Method for producing small-molecular ecological organic product by biomass multi-element catalytic hydrolysis

Abstract

The invention belongs to the technical field of biomass resource utilization, and particularly relates to a method for producing a small-molecule ecological organic product through biomass multi-element catalytic hydrolysis. The method comprises the following steps: S1, carrying out heating fermentation treatment on prepared biomass slurry to obtain fermented catalytic slurry; s2, carrying out heating and pressurizing catalytic treatment on the fermentation catalytic slurry, and combining the catalytic synergistic reaction of heating fermentation and heating and pressurizing to obtain multi-element catalytic slurry; s3, carrying out coupling hybridization synthesis and homogenization treatment on the multi-element catalytic slurry; and S4, performing solid-liquid separation on the slurry subjected to coupling hybridization synthesis and homogenization treatment to obtain a small-molecule ecological organic product which comprises a solid product and a liquid product. According to the method for producing the small-molecule ecological organic product through biomass multi-element catalytic hydrolysis, the high risk that organic matter easily generates toxic substances in a medium-high-temperature environment is avoided through a low-temperature and low-pressure multi-element catalytic coupling hybridization and organic conversion systematic technology, the production process is ecological and environmentally friendly, energy is saved, safety is achieved, and the product is friendly, ecological and healthy.

Description

Technical Field

[0001] This invention belongs to the field of biomass resource utilization technology, and in particular relates to a method for producing small molecule eco-organic products by biomass multi-component catalytic hydrolysis. Background Technology

[0002] Food, drug, and beverage processing waste (such as soybean residue, medicinal residue, fruit residue and extraction residue, rice, flour, and oil product processing waste, brewery mash and lees residue, etc.), cold chain supermarkets, markets, farms, agricultural waste (such as fruit peels, pulp, cores, vegetable tails, discarded fruit stalks, etc.), kitchen waste collected and treated in schools, mines, industrial parks, military camps, airports, and train stations, human excrement, livestock and poultry manure and dead poultry from farms, animal carcasses from slaughtering and processing livestock, poultry, aquatic products, and seafood, discarded fish and shrimp from fishing ports and wharves, activated sludge from urban and rural sewage treatment plants, waste liquid and sludge from food, drug, and beverage processing plants, and biomass and organic waste such as seaweed and seagrass accumulated on the coast are major environmental challenges facing the world. Current mainstream treatment methods, such as landfill, incineration, anaerobic / aerobic fermentation, wet oxidation, biological farming (black squid fly larvae, etc.), and traditional fermentation composting, have several drawbacks. These methods are rudimentary and primitive, require large land areas, have long processing times, low resource utilization efficiency, low product value, poor adaptability to application scenarios, require large investments, consume a lot of energy, and cause serious secondary pollution. Some methods even generate large amounts of toxic substances or their precursors, such as dioxins, benzopyrene, and heterocyclic amines, posing significant safety risks.

[0003] For example, the wet oxidation (WAO / CWAO) technology route, although producing humic byproducts that can be used as compost-like organic fertilizer, carries a high risk of generating toxic substances or their precursors such as acrylamide, heterocyclic amines, furans, and chloropropanol under high temperature and pressure conditions. Furthermore, it requires sophisticated equipment, consumes a lot of energy, and involves significant investment. Essentially, it represents the reduction of organic solid waste rather than its resource recovery.

[0004] For example, although the catalytic hydrolysis process using added acid (or alkali) and its formulations can efficiently degrade macromolecular organic matter and produce high-value-added resource products such as high-quality organic fertilizers, the added acid / alkali or its formulations are mostly hazardous chemicals that are strictly controlled by various countries. This not only results in high investment costs, rapid equipment corrosion, and high operation and maintenance costs, but also directly leads to a significant increase in safety risks, regulatory control risks, and costs in all aspects from production, transportation, storage to use and operation due to the inherent dangers of their use and social risks.

[0005] For example, due to the obvious and globally recognized drawbacks of landfill, incineration, and anaerobic / aerobic composting techniques, some developed countries have reluctantly turned to traditional fermentation composting for treating biomass organic waste. However, fermentation composting requires a large amount of space, has a long composting time, results in significant nutrient loss, produces a low glycemic index (GI), causes substantial secondary pollution, and has poor economic benefits. Some developed countries have even banned the direct contact of fermentation compost with crop surfaces due to the numerous prominent problems associated with it, such as the presence of pathogens, antibiotics, hormones, and heavy metal residues, in order to minimize harm to human health through the food chain.

[0006] Therefore, there is an urgent need for an advanced and innovative process technology that can not only efficiently and greenly solve the environmental challenges and pain points of biomass and its organic waste pollution, but also achieve efficient resource recycling of biomass and its organic waste. Summary of the Invention

[0007] The main objective of this invention is to provide a technical method for producing small-molecule eco-organic products by biomass multi-component catalytic hydrolysis, so as to overcome the problems in the prior art.

[0008] The technical solution adopted in this invention includes:

[0009] This invention provides a method for producing small-molecule eco-organic products by biomass multi-component catalytic hydrolysis, comprising the following steps:

[0010] S1. The biomass slurry is heated and fermented to obtain fermentation catalytic slurry;

[0011] S2. The fermented catalytic slurry is subjected to heating and pressurization catalytic treatment, and the synergistic reaction of heating and fermentation and heating and pressurization is combined to obtain a multi-element catalytic slurry;

[0012] S3. Grind and cut the multi-component catalytic slurry to complete the coupled hybrid synthesis and homogenization treatment of the multi-component catalytic slurry;

[0013] S4. The slurry after coupled hybrid synthesis and homogenization is subjected to solid-liquid separation to obtain the small molecule eco-organic product, which includes solid products and liquid products.

[0014] Furthermore, the reaction temperature of the heating fermentation treatment and the heating pressurized catalytic treatment is controlled at 40-140 ℃, and the pressure is controlled at 0.1-1.5 MPa.

[0015] Furthermore, the multi-element catalytic hydrolysis employs a combined catalytic reaction, in which one or more of the following are used in the combined catalytic reaction process: metal and its oxide catalysts required for the catalytic hydrolysis reaction, mixed organic acid reaction preparations, organic acid reaction preparations, inorganic acids, inorganic bases, inorganic acid-prepared reaction preparations, inorganic base-prepared reaction preparations, active oxygen species generation equipment or preparations, and enzyme preparations; when the liquid product is a drinkable beverage product, one or more of the following are selected for the catalytic hydrolysis reaction: metal or its oxide catalysts, mixed organic acids, or single organic acid reaction preparations.

