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CN-122010879-A - Method for preparing 2, 5-furandicarboxylic acid based on waste textiles

CN122010879ACN 122010879 ACN122010879 ACN 122010879ACN-122010879-A

Abstract

The invention discloses a method for preparing 2, 5-furandicarboxylic acid based on waste textiles, which relates to the field of organic high molecular compounds and comprises the following steps of S1, pretreating waste textiles to obtain cellulose powder, S2, adding the cellulose powder into a buffer system, then adding a cellulase composition, reacting to obtain a glucose solution, S3, mixing the glucose solution with a mixed solvent, in a fixed bed, through a solid phase catalyst to obtain a HMF crude product, S4, mixing the HMF crude product, an oxidation catalyst combination and an acid solvent, reacting in an oxidizing gas atmosphere, and crystallizing and separating to obtain the 2, 5-furandicarboxylic acid after the reaction. The invention takes the waste fabrics as raw materials, has low cost and wide sources, realizes the high-value utilization of wastes, and accords with the concept of green sustainable development. The yield and purity of the 2, 5-furandicarboxylic acid are obviously higher than those of the traditional hydrobromic acid process, and the corrosion of hydrobromic acid to equipment is avoided.

Inventors

  • XU HAI
  • XU QIANG
  • YU SANXI
  • LI XINGLONG

Assignees

  • 合肥利夫生物科技有限公司

Dates

Publication Date
20260512
Application Date
20260413

Claims (10)

  1. 1. A method for preparing 2, 5-furandicarboxylic acid based on waste textiles, which is characterized by comprising the following steps: S1, pretreating waste textiles to obtain cellulose powder; S2, adding cellulose powder into a buffer system, then adding a cellulase composition, and performing post-treatment after reaction to obtain a glucose solution; S3, mixing the glucose solution with a mixed solvent, reacting for 1-6 hours in a fixed bed under the pressure of 0.1-5MPa by using a solid phase catalyst to obtain a reaction solution containing HMF, concentrating and extracting to obtain a HMF crude product; S4, mixing the HMF crude product, an oxidation catalyst combination and an acid solvent, reacting at 120-200 ℃ under the atmosphere of oxidizing gas for 1-12h at the pressure of 0.1-5MPa, and crystallizing and separating to obtain the 2, 5-furandicarboxylic acid.
  2. 2. The method for preparing 2, 5-furandicarboxylic acid based on waste textiles according to claim 1, wherein the solid phase catalyst is a Sn-supported carbonized humin catalyst, and the Sn loading is 5-20wt%.
  3. 3. The method for preparing 2, 5-furandicarboxylic acid based on waste textiles according to claim 2, wherein the molar ratio of Sn in the solid phase catalyst to glucose in the glucose solution is (0.05-0.2): 1, the mixed solvent is a mixed solution of an organic solvent and water, the volume ratio of the organic solvent to the water is (3-10): 1, and the organic solvent comprises at least one of tetrahydrofuran, methyl isobutyl ketone, acetone, gamma valerolactone and gamma butyrolactone.
  4. 4. The method for preparing 2, 5-furandicarboxylic acid based on waste textiles according to claim 2, wherein the temperature of the fixed bed is 150-180 ℃, the bed volume of the fixed bed is 100mL, and the flow rate of the mixed solvent in the fixed bed is 1-50mL/min.
  5. 5. The method for preparing 2, 5-furandicarboxylic acid based on waste textiles according to claim 1, characterized in that the molar ratio of the oxidation catalyst combination to HMF in the crude HMF is (0.1-0.3): 1.
  6. 6. The method for preparing 2, 5-furandicarboxylic acid based on waste textiles according to claim 1, wherein the oxidation catalyst combination comprises cobalt acetate, manganese acetate, sodium bromide and a promoter comprising at least one of iron nitrate, copper nitrate or nickel nitrate.
  7. 7. The method for preparing 2, 5-furandicarboxylic acid based on waste textiles according to claim 6, wherein the molar ratio of cobalt acetate, manganese acetate, sodium bromide and promoter is (0.1-1): (0.1-1): (0.1-1).
  8. 8. The method for preparing 2, 5-furandicarboxylic acid based on waste textiles according to claim 1, characterized in that the oxygen content in the oxidizing gas atmosphere is 20-100vol%.
  9. 9. The method for preparing 2, 5-furandicarboxylic acid based on waste textiles according to claim 1, wherein the acid solvent comprises at least one of acetic acid, propionic acid or butyric acid.
  10. 10. The method for preparing 2, 5-furandicarboxylic acid based on waste textiles according to claim 1, wherein the waste textiles comprise at least one of rayon, viscose filament, lyocell, cuprammonium rayon blend, rayon nylon blend, cotton and polyester cotton.

