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

Abstract

The invention relates to a method for preparing 5-hydroxymethylfurfural through mild catalysis of aluminum ions. The method comprises the following steps that S1, carbohydrate and aluminum ion salt are dissolved in a solvent; s2, reacting for 24 to 48 hours in a reaction atmosphere under the condition of 80 to 120 DEG C; s3, filtering to obtain a 5-hydroxymethylfurfural sample; 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 (0.01-1g): 1mL. According to the scheme disclosed by the invention, 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 signal as a commercially available 5-hydroxymethylfurfural standard sample and the same infrared spectrum signal as the commercially available 5-hydroxymethylfurfural standard sample; no obvious by-product peak is observed in a nuclear magnetic resonance spectrogram of a 5-hydroxymethylfurfural sample, and the product purity is extremely high. Due to high selectivity and high yield of the reaction, separation and purification of the 5-hydroxymethylfurfural are simplified, and subsequent reaction is facilitated.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical synthesis, and in particular to a method for preparing 5-hydroxymethylfurfural by mild catalysis of aluminum ions. Background Art

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

[0003] In addition to being a homogeneous catalyst, aluminum ions can also act as a co-catalyst in heterogeneous catalytic systems, providing Lewis acidity and participating in the reaction, thereby increasing the yield of HMF. For example, Li et al. prepared a Lewis- A catalyst with acid sites. At 150°C, the catalyst achieved a HMF yield of about 70% [7]. Tana and Pengfei disclosed a system with aluminum nitrate nonahydrate and fulvic acid as catalysts. After 20 hours of illumination in a DMSO solution at 80°C, the system was able to photocatalyze glucose to produce a 60% HMF yield [8]. The main mechanism is that the coordination of fulvic acid with aluminum ions can enhance the light absorption capacity of the system and reduce the energy barrier required for the reaction.

[0004] In the study by Zhang et al., aluminum ions were loaded on acidic phenolic resin as a co-catalyst to effectively promote the conversion of glucose to HMF. After 2 hours of reaction at 170°C, the catalytic system successfully achieved a 47.4% HMF yield [9]. The study by Jiménez-Morales et al. demonstrated the significant catalytic effect of aluminum-doped MCM-41 silica catalyst in the dehydration of glucose to HMF. Its catalytic activity originated from the synergistic effect of the Brönsted acid sites in the catalyst and the Lewis acid sites provided by aluminum ions. After 2.5 hours of reaction at 195°C, the catalytic system obtained a 36% HMF yield

[10] . The study by Wang et al. further demonstrated that aluminum ions loaded on sulfonated carbon catalysts can effectively catalyze the conversion of glucose at 140°C with a yield of 75%

[11] . Similarly, the study by Hu et al. showed that zeolite can also effectively catalyze glucose in the presence of aluminum ions, with an HMF yield of 50.3% at 150°C

[12] .

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

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

[0006] Although aluminum ions have been widely used in the process of glucose conversion to HMF as a co-catalyst to increase Lewis acid active sites, there are still many problems with the existing technology.

[0007] Although the Lewis acidity of aluminum ions can promote the isomerization reaction of glucose, the reaction process in which aluminum ions participate often leads to the formation of by-products such as humus and humin 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 with the participation of aluminum ions, there is almost no case where a yield of more than 70% can be obtained. Its extremely low yield and weak selectivity limit its practical application in industrial scale-up.

[0008] In existing reactions involving aluminum ions, extremely high reaction temperatures (>120°C) are usually required to promote the isomerization of glucose to fructose, but harsh reaction conditions are often accompanied by the generation of by-products. This problem significantly increases the difficulty of subsequent product separation and purification. Under high temperature conditions, aluminum ions may react with other components in the reaction medium, causing the catalyst to gradually deactivate. 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, it is extremely difficult to separate the product from the solvent. 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 expensive and difficult to recycle on an industrial scale, further increasing the complexity and cost of the process.