[0016] Furthermore, the method for producing small-molecule eco-organic products by biomass multi-element catalytic hydrolysis also includes using enzyme preparations to carry out catalytic chain-breaking reactions in a temperature range of 40-80℃.

[0017] Furthermore, the coupled hybrid synthesis involves selectively adding inorganic nutrients to the slurry and bonding them with small molecule organic products via ionic and / or covalent bonds to achieve coupled hybrid synthesis of inorganic nutrients and small molecule organic nutrients.

[0018] Furthermore, the solid product after solid-liquid separation is used to produce solid fertilizer, solid feed, or solid beverage, while the liquid product is used to produce liquid fertilizer, liquid feed, or liquid beverage. The product may also be optionally subjected to ultrasonic treatment.

[0019] Furthermore, the method for producing small-molecule eco-organic products by biomass multi-element catalytic hydrolysis further includes adding biological strains to the small-molecule eco-organic products after solid-liquid separation to produce bio-small-molecule organic fertilizers / feeds / beverages.

[0020] Furthermore, the method for producing small-molecule eco-organic products by biomass multi-element catalytic hydrolysis uses a pump circulation selection combined with stirring reaction to ensure sufficient reaction and reduce reaction dead zones and sediment accumulation.

[0021] Furthermore, the method for producing small-molecule eco-organic products by biomass multi-element catalytic hydrolysis achieves zero emissions of waste gas, wastewater, and waste residue, wherein the liquid portion separated from the solid-liquid mixture is a liquid product, and the solid portion is a solid product.

[0022] Furthermore, the biomass slurry is made from biomass raw materials, which include one or more of the following: food, pharmaceutical, and beverage processing residues; agricultural waste from cold chain supermarkets, markets, farms, and agricultural facilities; kitchen waste and human excrement collected and treated in schools, factories, industrial parks, military camps, airports, and railway stations; livestock and poultry manure and dead livestock from farms; animal carcasses from livestock, poultry, and seafood slaughtering and processing plants; discarded fish and shrimp from fishing ports and wharves; activated sludge from urban and rural sewage treatment plants; waste liquid and sludge from food, pharmaceutical, and beverage factories; and seaweed and seagrass accumulated on the coast. The food, pharmaceutical, and beverage processing residues include soybean residue, medicinal residue, fruit residue, extraction residue, wine mash and lees residue, and sludge residue from rice, flour, oil, and sugar product processing. The agricultural waste from cold chain supermarkets, markets, and farms includes fruit peels, pulp, pits, vegetable scraps, and discarded fruit stalks.

[0023] Compared with the prior art, the advantages of the present invention include:

[0024] The method for producing small-molecule eco-organic products by biomass multi-element catalytic hydrolysis provided by this invention adopts a low-temperature and low-pressure process, which effectively avoids the risk of organic matter generating toxic substances under high temperature and high pressure environment, and the production process is safe and controllable.

[0025] This invention utilizes a "catalytic chain breaking" method rather than "deep oxidation," particularly by leveraging the self-generated organic acids and active oxygen catalysis of the material. Through the excitation and dissociation of the antibonding orbitals of oxygen molecules, the catalytic stabilization of atomic oxygen, the reaction of free radical oxygen with polymeric oxygen bonds to form O2, and the energy release mechanism of polymer breakage, it preserves small-molecule active nutrients such as amino acids, small peptides, oligosaccharides, fulvic acid, humic acid, and organic acids. The resulting organic nutrients not only achieve small-molecule nano-scale production but also exhibit high bioactivity, with nutritional value and actual efficacy far exceeding those of traditional oxidation / deep oxidation catalysis products.

[0026] This invention employs a multi-component combined catalytic system, which can flexibly utilize cascade catalytic operation steps of graded gradient catalytic hydrolysis for recalcitrant biomass, significantly improving reaction efficiency, greatly reducing dependence on external catalytic / oxidative reaction agents, saving energy and reducing consumption, lowering costs, and ensuring high safety.

[0027] This invention, when selectively incorporating inorganic nutrients to suit the needs of the end product, achieves efficient coupling and hybridization of mineral nutrients and small-molecule organic nutrients through molecular structure self-reorganization, such as the bonding of the added inorganic nutrient elements (e.g., nitrogen, phosphorus, and potassium required for fertilizers) with small-molecule organic products via ionic and / or covalent bonds. This improves the crop's absorption and utilization efficiency of nutrients, thereby reducing the amount of mineral nutrients applied. For example, in the application of small-molecule organic fertilizers: by synthesizing small-molecule organic coupling hybrids of nitrogen, phosphorus, and potassium, the direct use of such fertilizers is significantly reduced. Moreover, while optimizing the crop's needs for nitrogen, phosphorus, and potassium nutrients and their absorption efficiency, it greatly reduces the loss of nitrogen, phosphorus, and potassium from fertilizers and the pollution of soil, water, and air.

[0028] This invention utilizes multi-element catalytic hydrolysis of high-molecular organic compounds into nano-molecules. By selectively combining high-speed grinding at 2000-20000 rpm and / or pressure grinding at 0.1-1.5 MPa and / or ultrasonic stabilization, the small-molecule organic nutrients can form quantum high-energy states through the influence of electric fields, magnetic fields, and sound fields. These states not only have a large specific surface area but also high signal transmission and targeted delivery capabilities.

[0029] This invention also achieves the recycling of gas, water, slag, and heat within the process, with virtually no external pollutant discharge, making it environmentally friendly. The same process system can be flexibly applied to the production of various high-value-added ecological and organic products such as fertilizers, feeds, and beverages, and the process can be adjusted according to different ecological and organic product standards, exhibiting extremely high adaptability to multiple scenarios and markets. Attached Figure Description

[0030] Various other advantages and benefits will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments. The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings:

[0031] Figure 1 This is a schematic diagram of the production process of the present invention;

[0032] Figure 2 A comparison diagram of the mechanisms of sulfate catalysis and reactive oxygen species catalysis;

[0033] Figure 3 Diagram of nutrient retention mechanism under catalytic chain scission pathway;

[0034] Figure 4 Diagram of nutrient retention mechanism under deep oxidation pathway;

[0035] Figure 5 This is a diagram illustrating the basic reaction mechanism of reactive oxygen species catalytic chain scission.