Description

Method for preparing 2, 5-furandicarboxylic acid based on waste textiles Technical Field The invention relates to the field of organic high molecular compounds, in particular to a method for preparing 2, 5-furandicarboxylic acid based on waste textiles and application thereof. Background With exhaustion of fossil resources and increasing environmental problems, the use of bio-based polymer materials instead of traditional fossil-based materials is an important direction of material development. At present, inorganic acid or solid sulfonic acid catalyst is often adopted to catalyze monosaccharide to dehydrate, and 5-Hydroxymethylfurfural (HMF) is generated by dehydration and then is further oxidized to obtain the product. However, the inorganic acid catalyst is difficult to regenerate, and the activity of the solid sulfonic acid catalyst is easily reduced due to the formation of a humin polymer on the surface. Meanwhile, HMF has poor thermal stability, and tar-like degradation products are easy to form in the traditional distillation and purification process, so that equipment is stopped and the efficiency is reduced. In addition, hydrobromic acid is used in the traditional 2, 5-furandicarboxylic acid (FDCA) oxidation process, equipment corrosion is easy to occur, the requirement on the substrate concentration is severe, and the production efficiency is limited. Therefore, it is important to develop a preparation method of 2, 5-furandicarboxylic acid, which can achieve the product yield, purity and process economy in the subsequent conversion step. Chinese patent application CN118164928a discloses a method for preparing HMF by organic-inorganic two-phase continuous cellulose, which comprises mixing cellulose, inorganic salt, acid catalyst, organic solvent and water, catalytic converting in continuous reactor, extracting and distilling under reduced pressure to obtain HMF. The raw materials of the patent are cellulose derivatives with higher purity such as cellulose ether, methyl cellulose, carboxymethyl cellulose and the like, and the components are relatively single and controllable, but the raw materials have no wide raw material adaptability and waste recycling capability. Disclosure of Invention The waste textile is used as a natural cellulose material with wide sources and low cost, and is an ideal bio-based raw material. However, the natural cotton fiber has high crystallinity, compact structure and low direct conversion efficiency, and impurities such as sizing agent, auxiliary agent and the like contained in the fiber can influence the selectivity of subsequent reactions. In the prior art, a system process for efficiently converting waste textiles into FDCA is lacking, and how to break a cellulose compact structure and improve the reactivity through pretreatment, and meanwhile, optimize the subsequent conversion step to give consideration to the product yield, purity and process economy becomes a technical problem to be solved. In order to break the dense structure of cellulose and improve the reactivity through pretreatment and develop a preparation method of 2, 5-furandicarboxylic acid which can achieve the product yield, purity and process economy in the subsequent conversion step, the first aspect of the invention provides a method for preparing 2, 5-furandicarboxylic acid based on waste textiles, which comprises the following steps: S1, pretreating waste textiles to obtain cellulose powder; S2, adding cellulose powder into a buffer system, then adding a cellulase composition, and performing post-treatment after reaction to obtain a glucose solution; S3, mixing the glucose solution with a mixed solvent, reacting for 1-6 hours in a fixed bed under the pressure of 0.1-5MPa by using a solid phase catalyst to obtain a reaction solution containing HMF, concentrating and extracting to obtain a HMF crude product; S4, mixing the HMF crude product, an oxidation catalyst combination and an acid solvent, reacting at 120-200 ℃ under the atmosphere of oxidizing gas for 1-12h at the pressure of 0.1-5MPa, and crystallizing and separating to obtain the 2, 5-furandicarboxylic acid. At present, the preparation of 2, 5-furandicarboxylic acid is mainly carried out by taking monosaccharides such as fructose and the like as raw materials, dehydrating to generate 5-hydroxymethylfurfural, and further oxidizing. Inorganic acid or solid sulfonic acid catalyst is usually used for catalyzing monosaccharide to dehydrate, but the inorganic acid catalyst is difficult to regenerate, the solid sulfonic acid catalyst is easy to reduce activity due to the formation of a humin polymer on the surface, and the thermal stability of 5-hydroxymethylfurfural is poor. The application takes waste fabrics as raw materials, breaks the compact structure of cellulose through pretreatment, removes impurities and reduces crystallinity, then introduces a cellulase composition to realize enzymatic hydrolysis, forms glucose aqueous solution, and ge