[0010] Although aluminum ions themselves have low toxicity, they may have adverse effects on the environment and organisms at high concentrations, especially under long-term exposure. In addition, certain reaction conditions may require the use of strong acids or high-temperature operations, which not only increases the complexity of the process but also brings potential safety risks. For example, the use of strong acids may cause corrosive damage, while 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 issues 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 it is the most studied synthesis route at present. FDCA has a wide range of uses and can be used to produce succinic acid. As a macrocyclic ligand and anticorrosive agent, it is considered to be one of the 12 most valuable chemical products in biomass. However, due to the low yield and selectivity of HMF in the synthesis process mentioned above and the difficulty in product separation, 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 a certain yield

[19] . However, these processes are only applicable to low concentrations of HMF and the production efficiency is significantly reduced

[10] . In addition, the by-products produced during the preparation of HMF will significantly inhibit the catalytic activity of subsequent HMF oxidation

[21] . At present, the one-pot process for preparing FDCA from glucose or fructose generally has the problem of low yield and selectivity. The fundamental reason is that too many by-products are produced during the conversion of glucose or fructose to HMF, which hinders the conversion efficiency of HMF in subsequent oxidation reactions. For example, Chen et al. used fructose to prepare 2,5-furandicarboxylic acid (FDCA) with a total yield of 88.4%

[22] . However, high temperature and the addition of alkali lead to the formation of by-products, which limits the feasibility of higher yields and industrial production [22,23].

[0013] Naim et al. studied the common by-products in the HMF production process (such as glucose (GLU), fructose (FRU), lactic acid (LA), formic acid (FA) and sodium nitrate (NaNO3)). The results showed that in the presence of glucose (GLU), the yield of 2,5-furandicarboxylic acid (FDCA) dropped significantly from 100% to 24%, and fructose (FRU) was converted into unidentified by-products, thereby inhibiting the reaction

[24] . Their experiments also verified that the by-products in the HMF reaction solution would significantly affect the subsequent oxidation process of HMF, resulting in a decrease in product yield and the generation of non-target products such as . Similarly, Liu et al. found that compared with commercial HMF samples, laboratory-prepared HMF resulted in a significant decrease in the yield and selectivity of FDCA during oxidation, and a higher content of unreacted HMF. Specifically, the selectivity of FDCA dropped from 88.3% to 37.4%, and the yield dropped from 88.3% to 25.7%, which was mainly attributed to the influence of impurities in the sample

[25] . In addition, Zuo et al. used crude HMF solution dehydrated from fructose for oxidation without removing impurities. The obtained product contained a certain amount of 5-formyl-2-furancarboxylic acid (FFCA), with a content of about 4000 ppm

[26] . Tamboli et al. tried to prepare FDCA directly from glucose or fructose by a one-pot method, and the final FDCA yields were 56% and 78%, respectively

[27] . This lower yield is mainly attributed to the fact that the residual glucose or fructose in the solution will block the active sites of the catalyst, thereby inhibiting the oxidation reaction of HMF to FDCA. Summary of the invention

[0014] The purpose of the present disclosure is to provide a HMF preparation process with mild reaction conditions and to improve the yield and purity of HMF.

[0015] To achieve the above objectives, the present disclosure provides the following technical solutions:

[0016] A method for preparing 5-hydroxymethylfurfural by mild catalysis of aluminum ions comprises the following steps:

[0017] S1. dissolving a carbohydrate and an aluminum ion salt in a solvent;

[0018] S2. The reaction is carried out at 80 to 120 ° C in a reaction atmosphere for 24 to 48 hours;

[0019] S3. Filter to obtain a 5-hydroxymethylfurfural sample;

[0020] 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 g to 1 g: 1 mL.

[0021] Preferably, in step S2, the reaction temperature is 90°C.

[0022] Preferably, in step S2, the reaction time is 36 hours.

[0023] Preferably, the mass volume ratio of the carbohydrate to the solvent is 0.01 g to 0.2 g: 1 mL.

[0024] More preferably, the mass volume ratio of the carbohydrate to the solvent is 0.15 g:1 mL.

[0025] Preferably, the carbohydrate comprises glucose, fructose or sucrose.

[0026] Preferably, the aluminum ion salt includes aluminum nitrate, aluminum sulfate or aluminum chloride.

[0027] Preferably, the reaction atmosphere is an air atmosphere or an inert gas atmosphere.

[0028] Preferably, the solvent comprises dimethylformamide or dimethyl sulfoxide.