[0036] Figure 6A diagram illustrating the mechanism of nutrient delivery by nano-sized molecules;

[0037] Figure 7 Comparison of the effects of feeding freshwater shrimp with black soldier fly hydrolysate;

[0038] Figure 8 One of the on-site random sampling comparison images of rice grown using livestock and poultry manure multi-catalytic hydrolysis small molecule organic fertilizer;

[0039] Figure 9 The second image shows a random on-site sampling comparison of rice grown using livestock and poultry manure as a multi-catalytic hydrolysis small molecule organic fertilizer.

[0040] Figure 10 One of the random sampling comparison images of the root systems of crops planted with small-molecule organic fertilizer produced from the multi-element catalytic hydrolysis of kitchen waste;

[0041] Figure 11 The second image shows a random sampling comparison of the root systems of crops grown using small-molecule organic fertilizer derived from the multi-element catalytic hydrolysis of kitchen waste. Detailed Implementation

[0042] In view of the many shortcomings of the existing technology, the inventors of this invention, through extensive and in-depth practice and continuous research and innovation, have come up with the technical solution of this invention. The following will further explain and illustrate the technical solution, its implementation process, and its principles.

[0043] The present invention will now be described in further detail with reference to specific embodiments. The given embodiments are merely illustrative of the invention and not intended to limit its scope. The embodiments provided below can serve as a guide for further improvements by those skilled in the art and do not constitute a limitation on the invention in any way.

[0044] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials used in the following embodiments are commercially available.

[0045] like Figure 1 As shown in the figure, this invention provides a method for producing small-molecule eco-organic products by biomass multi-component catalytic hydrolysis, comprising the following steps:

[0046] S1. The biomass slurry is made from biomass raw materials, which include one or more of the following: food, medicine and beverage processing residues (such as soybean residue, medicinal residue, fruit residue, extraction residue, rice, flour and oil product processing residues, brewery mash and lees residue, etc.), agricultural waste from cold chain supermarkets, markets and farms (such as fruit peels, fruit pulp, fruit pits, fruit and vegetable tails, discarded fruit and straw, etc.), kitchen waste and human excrement collected and treated in schools, factories, industrial parks, military camps, airports and stations, livestock and poultry manure and dead poultry from farms, animal remains from slaughtering and processing livestock, poultry, aquatic products and seafood, abandoned fish and shrimp from fishing ports and wharves, activated sludge from urban and rural domestic sewage treatment plants, waste liquid sludge from food, medicine and beverage processing plants, seaweed and seagrass accumulated on the coast, etc. Figure 8 and 9 Comparison of random on-site sampling of rice grown using livestock and poultry manure multi-catalytic hydrolysis small molecule organic fertilizer;

[0047] S2. The biomass slurry is subjected to heating and fermentation treatment to obtain fermentation catalytic slurry; the reaction temperature of the heating and fermentation treatment is controlled at 40-140℃ and the pressure is controlled at 0.1-1.5 MPa.

[0048] S3. The fermentation catalytic slurry is subjected to heating and pressurization catalytic treatment, and the synergistic reaction of heating and fermentation and heating and pressurization is combined to obtain a multi-element catalytic slurry; the reaction temperature of the heating and pressurization catalytic treatment is controlled at 40-140℃ and the pressure is controlled at 0.1-1.5 MPa;

[0049] S4. Selectively add inorganic nutrients to the multi-element catalytic slurry for organic coupling hybrid synthesis and homogenization.

[0050] S5. The slurry after coupled hybrid synthesis and homogenization is subjected to solid-liquid separation to obtain solid products and liquid products; specifically, the solid part can be dehydrated and dried to prepare solid fertilizer / planting substrate or solid feed or solid beverage; the liquid part can be emulsified and stabilized to prepare liquid fertilizer, liquid feed or liquid beverage.

[0051] S6. Add biological strains to the liquid fertilizer product to make bio-organic fertilizer, or in cases where inorganic nutrients are not added for coupled hybrid synthesis, add inorganic nutrients to the solid / liquid product to make various mixed / compound fertilizer, feed and beverage products.

[0052] The advantages of this invention in producing small-molecule organic fertilizer compared to fermentation composting are: firstly, it overcomes the problems of long fermentation time, large space occupation, and inconvenient operation; secondly, it avoids the loss of a large amount of effective nutrients and pollution emissions during fermentation; and thirdly, it solves the problems of accumulation of pathogens, viruses, insect eggs, microbial toxins, hormones, antibiotics, heavy metals, and many secondary pollution associated with fermentation in fermentation composting.

[0053] The advantages of this invention in catalytic hydrolysis without the addition of inorganic acids (or bases) are threefold: First, it fully utilizes the large amount of organic acids naturally generated during the fermentation process of organic matter; second, it avoids the safety risks associated with production, transportation, storage, and operations, as well as the numerous operating costs, equipment space, and investment costs related to the strict control and regulation of hazardous chemicals, that would be incurred when using inorganic acids (or bases) and their formulations as reaction agents; and third, it changes the chemical technology path of adding inorganic acids (or bases) as a green technology path of high-energy free radical catalytic oxidation and chain scission. For example, the different mechanisms of sulfate reaction agent catalysis and reactive oxygen species catalysis are as follows... Figure 2 As shown.

[0054] Compared to wet oxidation (WAO) and wet catalytic oxidation (CWAO) methods, this invention offers several advantages: First, both temperature and pressure are significantly reduced to safe ranges where the formation of toxic organic substances is unlikely. Second, it significantly saves energy and reduces consumption. Third, the equipment system used in this invention simplifies the process, ensuring safety, reliability, cost control, and high-quality products. Fourth, this invention only performs catalytic chain breaking without deep, strong oxidation, preserving small-molecule nutrients such as amino acids, organic acids, sugars, and bioactive peptides. It achieves a small-molecule organic nutrient demand and supply pattern: protein → (chain breaking) → amino acids, small peptides → direct absorption and utilization by plants, promoting root growth; cellulose, starch → (chain breaking) → glucose, oligosaccharides → carbon source for soil microorganisms, stimulating the reproduction of beneficial bacteria; lipids → (chain breaking) → fatty acids, glycerol → increasing plant cell membrane strength and stress resistance. Further oxidation of these nutrients not only destroys their original nutritional structure, leading to a decline or even loss of their nutritional physiological functions, but also poses a high risk of generating numerous toxic substances. Figure 3 This diagram illustrates the nutrient retention mechanism along the catalytic chain scission pathway, demonstrating a high nutrient retention rate. Figure 4 This diagram illustrates the nutrient retention mechanism under the deep oxidation pathway, where the nutrient retention rate is low.

