CN112574143A - Method for preparing 5-hydroxymethylfurfural from waste cotton fabrics - Google Patents
Method for preparing 5-hydroxymethylfurfural from waste cotton fabrics Download PDFInfo
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Abstract
The invention discloses a method for preparing 5-hydroxymethylfurfural by utilizing waste cotton fabrics, which comprises the steps of mixing and heating anhydrous choline chloride and p-toluenesulfonic acid to obtain a choline eutectic solvent, adding the waste cotton fabrics, heating for degradation, and extracting 5-hydroxymethylfurfural from degradation products by using an organic solvent. The invention provides a method for directly degrading cellulose with high polymerization degree to obtain 5-hydroxymethylfurfural without adding any catalyst and recovering regenerated cellulose fiber powder, does not generate new environmental problems while utilizing waste cotton fabrics in a high-value manner, and lays a foundation for degrading high value-added chemicals by cellulose.
Description
Technical Field
The invention belongs to the technical field of recycling of waste cotton fabrics, and relates to a method for preparing valuable substances by degrading waste cotton fabrics.
Background
With the rapid development of economy and the continuous improvement of the living standard of people, the waste textiles are in a trend of rising year by year. The total storage capacity of waste textiles in 2020 of China is estimated to be nearly 2 hundred million tons, but the comprehensive utilization rate is less than 10 percent, and the burying and incineration treatment after the waste textiles cause serious environmental pollution and resource waste. Meanwhile, the cotton yield is reduced year by year, which causes a shortage of resources of textile raw materials. Therefore, comprehensive utilization of waste cotton textiles is well made, raw material gaps in the cotton textile industry of China can be effectively made up, and environmental pollution and resource waste can be reduced.
The method is a very effective resource utilization means by degrading waste cotton textiles to produce fuels and prepare high-value chemicals.
Wherein, the cellulose content in the waste cotton fabric is extremely high and can reach more than 90 percent. However, cellulose is a linear polymer, connected by hydrogen bonds and intramolecular van der waals forces, forming a complex degradation-resistant hydrogen bond network structure, and thus is difficult to be degraded by common organic solvents.
Cellulose can be used for the production of sugars (such as glucose and fructose) and can also be converted, directly or indirectly, into other important chemical substances, in particular 5-hydroxymethylfurfural (5-HMF).
5-hydroxymethylfurfural is considered an important platform compound, and many of its derivatives can be used as precursors and useful chemicals for biofuels. Therefore, the method for synthesizing the 5-HMF by utilizing the waste cellulose fiber materials such as the waste cotton fabrics and the like in an environment-friendly way is an effective method for realizing high-value utilization of the waste textiles, and has important theoretical significance and practical value.
Degradation is a key step in the efficient use of cellulose. In the degradation conversion process, the solvent system plays a crucial role in improving the yield of degradation products. At present, a solvent system for preparing 5-hydroxymethylfurfural by degrading cellulose mainly comprises water, a single organic solvent, an ionic liquid system, a mixed solvent system and a eutectic solvent system.
When a single organic solvent, an ionic liquid system or a mixed solvent system is used for preparing 5-hydroxymethylfurfural by conversion, various catalysts such as acid, alkali, metal halide and the like are required to be added, so that serious environmental pollution and equipment corrosion are caused, and the ionic liquid usually has strong toxicity and is difficult to realize industrialization.
Although the method for preparing 5-hydroxymethylfurfural by using water as a solvent through conversion is a green way, the requirements of high-temperature and high-pressure reaction conditions on equipment are very high, and meanwhile, the 5-hydroxymethylfurfural is easily converted into byproducts such as levulinic acid and the like in water, so that the yield is reduced.
With the development of sustainable development concepts and the increasing demand for the use of green solvents for cellulose degradation, researchers have turned their eyes to eutectic solvents (DESs).
