Deep eutectic solvent and method for synthesizing 5-hydroxymethylfurfural by catalyzing biomass through deep eutectic solvent

Abstract

The invention discloses a deep-eutectic solvent and a method for catalyzing biomass to synthesize 5-hydroxymethylfurfural by the deep-eutectic solvent, the deep-eutectic solvent is composed of choline chloride, polyhydric alcohol and lignin-derived phenolic acid, is used as a reaction catalyst and a solvent, can efficiently catalyze biomass to synthesize 5-hydroxymethylfurfural under mild conditions, and is high in product yield and high in product purity. Wide application prospects are realized; the raw materials for preparing the eutectic solvent are cheap and easy to obtain, wide in selection range and suitable for industrial production.

Description

Technical field:

[0001] The invention relates to the field of fine chemicals, and in particular to a low eutectic solvent and a method for catalyzing biomass synthesis of 5-hydroxymethylfurfural. Background technology:

[0002] Biomass carbohydrates, as a renewable carbon source, are a promising alternative to fossil energy and one of the raw materials for the production of bio-based chemicals. Lignocellulosic biomass is abundant in reserves, has multiple sources, is widely distributed, has a high carbohydrate content and is easy to extract, making it a biomass resource with great potential. 5-Hydroxymethylfurfural (5-HMF) is one of the key intermediate chemicals derived from carbohydrate dehydration. It is a widely used platform compound that can be used to synthesize a variety of bio-based chemicals, pharmaceutical intermediates and degradable materials. In the process of synthesizing 5-HMF from biomass, low eutectic solvents are widely used, especially those containing choline chloride as a hydrogen bond acceptor. Choline chloride-based binary low eutectic solvents have low activity and are difficult to efficiently catalyze the conversion of biomass into furan chemicals, limiting the efficiency of synthesizing 5-HMF from sugar biomass. Therefore, the development of a ternary renewable and efficient low eutectic solvent system to improve the efficiency of biomass conversion into furan chemicals will help promote the industrial application of homogeneous systems in the conversion of biomass into high added energy chemistry. Summary of the invention:

[0003] The invention provides a deep eutectic solvent and a method for catalyzing the synthesis of 5-hydroxymethylfurfural from biomass using the same. The deep eutectic solvent serves as both a catalyst and a solvent and can efficiently catalyze the synthesis of 5-hydroxymethylfurfural from biomass under mild conditions, thereby solving the problems of low activity of binary deep eutectic solvents and low efficiency of synthesizing 5-hydroxymethylfurfural from sugar biomass in the prior art.

[0004] The present invention is achieved through the following technical solutions:

[0005] A deep eutectic solvent consisting of choline chloride, polyols, and lignin-derived phenolic acids.

[0006] Preferably, the polyol includes one or more of ethylene glycol, glycerol, butanediol, pentanediol, and hexanetriol, but is not limited thereto.

[0007] Preferably, the lignin-derived phenolic acid includes one or more of vanillic acid, ferulic acid, syringic acid, and p-hydroxyphenylpropionic acid, but is not limited thereto.

[0008] Preferably, the molar ratio of choline chloride, polyol and lignin-derived phenolic acid is 1:(0.5-2):(0.05-2).

[0009] In some embodiments, the molar ratio of choline chloride, polyol and lignin-derived phenolic acid is any one of 1:2:0.05, 1:2:0.1, 1:2:0.25, 1:2:0.5, 1:2:1, 1:2:2, 1:0.5:0.1, and 1:1:0.1.

[0010] The preparation method of the low eutectic solvent is as follows: choline chloride, polyol and lignin-derived phenolic acid are mixed, and then heated to 80° C.-95° C. to dissolve and form a low eutectic solvent.

[0011] The present invention also protects a method for catalyzing biomass to synthesize 5-hydroxymethylfurfural, comprising the following steps: adding biomass to the above-mentioned low eutectic solvent, reacting at 100-150° C. for 1-180 minutes, and extracting and separating with an organic solvent to obtain 5-hydroxymethylfurfural after the reaction is completed.

[0012] Preferably, the reaction temperature is 100-130° C., and the reaction time is 1-120 min.

[0013] Preferably, after extraction and separation, high performance liquid chromatography is used to analyze the yield of 5-hydroxymethylfurfural, and the low eutectic solvent after separation of the product is recycled.

[0014] Preferably, the mass ratio of the biomass to the low eutectic solvent is (0.01-0.3):1.