[0055] This invention, based on practical application, utilizes an innovative process for the low-temperature, low-pressure, and multi-element catalytic hydrolysis of biomass and its waste. The resulting small-molecule organic fertilizer product highly aligns with the internationally leading scientific research conclusion that plant nutrient absorption includes not only inorganic salts (N, P, K, etc.) but also small-molecule organic nutrients (amino acids, organic acids, peptides, sugar alcohols, etc.) with higher biological activity and transport efficiency. It also aligns with the findings of long-term localization (LTE) experiments, both domestically and internationally, which have fully validated the limited and unscientific effects of simply organicating mineral nutrients. In particular, with the continuous development of nutritional science in recent years and the increasing ecological and human health hazards caused by chemical fertilizers and feed in planting and animal husbandry, people have fully recognized the growing importance of the scientific combination of inorganic and small-molecule organic nutrients for crop cultivation (agricultural fertilizers), animal (livestock feed), and human nutritional health.

[0056] For example, plants lack specialized mechanisms for efficiently absorbing and directly utilizing complex organic matter. Plant cells typically require further decomposition or transformation of organic matter before it can be utilized more effectively. Organic fertilizers should be in an active molecular state, somewhere between macromolecules and small molecules. After organic nutrients are broken down into smaller molecules, macromolecular organic matter is reduced to small molecules such as amino acids, organic acids, fatty acids, glycerol, sugars, and active peptides. This facilitates the rapid and continuous activation of the soil microbial ecosystem, promotes synergistic regulation between plants and microorganisms, and addresses soil acidification, compaction, and degradation caused by chemical fertilizer application. When inorganic mineral nutrients are coupled with small-molecule organic nutrients and hybridized into organic compounds, on the one hand, synergistic absorption with small-molecule organic nutrients is achieved, resulting in high crop absorption efficiency, minimal mineral nutrient loss, and a natural reduction in fertilizer residues and pollution. On the other hand, the small-molecule organicized mineral nutrients create a "slow-rapid-stable" three-phase supply effect, providing precise ecological mineral nutrient compensation and a more optimized and comprehensive nutrient supply for crop growth, meeting the balanced needs of crops for organic and mineral nutrients throughout the entire growth process. This invention converts mineral nutrients into small-molecule organic compounds, which not only better leverages the effectiveness of fertilizers and enables crops to efficiently and synergistically absorb organic and inorganic nutrients, but also reduces fertilizer application, significantly reduces fertilizer pollution, and yields high-quality, high-yield, and high-efficiency outputs.

[0057] The multi-element catalytic hydrolysis method of this invention for the resource recovery of biomass and its waste is a more scientific and safer preferred option.

[0058] In summary, the present invention achieves the following effects:

[0059] 1. Low temperature and low pressure combined with multi-element catalytic hydrolysis has become a more scientific, safer, and higher-value preferred option. The synergistic reaction of three different modes of action—biological fermentation, high temperature and high pressure catalysis, and mechanical grinding and cutting—has enabled the efficient treatment and utilization of different types of biomass slurry.

[0060] 2. Based on practical application, this invention has developed an innovative process for the low-temperature, low-pressure, and multi-element catalytic hydrolysis of biomass and its waste.

[0061] 3. The process method of this invention. Its environmental advantages not only avoid the well-known serious drawbacks of high input, high energy consumption, secondary pollution, or health hazards of methods such as incineration, anaerobic fermentation, and wet oxidation, but also overcome the prominent problems in agricultural application, such as long fermentation time, secondary pollution during fermentation, accumulation of bacteria, viruses, insect eggs, microbial toxins, hormones, antibiotics, heavy metal residues, large-scale volatilization or oxidation loss of effective nutrients, and the risk of producing toxic and harmful substances or their precursors.

[0062] 4. The ecological organic products produced by this invention can not only flexibly meet the diverse needs of producing a variety of products with different qualities, such as pure small molecule ecological organic products, small molecule organic-inorganic biochemical synthetic compound organic products, small molecule organic-inorganic mixed compound products, and small molecule organic microbial fungi products, but also meet the needs of the market for producing solid and liquid multi-property products. Moreover, it can achieve ecological planting and breeding, ecological health, and increased quality, production and efficiency.

[0063] 5. The aforementioned low temperature and low pressure means that the reaction temperature is controlled between 40-140 degrees Celsius and the pressure is controlled between 0.1-1.5 MPa, depending on the raw materials and the products being produced.

[0064] 6. The aforementioned multi-element catalytic hydrolysis combines various reaction agents and mechanisms, including metal and its oxide catalysts, mixed organic acids, organic acids (or bases) and their formulations, inorganic acids (or bases) and their formulations, reactive oxygen species generation equipment or formulations, and enzyme preparations. Different catalysts and reaction agents are used depending on the organic materials being treated and the products being produced, achieving a safe and efficient catalytic reaction process. For example, in the production of organic beverages, it is necessary to avoid using inorganic acids (or bases) and their formulations, and instead select one or more of the following: metal or composite metal oxide catalysts, mixed organic acids, or single organic acid reaction agents. This ensures that the produced products meet ecological, health, and safety requirements while avoiding the shortcomings of inorganic salt reaction agents, achieving the goal of a multi-element catalytic hydrolysis process that combines the advantages of different catalytic reaction agents. For example, in the production of eco-friendly fertilizers from organic waste, controlling the generation of large amounts of mixed organic acids during the fermentation catalysis process, even if a small amount of organic acid is added to the process to prepare a reaction agent for combined catalytic application, and combining temperature, pressure, etc. to improve catalytic efficiency, can achieve the goal of rapid and efficient catalytic hydrolysis. This significantly reduces the risks and costs associated with the production, storage, transportation, and application of hazardous chemicals that are associated with the addition of inorganic acid (or base) type reaction agents. In some embodiments, the multi-element catalytic hydrolysis uses a combined catalyst, which includes one or more of the following: metal and its oxide catalysts, active oxygen species generating agents, enzyme preparations, mixed organic acids, organic acids, inorganic acids or inorganic bases, and their prepared reaction agents.