The DESS is an ionic liquid which is formed by combining a hydrogen bond acceptor and a hydrogen bond donor, has a melting point which is obviously lower than the melting point of each component pure substance, and is in a liquid state at normal temperature. Abbott et al first discovered that a solution of choline chloride and urea was liquid at room temperature. DESs have the excellent characteristics of ionic liquids, as well as good chemical and thermal stability, with little vapor pressure. In addition, compared with the ionic liquid, the DESs have the advantages of low price, wide sources, simple preparation, biodegradability, cyclic utilization, low toxicity or no toxicity, and can realize industrial large-scale production.
The unique structure of choline eutectic solvents has a potential impact on the dissolution of cellulose. However, the choline eutectic solvent reported in the prior literature has high viscosity, generally more than 2000mPa · s, which is not only unfavorable for contacting reactants, but also slow in mass transfer and low in reaction efficiency.
Disclosure of Invention
The invention aims to provide a method for preparing 5-hydroxymethylfurfural by utilizing waste cotton fabrics, which degrades the waste cotton fabrics by adopting a novel choline eutectic solvent so as to not generate new environmental problems while utilizing the waste cotton fabrics at a high value.
The method for preparing 5-hydroxymethylfurfural by using waste cotton fabrics is characterized in that the waste cotton fabrics are placed in a choline eutectic solvent and are heated for degradation, and 5-hydroxymethylfurfural in degradation products is extracted by an organic solvent.
The choline eutectic solvent is colorless transparent liquid obtained by mixing and heating anhydrous choline chloride serving as a hydrogen bond acceptor material and p-toluenesulfonic acid serving as a hydrogen bond donor material.
Furthermore, in the choline eutectic solvent, the molar ratio of anhydrous choline chloride to p-toluenesulfonic acid is 1: 1-2.
Wherein, when the choline eutectic solvent is prepared, the mixing and heating temperature is preferably not more than 60 ℃.
Specifically, the waste cotton fabric is added into a choline eutectic solvent, heated to 100-140 ℃ and reacted for 90-120 min, and a degradation product 5-hydroxymethylfurfural is obtained under the condition that new environmental problems are not generated.
Furthermore, the addition amount of the waste cotton fabric is 5-10 wt% of the mass of the choline eutectic solvent.
The organic solvent used for extracting the 5-hydroxymethylfurfural from the degradation products is various conventional organic solvents with good solubility on the 5-hydroxymethylfurfural, and comprises but is not limited to any one of ethyl acetate, methyl isobutyl ketone, n-hexane or petroleum ether and the like.
Further, the present invention preferably employs ethyl acetate as an organic solvent for extraction.
Furthermore, the sources of the waste cotton fabrics of the invention include but are not limited to waste materials such as cotton fabric leftover materials, waste cotton clothes, waste cotton quilt covers and the like in clothing factories.
Furthermore, the waste cotton fabrics in the method need to be physically pretreated before use, and the method comprises the steps of crushing the waste cotton fabrics, sequentially carrying out alkali liquor treatment and hydrogen peroxide treatment, washing and drying.
Specifically, the waste cotton fabrics are crushed into fragments of less than 0.5 cm.
The alkali liquor treatment is to add broken waste cotton fabrics into a sodium hydroxide solution for heating and soaking treatment, and the hydrogen peroxide treatment is to remove residual colors in the fabrics.
The invention provides a method for directly degrading cellulose with high polymerization degree to obtain 5-hydroxymethylfurfural without adding any catalyst and recovering regenerated cellulose fiber powder, aiming at the problems that the existing catalyst system using strong acid, strong base, metal halide and the like is used for treating waste cotton fabric, so that the equipment is seriously corroded, a large amount of waste acid and waste alkali solution harmful to the environment is generated, and the like, and lays a foundation for degrading high value-added chemicals by cellulose.
According to the method for preparing 5-hydroxymethylfurfural from waste cotton fabrics, the viscosity of the used choline eutectic solvent is below 450mPa & s and is far lower than that of other common choline eutectic solvents, so that the mass transfer efficiency of the solvent can be improved, the dynamic feasibility of cellulose degradation reaction in the waste cotton fabrics is ensured, and the degradation efficiency of the waste cotton fabrics is improved.
