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CN-122011944-A - Method for recycling condensation polymerization byproduct humins in HMF production

CN122011944ACN 122011944 ACN122011944 ACN 122011944ACN-122011944-A

Abstract

The invention discloses a method for recycling a condensation polymerization byproduct humin in HMF production. The method comprises the steps of firstly carrying out pretreatment such as cleaning, drying and crushing on a solid byproduct humin in the industrial production of HMF, then carrying out copolymerization reaction on the treated humin fine powder and biomass alcohol (such as furfuryl alcohol) under the catalysis of acid to obtain a humin-biomass alcohol copolymerization liquid, finally mixing the copolymerization liquid with a proper amount of solvent/auxiliary agent, coating the mixture on a treated substrate, and curing to form the anti-corrosion coating. The invention successfully converts industrial waste residue humins into high-value products, and the prepared coating has excellent acid corrosion resistance, good adhesive force, film forming property and heat resistance, can be widely applied to the protection of materials such as metal, wood and the like, has huge potential especially in the field of vehicle and ship corrosion prevention, and realizes the organic combination of waste recycling and high-performance material preparation.

Inventors

  • ZHANG YIBIN
  • XIA ZHI
  • JIANG ZHIJIE
  • ZHANG YU

Assignees

  • 中科国生(杭州)科技有限公司

Dates

Publication Date
20260512
Application Date
20251128

Claims (10)

  1. 1. A method for recycling a polycondensation by-product humin in HMF production is characterized by comprising the following steps: S1, cleaning, drying, crushing and sieving the humins; s2, introducing a copolymerization system to perform copolymerization, namely mixing the humin fine powder obtained in the step S1 with biomass alcohol, and performing heating copolymerization under the action of an acid catalyst to obtain a humin-biomass alcohol reaction copolymerization liquid; S3, taking a certain mass of reaction copolymerization liquid, adding a certain solvent auxiliary agent, mixing and stirring to adjust the viscosity, and obtaining the bio-based anti-corrosion coating with different coating construction viscosities; S4, after the substrates to be coated of different materials are pretreated and cleaned, the bio-based anticorrosive paint obtained in the step S3 is coated on the surface of the pretreated substrate, and is cured into a film after drying treatment in an oven.
  2. 2. The method for recycling of a polycondensation by-product humin in HMF production according to claim 1, wherein step S1 specifically comprises: S11, primarily crushing the solid humins, transferring the crushed solid humins into a suction filtration bottle, and cleaning the solid with water to obtain the water-washed humins; S12, placing the water-washed humins into a baking oven for drying, and then pouring the dried humins into a pulverizer for pulverizing into black fine powder particles with different meshes; And S13, collecting the crushed fine powder through a 100-120 mesh sieve, and continuously placing the fine powder into an oven to dry to remove residual moisture, wherein the drying temperature is 40-80 ℃.
  3. 3. The method for recycling of a polycondensation by-product humin in HMF production according to claim 1, wherein step S2 specifically comprises the steps of: S21, premixing, namely adding pretreated humin fine powder particles and biomass alcohol into a three-neck flask with stirring according to a certain mass ratio, and stirring the three-neck flask in an oil bath at 25-50 ℃ to uniformly mix the three-neck flask; S22, adding and reacting a catalyst, namely raising the temperature of an oil bath to 50-60 ℃, adding an acid catalyst in a certain proportion, raising the temperature to 105-115 ℃ stepwise slowly, keeping the constant temperature for 1-2 hours, and monitoring the viscosity of the system; S23, immediately cooling to below 40 ℃ after the reaction reaches the end point, temporarily stopping the reaction, avoiding excessive reaction to form gel, and neutralizing the residual acid catalyst by adopting an alkali liquor titration mode to stop the reaction; and S24, carrying out post-treatment on the product, namely rapidly filtering the reaction mucus in the step S23 in a filter screen to remove larger unreacted particles, and obtaining the reaction copolymerization liquid with certain viscosity.
  4. 4. A method for recycling of a polycondensation by-product humin in HMF production according to claim 3, wherein in step S21, the biomass alcohol is selected from one or more of glycerol, furfuryl alcohol, sorbitol, isosorbide, bio-based ethylene glycol, 1, 3-propanediol.
  5. 5. The method for recycling of by-product humins in HMF production according to claim 4, wherein the mass ratio of added humins fine powder particles to biomass alcohol is 1 (1-4).
  6. 6. The method for recycling the by-product humins in the production of HMF according to claim 3, wherein in the step S21, an ethanol solvent accounting for 10-20wt% of the total mass of the reaction system is added for dissolution assistance during the stirring process.
  7. 7. The method for recycling the by-product humins in the production of HMF according to claim 3, wherein in the step S22, the acid catalyst is p-toluenesulfonic acid, the addition amount of the acid catalyst is 0.5-2wt% of the total mass of the reaction system, and the number of the filtering meshes in the step S24 is 60-100 meshes.
  8. 8. The method for recycling of the byproduct humins in HMF production according to claim 1, wherein in the step S3, the solvent auxiliary agent is one or more of acetone, ethanol, ethylene glycol, methanol, epichlorohydrin and bisphenol a epoxy resin.
  9. 9. The method for recycling the by-product humins in the production of HMF according to claim 1, wherein in the step S4, the drying treatment process is carried out at a drying temperature of 80-100 ℃ for 12-24 hours.
  10. 10. A bio-based anticorrosive paint, which is prepared by the process according to steps S1-S3 in claim 1.