[0065] 7. When using an enzyme preparation as a catalyst, the method further includes using the enzyme preparation to carry out a catalytic chain-splitting reaction within a temperature range of 40-80°C. Under controllable temperature and pH conditions, adding a specific enzyme preparation to the biomass slurry can selectively perform macromolecular chain splitting and preliminary hydrolysis of biomass structures such as lignocellulose (e.g., cellulose, hemicellulose, lignin). The 40-80°C temperature range allows the first step of bio-fermentation to proceed under milder conditions, and combined with the subsequent synergistic reaction of heating and pressurizing multi-element catalysis and mechanical homogenization, the application scenarios of the method of this invention are further enriched.

[0066] 8. Combined Application of Catalytic Reaction Agents: This process utilizes a combination of metal and oxide catalysts with organic acids, inorganic acids (or bases) and their formulated reaction agents, reactive oxygen species generation agents, and external or internal catalytic oxidant generation equipment for multi-element catalytic catalysis. This accelerates the reaction through self-valence cycling and surface active sites, initiating a chain-like series of continuous reactions of biomass in an aqueous medium. Highly reactive oxygen reacts with oxygen or hydrogen atoms in organic macromolecules to generate water, rapidly and efficiently breaking the chains of organic macromolecules. This reduces the cost of adding consumable reaction agents, lowers the reaction temperature, reduces energy consumption costs, and reduces the risk of generating toxic substances. Depending on the raw materials and products, the fermentation catalytic reaction temperature is controlled within a safe range of 40-140 degrees Celsius in a liquid-phase organic environment. Through the reaction conditions of the liquid-phase organic medium, a more efficient, complete, and safer catalytic chain-breaking reaction is achieved, rapidly degrading organic matter into micro- and nano-sized organic nutrients. This not only changes the high cost and high risk of hydrolysis relying solely on added acid (or alkali) and its formulations, but also changes the high risk of wet oxidation hydrolysis generating toxic substances or their precursors under high temperature and pressure.

[0067] In some more specific embodiments, when producing organic beverage products, metal oxide catalysts are selected, and one or more of a mixture of organic acids or a single organic acid reaction agent are used to carry out the catalytic reaction.

[0068] In some embodiments, the method for producing small-molecule eco-organic products by biomass multi-component catalytic hydrolysis further includes using an external or internal reactive oxygen species generator to generate reactive oxygen species to carry out catalytic chain scission reactions. The external or internal reactive oxygen species generator produces reactive oxygen species that rapidly react with oxygen atoms in a strongly oxidized state (O· or O¹D) with oxygen-containing groups (such as hydroxyl –OH, carbonyl –C=O, ether bonds –C–O–C–, etc.) in organic molecules. The reaction mechanism is as follows: Figure 5 As shown. In the case of an external active oxygen generation or injection device, active oxygen species are generated or directly injected under safe control conditions according to known principles and equipment systems;

[0069] With a built-in catalytic oxidation device, a highly active oxidation catalyst can be generated by directly using dissolved oxygen in a liquid organic medium, while simultaneously adding an oxidant (such as air, oxygen-enriched, or active oxygen) under catalytic oxidation reaction conditions.

[0070] External reactive oxygen species generation equipment systems and technologies are relatively mature, but they increase costs associated with equipment procurement, safety management, and environmental management. Therefore, if internal space allows, an internal method is preferred.

[0071] In the process of multi-component catalytic reaction, relatively easy-to-decompose organic matter can be rapidly reduced to small molecules, while relatively difficult-to-decompose organic matter such as lignin and cellulose can be loosened, broken up, or ring-opened to generate organic free radicals. Under further catalytic reaction conditions, a highly efficient catalytic isomorphic catalytic hydrolysis system is formed, generating a chain decomposition reaction, thereby achieving the preset technical process goal of catalytic hydrolysis and chain breaking of organic nutrient macromolecules and oxidative decomposition and removal of toxic and harmful substances.

[0072] In some embodiments, the solid product after solid-liquid separation is used to produce solid fertilizer, solid feed, or solid beverage, and the liquid product is used to produce liquid fertilizer, liquid feed, or liquid beverage.

[0073] The small-molecule liquid water-soluble fertilizer produced by the process of this invention solves the prominent problem of dripper and sprinkler clogging, which is common in many organic fertilizers on the market and is not adapted to the actual needs and development trends of modern agricultural technology. In modern facility agriculture, where drip irrigation, sprinkler irrigation, and unmanned fertilizer applicators are widely used, organic fertilizers face common problems and obstacles such as clogging of drip irrigation pipelines, drippers, and sprinklers, leading to incompatibility with irrigation methods. In practical applications, the liquid water-soluble fertilizer produced by this invention has good water solubility, high stability, good emulsification homogeneity, and is less prone to clogging pipelines, drippers, and sprinklers. It is better suited for drip and sprinkler irrigation systems and demonstrates good compatibility and adaptability to modern facility agriculture.

[0074] In practical implementation, the method for producing small-molecule eco-organic products through biomass multi-element catalytic hydrolysis, by combining pump-circulating grinding and shearing reactions with selective stirring, better ensures a complete reaction and reduces sediment buildup and reaction dead zones. Especially when addressing practical challenges such as insufficient initial moisture extraction, a relatively thick slurry, high energy consumption and loss during stirring, insufficient activation, and the presence of sediment buildup and stirring dead zones, the combination of pump-circulating grinding and shearing reactions with selective stirring results in a more complete reaction and higher efficiency.