[0029] Preferably, 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, iron oxide or tungsten oxide.

[0030] The technical solution claimed in the present disclosure has achieved the following beneficial effects:

[0031] 1) Under the catalytic action of various aluminum ion salts, sugars (such as glucose, fructose, sucrose, etc.) are selectively synthesized into 5-hydroxymethylfurfural under low temperature conditions. The reaction can be carried out in air or inert atmosphere, the reaction conditions are simple and mild, and the use of high temperature, high pressure and highly toxic chemical raw materials is avoided.

[0032] 2) The yield of the obtained 5-hydroxymethylfurfural sample can reach 99.8%, and it has the same HPLC signal as the commercial standard sample of 5-hydroxymethylfurfural, the same infrared spectrum signal as the commercial 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 obtained product has extremely high purity. The high selectivity and high yield of the reaction also greatly simplify the separation and purification of 5-hydroxymethylfurfural, which is conducive to the subsequent reaction.

[0033] 3) The aluminum ion salt catalyst used is cheap and readily available, and can be recycled and reused multiple times. At the same time, the method is compatible with other heterogeneous catalytic systems, and 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 broad application prospects, suitable for industrial-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the technical solutions in the embodiments of the present disclosure, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are merely embodiments of the present disclosure, and a person of ordinary skill in the art can obtain other drawings based on the provided drawings without paying any creative work.

[0035] Figure 1 Schematic diagram of the elution time of 5-hydroxymethylfurfural commercial standard sample (HMF STD) and the sample to be tested in high performance liquid chromatography (HPLC).

[0036] Figure 2 The standard curve of the concentration of commercially available 5-hydroxymethylfurfural standard samples versus HPLC signal.

[0037] Figure 3 This is a comparison chart of the nuclear magnetic resonance spectra (NMR) of the 5-hydroxymethylfurfural standard sample and the sample to be tested.

[0038] Figure 4 This is a comparison chart of the Fourier transform infrared spectra (FTIR) of 5-hydroxymethylfurfural standard sample and the test sample in DMSO solvent.

[0039] Figure 5 This is a comparison chart of the Fourier transform infrared spectra (FTIR) of the 5-hydroxymethylfurfural standard sample and the purified sample to be tested.

[0040] Figure 6 This is a correlation diagram between the yield of 5-hydroxymethylfurfural and the amount of aluminum nitrate nonahydrate added.

[0041] Figure 7 This is a correlation diagram between 5-hydroxymethylfurfural yield and reaction time.

[0042] Figure 8 This is a correlation diagram between 5-hydroxymethylfurfural yield and reaction temperature. DETAILED DESCRIPTION

[0043] In order to make the purpose, technical solution and beneficial effects of the embodiments of the present disclosure clearer, the technical solution in the embodiments of the present disclosure will be clearly and completely described below in conjunction with the drawings in the embodiments of the present disclosure. Obviously, the described embodiments are part of the embodiments of the present disclosure, not all of the embodiments. Based on the embodiments of the present disclosure, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present disclosure.

[0044] Example

[0045] This embodiment provides a method for preparing 5-hydroxymethylfurfural by mild catalysis of aluminum ions, comprising the following steps:

[0046] S1. dissolving a carbohydrate and an aluminum ion salt in a solvent;

[0047] S2. The reaction is carried out at 80 to 120 ° C in a reaction atmosphere for 24 to 48 hours;

[0048] S3. Filter to obtain a 5-hydroxymethylfurfural sample;

[0049] 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 g to 1 g: 1 mL.

[0050] In a preferred embodiment, in step S2, the reaction temperature is 90° C. and the reaction time is 36 hours.

[0051] In a preferred embodiment, the mass volume ratio of the carbohydrate to the solvent is 0.01 g to 0.2 g:1 mL, and more preferably 0.15 g:1 mL.

[0052] In a preferred embodiment, the carbohydrate includes glucose, fructose or sucrose, the aluminum ion salt includes aluminum nitrate, aluminum sulfate or aluminum chloride, the reaction atmosphere is air atmosphere or inert gas atmosphere, and the solvent includes dimethylformamide or dimethyl sulfoxide.

[0053] In a preferred 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, iron oxide or tungsten oxide.