Description

Method for recycling condensation polymerization byproduct humins in HMF production Technical Field The invention belongs to the field of raw material resource utilization, and particularly relates to a resource utilization method of a condensation polymerization byproduct humin in HMF production. Background The 5-Hydroxymethylfurfural (HMF) prepared by dehydration of saccharides is an increasingly ideal platform chemical due to the unique furan ring and hydroxyl and aldehyde functional groups, and particularly in the downstream market, 2, 5-furandicarboxylic acid (FDCA) is also of great interest in the polymerization industry. However, a problem of headache in practical industrial production is that polycondensation by-product humins (hereinafter abbreviated as humins) is inevitably produced in the process of dehydrating saccharides to produce HMF, lowering product selectivity and causing a lot of carbon loss. The origin of the term humins was traced back to 1849, and Muller et al used the term humins for the first time to describe the solid materials found in acid-catalyzed sucrose dehydration. Through many years of research and development, humins have been widely known as a class of solid by-products of dehydration of carbohydrate acid catalyzed polymerization. The recycling requirement is that the humins in the HMF production cause 10-50% carbon loss, the traditional treatment is mainly landfill, the cost is high and the resource is wasted. Due to the lack of sources of large-scale humins raw materials, while the structure and yield of humins in the laboratory for acid-catalyzed carbohydrate dehydration may vary depending on a variety of factors (e.g., temperature, catalyst, solvent, raw materials, concentration, residence time), some limitations in humins utilization result. The global HMF production is now expanding rapidly (e.g. the build-up of a tens of thousands of tons production line in chinese), and large scale by-product utilization is at odds with the eye, while the utilization of highly polymerized solid-type humins is still relatively lacking. It was found that humins can be represented in particular as black solids or high viscosity liquids. The reaction conditions of higher temperature, longer reaction time, higher acidity and higher raw material concentration tend to increase the degree of crosslinking of the humins, resulting in solid black masses formed by agglomeration of spherical particles with a wider size distribution. Solid humins are generally low in solubility, while viscous liquids of humins with low polymerization levels are often soluble in some organic solvents and can be modified and developed by some chemical means to valuable pathways such as pyrolysis to make oils, pyrolysis to make catalyst supports, activated carbon adsorption materials, making thermosets, and the like. On the other hand, the use of carbohydrates for preparing biobased coatings is a hotspot in current research and applications. The bio-based coating is used as an environment-friendly material, and the main raw material of the bio-based coating is derived from renewable resources (such as vegetable oil, natural rubber, rosin and the like) and has high bio-based carbon content (generally more than 20%), so that the dependence on fossil fuel is reduced, and the carbon footprint of the whole life cycle of the product is reduced. Bio-based coatings are becoming very popular with policy support, and solid humins are rich in carbon and often used as waste, so how to recycle headache-causing solid humins for preparing bio-based coatings is a valuable study. Disclosure of Invention Aiming at the problems, the invention provides a method for recycling the polycondensation solid byproduct humins in the production of HMF, which solves the problems in the prior recycling of the solid humins. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a method for recycling a polycondensation by-product humin in HMF production comprises the following steps: S1, cleaning, drying, crushing and sieving the humins; s2, introducing a copolymerization system to perform copolymerization, namely mixing the humin fine powder obtained in the step S1 with biomass alcohol, and performing heating copolymerization under the action of an acid catalyst to obtain a humin-biomass alcohol reaction copolymerization liquid; S3, taking a certain mass of reaction copolymerization liquid, adding a certain solvent auxiliary agent, mixing and stirring to adjust the viscosity, and obtaining the bio-based anti-corrosion coating with different coating construction viscosities; S4, after the substrates to be coated of different materials are pretreated and cleaned, the bio-based anticorrosive paint obtained in the step S3 is coated on the surface of the pretreated substrate, and is cured into a film after drying treatment in an oven. Further, the step S1 specifically includes: S11, primarily crushing the