[0015] In some embodiments, the mass ratio of the biomass to the deep eutectic solvent is any one of 0.01:1, 0.02:1, 0.05:1, 0.1:1, 0.2:1, and 0.3:1.

[0016] Preferably, the biomass is selected from cellulose derived monosaccharides or cellulose derived disaccharides.

[0017] More preferably, the cellulose-derived monosaccharide includes one or both of glucose and fructose, and the cellulose-derived disaccharide includes one or both of sucrose and cellobiose, but is not limited thereto.

[0018] Preferably, the organic solvent includes one or more of ethyl acetate, dichloromethane, and acetone, but is not limited thereto.

[0019] The beneficial effects of the present invention are as follows:

[0020] 1. The low eutectic solvent of the present invention serves as both a catalyst and a solvent, can efficiently catalyze the synthesis of 5-hydroxymethylfurfural from biomass, has mild reaction conditions, and has a high yield of the obtained target product, and has broad application prospects.

[0021] 2. The raw materials for preparing the low eutectic solvent of the present invention are cheap and readily available, have a wide selection range, and are suitable for industrial production. Description of the drawings:

[0022] Figure 1 It is a process principle diagram of synthesizing 5-hydroxymethylfurfural from fructose catalyzed by a low eutectic solvent in an embodiment of the present invention. Specific implementation method:

[0023] The present invention will be further described in detail with specific examples below, but the protection scope of the present invention is not limited to these specific examples. Unless otherwise specified, the raw materials used in the following examples can be obtained from the market or made by reference, and the production equipment, test equipment and test methods used can also be common equipment or methods in the art.

[0024] Example 1: Choline chloride, butanediol and p-hydroxyphenylpropionic acid with a total mass of 10 g are mixed and heated to 80° C. until they are dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and p-hydroxyphenylpropionic acid is 1:2:0.1; then 0.5 g of fructose is added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent is 0.05:1, and the mixture is reacted at 120° C. for 20 min. After the reaction is completed, the product is separated by extraction with ethyl acetate, and the mass of 5-hydroxymethylfurfural is analyzed and calculated by high performance liquid chromatography to be 341.2 mg, with a molar yield of 97.5%, and the low eutectic solvent after the separation of the product is recycled.

[0025] Comparative Example 1:

[0026] Refer to Example 1, except that the low eutectic solvent consists of choline chloride and butanediol, and does not contain p-hydroxyphenylpropionic acid, and the other steps are the same as Example 1.

[0027] After the reaction, the product was extracted and separated by ethyl acetate. The yield of 5-hydroxymethylfurfural was analyzed and calculated by high performance liquid chromatography to be 54.2%. The low eutectic solvent after the product was separated was recycled.

[0028] Comparative Example 2:

[0029] Refer to Example 1, except that p-hydroxyphenylpropionic acid is replaced by formic acid, the low eutectic solvent consists of choline chloride, butanediol and formic acid, and the other steps are the same as Example 1.

[0030] After the reaction, the product was separated by extraction with ethyl acetate. The mass of 5-hydroxymethylfurfural was calculated by high performance liquid chromatography to be 261.1 mg, and the molar yield was 74.6%. The low eutectic solvent after the product was separated was recycled.

[0031] Example 2: Choline chloride, butanediol and p-hydroxyphenylpropionic acid with a total mass of 10 g are mixed and heated to 80° C. until they are dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and p-hydroxyphenylpropionic acid is 1:2:0.05; then 0.1 g of fructose is added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent is 0.01:1, and the reaction is carried out at 120° C. for 30 minutes. After the reaction is completed, the product is separated by extraction with ethyl acetate for separation and purification, and the product is analyzed by high performance liquid chromatography, and the mass of 5-hydroxymethylfurfural is calculated to be 66.4 mg, and the molar yield is 94.8%, and the low eutectic solvent after the separation product is recycled.

[0032] Example 3: 10 g of choline chloride, butanediol and p-hydroxyphenylpropionic acid were mixed and heated to 80°C until they dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and p-hydroxyphenylpropionic acid was 1:2:0.25; then 0.5 g of fructose was added to the low eutectic solvent, the mass ratio of fructose to the low eutectic solvent was 0.05:1, the reaction temperature was 120°C, the time was 20 min, and after the reaction was completed, the product was separated by extraction with ethyl acetate for separation and purification, and the product was analyzed by high performance liquid chromatography, the mass of 5-hydroxymethylfurfural was 320.3 mg, the molar yield was 91.5%, and the low eutectic solvent after the separation of the product was recycled.