In addition, the choline eutectic solvent used in the invention has two acid sites, one acid site is arranged on the sulfonic chloride, and the other acid site is arranged on the protonic acid ligand, so that the acidity of the eutectic solvent is greatly enhanced; meanwhile, the acidity coefficient pKa of p-toluenesulfonic acid is =1.7, which is much smaller than that of other common organic acids, pKa (formic acid) =3.77, pKa (acetic acid) =4.74, pKa (malonic acid) =4.74, pKa (succinic acid) =4.87, pKa1(oxalic acid) =1.25 and pKa2(oxalic acid) =3.81, which also indicates that choline-based eutectic solvents having sulfonic acid groups are very beneficial for degradation processes of highly crystalline cellulose requiring a strongly acidic environment.
The invention utilizes the waste cotton fabrics as the raw material, realizes high-value utilization of the waste textiles without generating new environmental problems, changes waste into valuable, has good economic, environmental and social benefits, and meets the requirements of sustainable development strategy.
The method has mild preparation conditions and simple operation, realizes the organic coupling of the crystallization removal and degradation processes, and can recycle the used eutectic solvent by methods such as rotary evaporation and the like, thereby greatly reducing the energy consumption, being environment-friendly and meeting the standard of green chemical production.
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FIG. 1 is a liquid chromatogram of a supernatant after the waste cotton fabric is degraded in a eutectic solvent in example 1.
Detailed Description
The following further describes the embodiments of the present invention with reference to the drawings and examples. The following examples and comparative examples are only for more clearly illustrating the technical solutions of the present invention so that those skilled in the art can well understand and utilize the present invention, not to limit the scope of the present invention.
The names and abbreviations of the production processes, instruments and equipment related to the examples and comparative examples of the present invention are conventional in the art and are clearly understood and appreciated in the relevant fields of use, and one skilled in the art can understand the conventional process steps and apply the corresponding equipment according to the names and implement the processes according to the conventional conditions or conditions suggested by the manufacturer.
The various starting materials or reagents used in the examples of the present invention and comparative examples are not particularly limited in their sources, and are all conventional products commercially available.
In each of the following examples and comparative examples, the content of 5-hydroxymethylfurfural in the degradation product was analytically measured by Shodex-SH1100 column using a Perkin Elmer Flexar liquid chromatograph.
Example 1.
Weighing 3.50g of anhydrous choline chloride and 4.32g of p-toluenesulfonic acid, adding into a 20mL sample bottle, heating to 60 ℃, stirring for 20min until the anhydrous choline chloride and the p-toluenesulfonic acid are fully dissolved to form a uniform and transparent clear solution, and cooling to obtain the eutectic solvent which is stable in performance and cannot be crystallized after cooling.
The mol ratio of choline chloride to p-toluenesulfonic acid in the eutectic solvent is 1:1, and the viscosity value of the eutectic solvent is 99.00mPa & s through tests.
Shearing waste cotton fabrics into 0.5cm multiplied by 0.5cm, adding the waste cotton fabrics into 10wt% sodium hydroxide solution, heating to 80 ℃, stirring for 4 hours, taking out the waste cotton fabrics, cooling to room temperature, washing with deionized water for multiple times until the pH value is close to 10, adding the waste cotton fabrics into H with the volume concentration of 0.45%2O2Removing residual color on the cotton fabric in the aqueous solution, finally washing the cotton fabric for multiple times by using ethanol and deionized water in sequence until the pH value of the solution reaches 7, and drying the cotton fabric for 12 hours at 100 ℃.
0.78g (10wt%) of the treated waste cotton fabric is weighed and added into the prepared eutectic solvent, and the mixture is heated to 100 ℃ and stirred for 90 min.
And (3) rapidly placing the reaction product in ice water for quenching, centrifuging, taking the supernatant for high performance liquid chromatography analysis to obtain a chromatogram shown in figure 1, and showing that the 5-hydroxymethylfurfural is really obtained by degrading the waste cotton fabric.