[0054] The following further describes the solution of the above embodiment and the technical effect it brings in detail in combination with specific application examples.

[0055] Application Example 1

[0056] 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 stirred and heated for reaction at 90°C under an argon atmosphere for 24 hours. After the reaction was completed, the solution after the reaction 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.

[0057] The obtained dimethylformamide filtrate was washed with saturated brine several times, dried with anhydrous sodium sulfate, and then subjected to reduced pressure rotary evaporation and column chromatography separation and purification, and finally about 21.8 mg of 5-hydroxymethylfurfural product was obtained. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the results of high performance liquid chromatography, indicating that the product purity was extremely high.

[0058] Application Example 2

[0059] 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 stirred and heated for reaction for 24 hours under argon, nitrogen and air atmospheres at 90°C. After the reaction was completed, the solution after the reaction 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 the yields of about 99%, 97% and 98.3% were obtained respectively.

[0060] The obtained dimethyl sulfoxide filtrate was washed with saturated brine several times, dried with anhydrous sodium sulfate, and then subjected to reduced pressure rotary evaporation and separation and purification by column chromatography, and finally about 24 mg, 23.1 mg and 23.3 mg of 5-hydroxymethylfurfural products were obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the results of high performance liquid chromatography, indicating that the product purity was extremely high.

[0061] Application Example 3

[0062] 300 mg (15% by mass) of glucose and 300 mg (15% by mass) of aluminum chloride hexahydrate were dissolved in 2 mL of dimethyl sulfoxide solvent, and stirred and heated for 36 hours under argon, nitrogen and air atmospheres at 90°C. 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 a commercially available 5-hydroxymethylfurfural standard sample for comparison, and finally yields of about 56%, 54.9% and 54.2% were obtained, respectively.

[0063] The obtained dimethyl sulfoxide filtrate was washed with saturated brine several times, dried with anhydrous sodium sulfate, and then subjected to reduced pressure rotary evaporation and column chromatography separation and purification, and finally about 105.4 mg, 102.2 mg and 108.5 mg of 5-hydroxymethylfurfural products were obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the results of high performance liquid chromatography, indicating that the product purity was extremely high.

[0064] Application Example 4

[0065] 300 mg (15% by mass) of glucose and 300 mg (15% by mass) of aluminum sulfate 18 hydrate were dissolved in 2 mL of dimethyl sulfoxide solvent, and stirred and heated for 36 hours under argon, nitrogen and air atmospheres at 90°C. After the reaction was completed, the reaction solution was filtered and collected. The content of the generated 5-hydroxymethylfurfural was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with a commercially available 5-hydroxymethylfurfural standard sample for comparison, and the yields of about 44.5%, 41.7% and 42.8% were finally obtained, respectively.

[0066] The obtained dimethyl sulfoxide filtrate was washed with saturated brine several times, dried with anhydrous sodium sulfate, and then subjected to reduced pressure rotary evaporation and column chromatography separation and purification, and finally about 84.7 mg, 88.5 mg and 87.4 mg of 5-hydroxymethylfurfural products were obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the results of high performance liquid chromatography, indicating that the product purity was extremely high.

[0067] Application Example 5

[0068] 300 mg (15% by mass) of glucose and 300 mg (15% by mass) of aluminum nitrate nonahydrate were dissolved in 2 mL of dimethyl sulfoxide solvent, and stirred and heated for 36 hours under argon, nitrogen and air atmospheres at 90°C. After the reaction, the reaction solution was filtered and collected. The content of the generated 5-hydroxymethylfurfural was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with a commercially available 5-hydroxymethylfurfural standard sample for comparison, and finally the yields of about 99.8%, 99.7% and 99.5% were obtained respectively.

[0069] The obtained dimethyl sulfoxide filtrate was washed with saturated brine several times, dried with anhydrous sodium sulfate, and then subjected to reduced pressure rotary evaporation and separation and purification by column chromatography, and finally about 205 mg, 202.3 mg and 203.6 mg of 5-hydroxymethylfurfural products were obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the results of high performance liquid chromatography, indicating that the product purity was extremely high.