[0033] Example 4: Choline chloride, butanediol and p-hydroxyphenylpropionic acid with a total mass of 10 g are mixed and heated to 80° C. until they are dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and p-hydroxyphenylpropionic acid is 1:2:0.5; then 0.2 g of fructose is added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent is 0.02:1, and the mixture is reacted at 100° C. for 10 min. After the reaction is completed, the product is separated by extraction with ethyl acetate for separation and purification, and the product is analyzed by high performance liquid chromatography, and the mass of 5-hydroxymethylfurfural is calculated to be 126.1 mg, and the molar yield is 90.1%, and the low eutectic solvent after the separation product is recycled.

[0034] Example 5: Choline chloride, butanediol and p-hydroxyphenylpropionic acid with a total mass of 10 g are mixed and heated to 80°C until they are dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and p-hydroxyphenylpropionic acid is 1:2:1; then 0.2 g of fructose is added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent is 0.02:1, and the reaction is carried out at 110°C for 20 minutes. After the reaction is completed, the product is separated by extraction with ethyl acetate for separation and purification, and the product is analyzed by high performance liquid chromatography, and the mass of 5-hydroxymethylfurfural is calculated to be 119.3 mg, and the molar yield is 85.2%, and the low eutectic solvent after the separation product is recycled.

[0035] Example 6: 10 g of choline chloride, butanediol and p-hydroxyphenylpropionic acid were mixed and heated to 80°C until they dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and p-hydroxyphenylpropionic acid was 1:2:2; then 1 g of fructose was added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent was 0.1:1, and the mixture was reacted at 120°C for 40 min. After the reaction was completed, the product was separated by extraction with ethyl acetate for separation and purification, and the product was analyzed by high performance liquid chromatography. The mass of 5-hydroxymethylfurfural was calculated to be 575.4 mg, and the molar yield was 82.2%, and the low eutectic solvent after the separation of the product was recycled.

[0036] Example 7: 10 g of choline chloride, butanediol and p-hydroxyphenylpropionic acid were mixed and heated to 90°C until they dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and p-hydroxyphenylpropionic acid was 1:2:2; then 2 g of fructose was added to the low eutectic solvent, the mass ratio of fructose to the low eutectic solvent was 0.2:1, and the mixture was reacted at 130°C for 60 min. After the reaction was completed, the product was separated by extraction with ethyl acetate for separation and purification, and the product was analyzed by high performance liquid chromatography. The mass of 5-hydroxymethylfurfural was calculated to be 1099 mg, and the molar yield was 78.5%, and the low eutectic solvent after the separation of the product was recycled.

[0037] Example 8: 10 g of choline chloride, butanediol and p-hydroxyphenylpropionic acid were mixed and heated to 80°C until they dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and p-hydroxyphenylpropionic acid was 1:2:1; then 0.5 g of fructose was added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent was 0.05:1. The mixture was reacted at 130°C for 120 min. After the reaction was completed, the product was separated by extraction with ethyl acetate for separation and purification. The product was analyzed by high performance liquid chromatography, and the mass of 5-hydroxymethylfurfural was calculated to be 264.2 mg, with a yield of 75.5%. The low eutectic solvent after the separation of the product was recycled.

[0038] Example 9: 10 g of choline chloride, butanediol and p-hydroxyphenylpropionic acid were mixed and heated to 80°C until they dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and p-hydroxyphenylpropionic acid was 1:2:1; then 0.5 g of fructose was added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent was 0.05:1, and the mixture was reacted at 140°C for 30 min. After the reaction was completed, the product was separated by extraction with ethyl acetate for separation and purification, and the product was analyzed by high performance liquid chromatography. The mass of 5-hydroxymethylfurfural was calculated to be 211.8 mg, and the molar yield was 60.5%, and the low eutectic solvent after the separation of the product was recycled.

[0039] Example 10: 10 g of choline chloride, butanediol and p-hydroxyphenylpropionic acid were mixed and heated to 95°C until they dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and p-hydroxyphenylpropionic acid was 1:2:1; then 0.1 g of glucose was added to the low eutectic solvent, the mass ratio of glucose to the low eutectic solvent was 0.01:1, and the mixture was reacted at 130°C for 120 min. After the reaction was completed, the product was separated by extraction with ethyl acetate for separation and purification. The product was analyzed by high performance liquid chromatography, and the mass of 5-hydroxymethylfurfural was calculated to be 176.8 mg, with a molar yield of 50.6%, and the low eutectic solvent after the separation of the product was recycled.