The supernatant was further filtered, and an equal volume of ethyl acetate was added to the filtrate for extraction.
Collecting ethyl acetate extract phase, and removing the solvent by rotary evaporation to obtain the product 5-hydroxymethylfurfural.
The purity of the product is analyzed by a high performance liquid chromatography analyzer, and the yield of the 5-hydroxymethylfurfural is calculated to be 10.20%.
And collecting the solid residues obtained by centrifugation and filtration, washing the solid residues respectively by using the separated eutectic solvent and deionized water, drying the solid residues at the temperature of 80 ℃ for 12 hours, and grinding the solid residues to prepare regenerated cellulose fiber powder.
Comparative example 1.
Weighing 3.50g of anhydrous choline chloride and 2.26g of oxalic acid, adding the anhydrous choline chloride and the oxalic acid into a 20mL sample bottle, heating to 60 ℃, stirring for 15min until the anhydrous choline chloride and the oxalic acid are fully dissolved to form a uniform and transparent clear solution, and cooling to obtain the eutectic solvent which is stable in performance and cannot be crystallized after cooling.
The mol ratio of choline chloride to oxalic acid in the eutectic solvent is 1:1, and the viscosity value of the eutectic solvent is 47.50mPa & s through tests.
0.58g (10wt%) of the waste cotton fabric treated in example 1 is weighed and added into the prepared eutectic solvent, and the mixture is heated to 100 ℃ and stirred for 90 min.
Quickly quenching the reaction product in ice water, centrifuging, taking supernatant, filtering, and adding equal volume of ethyl acetate into filtrate for extraction.
Collecting ethyl acetate extract phase, and removing the solvent by rotary evaporation to obtain the product 5-hydroxymethylfurfural.
The purity of the product is analyzed by a high performance liquid chromatography analyzer, and the yield of the 5-hydroxymethylfurfural is calculated to be 3.68 percent.
And collecting the solid residues obtained by centrifugation and filtration, washing the solid residues respectively by using the separated eutectic solvent and deionized water, drying the solid residues at the temperature of 80 ℃ for 12 hours, and grinding the solid residues to prepare regenerated cellulose fiber powder.
Comparative example 2.
Weighing 3.50g of anhydrous choline chloride and 2.60g of malonic acid, adding the anhydrous choline chloride and the malonic acid into a 20mL sample bottle, heating to 60 ℃, stirring for 25min until the anhydrous choline chloride and the malonic acid are fully dissolved to form a uniform and transparent clear solution, and cooling to obtain the eutectic solvent which is stable in performance and cannot be crystallized after cooling.
The mol ratio of choline chloride to malonic acid in the eutectic solvent is 1:1, and the viscosity value of the eutectic solvent is 42.8mPa & s through tests.
0.61g (10wt%) of the waste cotton fabric treated in example 1 was weighed, added to the eutectic solvent prepared above, heated to 100 ℃ and stirred for 90 min.
Quickly quenching the reaction product in ice water, centrifuging, taking supernatant, filtering, and adding equal volume of ethyl acetate into filtrate for extraction.
Collecting ethyl acetate extract phase, and removing the solvent by rotary evaporation to obtain the product 5-hydroxymethylfurfural.
The purity of the product is analyzed by a high performance liquid chromatography analyzer, and the yield of the 5-hydroxymethylfurfural is calculated to be 1.39%.
And collecting the solid residues obtained by centrifugation and filtration, washing the solid residues respectively by using the separated eutectic solvent and deionized water, drying the solid residues at the temperature of 80 ℃ for 12 hours, and grinding the solid residues to prepare regenerated cellulose fiber powder.
Example 2.
