Method for cogeneration of 5-hydroxymethyl-furfural, acetylpropionic acid and formic acid by high temperature catalytic dehydration of glucose in formic acid

Abstract

The invention discloses a method for coproduction of 5-hydroxymethyl furfural, an acetylpropionic acid and a formic acid through high-temperature catalysis and dehydration of the formic acid of glucose. The method specifically comprises the following steps: firstly, establishment of a formic acid reaction system, namely the glucose is added into the formic acid solution, and the weight ratio of the glucose to the formic acid in the reaction system is 0.05-0.2 to 1; and the mixture is reacted for 2 to 6 hours in the presence of the catalyst at a temperature of between 120 and 220 DEG C which is higher than the boiling temperature of the formic acid, and the reaction system is single-phase reaction or biphase reaction; and secondly, separation of products after reaction by a fractionating tower device, namely graded separation of 5-HMF, LA and the formic acid. The method can convert the glucose into the products, namely the 5-HMF, the LA and the formic acid with high added values through effective acid catalysis and dehydration, and has high conversion of reactant during the reaction process and obvious economic benefit; and the 5-HMF, the LA and the formic acid can be directly taken as chemical products to be further converted, and are good raw materials for synthesizing other chemical products.

Description

technical field

[0001] The invention relates to the preparation of 5-hydroxymethylfurfural, levulinic acid and formic acid, in particular to a method for co-producing 5-hydroxymethylfurfural, levulinic acid and formic acid through high-temperature catalytic dehydration of glucose with formic acid. Background technique

[0002] 5-Hydroxymethylfurfural (5-HMF), levulinic acid (LA) and formic acid (FA) are important chemicals that belong to the "Platform Chemicals". In the nineteenth and early twentieth centuries, the organic chemical industry was based on coal chemistry, and many platform compounds were derived from coal. After the middle of the twentieth century, most of these compounds came from oil and natural gas. However, these mineral resources are non-renewable and cause serious environmental pollution during processing and utilization. Since the beginning of the 21st century, the traditional chemical industry has faced serious challenges to the sustainable developmen...

Examples

Embodiment 1

[0021] Glucose produced by the hydrolysis of agricultural stalks and wheatgrass with dilute sulfuric acid (hydrolysis conditions: 5% (weight) concentration of sulfuric acid, temperature 120° C., hydrolysis time 2 h) was used as a reactant. After the hydrolyzate was filtered through four layers of gauze for 4 times, it was concentrated and vacuum-dried to obtain glucose with a purity of 85% (mass), which was directly added to the formic acid reaction system.

[0022] In the formic acid reaction system, the weight ratio of glucose to formic acid is 0.05:1 (W / W, relative to the weight of formic acid added in the reaction system). The mass concentration of the formic acid solution used is 80%; the water content in the reaction system is 10% (V / V, relative to the total volume of the reaction solution); single-phase reaction, adding water-soluble organic solvent ethyl acetate, water and ethyl acetate The volume ratio of water and ethyl acetate to the volume ratio of formic acid is 1...

Embodiment 2

[0026]Bagasse sulfite pulp (purchased from Guangdong Jiangmen Ganhua Group Co., Ltd.) was hydrolyzed by cellulase to obtain glucose. Cellulase is a product of Ningxia Haosheng Company, containing filter paper enzyme activity (FPA) 210U / g, cellobiohydrolase activity 653U / g, endoglucanase activity (CMCase) 338U / g, β-glucoside Enzyme activity (β-Glase) is 500U / g. The pH value of enzymatic hydrolysis is 3.5; the enzymatic hydrolysis temperature is 45°C, and the reaction time is 48h; the buffer solution is sodium hydrogen phosphate-disodium hydrogen phosphate, the concentration is 0.05mol / L. The cellulase hydrolysis rate was 91.3%, and the glucose yield was 85.7%. The obtained glucose solution was filtered through four layers of gauze, concentrated and then vacuum-dried to obtain glucose with a purity of 70% (mass), which was directly added to the formic acid reaction system.

[0027] In the formic acid reaction system, the weight ratio of glucose to formic acid is 0.2:1 (W / W, rel...

