated brine several times, dried with anhydrous sodium sulfate, and then rotary evaporated under reduced pressure, and then purified by column chromatography. Finally, 5-hydroxymethylfurfural products of about 21.5 g, 21.4 g, and 20.7 g were obtained, respectively. No obvious by-product peaks were observed in the nuclear magnetic resonance spectrogram, which was consistent with the results of high-performance liquid chromatography, indicating that the product purity was extremely high.

[0090] Application Example 12

[0091] 300 g (15% by mass) of glucose and 300 g (15% by mass) of aluminum nitrate nonahydrate were dissolved in 2 L of dimethyl sulfoxide solvent, and the reaction was stirred and heated at 90°C for 48 hours under an argon, nitrogen, and air atmosphere, respectively. After the reaction was completed, the reaction solution was filtered and collected. The content of 5-hydroxymethylfurfural generated was determined by high-performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, in comparison with a commercially available 5-hydroxymethylfurfural standard sample, and finally, yields of about 97%, 94%, and 95.3% were obtained, respectively.

[0092] The obtained dimethyl sulfoxide filtrate was washed with saturated brine for multiple times, dried with anhydrous sodium sulfate, then rotary evaporated under reduced pressure, and finally purified by column chromatography to obtain about 202.5 g, 207.2 g and 204.8 g of 5-hydroxymethylfurfural product respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the result of high performance liquid chromatography, indicating that the product purity was extremely high.

[0093] Application Example 13

[0094] In this application example, HMF obtained from application examples 1 to 12 was directly used to synthesize 2,5-furan dicarboxylic acid (FDCA), and the synthesis route, reaction conditions and selection of solid catalysts strictly referred to existing prior art [1] to [8]. In this application example, HMF solution containing 20% glucose was used as a control group for simulating impurities, and the following table shows the FDCA yield of commercially available HMF, HMF obtained from example 5 and HMF containing 20% glucose in different systems.

[0095] The prior art used in this application example is as follows:

[0096] [1] F. Liguori, P. Barbaro, N. Calisi, ChemSusChem, 2019, 12, 2558-2563.

[0097] [2] Y. Wei, Y. Zhang, Y. Chen, F. Wang, Y. Cao, W. Guan, X. Li, ChemSusChem, 2022, 15, e202101983.

[0098] [3] A. Villa, M. Schiavoni, S. Campisi, G. M. Veith, L. Prati, ChemSusChem, 2013, 6, 609-612.

[0099] [4] A. Tirsoaga, M. El Fergani, N. Nuns, P. Simon, P. Granger, V. I. Parvulescu, S. M. Coman, Applied Catalysis B: Environmental, 2020, 278, 119309.

[0100] [5] S. Zhang, G. Chu, S. Wang, J. Ma, C. Wang, Molecules, 2024, 29, 3213.

[0101] [6] X. Liu, M. Zhang, Z. Li, ACS Sustainable Chemistry & Engineering, 2020, 8, 4801-4808.

[0102] [7] F. Qi, W. Yang, H. Yu, L. L. Lou, S. Liu, K. Yu, Applied Surface Science, 2022, 598, 153769.

[0103] [8] F. Wang, C. Yan, R. Jiang, Y. Chen, Y. Wei, Y. Cao, Y. Zhang, Applied Clay Science, 2023, 235, 106872.

[0104] From the above results, since the preparation method adopted by the present application can obtain high-purity HMF, when used in the synthesis of FDAC without further purification, it can significantly improve the yield of FDAC, and the yield is close to that using commercially available HMF with high purity. The HMF control group containing 20% glucose significantly inhibited the oxidation reaction of HMF due to the presence of glucose, resulting in very low yield.

[0105] Application Example 14

[0106] In this application example, a certain amount of solid heterogeneous catalyst is added to the reaction system under the same conditions as in Application Example 8 to explore the application range of the reaction system of the present application.

[0107] In this application example, the solid heterogeneous catalyst is selected from zirconium oxide (ZrO2), cerium dioxide (CeO2), aluminum oxide (Al2O3), activated carbon, silicon dioxide (SiO2), titanium dioxide (TiO2), iron oxide (Fe2O3), and tungsten oxide (WO3), etc. (refer to prior art [1] to [8]).