[0070] Application Example 6

[0071] 300 mg (15% by mass) of fructose and 300 mg (15% by mass) of aluminum nitrate nonahydrate were dissolved in 2 mL of dimethyl sulfoxide solvent, and stirred and heated for 36 hours under argon, nitrogen and air atmospheres at 90°C. After the reaction, the reaction solution was filtered and collected. The content of the generated 5-hydroxymethylfurfural was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with a commercially available 5-hydroxymethylfurfural standard sample for comparison, and finally the yields of about 99.8%, 99.7% and 99.5% were obtained respectively.

[0072] The obtained dimethyl sulfoxide filtrate was washed with saturated brine several times, dried with anhydrous sodium sulfate, and then subjected to reduced pressure rotary evaporation and separation and purification by column chromatography, and finally about 202.4 mg, 204 mg and 207.5 mg of 5-hydroxymethylfurfural products were obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the results of high performance liquid chromatography, indicating that the product purity was extremely high.

[0073] Application Example 7

[0074] 300 mg (15% by mass) of sucrose and 300 mg (15% by mass) of aluminum nitrate nonahydrate were dissolved in 2 mL of dimethyl sulfoxide solvent, and stirred and heated for 36 hours under argon, nitrogen and air atmospheres at 90°C. After the reaction was completed, the reaction solution was filtered and collected. The content of the generated 5-hydroxymethylfurfural was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with a commercially available 5-hydroxymethylfurfural standard sample for comparison, and finally yields of about 90%, 83% and 84.3% were obtained, respectively.

[0075] The obtained dimethyl sulfoxide filtrate was washed with saturated brine several times, dried with anhydrous sodium sulfate, and then subjected to reduced pressure rotary evaporation and separation and purification by column chromatography, and finally about 219 mg, 213 mg and 218.7 mg of 5-hydroxymethylfurfural products were obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the results of high performance liquid chromatography, indicating that the product purity was extremely high.

[0076] Application Example 8

[0077] 3g (15% by mass) glucose and 3g (15% by mass) aluminum nitrate nonahydrate were dissolved in 20mL of dimethyl sulfoxide solvent, and stirred and heated for 36 hours under argon, nitrogen and air atmospheres at 90°C. After the reaction, the reaction solution was filtered and collected. The content of the generated 5-hydroxymethylfurfural was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with a commercially available 5-hydroxymethylfurfural standard sample for comparison, and finally the yields of about 95%, 93% and 94.3% were obtained respectively.

[0078] The obtained dimethyl sulfoxide filtrate was washed with saturated brine several times, dried with anhydrous sodium sulfate, and then subjected to reduced pressure rotary evaporation and separation and purification by column chromatography, and finally about 2.07g, 1.96g and 2.05g of 5-hydroxymethylfurfural products were obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the results of high performance liquid chromatography, indicating that the product purity was extremely high.

[0079] Application Example 9

[0080] 30g (15% by mass) glucose and 30g (15% by mass) aluminum nitrate nonahydrate were dissolved in 200mL of dimethyl sulfoxide solvent, and stirred and heated for 48 hours under argon, nitrogen and air atmospheres at 90°C. After the reaction, the reaction solution was filtered and collected. The content of the generated 5-hydroxymethylfurfural was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with a commercially available 5-hydroxymethylfurfural standard sample for comparison, and finally the yields of about 98%, 96.8% and 95% were obtained respectively.

[0081] 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 separated and purified by column chromatography, and finally about 18.9g, 19.3g and 19.1g of 5-hydroxymethylfurfural products were obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which is consistent with the results of high performance liquid chromatography, indicating that the product purity is extremely high.

[0082] Application Example 10

[0083] 30g (15% by mass) fructose and 30g (15% by mass) aluminum nitrate nonahydrate were dissolved in 200mL of dimethyl sulfoxide solvent, and stirred and heated for 48 hours under argon, nitrogen and air atmospheres at 90°C. After the reaction, the reaction solution was filtered and collected. The content of the generated 5-hydroxymethylfurfural was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with a commercially available 5-hydroxymethylfurfural standard sample for comparison, and finally the yields of about 97%, 96.6% and 94.8% were obtained respectively.

[0084] 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 separated and purified by column chromatography, and finally about 20.7g, 20.4g and 20.3g of 5-hydroxymethylfurfural products were obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the results of high performance liquid chromatography, indicating that the product purity was extremely high.