Weighing 3.50g of anhydrous choline chloride and 8.64g of p-toluenesulfonic acid, adding the anhydrous choline chloride and the p-toluenesulfonic acid into a 20mL sample bottle, heating to 60 ℃, stirring for 20min until the anhydrous choline chloride and the p-toluenesulfonic acid are fully dissolved to form a uniform and transparent clear solution, and cooling to obtain the eutectic solvent which is stable in performance and cannot be crystallized after cooling.
The mol ratio of choline chloride to p-toluenesulfonic acid in the eutectic solvent is 1:2, and the viscosity value of the eutectic solvent is 103.4mPa & s through tests.
1.21g (10wt%) of the waste cotton fabric treated in example 1 was weighed, added to the eutectic solvent prepared above, heated to 100 ℃ and stirred for 90 min.
Quickly quenching the reaction product in ice water, centrifuging, taking supernatant, filtering, and adding equal volume of ethyl acetate into filtrate for extraction.
Collecting ethyl acetate extract phase, and removing the solvent by rotary evaporation to obtain the product 5-hydroxymethylfurfural.
The purity of the product is analyzed by a high performance liquid chromatography analyzer, and the yield of the 5-hydroxymethylfurfural is calculated to be 9.05%.
And collecting the solid residues obtained by centrifugation and filtration, washing the solid residues respectively by using the separated eutectic solvent and deionized water, drying the solid residues at the temperature of 80 ℃ for 12 hours, and grinding the solid residues to prepare regenerated cellulose fiber powder.
Comparative example 3.
Weighing 3.50g of anhydrous choline chloride and 3.01g of acetic acid, adding the anhydrous choline chloride and the acetic acid into a 20mL sample bottle, heating to 60 ℃, stirring for 10min until the anhydrous choline chloride and the acetic acid are fully dissolved to form a uniform and transparent clear solution, and cooling to obtain the eutectic solvent which is stable in performance and cannot be crystallized after cooling.
The mol ratio of choline chloride to acetic acid in the eutectic solvent is 1:2, and the viscosity value of the eutectic solvent is 20.80mPa & s through tests.
0.65g (10wt%) of the waste cotton fabric treated in example 1 is weighed and added into the prepared eutectic solvent, and the mixture is heated to 100 ℃ and stirred for 90 min.
Quickly quenching the reaction product in ice water, centrifuging, taking supernatant, filtering, and adding equal volume of ethyl acetate into filtrate for extraction.
Collecting ethyl acetate extract phase, and removing the solvent by rotary evaporation to obtain the product 5-hydroxymethylfurfural.
The purity of the product is analyzed by a high performance liquid chromatography analyzer, and the yield of the 5-hydroxymethylfurfural is calculated to be 0.23%.
And collecting the solid residues obtained by centrifugation and filtration, washing the solid residues respectively by using the separated eutectic solvent and deionized water, drying the solid residues at the temperature of 80 ℃ for 12 hours, and grinding the solid residues to prepare regenerated cellulose fiber powder.
Comparative example 4.
Weighing 3.50g of anhydrous choline chloride and 3.00g of ethylene glycol, adding the anhydrous choline chloride and the ethylene glycol into a 20mL sample bottle, heating to 60 ℃, stirring for 15min until the anhydrous choline chloride and the ethylene glycol are fully dissolved to form a uniform and transparent clear solution, and cooling to obtain the eutectic solvent which is stable in performance and cannot be crystallized after cooling.
The mol ratio of choline chloride to glycol in the eutectic solvent is 1:2, and the viscosity value of the eutectic solvent is 17.5mPa & s through tests.
0.65g (10wt%) of the waste cotton fabric treated in example 1 is weighed and added into the prepared eutectic solvent, and the mixture is heated to 100 ℃ and stirred for 90 min.
Quickly quenching the reaction product in ice water, centrifuging, taking supernatant, filtering, and adding equal volume of ethyl acetate into filtrate for extraction.
Collecting ethyl acetate extract phase, and removing the solvent by rotary evaporation to obtain the product 5-hydroxymethylfurfural.
The purity of the product is analyzed by a high performance liquid chromatography analyzer, and the yield of the 5-hydroxymethylfurfural is calculated to be 0.16%.