[0075] In some embodiments, the method for producing small-molecule eco-organic products through biomass multi-component catalytic hydrolysis achieves zero wastewater, waste residue, waste gas, and waste heat emissions. The liquid portion separated from the solid-liquid mixture is a liquid product, and the solid portion is a solid product. Water evaporated to meet the concentration standards of the final product can be recycled back into the front-end water supply for reuse. This not only avoids wastewater discharge, thus reducing the environmental treatment burden and cost, but also increases organic nutrients through the reuse of the organic-containing liquid at the back end. Solid residue can be directly mixed with the solid product, avoiding emissions that increase the environmental treatment burden and cost, while still meeting the requirements of the solid product. After staged heat recovery, the finished product is near room temperature, with no significant waste heat or evaporation emissions. The small amount of waste gas emitted through the safety valve during the process can be recovered for preheating and absorption of the front-end slurry, avoiding waste gas emissions and the investment, operation, and maintenance costs of conventional waste gas scrubbing devices, as well as equipment space occupancy costs.

[0076] Furthermore, given the inherent difficulty and hazards of treating organic solid waste, and the generally increased tolerance for derivative hazards during organic waste treatment (for example, fertilizer standards rarely include heterocyclic amines, benzo[a]pyrene, and other toxic substances in mandatory safety standards), some organic waste reduction processes using high temperature and high pressure, which may generate large amounts of toxic substances or their precursors, are being treated as resource-based treatment technologies for producing organic fertilizers. This mistakenly treats farmland, essential for life and health, as a disposal site for hazardous waste, endangering ecological security and human health. Studies show that at temperatures of 150–300℃ and higher, especially under high-temperature and aerobic conditions, complex organic solid wastes such as kitchen waste and activated sludge objectively pose a high risk of generating various harmful substances, particularly acrylamide, heterocyclic amines, furans, chloropropanol, and their derivatives. According to relevant research, the hydrolysis of kitchen waste above 150℃ can generate a significant amount of chloropropanol, and the risk of chloropropanol (especially 3-MCPD) and furans increases substantially with increasing temperature, and should be avoided as much as possible. Therefore, the low-temperature, low-pressure, and multi-element catalytic hydrolysis process of this invention is a more scientific and safer preferred option.

[0077] This invention is an innovative low-temperature, low-pressure, multi-element catalytic hydrolysis process for the resource recovery of biomass and its waste, developed based on practical applications. The advantages of this invention are twofold: first, it overcomes the problems of long composting fermentation times, significant loss of effective nutrients due to volatilization, accumulation of pathogens, viruses, insect eggs, microbial toxins, hormones, antibiotics, heavy metals, and substantial secondary pollution during fermentation; second, it overcomes the high safety risks and equipment corrosion risks associated with adding inorganic acids (or alkalis) or their formulations, which increases the need for hazardous chemical storage, transportation, production, and maintenance, while also saving on land area and equipment investment. The multi-element catalytic hydrolysis utilizes a combination of metal and oxide catalysts, mixed with organic acids, inorganic acids (or alkalis) and their formulations, and reactive oxygen species generation formulations. Based on the characteristics of different organic materials and end products, multi-element catalytic hydrolysis is performed to achieve the resource recovery goals of safety, efficiency, ecological health, and value enhancement.

[0078] For example, when producing organic beverage products, it is necessary to avoid using inorganic acid reaction agents and instead choose one or more of the following: composite metal catalysts, mixed organic acids, or single organic acid reaction agents to carry out multi-element catalytic reactions. This ensures that the produced products meet the requirements for ecological health and safety, while avoiding the shortcomings of inorganic salt agents, and achieving the process goal of combining the advantages of different catalytic reaction agents.

[0079] For example, when using organic waste to produce eco-friendly fertilizers, the fermentation process generates a large amount of mixed organic acids. Active oxygen species are selected to be added to the process, and temperature and pressure are combined to achieve the goal of rapid and efficient catalytic hydrolysis while avoiding the series of risks and costs associated with the addition of inorganic acids (or alkalis) and their formulations.

[0080] The solid and liquid fertilizers prepared using this invention, and their formulation for producing small-molecule organic fertilizers with different functional properties, have the following advantages:

[0081] (1) It has high organic matter content and quality, and excellent water and fertilizer retention performance, which is far superior to traditional organic fertilizers.

[0082] (2) This method selects and adds inorganic nutrients to produce solid fertilizers and liquid fertilizers. Through the self-reorganization of the molecular structure of the added inorganic nutrients (such as nitrogen, phosphorus and potassium required by fertilizers) and organic small molecule products by bonding with ionic bonds and / or covalent bonds, the organic coupling and hybrid synthesis of inorganic nutrients and small molecule organic nutrients is realized. The resulting fertilizer contains a variety of highly efficient small molecule organic and inorganic nutrients, which are rich in nutrients, balanced and stable, far superior to organic fertilizers and fertilizer formulations produced by many compound, blending, oxidation and other process technologies.

[0083] (3) The viruses, bacteria, and insect eggs in the prepared solid and liquid fertilizers are completely killed, and toxic and harmful substances are fully removed, making them healthy, safe, stable, with a high germination index (GI value) and well-developed root system. Figure 10 As shown in Figure 11.

[0084] (4) Figure 6 As shown, this invention utilizes multi-element catalytic hydrolysis of high-molecular organic compounds into nano-sized molecules. It selectively employs high-speed grinding and / or pressure grinding and / or ultrasonic stabilization techniques, resulting in small-molecule organic nutrients with large specific surface areas and high signal transduction and targeted delivery capabilities. Pressure grinding achieves superior homogenization and micronization through the combined mechanical force, forcing rapid and efficient cutting of the liquid in a closed environment, which facilitates smooth operation of the overall process in the integrated closed-loop equipment.

[0085] (5) The product produced by this method emits a pleasant aroma such as soy sauce. In practical applications, it has also been found that the fertilizer is rich in a variety of insect-repelling substances such as phenols and aromatic compounds, which are very effective in repelling pests. This directly reduces the amount and frequency of pesticide application, and in some field applications, it even achieves complete pesticide-free application, demonstrating excellent ecological and health advantages.

[0086] (6) The solid and liquid fertilizers produced by this method can be formulated into a variety of organic fertilizers according to different needs. The solid organic fertilizer can also be used as a planting substrate, with excellent performance and high commercial value. The liquid fertilizer is highly compatible with modern agricultural drip irrigation, micro-irrigation and sprinkler irrigation, which greatly improves the fertilizer products produced by the inventor's previous technology and processes. Many organic fertilizer products on the market claim to be suitable for drip irrigation, micro-irrigation and aircraft spraying, but in actual application, they generally have serious problems of clogging drippers and nozzles. This process improvement is not only a major leap forward of the invention compared with previous technologies, but also a significant technical and application advantage compared with many organic fertilizers on the market.