[0040] Example 11: 10 g of choline chloride, butanediol and p-hydroxyphenylpropionic acid were mixed and heated to 80°C until they dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and p-hydroxyphenylpropionic acid was 1:2:1; then 0.1 g of sucrose was added to the low eutectic solvent, and the mass ratio of sucrose to the low eutectic solvent was 0.01:1, and the mixture was reacted at 140°C for 180 min. After the reaction was completed, the product was separated by extraction with ethyl acetate for separation and purification, and the product was analyzed by high performance liquid chromatography, and the mass of 5-hydroxymethylfurfural was calculated to be 23.0 mg, with a molar yield of 62.5%, and the low eutectic solvent after the separation of the product was recycled.

[0041] Example 12: 10 g of choline chloride, butanediol and p-hydroxyphenylpropionic acid were mixed and heated to 80°C until they dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and p-hydroxyphenylpropionic acid was 1:2:1; then 0.2 g of cellobiose was added to the low eutectic solvent, and the mass ratio of cellobiose to the low eutectic solvent was 0.02:1. The mixture was reacted at 150°C for 180 min. After the reaction was completed, the product was separated by extraction with ethyl acetate for separation and purification. The product was analyzed by high performance liquid chromatography, and the mass of 5-hydroxymethylfurfural was calculated to be 20.8 mg, with a molar yield of 56.7%. The low eutectic solvent after the separation of the product was recycled.

[0042] Example 13: Choline chloride, ethylene glycol and p-hydroxyphenylpropionic acid with a total mass of 10 g are mixed and heated to 80°C until they are dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, ethylene glycol and p-hydroxyphenylpropionic acid is 1:2:0.1; then 0.2 g of fructose is added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent is 0.02:1, and the reaction is carried out at 120°C for 20 minutes. After the reaction is completed, the product is separated by extraction with ethyl acetate for separation and purification, and the product is analyzed by high performance liquid chromatography, and the mass of 5-hydroxymethylfurfural is calculated to be 127.8 mg, and the molar yield is 91.3%, and the low eutectic solvent after the separation product is recycled.

[0043] Example 14: 10 g of choline chloride, pentanediol and p-hydroxyphenylpropionic acid were mixed and heated to 80°C until they dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, pentanediol and p-hydroxyphenylpropionic acid was 1:2:0.5; then 0.2 g of fructose was added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent was 0.02:1, and the mixture was reacted at 120°C for 60 min. After the reaction was completed, the product was separated by extraction with ethyl acetate for separation and purification, and the product was analyzed by high performance liquid chromatography, and the mass of 5-hydroxymethylfurfural was calculated to be 115.6 mg, with a molar yield of 82.6%, and the low eutectic solvent after the separation of the product was recycled.

[0044] Example 15: 10 g of choline chloride, hexanetriol and p-hydroxyphenylpropionic acid were mixed and heated to 80°C until they dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, hexanetriol and p-hydroxyphenylpropionic acid was 1:2:0.5; then 0.2 g of fructose was added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent was 0.02:1, and the mixture was reacted at 130°C for 30 min. After the reaction was completed, the product was separated by extraction with ethyl acetate for separation and purification, and the product was analyzed by high performance liquid chromatography, and the mass of 5-hydroxymethylfurfural was calculated to be 112.8 mg, with a molar yield of 80.2%, and the low eutectic solvent after the separation of the product was recycled.

[0045] Example 16: 10 g of choline chloride, butanediol and vanillic acid were mixed and heated to 80°C until they dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and vanillic acid was 1:2:0.1; then 0.1 g of fructose was added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent was 0.01:1. The mixture was reacted at 120°C for 30 min. After the reaction was completed, the product was separated by extraction with ethyl acetate for separation and purification. The product was analyzed by high performance liquid chromatography, and the mass of 5-hydroxymethylfurfural was calculated to be 58.5 mg, with a molar yield of 83.5%. The low eutectic solvent after the separation of the product was recycled.