And collecting the solid residues obtained by centrifugation and filtration, washing the solid residues respectively by using the separated eutectic solvent and deionized water, drying the solid residues at the temperature of 80 ℃ for 12 hours, and grinding the solid residues to prepare regenerated cellulose fiber powder.
Example 3.
Weighing 3.50g of anhydrous choline chloride and 8.64g of p-toluenesulfonic acid, adding the anhydrous choline chloride and the p-toluenesulfonic acid into a 20mL sample bottle, heating to 60 ℃, stirring for 20min until the anhydrous choline chloride and the p-toluenesulfonic acid are fully dissolved to form a uniform and transparent clear solution, and cooling to obtain the eutectic solvent which is stable in performance and cannot be crystallized after cooling.
The mol ratio of choline chloride to p-toluenesulfonic acid in the eutectic solvent is 1:2, and the viscosity value of the eutectic solvent is 103.4mPa & s through tests.
1.21g (10wt%) of the waste cotton fabric treated in example 1 was weighed, added to the eutectic solvent prepared above, heated to 120 ℃ and stirred for 90 min.
Quickly quenching the reaction product in ice water, centrifuging, taking supernatant, filtering, and adding equal volume of ethyl acetate into filtrate for extraction.
Collecting ethyl acetate extract phase, and removing the solvent by rotary evaporation to obtain the product 5-hydroxymethylfurfural.
The purity of the product is analyzed by a high performance liquid chromatography analyzer, and the yield of the 5-hydroxymethylfurfural is calculated to be 11.24%.
And collecting the solid residues obtained by centrifugation and filtration, washing the solid residues respectively by using the separated eutectic solvent and deionized water, drying the solid residues at the temperature of 80 ℃ for 12 hours, and grinding the solid residues to prepare regenerated cellulose fiber powder.
Comparative example 5.
Weighing 3.50g of anhydrous choline chloride and 2.30g of formic acid, adding the anhydrous choline chloride and the formic acid into a 20mL sample bottle, heating to 60 ℃, stirring for 10min until the anhydrous choline chloride and the formic acid are fully dissolved to form a uniform and transparent clear solution, and cooling to obtain the eutectic solvent which is stable in performance and cannot be crystallized after cooling.
The mol ratio of choline chloride to formic acid in the eutectic solvent is 1:2, and the viscosity value of the eutectic solvent is 11.30mPa & s through tests.
0.58g (10wt%) of the waste cotton fabric treated in example 1 is weighed and added into the prepared eutectic solvent, and the mixture is heated to 120 ℃ and stirred for 90 min.
Quickly quenching the reaction product in ice water, centrifuging, taking supernatant, filtering, and adding equal volume of ethyl acetate into filtrate for extraction.
Collecting ethyl acetate extract phase, and removing the solvent by rotary evaporation to obtain the product 5-hydroxymethylfurfural.
The purity of the product is analyzed by a high performance liquid chromatography analyzer, and the yield of the 5-hydroxymethylfurfural is calculated to be 1.31 percent.
And collecting the solid residues obtained by centrifugation and filtration, washing the solid residues respectively by using the separated eutectic solvent and deionized water, drying the solid residues at the temperature of 80 ℃ for 12 hours, and grinding the solid residues to prepare regenerated cellulose fiber powder.
Comparative example 6.
Weighing 3.50g of anhydrous choline chloride and 4.61g of glycerol, adding the anhydrous choline chloride and the glycerol into a 20mL sample bottle, heating to 60 ℃, stirring for 15min until the anhydrous choline chloride and the glycerol are fully dissolved to form a uniform and transparent clear solution, and cooling to obtain the eutectic solvent which is stable in performance and cannot be crystallized after cooling.
The mol ratio of choline chloride to glycerol in the eutectic solvent is 1:2, and the viscosity value of the eutectic solvent is 75.00mPa & s through tests.