[0087] (7) Heat is recovered through a heat recycling system during the production process, and a small amount of heat-containing gas emitted is recycled for slurry preheating or environmental protection treatment.

[0088] When producing ecological organic feed products, biomass raw materials can be used to produce aquatic feed or additives, livestock feed or additives according to the prescribed list of feed raw materials. Examples include soybean residue, fruit residue, plant-derived medicinal residue, crop straw, and insects raised on black water slugs. The method of this invention can produce solid, paste, and liquid small-molecule ecological organic feeds or additives. Furthermore, various types of feed products, such as biological microbial feeds, can be flexibly produced according to market demand.

[0089] For example, using soybean residue from a soybean product factory, the method of this invention can process wet soybean residue into feed ingredients, achieving a moisture content of less than 13% (actually around 12%), crude protein degradation into small molecule peptones, peptones, and protein peptides, with a small molecule crude protein content >14%, and the crude fiber and crude protein molecules in the soybean residue are degraded, with crude fiber degraded into polysaccharides, crude fiber content around 5%, and crude ash content around 3%, meeting and exceeding the "NY / T211-92 Quality Control Standard for Feed Milling," thus significantly improving the quality of feed ingredients.

[0090] For example, feed additives can be produced by multi-stage catalytic hydrolysis of fresh blackwater worms. Blackwater worms are hydrolyzed using multi-stage catalytic hydrolysis into feed additives rich in small-molecule organic nutrients such as oligopeptides, chitosan (or chitosan oligosaccharides), short-chain carbon sources, peptide calcium, and fatty acids. When mixed with feed and fed to fresh shrimp, the shrimp's growth rate, intestinal cleanliness, and yield are significantly improved. From the time of feeding to the first harvest, shrimp ponds that previously easily developed duckweed largely stopped growing duckweed, aquatic plants flourished, aquatic pests were significantly reduced, and water quality remained stable. At harvest, water quality tests showed ammonia nitrogen of 0.2–0.5 mg / L, nitrite of 0.01–0.05 mg / L, total alkali (calculated as hydrogen ions) of 1.8 mmol / L, and (calculated as calcium carbonate) of 90 mg / L. The protein powder prepared from the hydrolysate of black water slug after drying contains 5% moisture, 9.4% crude ash, 48.96% crude protein, 10.49% crude fat, 1.23% calcium, 0.58g total phosphorus, 1543.8mg / 100g volatile basic nitrogen, 0.052mg / 100g peroxide value (based on fat), 0.0506mg / kg total arsenic, no detectable lead or cadmium, no detectable Salmonella, <2.8 MPN / g Escherichia coli, 6.14 mg / g acid value (based on KOH), and 33.23% hydrolyzed amino acids (total). In control studies, it significantly improved the growth capacity, antioxidant capacity, glandular health, and muscle color and texture of shrimp, crabs, and fish. Shrimp exhibited uniform growth, plumpness, and good vitality. Figure 7 As shown.

[0091] For example, fermented liquor residues containing large amounts of rice husks, sorghum husks, barley husks, etc., and fermented vinegar residues from vinegar factories, are traditionally transported outside the factory for drying or other treatments, or directly used as feed additives in livestock farms for cattle, sheep, and pigs. However, using them as cattle and sheep feed raw materials faces problems such as low digestibility, and using them as pig feed raw materials is problematic because rice husks are undigested, making them unsuitable for direct use. Moreover, due to their high moisture content and high ambient temperature, these materials are prone to fermentation and spoilage, producing foul odors and easily triggering epidemics and infectious diseases. Using the process method of this invention, crude fiber is separated into cellulose, hemicellulose, and lignin. Cellulose is further degraded into polysaccharides and oligosaccharides, hemicellulose into polysaccharides and uronic acids, and lignin into oligosaccharides. The energy value and digestibility of fermented liquors containing rice husks, sorghum husks, barley husks, etc., are improved, allowing them to replace a portion of the energy in concentrated feed, and also serving as a substitute for starchy energy raw materials in pig feed, replacing part of the grain. After adding auxiliary materials and controlling fermentation and dehydration, high-quality small-molecule ecological organic feed raw materials can be produced with a moisture content of ≤13%, crude protein content of about 36%, crude fiber of about 6.51%, and crude ash of about 12.32%. The process of this invention not only effectively solves the problems of spoilage and odor, and environmental pollution, thus preventing the occurrence of infectious diseases, but also improves the digestibility of feed raw materials, allowing them to replace some grains and efficiently meet or exceed feed raw material standards.

[0092] To better understand the technical solution of the present invention, the following detailed description is provided in conjunction with specific embodiments:

[0093] Example 1: Preparation of small-molecule organic liquid water-soluble fertilizer using kitchen waste and traditional Chinese medicine residue

[0094] 1. Ingredients: A mixture of kitchen waste, citric acid residue, and Chinese medicine residue.

[0095] 2. Pulping and Activation: The raw materials are sorted, crushed, and the moisture content is adjusted to about 85% to obtain a homogeneous pulp.

[0096] 3. Heating and Fermentation: The slurry is heated to 90°C and 0.8 MPa in a fermentation tank using steam for 30 minutes. During this stage, the material itself ferments, producing a large amount of mixed organic acids.

[0097] 4. Multi-component catalytic hydrolysis: The slurry is pumped into the catalytic reactor, and nitrogen, phosphorus, potassium, and trace elements are added. The temperature is maintained at 115°C, and the pressure is increased to 1.0 MPa. Dissolved oxygen is activated through the built-in catalytic system, generating active oxides such as hydroxyl radicals. The reaction takes 120 minutes. This process efficiently breaks down the chains of organic macromolecules such as proteins, cellulose, and fats.

[0098] 5. Organic coupling and homogenization: Further grinding, emulsification and organic synthesis were carried out at 60°C and 0.6 MPa.

[0099] 6. Solid-liquid separation and packaging: After solid-liquid separation, lauryl alcohol, a stabilizer, is added to the liquid portion, which is then homogenized and bottled to obtain a small-molecule organic water-soluble fertilizer. The solid portion is dried to become solid fertilizer or planting substrate.