[0085] Application Example 11

[0086] 30g (15% by mass) sucrose and 30g (15% by mass) aluminum nitrate nonahydrate were dissolved in 200mL dimethyl sulfoxide solvent, and stirred and heated for 48 hours under argon, nitrogen and air atmospheres at 90°C. After the reaction, the reaction solution was filtered and collected. The content of the generated 5-hydroxymethylfurfural was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with a commercially available 5-hydroxymethylfurfural standard sample for comparison, and finally yields of about 91.4%, 94.7% and 94.2% were obtained respectively.

[0087] 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 separated and purified by column chromatography, and finally about 21.5g, 21.4g and 20.7g of 5-hydroxymethylfurfural products were obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the results of high performance liquid chromatography, indicating that the product purity was extremely high.

[0088] Application Example 12

[0089] 300g (15% by mass) glucose and 300g (15% by mass) aluminum nitrate nonahydrate were dissolved in 2L of dimethyl sulfoxide solvent, and stirred and heated for 48 hours under argon, nitrogen and air atmospheres at 90°C. After the reaction, the reaction solution was filtered and collected. The content of the generated 5-hydroxymethylfurfural was determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR) analysis, combined with a commercially available 5-hydroxymethylfurfural standard sample for comparison, and finally the yields of about 97%, 94% and 95.3% were obtained respectively.

[0090] The obtained dimethyl sulfoxide filtrate was washed with saturated brine several times, dried with anhydrous sodium sulfate, and then subjected to reduced pressure rotary evaporation and separation and purification by column chromatography, and finally about 202.5g, 207.2g and 204.8g of 5-hydroxymethylfurfural products were obtained respectively. No obvious by-product peak was observed in the nuclear magnetic resonance spectrum, which was consistent with the results of high performance liquid chromatography, indicating that the product purity was extremely high.

[0091] Application Example 13

[0092] In this application example, the HMF obtained from application examples 1 to 12 is directly used to synthesize 2,5-furandicarboxylic acid (FDCA), and the synthesis route, reaction conditions and selection of solid catalysts are strictly referred to the existing prior art [1] to [8]. In this application example, an HMF solution containing 20% ​​glucose is used as a control group for simulating impurities. The following table shows the FDAC yields of commercially available HMF, HMF obtained in Example 5, and HMF containing 20% ​​glucose in different systems.

[0093]

[0094]

[0095] The existing technologies used in this application example are 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, GM Veith, L. Prati, ChemSusChem, 2013, 6, 609-612.

[0099] [4]A.Tirsoaga,M.El Fergani,N.Nuns,P.Simon,P.Granger,VIParvulescu,SMComan,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,LLLou,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 ClayScience, 2023, 235, 106872.

[0104] From the above results, it can be seen that since the preparation method adopted in the present disclosure can obtain high-purity HMF, when used in the synthesis of FDAC without further purification, the yield of FDAC can be significantly improved, and the yield is close to that of using commercially available HMF. However, the HMF control group containing 20% ​​glucose significantly inhibited the oxidation reaction of HMF due to the presence of glucose, resulting in an extremely low yield.

[0105] Application Example 14

[0106] This application example uses the same conditions as application example 8, and adds a certain amount of solid heterogeneous catalyst to the reaction system to explore the application scope of the reaction system disclosed in the present invention.

[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) in the prior art (refer to the prior art [1] to [8]).

[0108] Specifically, 3g (15% mass fraction) of glucose and 3g (15% mass fraction) of aluminum nitrate nonahydrate were dissolved in 20mL of dimethyl sulfoxide solvent, 1g of solid heterogeneous catalyst was added, and the reaction was stirred and heated under an argon atmosphere at 90°C for 36 hours. After the reaction was completed, the reaction solution was filtered and collected. The HMF yields under different solid heterogeneous catalyst additions were compared with commercially available 5-hydroxymethylfurfural standard samples by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy (NMR).