[0108] Specifically, 3 g (15% by mass) of glucose and 3 g (15% by mass) of aluminum nitrate nonahydrate are dissolved in 20 mL of dimethyl sulfoxide solvent, 1 g of solid heterogeneous catalyst is added, and the reaction is stirred and heated at 90°C under an argon atmosphere for 36 hours. After the reaction is completed, the reaction solution is filtered and collected. By high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with comparison with commercially available 5-hydroxymethylfurfural standard sample, the following table shows the HMF yield under the addition of different solid heterogeneous catalysts.

[0109] The prior art referred to in this application example is as follows:

[0110] [1] A. Teimouri, M. Mazaheri, A. N. Chermahini, H. Salavati, F. Momenbeik, & M. Fazel-Najafabadi, Journal of the Taiwan Institute of Chemical Engineers, 2015, 49, 40-50.

[0111] [2] D. B. D. A. Pryston, T. V. D. S. Martins, J. A. D. Vasconcelos Junior, D. O. D. S. Avelino, M. R. Meneghetti, & S. M. P. Meneghetti, Catalysts, 2022, 13(1), 4.

[0112] [3] B. Torres-Olea, S. Mérida-Morales, C. García-Sancho, J. A. Cecilia, & P. Maireles-Torres, Catalysts, 2020, 10(8), 878.

[0113] [4] A. Rusanen, R. Lahti, K. Lappalainen, J. T. Hu, H. Romar, & U. Lassi, Catalysis Today, 2020, 357, 94-101.

[0114] [5] I. Lestari & H. Helmiyati, IOP Conference Series: Materials Science and Engineering, 2020, 763(1), 012037.

[0115] [6] A. A. Silahua-Pavon, C. G. Espinosa-Gonzalez, F. Ortiz-Chi, J. G. Pacheco-Sosa, H. Perez-Vidal, J. C. Arevalo-Perez,... & J. G. Torres-Torres, Catalysis Communications, 2019, 129, 105723.

[0116] [7] J. Lan & Z. Zhang, Journal of Industrial and Engineering Chemistry, 2015, 23, 200-205.

[0117] [8] P. Ganji & S. Roy, Energy & Fuels, 2019, 33(6), 5293-5303.

[0118] From the above results, it can be seen that when combined with zirconium oxide, aluminum oxide, activated carbon, silicon dioxide and titanium dioxide, the reaction system used in the present application can obtain a 5-hydroxymethylfurfural yield of more than 90%, and when combined with aluminum oxide, the yield of 5-hydroxymethylfurfural can reach 99.3%. The results show that the reaction method provided in the present application is not only limited to homogeneous catalysis, but also suitable for compatibility with other heterogeneous catalytic systems to obtain high yield of 5-hydroxymethylfurfural, and has a wide range of applications.

[0119] Application Example 15

[0120] Dissolve 1.5 kg (15% by mass) of glucose and 1.5 kg (15% by mass) of aluminum nitrate nonahydrate in 10 L of dimethyl sulfoxide solvent, and stir and heat the reaction at 90°C under argon, nitrogen and air atmospheres, respectively, for 72 hours. After the reaction is completed, filter and collect the reaction solution. By high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with comparison with commercially available 5-hydroxymethylfurfural standard samples, the content of the generated 5-hydroxymethylfurfural is determined, and finally about 94%, 93.1% and 92.5% yields are obtained, respectively.

[0121] The obtained dimethyl sulfoxide filtrate is washed with saturated brine for multiple times, dried with anhydrous sodium sulfate, then rotary evaporated under reduced pressure, and purified by column chromatography. Finally, about 0.94 kg, 0.97 kg and 0.905 kg of 5-hydroxymethylfurfural product is obtained, respectively. No obvious by-product peak is observed in the nuclear magnetic resonance spectrogram, which is consistent with the result of high performance liquid chromatography, indicating that the product purity is extremely high.

[0122] Application Example 16

[0123] Dissolve 3 kg (15% by mass) of glucose and 3 kg (15% by mass) of aluminum nitrate nonahydrate in 20 L of dimethyl sulfoxide solvent, and stir and heat the reaction at 90°C under argon, nitrogen and air atmospheres, respectively, for 72 hours. After the reaction is completed, filter and collect the reaction solution. By high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with comparison with commercially available 5-hydroxymethylfurfural standard samples, the content of the generated 5-hydroxymethylfurfural is determined, and finally about 92.4%, 91.7% and 89.3% yields are obtained, respectively.