Embodiment 3

[0031] Rice straw is cooked by alkaline method (cooking condition: 8% (weight) NaOH dosage, cooking at 135° C. for 1.5 h), and the resulting pulp is washed and hydrolyzed by cellulase to obtain glucose. Cellulase is a product of Novozymes, containing filter paper enzyme activity (FPA) 245U / g, cellobiohydrolase activity 732U / g, endoglucanase activity (CMCase) 3653 / g, β-glucoside The enzyme activity (β-Glase) is 519U / g. The pH value of enzymatic hydrolysis is 3.7; the enzymatic hydrolysis temperature is 47°C, and the reaction time is 42h; the buffer solution is acetic acid-sodium acetate, the concentration is 0.03mol / L. The cellulase hydrolysis rate was 95.6%, and the glucose yield was 81.3%. The obtained glucose solution was filtered through four layers of gauze, concentrated and vacuum-dried to obtain glucose with a purity of 72.8% (mass), which was directly added to the formic acid reaction system.

[0032] In the formic acid reaction system, glucose is added to a formic aci...

technical field

[0001] The invention relates to the preparation of 5-hydroxymethylfurfural, levulinic acid and formic acid, in particular to a method for co-producing 5-hydroxymethylfurfural, levulinic acid and formic acid through high-temperature catalytic dehydration of glucose with formic acid. Background technique

[0002] 5-Hydroxymethylfurfural (5-HMF), levulinic acid (LA) and formic acid (FA) are important chemicals that belong to the "Platform Chemicals". In the nineteenth and early twentieth centuries, the organic chemical industry was based on coal chemistry, and many platform compounds were derived from coal. After the middle of the twentieth century, most of these compounds came from oil and natural gas. However, these mineral resources are non-renewable and cause serious environmental pollution during processing and utilization. Since the beginning of the 21st century, the traditional chemical industry has faced serious challenges to the sustainable developmen...

Examples

Embodiment 1

[0021] Glucose produced by the hydrolysis of agricultural stalks and wheatgrass with dilute sulfuric acid (hydrolysis conditions: 5% (weight) concentration of sulfuric acid, temperature 120° C., hydrolysis time 2 h) was used as a reactant. After the hydrolyzate was filtered through four layers of gauze for 4 times, it was concentrated and vacuum-dried to obtain glucose with a purity of 85% (mass), which was directly added to the formic acid reaction system.

[0022] In the formic acid reaction system, the weight ratio of glucose to formic acid is 0.05:1 (W / W, relative to the weight of formic acid added in the reaction system). The mass concentration of the formic acid solution used is 80%; the water content in the reaction system is 10% (V / V, relative to the total volume of the reaction solution); single-phase reaction, adding water-soluble organic solvent ethyl acetate, water and ethyl acetate The volume ratio of water and ethyl acetate to the volume ratio of formic acid is 1...

Embodiment 2

[0026]Bagasse sulfite pulp (purchased from Guangdong Jiangmen Ganhua Group Co., Ltd.) was hydrolyzed by cellulase to obtain glucose. Cellulase is a product of Ningxia Haosheng Company, containing filter paper enzyme activity (FPA) 210U / g, cellobiohydrolase activity 653U / g, endoglucanase activity (CMCase) 338U / g, β-glucoside Enzyme activity (β-Glase) is 500U / g. The pH value of enzymatic hydrolysis is 3.5; the enzymatic hydrolysis temperature is 45°C, and the reaction time is 48h; the buffer solution is sodium hydrogen phosphate-disodium hydrogen phosphate, the concentration is 0.05mol / L. The cellulase hydrolysis rate was 91.3%, and the glucose yield was 85.7%. The obtained glucose solution was filtered through four layers of gauze, concentrated and then vacuum-dried to obtain glucose with a purity of 70% (mass), which was directly added to the formic acid reaction system.

[0027] In the formic acid reaction system, the weight ratio of glucose to formic acid is 0.2:1 (W / W, rel...

Embodiment 3

[0031] Rice straw is cooked by alkaline method (cooking condition: 8% (weight) NaOH dosage, cooking at 135° C. for 1.5 h), and the resulting pulp is washed and hydrolyzed by cellulase to obtain glucose. Cellulase is a product of Novozymes, containing filter paper enzyme activity (FPA) 245U / g, cellobiohydrolase activity 732U / g, endoglucanase activity (CMCase) 3653 / g, β-glucoside The enzyme activity (β-Glase) is 519U / g. The pH value of enzymatic hydrolysis is 3.7; the enzymatic hydrolysis temperature is 47°C, and the reaction time is 42h; the buffer solution is acetic acid-sodium acetate, the concentration is 0.03mol / L. The cellulase hydrolysis rate was 95.6%, and the glucose yield was 81.3%. The obtained glucose solution was filtered through four layers of gauze, concentrated and vacuum-dried to obtain glucose with a purity of 72.8% (mass), which was directly added to the formic acid reaction system.

[0032] In the formic acid reaction system, glucose is added to a formic aci...