[0046] Example 17: 10 g of choline chloride, ethylene glycol and ferulic acid were mixed and heated to 80°C until they dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, ethylene glycol and ferulic acid was 1:2:0.1; then 0.1 g of fructose was added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent was 0.01:1, and the mixture was reacted at 120°C for 30 min. After the reaction was completed, the product was separated by extraction with ethyl acetate for separation and purification, and the product was analyzed by high performance liquid chromatography. The mass of 5-hydroxymethylfurfural was calculated to be 56.1 mg, and the molar yield was 80.1%, and the low eutectic solvent after the separation of the product was recycled.

[0047] Example 18: 10 g of choline chloride, glycerol and syringic acid were mixed and heated to 80°C until they dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, glycerol and syringic acid was 1:2:0.5; then 0.2 g of fructose was added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent was 0.02:1, and the mixture was reacted at 130°C for 40 min. After the reaction was completed, the product was separated by extraction with dichloromethane for separation and purification, and the product was analyzed by high performance liquid chromatography, and the mass of 5-hydroxymethylfurfural was calculated to be 105.6 mg, with a molar yield of 75.4%, and the low eutectic solvent after the separation of the product was recycled.

[0048] Example 19: Choline chloride, butanediol and p-hydroxyphenylpropionic acid with a total mass of 10 g are mixed and heated to 80°C until they are dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and p-hydroxyphenylpropionic acid is 1:2:0.5; then 0.5 g of fructose is added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent is 0.05:1, and the reaction is carried out at 120°C for 30 minutes. After the reaction is completed, the product is separated by acetone extraction and purified, and the product is analyzed by high performance liquid chromatography, and the mass of 5-hydroxymethylfurfural is calculated to be 267.4 mg, and the molar yield is 76.5%, and the low eutectic solvent after the separation product is recycled.

[0049] Example 20: 10 g of choline chloride, butanediol and p-hydroxyphenylpropionic acid were mixed and heated to 80°C until they dissolved to form a low eutectic solvent, wherein the molar ratio of choline chloride, butanediol and p-hydroxyphenylpropionic acid was 1:1:0.5; then 0.5 g of fructose was added to the low eutectic solvent, and the mass ratio of fructose to the low eutectic solvent was 0.05:1, and the mixture was reacted at 120°C for 30 min. After the reaction was completed, the product was separated and purified by acetone extraction, and the product was analyzed by high performance liquid chromatography. The mass of 5-hydroxymethylfurfural was calculated to be 309.0 mg, and the molar yield was 88.3%, and the low eutectic solvent after the separation of the product was recycled.

Claims

1. A deep eutectic solvent, characterized in that: It is composed of choline chloride, polyols and lignin-derived phenolic acids.

2. The deep eutectic solvent according to claim 1, characterized in that The polyol includes one or more of ethylene glycol, propylene glycol, butylene glycol, pentanediol and hexanetriol.

3. The deep eutectic solvent according to claim 1, characterized in that The lignin-derived phenolic acid includes one or more of vanillic acid, ferulic acid, syringic acid, and p-hydroxyphenylpropionic acid.

4. The deep eutectic solvent according to claim 1, 2 or 3, characterized in that The molar ratio of the choline chloride, the polyol and the lignin-derived phenolic acid is 1:(0.5-2):(0.05-2).

5. The method for preparing the deep eutectic solvent according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: mixing choline chloride, polyol and lignin-derived phenolic acid, and then heating to 80-95° C. to dissolve and form a low eutectic solvent.

6. A method for catalyzing biomass to synthesize 5-hydroxymethylfurfural, characterized in that: The following steps are involved: Add biomass to the low eutectic solvent according to claim 1, 2 or 3, react at 100-150° C. for 1-180 min, and extract and separate 5-hydroxymethylfurfural with an organic solvent after the reaction is completed.

7. The method according to claim 6, characterized in that The reaction temperature is 100-130° C., the reaction time is 1-120 min, and the mass ratio of the biomass to the low eutectic solvent is (0.01-0.3):

1.

8. The method according to claim 6 or 7, characterized in that: The biomass is selected from cellulose derived monosaccharides or cellulose derived disaccharides.

9. The method according to claim 8, characterized in that The cellulose-derived monosaccharide includes one or both of glucose and fructose, and the cellulose-derived disaccharide includes one or both of sucrose and cellobiose.

10. The method according to claim 6 or 7, characterized in that: The organic solvent includes one or more of ethyl acetate, dichloromethane and acetone.

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