[0100] Example 2: Preparation of small-molecule feed ingredients using soybean residue

[0101] 1. Raw material: wet soybean residue from a soybean product factory.

[0102] 2. Pulping and catalytic hydrolysis: The moisture content of soybean residue was adjusted to 80%, and the reaction was carried out at 75°C and 1.5 MPa using a combination of composite metal oxide catalyst and self-generated organic acid for 150 minutes.

[0103] 3. Post-processing: Solid-liquid separation of the slurry after reaction. The solid portion is dried by a drying system, and the final product has a moisture content of ≤13%, a small molecule crude protein content of >14%, and a crude fiber content of ≤5%, meeting the quality standards of feed millings in NY / T211-92.

[0104] Example 3: Preparation of aquatic feed additives using black soldier fly larvae

[0105] 1. Raw material: fresh black soldier fly larvae.

[0106] 2. Catalytic hydrolysis: The insect body fragments were subjected to multi-element catalytic hydrolysis at 55°C and 1.4 MPa for 180 minutes.

[0107] 3. Products and Applications: The hydrolysate is rich in oligopeptides, chitosan, short-chain carbon sources, peptide calcium, fatty acids, etc. Mixing it into feed for freshwater prawns can significantly improve their growth rate, gut health, feed conversion ratio, and yield. The dried protein powder has a crude protein content of 47.96% and a total hydrolyzed amino acid content of 33.11%, and is safe and non-toxic (lead, cadmium, and Salmonella were not detected).

[0108] Example 4: Preparation of small molecule liquid beverage using dried tangerine peel pulp

[0109] 1. Raw material: Waste pulp from the processing of dried tangerine peel.

[0110] 2. Catalytic hydrolysis: After the pulp is mashed, catalytic hydrolysis is carried out using only the built-in precious metal catalyst at 40°C and 0.8 MPa, eliminating inorganic acids, and the reaction takes 75 minutes.

[0111] 3. Post-processing: The pulp undergoes solid-liquid separation, fine filtration, and adjustment of sweetness and astringency to obtain a small-molecule organic tangerine peel pulp liquid beverage, which is rich in small-molecule sugars, organic acids, and active ingredients of tangerine peel.

[0112] The above descriptions are merely some embodiments of the present invention. It should be noted that those skilled in the art can make other modifications and improvements without departing from the inventive concept of the present invention, and these all fall within the protection scope of the present invention.

Claims

1. A method for producing small-molecule eco-organic products by biomass multi-component catalytic hydrolysis, characterized in that, Includes the following steps: S1. The biomass slurry is heated and fermented to obtain fermentation catalytic slurry; S2. The fermented catalytic slurry is subjected to heating and pressurization catalytic treatment, and the synergistic reaction of heating and fermentation and heating and pressurization is combined to obtain a multi-element catalytic slurry; S3. Grind and cut the multi-component catalytic slurry to complete the coupled hybrid synthesis and homogenization treatment of the multi-component catalytic slurry; S4. The slurry after coupled hybrid synthesis and homogenization is subjected to solid-liquid separation to obtain the small molecule eco-organic product, which includes solid products and liquid products. The reaction temperature for the heating fermentation treatment and the heating and pressurizing catalytic treatment is controlled at 40-140℃, and the pressure is controlled at 0.1-1.5 MPa.

2. The method for producing small-molecule eco-organic products by biomass multi-component catalytic hydrolysis according to claim 1, characterized in that, The multi-element catalytic hydrolysis employs a combined catalytic reaction, which combines one or more of the following: metal and oxide catalysts required for the catalytic hydrolysis reaction, mixed organic acid reaction preparations, organic acid reaction preparations, inorganic acids, inorganic bases, inorganic acid-based reaction preparations, inorganic base-based reaction preparations, active oxygen species generation equipment or preparations, and enzyme preparations. When the liquid product is a drinkable beverage product, one or more of the following can be selected for the catalytic hydrolysis reaction: metal or oxide catalysts, mixed organic acids, or single organic acid reaction preparations.

3. The method for producing small-molecule eco-organic products by biomass multi-component catalytic hydrolysis according to claim 1, characterized in that, The method also includes using enzyme preparations to carry out catalytic chain scission reactions in a temperature range of 40-80°C.

4. The method for producing small-molecule eco-organic products by biomass multi-component catalytic hydrolysis according to claim 1, characterized in that, The coupled hybrid synthesis involves selectively adding inorganic nutrients to the slurry and then bonding and recombining them with small-molecule organic products via ionic and / or covalent bonds to achieve the coupled hybrid synthesis of inorganic nutrients and small-molecule organic nutrients.

5. The method for producing small-molecule eco-organic products by biomass multi-component catalytic hydrolysis according to claim 1, characterized in that, The solid product after solid-liquid separation is used to produce solid fertilizer, solid feed, or solid beverage, while the liquid product is used to produce liquid fertilizer, liquid feed, or liquid beverage.

6. The method for producing small-molecule eco-organic products by biomass multi-component catalytic hydrolysis according to claim 1, characterized in that, The method further includes adding biological strains to the small molecule ecological organic product after solid-liquid separation to produce biological small molecule organic fertilizer / feed / beverage.

7. The method for producing small-molecule eco-organic products by biomass multi-component catalytic hydrolysis according to claim 1, characterized in that, The method combines pump circulation with stirring to ensure a complete reaction and reduce dead zones and sediment buildup.

8. The method for producing small-molecule eco-organic products by biomass multi-component catalytic hydrolysis according to claim 1, characterized in that, The method achieves zero emissions of waste gas, wastewater, and waste residue. The liquid portion separated from the solid-liquid mixture is a liquid product, and the solid portion is a solid product. During the production process, heat is recovered through a heat recycling system, and the small amount of heat-containing gas emitted is reused for slurry preheating or environmental treatment.

9. The method for producing small-molecule eco-organic products by biomass multi-component catalytic hydrolysis according to claim 1, characterized in that, The biomass slurry is made from biomass raw materials, which include one or more of the following: fruit pomace, soybean residue, medicinal residue, rice, flour, oil and sugar processing residue, wine mash and lees, fruit peels, pulp, pits, vegetable waste, crop straw, waste fish and shrimp, animal remains, kitchen waste, waste residue, waste liquid and sludge from food and beverage factories, activated sludge from urban sewage treatment plants, and human and animal excrement.

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