0.81g (10wt%) of the waste cotton fabric treated in example 1 is weighed and added into the prepared eutectic solvent, and the mixture is heated to 120 ℃ and stirred for 90 min.
Quickly quenching the reaction product in ice water, centrifuging, taking supernatant, filtering, and adding equal volume of ethyl acetate into filtrate for extraction.
Collecting ethyl acetate extract phase, and removing the solvent by rotary evaporation to obtain the product 5-hydroxymethylfurfural.
The purity of the product is analyzed by a high performance liquid chromatography analyzer, and the yield of the 5-hydroxymethylfurfural is calculated to be 0.08%.
And collecting the solid residues obtained by centrifugation and filtration, washing the solid residues respectively by using the separated eutectic solvent and deionized water, drying the solid residues at the temperature of 80 ℃ for 12 hours, and grinding the solid residues to prepare regenerated cellulose fiber powder.
Example 4.
Weighing 3.50g of anhydrous choline chloride and 4.32g of p-toluenesulfonic acid, adding into a 20mL sample bottle, heating to 60 ℃, stirring for 20min until the anhydrous choline chloride and the p-toluenesulfonic acid are fully dissolved to form a uniform and transparent clear solution, and cooling to obtain the eutectic solvent which is stable in performance and cannot be crystallized after cooling.
The mol ratio of choline chloride to p-toluenesulfonic acid in the eutectic solvent is 1:1, and the viscosity value of the eutectic solvent is 99.0mPa & s through tests.
0.78g (10wt%) of the waste cotton fabric treated in example 1 is weighed and added into the prepared eutectic solvent, and the mixture is heated to 100 ℃ and stirred for 120 min.
Quickly quenching the reaction product in ice water, centrifuging, taking supernatant, filtering, and adding equal volume of ethyl acetate into filtrate for extraction.
Collecting ethyl acetate extract phase, and removing the solvent by rotary evaporation to obtain the product 5-hydroxymethylfurfural.
The purity of the product is analyzed by a high performance liquid chromatography analyzer, and the yield of the 5-hydroxymethylfurfural is calculated to be 10.85%.
And collecting the solid residues obtained by centrifugation and filtration, washing the solid residues respectively by using the separated eutectic solvent and deionized water, drying the solid residues at the temperature of 80 ℃ for 12 hours, and grinding the solid residues to prepare regenerated cellulose fiber powder.
Comparative example 7.
Weighing 3.50g of anhydrous choline chloride and 2.26g of oxalic acid, adding the anhydrous choline chloride and the oxalic acid into a 20mL sample bottle, heating to 60 ℃, stirring for 15min until the anhydrous choline chloride and the oxalic acid are fully dissolved to form a uniform and transparent clear solution, and cooling to obtain the eutectic solvent which is stable in performance and cannot be crystallized after cooling.
The mol ratio of choline chloride to oxalic acid in the eutectic solvent is 1:1, and the viscosity value of the eutectic solvent is 47.5mPa & s through tests.
0.576g (10wt%) of the waste cotton fabric treated in example 1 was weighed and added to the eutectic solvent prepared above, and heated to 100 ℃ and stirred for 120 min.
Quickly quenching the reaction product in ice water, centrifuging, taking supernatant, filtering, and adding equal volume of ethyl acetate into filtrate for extraction.
Collecting ethyl acetate extract phase, and removing the solvent by rotary evaporation to obtain the product 5-hydroxymethylfurfural.
The purity of the product is analyzed by a high performance liquid chromatography analyzer, and the yield of the 5-hydroxymethylfurfural is calculated to be 4.02%.
And collecting the solid residues obtained by centrifugation and filtration, washing the solid residues respectively by using the separated eutectic solvent and deionized water, drying the solid residues at the temperature of 80 ℃ for 12 hours, and grinding the solid residues to prepare regenerated cellulose fiber powder.
Comparative example 8.