[0109] Prior Art No. Heterogeneous Catalysts 5-Hydroxymethylfurfural yield (%) [1] <![CDATA[Zirconia ZrO2]]> 96.3 [2] <![CDATA[Cerium dioxide CeO2]]> 67 [3] <![CDATA[Aluminum oxide Al2O3]]> 99.3 [4] Activated carbon 96 [5] <![CDATA[Silicon dioxide SiO2]]> 96.5 [6] <![CDATA[Titanium dioxide TiO2]]> 92 [7] <![CDATA[Iron oxide Fe2O3]]> 89.3 [8] <![CDATA[Tungsten Oxide WO3]]> 89.3

[0110] The prior art referenced in this application example is as follows:

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[0119] 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 disclosure can obtain a 5-hydroxymethylfurfural yield of more than 90%, wherein the yield of 5-hydroxymethylfurfural can reach 99.3% when combined with aluminum oxide. This result shows that the reaction method provided by the present disclosure is not limited to homogeneous catalysis, but is also suitable for being compatible with other heterogeneous catalytic systems to obtain high yields of 5-hydroxymethylfurfural, and has a wide range of applications.

[0120] The method provided by the present disclosure selectively synthesizes 5-hydroxymethylfurfural from sugars (such as glucose, fructose, sucrose, etc.) under low temperature conditions under the catalytic action of various aluminum ion salts. The reaction can be carried out in air or inert atmosphere, the reaction conditions are simple and mild, and the use of high temperature, high pressure and highly toxic chemical raw materials is avoided.

[0121] The yield of the obtained 5-hydroxymethylfurfural sample can reach 99.8%, and it has the same HPLC signal as the commercial standard sample of 5-hydroxymethylfurfural (reference Figure 1 to Figure 2 ), the infrared spectrum signal is the same as that of the commercial standard sample of 5-hydroxymethylfurfural (reference Figure 4 ), and no obvious by-product peaks were observed in the nuclear magnetic resonance spectrum of the 5-hydroxymethylfurfural sample (reference Figure 3 ), indicating that the obtained product is of extremely high purity.

[0122] The high selectivity and high yield of the reaction greatly simplify the separation of 5-hydroxymethylfurfural, which is beneficial to its subsequent reactions such as FDAC synthesis. It is a green, environmentally friendly, economical and efficient synthesis method with broad application prospects, suitable for industrial-scale production. In addition, the aluminum ion salt catalyst used is cheap and easy to obtain, and can be recycled and reused many 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.

[0123] The embodiments and application examples described above are merely illustrative descriptions of the present disclosure and are not intended to limit the scope of the present disclosure. Without departing from the design spirit of the present disclosure, various modifications and improvements made to the technical solutions of the present disclosure by ordinary technicians in this field should all fall within the protection scope determined by the present disclosure.

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Claims

1. A method for preparing 5-hydroxymethylfurfural by mild catalysis of aluminum ions, characterized in that: The following steps are involved: S1. dissolving a carbohydrate and an aluminum ion salt in a solvent; S2. The reaction is carried out at 80 to 120 ° C in a reaction atmosphere for 24 to 48 hours; S3. Filter to obtain a 5-hydroxymethylfurfural sample; 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 g to 1 g: 1 mL.

2. The method according to claim 1, characterized in that In step S2, the reaction temperature is 90°C.

3. The method according to claim 1, characterized in that In step S2, the reaction time is 36 hours.

4. The method according to claim 1, characterized in that: The mass volume ratio of the carbohydrate to the solvent is 0.01 g to 0.2 g: 1 mL.

5. The method according to claim 4, characterized in that The mass volume ratio of the carbohydrate to the solvent is 0.15 g:1 mL.

6. The method according to claim 1, characterized in that The carbohydrates include glucose, fructose or sucrose.

7. The method according to claim 1, characterized in that The aluminum ion salt includes aluminum nitrate, aluminum sulfate or aluminum chloride.

8. The method according to claim 1, characterized in that The reaction atmosphere is air atmosphere or inert gas atmosphere.

9. The method according to claim 1, characterized in that: The solvent includes dimethylformamide or dimethyl sulfoxide.

10. The method according to any one of claims 1 to 9, characterized in that: The reaction system also includes a solid heterogeneous catalyst, which includes zirconium oxide, cerium dioxide, aluminum oxide, activated carbon, silicon dioxide, titanium dioxide, iron oxide or tungsten oxide.

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