[0124] The obtained dimethyl sulfoxide filtrate was washed with saturated brine for multiple times, dried with anhydrous sodium sulfate, then rotary evaporated under reduced pressure, and purified by column chromatography, finally about 1.77 kg, 1.85 kg and 1.71 kg of 5-hydroxymethylfurfural product was obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the result of high performance liquid chromatography, indicating that the product purity was extremely high.

[0125] The method provided by the application can selectively synthesize 5-hydroxymethylfurfural from sugars (such as glucose, fructose, sucrose and the like) under low temperature conditions under the catalysis of various aluminum ion salts. The reaction can be carried out in air or inert atmosphere, the reaction condition is simple and mild, and the use of high temperature and high pressure and highly toxic chemical raw materials is avoided.

[0126] The obtained 5-hydroxymethylfurfural sample has a yield of 99.8%, has the same HPLC signal as the commercially available standard sample of 5-hydroxymethylfurfural (see FIGS. 1-2), has the same infrared spectrum signal as the commercially available standard sample of 5-hydroxymethylfurfural (see FIG. 4), and no obvious by-product peak is observed in the nuclear magnetic resonance spectrum of the 5-hydroxymethylfurfural sample (see FIG. 3), indicating that the obtained product has extremely high purity.

[0127] The high selectivity and high yield of the reaction greatly simplify the separation of 5-hydroxymethylfurfural, facilitate the subsequent reaction such as FDAC synthesis, and are a green, economical and efficient synthesis method with wide application prospect, suitable for industrialized production. Moreover, the aluminum ion salt catalyst used is cheap and easy to obtain, and can be recycled and reused multiple times. At the same time, the method can be compatible with other heterogeneous catalytic systems to prepare high-yield 5-hydroxymethylfurfural, and has a wide range of applications.

[0128] The above examples and application examples are only exemplary descriptions of the application, and do not limit the scope of the application. Without departing from the design spirit of the application, various modifications and improvements of the technical solutions of the application made by those skilled in the art shall fall within the protection scope of the application.

[0129] Reference literature mentioned in the background art:

[0130] [1] V. Tangsermvit, T. Pila, B. Boekfa, V. Somjit, W. Klysubun, J. Limtrakul,... & K. Kongpatpanich, Small, 2021, 17, 2006541.

[0131] [2] M. Zuo, W. Jia, Y. Feng, X. Zeng, X. Tang, Y. Sun, & L. Lin, Renewable Energy, 2021, 164, 23-33.

[0132] [3] M. Zuo, X. Wang, W. Jia, Y. Zhu, X. Zeng, & L. Lin, Fuel, 2022, 326, 125062.

[0133] [4] S. De, S. Dutta, & B. Saha, Green Chemistry, 2011, 13, 2859-2868.

[0134] [5] N. Shi, Y. Zhu, B. Qin, T. Zhu, H. Huang, & Y. Liu, ACS Sustainable Chemistry & Engineering, 2022, 10, 10444-10456.

[0135] [6] N. Shi, Y. Zhu, B. Qin, Y. Liu, H. Zhang, H. Huang, & Y. Liu, Cellulose, 2022, 29, 2257-2272.

[0136] [7] M. Li, L. Jiang, S. Feng, J. Huang, P. Zhang, & J. Zhang, Dalton Transactions, 2024, 53, 3386-3396.

[0137] [8] T. Tana, P. Han, A. J. Brock, X. Mao, S. Sarina, E. R. Waclawik,... & H. Y. Zhu, Nature Communications, 2023, 14, 4609.

[0138] [9] T. Zhang, W. Li, H. Xin, L. Jin, & Q. Liu, Catalysis Communications, 2019, 124, 56-61.

[0139]

[0010] I. Jiménez-Morales, M. Moreno-Recio, J. Santamaría-González, P. Maireles-Torres, & A. Jiménez-López, Applied Catalysis B: Environmental, 2015, 164, 70-76.

[0140]

[0011] K. Wang, S. Liu, R. Hao, A. Du, & Y. Wang, AIChE Journal, 2021, 67(10), e17345.

[0141]

[0012] L. Hu, Z. Wu, J. Xu, Y. Sun, L. Lin, & S. Liu, Chemical Engineering Journal, 2014, 244, 137-144.

[0142]

[0013] Y. Zhang, J. Wang, J. Wang, Y. Wang, M. Wang, H. Cui,... & W. Yi, Chemistry Select, 2019, 4(19), 5724-5731.