Weighing 3.50g of anhydrous choline chloride and 2.60g of succinic acid, adding the anhydrous choline chloride and the succinic acid into a 20mL sample bottle, heating to 60 ℃, stirring for 15min until the anhydrous choline chloride and the succinic acid are fully dissolved to form a uniform and transparent clear solution, and cooling to obtain the eutectic solvent which is stable in performance and cannot be crystallized after cooling.
The mol ratio of choline chloride to succinic acid in the eutectic solvent is 1:1, and the viscosity value of the eutectic solvent is 38.5mPa & s through tests.
0.61g (10wt%) of the waste cotton fabric treated in example 1 was weighed, added to the prepared eutectic solvent, heated to 100 ℃ and stirred for 120 min.
Quickly quenching the reaction product in ice water, centrifuging, taking supernatant, filtering, and adding equal volume of ethyl acetate into filtrate for extraction.
Collecting ethyl acetate extract phase, and removing the solvent by rotary evaporation to obtain the product 5-hydroxymethylfurfural.
The purity of the product is analyzed by a high performance liquid chromatography analyzer, and the yield of the 5-hydroxymethylfurfural is calculated to be 1.53 percent.
And collecting the solid residues obtained by centrifugation and filtration, washing the solid residues respectively by using the separated eutectic solvent and deionized water, drying the solid residues at the temperature of 80 ℃ for 12 hours, and grinding the solid residues to prepare regenerated cellulose fiber powder.
The above embodiments of the present invention are not intended to be exhaustive or to limit the invention to the precise form disclosed. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.
Claims (10)
1. A method for preparing 5-hydroxymethylfurfural by using waste cotton fabrics comprises the steps of putting the waste cotton fabrics in a choline eutectic solvent, heating for degradation, and extracting 5-hydroxymethylfurfural in a degradation product by using an organic solvent;
the choline eutectic solvent is colorless transparent liquid obtained by mixing and heating anhydrous choline chloride serving as a hydrogen bond acceptor material and p-toluenesulfonic acid serving as a hydrogen bond donor material.
2. The method for preparing 5-hydroxymethylfurfural from waste cotton fabrics as claimed in claim 1, wherein the molar ratio of anhydrous choline chloride to p-toluenesulfonic acid in the choline eutectic solvent is 1: 1-2.
3. The method for preparing 5-hydroxymethylfurfural from waste cotton fabrics as claimed in claim 1, wherein the mixing heating temperature for preparing the choline eutectic solvent is not more than 60 ℃.
4. The method for preparing 5-hydroxymethylfurfural from waste cotton fabrics according to claim 1, wherein the waste cotton fabrics are added into a choline eutectic solvent, heated to 100-140 ℃ and reacted for 90-120 min to obtain a degradation product 5-hydroxymethylfurfural.
5. The method for preparing 5-hydroxymethylfurfural from waste cotton fabrics as claimed in claim 1 or 4, wherein the addition amount of the waste cotton fabrics is 5-10 wt% of the mass of the choline eutectic solvent.
6. The method for preparing 5-hydroxymethylfurfural from waste cotton fabrics according to claim 1, wherein the organic solvent used for extracting the 5-hydroxymethylfurfural from the degradation products is any one of ethyl acetate, methyl isobutyl ketone, n-hexane or petroleum ether.
7. The method for preparing 5-hydroxymethylfurfural from waste cotton fabrics according to claim 6, characterized in that the organic solvent is ethyl acetate.
8. The method for preparing 5-hydroxymethylfurfural from waste cotton fabrics according to claim 1, wherein the waste cotton fabrics are cotton fabric scraps, waste cotton clothes or waste cotton quilt covers of clothing factories.
9. The method for preparing 5-hydroxymethylfurfural from waste cotton fabrics as claimed in claim 1, wherein the waste cotton fabrics are subjected to physical pretreatment, including crushing of the waste cotton fabrics, alkali treatment and hydrogen peroxide treatment.
10. The method for preparing 5-hydroxymethylfurfural from waste cotton fabrics according to claim 9, wherein the waste cotton fabrics are crushed into fragments of less than 0.5 cm.
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