[0143]

[0014] A. Teimouri, M. Mazaheri, A. N. Chermahini, H. Salavati, F. Momenbeik, & M. Fazel-Najafabadi, Journal of the Taiwan Institute of Chemical Engineers, 2015, 49, 40-50.

[0144]

[0015] P. Tosuwan, S. Y. Chen, H. Tateno, T. Mochizuki, & A. Luengnaruemitchai, Catalysis Communications, 2022, 170, 106488.

[0145]

[0016] K. M. Iris, X. Xiong, D. C. Tsang, L. Wang, A. J. Hunt, H. Song,... & C. S. Poon, Green Chemistry, 2019, 21(6), 1267-1281.

[0146]

[0017] Y. Yang, C. W. Hu, & M. M. Abu-Omar, Green Chemistry, 2012, 14(2), 509-513.

[0147]

[0018] Y. Wang, L. Zhu, Y. Zhang, H. Cui, W. Yi, F. Song,... & Z. Li, Chemistry Select, 2018, 3(12), 3555-3560.

[0148]

[0019] H. Ban, Y. Zhang, S. Chen, Y. Cheng, T. Pan, L. Wang, & X. Li, ACS Sustainable Chemistry & Engineering, 2020, 8, 8011-8023.

[0149]

[0020] M. Sajid, X. Zhao, & D. Liu, Green Chemistry, 2018, 20, 5427-5453.

[0150] 21] M. G. Davidson, S. Elgie, S. Parsons, & T. J. Young, Green Chemistry, 2021, 23, 3154-3171.

[0151]

[0022] G. Chen, L. Wu, H. Fan, & B. G. Li, Industrial & Engineering Chemistry Research, 2018, 57, 16172-16181.

[0152]

[0023] A. Lolli, S. Albonetti, L. Utili, R. Amadori, F. Ospitali, C. Lucarelli, & F. Cavani, Applied Catalysis A: General, 2015, 504, 408-419.

[0153]

[0024] W. Naim, O. R. Schade, E. D. Wüst, A. Kruse, & J. D. Grunwaldt, ACS Sustainable Chemistry & Engineering, 2020, 8, 11512-11521.

[0154]

[0025] L. Liu, H. M. Chang, H. Jameel, J. Y. Park, & S. Park, Industrial & Engineering Chemistry Research, 2017, 56, 14447-14453.

[0155]

[0026] X. Zuo, P. Venkitasubramanian, K. J. Martin, & B. Subramaniam, ChemSusChem, 2022, 15, e202102050.

[0156]

[0027] A. T. B. Tamboli, S. P. Kirdant, & V. H. Jadhav, New Journal of Chemistry, 2022, 46, 10272-10279.

Claims

1. A method for preparing 5-hydroxymethylfurfural by mild catalysis of aluminum ions, comprising the following steps: S1. dissolving a carbohydrate and an aluminum ion salt in a solvent; S2. reacting under a reaction atmosphere at 80-120 ℃ for 24-48 hours; S3. filtering to obtain a 5-hydroxymethylfurfural sample; The mass ratio of the carbohydrate and the aluminum ion salt is 1:1, and the mass-volume ratio of the carbohydrate and the solvent is 0.01 g-1 g: 1 mL.

2. The method of claim 1, wherein, In step S2, the reaction temperature is 90 ℃.

3. The method of claim 1, wherein, In step S2, the reaction time is 36 hours.

4. The method of claim 1, wherein, The mass-volume ratio of the carbohydrate and the solvent is 0.01 g-0.2 g: 1 mL.

5. The method of claim 4, wherein, The mass-volume ratio of the carbohydrate and the solvent is 0.15 g: 1 mL.

6. The method of claim 1, wherein, The carbohydrate comprises glucose, fructose or sucrose.

7. The method of claim 1, wherein, The aluminum ion salt comprises aluminum nitrate, aluminum sulfate or aluminum chloride.

8. The method of claim 1, wherein, The reaction atmosphere is an air atmosphere or an inert gas atmosphere.

9. The method of claim 1, wherein, The solvent comprises dimethylformamide or dimethyl sulfoxide.

10. The method according to any one of claims 1 to 9, wherein, A solid heterogeneous catalyst is further included in the reaction system, and the solid heterogeneous catalyst comprises zirconium oxide, cerium dioxide, aluminum oxide, activated carbon, silicon dioxide, titanium dioxide, diiron trioxide or tungsten oxide.

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